CN110752147A - Method for nitriding substrate - Google Patents

Method for nitriding substrate Download PDF

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Publication number
CN110752147A
CN110752147A CN201911047844.0A CN201911047844A CN110752147A CN 110752147 A CN110752147 A CN 110752147A CN 201911047844 A CN201911047844 A CN 201911047844A CN 110752147 A CN110752147 A CN 110752147A
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substrate
oxygen
layer
cavity
microwave
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王青
董雅娟
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Shanghai Huali Microelectronics Corp
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Shanghai Huali Microelectronics Corp
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Priority to CN201911047844.0A priority Critical patent/CN110752147A/en
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02107Forming insulating materials on a substrate
    • H01L21/02109Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112Forming 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
    • H01L21/02123Forming 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
    • H01L21/0217Forming 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
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02107Forming insulating materials on a substrate
    • H01L21/02225Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/02227Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process
    • H01L21/02247Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by nitridation, e.g. nitridation of the substrate
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02107Forming insulating materials on a substrate
    • H01L21/02225Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/02227Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process
    • H01L21/02252Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by plasma treatment, e.g. plasma oxidation of the substrate
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02107Forming insulating materials on a substrate
    • H01L21/02296Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
    • H01L21/02299Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02107Forming insulating materials on a substrate
    • H01L21/02296Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
    • H01L21/02299Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment
    • H01L21/02312Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment treatment by exposure to a gas or vapour

Abstract

The invention provides a nitridation treatment method of a substrate, which comprises the following steps: providing a plasma nitriding device, wherein the device comprises a cavity, a gas conveying channel communicated with the cavity and a microwave transmission plate arranged in the cavity, and the microwave transmission plate is used for transmitting microwaves so as to form an electromagnetic field in the cavity and further plasmatize gas in the cavity; introducing a predetermined gas to convert the surface layer of the microwave transmission plate into a nitride layer or a oxynitride layer; providing at least one substrate and placing the substrate in the cavity to perform nitridation treatment on the substrate; wherein, when the substrate comprises a non-oxygen-containing substrate, the surface layer of the microwave transmission plate is converted into a nitride layer before the substrate is placed in the cavity; when the substrate comprises an oxygen-containing substrate, the surface layer of the microwave transmission plate is a nitrogen oxide layer before the substrate is placed in the cavity. When the nitridation method provided by the invention is adopted to carry out nitridation treatment on the substrate, the stability is higher.

Description

Method for nitriding substrate
Technical Field
The invention relates to the technical field of semiconductors, in particular to a nitridation treatment method of a substrate.
Background
In the semiconductor field, it is generally required to perform a nitridation process on a semiconductor substrate, for example, in the fabrication of a memory device, a bird's beak effect can be prevented and the data retention capability and reliability of the finally formed memory device can be enhanced by forming a nitride layer on a surface layer of the semiconductor substrate.
In the related art, the method for performing nitridation on a semiconductor substrate specifically includes: firstly, introducing nitrogen into the cavity, radiating microwaves by using the planar antenna, transmitting the microwaves into the cavity by using the microwave transmission plate connected with the planar antenna so as to form an electromagnetic field in the cavity, converting the nitrogen in the cavity into nitrogen plasma by plasma under the action of the electromagnetic field, and infiltrating the nitrogen plasma into the surface layer of the semiconductor substrate to form a nitrogen-containing region so as to form a nitride layer on the surface layer of the semiconductor substrate, thereby achieving the aim of nitriding.
However, in practice, the inventors of the present invention have found that, when a nitridation process is performed on a plurality of substrates, the nitridation rate between the respective substrates is unstable, resulting in a difference in the degree of nitridation between the plurality of substrates, affecting the stability of the nitridation process, and affecting the performance of the finally formed semiconductor device.
Disclosure of Invention
The invention aims to provide a method for nitriding a substrate, which solves the problem of unstable nitriding treatment caused by the conventional nitriding treatment method.
In order to solve the above technical problem, the present invention provides a method for nitriding a substrate, the method comprising:
providing a plasma nitriding device, wherein the device comprises a cavity, a gas conveying channel communicated with the cavity and a microwave transmission plate arranged in the cavity, and the microwave transmission plate is used for transmitting microwaves so as to form an electromagnetic field in the cavity and further plasmatize gas in the cavity;
introducing a predetermined gas to convert the surface layer of the microwave transmission plate into a nitride layer or a oxynitride layer;
providing at least one substrate and placing the substrate in the cavity to perform a nitridation process on the substrate;
wherein, when the substrate comprises a non-oxygen containing substrate, the surface layer of the microwave transparent plate is converted into a nitride layer before the substrate is placed in the cavity; when the substrate comprises an oxygen-containing substrate, the surface layer of the microwave transmission plate is a nitrogen oxide layer before the substrate is placed in the cavity.
Optionally, when the substrate includes a non-oxygen-containing substrate, before the non-oxygen-containing substrate is placed in the cavity, a predetermined gas is introduced into the cavity, where the predetermined gas includes nitrogen, so that the surface layer of the microwave-transparent plate is converted into a nitride layer.
Optionally, when the substrate includes an oxygen-containing substrate and before the predetermined gas is introduced, the predetermined gas is introduced into the chamber before the oxygen-containing substrate is placed in the chamber, where the predetermined gas includes nitrogen gas, so that the surface layer of the microwave-transparent plate is converted into a nitrogen oxide layer.
Optionally, when the substrate includes an oxygen-containing substrate and before the predetermined gas is introduced, when the surface layer of the microwave-transparent plate is a non-oxide, before the oxygen-containing substrate is placed in the chamber, the predetermined gas is introduced into the chamber, where the predetermined gas includes oxygen, so that the surface layer of the microwave-transparent plate is converted into a nitrogen oxide layer.
Optionally, when the surface layer of the microwave transmission plate is a nitride before the predetermined gas is introduced, the predetermined gas is oxygen, so that the surface layer of the microwave transmission plate is converted into a oxynitride layer; when the surface layer of the microwave transmission plate is silicon before the predetermined gas is introduced, the predetermined gas further comprises nitrogen so as to convert the surface layer of the microwave transmission plate into a silicon oxynitride layer by using the oxygen and the nitrogen.
Optionally, after performing nitridation on the oxygen-containing substrate, the surface layer of the microwave transmission plate is a nitrogen oxide layer; and
after performing the nitridation process on the oxygen-containing substrate and before performing the nitridation process on the non-oxygen-containing substrate, the method further comprises:
taking out the oxygen-containing substrate from the cavity, so that no substrate is placed in the cavity;
introducing nitrogen into the cavity, carrying out plasma transformation to obtain nitrogen atoms, and replacing the nitrogen atoms from the nitrogen oxide layer on the surface layer of the microwave transmission plate with oxygen atoms so as to change the nitrogen oxide layer into a nitride layer; and the number of the first and second groups,
and placing the non-oxygen-containing substrate in the cavity, and introducing nitrogen into the cavity to perform nitridation treatment on the non-oxygen-containing substrate.
Optionally, after performing nitridation treatment on the non-oxygen-containing substrate, the surface layer of the microwave-transparent plate is a nitrided layer; and
after performing the nitridation process on the non-oxygen containing substrate and before performing the nitridation process on the oxygen containing substrate, the method further comprises:
taking out the non-oxygen-containing substrate to ensure that no substrate is placed in the cavity;
introducing oxygen into the cavity, carrying out plasma treatment to obtain oxygen atoms, and replacing partial nitrogen atoms from the nitride layer on the surface layer of the microwave transmission plate by the oxygen atoms so as to change the nitride layer into a oxynitride layer;
and placing the oxygen-containing substrate in the cavity, and introducing nitrogen into the cavity to perform nitridation treatment on the oxygen-containing substrate.
Optionally, when the substrate includes an oxygen-containing substrate, during the nitridation process performed on the oxygen-containing substrate, a rate at which nitrogen atoms in the cavity are displaced from the nitrogen oxide layer of the microwave-transparent plate is dynamically balanced with a rate at which oxygen atoms in the cavity are displaced from the nitrogen oxide layer of the microwave-transparent plate.
Optionally, before placing the substrate in the cavity, the method further comprises: and performing vacuum pumping treatment on the cavity.
Optionally, before the predetermined gas is introduced, the microwave transmission plate is made of silicon dioxide, silicon nitride, or silicon; and the nitrided layer on the surface layer of the microwave transmission plate comprises silicon nitride, and the oxidized layer on the surface layer of the microwave transmission plate comprises a nitrogen oxidized layer comprising a silicon oxynitride layer.
Optionally, the oxygen-containing substrate includes a silicon oxide substrate, and the non-oxygen-containing substrate includes a silicon substrate or a silicon nitride substrate.
In summary, in the substrate nitridation method provided by the present invention, before performing nitridation on the non-oxygen-containing substrate, a predetermined gas is introduced to pre-convert the surface layer of the microwave transparent plate into a nitrided layer, so that when nitrogen is introduced into the cavity to be plasmatized to obtain nitrogen atoms in the subsequent process of nitriding the non-oxygen-containing substrate, the nitrogen atoms do not change the nitrided layer on the surface layer of the microwave transparent plate; and in the application, before the nitriding treatment is performed on the oxygen-containing substrate, predetermined gas is introduced to ensure that the microwave penetrates through the surface layer of the plate to be converted into the nitrogen oxide layer in advance, so that in the subsequent process of nitriding the oxygen-containing substrate, when nitrogen is introduced into the cavity and nitrogen atoms are obtained through plasma ionization, even if the nitrogen atoms can replace the oxygen atoms from the oxygen-containing substrate, the oxygen atoms and the nitrogen atoms exist in the cavity, but because the nitrogen oxide layer comprising the nitrogen atoms and the oxygen atoms is formed in advance on the surface layer of the microwave-permeable plate, the oxygen atoms and the nitrogen atoms in the cavity cannot enable the microwave to penetrate through the nitrogen oxide layer on the surface layer of the plate to be changed.
That is, the substrate nitridation method provided by the present invention can prevent the material of the surface layer of the microwave transparent plate from changing during the substrate nitridation process, and ensure that the microwave transparent plate can maintain stable microwave transmission capability, and further stabilize the intensity of the electromagnetic field in the cavity, so that when a plurality of substrates are subjected to nitridation, the difference in nitridation degree between the substrates can be reduced, the stability of nitridation can be ensured, and the performance of the finally formed semiconductor device can be ensured.
Drawings
FIG. 1 is a schematic diagram of a prior art plasma nitridation apparatus configured to perform nitridation on non-oxygen containing substrates;
FIG. 2 is a schematic diagram of a prior art plasma nitridation apparatus configured to perform nitridation on an oxygen-containing substrate;
FIG. 3 is a flowchart illustrating a substrate nitridation processing method according to an embodiment of the present invention;
FIG. 4 is a schematic diagram illustrating a plasma nitridation apparatus according to an embodiment of the present invention;
FIG. 5 is a schematic diagram illustrating a plasma nitridation apparatus according to an embodiment of the present invention after a predetermined gas is introduced before nitridation is performed on a non-oxygen-containing substrate;
FIG. 6 is a schematic structural diagram of a plasma nitridation apparatus according to one embodiment of the present invention, after a predetermined gas is introduced into the apparatus before nitridation is performed on an oxygen-containing substrate;
fig. 7 is a schematic diagram illustrating the content of nitrogen atoms infiltrated into each oxygen-containing substrate when the non-oxygen-containing substrate is nitrided and then the oxygen-containing substrate is nitrided according to this embodiment.
Detailed Description
As described in the background, in the related art, a nitridation process is performed on a plurality of substrates, wherein the substrates typically include oxygen-containing substrates (e.g., silicon oxide substrates) or non-oxygen-containing substrates (e.g., silicon substrates or silicon nitride substrates). In general, in the art, a plurality of substrates are nitrided in the same chamber, and when a plurality of substrates are processed, the material of the surface layer of the microwave-transparent plate changes, which makes the nitriding unstable.
Specifically, the material of the microwave-transparent plate is generally silicon dioxide, and on this basis, when a plurality of non-oxygen-containing substrates are processed in the cavity, after nitrogen gas introduced into the cavity is ionized to form nitrogen atoms when the first few non-oxygen-containing substrates are processed, part of the nitrogen atoms penetrate into the surface layer of the microwave-transparent plate and form polar bonds with silicon atoms in the microwave-transparent plate, so that the surface layer of the microwave-transparent plate is changed from silicon dioxide to silicon nitride.
For example, fig. 1 is a schematic structural diagram of a plasma nitridation apparatus for performing nitridation on a non-oxygen-containing substrate a in the prior art, as shown in fig. 1, when performing nitridation on a non-oxygen-containing substrate a, a part of nitrogen atoms (i.e., N shown in fig. 1) in a cavity 1 may penetrate into a surface layer of a microwave-transmissive plate 01 and form polar bonds with silicon atoms on the surface layer of the microwave-transmissive plate, so that the surface layer of the microwave-transmissive plate is changed into silicon nitride (not numbered in the figure).
And if a plurality of oxygen-containing substrates are processed in the cavity, after nitrogen is formed by plasma of introduced nitrogen when the first oxygen-containing substrates are processed, part of nitrogen atoms penetrate into the surface layer of the oxygen-containing substrates and are replaced by oxygen atoms, and part of nitrogen atoms in the cavity and the replaced oxygen atoms penetrate into the surface layer of the microwave transmission plate, so that the surface layer of the microwave transmission plate is changed into silicon oxynitride.
Fig. 2 is a schematic structural diagram of a plasma nitridation apparatus for performing nitridation on an oxygen-containing substrate B in the prior art, wherein during the nitridation on the oxygen-containing substrate B, nitrogen atoms in the cavity 1 are replaced by oxygen atoms (i.e., O shown in fig. 2) from a surface layer of the oxygen-containing substrate B, and the replaced oxygen atoms and a part of the nitrogen atoms in the cavity penetrate into a surface layer of the microwave-transmissive plate 01 to form polar bonds with silicon atoms on the surface layer of the microwave-transmissive plate 01, so that the surface layer of the microwave-transmissive plate is changed to silicon oxynitride.
Further, it is common in the art to nitride the non-oxygen containing substrate prior to nitriding the oxygen containing substrate. In the above, after the non-oxygen-containing substrate is nitrided, the surface layer of the microwave-transparent plate is changed from silicon dioxide to silicon nitride, and therefore, if the oxygen-containing substrate is continuously nitrided in the same chamber, after nitrogen is introduced to obtain nitrogen atoms, part of the nitrogen atoms are replaced by oxygen atoms from the oxygen-containing substrate, and the replaced oxygen atoms are permeated into the silicon nitride on the surface layer of the microwave-transparent plate, so that the silicon nitride is changed into silicon oxynitride.
As can be seen from the above, if only a plurality of non-oxygen-containing substrates are nitrided, the surface layer of the microwave-transmissive plate is changed from silicon dioxide to silicon nitride when the non-oxygen-containing substrates are treated before; if only a plurality of oxygen-containing substrates are subjected to nitridation treatment, the surface layer of the microwave transmission plate is changed from silicon dioxide to silicon oxynitride when the first oxygen-containing substrates are treated; if the non-oxygen-containing substrate is nitrided in the same cavity and then the oxygen-containing substrate is nitrided, the surface layer of the microwave transmission plate is changed from silicon dioxide to silicon nitride and then to silicon oxynitride.
However, when the microwave transmission ability of the silicon dioxide, the silicon nitride, and the silicon oxynitride is different, in the process of nitriding the plurality of substrates, if the material of the surface layer of the microwave-transparent plate changes (for example, the silicon dioxide is changed to the silicon nitride, the silicon dioxide is changed to the silicon oxynitride, or the silicon nitride is changed to the silicon oxynitride), the microwave transmission ability of the microwave-transparent plate is unstable, and further the intensity of the electromagnetic field formed in the cavity fluctuates, so that the concentration of the nitrogen atoms ionized by the electromagnetic field is unstable, and further the concentration of the nitrogen atoms penetrating into each substrate is different, which causes the difference in the nitridation degree among the plurality of substrates, affects the stability of the nitridation process, and affects the performance of the finally formed semiconductor device.
In view of the above, the present invention provides a method for nitriding a substrate, which can reduce the difference in the degree of nitridation between substrates and ensure the stability of the nitriding process when the nitriding process is performed on a plurality of substrates. The method for nitriding a substrate according to the present invention will be described in further detail with reference to the accompanying drawings and specific examples. The advantages and features of the present invention will become more apparent from the following description. It is to be noted that the drawings are in a very simplified form and are not to precise scale, which is merely for the purpose of facilitating and distinctly claiming the embodiments of the present invention.
Fig. 3 is a schematic flow chart of a substrate nitridation processing method according to an embodiment of the present invention, as shown in fig. 3, the method may include:
a plasma nitridation apparatus is provided, step 100.
Fig. 4 is a schematic structural diagram of a plasma nitridation apparatus according to an embodiment of the present invention, and as shown in fig. 4, the apparatus may include a chamber 10, a gas transmission channel 11 communicating with the chamber 10, and a microwave transparent plate 12 disposed in the chamber 10. Wherein, the gas transmission pipeline 11 is used for inputting gas into the cavity 10; the microwave transparent plate 12 is used for transmitting microwaves to form an electromagnetic field in the cavity, so as to plasmatize gas in the cavity. And the joint of the gas transmission pipeline 11 and the cavity 10 is close to the microwave transmission plate 12, so as to ensure that the gas which is introduced into the cavity can be well plasmatized.
Further, the apparatus further comprises a microwave generator 20 connected to the microwave-transparent plate 12, a susceptor 13 disposed in the chamber 10 and opposite to the microwave-transparent plate 12, and a vacuum extractor (not shown) in communication with the chamber. Wherein the microwave generator 20 is used for generating microwaves and transmitting the microwaves to the microwave transparent plate 12, and the microwave generator 20 may be a planar antenna, for example; the bearing table 13 is used for bearing a substrate so as to carry out nitridation treatment on the substrate; and the vacuum extractor is used for performing vacuum extraction treatment on the cavity.
Step 200, introducing a predetermined gas to convert the surface layer of the microwave transmission plate 12 into a nitride layer or a oxynitride layer. The surface layer of the microwave transmission plate is specifically located on one side of the microwave transmission plate facing the bearing table, the nitride layer can be a silicon nitride layer, and the oxynitride layer can be a silicon oxynitride layer.
In the present embodiment, the selection of the predetermined gas is different based on the conversion result required for the surface layer of the microwave-transparent plate (i.e., whether the conversion result is a nitride layer or a silicon nitride layer), and the selection of the predetermined gas is also affected by the material of the microwave-transparent plate before the predetermined gas is introduced.
Specifically, on the premise that the surface layer of the microwave-transparent plate 12 needs to be converted into a nitrogen oxide layer, if the material of the microwave-transparent plate is an oxide (e.g., silicon dioxide) before a predetermined gas is introduced, the predetermined gas may be nitrogen, and after the nitrogen is plasmatized in a cavity to form nitrogen atoms, the nitrogen will penetrate into the surface layer of the microwave-transparent plate, so that the surface layer of the microwave-transparent plate is changed from the oxide to a nitrogen oxide; if the material of the microwave transmission plate is a nitride (e.g., silicon nitride) before the predetermined gas is introduced, the predetermined gas may be oxygen, and the oxygen may penetrate into the surface layer of the microwave transmission plate after being plasmatized in the cavity to form oxygen atoms, so that the surface layer of the microwave transmission plate is changed from the nitride to an oxynitride; if the microwave transmission plate is made of silicon before the predetermined gas is introduced, the predetermined gas can be oxygen and nitrogen, and the nitrogen can penetrate into the surface layer of the microwave transmission plate after being formed into nitrogen atoms and nitrogen atoms in a plasma mode in the cavity, so that the surface layer of the microwave transmission plate is changed from silicon to nitrogen oxide.
And, further, when the surface layer of the microwave-transparent plate 12 needs to be converted into a nitride layer, no matter the material of the microwave-transparent plate is oxide or silicon, the predetermined gas is nitrogen, and after nitrogen atoms are formed in the cavity by plasma formation, the nitrogen gas will penetrate into the surface layer of the microwave-transparent plate and form polar bonds with atoms (such as silicon atoms) in the microwave-transparent plate, so that the surface layer of the microwave-transparent plate is changed into nitride.
Step 300, providing at least one substrate, and placing the substrate in the cavity 10 to perform a nitridation process on the substrate.
When the substrate comprises a non-oxygen-containing substrate (such as a silicon nitride substrate or a silicon substrate), the surface layer of the microwave transmission plate is converted into a nitride layer before the non-oxygen-containing substrate is placed in the cavity, so that when nitrogen is subsequently introduced to nitride the non-oxygen-containing substrate, the nitrogen does not change the nitride layer, and the material of the surface layer of the microwave transmission plate can not change in the process of nitriding the non-oxygen-containing substrate, thereby ensuring the stability of nitriding treatment.
For example, fig. 5 is a schematic structural diagram of a plasma nitridation apparatus according to an embodiment of the present invention, after a predetermined gas is introduced into the plasma nitridation apparatus before nitridation is performed on a non-oxygen-containing substrate, as shown in fig. 5, the surface layer of the microwave-transparent plate 12 of the chamber 10 has been converted into a silicon nitride layer (not numbered).
And when the substrate comprises an oxygen-containing substrate (such as a silicon oxide substrate), before the oxygen-containing substrate is placed in the cavity, the surface layer of the microwave transmission plate is converted into a nitrogen oxide layer, so that even if nitrogen is introduced to nitride the oxygen-containing substrate subsequently, nitrogen atoms formed after nitrogen plasma is ionized can be replaced by oxygen atoms from the oxygen-containing substrate, however, because the nitrogen atoms and the oxygen atoms in the cavity can not change the nitrogen oxide layer, the material of the surface layer of the microwave transmission plate can not change in the process of nitriding the oxygen-containing substrate, and further the stability of nitriding treatment can be ensured.
For example, fig. 6 is a schematic structural diagram of a plasma nitridation apparatus according to an embodiment of the present invention, after predetermined gas is introduced before nitridation processing is performed on an oxygen-containing substrate, as shown in fig. 6, before the predetermined gas is introduced, the material of the microwave transparent plate 12 includes silicon, and the predetermined gas introduced includes nitrogen and oxygen, after the predetermined gas is introduced, the surface layer of the microwave transparent plate 12 of the chamber 10 is converted into a silicon oxynitride layer (not numbered in the figure).
In this embodiment, the same cavity is also used to perform nitridation on the plurality of substrates, and specifically, the nitridation methods for the plurality of substrates are divided into the following methods:
firstly, only carrying out nitridation treatment on a plurality of non-oxygen-containing substrates;
secondly, only carrying out nitridation treatment on a plurality of oxygen-containing substrates;
thirdly, firstly carrying out nitridation treatment on at least one non-oxygen-containing substrate, and then carrying out nitridation treatment on at least one oxygen-containing substrate;
and fourthly, firstly carrying out nitridation treatment on at least one oxygen-containing substrate, and then carrying out nitridation treatment on at least one non-oxygen-containing substrate.
The specific implementation manners of the steps 200 and 300 are different from each other, and the following is a detailed description of the four ways of nitriding a plurality of substrates:
first, only non-oxygen containing substrates are subjected to a nitridation process.
The predetermined gas introduced into the chamber 10 in step 200a should be nitrogen gas so that the microwave-transparent plate surface layer is changed into a nitride layer. Thereafter, a vacuum process may be performed on the chamber to ensure that the chamber is in a vacuum state. Then, step 300 is performed, i.e., a non-oxygen-containing substrate is provided, and the non-oxygen-containing substrate is placed in the chamber 10, and nitrogen is introduced to nitride the non-oxygen-containing substrate.
Before the non-oxygen-containing substrate is nitrided, the surface layer of the microwave transmission plate is changed into a nitrided layer in advance, and in the process of nitriding the non-oxygen-containing substrate, the nitrided layer cannot be changed due to nitrogen atoms in the cavity, so that the material of the nitrided layer on the surface layer of the microwave transmission plate cannot be changed in the process of nitriding the non-oxygen-containing substrate, the stability of the microwave transmission capacity of the microwave transmission plate can be ensured, and the stability of nitriding treatment can be ensured.
After the non-oxygen-containing substrate is nitrided, the material of the surface layer of the microwave-transparent plate is still a nitrided layer.
Second, only the oxygen-containing substrate is subjected to a nitriding treatment.
The predetermined gas is introduced into the chamber 10 in step 200a such that the microwave-transparent plate surface layer is changed into the oxynitride layer. The selection of the predetermined gas is mainly determined based on the material of the microwave transmission plate before the predetermined gas is introduced, and the specific selection mode of the predetermined gas is described in detail in the step 200, which is not repeated herein. And after the microwave transmission plate surface layer is changed into the oxynitride layer in advance, performing vacuum-pumping treatment on the cavity to ensure that the cavity is in a vacuum state. Then, step 300 is performed, in which an oxygen-containing substrate is provided, and the oxygen-containing substrate is placed on the susceptor, and nitrogen is introduced to nitride the oxygen-containing substrate.
Because the material of the surface layer of the microwave transmission plate is changed into the nitrogen oxide layer in advance before the non-oxygen-containing substrate is nitrided, even if nitrogen is introduced into the cavity to form nitrogen atoms through plasma during subsequent nitriding of the oxygen-containing substrate, part of the nitrogen atoms can replace oxygen atoms from the oxygen-containing substrate, however, the nitrogen oxide layer cannot be changed due to the oxygen atoms and the nitrogen atoms in the cavity, so that the material of the nitrogen oxide layer of the surface layer of the microwave transmission plate cannot be changed during nitriding of the oxygen-containing substrate, the stability of the microwave transmission capacity of the microwave transmission plate can be ensured, and the stability of nitriding treatment can be further ensured.
In addition, in the embodiment, during the process of nitriding the oxygen-containing substrate, the oxygen atoms in the cavity may displace the nitrogen atoms from the oxynitride layer, the nitrogen atoms in the cavity may displace the oxygen atoms from the oxynitride layer, and a dynamic balance between a rate of displacing the oxygen atoms from the oxynitride layer of the microwave-transparent plate and a rate of displacing the nitrogen atoms from the oxynitride layer of the microwave-transparent plate is maintained between the nitrogen atoms in the cavity and the rate of displacing the oxygen atoms from the oxynitride layer of the microwave-transparent plate, so that after the nitriding of the oxygen-containing substrate is completed, the material of the surface layer of the microwave-transparent plate remains the oxynitride layer.
As can be seen from the above, if only the oxygen-containing substrates or the non-oxygen-containing substrates are subjected to the nitridation treatment, before the oxygen-containing substrates or the non-oxygen-containing substrates are placed in the cavity, a predetermined gas is introduced into the cavity without the substrates, so as to form a nitrided layer or an oxynitride layer on the surface layer of the microwave-transparent plate in advance, thereby ensuring that the material of the surface layer of the microwave-transparent plate is not changed when the oxygen-containing substrates or the non-oxygen-containing substrates are subjected to the nitridation treatment.
And thirdly, firstly carrying out nitridation treatment on at least one non-oxygen-containing substrate, and then carrying out nitridation treatment on at least one oxygen-containing substrate.
The predetermined gas introduced in step 200 should be nitrogen gas so that the material of the surface layer of the microwave-transparent plate is changed to a nitride layer in advance. And then, performing vacuum pumping treatment on the cavity to ensure that the cavity is in a vacuum state.
Then, step 300 is performed, in which at least one non-oxygen-containing substrate is nitrided, and at least one oxygen-containing substrate is nitrided. Specifically, the method can comprise the following steps:
step one, providing a non-oxygen-containing substrate, placing the non-oxygen-containing substrate on a bearing table of a cavity, and introducing nitrogen to perform nitridation treatment on the oxygen-containing substrate.
And step two, taking out the non-oxygen-containing substrate to ensure that no substrate is placed in the cavity. At this time, the surface layer of the microwave transmission plate is a nitride layer.
And thirdly, introducing oxygen into the cavity, carrying out plasma treatment to obtain oxygen atoms, and replacing partial nitrogen atoms from the nitride layer on the surface layer of the microwave transmission plate by the oxygen atoms so as to change the nitride layer into a nitrogen oxide layer.
And step four, providing an oxygen-containing substrate, placing the oxygen-containing substrate in the cavity, and introducing nitrogen into the cavity to perform nitridation treatment on the oxygen-containing substrate.
In this embodiment, after the nitridation treatment is performed on the non-oxygen-containing substrate and the non-oxygen-containing substrate is taken out from the cavity, instead of directly placing the oxygen-containing substrate in the cavity for nitridation treatment as in the prior art, oxygen is introduced into the cavity in which the substrate is not placed, so that the oxygen oxidizes the microwaves to penetrate through the nitrided layer on the surface layer of the plate to obtain the oxynitride layer, and then the oxygen-containing substrate is placed in the cavity for nitridation treatment. That is, compared to the prior art, in the embodiment, after the nitridation process is performed on the non-oxygen-containing substrate and before the nitridation process is performed on the oxygen-containing substrate, the oxynitride layer is formed in the cavity, so that it is ensured that the material of the surface layer of the microwave transmissive plate does not change during the subsequent processing on the oxygen-containing substrate, the stability of the microwave transmission capability of the microwave transmissive plate is ensured, and further the stability of the intensity of the electromagnetic field formed in the cavity is ensured, so that the concentration of the nitrogen atoms plasmatized in the electromagnetic field is stable, the difference in the concentration of the nitrogen atoms penetrating into each substrate is reduced, and the stability of the nitridation process is ensured.
For example, fig. 7 is a schematic diagram of the content of nitrogen atoms permeated into each oxygen-containing substrate when the oxygen-containing substrate is subjected to a nitridation process after the non-oxygen-containing substrate is subjected to the nitridation process, in which the horizontal axis in the graph of fig. 7 represents the ith oxygen-containing substrate processed after the non-oxygen-containing substrate is subjected to the nitridation process, i is a positive integer, and the vertical axis represents the content of nitrogen atoms of the ith oxygen-containing substrate after the ith oxygen-containing substrate is subjected to the nitridation process, and the dotted line in fig. 7 represents the content of nitrogen atoms of the ith oxygen-containing substrate when the method of the present embodiment is adopted, and the solid line in fig. 7 represents the content of nitrogen atoms of the ith oxygen-containing substrate when the method of the related art is adopted. Then, by comparison, when the method in the prior art is adopted, the content of nitrogen atoms in the 1 st oxygen-containing substrate is greatly different from the content of nitrogen atoms in the 10 th oxygen-containing substrate (for example, by 4%), then the nitridation process in the prior art is not stable; when the method of this embodiment is adopted, the content of nitrogen atoms in the 1 st oxygen-containing substrate is very small (for example, 0.5% different) from the content of nitrogen atoms in the 10 th oxygen-containing substrate, and the nitridation process in this embodiment is stable.
And fourthly, firstly carrying out nitridation treatment on at least one oxygen-containing substrate, and then carrying out nitridation treatment on at least one non-oxygen-containing substrate.
The predetermined gas is introduced into the chamber 10 in step 200a such that the microwave-transparent plate surface layer is changed into the oxynitride layer. The selection of the predetermined gas is determined based on the material of the microwave transmission plate before the predetermined gas is introduced, and the specific selection mode of the predetermined gas is described in detail in step 200, which is not repeated herein. Thereafter, a vacuum process may be performed on the chamber to ensure that the chamber is in a vacuum state.
Then, step 300 is performed, in which at least one oxygen-containing substrate is nitrided, and at least one non-oxygen-containing substrate is nitrided. Specifically, the method can comprise the following steps:
the method comprises the steps of firstly, providing an oxygen-containing substrate, placing the oxygen-containing substrate on a bearing table, and introducing nitrogen to perform nitridation treatment on the oxygen-containing substrate.
And secondly, taking out the oxygen-containing substrate from the cavity, so that the substrate is not placed in the cavity, and at the moment, the microwave penetrates through the nitrogen oxide layer on the surface layer of the plate.
And thirdly, introducing nitrogen into the cavity, carrying out plasma treatment to obtain nitrogen atoms, and replacing the nitrogen atoms from the nitrogen oxide layer on the surface layer of the microwave transmission plate to obtain oxygen atoms so as to change the nitrogen oxide layer into a nitride layer.
And fourthly, providing a non-oxygen-containing substrate, placing the non-oxygen-containing substrate in the bearing table, and introducing nitrogen into the cavity so as to perform nitridation treatment on the non-oxygen-containing substrate.
In addition, when the four methods are used to perform the nitridation process on the plurality of substrates, the step of introducing the predetermined gas is only performed before the first substrate is placed in the chamber, and if the subsequent nitridation process is performed on the substrate of the same type as the previous substrate (i.e., the substrate types are both oxygen-containing substrates or both non-oxygen-containing substrates), the predetermined gas does not need to be introduced, and if the subsequent nitridation process is performed on the substrate of the different type from the previous substrate, the predetermined gas introduction operation needs to be performed again. For example, if a plurality of non-oxygen-containing substrates are nitrided first and then a plurality of oxygen-containing substrates are nitrided, it is only necessary to perform an operation of introducing a predetermined gas into the cavity before the first non-oxygen-containing substrate is placed into the cavity for nitriding, so that the microwave transmission plate surface layer is converted into a nitrided layer, and then, when the second and third non-oxygen-containing substrates are nitrided, the operation of introducing the predetermined gas is not required; and after the nitridation treatment is carried out on the non-oxygen-containing substrates and before the nitridation treatment is carried out on the first oxygen-containing substrate, the operation of introducing the preset gas into the cavity is carried out so that the microwave is converted into the oxynitride layer through the surface layer of the plate, and then the operation of introducing the preset gas is not required to be carried out when the nitridation treatment is carried out on the second oxygen-containing substrate and the third oxygen-containing substrate.
In summary, in the substrate nitridation method provided by the present invention, before performing nitridation on the non-oxygen-containing substrate, a predetermined gas is introduced to pre-convert the surface layer of the microwave transparent plate into a nitrided layer, so that when nitrogen is introduced into the cavity to be plasmatized to obtain nitrogen atoms in the subsequent process of nitriding the non-oxygen-containing substrate, the nitrogen atoms do not change the nitrided layer on the surface layer of the microwave transparent plate; and in the application, before the nitriding treatment is performed on the oxygen-containing substrate, predetermined gas is introduced to ensure that the microwave penetrates through the surface layer of the plate to be converted into the nitrogen oxide layer in advance, so that in the subsequent process of nitriding the oxygen-containing substrate, when nitrogen is introduced into the cavity and nitrogen atoms are obtained through plasma ionization, even if the nitrogen atoms can replace the oxygen atoms from the oxygen-containing substrate, the oxygen atoms and the nitrogen atoms exist in the cavity, but because the nitrogen oxide layer comprising the nitrogen atoms and the oxygen atoms is formed in advance on the surface layer of the microwave-permeable plate, the oxygen atoms and the nitrogen atoms in the cavity cannot enable the microwave to penetrate through the nitrogen oxide layer on the surface layer of the plate to be changed.
That is, the substrate nitridation method provided by the present invention can prevent the material of the surface layer of the microwave transparent plate from changing during the substrate nitridation process, and ensure that the microwave transparent plate can maintain stable microwave transmission capability, and further stabilize the intensity of the electromagnetic field in the cavity, so that when a plurality of substrates are subjected to nitridation, the difference in nitridation degree between the substrates can be reduced, the stability of nitridation can be ensured, and the performance of the finally formed semiconductor device can be ensured.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. For the system disclosed by the embodiment, the description is relatively simple because the system corresponds to the method disclosed by the embodiment, and the relevant points can be referred to the method part for description.
The above description is only for the purpose of describing the preferred embodiments of the present invention, and is not intended to limit the scope of the present invention, and any variations and modifications made by those skilled in the art based on the above disclosure are within the scope of the appended claims.

Claims (11)

1. A method of nitriding a substrate, the method comprising:
providing a plasma nitriding device, wherein the device comprises a cavity, a gas conveying channel communicated with the cavity and a microwave transmission plate arranged in the cavity, and the microwave transmission plate is used for transmitting microwaves so as to form an electromagnetic field in the cavity and further plasmatize gas in the cavity;
introducing a predetermined gas to convert the surface layer of the microwave transmission plate into a nitride layer or a oxynitride layer;
providing at least one substrate and placing the substrate in the cavity to perform a nitridation process on the substrate;
wherein, when the substrate comprises a non-oxygen containing substrate, the surface layer of the microwave transparent plate is converted into a nitride layer before the substrate is placed in the cavity; when the substrate comprises an oxygen-containing substrate, the surface layer of the microwave transmission plate is a nitrogen oxide layer before the substrate is placed in the cavity.
2. The method of claim 1, wherein when the substrate comprises a non-oxygen containing substrate, the predetermined gas comprising nitrogen is introduced into the chamber prior to placing the non-oxygen containing substrate in the chamber to convert the surface layer of the microwave transparent plate into a nitride layer.
3. The method of claim 1, wherein when the substrate comprises an oxygen-containing substrate and the surface layer of the microwave-transparent plate is an oxide before the predetermined gas is introduced, the predetermined gas comprising nitrogen is introduced into the chamber before the oxygen-containing substrate is placed in the chamber, such that the surface layer of the microwave-transparent plate is converted to a nitride oxide layer.
4. The method of claim 1, wherein when the substrate comprises an oxygen-containing substrate and the surface layer of the microwave-transparent plate is a non-oxide before the predetermined gas is introduced, the predetermined gas comprising oxygen is introduced into the chamber before the oxygen-containing substrate is placed in the chamber to convert the surface layer of the microwave-transparent plate into a oxynitride layer.
5. The method according to claim 4, wherein when the surface layer of the microwave-transparent plate is a nitride before the predetermined gas is introduced, the predetermined gas is oxygen gas to convert the surface layer of the microwave-transparent plate into a oxynitride layer; when the surface layer of the microwave transmission plate is silicon before the predetermined gas is introduced, the predetermined gas further comprises nitrogen so as to convert the surface layer of the microwave transmission plate into a silicon oxynitride layer by using the oxygen and the nitrogen.
6. The method according to claim 1, wherein the microwave-transparent plate has a nitrided oxide layer on a surface thereof after the nitriding process is performed on the oxygen-containing substrate; and
after performing the nitridation process on the oxygen-containing substrate and before performing the nitridation process on the non-oxygen-containing substrate, the method further comprises:
taking out the oxygen-containing substrate from the cavity, so that no substrate is placed in the cavity;
introducing nitrogen into the cavity, carrying out plasma transformation to obtain nitrogen atoms, and replacing the nitrogen atoms from the nitrogen oxide layer on the surface layer of the microwave transmission plate with oxygen atoms so as to change the nitrogen oxide layer into a nitride layer; and the number of the first and second groups,
and placing the non-oxygen-containing substrate in the cavity, and introducing nitrogen into the cavity to perform nitridation treatment on the non-oxygen-containing substrate.
7. The method of claim 1, wherein after the nitriding process is performed on the non-oxygen-containing substrate, the surface layer of the microwave-transparent plate is a nitride layer; and
after performing the nitridation process on the non-oxygen containing substrate and before performing the nitridation process on the oxygen containing substrate, the method further comprises:
taking out the non-oxygen-containing substrate to ensure that no substrate is placed in the cavity;
introducing oxygen into the cavity, carrying out plasma treatment to obtain oxygen atoms, and replacing partial nitrogen atoms from the nitride layer on the surface layer of the microwave transmission plate by the oxygen atoms so as to change the nitride layer into a oxynitride layer;
and placing the oxygen-containing substrate in the cavity, and introducing nitrogen into the cavity to perform nitridation treatment on the oxygen-containing substrate.
8. The method of claim 1, wherein when the substrate comprises an oxygen-containing substrate, the nitrogen atoms in the cavity are displaced from the nitrogen oxide layer of the microwave-transparent plate at a rate that is dynamically balanced with the displacement of the nitrogen atoms in the cavity from the nitrogen oxide layer of the microwave-transparent plate during the nitridation of the oxygen-containing substrate.
9. The method of claim 1, wherein prior to placing the substrate in the cavity, the method further comprises: and performing vacuum pumping treatment on the cavity.
10. The method according to claim 1, wherein before the predetermined gas is introduced, the microwave-transparent plate is made of silicon dioxide, silicon nitride, or silicon; and the nitrided layer on the surface layer of the microwave transmission plate comprises silicon nitride, and the oxidized layer on the surface layer of the microwave transmission plate comprises a nitrogen oxidized layer comprising a silicon oxynitride layer.
11. The method of claim 1, wherein the oxygen-containing substrate comprises a silicon oxide substrate and the non-oxygen-containing substrate comprises a silicon substrate or a silicon nitride substrate.
CN201911047844.0A 2019-10-30 2019-10-30 Method for nitriding substrate Pending CN110752147A (en)

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KR20060124591A (en) * 2005-05-30 2006-12-05 동경 엘렉트론 주식회사 Plasma processing method
CN101681836A (en) * 2007-05-29 2010-03-24 东京毅力科创株式会社 Method for pretreating inner space of chamber in plasma nitridation, plasma processing method and plasma processing apparatus
CN102725834A (en) * 2010-03-31 2012-10-10 东京毅力科创株式会社 Plasma nitriding treatment method and plasma nitriding treatment device
CN102725835A (en) * 2010-03-31 2012-10-10 东京毅力科创株式会社 Plasma nitridization method

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20060124591A (en) * 2005-05-30 2006-12-05 동경 엘렉트론 주식회사 Plasma processing method
CN101681836A (en) * 2007-05-29 2010-03-24 东京毅力科创株式会社 Method for pretreating inner space of chamber in plasma nitridation, plasma processing method and plasma processing apparatus
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