CN115976492A - Film deposition method - Google Patents
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- CN115976492A CN115976492A CN202211525793.XA CN202211525793A CN115976492A CN 115976492 A CN115976492 A CN 115976492A CN 202211525793 A CN202211525793 A CN 202211525793A CN 115976492 A CN115976492 A CN 115976492A
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- 238000000151 deposition Methods 0.000 title description 12
- 238000000034 method Methods 0.000 claims abstract description 161
- 239000002243 precursor Substances 0.000 claims abstract description 112
- 239000000376 reactant Substances 0.000 claims abstract description 112
- 238000007736 thin film deposition technique Methods 0.000 claims abstract description 66
- 238000002347 injection Methods 0.000 claims abstract description 58
- 239000007924 injection Substances 0.000 claims abstract description 58
- 239000010409 thin film Substances 0.000 claims abstract description 46
- 238000010926 purge Methods 0.000 claims abstract description 29
- 239000007789 gas Substances 0.000 claims description 251
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 21
- 239000001257 hydrogen Substances 0.000 claims description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 229910021529 ammonia Inorganic materials 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 150000002431 hydrogen Chemical class 0.000 claims description 9
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 6
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 6
- 239000012686 silicon precursor Substances 0.000 claims description 5
- 239000004065 semiconductor Substances 0.000 abstract description 12
- 239000010408 film Substances 0.000 description 44
- 238000010586 diagram Methods 0.000 description 12
- 238000002513 implantation Methods 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 230000008021 deposition Effects 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- -1 halogen silane compound Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 2
- 150000002366 halogen compounds Chemical class 0.000 description 2
- OWKFQWAGPHVFRF-UHFFFAOYSA-N n-(diethylaminosilyl)-n-ethylethanamine Chemical compound CCN(CC)[SiH2]N(CC)CC OWKFQWAGPHVFRF-UHFFFAOYSA-N 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- LXEXBJXDGVGRAR-UHFFFAOYSA-N trichloro(trichlorosilyl)silane Chemical compound Cl[Si](Cl)(Cl)[Si](Cl)(Cl)Cl LXEXBJXDGVGRAR-UHFFFAOYSA-N 0.000 description 2
- 238000000231 atomic layer deposition Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000427 thin-film deposition Methods 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
The present application relates to a thin film deposition method. In one embodiment of the present application, a thin film deposition method includes: injecting a precursor from a precursor source into the process chamber; and providing a reactant from a reactant source to the process chamber and applying a plasma to the process chamber to deposit a thin film, wherein the reactant is provided to the process chamber simultaneously with a first gas from a first gas source in a precursor injection step and/or a plasma applying step, and the first gas is not provided to the process chamber in a purge step between the precursor injection step and the plasma applying step. The thin film deposition method according to the embodiment of the present application can independently control the growth rate, the quality, the profile, and the like of the thin film, and thus can prepare thin films having different process requirements using the same semiconductor processing apparatus.
Description
Technical Field
The present application relates generally to the field of semiconductor manufacturing, and in particular, to a thin film deposition method.
Background
In the field of semiconductor manufacturing, the Plasma Enhanced Atomic Layer Deposition (PEALD) process is one of the most widely used deposition processes. In a PEALD process, a precursor (precursor) and a reactant (reactant) are typically provided to a process chamber and a plasma is applied to deposit a thin film. Different deposition films need to meet different process requirements, such as film growth rate, film quality, film profile, etc. To obtain films of different process requirements, it is often necessary to replace the hardware of the semiconductor processing apparatus and adjust the process steps, which greatly increases the time cost and process cost of depositing the films.
Therefore, there is a need for an improved thin film deposition method to achieve the purpose of using the same semiconductor processing apparatus to prepare thin films with different process requirements, thereby improving the process compatibility of the semiconductor manufacturing equipment.
Disclosure of Invention
The application provides a film deposition method which can independently regulate and control the growth rate, the film quality, the film profile and the like of a film, thereby meeting the process requirements of different films.
According to some embodiments of the present application, a thin film deposition method may include: injecting a precursor from a precursor source into the process chamber; and providing a reactant from a reactant source to the process chamber and applying a plasma to the process chamber to deposit a thin film, wherein the reactant is provided to the process chamber simultaneously with a first gas from a first gas source in a precursor injection step and/or a plasma applying step, and the first gas is not provided to the process chamber in a purge step between the precursor injection step and the plasma applying step.
According to some embodiments of the present application, the reactant may include nitrogen.
According to some embodiments of the present application, the first gas may include at least one of hydrogen and ammonia.
According to some embodiments of the present application, when the first gas is hydrogen, a flow ratio of the first gas to the reactant simultaneously supplied to the process chamber may be 0.025% to 0.1%.
According to some embodiments of the present application, when the first gas is ammonia, a flow ratio of the first gas to the reactant supplied to the process chamber may be 2.5% to 50%.
According to some embodiments of the present application, the reactant may be provided to the process chamber during the purging step.
According to some embodiments of the present application, the reactant gas may be a gas, and the reactant gas and the first gas may be provided to the process chamber via at least one gas line.
According to some embodiments of the present application, the at least one gas line can include a first gas line coupled to a central location of the process chamber and a second gas line coupled to an edge location of the process chamber.
According to some embodiments of the present application, the first gas and the reactant gas can both flow into the first gas line and the second gas line, and the first gas in the first gas line has a first flow ratio to the reactant gas and the first gas in the second gas line has a second flow ratio to the reactant gas, the first flow ratio being different from the second flow ratio.
According to some embodiments of the present application, the first flow ratio in the precursor injection step may be different from the first flow ratio in the plasma application step.
According to some embodiments of the present application, the second flow ratio in the precursor injection step may be different from the second flow ratio in the plasma application step.
According to some embodiments of the present application, the at least one gas line further can comprise a third gas line, which can be coupled to any position between the center position and the edge position of the process chamber.
According to some embodiments of the present application, the first gas and the reactant gas may both flow into a third gas line, and the first gas and the reactant gas in the third gas line have a third flow ratio, which may be different from the first flow ratio or the second flow ratio.
According to some embodiments of the present application, the precursor comprises a silicon precursor, the reactant comprises nitrogen, and the film may be a silicon nitride film.
According to some embodiments of the present application, a thin film deposition method may include: injecting a precursor from a precursor source into the process chamber; and a reactant gas from a reactant source is supplied to the process chamber and a plasma is applied to the process chamber to deposit a thin film, wherein, in the precursor injection step and/or the plasma applying step, the reactant gas and a first gas from a first gas source are simultaneously supplied to the process chamber via at least a first gas line and a second gas line, the first gas in the first gas line and the reactant gas having a first flow ratio, the first gas in the second gas line and the reactant gas having a second flow ratio, the first flow ratio being different from the second flow ratio.
According to some embodiments of the present application, the first gas line may be coupled to a central location of the process chamber and the second gas line may be coupled to an edge location of the process chamber.
According to some embodiments of the present application, the first flow ratio in the precursor injection step may be different from the first flow ratio in the plasma application step.
According to some embodiments of the present application, the second flow ratio in the precursor injection step may be different from the second flow ratio in the plasma application step.
According to some embodiments of the present application, the reactant gas and the first gas may be further provided to the process chamber via a third gas line, which may be coupled to any position between the center position and the edge position of the process chamber, in a precursor injection step and/or a plasma applying step.
According to some embodiments of the application, the first gas in the third gas line and the reactant gas may have a third flow ratio, which may be different from the first flow ratio or the second flow ratio.
According to some embodiments of the present application, the precursor comprises a silicon precursor, the reactant gas may comprise nitrogen gas, the first gas may comprise at least one of hydrogen gas and ammonia gas, and the film is a silicon nitride film.
According to some embodiments of the present application, when the first gas is hydrogen, the first flow ratio or the second flow ratio may be 0.025% to 0.1%.
According to some embodiments of the present application, when the first gas is ammonia, the first flow ratio or the second flow ratio may be 2.5% to 50%.
According to some embodiments of the present application, the method may further include a purging step in which the reactant is provided to the process chamber while the first gas is not provided to the process chamber.
The application also provides a semiconductor processing device using the film deposition method, and the semiconductor processing device has good process compatibility and can meet the films with various process requirements.
The details of one or more examples of the application are set forth in the accompanying drawings and the description below. Other features, objects, and advantages will be apparent from the description and drawings, and from the claims.
Drawings
The disclosure in this specification refers to and includes the following figures:
fig. 1 is a process flow diagram of a thin film deposition method in the prior art.
FIG. 2 is a process flow diagram of another prior art method of thin film deposition.
Figure 3 shows the growth rates of the films obtained with different hydrogen flow rates.
Fig. 4 is a process flow diagram of a thin film deposition method according to an embodiment of the present application.
Fig. 5 is a process flow diagram of a thin film deposition method according to another embodiment of the present application.
Fig. 6 is a process flow diagram of a thin film deposition method according to yet another embodiment of the present application.
Fig. 7 is a schematic structural diagram of a semiconductor processing apparatus according to an embodiment of the present application.
In accordance with common practice, the various features illustrated in the drawings may not be drawn to scale. Accordingly, the dimensions of the various features may be arbitrarily expanded or reduced for clarity. The shapes of the respective members illustrated in the drawings are merely exemplary shapes, and do not limit the actual shapes of the members. Additionally, the implementations illustrated in the figures may be simplified for clarity. Thus, the figures may not illustrate all of the components of a given device or apparatus. Finally, the same reference numerals may be used throughout the description and figures to denote the same features.
Detailed Description
In order to better understand the spirit of the present invention, the following embodiments of the present invention are further described.
The use of the phrases "in one embodiment" or "according to one embodiment" in this specification does not necessarily refer to the same embodiment, and the use of "in other embodiment(s)" or "according to other embodiment(s)" in this specification does not necessarily refer to a different embodiment. It is intended that, for example, claimed subject matter include all or a portion of the exemplary embodiments in combination. The meaning of "up" and "down" referred to herein is not limited to the relationship directly presented by the drawings, and shall include descriptions with explicit correspondence, such as "left" and "right", or the reverse of "up" and "down". References herein to "coupled" or "connected" are to be understood to encompass "directly coupled," "directly connected," and "coupled via" or "connected via" one or more intermediate components. The names of the various components used in the present specification are for illustrative purposes only and are not intended to be limiting, and different manufacturers may refer to components having the same function using different names.
Various embodiments of the present application are discussed in detail below. While specific implementations are discussed, it should be understood that these implementations are for illustration purposes only. A person skilled in the relevant art will recognize that other components and configurations may be used without parting from the spirit and scope of the application. The implementation of the present application may not necessarily include all the components or steps in the embodiments described in the specification, and the execution sequence of each step may be adjusted according to the actual application.
FIG. 1 shows the prior artProcess flow diagram of a thin film deposition method in the art. As shown in fig. 1, the related art thin film deposition method includes a plurality of process cycles, each of which includes a precursor injection step, a plasma application step, and two purge steps. In the precursor implantation step, a precursor is implanted into the process chamber from a precursor source. In the applying plasma step, a reactant from a reactant source is provided to the process chamber and plasma is applied to the process chamber to deposit a thin film. During the purging step, excess precursor or reaction by-products are removed from the process chamber to purge the process chamber. In the thin film deposition method shown in fig. 1, the reactant is supplied to the process chamber at a constant flow rate without interruption, and the precursor is supplied to the process chamber only at the precursor injection step. The reactant may be nitrogen (N) 2 ). The precursor may be bis (diethylamino) silane (sam.24), a halogen silane compound, a polysilicone halogen compound, or the like. When different films are prepared (e.g., different film qualities), it is often necessary to adjust the process steps and sometimes even to replace hardware equipment, which results in increased time and process costs for depositing the films.
FIG. 2 is a process flow diagram of another prior art thin film deposition method. The thin film deposition method shown in fig. 2 is different from the thin film deposition method shown in fig. 1 in that hydrogen gas is supplied to the process chamber at a constant flow rate without interruption in each process cycle in addition to the reactant. In the thin film deposition method shown in fig. 2, supplying hydrogen gas into the process chamber may increase the growth rate (GPC) of the thin film.
Figure 3 shows the growth rates of the films obtained with different hydrogen flow rates. As shown in fig. 3, when hydrogen gas is supplied to the process chamber at different flow rates without interruption using the thin film deposition method shown in fig. 2, the growth rate of the thin film is positively correlated with the flow rate of hydrogen gas. Therefore, the growth rate of the thin film can be increased by increasing the flow rate of hydrogen.
The thin film deposition method shown in fig. 2 can improve the growth rate of the thin film compared to the thin film deposition method shown in fig. 1. However, the introduction of hydrogen during the plasma application step can alter the film quality, for example, resulting in an increase in Wet Etch Rate (WER). Therefore, the thin film deposition method shown in fig. 2 simultaneously changes the growth rate and the quality of the thin film, but cannot separately control both. Therefore, the related art thin film deposition method shown in fig. 1 and 2 requires frequent replacement of hardware and adjustment of process steps when depositing thin films with different process requirements, resulting in high time cost and process cost for depositing thin films.
To address the deficiencies of the prior art, the present application provides an improved thin film deposition method to address at least one of the problems discussed above. A thin film deposition method according to an embodiment of the present application will be described in detail below with reference to fig. 4 to 6.
Fig. 4 is a process flow diagram of a thin film deposition method according to an embodiment of the present application. As shown in fig. 4, the thin film deposition method according to an embodiment of the present application includes a plurality of process cycles, each process cycle including a precursor injection step, a plasma application step, and two purge steps. In the precursor implantation step, a precursor is implanted into the process chamber from a precursor source. In the applying plasma step, a reactant is supplied from a reactant source to the process chamber and plasma is applied to the process chamber to deposit a thin film. During the purging step, excess precursor or reaction by-products are removed from the process chamber to purge the process chamber. In the precursor injection step, simultaneously providing a reactant and a first gas from a first gas source to the process chamber while injecting the precursor into the process chamber; and the first gas is not provided to the process chamber during the purging step between the precursor injection step and the applying plasma step, and the purging step between the applying plasma step and the precursor injection step of another cycle. As shown in fig. 4, the first gas is provided to the process chamber during each process cycle only during the precursor injection step.
The duration of the precursor injection step, the plasma application step and the two purge steps may be set according to the process requirements and is not particularly limited herein.
The precursor can be any suitable precursor for preparing a thin film. In some embodiments, the precursor may be a silicon precursor for depositing a silicon nitride film. In some embodiments, the precursor comprises bis (diethylamino) silane (sam.24), a halogen silane compound, or a polysilicone halogen compound, among others, wherein examples of halogen silane compounds include, but are not limited to, hexachlorodisilane (HCDS), monochlorosilane, and Dichlorosilane (DCS). The precursor can be injected into the process chamber at a suitable flow rate according to the process requirements.
The reactant may be any suitable reactant for preparing a thin film. In some embodiments, the reactant may be a gas. In some embodiments, the reactant may be a reactant for preparing a silicon nitride film. In some embodiments, the reactant comprises nitrogen (N) 2 ). In addition to reacting with the precursor to form the thin film, the reactant may be provided to the process chamber during the precursor injection step to serve as a carrier gas for carrying the precursor and during the purge step to serve as a purge gas for purging the process chamber. Thus, the reactant may be supplied to the process chamber at a constant flow rate without interruption during each process cycle. In some embodiments, the reactant may be provided to the process chamber at a flow rate of about 10000sccm to about 20000sccm, such as about 10000sccm, 12000sccm, about 15000sccm, 18000sccm, or about 20000sccm, or any two of the above ranges, such as about 10000sccm to about 15000sccm, about 12000sccm to about 20000sccm, or about 10000sccm to about 18000 sccm. In some embodiments, the reactive species may be provided to the process chamber in a discontinuous manner, such as only during the precursor implantation step and the plasma application step.
The first gas may be a gas that improves adsorption of the precursor. Introducing the first gas into the process chamber may increase the active sites of the deposition surface, thereby improving adsorption of the precursor. In some embodiments, the introduction of the first gas can increase nitrogen hydrogen bonding at the deposition surface, thereby increasing active sites and improving adsorption of the precursor. In some embodiments, the first gas comprises hydrogen (H) 2 ) Or ammonia (NH) 3 ) At least one of (a). In some embodiments, the first gas is hydrogen and can be provided to the process chamber at a flow rate of about 5sccm to about 10sccm, e.g., about 5sccm, about 6sccm, about 7sccmsccm, about 8sccm, or about 10sccm, or any combination thereof, such as about 5sccm to about 8sccm, or about 7sccm to about 10 sccm. In some embodiments, the first gas is ammonia gas and can be provided to the process chamber at a flow rate of about 500sccm to about 5000sccm, such as about 500sccm, about 1000sccm, about 2000sccm, about 3000sccm, about 4000sccm, or about 5000sccm, or any combination thereof, such as about 500sccm to about 1000sccm, about 500sccm to about 3000sccm, or about 1000sccm to about 5000sccm, etc.
In some embodiments, when the first gas is hydrogen, the flow ratio of the first gas to the reactant supplied to the process chamber may be in the range of about 0.025% to about 0.1%, for example, about 0.025%, about 0.03%, about 0.05%, about 0.08%, or about 0.1% or any two of the above, such as about 0.025% to about 0.05%, or about 0.05% to about 0.1%, and the like.
In some embodiments, when the first gas is ammonia, the flow ratio of the first gas to the reactant supplied to the process chamber may be about 2.5% to about 50%, for example, about 2.5%, about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 40%, or about 50%, or any two of the above ranges, such as about 2.5% to about 25%, about 5% to about 25%, or about 5% to about 50%.
The reactant gas and the first gas can be provided to the process chamber via at least one gas line. In some embodiments, the at least one gas line includes a first gas line coupled to a central location of the process chamber and a second gas line coupled to an edge location of the process chamber, both the first gas and the reactant gas flow into the first gas line and the second gas line, and the first gas in the first gas line has a first flow ratio to the reactant gas and the first gas in the second gas line has a second flow ratio to the reactant gas, the first flow ratio being different from the second flow ratio. In some embodiments, the at least one gas line further comprises a third gas line coupled to any position between the center position and the edge position of the process chamber, both the first gas and the reactant gas flow into the third gas line, and the first gas and the reactant gas in the third gas line have a third flow ratio, the third flow ratio being different from the first flow ratio or the second flow ratio. As will be described in detail later with reference to fig. 7.
Since the first gas is supplied to the process chamber only at the precursor injection step, the thin film deposition method shown in fig. 4 can improve the growth rate of the thin film by increasing the flow rate of the first gas without affecting the quality of the thin film, thereby achieving individual control of the growth rate of the deposited thin film. Therefore, the thin film deposition method shown in fig. 4 can control the thickness and profile of the thin film without affecting the quality of the thin film.
Fig. 5 is a process flow diagram of a thin film deposition method according to another embodiment of the present application. The thin film deposition method illustrated in fig. 5 is different from the thin film deposition method illustrated in fig. 4 in that a reactant gas is simultaneously supplied to the process chamber with the first gas in the step of applying the plasma.
As shown in fig. 5, the thin film deposition method according to an embodiment of the present application includes a plurality of process cycles, each process cycle including a precursor injection step, a plasma application step, and two purge steps. In a precursor implantation step, a precursor is implanted into the process chamber from a precursor source. In the applying plasma step, a reactant is supplied from a reactant source to the process chamber and plasma is applied to the process chamber to deposit a thin film. During the purging step, excess precursor or reaction by-products are removed from the process chamber to purge the process chamber. Providing a reactant gas to the process chamber simultaneously with a first gas from a first gas source during the applying a plasma step; and the first gas is not provided to the process chamber during the precursor injection step, the purge step between the precursor injection step and the plasma application step, and the purge step between the plasma application step and the precursor injection step of another cycle. As shown in fig. 5, in each process cycle, the first gas is provided to the process chamber only during the step of applying the plasma. The precursor, the reactant, and the first gas in fig. 5 are the same as those in fig. 4, and thus, detailed description thereof is omitted.
As shown in fig. 5, since the first gas is supplied to the process chamber only during the step of applying the plasma, the film quality can be changed (e.g., the WER can be increased) by increasing the flow rate of the first gas without affecting the growth rate of the film, thereby achieving individual control of the film quality.
Fig. 6 is a process flow diagram of a thin film deposition method according to yet another embodiment of the present application. The thin film deposition method illustrated in fig. 6 is different from the thin film deposition method illustrated in fig. 4 in that a reactant is simultaneously supplied to the process chamber with the first gas in the precursor injection step and the plasma application step.
As shown in fig. 6, the thin film deposition method according to an embodiment of the present application includes a plurality of process cycles, each process cycle including a precursor injection step, a plasma application step, and two purge steps. In the precursor implantation step, a precursor is implanted into the process chamber from a precursor source. In the applying plasma step, a reactant is supplied to the process chamber and plasma is applied to the process chamber to deposit the thin film. During the purging step, excess precursor or reaction by-products are removed from the process chamber to purge the process chamber. Providing a reactant gas to the process chamber simultaneously with a first gas from a first gas source in the precursor injecting step and the applying a plasma step; and the first gas is not provided to the process chamber during a purge step between the precursor injection step and the applying plasma step and a purge step between the applying plasma step and the precursor injection step of another cycle. Thus, in the process cycle shown in FIG. 6, the first gas is provided to the process chamber in both the precursor injection and plasma application steps. The precursor, the reactant, and the first gas in fig. 6 are the same as those in fig. 4, and thus, detailed description thereof is omitted.
The first gas is provided to the process chamber at a first flow rate F1 during the precursor injection step and at a second flow rate F2 during the plasma applying step. In some embodiments, the first flow rate F1 is equal to the second flow rate F2. In some embodiments, the first flow rate F1 is greater than or less than the second flow rate F2. When the first gas is hydrogen, the first flow rate F1 and/or the second flow rate F2 can be about 5sccm to about 10sccm, such as about 5sccm, about 6sccm, about 7sccm, about 8sccm, or about 10sccm, or any two of the above ranges, such as about 5sccm to about 8sccm, or about 7sccm to about 10 sccm. When the first gas is ammonia, the first flow rate F1 and/or the second flow rate F2 can be about 500sccm to about 5000sccm, such as about 500sccm, about 1000sccm, about 2000sccm, about 3000sccm, about 4000sccm, or about 5000sccm, or any two of the above ranges, such as about 500sccm to about 1000sccm, about 500sccm to about 3000sccm, or about 1000sccm to about 5000sccm, etc.
In some embodiments, the flow ratio of the first gas to the reactant in the precursor injection step is equal to the flow ratio of the first gas to the reactant in the plasma application step. In some embodiments, the flow ratio of the first gas to the reactant in the precursor injection step is different from the flow ratio of the first gas to the reactant in the plasma application step.
In some embodiments, when the first gas is hydrogen, the flow ratio of the first gas to the reactant in the precursor injection step and/or the plasma application step can be about 0.025% to about 0.1%, for example, about 0.025%, about 0.03%, about 0.05%, about 0.08%, or about 0.1% or a range of any two of the above numerical compositions, such as about 0.025% to about 0.05% or about 0.05% to about 0.1%, and the like.
In some embodiments, when the first gas is ammonia, the flow ratio of the first gas to the reactant in the precursor injection step and/or the plasma applying step may be in a range of about 2.5% to about 50%, for example, about 2.5%, about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 40%, or about 50% or any two of the above numerical compositions, such as about 2.5% to about 25%, about 5% to about 25%, or about 5% to about 50%, etc.
As shown in fig. 6, the first gas may be supplied to the process chamber at different flow rates (or different flow rate ratios of the first gas to the reactant) in the precursor injection step and the plasma application step, so that the growth rate and the film quality of the deposited film can be independently controlled by setting different flow rates of the first gas (or different flow rate ratios of the first gas to the reactant). Therefore, the thin film deposition method shown in fig. 6 can independently control the profile and quality of the thin film.
The thin films were deposited using the thin film deposition methods of fig. 1 to 5, respectively, and the growth rate and wet etching rate of the thin films are shown in table 1. In table 1, comparative example 1 and comparative document 2 use the thin film deposition methods shown in fig. 1 and 2, respectively, and examples 1 to 3 use the thin film deposition methods shown in fig. 4 to 6, respectively. In comparative examples 1 and 2 and examples 1 to 3, the precursor was Hexachlorodisilane (HCDS), the reactant was nitrogen, and the flow rate of nitrogen was 10000sccm. In comparative example 2, the flow rate of hydrogen was 1sccm. In examples 1 to 3, the first gas was hydrogen, and the flow rate of hydrogen was 5sccm (F1 in example 3 was equal to F2).
TABLE 1 growth rate and Wet etch rate of the films
As can be seen from table 1, when the first gas is introduced in the precursor-only injection step, the growth rate of the thin film is significantly increased while the quality of the thin film is substantially unchanged; when the first gas is introduced in the step of applying only the plasma, the growth rate of the thin film is substantially unchanged, and the quality of the thin film is changed, so that the profile and quality of the thin film can be independently controlled; when the first gas is introduced and the flow rate of the first gas is increased in the precursor injection step and the plasma application step, the growth rate of the thin film can be increased and the quality of the thin film can be changed. Although F1 is equal to F2 in embodiment 3, F1 may be different from F2. In some embodiments, F2 is less than F1, a significant increase in GPC can be achieved with substantially unchanged WER.
The application of the thin film deposition method of the present application to a semiconductor processing apparatus will be described in detail with reference to fig. 7.
Fig. 7 is a schematic structural diagram of a semiconductor processing apparatus according to an embodiment of the present application. As shown in fig. 7, the semiconductor processing apparatus 10 includes a process chamber 1, and a precursor line 3 and a plurality of gas lines 4, 5, and 6 coupled to the process chamber 1. A precursor line 3 is coupled to a central position of the process chamber 1, and the precursor enters the process chamber 1 via the precursor line 3. The first gas line 4 is coupled to a central position of the process chamber 1, the second gas line 5 is coupled to an edge position of the process chamber 1, and the third gas line 6 is coupled to any position between the central position and the edge position of the process chamber 1, for example, 1/2 or 1/4 of the position between the central position and the edge position. The reactant gas from the reactant source and the first gas from the first gas source may be flowed together into at least one of the first gas line 4, the second gas line 5, and the third gas line 6 to be provided to the process chamber 1. Although three gas lines are shown in fig. 7, more or fewer gas lines may be provided.
As shown in fig. 7, changing the flow ratio of the first gas to the reactant in the first gas line 4 can regulate the thin film in the first region 21 of the substrate 2; changing the flow ratio of the first gas to the reactant gas in the second gas line 5 can control the thin film in the second region 22 of the substrate 2; varying the flow ratio of the first gas to the reactant in the third gas line 6 can modulate the film in the third region 23 of the substrate 2. Accordingly, the growth rate and/or the film quality of the thin film of different regions of the substrate 2 can be adjusted by regulating the flow ratio of the first gas to the reactant gas in the first gas line 4, the second gas line 5, and the third gas line 6 at each step, thereby changing the thickness and profile of the thin film.
In some embodiments, the reactant gas and the first gas are provided to the process chamber 1 via the first gas line 4 simultaneously during the precursor injection step and/or the plasma application step. The first gas in the first gas line 4 has a first flow ratio to the reactant. In some embodiments, when the reactant gas and the first gas are simultaneously provided to the process chamber 1 in the precursor injection step and the plasma applying step, the first flow ratio in the precursor injection step may be different from the first flow ratio in the plasma applying step. By adjusting the first flow ratio in the precursor injection step and/or the plasma applying step, the growth rate and/or the quality of the film can be regulated, and the films with different profiles and/or film qualities can be obtained.
In some embodiments, the reactant gas is provided to the process chamber 1 simultaneously with the first gas via the first gas line 4 and the second gas line 5 during the precursor injection step and/or the plasma application step. The first gas in the first gas line 4 has a first flow ratio to the reactant and the first gas in the second gas line 5 has a second flow ratio to the reactant. In some embodiments, the first flow ratio may be different than the second flow ratio. In some embodiments, the first flow ratio in the precursor injection step may be different from the first flow ratio in the plasma application step. In some embodiments, the second flow ratio in the precursor injection step may be different from the second flow ratio in the plasma application step. By adjusting the first flow ratio and the second flow ratio in the precursor injection step and/or the plasma applying step, the growth rate and/or the film quality of the films in different areas can be regulated, and the films with different profiles and/or film qualities can be obtained.
In some embodiments, the reactant gas is provided to the process chamber 1 simultaneously with the first gas via the first gas line 4, the second gas line 5, and the third gas line 6 during the precursor injection step and/or the plasma application step. The first gas in the first gas line 4 has a first flow ratio to the reactant gas, the first gas in the second gas line 5 has a second flow ratio to the reactant gas, and the first gas in the third gas line 6 has a third flow ratio to the reactant gas. In some embodiments, the first flow ratio may be different than the second flow ratio, and the third flow ratio may be different than either the first flow or the second flow ratio. In some embodiments, the first flow ratio may be different than the second flow ratio, and the third flow ratio may be the same as either the first flow ratio or the second flow ratio. In some embodiments, the first flow ratio in the precursor injection step may be different from the first flow ratio in the plasma application step. In some embodiments, the second flow ratio in the precursor injection step may be different from the second flow ratio in the plasma application step. In some embodiments, the third flow ratio in the precursor injection step may be different from the third flow ratio in the plasma application step. By adjusting the first flow ratio, the second flow ratio and the third flow ratio in the precursor injection step and/or the plasma applying step, the growth rate and/or the quality of the film in different areas can be regulated, and the film with different profiles and/or film quality can be obtained.
In some embodiments, when the first gas is hydrogen, the first flow ratio, the second flow ratio, or the third flow ratio can be in a range of about 0.025% to about 0.1%, e.g., about 0.025%, about 0.03%, about 0.05%, about 0.08%, or about 0.1% or any two of the above numerical compositions, e.g., about 0.025% to about 0.05%, or about 0.05% to about 0.1%, etc.
In some embodiments, when the first gas is ammonia, the first flow ratio, the second flow ratio, or the third flow ratio may be about 2.5% to about 50%, for example, about 2.5%, about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 40%, or about 50% or a range of any two of the above numerical compositions, such as about 2.5% to about 25%, about 5% to about 25%, or about 5% to about 50%, etc.
The description in this specification is provided to enable any person skilled in the art to make or use the invention. Various modifications to the disclosure will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other variations without departing from the spirit or scope of the disclosure. Thus, the present invention is not intended to be limited to the examples and designs described herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (24)
1. A thin film deposition method, comprising:
injecting a precursor from a precursor source into the process chamber; and
providing a reactant from a reactant source to the process chamber and applying a plasma to the process chamber to deposit a thin film,
wherein the reactant gas is provided to the process chamber simultaneously with a first gas from a first gas source in a precursor injection step and/or a plasma applying step, and the first gas is not provided to the process chamber in a purge step between the precursor injection step and the plasma applying step.
2. The thin film deposition method of claim 1, wherein the reactant comprises nitrogen.
3. The thin film deposition method of claim 2, wherein the first gas comprises at least one of hydrogen and ammonia.
4. The thin film deposition method as claimed in claim 3, wherein when the first gas is hydrogen, a flow ratio of the first gas to the reactant simultaneously supplied to the process chamber is 0.025% to 0.1%.
5. The thin film deposition method as claimed in claim 3, wherein when the first gas is ammonia gas, a flow ratio of the first gas to the reactant supplied to the process chamber is 2.5-50%.
6. The thin film deposition method of claim 1, wherein the reactant is supplied to the process chamber during the purging step.
7. The thin film deposition method of claim 1, wherein the reactant gas is a gas and the reactant gas and the first gas are provided to the process chamber via at least one gas line.
8. The thin film deposition method of claim 7, wherein the at least one gas line comprises a first gas line coupled to a center location of the process chamber and a second gas line coupled to an edge location of the process chamber.
9. The thin film deposition method of claim 8, wherein the first gas and the reactant gas flow into the first gas line and the second gas line, and the first gas and the reactant gas in the first gas line have a first flow ratio and the first gas and the reactant gas in the second gas line have a second flow ratio, the first flow ratio being different from the second flow ratio.
10. The thin film deposition method of claim 9, wherein the first flow ratio in the precursor injection step is different from the first flow ratio in the applying plasma step.
11. The thin film deposition method of claim 9, wherein the second flow ratio in the precursor injection step is different from the second flow ratio in the applying plasma step.
12. The thin film deposition method of claim 9, wherein the at least one gas line further comprises a third gas line coupled to any position between the center position and the edge position of the process chamber.
13. The thin film deposition method of claim 12, wherein both the first gas and the reactant gas flow into a third gas line, and the first gas and the reactant gas in the third gas line have a third flow ratio different from the first flow ratio or the second flow ratio.
14. The thin film deposition method of any one of claims 1 to 13, the precursor comprising a silicon precursor, the reactant comprising nitrogen, and the thin film being a silicon nitride thin film.
15. A thin film deposition method, comprising:
injecting a precursor from a precursor source into the process chamber; and
a reactant from a reactant source is provided to the process chamber and a plasma is applied to the process chamber to deposit a thin film,
wherein, in the precursor injection step and/or the plasma applying step, the reactant gas and a first gas from a first gas source are simultaneously provided to the process chamber via at least a first gas line and a second gas line, the first gas in the first gas line and the reactant gas having a first flow ratio, the first gas in the second gas line and the reactant gas having a second flow ratio, the first flow ratio being different from the second flow ratio.
16. The thin film deposition method of claim 15, wherein the first gas line is coupled to a center position of the process chamber and the second gas line is coupled to an edge position of the process chamber.
17. The thin film deposition method of claim 16, wherein the first flow ratio in the precursor injection step is different from the first flow ratio in the plasma applying step.
18. The thin film deposition method of claim 16, wherein the second flow ratio in the precursor injection step is different from the second flow ratio in the plasma application step.
19. The thin film deposition method of claim 15, wherein the reactant gas and the first gas are further provided to the process chamber via a third gas line coupled to any position between the center position and the edge position of the process chamber in a precursor injection step and/or a plasma application step.
20. The thin film deposition method of claim 19, wherein the first gas in the third gas line and the reactant body have a third flow ratio, the third flow ratio being different from the first flow ratio or the second flow ratio.
21. The thin film deposition method of claim 15, wherein the precursor comprises a silicon precursor, the reactant comprises nitrogen, the first gas comprises at least one of hydrogen and ammonia, and the thin film is a silicon nitride thin film.
22. The thin film deposition method of claim 21, wherein the first flow ratio or the second flow ratio is 0.025% -0.1% when the first gas is hydrogen.
23. The thin film deposition method of claim 21, wherein when the first gas is ammonia, the first flow ratio or the second flow ratio is 2.5% -50%.
24. The thin film deposition method of claim 15, wherein the method further comprises a purging step in which the reactant is provided to the process chamber while the first gas is not provided to the process chamber.
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| US20170241019A1 (en) * | 2016-02-22 | 2017-08-24 | Ultratech, Inc. | Pe-ald methods with reduced quartz-based contamination |
| KR20220042442A (en) * | 2019-08-06 | 2022-04-05 | 램 리써치 코포레이션 | Thermal atomic layer deposition of silicon-containing films |
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| CN111364017B (en) * | 2020-04-20 | 2022-04-22 | 国家纳米科学中心 | Aluminum nitride film and preparation method and application thereof |
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