CN114639590A - Method and apparatus for forming thin film - Google Patents

Method and apparatus for forming thin film Download PDF

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Publication number
CN114639590A
CN114639590A CN202110935574.8A CN202110935574A CN114639590A CN 114639590 A CN114639590 A CN 114639590A CN 202110935574 A CN202110935574 A CN 202110935574A CN 114639590 A CN114639590 A CN 114639590A
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containing gas
oxygen
silicon oxynitride
silicon
nitrogen
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CN202110935574.8A
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Chinese (zh)
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韩奭俊
李太浣
洪荣俊
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Wonik IPS Co Ltd
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Wonik IPS Co Ltd
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    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/02126—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
    • H01L21/0214—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC the material being a silicon oxynitride, e.g. SiON or SiON:H
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    • 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
    • C23C16/22—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 deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/308—Oxynitrides
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    • 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
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    • C23C16/40—Oxides
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    • C23C16/45529—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations specially adapted for making a layer stack of alternating different compositions or gradient compositions
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    • 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
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Abstract

The present invention relates to a method and an apparatus for forming a thin film, and more particularly, to a method and an apparatus for forming a gate oxide film. An embodiment of a film forming method of the present invention includes: a silicon oxide film forming step of forming a silicon oxide film on a substrate; a first silicon oxynitride film forming step of forming a first silicon oxynitride film on the silicon oxide film, and further including a first process condition of adjusting a nitrogen (N) content in the first silicon oxynitride film to form a first silicon oxynitride film; a second silicon oxynitride film forming step of forming a second silicon oxynitride film on the first silicon oxynitride film and further including a second process condition of adjusting a nitrogen (N) content in the second silicon oxynitride film to form a second silicon oxynitride film; wherein the first process condition and the second process condition are adjusted such that a nitrogen (N) content in the first silicon oxynitride film is greater than a nitrogen (N) content in the second silicon oxynitride film.

Description

Method and apparatus for forming thin film
Technical Field
The present invention relates to a method and an apparatus for forming a thin film, and more particularly, to a method and an apparatus for forming a gate oxide film.
Background
Field Effect Transistors (FETs), such as NFETs and PFETs, are commonly found in CMOS (Complementary Metal Oxide Semiconductor) devices. In a MOSFET device, the gate electrode or gate may comprise an insulator such as a gate oxide film or a doped polysilicon or metal conductor formed on the gate insulator. In addition, the gate electrode stack (stack) includes a semiconductor layer or a substrate formed with a gate insulating film. The substrate area under the gate oxide film is a channel area, and source/drain pairs are formed in the substrate on both sides of the channel.
In a semiconductor process, silicon (Si) may be used as a substrate material. Silicon germanium (SiGe) is used as a substitute for silicon, enabling transistors to switch faster and achieve high performance. For example, SiGe can be used for high frequency devices, and SiGe processing improves the PMOS performance of nano devices.
SiGe has a larger lattice constant than Si and is more easily deformed (dislocated) than Si when oxidized. As a result, an alternative method to oxidation process is used on the SiGe surface.
Therefore, a gate oxide film formed by an alternative method of an oxidation process is required. For this reason, studies are being made on a gate oxide film having a structure in which a portion of a silicon oxide film is subjected to a Nitridation (Nitridation) process to form a silicon oxide film containing nitrogen (N) on the surface of the silicon oxide film. The nitrogen (N) content of the gate oxide film of this structure is shown in fig. 1. If nitrogen (N) is added to the silicon oxide film, the dielectric constant can be easily adjusted. Such a gate oxide film has a problem that, after forming a silicon oxide film, complicated heat treatment and plasma treatment such as heat treatment in an oxygen atmosphere, plasma treatment for nitridation treatment, heat treatment in an oxygen atmosphere, and heat treatment in a nitrogen atmosphere are required, and thus productivity is lowered. In addition, since the gate oxide film is manufactured by the above-described method, the gate oxide film cannot be manufactured in-situ (in-situ) in one apparatus.
When a gate oxide film is formed by the above-described method, nitrogen is deposited (pile-up) between the substrate and the interface of the silicon oxide thin film as shown in fig. 1, which causes a problem of deterioration of electrical characteristics.
Disclosure of Invention
Problems to be solved
The present invention has been made to solve the above-described conventional problems, and an object of the present invention is to provide a thin film forming method and apparatus for forming a gate oxide film including a silicon oxynitride thin film for adjusting a dielectric constant, forming the gate oxide film in situ (in-situ), and minimizing nitrogen deposition at an interface between a substrate and the oxide film.
Means for solving the problems
An embodiment of the thin film forming method of the present invention for solving the above technical problem includes: a silicon oxide film forming step of forming a silicon oxide film on a substrate; a first silicon oxynitride film forming step of forming a first silicon oxynitride film on the silicon oxide film, and further including a first process condition of adjusting a nitrogen (N) content in the first silicon oxynitride film to form a first silicon oxynitride film; a second silicon oxynitride film forming step of forming a second silicon oxynitride film on the first silicon oxynitride film and further including a second process condition of adjusting a nitrogen (N) content in the second silicon oxynitride film to form a second silicon oxynitride film; wherein the first process condition and the second process condition are adjusted such that a nitrogen (N) content in the first silicon oxynitride film is greater than a nitrogen (N) content in the second silicon oxynitride film.
In some embodiments of the thin film forming method of the present invention, the first silicon oxynitride thin film forming step is performed by an Atomic Layer Deposition (ALD) method repeatedly performing a first cycle period including at least one of the first silicon (Si) -containing gas supplying step, the first oxygen (O) -containing gas supplying step, and the first nitrogen (N) -containing gas supplying step; the second silicon nitride film forming step is performed by an Atomic Layer Deposition (ALD) method repeatedly performing a second cycle period including at least one second silicon (Si) -containing gas supplying step, a second oxygen (O) -containing gas supplying step, and a second nitrogen (N) -containing gas supplying step.
In some embodiments of the thin film forming method of the present invention, the first process condition and the second process condition are oxygen (O) -containing gas species, and the first oxygen (O) -containing gas supplied in the first silicon oxynitride film forming step and the second oxygen (O) -containing gas supplied in the second silicon oxynitride film forming step may be different species of gases from each other.
In some embodiments of the thin film forming method of the present invention, the first oxygen (O) -containing gas is nitrous oxide (N2O), and the second oxygen (O) -containing gas may be oxygen (O2).
In some embodiments of the thin film forming method of the present invention, a third silicon oxynitride thin film forming step of forming a third silicon oxynitride thin film on the silicon oxide thin film and forming a third silicon oxynitride thin film under third process conditions that can adjust the nitrogen (N) content in the third silicon oxynitride thin film is further included between the silicon oxide thin film forming step and the first silicon oxynitride thin film forming step; adjusting the first process condition, the second process condition and the third process condition to make the content of nitrogen (N) in the third silicon oxynitride film smaller than the content of nitrogen (N) in the second silicon oxynitride film; the first silicon oxynitride film forming step is performed by an Atomic Layer Deposition (ALD) method repeatedly performing a first cycle period including at least one of a first silicon (Si) -containing gas supplying step, a first oxygen (O) -containing gas supplying step, and a first nitrogen (N) -containing gas supplying step; the second silicon nitride film forming step is performed by an Atomic Layer Deposition (ALD) method repeatedly performing a second cycle period including at least one of a second silicon (Si) -containing gas supplying step, a second oxygen (O) -containing gas supplying step, and a second nitrogen (N) -containing gas supplying step; the third silicon nitride film forming step is performed by an Atomic Layer Deposition (ALD) method repeatedly performing a third cycle period including at least one of a third silicon (Si) -containing gas supplying step, a third oxygen (O) -containing gas supplying step, and a third nitrogen (N) -containing gas supplying step.
In some embodiments of the thin film forming method of the present invention, the first process condition, the second process condition, and the third process condition are oxygen (O) -containing gas species, the first oxygen (O) -containing gas is nitrous oxide (N2O), the second oxygen (O) -containing gas is oxygen (O2), and the third oxygen (O) -containing gas may be at least one of oxygen (O2) and a mixed gas of oxygen (O2) and hydrogen (H2).
In some embodiments of the thin film forming method of the present invention, the first process condition, the second process condition, and the third process condition may be adjusted such that the content of nitrogen (N) in the first silicon oxynitride thin film is 20 to 40%, the content of nitrogen (N) in the second silicon oxynitride thin film is 10 to 20%, and the content of nitrogen (N) in the third silicon oxynitride thin film is less than 10%.
In some embodiments of the thin film forming method of the present invention, the silicon oxide thin film forming step may be performed by Atomic Layer Deposition (ALD).
In some embodiments of the film forming method of the present invention, the second silicon oxynitride film forming step may be followed by a step of heat-treating the film.
In some embodiments of the thin film forming method of the present invention, the heat treatment step may be performed in an atmosphere of at least one gas of nitrogen (N2), nitrous oxide (N2O), Nitric Oxide (NO), hydrogen (H2), and ammonia (NH 3).
In some embodiments of the thin film forming method of the present invention, the silicon oxide film forming step, the first silicon oxynitride film forming step, the second silicon oxynitride film forming step, the third silicon oxynitride film forming step and the heat treatment step may be performed in-situ.
In some embodiments of the thin film forming method of the present invention, the oxygen (O) -containing gas may include: oxygen (O2), ozone (O3), nitrous oxide (N2O), Nitric Oxide (NO), and a mixed gas of oxygen (O2) and hydrogen (H2).
In some embodiments of the thin film forming method of the present invention, the nitrogen (N) -containing gas may include ammonia (NH 3).
In some embodiments of the thin film forming method of the present invention, the silicon (Si) -containing gas may include at least one of a silane-based gas and a siloxane-based gas.
In some embodiments of the thin film forming method of the present invention, the step of heat-treating the silicon oxide thin film with a mixed gas of oxygen (O2) and hydrogen (H2) may be further included after the silicon oxide thin film forming step.
In a part of embodiments of the thin film forming method of the present invention, the first process condition, the second process condition, and the third process condition are the number of oxygen (O) -containing gas supply steps included in one cycle period; the first cycle period is that the first nitrogen (N) -containing gas supplying step is performed after repeating the first silicon (Si) -containing gas supplying step and the first oxygen (O) -containing gas supplying step N (N is a natural number) times; the second cycle period is that the second nitrogen (N) -containing gas supplying step is performed after repeating the second silicon (Si) -containing gas supplying step and the second oxygen (O) -containing gas supplying step m (m is a natural number) times; the third cycle period is that the third nitrogen (N) -containing gas supplying step is performed after repeating the third silicon (Si) -containing gas supplying step and the third oxygen (O) -containing gas supplying step l (l is a natural number) times; can be l > m > n.
In some embodiments of the thin film forming method of the present invention, the first process condition, the second process condition, and the third process condition may be at least one of a supply time of an oxygen (O) -containing gas, a pressure of the supplied oxygen (O) -containing gas, a flow rate of the supplied oxygen (O) -containing gas, a supply time of a nitrogen (N) -containing gas, a pressure of the supplied nitrogen (N) -containing gas, a flow rate of the supplied nitrogen (N) -containing gas, a number of nitrogen (N) -containing gas supply steps included in one cycle period, and a process temperature.
In some embodiments of the thin film forming method of the present invention, the thin film may be a gate oxide film.
An embodiment of the thin film forming apparatus according to the present invention for solving the above problems is an apparatus for forming a thin film on a silicon substrate, the thin film being formed by the thin film forming method described above.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, the formation of the silicon oxide film, the formation of the silicon oxynitride film and the heat treatment process can all be performed in-situ, thereby improving productivity. That is, the gate oxide film including the silicon oxynitride film whose dielectric constant is adjusted can be formed more easily. In addition, in the case where the silicon oxide film and the silicon oxynitride film are all formed by deposition as in the present invention, the phenomenon of nitrogen deposition at the interface between the substrate and the oxide film can be minimized, and thus the electrical characteristics can be improved.
Drawings
Fig. 1 is a graph schematically showing the nitrogen concentration in a gate oxide film in the case where the gate oxide film is formed by a conventional method.
Fig. 2 is a diagram schematically showing an example of an apparatus for performing the thin film forming method of the present invention.
Fig. 3 is a flowchart schematically showing the execution of an embodiment of the thin film forming method of the present invention.
Fig. 4 to 7 are diagrams for explaining an implementation of the embodiment shown in fig. 3.
Fig. 8 and 9 are views for explaining a schematic gas supply procedure for forming a silicon oxynitride thin film in the thin film forming method of the present invention.
Fig. 10 is a graph showing the nitrogen concentration in the thin film formed by the thin film forming method of the present invention.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. The embodiments of the present invention are provided to more fully explain the present invention to those having ordinary skill in the art to which the present invention pertains, and the following embodiments may be modified into various forms without limiting the scope of the present invention to the following embodiments. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of the invention to those skilled in the art.
In the figures, the deformation of the illustrated shape can be predicted, for example, according to manufacturing techniques and/or tolerances (tolerance). Thus, embodiments of the present invention should not be construed as limited to the particular shapes of regions illustrated herein but are to include deviations in shapes that result, for example, from manufacturing. Like reference numerals refer to like elements throughout. Further, various constituent elements and regions are generally drawn in the drawings. Thus, the present invention is not limited to the relative sizes or spacings shown in the drawings.
Fig. 2 is a diagram schematically showing an example of an apparatus for performing the thin film forming method of the present invention. The apparatus shown in fig. 2 is a vertical batch-type substrate processing apparatus, and is an example of a substrate processing apparatus for carrying out the oxide film forming method of the present invention. The apparatus for performing the oxide film forming method of the present invention is not limited to the substrate processing apparatus shown in fig. 2, and other substrate processing apparatuses to which the technical idea of the present invention is applicable may be used, and therefore, the structure may be increased or changed to a degree that is obvious to those skilled in the art.
Referring to fig. 2, an example 100 of an apparatus for performing the thin film forming method of the present invention has reaction vessels 110 and 120, a manifold 160, a boat 140, a lid flange 150, and a heater 130.
The reaction vessels 110 and 120 are composed of an inner tube 120 and an outer tube 110, and may be composed of a heat-resistant material such as quartz. The outer tube 110 is formed in a cylindrical shape with an open lower portion, and has a receiving portion formed therein. The inner tube 120 is disposed in an inner receiving portion of the outer tube 110, has a cylindrical shape with an open lower portion, and receives the boat 140 therein, and further has a substrate processing space for performing a substrate process in the inner tube 120. An exhaust port 122 for discharging gas in the inner tube 120 is formed at a sidewall of the inner tube 120. An exhaust port 111 for exhausting the inside of the outer tube 110 is formed at a lower side surface of the outer tube 110, and the exhaust port 111 is connected to a pump (not shown) having an air exhaust capability. A contour temperature sensor is disposed inside a temperature sensor protection tube 183 extending in the vertical direction inside the inner tube 120.
The outer tube 110 is positioned above the manifold 160, and the outer tube 110 is fixed above the manifold 160 by fixing an outer tube protruding portion 113 protruding on the outer peripheral side of the lower end of the outer tube 110 by an outer tube fixing flange 115. An inner-tube protrusion 125 protruding on the outer peripheral side of the lower end of the inner tube 120 is also located above the manifold 160.
The manifold 160 is provided with a plurality of gas supply ports 165 for supplying gas to the inner tube 120. The plurality of gas supply ports 165 may be connected to a silicon-containing gas supply tool 192, an oxygen-containing gas supply tool 194, a nitrogen-containing gas supply tool 196, and a purge gas supply tool 197 for forming a silicon oxide film or a silicon oxynitride film. In addition, the gas supply port 165 may be connected to a process gas supply tool 198 for heat-treating the silicon oxide thin film or the oxide film. The plurality of gas supply ports 165 are respectively combined with the gas nozzles 162 inside the manifold 160. A plurality of gas nozzles 162 are formed to extend above the inside of the inner tube 120 to supply a silicon-containing gas, an oxygen-containing gas, a nitrogen-containing gas, a purge gas, and a heat treatment gas. The gas nozzles 162 are formed to extend toward the upper portion of the inner pipe 120, have a spray hole shape capable of horizontally spraying gas, and can spray gas onto the substrates stacked in the vertical direction.
The silicon-containing gas supply means 192 supplies a silicon (Si) -containing gas onto the substrate, and may supply, for example, SiH4, Si2H6, a silane-based gas such as hcds (hexachlorodisilane), or a siloxane-based gas such as hcdso (hexachlorodisilane). The oxygen-containing gas supply means 194 supplies an oxygen (O) -containing gas to the substrate, and may supply a gas such as oxygen (O2), ozone (O3), nitrous oxide (N2O), Nitric Oxide (NO), a mixed gas of oxygen (O2) and hydrogen (H2). The mixed gas of oxygen (O2) and hydrogen (H2) may be supplied to the inside of the inner tube 120 through separate oxygen (O2) gas supply means and hydrogen (H2) gas supply means, respectively. The nitrogen-containing gas supply tool 196 supplies a nitrogen (N) -containing gas, such as ammonia (NH3), onto the substrate. The purge gas supply tool 197 supplies a purge gas to the substrate, and may supply an inert gas, such as nitrogen (N2). The heat treatment gas supply tool 198 is provided to create a heat treatment environment, and may supply, for example, oxygen (O2), hydrogen (H2), nitrogen (N2), nitrous oxide (N2O), Nitric Oxide (NO), ammonia (NH3), and other gases. When the same gas is used for the gas supply means 192, 194, 196, 197 and 198, one gas supply means can be used for two or more purposes. For example, in the case where the purge gas and the heat treatment gas all use nitrogen (N2), the purge gas supply means 197 and the heat treatment gas supply means 198 may be provided with only one; in the case where the oxygen-containing gas and the heat treatment gas both use nitrous oxide (N2O), only one of the oxygen-containing gas supply means 194 and the heat treatment gas supply means 198 may be provided.
The gas supply means 192, 194, 196, 197, 198 may have a gas storage container or vaporizer, a gas line, a flow regulator, etc., respectively, and receive a control signal, and the gas may be supplied or blocked by the flow regulator or the gas valve, etc., and the flow rate of the supplied gas may be adjusted.
A cover flange 150 is disposed below the reaction vessels 110 and 120, and the cover flange 150 has a disk shape capable of opening and closing lower openings of the reaction vessels 110 and 120. The lid flange 150 is connected to a lifting tool (not shown) for lifting. The lid flange 150 disposed below the reaction vessels 110 and 120 is raised to seal the manifold 160 disposed below the reaction vessels 110 and 120, and further seal the lower openings of the reaction vessels 110 and 120. The lid flange 150 is then lowered, spacing the manifold 160 from the lid flange 150, thereby opening the lower openings of the reaction vessels 110, 120. A sealing member (not shown) is disposed on the upper surface of the lid flange 150. When the cover flange 150 is raised to seal against the manifold 160, a sealing member is interposed between the cover flange 150 and the manifold 160, thereby sealing between the cover flange 150 and the manifold 160.
The boat 140 is disposed on the lid flange 150, and includes a substrate loading unit 142 on which a plurality of substrates are placed in the vertical direction, and a heat shield unit 144. The heat insulating part 144 supports the substrate loading part 142, and has a structure and material that the heat transferred to the inside of the reaction vessels 110 and 120 is not easily transferred to the lid flange 150. The substrate loading unit 142 is configured to be able to place a plurality of substrates at intervals in the vertical direction. The substrate loading unit 142 has a plurality of support columns 141, and the support columns 141 are formed in a strip shape elongated in the vertical direction and have a structure in which a plurality of slots are vertically arranged in parallel, thereby supporting the substrate. In order to stably support the substrate, an auxiliary support column (not shown) may be disposed in addition to the support column 141. The wafer boat 140 is rotated by a rotating shaft 155 provided through the cover flange 150, and substrates arranged on the wafer boat 140 are also rotated as the wafer boat 140 is rotated.
The heater 130 is supported by being mounted on a heater base 135, surrounds both the heating reaction vessels 110 and 120 of the outer tube 110, and heats the substrates of the boat 140 placed in the inner tube 120. Heater 130 is composed of a heat insulating wall and a heat line (not shown) located at an inner peripheral surface of the heat insulating wall, and a cooling passage (not shown) having a cylindrical space is formed inside the heat insulating wall of heater 130. The cooling passage is supplied with gas for rapid cooling.
Fig. 3 is a flowchart schematically showing the execution of an embodiment of the thin film forming method of the present invention. Fig. 4 to 7 are diagrams for explaining an implementation process of the embodiment shown in fig. 3. An embodiment of the thin film forming method of the present invention shown in fig. 3 may be performed using the apparatus shown in fig. 2, but is not limited thereto.
Referring to fig. 3 and 4 to 7 together, in one embodiment of the method for forming a thin film according to the present invention, as shown in fig. 4, a silicon oxide thin film 320 is first formed on a substrate 310 (S210). The silicon oxide film 320 may be formed by a Deposition method, which is not particularly limited, and may be deposited by Atomic Layer Deposition (ALD). As the silicon (Si) -containing gas, a silane-based gas such as HCDS can be used, and as the oxygen (O) -containing gas, a mixed gas of hydrogen (H2) and oxygen (O2) can be used.
After performing the step S210, the silicon oxide film 320 may be heat-treated. At this time, the heat treatment may be performed by a radical oxidation (chemical oxidation) method performed under a mixed gas atmosphere of oxygen (O2) and hydrogen (H2). Thus, when the silicon oxide thin film 320 is radical-oxidized, the physical properties of the silicon oxide thin film 320 are improved.
Then, as shown in fig. 5, a third silicon oxynitride film 330 is formed on the silicon oxide film 320 (S220). Next, as shown in fig. 6, a first silicon oxynitride film 340 is formed on the third silicon oxynitride film 330 (S230). Next, as shown in fig. 7, a second silicon oxynitride film 350 is formed on the first silicon oxynitride film 340 (S240).
The step S230 of forming the first silicon oxynitride film 340 is performed by a first process condition including adjusting the nitrogen (N) content in the first silicon oxynitride film 340; the second silicon oxynitride film 350 forming step S240 includes performing a second process condition that can adjust the nitrogen (N) content in the second silicon oxynitride film 350; the third silicon nitride film 330 formation step S220 includes adjusting a third process condition of nitrogen (N) content in the third silicon nitride film 330. At this time, the first, second, and third process conditions are adjusted such that the nitrogen (N) content in the first silicon oxynitride film 340 is the largest, the nitrogen (N) content in the third silicon oxynitride film 330 is the smallest, and the nitrogen (N) content in the second silicon oxynitride film 350 is in the middle, and then steps S220 to S250 are performed. For example, the step S230 is performed by adjusting the first process condition to make the nitrogen (N) content in the first silicon oxynitride film 340 reach 20-40%, the step S240 is performed by adjusting the second process condition to make the nitrogen (N) content in the second silicon oxynitride film 350 reach 10-20%, and the step S220 is performed by adjusting the third process condition to make the nitrogen (N) content in the third silicon oxynitride film 330 below 10%.
The silicon oxynitride films 330, 340, 350 may all be formed by a deposition method, which is not particularly limited and may be deposited using an atomic layer deposition method. The silicon oxide film 320 and the silicon oxynitride films 330, 340, 350 may all be deposited using atomic layer deposition and may be deposited in-situ in the same apparatus as shown in fig. 2.
Specifically, the first silicon oxynitride film 340 forming step S230 may be performed by an Atomic Layer Deposition (ALD) method repeatedly performing a first cycle period including at least one of the first silicon (Si) -containing gas supplying step, the first oxygen (O) -containing gas supplying step, and the first nitrogen (N) -containing gas supplying step; the second silicon nitride film 350 forming step S240 may be performed by repeating the atomic layer deposition method for a second cycle period including at least one of the second silicon (Si) -containing gas supplying step, the second oxygen (O) -containing gas supplying step, and the second nitrogen (N) -containing gas supplying step; the third silicon nitride film 330 forming step S220 is performed by repeating the atomic layer deposition method for a third cycle period including at least one of the third silicon (Si) -containing gas supplying step, the third oxygen (O) -containing gas supplying step, and the third nitrogen (N) -containing gas supplying step. As the silicon (Si) -containing gas, a silane-based gas such as HCDS or a siloxane-based gas such as HCDSO may be used; as the oxygen (O) -containing gas, a mixed gas of oxygen (O2), ozone (O3), nitrous oxide (N2O), Nitric Oxide (NO), oxygen (O2), and hydrogen (H2), or a combination of these can be used; a nitrogen (N) -containing gas such as ammonia (NH3) may be used.
The first embodiment of the first, second, and third process conditions for adjusting the nitrogen (N) content in the silicon oxynitride films 330, 340, 350 is to adjust the nitrogen (N) content in the silicon oxynitride films 330, 340, 350 using oxygen (O) -containing gases of different kinds from each other for the oxygen (O) -containing gas kind. For example, dinitrogen monoxide (N2O) is used as the first oxygen (O) -containing gas in the first silicon oxynitride film 340 forming step S230, oxygen (O2) is used as the second oxygen (O) -containing gas in the second silicon oxynitride film 350 forming step S240, and a mixed gas of oxygen (O2) and hydrogen (H2) is used as the third oxygen (O) -containing gas in the third silicon oxynitride film 330 forming step S220. The process condition that can maximize the variation of the nitrogen (N) content among the first, second, and third process conditions for adjusting the nitrogen (N) content in the silicon oxynitride films 330, 340, 350 is to change the kind of the oxygen (O) -containing gas.
Hereinafter, the first process condition, the second process condition, and the third process condition for adjusting the nitrogen (N) content in the silicon oxynitride films 330, 340, 350 within a small range, as compared to the case of changing the kind of the oxygen (O) -containing gas.
A second embodiment of the first, second, and third process conditions for adjusting the nitrogen (N) content in the silicon oxynitride films 330, 340, 350 is that the nitrogen (N) content in the silicon oxynitride films 330, 340, 350 can be adjusted by supplying the oxygen (O) -containing gas at mutually different times for the supply time of the oxygen (O) -containing gas. For example, the first oxygen (O) -containing gas may be supplied for the shortest time in the first silicon oxynitride film 340 forming step S230, the second oxygen (O) -containing gas may be supplied for the middle time in the second silicon oxynitride film 350 forming step S240, and the third oxygen (O) -containing gas may be supplied for the longest time in the third silicon oxynitride film 330 forming step S220.
A third embodiment of the first, second, and third process conditions for adjusting the nitrogen (N) content in the silicon oxynitride films 330, 340, 350 is that the nitrogen (N) content in the silicon oxynitride films 330, 340, 350 can be adjusted by supplying the oxygen (O) -containing gas at mutually different pressures with respect to the pressure of the supplied oxygen (O) -containing gas. For example, the first oxygen (O) -containing gas pressure supplied in the first silicon oxynitride film 340 forming step S230 may be the smallest, the second oxygen (O) -containing gas pressure supplied in the second silicon oxynitride film 350 forming step S240 may be the middle, and the third oxygen (O) -containing gas pressure supplied in the third silicon oxynitride film 330 forming step S220 may be the largest.
A fourth embodiment of the first, second, and third process conditions for adjusting the nitrogen (N) content in the silicon oxynitride films 330, 340, 350 is that the nitrogen (N) content in the silicon oxynitride films 330, 340, 350 is adjusted by supplying the oxygen (O) -containing gas at mutually different flow rates with respect to the flow rate of the supplied oxygen (O) -containing gas. For example, the flow rate of the first oxygen (O) -containing gas supplied in the first silicon oxynitride film 340 forming step S230 may be the smallest, the flow rate of the second oxygen (O) -containing gas supplied in the second silicon oxynitride film 350 forming step S240 may be the middle, and the flow rate of the third oxygen (O) -containing gas supplied in the third silicon oxynitride film 330 forming step S220 may be the largest.
A fifth embodiment of the first, second, and third process conditions for adjusting the nitrogen (N) content in the silicon oxynitride films 330, 340, and 350 is that the nitrogen (N) content in the silicon oxynitride films 330, 340, and 350 can be adjusted by having the oxygen (O) -containing gas supply steps different from each other for the number of times of the oxygen (O) -containing gas supply step included in one cycle period in each cycle period. For example, the number of the first oxygen (O) -containing gas supplying step per one first cycle period in the first silicon oxynitride film 340 forming step S230 is the smallest, the number of the second oxygen (O) -containing gas supplying step per one second cycle period in the second silicon oxynitride film 350 forming step S240 is the middle, and the number of the third oxygen (O) -containing gas supplying step per one third cycle period in the third silicon oxynitride film 330 forming step S220 may be the largest.
More specifically, the first cycle period in the first silicon oxynitride film 340 forming step S230 is such that the first silicon (Si) -containing gas supplying step and the first oxygen (O) -containing gas supplying step are repeated N (N is a natural number) times and then the first nitrogen (N) -containing gas supplying step is performed; the second nitrogen (N) -containing gas supplying step is performed after repeating the second silicon (Si) -containing gas supplying step and the second oxygen (O) -containing gas supplying step m (m is a natural number) times in a second cycle period in the second silicon nitride film 350 forming step S240; the third cycle period in the third silicon nitride film 330 formation step S220 is that the third nitrogen (N) -containing gas supply step may be performed after repeating the third silicon (Si) -containing gas supply step and the third oxygen (O) -containing gas supply step l (where l is a natural number) times. At this time, steps S220 to S240 may be performed l > m > n.
The schematic gas supply sequence described above is shown in fig. 8 and 9.
As shown in fig. 8, the atomic layer deposition method may be performed with sequential supply of a silicon (Si) -containing gas, a purge gas, an oxygen (O) -containing gas, a purge gas, a nitrogen (N) -containing gas, and a purge gas as one cycle period, and at this time, the nitrogen (N) -content in the silicon oxynitride films 330, 340, 350 may be adjusted by changing the supply time of the oxygen-containing gas or the nitrogen-containing gas, and the like.
Then, as shown in fig. 9, the atomic layer deposition method may be performed with sequential supply of a silicon (Si) -containing gas, a purge gas, an oxygen (O) -containing gas, a purge gas, a nitrogen (N) -containing gas, and a purge gas as one cycle.
If the gases are supplied in the gas supply order as shown in fig. 9, the oxygen (O) -containing gas is supplied three times per one cycle period; if the gases are supplied in the gas supply sequence as shown in fig. 8, the oxygen (O) -containing gas is supplied once per one cycle period. Accordingly, if the silicon oxynitride film is formed by the gas supply sequence shown in fig. 8, the nitrogen (N) content is increased compared to the case of forming the silicon oxynitride film by the gas supply sequence shown in fig. 9. Thus, the first silicon oxynitride film 340 forming step S230 supplies gases in the gas supply order as shown in fig. 8, and the second silicon oxynitride film 350 forming step S240 can supply gases in the gas supply order as shown in fig. 9.
In addition, the first, second, and third process conditions for adjusting the nitrogen (N) content of the silicon oxynitride films 330, 340, 350 may be at least one of a nitrogen (N) -containing gas supply time, a pressure of the supplied nitrogen (N) -containing gas, a flow rate of the supplied nitrogen (N) -containing gas, the number of nitrogen (N) -containing gas supply steps included in one cycle period, and a process temperature.
In order to increase the nitrogen content in the silicon oxynitride films 330, 340, 350, the nitrogen (N) -containing gas supply time is increased or the pressure of the supplied nitrogen (N) -containing gas is increased, the flow rate of the supplied nitrogen (N) -containing gas is increased, and the number of times the nitrogen (N) -containing gas is supplied per cycle period is increased.
Then, in the case where the activation energy of the oxidation reaction by supplying the oxygen (O) -containing gas is larger than the activation energy of the nitridation reaction by supplying the nitrogen (N) -containing gas, the nitrogen (N) content in the silicon oxynitride films 330, 340, 350 increases when the process temperature is lowered; in the case where the activation energy of the oxidation reaction by supplying the oxygen (O) -containing gas is smaller than the activation energy of the nitridation reaction by supplying the nitrogen (N) -containing gas, the nitrogen (N) content of the silicon oxynitride films 330, 340, 350 increases as the process temperature is increased.
In contrast, in order to reduce the nitrogen (N) content in the silicon oxynitride films 330, 340, 350, the nitrogen (N) -containing gas supply time is reduced or the pressure of the supplied nitrogen (N) -containing gas is reduced, the flow rate of the supplied nitrogen (N) -containing gas is reduced, and the number of times the nitrogen (N) -containing gas is supplied per cycle period is reduced.
Then, in the case where the activation energy of the oxidation reaction by supplying the oxygen (O) -containing gas is larger than the activation energy of the nitridation reaction by supplying the nitrogen (N) -containing gas, the nitrogen (N) content in the silicon oxynitride films 330, 340, 350 is decreased when the process temperature is increased; in the case where the activation energy of the oxidation reaction by supplying the oxygen (O) -containing gas is smaller than the activation energy of the nitridation reaction by supplying the nitrogen (N) -containing gas, the nitrogen (N) content of the silicon oxynitride films 330, 340, 350 may increase when the process temperature is lowered.
As described above, if the first process condition, the second process condition and the third process condition are adjusted to perform the steps S220, S230 and S240, the content of nitrogen (N) in the silicon oxynitride films 330, 340 and 350 is adjusted so that the content of nitrogen (N) in the first silicon oxynitride film 340 is the largest, the content of nitrogen (N) in the second silicon oxynitride film 350 is the second largest, the content of nitrogen (N) in the third silicon oxynitride film 330 is the smallest, and the concentration of nitrogen (N) in the oxide film is adjusted as shown in fig. 10. If the silicon oxide film 320 and the silicon oxynitride film 330, 340, 350 are formed by a deposition method as in the present invention, they can be formed in situ in the apparatus shown in fig. 2, and thus, the deposition of nitrogen (N) at the interface between the silicon oxide film 320 and the substrate 310 can be minimized.
Then, the films 320, 330, 340, 350 are all heat-treated (S250). The density (density) of all the thin films 320, 330, 340, 350 is increased or the nitrogen (N) content of the surfaces of all the thin films 320, 330, 340, 350 may be adjusted through the S250 step. For this, the S250 step may be performed under nitrogen (N2), nitrous oxide (N2O), Nitric Oxide (NO), hydrogen (H2), and ammonia (NH3) environments. Then, the step S250 can also be performed in situ with the steps S210 to S240. That is, all of the steps S210 to S250 may be performed in situ using the apparatus shown in fig. 2. The thin films 320, 330, 340, 350 thus formed may be used as gate oxide films.
As described above, according to the present invention, the formation of the silicon oxide film, the formation of the silicon oxynitride film, and the heat treatment process can all be performed in-situ (in-situ), thereby improving productivity. That is, a gate oxide film including a silicon oxynitride thin film for adjusting a dielectric constant can be formed more easily. In addition, in the case where the silicon oxide film and the silicon oxynitride film are all formed by deposition as in the present invention, the phenomenon of nitrogen deposition at the interface between the substrate 310 and the silicon oxide film 320 can be minimized to improve the electrical characteristics, and thus, the silicon oxide film and the silicon oxynitride film are suitable for use as a gate oxide film.
While the embodiments of the present invention have been shown and described, the present invention is not limited to the specific embodiments described above, but can be naturally implemented in various modifications by anyone having ordinary knowledge in the technical field to which the present invention pertains without exceeding the gist of the present invention claimed in the claims, and such modifications are within the scope of the claims.

Claims (19)

1. A method of forming a thin film, comprising:
a silicon oxide film forming step of forming a silicon oxide film on a substrate;
a first silicon oxynitride film forming step of forming a first silicon oxynitride film on the silicon oxide film, and further including a first process condition of adjusting a nitrogen content in the first silicon oxynitride film to form a first silicon oxynitride film;
a second silicon oxynitride film forming step of forming a second silicon oxynitride film on the first silicon oxynitride film and further including a second process condition of adjusting a nitrogen content in the second silicon oxynitride film to form a second silicon oxynitride film;
wherein the first process condition and the second process condition are adjusted so that the nitrogen content in the first silicon oxynitride film is greater than the nitrogen content in the second silicon oxynitride film.
2. The method of forming a thin film according to claim 1,
the first silicon oxynitride film forming step is performed by an atomic layer deposition method repeatedly performing a first cycle period including at least one of the first silicon-containing gas supplying step, the first oxygen-containing gas supplying step, and the first nitrogen-containing gas supplying step;
the second silicon nitride film forming step is performed by an atomic layer deposition method repeatedly performing a second cycle period including at least one of a second silicon-containing gas supplying step, a second oxygen-containing gas supplying step, and a second nitrogen-containing gas supplying step.
3. The method of forming a thin film according to claim 2,
the first process condition and the second process condition are oxygen-containing gas species,
the first oxygen-containing gas supplied in the first silicon oxynitride film forming step and the second oxygen-containing gas supplied in the second silicon oxynitride film forming step are gases of mutually different kinds.
4. The film forming method according to claim 3,
the first oxygen-containing gas is nitrous oxide,
the second oxygen-containing gas is oxygen.
5. The method of forming a thin film according to claim 1,
a third silicon oxynitride film forming step is further included between the silicon oxide film forming step and the first silicon oxynitride film forming step, a third silicon oxynitride film is formed on the silicon oxide film, and a third process condition for adjusting the nitrogen content in the third silicon oxynitride film is further included to form a third silicon oxynitride film;
adjusting the first process condition, the second process condition and the third process condition to enable the nitrogen content in the third silicon oxynitride film to be smaller than the nitrogen content in the second silicon oxynitride film;
the first silicon oxynitride film forming step is performed by an atomic layer deposition method repeatedly performing a first cycle period including at least one of the first silicon-containing gas supplying step, the first oxygen-containing gas supplying step, and the first nitrogen-containing gas supplying step;
the second silicon nitride film forming step is performed by repeating the atomic layer deposition method for a second cycle period including at least one of the second silicon-containing gas supplying step, the second oxygen-containing gas supplying step, and the second nitrogen-containing gas supplying step;
the third silicon nitride film forming step is performed by repeating the atomic layer deposition method for a third cycle period including at least one of the third silicon-containing gas supplying step, the third oxygen-containing gas supplying step, and the third nitrogen-containing gas supplying step.
6. The method of forming a thin film according to claim 5,
the first process condition, the second process condition, and the third process condition are oxygen-containing gas species,
the first oxygen-containing gas is nitrous oxide,
the second oxygen-containing gas is oxygen,
the third oxygen-containing gas is at least one of a mixed gas of oxygen and hydrogen and oxygen.
7. The film forming method according to claim 5,
adjusting the first process condition, the second process condition, and the third process condition,
so that the nitrogen content in the first silicon oxynitride film is 20-40%,
The nitrogen content in the second silicon oxynitride film is 10-20%,
The nitrogen content in the third silicon nitride film is below 10%.
8. The film forming method according to claim 5,
the silicon oxide thin film forming step is performed by an atomic layer deposition method.
9. The film forming method according to any one of claims 5 to 8,
the step of heat-treating the film is further included after the second silicon oxynitride film forming step.
10. The film forming method according to claim 9,
the heat treatment step is performed in an atmosphere of at least one gas of nitrogen, nitrous oxide, nitric oxide, hydrogen, and ammonia.
11. The film forming method according to claim 9,
the step of forming the silicon oxide film, the step of forming the first silicon oxynitride film and the step of forming the second silicon oxynitride film, wherein the step of forming the third silicon oxynitride film and the step of heat treatment are performed in situ.
12. The thin film forming method according to any one of claims 1 to 8,
the oxygen-containing gas comprises: at least one of oxygen, ozone, nitrous oxide, nitric oxide, and a mixed gas of oxygen and hydrogen.
13. The thin film forming method according to any one of claims 1 to 8,
the nitrogen-containing gas comprises ammonia.
14. The thin film forming method according to any one of claims 1 to 8,
the silicon-containing gas contains at least one of a silane-based gas and a siloxane-based gas.
15. The film forming method according to any one of claims 1 to 8,
the step of heat-treating the silicon oxide film with a mixed gas of oxygen and hydrogen is further included after the silicon oxide film forming step.
16. The thin film forming method according to any one of claims 5 to 8,
the first process condition, the second process condition and the third process condition are the number of oxygen-containing gas supply steps included in one cycle period;
the first cycle period is that the first nitrogen-containing gas supply step is executed after repeating the first silicon-containing gas supply step and the first oxygen-containing gas supply step n times, wherein n is a natural number;
the second cycle period is that the second nitrogen-containing gas supply step is executed after the second silicon-containing gas supply step and the second oxygen-containing gas supply step are repeated m times, wherein m is a natural number;
the third cycle period is that the third nitrogen-containing gas supply step is executed after the third silicon-containing gas supply step and the third oxygen-containing gas supply step are repeated for l times, wherein l is a natural number;
l>m>n。
17. the thin film forming method according to any one of claims 5 to 8,
the first process condition, the second process condition, and the third process condition are at least one of a time of supply of an oxygen-containing gas, a pressure of the supplied oxygen-containing gas, a flow rate of the supplied oxygen-containing gas, a time of supply of a nitrogen-containing gas, a pressure of the supplied nitrogen-containing gas, a flow rate of the supplied nitrogen-containing gas, a number of nitrogen-containing gas supply steps included in one cycle period, and a process temperature.
18. The film forming method according to any one of claims 1 to 8,
the thin film is a gate oxide film.
19. A thin film forming apparatus for forming a thin film on a silicon substrate,
the thin film is formed by the thin film forming method according to any one of claims 1 to 8.
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