JP6650597B2 - Method of manufacturing oxynitride film - Google Patents

Description

  The present disclosure relates to a method for manufacturing an oxynitride film using an ALD method. More specifically, the present invention relates to a method for producing an oxynitride film containing a metal element (alkali metal element or alkaline earth metal element) and an element constituting a network former using an ALD method.

  The secondary battery is provided with a positive electrode, a negative electrode, and an electrolyte layer disposed therebetween, and the electrolyte used for the electrolyte layer is, for example, a non-aqueous solution (hereinafter, referred to as “electrolyte solution”) or a solid substance. (Hereinafter, “solid electrolyte”) is known. When an electrolytic solution is used, the electrolytic solution easily penetrates into the inside of the positive electrode or the negative electrode. Therefore, an interface between the active material contained in the positive electrode or the negative electrode and the electrolyte is easily formed, and the performance is easily improved. On the other hand, in a secondary battery using an electrolytic solution, there is a possibility of liquid leakage. Further, since most of the electrolytes are flammable, it is necessary to mount a system for ensuring safety.

  On the other hand, since the solid electrolyte is not liquid, there is no possibility of liquid leakage, and since it is flame retardant, safety can be ensured. Further, in the electrolytic solution, the organic solvent component is decomposed during repeated charge / discharge, thereby deteriorating battery performance. Furthermore, since all components are solid-state batteries, it is possible to make the batteries smaller and thinner. From such a viewpoint, development of an all-solid secondary battery in a form including a layer containing a solid electrolyte (hereinafter, “solid electrolyte layer”) is being promoted. In particular, for small electronic devices such as wearable electronic devices, the development of a thin-film all-solid battery provided with a thin-film solid electrolyte layer has been promoted.

In an all-solid secondary battery, a solid electrolyte is one of important components. For example, lithium nitride phosphate (LiPON) is used as a solid electrolyte in thin-film all-solid lithium-ion secondary batteries currently on the market and in all-solid-state batteries reported so far (for example, Patent Document 1). Compared to Li ₃ PO ₄ , LiPON improves ionic conductivity by about two orders of magnitude. In Patent Document 1, a LiPON film in which nitrogen is introduced into Li ₃ PO ₄ is obtained by performing sputtering in a nitrogen atmosphere using a Li ₃ PO ₄ target.

U.S. Pat. No. 5,597,660

  Heretofore, it has been difficult to produce a thin-film solid electrolyte layer that is rich in conformality (shape adaptability). Therefore, an object of the present disclosure is to provide a novel method of manufacturing an oxynitride film that is rich in conformality (shape adaptability) and can be used as a thin film solid electrolyte layer. Another object of the present disclosure is to provide a method for manufacturing an oxynitride film that enables stable nitriding without being affected by variations in the temperature inside the reactor (sample substrate temperature) or the degree of vacuum. I do.

The present disclosure is a method for producing an oxynitride film containing a metal element and an element constituting a network former, wherein the metal element is an alkali metal element or an alkaline earth metal element,
Arranging a substrate in a reactor of an apparatus having a reactor (a),
Supplying a network former precursor (P-1) containing an element constituting the network former into the reactor, (b)
A metal supply step (c) of supplying a metal precursor (P-2) containing the metal element into the reactor;
An oxygen supply step (d) for supplying oxygen gas and / or ozone gas into the reactor;
A nitrogen supply step (e) for supplying ammonia gas and / or nitrogen gas into the reactor, and an air supply gas supply step (f) for supplying air supply gas into the reactor.
Provided is a method for manufacturing an oxynitride film containing a metal element and an element constituting a network former.

  According to the present disclosure, an oxynitride film (i.e., a quaternary oxynitride film) containing a metal element (alkali metal element or alkaline earth metal element) and an element constituting a network former, which is excellent in conformality. Can be manufactured. By using the oxynitride film obtained by the manufacturing method of the present disclosure, a solid electrolyte, all-solid lithium, and a post-lithium ion secondary battery capable of reducing ionic resistance and a method for forming the same can be provided. Further, according to the present disclosure, it is possible to perform stable nitriding without being affected by variations in the temperature inside the reactor (sample substrate temperature) or the degree of vacuum. In particular, it becomes possible to stabilize the composition ratio of nitrogen in the film when the film is formed over a long time.

1 is a configuration diagram of a reaction device according to an embodiment of the present disclosure. 1 is a configuration diagram of a reaction cycle according to an embodiment of the present disclosure. FIG. 9 is a diagram illustrating a result of impedance measurement of the oxynitride film obtained by the manufacturing method of the present disclosure. FIG. 3 is a diagram illustrating an Arrhenius plot of an oxynitride film obtained by a manufacturing method according to an embodiment of the present disclosure. 5 is an SEM observation image of an oxynitride film obtained by a manufacturing method according to an embodiment of the present disclosure. FIG. 4 is a diagram illustrating a result of element concentration measurement in a depth direction of an oxynitride film obtained by a manufacturing method according to an embodiment of the present disclosure. 5 is an SEM observation image of a cross section of a structure in which an oxynitride film is formed on a LiCoO ₂ layer formed on a substrate. FIG. 7A is an SEM observation image of a cross section of a structure (Example 3) in which an oxynitride film of the present disclosure is formed on a LiCoO ₂ layer formed on a substrate. FIG. 7B is an SEM observation image of a cross section of a structure (Comparative Example 5) in which an oxynitride film is formed by sputtering on a LiCoO ₂ layer formed on a substrate. 4 is an SEM observation image of an upper surface of a structure in which an oxynitride film obtained by a manufacturing method according to an embodiment of the present disclosure is formed on a substrate (quartz glass). 4 is an image obtained by STEM observation of a cross section of a structure in which an oxynitride film obtained by a manufacturing method according to an embodiment of the present disclosure is formed on a substrate (quartz glass). FIG. 4 is a diagram illustrating a result of XPS measurement of an oxynitride film obtained by a manufacturing method according to an embodiment of the present disclosure. FIG. 3 is a diagram showing the results of XPS measurement of an oxynitride film manufactured by a sputtering method.

(Knowledge by the present inventors)
First, the findings obtained by the present inventors will be described.

  The all-solid-state battery described in Patent Literature 1 and the thin-film all-solid lithium-ion secondary battery currently on the market have small battery capacities and have limited applications. An all-solid-state battery having a three-dimensional structure for increasing the capacity has been proposed (Advanced Functional Materials. Volume 18, Issue 7, pages 1057-1066, April 11, 2008.). On this three-dimensional structure, for example, a LiPON film can be arranged as a solid electrolyte. However, when a LiPON film is formed on the three-dimensional structure by, for example, a sputtering method, the LiPON film lacks uniformity of the film composition. Therefore, the function as a solid electrolyte is reduced. Therefore, the materials that can realize the three-dimensional structure are limited, which has a great influence on the development of a practical thin-film all-solid-state battery having a three-dimensional structure.

  Further, the solid electrolyte has a higher ionic resistance than a general electrolytic solution. Further, there is a problem that the resistance of each solid-solid interface between the positive electrode active material / solid electrolyte / negative electrode active material is high, and the internal resistance in the battery is increased. The tendency becomes remarkable as the thickness of the solid electrolyte layer increases. Therefore, the voltage drop is large, and it is difficult to obtain good large-current charge / discharge characteristics. For example, there is a problem that the charge / discharge rate is limited and a short charge time cannot be realized.

  In order to solve these problems, it is necessary to produce a thin film solid electrolyte layer having high conformality.

  As a manufacturing method of the Li-containing thin film, a pulse laser deposition method (PLD), a sputtering method (Japanese Patent Application Laid-Open No. 2012-23032), and the like are known. With these methods, it is difficult to form a defect-free or pinhole-free layer, which is desired in many industrial applications. Also, it is very difficult to cover the entire surface of the substrate or the underlayer with a uniform film, for example. Specifically, the sputtering method currently used for forming a LiPON film has a problem that pinholes are generated in the film. At the start of film formation, a LiPON film formed by a sputtering method grows in an island shape and is formed as a film exceeding 50 nm at last, so that it is difficult to reduce the film thickness (particularly, 50 nm or less). It is said that the film thickness that can be formed on a large area at a high yield is about 2 μm.

  Furthermore, in these methods, since high energy is applied to the substrate (or the underlying layer) during film formation, the substrate (or the underlying layer) may be damaged.

  For this reason, proposals have been made regarding ALD (Atomic Layer Deposition: Atomic Layer Deposition) as a method for producing a pin-free and ultra-thin Li-containing thin film.

  However, it has not been possible to produce a Li-containing thin film composed of four or more elements and containing nitrogen by the ALD method. For example, a lithium nitride phosphate (LiPON) thin film functioning as a solid electrolyte could not be produced. On the other hand, according to an embodiment of the present disclosure, an oxynitride film containing an alkali metal element or an alkaline earth metal element and an element constituting a network former, which is excellent in shape adaptability (conformal property). A manufacturing method can be provided.

First, the ALD method according to the present disclosure will be described.
ALD is a thin film deposition technique that relies on a self-contained alternating reaction of gas to the surface. The membrane is formed by sequential pulsing of two or more reactants, and a purge with an inert gas is used during the pulsing of the precursor to avoid gas phase reactions. If the operation is carried out under ideal conditions, it is ensured that all the surfaces are saturated by the precursor during the pulsing of the precursor. As a result, the growth of the film depends on the saturation density of the precursor during pulse supply. Unlike most other deposition and crystal growth methods, in the ideal case, it does not depend on the precursor distribution or the rate of formation of the bonds that form the film. This assures uniform film growth on all exposed surfaces for each pulse supply. Further, damage to the underlying layer that can occur in the PLD method or the sputtering method can be avoided by the ALD method.

  As described above, for example, although there is no report of a successful film formation of lithium nitride phosphate (LiPON), the inventors succeeded in film formation.

  Since the LiPON thin film using the ALD method has a high shape adaptability (conformal property), a coating film can be formed on a 3D structure of any shape. In addition, high conformality can follow irregularities of the underlying film and the like, and the resistance at each solid-solid interface between the positive electrode active material / solid electrolyte / negative electrode active material can be reduced. Further, since the film is formed at the atomic layer level, it is possible to form an extremely thin film having a thickness of about several nm, and it is possible to reduce the ionic resistance in the solid electrolyte layer.

A first aspect of the present disclosure is a method for manufacturing an oxynitride film containing a metal element and an element constituting a network former,
The metal element is an alkali metal element or an alkaline earth metal element,
Arranging a substrate in a reactor of an apparatus having a reactor (a),
Supplying a network former precursor (P-1) containing an element constituting the network former into the reactor, (b)
A metal supply step (c) of supplying a metal precursor (P-2) containing the metal element into the reactor;
An oxygen supply step (d) for supplying oxygen gas and / or ozone gas into the reactor;
A nitrogen supply step (e) for supplying ammonia gas and / or nitrogen gas into the reactor, and an air supply gas supply step (f) for supplying air supply gas into the reactor.
Provided is a method for manufacturing an oxynitride film containing a metal element and an element constituting a network former.

  According to the manufacturing method of the first aspect, an oxynitride film (that is, a quaternary system) containing a metal element (alkali metal element or alkaline earth metal element) and an element constituting a network former having excellent conformability. Oxynitride film). By using the oxynitride film obtained by the manufacturing method of the present disclosure, a solid electrolyte, all-solid lithium, and a post-lithium ion secondary battery capable of reducing ionic resistance and a method for forming the same can be provided.

  According to a second aspect of the present disclosure, for example, in addition to the first aspect, the mesh forming body supply step (b), the metal supply step (c), the oxygen supply step (d), and the air supply gas supply step (F) A method for producing an oxynitride film, wherein ammonia gas is simultaneously supplied in at least one step selected from the group consisting of (f).

  According to the second aspect, it is possible to stably nitride the film without being affected by variations in the temperature (sample substrate temperature) in the reactor or the degree of vacuum. In particular, it becomes possible to stabilize the composition ratio of nitrogen in the film when the film is formed over a long time.

  According to a third aspect of the present disclosure, for example, in addition to the first aspect or the second aspect, a method for producing an oxynitride film, in which the network forming step (b) and the metal supplying step (c) are separately performed. provide.

  According to the third aspect, an oxynitride film (that is, a quaternary oxynitride film) excellent in conformality and containing a metal element (alkali metal element or alkaline earth metal element) and an element constituting a network former ) Can be manufactured.

  According to a fourth aspect of the present disclosure, for example, in addition to any one of the first to third aspects, the metal element includes at least one selected from the group consisting of Li, Na, Mg, and Ca. Provided is a method for manufacturing an oxynitride film.

  According to the fourth aspect, an oxynitride film (that is, a quaternary oxynitride film) which is excellent in conformality and contains a metal element (alkali metal element or alkaline earth metal element) and an element constituting a network former ) Can be manufactured.

  According to a fifth aspect of the present disclosure, for example, in addition to any one of the first to fourth aspects, at least an element constituting the network former is selected from the group consisting of P, B, Si, and V A method for producing an oxynitride film including one type is provided.

  According to the fifth aspect, an oxynitride film (that is, a quaternary oxynitride film) which is excellent in conformality and contains a metal element (alkali metal element or alkaline earth metal element) and an element constituting the network former. ) Can be manufactured.

  According to a sixth aspect of the present disclosure, for example, in addition to any one of the first to fifth aspects, the metal element contains Li, the element constituting the network former contains P, and the oxynitride film Provides a method for producing an oxynitride film containing Li, P, O, and N.

  According to the sixth aspect, an oxynitride film (that is, a quaternary oxynitride film) which is excellent in conformability and contains a metal element (alkali metal element or alkaline earth metal element) and an element constituting the network former ) Can be manufactured.

  A seventh aspect of the present disclosure provides, for example, a method for manufacturing an oxynitride film having a thickness of 200 nm or less, in addition to any one of the first to sixth aspects.

  According to the seventh aspect, an oxynitride film (that is, a quaternary oxynitride film) excellent in conformability and containing a metal element (alkali metal element or alkaline earth metal element) and an element constituting a network former. ) Can be manufactured.

  According to an eighth aspect of the present disclosure, for example, in addition to any one of the first to seventh aspects, a pipe and a metal precursor (P-2) connected to a supply unit and a reactor of the network former precursor (P-1) are provided. ) Is 55% higher than the temperature of the higher of the temperature of the supply unit of the precursor (P-1) and the temperature of the supply unit of the metal precursor (P-2). Provided is a method for manufacturing an oxynitride film which is higher by at least C.

  According to the eighth aspect, an oxynitride film (that is, a quaternary oxynitride film) excellent in conformality and containing a metal element (alkali metal element or alkaline earth metal element) and an element constituting a network former. ) Can be manufactured.

  A ninth aspect of the present disclosure provides a reactor, a controller, a network former precursor (P-1) supply unit that supplies a network former precursor (P-1) containing an element constituting the network former into the reactor, A metal supply unit for supplying a metal precursor (P-2) containing a metal element into the reactor, an oxygen supply unit for supplying oxygen gas and / or ozone gas into the reactor, and an ammonia gas and / or nitrogen gas within the reactor. An apparatus for producing an oxynitride film, comprising: a nitrogen supply unit for supplying gas to a reactor;

  According to the ninth aspect, an oxynitride film (that is, a quaternary oxynitride film) excellent in conformality and containing a metal element (alkali metal element or alkaline earth metal element) and an element constituting a network former ) Can be manufactured.

  FIG. 1 shows an example of an ALD apparatus configuration used in the method of manufacturing an oxynitride film by the ALD method according to the present disclosure. An apparatus for manufacturing an oxynitride film according to an embodiment of the present disclosure includes a network forming body that supplies a reactor 2 (hereinafter, a process chamber), a control unit, and a network forming body precursor (P-1) including elements constituting the network forming body into the reactor. A precursor (P-1) supply unit, a metal precursor (P-2) supply unit that supplies a metal precursor (P-2) containing a metal element into the reactor, and an oxygen supply that supplies oxygen gas and / or ozone gas into the reactor. Unit, a nitrogen supply unit and an air supply gas supply unit.

  As such an ALD apparatus, a commercially available product can be used according to the type of the target oxynitride film. Commercially available products include, for example, Savannah Systems, Fiji Systems, Phoenix Systems (Ultratech / Cambridge NanoTech), ALD-series (Showa Vacuum Co., Ltd.), TFS 200, TFS 500, TFS 120P400A, P800, etc. (Beneq ), OpAL, FlexAL (Oxford Instruments), InPassion ALD 4, InPassion ALD 6, InPassion ALD 8 (above, SoLay Tec), AT-400 ALD System (ANRIC TECHNOLOGIES), LabNano, LabNano-PE (Ensure NanoTech) Corporation).

  The control unit of the apparatus 1 includes a network former supplying step (b) for supplying a network former precursor (P-1) containing an element constituting the network former into the reactor, a metal precursor (P-) containing a metal element. 2) supplying metal into the reactor (c), supplying oxygen gas and / or ozone gas into the reactor (d), supplying ammonia gas and / or nitrogen gas into the reactor A nitrogen supply step (e) and an air supply gas supply step (f) for supplying an air supply gas into the reactor can be performed.

Examples of substrates provided in the reactor 2 of the apparatus 1 include a Si substrate on which a thermal oxide film of 400 nm of SiO ₂ is formed; a quartz substrate; and a glass substrate.

[Step (a)]
In the step (a) of the manufacturing method according to the present disclosure, a substrate is arranged in the reactor 2. Although the material used for the substrate is not particularly limited, for example, a metal (Au or the like), a metal composite oxide, a resin (a polyester-based substrate, a polycarbonate-based substrate, a fluororesin-based substrate, an acrylic resin-based substrate, etc.) , Glass (soda lime glass, quartz glass, etc.), ceramics (aluminum oxide, silicon, gallium nitride, sapphire, silicon carbide, etc.). The temperature in the process chamber 2 is not particularly limited, but may be 250 to 550 ° C., 300 to 500 ° C., or 320 to 480 ° C. from the viewpoint of favorably forming a film. If the temperature of the process chamber is too high, the film formation may not proceed satisfactorily. If the temperature is too low, the precursor may contain carbon and may not burn.

  Hereinafter, description will be made in order from the network forming body supply step (b) to the air supply gas supply step (f). In the manufacturing method of the present disclosure, since the order of each step is repeated film formation, the network forming body supply step (b) is performed at least once before the oxygen supply step (d) or the nitrogen supply step (e). It is not limited unless otherwise specified. Also, each step may be performed simultaneously, except that at least the network forming body supply step (b) and the metal supply step (c) are separately performed. Simultaneous means that the valves for each step are simultaneously opened in the apparatus of FIG. By performing the network former supplying step (b) before the oxygen supplying step (d) or the nitrogen supplying step (e), an oxidized network former skeleton is obtained. An intended oxynitride film is obtained by introducing an alkali metal element or an alkaline earth metal element into this skeleton and further causing nitrogen substitution.

[Step (b)]
In the network forming body supply step (b), a network forming body precursor (P-1) containing the elements constituting the network forming body is supplied into the reactor 2. In FIG. 1, the valve V <b> 2 is opened to supply the network former precursor (P- 1) to the reactor 2 from a supply unit (for example, a bottle) 3 including the network former precursor (P- 1). The temperature of the supply section 3 is not particularly limited, but may be 1 to 50 ° C or about 5 to 45 ° C in consideration of the high vapor pressure of the network former (P-1). In the apparatus 1 of FIG. 1, the network former precursor (P- 1) discharged into the pipe from the supply unit 3 is pushed into the process chamber 2 from the supply unit 3 for the purpose of flushing the precursor (P- 1) into the process chamber 2. In order to supply the auxiliary gas from the auxiliary gas supply unit 7, the manual valve (Mv8) may be kept open during the film formation. The flow rate of the auxiliary gas supplied through the manual valve (Mv8) is not particularly limited, but may be 20 to 60 ml / min or 25 to 50 ml / min. Further, in the apparatus 1 of FIG. 1, the needle valve 4 (Vneedle) for controlling the flow rate of the network former precursor is set to an optimal opening degree (for example, 10 to 60%) according to the release amount of the metal precursor (P-2). By adjusting, the flow rate of the network former precursor (P-1) can be controlled.

  Depending on the type of the elements constituting the network former, if necessary, the valve V5 is opened to supply the auxiliary gas from the auxiliary gas supply unit 8, and the network former precursor (P-1) is extruded. Good. The flow rate of the auxiliary gas can be controlled by a mass flow controller (MFC) 5. The temperature of the auxiliary gas used in step (b) is not particularly limited, but may be 100 to 300 ° C. or 120 to 280 ° C. because it affects the film formation.

  The auxiliary gas may be one containing an inert gas as a main component. Examples of the inert gas include an argon gas and a nitrogen gas. These may be used alone or in combination of two or more. “Main component” means a component contained in the auxiliary gas in the largest volume ratio.

  The components of the auxiliary gas used in the network forming body supply step (b) may be the same as or different from the gas supplied in the gas supply step (f).

  The element constituting the network former is not particularly limited, but includes, for example, at least one selected from the group consisting of P, B, Si, and V, and may include at least P.

The network former precursor (P-1) is not particularly limited, and examples thereof include tris (dimethylamino) phosphine (TDMAP), trimethylphosphine (TMP), triethylphosphine (TEP), and tert-butylphosphine (TBP). phosphorus-containing compounds; tetrakis diethylamide vanadium _{(V [N (C 2 H} 5) 2] 4), tetrakis dimethylamide vanadium _{(V [N (CH 3)} 2] 4) a vanadium compound such as, tris (dimethylamino) silane (3DMAS), Examples include silane compounds such as bisethylmethylaminosilane (BEMAS). These may be used alone or in combination of two or more.

  By closing the valve V2, the network forming body supply step (b) can be completed. The duration of step (b) (the time from opening the valve V2 to closing it) is not particularly limited, but may be about 0.01 to 10 seconds, about 0.05 to 8 seconds, or about 0.1 It may be up to 5 seconds.

[Step (c)]
In the metal supply step (c), a metal precursor (P-2) containing an alkali metal element or an alkaline earth metal element is supplied into the reactor 2. In FIG. 1, the valve V1 is opened to supply the metal precursor (P-2) to the reactor 2 from the supply unit 6 including the metal precursor (P-2). The temperature of the supply unit 6 is not particularly limited, but may be 90 to 190 ° C or 95 to 180 ° C in consideration of the low vapor pressure of the metal precursor (P-2). In the apparatus 1 of FIG. 1, an auxiliary gas is supplied into a pipe connected from the supply unit 6 to the process chamber 2 for the purpose of flushing the metal precursor (P-2) discharged from the supply unit 6 into the pipe into the process chamber 2. In order to supply the auxiliary gas from the supply unit 9, the manual valve (Mv9) may be kept open during the film formation. The flow rate of the auxiliary gas supplied through the manual valve (Mv9) is not particularly limited, but may be 20 to 60 ml / min or 30 to 55 ml / min. Depending on the type of the metal precursor (P-2), if necessary, the valve V4 may be opened to supply the auxiliary gas from the auxiliary gas supply unit 10 to extrude the metal precursor (P-2). The flow rate of the auxiliary gas can be controlled by the mass flow controller 5 and is not particularly limited, but may be 1 to 30 ml / min or 5 to 20 ml / min. The temperature of the auxiliary gas used in step (c) is not particularly limited, but may be 100 to 300 ° C. or 120 to 280 ° C. because it affects the film formation.

  The auxiliary gas used in the metal supply step (c) may be the same as that used in the network formation body supply step (b). The component of the auxiliary gas used in the metal supply step (c) may be the same as or different from the gas supply gas used in the gas supply step (f).

  Examples of the alkali metal element include Li, Na, K, Rb, Cs, and Fr, and may be Li, Na, K, or Li. Examples of the alkaline earth metal element include Be, Mg, Ca, Sr, Ba, and Ra, and may be Mg or Ca. Note that Be and Mg are not included in the narrowly defined alkaline earth metal element due to the difference in properties, but the alkaline earth metal element according to the present disclosure is a broadly defined alkaline earth metal element. And Mg are also included in the alkaline earth metal element. The above-mentioned metal elements may be used alone or in combination of two or more. The metal contained in the metal precursor may be at least one selected from the group consisting of Li, Na, Mg, and Ca.

The metal precursor (P-2) is not particularly limited. For example, Li (thd) (lithium 2,2,6,6-tetramethylheptane-3,5-dionate); Li (t-OBu) (lithium lithium alkoxides such as tert-butoxide); alkyl lithiums such as n-BuLi (n-butyl lithium); cyclic lithium compounds such as LiCp (lithium cyclopentadienyl) and lithium dicyclohexylamide; bis (cyclopentadienyl) magnesium Cp ₂ Mg), bis (methylcyclopentadienyl) magnesium (MeCp ₂ Mg), bis (ethylcyclopentadienyl) magnesium (EtCp ₂ Mg) and the like. These may be used alone or in combination of two or more.

  By closing the valve V1, the metal supply step (c) can be completed. The duration of step (c) (the time from opening the valve V1 to closing it) is not particularly limited, but may be about 0.01 to 10 seconds, about 0.05 to 8 seconds, or about 0.1 It may be up to 5 seconds.

[Step (d)]
In the oxygen supply step (d), oxygen gas and / or ozone gas is supplied into the reactor 2. In the case of plasma ALD, step (d) can be an oxygen supply step (d ′) of supplying radical oxygen into the reactor 2 by plasma processing. Ozone gas can be produced, for example, by supplying oxygen gas to an OT-020 ozone generator (Ozone Technology), as described in JP-T-2011-508826. In FIG. 1, a valve V7 is opened, and a gas (oxygen gas and / or ozone gas) serving as an oxygen supply source is supplied from the oxygen supply unit 12 into the reactor 2. The flow rate of the gas serving as the oxygen supply source can be controlled by the mass flow controller 5 and may be 20 to 60 ml / min, or 30 to 50 ml / min. The concentration of the gas serving as the oxygen supply source is not particularly limited, but may be 100% (for example, 100% oxygen gas). The temperature of the gas serving as an oxygen supply source is not particularly limited, but may be 100 to 300 ° C. or 120 to 280 ° C. because it affects the film formation.

  By closing the valve V7, the oxygen supply step (d) or step (d ') can be completed. The duration of step (d) or step (d ′) (the time from opening to closing of the valve V5) is not particularly limited, but may be about 0.1 to 15 seconds, or about 0.2 to 10 seconds. Good, about 0.2 to 8 seconds.

[Step (e)]
In the nitrogen supply step (e), ammonia gas and / or nitrogen gas is supplied into the reactor 2. In the case of plasma ALD, step (e) can be a nitrogen supply step (e ′) of supplying radical nitrogen into the reactor 2 by plasma processing. In FIG. 1, a valve V6 is opened, and a gas (ammonia gas and / or nitrogen gas) serving as a nitrogen supply source is supplied from the nitrogen supply unit 13 into the reactor 2. The flow rate of the gas serving as the nitrogen supply source can be controlled by the mass flow controller 5 and may be 20 to 60 ml / min, or 30 to 50 ml / min. The concentration of the gas serving as the nitrogen supply source is not particularly limited, but may be 100% (for example, 100% ammonia gas). The temperature of the gas serving as a nitrogen supply source is not particularly limited, but may be 100 to 300 ° C. or 120 to 280 ° C. because it affects the film formation.

  By closing the valve V6, the nitrogen supply step (e) or step (e ') can be completed. The duration of step (e) or step (e ′) (the time from opening the valve V5 to closing it) is not particularly limited, but may be about 0.1 to 15 seconds, or about 0.2 to 10 seconds. Good, about 0.2 to 8 seconds.

[Step (f)]
In the air supply gas supply step (f), the air supply gas is supplied into the reactor 2. Purging is performed by supplying the supply gas into the reactor 2. In FIG. 1, the valve V3 is opened to supply the supply gas from the supply gas supply unit 14 into the reactor 2. The flow rate of the supplied gas can be controlled by the mass flow controller 5 and may be 20 to 60 ml / min, or 30 to 50 ml / min. Although the temperature of the gas to be supplied is not particularly limited, it may be 100 to 300 ° C. or 120 to 280 ° C. because it affects the film formation.

  Step (f) may be performed in order after completion of the mesh forming body supply step (b), the metal supply step (c), and the like, for example. For example, after any step or during any two steps selected from the group consisting of a network forming body supply step (b), a metal supply step (c), an oxygen supply step (d) and a nitrogen supply step (e) May be performed simultaneously with these optional steps. From the viewpoint of sufficiently exhausting the inside of the process chamber, a raw material supply step (a mesh forming body supply step (b), a metal supply step (c), and an oxygen supply step (d)) to be performed first after the step (a) is performed. Alternatively, before the start of the nitrogen supply step (e)), the valve V3 may be kept open until the film formation is completed, and the process may be continuously performed as a background process. Step (f) may be continuously performed as a background process in terms of sufficiently exhausting the inside of the process chamber. The duration (purge time) of step (f) is not particularly limited, but may be about 0.1 to 20 seconds, about 0.5 to 15 seconds, or about 1.0 to 10 seconds.

  An inert gas can be used as the gas to be supplied. Examples of the inert gas include an argon gas and a nitrogen gas. These may be used alone or in combination of two or more.

  The manufacturing method according to the present disclosure includes, in addition to the step (e), a network forming body supply step (b), a metal supply step (c), an oxygen supply step (d), and an air supply gas supply step (f). Ammonia gas may be supplied simultaneously in at least one step selected from the group. By supplying the ammonia gas simultaneously with the above steps, nitrogen can be more stably introduced into the oxynitride film. In the apparatus shown in FIG. 1, the supply of ammonia gas may be performed by opening the valve V6 during the execution of at least one of the steps described above, and the valve V6 is always opened until the formation of the oxynitride film is completed. You may go. The flow rate of the ammonia gas is not particularly limited, but may be, for example, 30 to 100 ml / min or 50 to 100 ml / min. The concentration of the ammonia gas is not particularly limited, but may be 100% (for example, 100% ammonia gas). The temperature of the ammonia gas is not particularly limited, but may be 100 to 200 ° C. because it affects the film formation. Since the decrease in the process chamber temperature can be reduced, the temperature may be 180 ° C to 200 ° C. The supply time of the ammonia gas is not particularly limited as long as it is performed simultaneously with any of the above-described steps.

  In the manufacturing method according to the present disclosure, in at least one of the steps described above, by simultaneously supplying the ammonia gas, the nitrogen abundance ratio in the obtained oxynitride film can be easily improved.

  In the manufacturing method according to the present disclosure, the degree of vacuum in the process chamber 2 is controlled. In FIG. 1, the degree of vacuum in the process chamber 2 can be controlled by adjusting the opening of the manual exhaust valve 11 (Vexhaust). The degree of vacuum can be changed according to the type of the target oxynitride film, but may be, for example, 0.1 to 8.0 Torr or 0.5 to 5.0 Torr. At a low vacuum, the precursor is supplied into the process chamber at one time, the oxidation process becomes insufficient, and the amount of carbon in the film increases. At a high vacuum, the metal precursor (P-2) having a high vapor pressure becomes excessive. Is not preferred because it is supplied to The degree of vacuum in the process chamber can be measured with a Pirani gauge (TPR280 DN16 ISO-KF: manufactured by PFEIFFER VACUUM).

  In the manufacturing method according to the present disclosure, the pipe temperature is one of important factors. In particular, in FIG. 1, the temperature of the pipe from the outlet of the supply unit 3 and the supply unit 6 to the inlet of the reactor 2 depends on the boiling point of the network former precursor (P-1) (for example, the network former precursor (P-1)). Is tris (dimethylamino) phosphine, the boiling point is 48 to 50 ° C.) and the boiling point of the metal precursor (P-2) (for example, when the metal precursor (P-2) is lithium tert-butoxide, the boiling point is 68 to 70). C) or higher than their sublimation temperature and higher than the temperature of the supply unit 3 and the supply unit 6. By setting the temperature of the pipe higher than the temperatures of the supply unit 3 and the supply unit 6, clogging can be avoided. If the temperature of the pipe is lower than the temperature of the supply section 3 and the supply section 6, the precursor solidifies in the pipe and causes clogging. The temperature of the pipe may be 55 ° C. or more higher than the temperature of both the supply unit 3 and the supply unit 6, and may be 60 ° C. or more higher than the higher one of the supply unit 3 and the supply unit 6. For example, when the temperature of the supply unit 3 is 35 ° C. and the temperature of the supply unit 6 is 100 ° C., the temperature of the piping from the supply unit 3 and the outlet of the supply unit 6 to the inlet of the reactor 2 is set to about 180 ° C. be able to.

  In the manufacturing method according to an embodiment of the present disclosure, a mesh forming body supply step (b), a metal supply step (c), an oxygen supply step (d), a nitrogen supply step (e), and an air supply gas supply step (f). By repeating a cycle including at least one step selected from the group consisting of a plurality of times, a target oxynitride film can be obtained. As the cycle, for example, as in a repetition cycle shown in a portion surrounded by a broken line in FIG. 2, a network forming body supply step (b), a metal supply step (c), an oxygen supply step (d), a nitrogen supply step (E) and a cycle including at least one gas supply step (f), and each step (b), (c), (d) and (e) followed by a gas supply step (f) Is mentioned. The number of repetitions of the cycle is not particularly limited, and may be appropriately determined according to the intended thickness of the oxynitride film, the type of the network former precursor (P-1), the type of the metal precursor (P-2), and the like. Can be changed. The number of cycle repetitions may be, for example, about 1 to 8000 cycles, or about 5 to 3000 cycles. For example, when the thickness of the oxynitride film is about 500 nm, the cycle may be set to 7000 to 8000 cycles, and when the thickness of the oxynitride film is set to 50 nm or less, the cycle may be set to 300 cycles or less.

  The thickness of the oxynitride film obtained by the manufacturing method according to an embodiment of the present disclosure is not particularly limited because it can be controlled by increasing or decreasing the number of repetitions of the above-described cycle depending on the purpose of use. The thickness of the oxynitride film may be, for example, 550 nm or less, or 300 nm or less. However, when used as an extremely thin film, the thickness may be 200 nm or less, 150 nm or less, or 110 nm or less. It may be 100 nm or less, or 50 nm or less. Further, since the film thickness can be adjusted by the number of cycles, the lower limit is not particularly limited, but may be 0.1 nm or more or 1 nm or more depending on the purpose of use.

  The composition ratio of each element in the oxynitride film is controlled mainly by controlling the precursors (P-1) and (P-2). Specifically, the process is performed with the gas flow rate and the film formation (pulse / purge) time. An optimal composition ratio can be obtained by controlling the gas flow rate and pulse time of other elements based on the amount of the precursor having the lowest vapor pressure.

  Further, as described above, the plasma ALD can be used in the manufacturing method according to the embodiment of the present disclosure. By using plasma, the reactivity can be increased and the temperature of the system can be further lowered.

As a preferred embodiment according to the present disclosure, a manufacturing method in a case where the oxynitride film is LiPON will be described as an example. Although the order of each step is not limited, in the present disclosure, it is necessary to form at least a phosphate skeleton, and before or after the formation, a step of supplying a lithium supply source and a nitrogen supply source is performed to form a LiPON film. Becomes possible. If the phosphoric acid skeleton is not formed, lithium will diffuse into the substrate, and a film cannot be formed. Further, if the amount of lithium is too small, the film does not grow, and if the amount of lithium is too large, nitrogen is not introduced into the film. It is thought that by substituting a part of the oxygen of Li ₃ PO ₄ with nitrogen, it can be introduced into the film.

  The formation of the phosphate skeleton is performed by supplying the network former precursor (P-1) containing the phosphorus-containing compound into the reactor 2 before the oxygen supply step (d) or the nitrogen supply step (e). It is formed by performing (b) at least once. As a specific example, after the precursor (P-1) containing the phosphorus-containing compound is supplied into the reactor 2 in the order of the network forming body supply step (b) and the air supply gas supply step (f), the oxygen supply step (D) or a nitrogen supply step (e) and an air supply gas supply step (f) in this order to form a phosphate skeleton by oxidation. In this case, the supply step (c) of the lithium-based precursor (P-2) may be after the oxygen supply step (d) or the nitrogen supply step (e), and may be performed before the network forming body supply step (b). It may be. If phosphoric acid is formed, the supply step (c) of the lithium-based precursor (P-2) may be before the oxygen supply step (d) or the nitrogen supply step (e).

  Further, the composition ratio of each element is controlled mainly by controlling the precursors (P-1) and (P-2). Specifically, the process is performed with the gas flow rate and the film formation (pulse / purge) time. In the case of LiPON, an optimal composition ratio can be obtained by controlling the gas flow rate and pulse time of other elements based on the amount of the lithium-based precursor (P-2) having the lowest vapor pressure.

  When manufacturing LiPON, the temperature in the process chamber may be 400 ° C. or more and less than 480 ° C.

  In the case of producing LiPON, the vapor pressure of the phosphorus-containing compound of the network former (P-1) is high. Therefore, in the apparatus of FIG. 1, the temperature of the supply unit 3 may be 1 to 50 ° C., or 5 to 45 ° C. Degree. Further, since the vapor pressure of the lithium-based precursor (P-2) is low, the temperature of the supply unit 6 may be 100 ° C to 180 ° C. The temperature of the gas to be supplied may be 150 to 250 ° C. because it affects the temperature of the sample during film formation and causes a variation in film formation. Since the temperature of the gas serving as the oxygen supply source in the oxygen supply step (d) and the temperature of the gas serving as the nitrogen supply source in the nitrogen supply step (e) also affect the sample temperature during film formation and become a factor of film formation variation, It may be 150 to 250 ° C. The flow rate of each component, the processing time (pulse time / purge time), and the like can be appropriately selected from the above conditions.

  As the LiPON film according to the present disclosure, the entire LiPON film is 100 at. %, The phosphorus concentration is 5 to 30 at. % May be in the range of 8 to 25 at. % May be in the range of 10 to 20 at. %. Further, as the LiPON film according to the present disclosure, the entire LiPON film is 100 at. %, The nitrogen concentration is 0.2 to 15 at. % May be in the range of 0.5 to 12 at. % May be in the range of 1.0 to 10 at. %. Further, as the LiPON film according to the present disclosure, the entire LiPON film is 100 at. %, The oxygen concentration is 40 to 70 at. % May be in the range of 45 to 65 at. % May be in the range of 50 to 60 at. %. Further, as the LiPON film according to the present disclosure, the entire LiPON film is 100 at. %, The lithium concentration is 10 to 40 at. % May be in the range of 15 to 35 at. % May be in the range of 17 to 30 at. %. Further, the composition may be uniform in the depth direction. The method and conditions for the composition analysis are as described in Examples described later.

As the oxynitride film according to the present disclosure, a double bond nitrogen (-N =) (hereinafter, also referred to as Nd) having a peak intensity derived from a single bond nitrogen (hereinafter, also referred to as Nt) in X-ray photoelectron spectroscopy (XPS measurement). ) May be 50% or less, may be 40% or less, or may be 30% or less. Here, the single bond nitrogen means a nitrogen atom having only a single bond. Further, the double bond nitrogen means a nitrogen atom having a double bond. The single bond nitrogen means a structure represented by the following formula (1).

  Next, the production method according to the present disclosure and the oxynitride film obtained thereby will be described more specifically with reference to examples, but the present disclosure is not limited to these examples.

[Example 1]
A LiPON film was manufactured by the following method. As the apparatus, an apparatus having the configuration shown in FIG. 1 was used. A precursor bottle (manufactured by Japan Advanced Chemicals Ltd.) was used for the supply section in which the precursor was arranged. SUS316 was used for the process chamber, precursor bottle, and piping. The heating was performed by winding a ribbon heater around the process chamber, the precursor bottle, and the piping, and heating the ribbon heater. Each temperature described below was measured using a thermocouple, and the temperature was controlled for each part using a temperature controller. SUS316 was used for the sample holder arranged in the reactor 2. Control of each mass flow controller (MFC) and valve was performed using a sequencer MELSEC-Q (manufactured by Mitsubishi Electric Corporation) and a control program (manufactured by Nippon Spread Co., Ltd.). As the MFC, SEC-E40 (model; manufactured by Horiba Stech Co., Ltd.) was used for controlling the flow rate of argon and oxygen gas, and SEC-N112MGM (model; manufactured by Horiba Stech Co., Ltd.) was used for ammonia. As the needle valve 4, a bellows seal valve (model number: SS-4BMG, manufactured by Swagelok) was used to control the flow rate of TDMAP having a high vapor pressure. The degree of vacuum in the process chamber was measured with a Pirani gauge (TPR280 DN16 ISO-KF: manufactured by PFEIFFER VACUUM). The degree of vacuum in the process chamber during film formation was controlled to 10 ^-1 Pa to 10 ³ Pa by opening the angle valve.

  As the substrate, a glass substrate on which a 5 μm pitch comb-shaped electrode (Au) was formed was used. The electrodes were arranged in a process chamber (reactor 2). Tris (dimethylamino) phosphine (TDMAP) was used as the network former precursor (P-1), and Li (t-OBu) (lithium tert-butoxide) was used as the lithium precursor (P-2). Argon gas was used as the gas to be supplied. Oxygen gas was used as an oxygen supply source. Ammonia gas was used as a nitrogen supply source. The temperature inside the reactor 2 was set to 450 ° C. The temperature of the supply part 3 of the network former precursor (P-1) was set to 40 ° C. The temperature of the supply part 6 of the metal precursor (P-2) was set to 100 ° C. The temperature of the piping from the outlets of the supply units 3 and 6 to the inlet of the process chamber was set to 170 ° C. The temperature of the pipes other than the pipes from the auxiliary gas supply unit 10 to the supply unit 6 and the two pipes was set to 200 ° C. The flow rates of the oxygen gas, the ammonia gas, and the supply gas were set to 50 ml / min. The manual valves Mv8 and Mv9 were always opened, and the flow rate of the auxiliary gas was set to 50 ml / min. The opening of the needle valve 4 was 50%.

In the apparatus shown in FIG. 1, the valve V3 was opened and the gas was supplied for about 1800 seconds. Next, after opening the valve V7 and supplying oxygen gas for 2 seconds (step (d)), the valve V7 was closed and the air supply gas supply step (f) was performed for 8 seconds. Next, the repetition cycle shown in Table 1 was performed 7246 times by opening and closing each valve. The valve V6 was opened simultaneously with the start of step (1) in the first cycle, and the valve V6 was closed simultaneously with the end of step (8) in the 7246th cycle. That is, in all the steps except the step (e), the ammonia gas was continuously supplied. The flow rate of the supplied ammonia gas was 100 ml / min. The temperature of the ammonia gas was 200 ° C.

  When the obtained LiPON film was observed by SEM, the film thickness was 524.5 nm.

The impedance of the obtained LiPON film was measured using an impedance measuring device (trade name: Modulab, Solartron). The results are shown in FIG. The ionic conductivity was 3.2 × 10 ⁻⁷ Scm ⁻¹ . FIG. 4 shows the results of the Arrhenius plot. The activation energy calculated from FIG. 4 was Ea = 0.54 eV. From these results, it was confirmed that the obtained LiPON film had a function as a solid electrolyte.

[Example 2]
Using the process shown in FIG. 2, except that the number of repeating cycles was 250, in the same manner as in Example 1 to produce the LiPON film _{(composition: L i2.35 PO 3.58 N 0.28)} .

  When the obtained LiPON film was observed with a STEM (scanning transmission electron microscope, trade name: FB2100, Hitachi High-Technologies Corporation), the film thickness was 49 nm. The results are shown in FIG.

[Example 3]
A LiPON film was manufactured in the same manner as in Example 1 except that a lithium cobalt oxide (LiCoO ₂ ) layer was provided on the substrate, and was manufactured thereon. Further, an osmium film was formed as a protective film on the LiPON film by a sputtering method using a sputtering apparatus (HPC-1SW, Vacuum Device Co., Ltd.) for observation. Observation of the obtained LiPON film by STEM revealed that the film thickness was about 340 nm.

[Examples 4 and 5]
A LiPON film was manufactured in the same manner as in Example 1 except that the pulse time of the lithium-based precursor and the number of repetition cycles in step (c) were changed as shown in Table 2.

[Example 6]
Same as Example 1 except that the valve V6 is not opened in steps other than step (e), the pulse time of the lithium-based precursor in step (c) is 3 seconds, and the number of repetition cycles is 900. To produce a LiPON film.

[Examples 7 and 8]
A LiPON film was manufactured in the same manner as in Example 6, except that the pulse time of the lithium-based precursor and the number of repetition cycles in step (c) were changed as shown in Table 3.

<Composition analysis>
For the LiPON films obtained in Example 1 and Examples 4 to 8, composition analysis in the depth direction was performed by X-ray photoelectric spectroscopy (XPS). Specifically, using a device (trade name: PHI 5000 Versaprobe, ULVAC-PHI, Inc.), the XPS measurement and the Ar sputtering were repeated on the LiPON film, thereby measuring the change in the element concentration in the depth direction of the film.

  FIG. 6 shows the result of the composition analysis in the depth direction of the LiPON film obtained in Example 1. In the figure, the vertical axis represents the element concentration (at.%), And the horizontal axis represents the analysis depth (nm).

  As shown in FIG. 6, the composition of the LiPON film obtained by the manufacturing method according to the embodiment of the present disclosure was substantially constant in the depth direction for each of Li, P, O, and N.

  Table 4 shows the film thickness and the average nitrogen abundance ratio in the LiPON films obtained in Examples 4 to 8 obtained by composition analysis in the depth direction. The average nitrogen abundance ratio in the film was calculated by averaging the nitrogen abundance ratios at 3 to 8 points where the XPS measurement was performed. Here, the abundance ratio of nitrogen is the ratio of the elemental concentration of nitrogen (at.%) When the elemental concentration of phosphorus (at.%) Determined by XPS measurement is 1.

  From Table 4, it can be seen that the supply ratio of the nitrogen introduced into the oxynitride film can be further increased by supplying the ammonia gas in the steps other than the step (e).

[Example 9]
At the same time as the start of step (b) of the first cycle, the valve V6 was not opened, the valve V6 was kept closed, quartz glass was used for the substrate, and the number of repetition cycles was set to 999. A LiPON film was manufactured.

  FIG. 8A shows an image obtained by observing the obtained LiPON film with an SEM (scanning electron microscope, trade name: S-5500, Hitachi High-Technologies Corporation) equipped with an in-lens (In-Lens) detector. FIG. 8B is an image obtained by SEM observation of a state before film formation.

  Further, as in Example 3, an osmium film was formed as a protective film on the obtained LiPON film using an osmium coater (trade name: HPC-1SW, Vacuum Device Co., Ltd.). Next, coating with tungsten was performed to obtain a laminate. The obtained laminate was cut by a FIB (Focused Ion Beam) processing device (trade name: Focused Ion Beam Device FB-2100, Hitachi High-Technologies Corporation), and the cut surface was observed with a STEM. The observation image is shown in FIG. 9A and 9B show a BF (bright field) image, and FIGS. 9C and 9D show a DF (Dark field). 9B is an enlarged view of FIG. 9A, and FIG. 9D is an enlarged view of FIG. 9C. From FIG. 9B, the thickness of the LiPON film was 210 to 220 nm.

  FIG. 10 shows the result of XPS measurement of the LiPON film of Example 2. In FIG. 10, the dashed line represents the peak intensity derived from nitrogen having only a single bond, and the broken line represents the peak intensity derived from nitrogen having a double bond. The XPS spectrum was measured using an XPS apparatus (model number: PHI 5000 Versaprobe, ULVAC-PHI, Inc.). For the XPS spectrum fitting (Gaussian fitting), peak analysis software (trade name: Multipack, ULVAC-PHI, Inc.) was used. Waveform separation and baseline setting were performed using the “Fit” menu of the peak analysis software, and each was quantified from the area ratio of the peak indicating single-bonded nitrogen to the peak indicating double-bonded nitrogen. The background of the XPS spectrum represented by "BG" in FIG. 10 was determined by the shirlry method.

[Comparative Example 1]
The LiPON film was manufactured not by the ALD method but by the sputtering method. Specifically, it was manufactured by a planar magnetron sputtering apparatus.

  The cross sections of the laminates obtained in Example 3 and Comparative Example 1 were observed by SEM. FIG. 7 shows the results. 7A is an observation image of Example 3, and FIG. 7B is an observation image of Comparative Example 1. From FIG. 7A, it was confirmed that the LiPON could be formed not only along the interface of lithium cobalt oxide but also on the boundary between the crystals. This indicates that the oxynitride film obtained by the manufacturing method according to the present disclosure has high shape adaptability. On the other hand, in FIG. 7B, voids were confirmed in many places, and it is clear that shape adaptability was poor. FIG. 11 shows a measurement result of an XPS spectrum of the LiPON film manufactured by the sputtering method as a reference diagram. In each case, the ratio of the peak intensity derived from single bond nitrogen to the peak intensity derived from double bond nitrogen was 50% or more.

  INDUSTRIAL APPLICABILITY The present disclosure is useful for manufacturing a quaternary oxynitride film having excellent shape adaptability (conformal property). The oxynitride film obtained according to the present disclosure is useful as a solid electrolyte, and is useful for manufacturing an all-solid lithium battery and a post-lithium ion secondary battery. Further, the oxynitride film obtained according to the present disclosure can also be used as a protective film for protecting the active material surface of a non-aqueous lithium ion secondary battery. It can also be used as a gate insulating film of an electric double layer transistor. Furthermore, according to the present disclosure, it is possible to perform stable nitriding without being affected by variations in the temperature inside the reactor (sample substrate temperature) or the degree of vacuum. In particular, it becomes possible to stabilize the composition ratio of nitrogen in the film when the film is formed over a long time.

1 reactor with reactor 2 reactor (process chamber)
Reference Signs List 3 Supply unit for mesh forming body precursor 4 Needle valve for controlling flow rate of network forming body precursor 5 Mass flow controller 6 Supply unit for metal precursor 7, 8, 9, 10 Auxiliary gas supply unit 11 Exhaust manual valve 12 Oxygen supply unit 13 Nitrogen supply unit 14 Gas supply section

Claims (9)

A method for producing an oxynitride film containing a metal element and an element constituting a network former,
The metal element is an alkali metal element or an alkaline earth metal element,
Arranging a substrate in a reactor of an apparatus having a reactor (a),
Supplying a network former precursor (P-1) containing an element constituting the network former into the reactor, (b)
A metal supply step (c) of supplying a metal precursor (P-2) containing the metal element into the reactor;
An oxygen supply step (d) for supplying oxygen gas and / or ozone gas into the reactor;
Ammonia gas ammonia supply step of supplying into the reactor (e), and insufflation gas supply step of supplying insufflation gas into the reactor (f), only contains,
While repeating the cycle including the network forming body supply step (b), the metal supply step (c), the oxygen supply step (d), and the air supply gas supply step (f), the ammonia gas Continue to supply,
A method for producing an oxynitride film containing a metal element and an element constituting a network former. In at least one step selected from the group consisting of the mesh forming body supply step (b), the metal supply step (c), the oxygen supply step (d), and the air supply gas supply step (f), ammonia gas is supplied. Supply at the same time,
A method for manufacturing an oxynitride film according to claim 1.   3. The method for producing an oxynitride film according to claim 1, wherein the network forming step (b) and the metal supplying step (c) are performed separately. 4.   The method for producing an oxynitride film according to any one of claims 1 to 3, wherein the metal element includes at least one selected from the group consisting of Li, Na, Mg, and Ca.   The method for producing an oxynitride film according to any one of claims 1 to 4, wherein the elements constituting the network former include at least one selected from the group consisting of P, B, Si, and V. The metal element includes Li,
Elements constituting the network forming body include P;
The oxynitride film contains Li, P, O, and N;
A method for manufacturing an oxynitride film according to claim 1.   The method for producing an oxynitride film according to any one of claims 1 to 6, wherein the film thickness is 200 nm or less.   The temperature of the pipe connected to the supply part of the network former precursor (P-1) and the reactor, and the supply part of the metal precursor (P-2) and the pipe connected to the reactor depends on the supply of the precursor of the network former (P-1). The method for producing an oxynitride film according to claim 1, wherein the temperature is higher by 55 ° C. or more than the higher one of the temperature of the part and the temperature of the supply part of the metal precursor (P-2). Reactor, control unit,
A network former precursor (P-1) supply unit for supplying a network former precursor (P-1) containing an element constituting the network former into the reactor;
A metal supply unit for supplying a metal precursor (P-2) containing a metal element into the reactor;
An oxygen supply unit for supplying oxygen gas and / or ozone gas into the reactor,
Ammonia supply unit for supplying the ammonia gas in the reactor, and the insufflation gas supply unit for supplying the insufflation gas into the reactor, Bei give a,
A network forming body supplying step (b) in which the control unit supplies a network forming body precursor (P-1) containing an element constituting the network forming body into the reactor; a metal precursor (P-2) containing a metal element; Supplying metal into the reactor (c), supplying oxygen gas and / or ozone gas into the reactor (d), supplying ammonia gas into the reactor (e), And an air supply gas supply step (f) of supplying an air supply gas into the reactor.
While repeating the cycle including the network forming body supply step (b), the metal supply step (c), the oxygen supply step (d), and the air supply gas supply step (f), the ammonia gas Continue to supply,
Equipment for manufacturing oxynitride films.