JP2012188735A - Silicon nitride film deposition method, manufacturing method of organic electronic device, and silicon nitride film deposition apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To appropriately deposit a silicon nitride film on a substrate in low-temperature environment in which the temperature of the substrate is 100°C or lower to improve film characteristic of the silicon nitride film.SOLUTION: An anode layer 20, a light emitting layer 21, a cathode layer 22 and a silicon nitride film 23 are deposited in sequence on a glass substrate G, to manufacture an organic EL device A. The silicon nitride film 23 is deposited by supplying a processing gas containing a silane gas, a nitrogen gas and a hydrogen gas to a processing vessel of a plasma deposition apparatus, exciting the processing gas to generate plasma while maintaining the temperature of the substrate inside the processing vessel at 100°C or lower and the pressure inside the processing vessel at 20-60 Pa, and applying plasma processing using the plasma.

Description

  The present invention relates to a silicon nitride film forming method, an organic electronic device manufacturing method, and a silicon nitride film forming apparatus.

  In recent years, an organic EL element using organic electroluminescence (EL), which is a light-emitting device including an organic layer, has been developed. Since organic EL elements emit light by themselves, they have advantages such as low power consumption and superior viewing angle as compared with liquid crystal displays (LCDs).

  The most basic structure of the organic EL element is a sandwich structure in which an anode (anode) layer, a light emitting layer, and a cathode (cathode) layer are formed on a glass substrate. Among these, the light emitting layer is weak to moisture and oxygen, and when moisture and oxygen are mixed, the characteristics change and non-light emitting points (dark spots) are generated, which contributes to shortening the lifetime of the organic EL element. For this reason, in the manufacture of an organic electronic device, an organic element is sealed so that external moisture and oxygen are not transmitted into the device. That is, in the manufacture of an organic electronic device, an anode layer, a light emitting layer, and a cathode layer are sequentially formed on a glass substrate, and a sealing film layer is further formed.

For example, a silicon nitride film (SiN film) is used as the sealing film described above. The silicon nitride film is formed by, for example, plasma CVD (Chemical Vapor Deposition). Specifically, for example, a source gas containing silane (SiH ₄ ) gas or nitrogen (N ₂ ) gas is excited by microwave power to generate plasma, and a silicon nitride film is formed using the generated plasma. . Further, since the organic EL element may be damaged when the temperature of the glass substrate reaches a high temperature of 100 ° C. or higher, the silicon nitride film is formed in a low temperature environment of 100 ° C. or lower (Patent Document 1).

JP 2010-219112 A

  However, when the method described in Patent Document 1 is used, since the silicon nitride film is formed in a low temperature environment, the film characteristics of the silicon nitride film may be deteriorated. Specifically, for example, the step coverage (step coverage) and film quality (eg, the density related to the wet etching rate for hydrofluoric acid) of the silicon nitride film may be low, and the film stress (film stress) of the silicon nitride film May not be appropriate.

  In the above description, a silicon nitride film is formed on a glass substrate as a sealing film for an organic electronic device. However, such a problem occurs when a silicon nitride film is formed for uses other than the sealing film for an organic electronic device. May also occur. That is, when the silicon nitride film is formed on the substrate in a low temperature environment where the temperature of the substrate is 100 ° C. or lower, for example, the film quality of the silicon nitride film may be deteriorated as described above.

  The present invention has been made in view of such points, and in a low temperature environment where the temperature of the substrate is 100 ° C. or lower, a silicon nitride film is appropriately formed on the substrate, and the film characteristics of the silicon nitride film are improved. The purpose is to let you.

In order to achieve the above object, according to one aspect of the present invention, there is provided a film forming method for forming a silicon nitride film on a substrate accommodated in a processing container, wherein an organic silane gas is contained in the processing container, A processing gas containing nitrogen (N ₂ ) gas and hydrogen (H ₂ ) gas is supplied, the processing gas is excited to generate plasma, and plasma processing using the plasma is performed to form a silicon nitride film on the substrate. It is characterized by doing.

  As a result of intensive studies by the inventors, when a silicon nitride film is formed on a substrate by a plasma film forming method, if a processing gas containing organosilane gas, nitrogen gas, and hydrogen gas is used, the wet etching rate of the silicon nitride film It was found that the etching characteristics of the were improved. Specifically, it has been found that by adding hydrogen gas to the processing gas, the wet etching rate is reduced and the step coverage of the silicon nitride film is improved. Further, when the amount of hydrogen gas added to the processing gas is increased, the film stress of the silicon nitride film becomes negative. That is, it was found that the film stress of the silicon nitride film can be appropriately controlled. Therefore, according to the present invention, the controllability of the formation of the silicon nitride film formed on the substrate can be improved even in a low temperature environment where the temperature of the substrate in the processing container is 100 ° C. or less, for example. it can. The fact that the controllability of the film characteristics is improved by adding hydrogen gas to the processing gas will be described in detail later.

  The silicon nitride film may be used as a sealing film for organic electronic devices.

  During the plasma processing using the plasma, the pressure in the processing container may be maintained at 20 Pa to 60 Pa.

  In controlling the film stress (film stress) of the silicon nitride film, it is preferable to control the supply flow rate of the hydrogen gas.

  The plasma may be generated by exciting the processing gas with microwaves.

  The film power of the silicon nitride film may be controlled by controlling the power of the microwave.

  The processing gas includes a source gas for forming the silicon nitride film and a plasma excitation gas for generating the plasma, and the supply of the source gas is performed by the plasma excitation gas. It may be performed simultaneously with the generation or before the generation of the plasma. For example, organic silane gas, nitrogen gas, hydrogen gas, or the like is used as the source gas, and argon gas, nitrogen gas, hydrogen gas, or the like is used as the plasma excitation gas.

  In the processing gas supplied into the processing container, the ratio of the supply flow rate of the nitrogen gas to the supply flow rate of the organosilane gas is preferably 1 to 1.5.

  According to another aspect of the present invention, there is provided a method for manufacturing an organic electronic device, in which an organic element is formed on a substrate, and thereafter, an organic silane gas, a nitrogen gas, and a hydrogen gas are contained in a processing container containing the substrate. A process gas is supplied, plasma is generated by exciting the process gas, a plasma process using the plasma is performed, and a silicon nitride film is formed as a sealing film so as to cover the organic element .

  During the plasma processing using the plasma, the pressure in the processing container may be maintained at 20 Pa to 60 Pa.

  In controlling the film stress of the silicon nitride film, it is preferable to control the supply flow rate of the hydrogen gas.

  The plasma may be generated by exciting the processing gas with microwaves.

  The film power of the silicon nitride film may be controlled by controlling the power of the microwave.

  The processing gas includes a source gas for forming the silicon nitride film and a plasma excitation gas for generating the plasma, and the supply of the source gas is performed by the plasma excitation gas. It may be performed simultaneously with the generation or before the generation of the plasma.

  In the processing gas supplied into the processing container, the ratio of the supply flow rate of the nitrogen gas to the supply flow rate of the organosilane gas is preferably 1 to 1.5.

  According to another aspect of the present invention, there is provided a film forming apparatus for forming a silicon nitride film on a substrate, a processing container for storing and processing the substrate, and an organic silane gas, nitrogen gas, and A process gas supply unit that supplies a process gas containing hydrogen gas, a plasma excitation unit that generates plasma by exciting the process gas, and a plasma process using the plasma to form a silicon nitride film on the substrate And a control unit that controls the processing gas supply unit and the plasma excitation unit.

  The silicon nitride film may be used as a sealing film for organic electronic devices.

  The control unit may control the processing gas supply unit so that the pressure in the processing container is maintained at 20 Pa to 60 Pa during plasma processing using the plasma.

  The control unit may control a film stress of the silicon nitride film by controlling a supply flow rate of the hydrogen gas.

  The plasma excitation unit may excite the processing gas by supplying a microwave.

  The control unit may control the film stress of the silicon nitride film by controlling the power of the microwave.

  The processing gas includes a source gas for forming the silicon nitride film and a plasma excitation gas for generating the plasma, and the control unit supplies the source gas for the plasma excitation. You may control the said process gas supply part and the said plasma excitation part so that it may be performed simultaneously with the production | generation of the said plasma by gas, or before the production | generation of the said plasma.

  The control unit may control the processing gas supply unit so that a ratio of a supply flow rate of the nitrogen gas to a supply flow rate of the organosilane gas becomes 1 to 1.5.

  The processing gas includes a source gas for forming the silicon nitride film and a plasma excitation gas for generating the plasma, and the plasma excitation unit is provided on an upper portion of the processing container. A placement part for placing a substrate is provided at a lower part of the processing container, and the processing gas supply part is configured by dividing the inside of the processing container between the plasma excitation part and the placement part. A plasma excitation gas supply structure and a source gas supply structure are provided, and the plasma excitation gas supply structure supplies the plasma excitation gas to the region on the plasma excitation section side. An opening and an opening through which the plasma generated in the region on the plasma excitation unit side passes through the region on the placement unit side are formed, and the source gas supply structure includes a region on the placement unit side To the original And the raw material gas supply port for supplying gas, an opening for passing the plasma generated in the region of the plasma excitation portion in the region of the mounting section side may be formed.

  The gas supply structure for plasma excitation may be arranged at a position within 30 mm from the plasma excitation part.

  The source gas supply port may be formed in the horizontal direction.

  The source gas supply port may be formed such that its inner diameter expands in a tapered shape from the inside toward the outside.

  According to the present invention, it is possible to appropriately form a silicon nitride film on a substrate in a low temperature environment where the temperature of the substrate is 100 ° C. or lower, and to improve the controllability of the film characteristics of the silicon nitride film.

It is explanatory drawing which shows the outline of a structure of the substrate processing system for enforcing the manufacturing method of the organic EL device concerning this Embodiment. It is explanatory drawing which shows the manufacturing process of the organic EL device concerning this Embodiment. It is a longitudinal cross-sectional view which shows the outline of a structure of a plasma film-forming apparatus. It is a top view of a source gas supply structure. It is a top view of the gas supply structure for plasma excitation. 6 is a graph showing a relationship between a supply flow rate of hydrogen gas and a wet etching rate of a silicon nitride film when the plasma film forming method according to the present embodiment is used. 6 is a graph showing the relationship between the supply flow rate of hydrogen gas and the film stress of a silicon nitride film when the plasma film forming method according to the present embodiment is used. 6 is a graph showing the relationship between the microwave power and the film stress of the silicon nitride film when the plasma film forming method according to the present embodiment is used. A silicon nitride film is formed using a processing gas containing silane gas, nitrogen gas and hydrogen gas as in the present embodiment, and a silicon nitride film is formed using a processing gas containing silane gas and ammonia gas as in the prior art. It is explanatory drawing compared with the case where it forms into a film. It is a top view of the source gas supply structure concerning other embodiments. It is sectional drawing of the source gas supply pipe | tube concerning other embodiment. It is sectional drawing of the source gas supply pipe | tube concerning other embodiment.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. In addition, in this specification and drawing, about the component which has the substantially same function structure, duplication description is abbreviate | omitted by attaching | subjecting the same code | symbol.

  First, the manufacturing method of the organic electronic device concerning embodiment of this invention is demonstrated with the substrate processing system for implementing the said manufacturing method. FIG. 1 is an explanatory diagram showing an outline of the configuration of the substrate processing system 1. FIG. 2 is an explanatory view showing a manufacturing process of the organic EL device. In the present embodiment, a case where an organic EL device is manufactured as an organic electronic device will be described.

  As shown in FIG. 1, the cluster type substrate processing system 1 has a transfer chamber 10. The transfer chamber 10 has, for example, a substantially polygonal shape (in the illustrated example, a hexagonal shape) in plan view, and is configured to be able to seal the inside. Around the transfer chamber 10, a load lock chamber 11, a cleaning device 12, a vapor deposition device 13, a sputtering device 14, an etching device 15, and a plasma film forming device 16 are arranged in this order in the clockwise direction in plan view. Has been.

  An articulated transfer arm 17 that can bend and stretch and turn is provided inside the transfer chamber 10. A glass substrate as a substrate is transferred to the load lock chamber 11 and the processing apparatuses 12 to 16 by the transfer arm 17.

  The load lock chamber 11 is a vacuum transfer chamber in which a glass substrate transferred from the atmospheric system is held in a predetermined reduced pressure state in order to transfer the glass substrate to the transfer chamber 10 in a reduced pressure state.

  The configuration of the plasma film forming apparatus 16 will be described in detail later. Moreover, about the washing | cleaning apparatus 12, the vapor deposition apparatus 13, the sputtering apparatus 14, and the etching apparatus 15 which are other processing apparatuses, a common apparatus may be used and description of the structure is abbreviate | omitted.

  Next, a method for manufacturing an organic EL device performed in the substrate processing system 1 configured as described above will be described.

  As shown in FIG. 2A, an anode (anode) layer 20 is formed on the upper surface of the glass substrate G in advance. The anode layer 20 is made of a transparent conductive material such as indium tin oxide (ITO). The anode layer 20 is formed on the upper surface of the glass substrate G, for example, by sputtering.

  Then, after cleaning the surface of the anode layer 20 on the glass substrate G in the cleaning device 12, the light emitting layer (organic layer) 21 is formed on the anode layer 20 in the vapor deposition device 13 as shown in FIG. The film is formed by vapor deposition. The light emitting layer 21 has, for example, a multilayer structure in which a hole transport layer, a non-light emitting layer (electron block layer), a blue light emitting layer, a red light emitting layer, a green light emitting layer, and an electron transport layer are stacked.

  Next, as shown in FIG. 2B, in the sputtering apparatus 14, a cathode (cathode) layer 22 made of, for example, Ag or Al is formed on the light emitting layer 21. The cathode layer 22 is formed by depositing target atoms on the light emitting layer 21 through a pattern mask by sputtering, for example. The anode layer 20, the light emitting layer 21, and the cathode layer 22 constitute the organic EL element of the present invention, and may be simply referred to as “organic EL element” below.

  Next, as shown in FIG. 2C, in the etching apparatus 15, the light emitting layer 21 is dry etched using the cathode layer 22 as a mask. Thus, the light emitting layer 21 is patterned into a predetermined pattern.

  In addition, after the light emitting layer 21 is etched, the exposed portion of the organic EL element and the glass substrate G (anode layer 20) is cleaned to remove a substance adsorbed on the organic EL element, such as an organic substance, so-called precleaning. Also good. Further, after pre-cleaning, for example, a silylation treatment using a coupling agent may be performed to form an extremely thin adhesion layer (not shown) on the cathode layer 22. The adhesion layer and the organic EL element are firmly adhered, and the adhesion layer and a silicon nitride film 23 described later are firmly adhered.

  Next, as shown in FIG. 2D, in the plasma film forming apparatus 16, for example, silicon nitride which is a sealing film so as to cover the periphery of the light emitting layer 21 and the cathode layer 22 and the exposed portion of the anode layer 20. A film (SiN film) 23 is formed. The silicon nitride film 23 is formed by, for example, a microwave plasma CVD method as will be described later.

  Thus, the manufactured organic EL device A can make the light emitting layer 21 emit light by applying a voltage between the anode layer 20 and the cathode layer 22. Such an organic EL device A can be applied to a display device and a surface light emitting element (illumination, light source, etc.), and can be used for various other electronic devices.

  Next, a film forming method for forming the silicon nitride film 23 will be described together with the plasma film forming apparatus 16 for forming the silicon nitride film 23. FIG. 3 is a longitudinal sectional view showing an outline of the configuration of the plasma film forming apparatus 16. The plasma film forming apparatus 16 of the present embodiment is a CVD apparatus that generates plasma using a radial line slot antenna.

  The plasma film forming apparatus 16 includes, for example, a bottomed cylindrical processing container 30 having an upper surface opened. The processing container 30 is made of, for example, an aluminum alloy. The processing container 30 is grounded. A mounting table 31 as a mounting unit for mounting a glass substrate G, for example, is provided at a substantially central portion of the bottom of the processing container 30.

  For example, an electrode plate 32 is built in the mounting table 31, and the electrode plate 32 is connected to a DC power source 33 provided outside the processing container 30. The DC power source 33 can generate electrostatic force on the surface of the mounting table 31 so that the glass substrate G can be electrostatically adsorbed onto the mounting table 31. The electrode plate 32 may be connected to, for example, a bias high-frequency power source (not shown).

A dielectric window 41 is provided in the upper opening of the processing container 30 via a sealing material 40 such as an O-ring for ensuring airtightness, for example. The inside of the processing container 30 is closed by the dielectric window 41. On the top of the dielectric window 41, a radial line slot antenna 42 is provided as a plasma excitation unit for supplying microwaves for plasma generation. For example, alumina (Al ₂ O ₃ ) is used for the dielectric window 41. In such a case, the dielectric window 41 is resistant to nitrogen trifluoride (NF ₃ ) gas used in dry cleaning. Further, in order to further improve the resistance to nitrogen trifluoride gas, the surface of the alumina of the dielectric window 41 is coated with yttria (Y ₂ O ₃ ), spinel (MgAl ₂ O ₄ ), or aluminum nitride (AlN). Also good.

  The radial line slot antenna 42 includes a substantially cylindrical antenna body 50 having an open bottom surface. A disc-shaped slot plate 51 in which a large number of slots are formed is provided in the opening on the lower surface of the antenna body 50. A dielectric plate 52 made of a low-loss dielectric material is provided on the upper portion of the slot plate 51 in the antenna body 50. A coaxial waveguide 54 communicating with the microwave oscillating device 53 is connected to the upper surface of the antenna body 50. The microwave oscillating device 53 is installed outside the processing container 30 and can oscillate a microwave having a predetermined frequency, for example, 2.45 GHz, with respect to the radial line slot antenna 42. With this configuration, the microwave oscillated from the microwave oscillating device 53 is propagated in the radial line slot antenna 42, compressed by the dielectric plate 52 and shortened in wavelength, and then circularly polarized in the slot plate 51. And radiated from the dielectric window 41 into the processing container 30.

  Between the mounting table 31 in the processing container 30 and the radial line slot antenna 42, for example, a substantially flat source gas supply structure 60 is provided. The source gas supply structure 60 is formed in a circular shape whose outer shape is at least larger than the diameter of the glass substrate G when viewed from the plane. By this source gas supply structure 60, the inside of the processing vessel 30 is partitioned into a plasma generation region R1 on the radial line slot antenna 42 side and a source gas dissociation region R2 on the mounting table 31 side. For example, alumina may be used for the source gas supply structure 60. In such a case, since alumina is a ceramic, it has higher heat resistance and higher strength than a metal material such as aluminum. Moreover, since the plasma produced | generated in plasma production area | region R1 is not trapped, sufficient ion irradiation can be obtained with respect to a glass substrate. A dense film can be generated by sufficient ion irradiation to the film on the glass substrate. The source gas supply structure 60 has resistance to nitrogen trifluoride gas used in dry cleaning. Furthermore, in order to improve the resistance to nitrogen trifluoride gas, the alumina surface of the raw material gas supply structure 60 may be coated with yttria, spinel or aluminum nitride.

  As shown in FIG. 4, the source gas supply structure 60 includes a series of source gas supply pipes 61 arranged in a substantially lattice pattern on the same plane. The raw material gas supply pipe 61 has a rectangular longitudinal section when viewed from the axial direction. A large number of openings 62 are formed in the gaps between the source gas supply pipes 61. The plasma and radicals generated in the plasma generation region R1 on the upper side of the source gas supply structure 60 can enter the source gas dissociation region R2 on the mounting table 31 side through the opening 62.

A large number of source gas supply ports 63 are formed on the lower surface of the source gas supply pipe 61 of the source gas supply structure 60 as shown in FIG. These source gas supply ports 63 are evenly arranged in the surface of the source gas supply structure 60. A gas pipe 65 that communicates with a source gas supply source 64 installed outside the processing container 30 is connected to the source gas supply pipe 61. In the source gas supply source 64, for example, silane (SiH ₄ ) gas and hydrogen (H ₂ ) gas, which are organic silane gases, are individually sealed as source gases. The gas pipe 65 is provided with a valve 66 and a mass flow controller 67. With this configuration, a predetermined flow rate of silane gas and hydrogen gas are respectively introduced from the source gas supply source 64 into the source gas supply pipe 61 through the gas pipe 65. And these silane gas and hydrogen gas are supplied toward each lower raw material gas dissociation area | region R2 from each raw material gas supply port 63. FIG.

  A first plasma excitation gas supply port 70 is formed on the inner peripheral surface of the processing container 30 covering the outer peripheral surface of the plasma generation region R1 to supply a plasma excitation gas serving as a plasma raw material. For example, the first plasma excitation gas supply ports 70 are formed at a plurality of locations along the inner peripheral surface of the processing container 30. The first plasma excitation gas supply port 70 penetrates, for example, a side wall portion of the processing container 30 and communicates with a first plasma excitation gas supply source 71 installed outside the processing container 30. A working gas supply pipe 72 is connected. The first plasma excitation gas supply pipe 72 is provided with a valve 73 and a mass flow controller 74. With this configuration, a plasma excitation gas having a predetermined flow rate can be supplied from the side into the plasma generation region R1 in the processing container 30. In the present embodiment, argon (Ar) gas, for example, is sealed in the first plasma excitation gas supply source 71 as the plasma excitation gas.

  On the upper surface of the source gas supply structure 60, for example, a substantially flat plate-shaped plasma excitation gas supply structure 80 having the same configuration as the source gas supply structure 60 is laminated and disposed. As shown in FIG. 5, the plasma excitation gas supply structure 80 includes second plasma excitation gas supply tubes 81 arranged in a lattice pattern. For example, alumina may be used for the plasma excitation gas supply structure 80. Even in such a case, since alumina is a ceramic as described above, it has higher heat resistance and higher strength than a metal material such as aluminum. Moreover, since the plasma produced | generated in plasma production area | region R1 is not trapped, sufficient ion irradiation can be obtained with respect to a glass substrate. A dense film can be generated by sufficient ion irradiation to the film on the glass substrate. The plasma excitation gas supply structure 80 is resistant to nitrogen trifluoride gas used in dry cleaning. Furthermore, in order to improve resistance to nitrogen trifluoride gas, the surface of the alumina of the plasma excitation gas supply structure 80 may be coated with yttria or spinel.

A plurality of second plasma excitation gas supply ports 82 are formed on the upper surface of the second plasma excitation gas supply pipe 81 as shown in FIG. The plurality of second plasma excitation gas supply ports 82 are evenly arranged in the surface of the plasma excitation gas supply structure 80. Thereby, the plasma excitation gas can be supplied from the lower side to the upper side with respect to the plasma generation region R1. In the present embodiment, this plasma excitation gas is, for example, argon gas. In addition to the argon gas, nitrogen (N ₂ ) gas that is a source gas is also supplied from the plasma excitation gas supply structure 80 to the plasma generation region R1.

  An opening 83 is formed in the gap between the lattice-shaped second plasma excitation gas supply pipes 81, and the plasma and radicals generated in the plasma generation region R <b> 1 are exchanged with the plasma excitation gas supply structure 80. It can enter the lower source gas dissociation region R2 through the source gas supply structure 60.

  A gas pipe 85 communicating with a second plasma excitation gas supply source 84 installed outside the processing container 30 is connected to the second plasma excitation gas supply pipe 81. In the second plasma excitation gas supply source 84, for example, argon gas, which is a plasma excitation gas, and nitrogen gas, which is a source gas, are individually sealed. The gas pipe 85 is provided with a valve 86 and a mass flow controller 87. With this configuration, it is possible to supply a predetermined flow rate of nitrogen gas and argon gas from the second plasma excitation gas supply port 82 to the plasma generation region R1.

  The source gas and the plasma excitation gas described above constitute the processing gas of the present invention. The source gas supply structure 60 and the plasma excitation gas supply structure 80 constitute a processing gas supply unit of the present invention.

  Exhaust ports 90 for exhausting the atmosphere in the processing container 30 are provided on both sides of the mounting table 31 at the bottom of the processing container 30. An exhaust pipe 92 communicating with an exhaust device 91 such as a turbo molecular pump is connected to the exhaust port 90. By exhausting from the exhaust port 90, the inside of the processing container 30 can be maintained at a predetermined pressure, for example, 20 Pa to 60 Pa as described later.

  The plasma film forming apparatus 16 is provided with a control unit 100. The control unit 100 is, for example, a computer and has a program storage unit (not shown). The program storage unit stores a program for controlling the film forming process of the silicon nitride film 23 on the glass substrate G in the plasma film forming apparatus 16. The program storage unit controls the supply of the above-described source gas, the supply of plasma excitation gas, the emission of microwaves, the operation of the drive system, and the like, thereby realizing the film forming process in the plasma film forming apparatus 16. A program is also stored. The program is recorded on a computer-readable storage medium such as a computer-readable hard disk (HD), flexible disk (FD), compact disk (CD), magnetic optical desk (MO), or memory card. Or installed in the control unit 100 from the storage medium.

  Next, a method for forming the silicon nitride film 23 performed in the plasma film forming apparatus 16 configured as described above will be described.

  First, for example, when the plasma film forming apparatus 16 is started up, the supply flow rate of the argon gas supplied from the first plasma excitation gas supply port 70 and the argon gas supplied from the second plasma excitation gas supply port 82 are changed. The supply flow rate is adjusted so that the concentration of the argon gas supplied into the plasma generation region R1 is uniform. In this supply flow rate adjustment, for example, the exhaust device 91 is operated, and an appropriate air supply is supplied from each of the plasma excitation gas supply ports 70 and 82 in a state where an air flow similar to that in the actual film formation process is formed in the processing container 30. Argon gas set at a flow rate is supplied. Then, with the supply flow rate setting, a film is actually formed on the test substrate, and it is inspected whether or not the film is uniformly formed on the substrate surface. When the argon gas concentration in the plasma generation region R1 is uniform, film formation in the substrate surface is performed uniformly. As a result of the inspection, when film formation is not performed uniformly in the substrate surface, The setting of the supply flow rate of each argon gas is changed, and film formation is performed again on the test substrate. By repeating this, the supply flow rate from each of the plasma excitation gas supply ports 70 and 82 is set so that film formation is performed uniformly on the substrate surface and the concentration of argon gas in the plasma generation region R1 becomes uniform. The

  After the supply flow rates of the plasma excitation gas supply ports 70 and 82 are set as described above, the film forming process of the glass substrate G in the plasma film forming apparatus 16 is started. First, the glass substrate G is carried into the processing container 30 and sucked and held on the mounting table 31. At this time, the temperature of the glass substrate G is maintained at 100 ° C. or lower, for example, 50 ° C. to 100 ° C. Subsequently, exhaust in the processing container 30 is started by the exhaust device 91, the pressure in the processing container 30 is reduced to a predetermined pressure, for example, 20 Pa to 60 Pa, and the state is maintained. Note that the temperature of the glass substrate G is not limited to 100 ° C. or lower, and may be any temperature as long as the organic EL device A is not damaged, and is determined by the material of the organic EL device A and the like.

  Here, as a result of intensive studies by the inventors, it has been found that if the pressure in the processing container 30 is lower than 20 Pa, the silicon nitride film 23 may not be appropriately formed on the glass substrate G. Moreover, when the pressure in the processing container 30 exceeded 60 Pa, it turned out that the reaction between the gas molecules in a gaseous phase increases, and there exists a possibility that a particle | grain may generate | occur | produce. For this reason, the pressure in the processing container 30 was maintained at 20 Pa to 60 Pa as described above.

  When the inside of the processing container 30 is depressurized, argon gas is supplied from the lateral first plasma excitation gas supply port 70 into the plasma generation region R1, and a lower second plasma excitation gas supply port is provided. Nitrogen gas and argon gas are supplied from 82. At this time, the concentration of argon gas in the plasma generation region R1 is uniformly maintained in the plasma generation region R1. Nitrogen gas is supplied at a flow rate of 21 sccm, for example. From the radial line slot antenna 42, for example, a microwave with a power of 2.5 kW to 3.0 kW is radiated at a frequency of 2.45 GHz toward the plasma generation region R1 directly below. By this microwave radiation, the argon gas is turned into plasma in the plasma generation region R1, and the nitrogen gas is radicalized (or ionized). At this time, the microwave traveling downward is absorbed by the generated plasma. As a result, high-density plasma is generated in the plasma generation region R1.

  The plasma and radicals generated in the plasma generation region R1 pass through the plasma excitation gas supply structure 80 and the source gas supply structure 60 and enter the lower source gas dissociation region R2. Silane gas and hydrogen gas are supplied from the source gas supply ports 63 of the source gas supply structure 60 to the source gas dissociation region R2. At this time, the silane gas is supplied at a flow rate of 18 sccm, for example, and the hydrogen gas is supplied at a flow rate of 64 sccm, for example. The supply flow rate of this hydrogen gas is set according to the film characteristics of the silicon nitride film 23 as will be described later. Silane gas and hydrogen gas are dissociated by plasma entering from above. Then, the silicon nitride film 23 is deposited on the glass substrate G by these radicals and radicals of nitrogen gas supplied from the plasma generation region R1.

  Thereafter, when the silicon nitride film 23 is formed and the silicon nitride film 23 having a predetermined thickness is formed on the glass substrate G, the emission of microwaves and the supply of the processing gas are stopped. Thereafter, the glass substrate G is unloaded from the processing container 30 and a series of plasma film forming processes is completed.

  Here, as a result of intensive studies by the inventors, when the silicon nitride film 23 is formed on the glass substrate G by the plasma film forming process described above, if a processing gas containing silane gas, nitrogen gas, and hydrogen gas is used, silicon It has been found that the controllability of the film characteristics of the nitride film 23 is improved.

  FIG. 6 shows how the wet etching rate of the silicon nitride film 23 with respect to hydrofluoric acid changes when the supply flow rate of hydrogen gas in the processing gas is changed using the plasma film forming method of the above embodiment. ing. At this time, the supply flow rate of silane gas was 18 sccm, and the supply flow rate of nitrogen gas was 21 sccm. Moreover, the temperature of the glass substrate G was 100 degreeC during the plasma film-forming process.

  Referring to FIG. 6, it was found that the wet etching rate of the silicon nitride film 23 is reduced by further adding hydrogen gas to the processing gas containing silane gas and nitrogen gas. Accordingly, the density of the silicon nitride film 23 is improved by the hydrogen gas in the processing gas, and the film quality (chemical resistance and density) of the silicon nitride film 23 is improved. Also, the step coverage of the silicon nitride film 23 is improved. Further, it has been found that the refractive index of the silicon nitride film 23 is improved to, for example, 2.0 ± 0.1. Therefore, by controlling the supply flow rate of hydrogen gas, the wet etching rate of the silicon nitride film 23 can be controlled, and the film characteristics of the silicon nitride film 23 can be controlled.

  FIG. 7 shows how the film stress of the silicon nitride film 23 changes when the supply flow rate of the hydrogen gas in the processing gas is changed using the plasma film forming method of the above embodiment. At this time, the supply flow rate of silane gas was 18 sccm, and the supply flow rate of nitrogen gas was 21 sccm. Moreover, the temperature of the glass substrate G was 100 degreeC during the plasma film-forming process.

  Referring to FIG. 7, it was found that the film stress of the silicon nitride film 23 is changed to the negative side (compression side) by further adding hydrogen gas to the processing gas containing silane gas and nitrogen gas. Therefore, the film stress of the silicon nitride film 23 can be controlled by controlling the supply flow rate of the hydrogen gas.

  As described above, according to the present embodiment, the film characteristics of the silicon nitride film 23 can be changed by changing the flow rate of the hydrogen gas in the processing gas. Therefore, since the silicon nitride film 23 can be appropriately formed as a sealing film in the organic EL device A, the organic EL device A can be appropriately manufactured. When used as a sealing film, the absolute value of the magnitude of stress in the sealing film is preferably small.

  In the plasma film forming method of the present embodiment, plasma is generated using microwaves radiated from the radial line slot antenna 42. Here, as a result of intensive studies by the inventors, when the processing gas contains silane gas, nitrogen gas, and hydrogen gas, for example, as shown in FIG. 8, the power of the microwave and the film stress of the silicon nitride film 23 are approximately proportional. I found out that there was a relationship. Therefore, according to the present embodiment, the film stress of the silicon nitride film 23 can also be controlled by controlling the microwave power. By optimizing the flow rate of hydrogen gas and optimizing the microwave power, a film having desired film characteristics can be obtained precisely. Specifically, after determining the power of the microwave, the flow rate of hydrogen gas may be optimized.

By the way, conventionally, when a silicon nitride film is formed on a glass substrate, a processing gas containing the above-described silane gas and ammonia (NH ₃ ) gas is also used. However, in a low temperature environment where the temperature of the glass substrate is 100 ° C. or lower, ammonia gas supplied before the formation of the silicon nitride film corrodes a metal electrode, for example, an aluminum electrode, formed on the base of the silicon nitride film. Resulting in. Further, since the film is formed in a low temperature environment, unreacted ammonia is trapped in the silicon nitride film. If ammonia is trapped in the silicon nitride film, after performing an environmental test or the like, the ammonia may be degassed from the silicon nitride film, which may deteriorate the organic EL device.

  In contrast, in the present embodiment, nitrogen gas is used instead of ammonia gas. Therefore, the above-described corrosion of the underlying metal electrode and the deterioration of the organic EL device can be prevented.

  In addition, when nitrogen gas is used instead of ammonia gas and hydrogen gas is added to the processing gas as in the present embodiment, the film characteristics of the silicon nitride film formed as shown in FIG. 9 are improved. Can do. That is, the film quality (density) of the silicon nitride film in the step portion can be improved. 9 shows the state of the silicon nitride film when a processing gas containing silane gas and ammonia gas is used, and the lower stage shows the silicon nitride film when a processing gas containing silane gas, nitrogen gas and hydrogen gas is used. It shows a state. Further, the left column in FIG. 9 shows the state of the silicon nitride film immediately after the film formation, and the right column shows the state of the silicon nitride film after performing the wet etching with buffered hydrofluoric acid (BHF) for 120 seconds.

  In the plasma film forming apparatus 16 of the above embodiment, the silane gas and the hydrogen gas are supplied from the source gas supply structure 60 and the nitrogen gas and the argon gas are supplied from the plasma excitation gas supply structure 80. The gas may be supplied from the plasma excitation gas supply structure 80. Alternatively, the hydrogen gas may be supplied from both the source gas supply structure 60 and the plasma excitation gas supply structure 80. In any case, the film characteristics of the silicon nitride film 23 can be controlled by controlling the supply flow rate of the hydrogen gas as described above.

  Here, as a result of intensive studies by the inventors, when the film quality of the silicon nitride film 23, particularly a dense film quality having the highest Si-N bond density in the film, the refractive index of the silicon nitride film 23 is about 2.0. I found out that Further, it was found that the refractive index is preferably 2.0 ± 0.1 from the viewpoint of the barrier property (sealing property) of the silicon nitride film 23.

  Therefore, in order to obtain the above-described refractive index of 2.0 ± 0.1, the ratio of the nitrogen gas supply flow rate to the silane gas supply flow rate is preferably set to 1 to 1.5 in the plasma film forming apparatus 16. On the other hand, when a silicon nitride film is formed with silane gas and nitrogen gas in a normal (conventional) plasma CVD apparatus, the ratio of the nitrogen gas supply flow rate to the silane gas supply flow rate is generally 10 to 50. Since a normal plasma CVD apparatus requires a large amount of nitrogen in this manner, the flow rate of silane gas is increased to increase the film formation rate, and at the same time, a nitrogen flow rate corresponding to the increase is required, which limits the exhaust system. For this reason, it is difficult to maintain the above-described refractive index of 2.0 ± 0.1 as the refractive index of the silicon nitride film under conditions where the film formation rate is high. Therefore, the plasma film-forming apparatus 16 of this Embodiment has an extremely excellent effect compared with a normal plasma CVD apparatus.

  Further, by controlling the ratio of the nitrogen gas supply flow rate to the silane gas supply flow rate, the film stress of the silicon nitride film 23 can be controlled within the range of the refractive index of 2.0 ± 0.1. Specifically, the film stress can be brought close to zero. Further, this film stress can be controlled by adjusting the microwave power from the radial line slot antenna 42 and the supply flow rate of hydrogen gas.

  Note that, as described above, the supply flow rate of nitrogen gas in the plasma film forming apparatus 16 can be reduced compared to a normal plasma CVD apparatus because the supplied nitrogen gas is easily activated and the degree of dissociation is increased. Because it can. That is, when the nitrogen gas is supplied from the plasma excitation gas supply structure 80, the second plasma excitation of the plasma excitation gas supply structure 80 is achieved by being sufficiently close to the dielectric window 41 where plasma is generated. The nitrogen gas released to the plasma generation region R1 in the processing vessel 30 in a relatively high pressure state from the gas supply port 82 is easily ionized to generate a large amount of active nitrogen radicals and the like. In order to increase the degree of dissociation of nitrogen gas in this way, the plasma excitation gas supply structure 80 is disposed at a position within 30 mm from the radial line slot antenna 42 (strictly, the dielectric window 41). As a result of investigation by the inventors, when the plasma excitation gas supply structure 80 is disposed at such a position, the plasma excitation gas supply structure 80 itself is disposed in the plasma generation region R1. For this reason, the dissociation degree of nitrogen gas can be raised.

  In the plasma film forming apparatus 16 of the above embodiment, the supply of the source gas may be performed simultaneously with the generation of the plasma or before the plasma generation. That is, first, silane gas and hydrogen gas (or only silane gas) are supplied from the source gas supply structure 60. At the same time as or after supplying the silane gas and hydrogen gas, argon gas and nitrogen gas (and hydrogen gas) are supplied from the plasma excitation gas supply structure 80, and microwaves are radiated from the radial line slot antenna 42. Then, plasma is generated in the plasma generation region R1.

  Here, the cathode layer 22 containing a metal element is formed on the glass substrate G on which the silicon nitride film 23 is formed. For example, when the organic EL device A including the cathode layer 22 is exposed to plasma, the cathode layer 22 may be peeled off from the light emitting layer 21 and the organic EL element A may be damaged. In contrast, in the present embodiment, plasma is generated at the same time as or after the supply of the silane gas and the hydrogen gas, so that the formation of the silicon nitride film 23 is started simultaneously with the generation of the plasma. Therefore, the surface of the cathode layer 22 is protected, and the organic EL device A can be appropriately manufactured without exposing the organic EL device A to plasma.

  In the above embodiment, the source gas supply port 63 is formed downward from the source gas supply structure 60, and the second plasma excitation gas supply port 82 is upward from the plasma excitation gas supply structure 80. However, the source gas supply port 63 and the second plasma excitation gas supply port 82 are in the horizontal direction or in an oblique direction other than the vertically downward direction, and more preferably in the direction of 45 degrees obliquely from the horizontal direction. It may be formed toward.

  In such a case, as shown in FIG. 10, the source gas supply structure 60 is formed with a plurality of source gas supply pipes 61 extending in parallel with each other. The source gas supply pipes 61 are arranged at equal intervals in the source gas supply structure 60. On both sides of the side surface of the source gas supply pipe 61, source gas supply ports 63 for supplying the source gas in the horizontal direction are formed as shown in FIG. The source gas supply ports 63 are arranged at equal intervals in the source gas supply pipe 61 as shown in FIG. Adjacent source gas supply ports 63 are formed in directions opposite to each other in the horizontal direction. The plasma excitation gas supply structure 80 may also have the same configuration as the source gas supply structure 60. Then, the source gas supply structure 61 and the source gas supply pipe 61 of the source gas supply structure 60 and the second plasma excitation gas supply pipe 81 of the plasma excitation gas supply structure 80 are substantially lattice-shaped. 60 and a gas supply structure 80 for plasma excitation are arranged.

  Since the source gas supplied from the source gas supply port 63 is mainly deposited on the source gas supply port 63 as silicon nitride, the deposited silicon nitride is removed by dry cleaning during maintenance. In such a case, if the source gas supply port 63 is formed downward, it is difficult for plasma to enter the source gas supply port 63, so that the silicon nitride deposited in the source gas supply port 63 reaches the inside. It may not be completely removed. In this regard, when the source gas supply port 63 is oriented in the horizontal direction as in the present embodiment, plasma generated during dry cleaning enters the inside of the source gas supply port 63. For this reason, silicon nitride can be completely removed up to the inside of the source gas supply port 63. Therefore, after maintenance, the source gas can be appropriately supplied from the source gas supply port 63, and the silicon nitride film 23 can be formed more appropriately.

  In addition, the source gas supply structure 61 so that the source gas supply pipe 61 of the source gas supply structure 60 and the second plasma excitation gas supply pipe 81 of the plasma excitation gas supply structure 80 are substantially lattice-shaped. 60 and a gas supply structure 80 for plasma excitation are arranged. Therefore, it is easier to manufacture the source gas supply structure 60 and the plasma excitation gas supply structure 80 than to make each source gas supply structure 60 and the plasma excitation gas supply structure 80 itself into a substantially lattice shape. Can do. Further, it is possible to easily pass the plasma generated in the plasma generation region R1.

  The source gas supply port 63 may be formed such that its inner diameter expands in a tapered shape from the inside to the outside as shown in FIG. In such a case, plasma is more likely to enter the source gas supply port 63 during dry cleaning. Therefore, silicon nitride deposited on the source gas supply port 63 can be more reliably removed. Similarly, the second plasma excitation gas supply port 82 may be formed so that its inner diameter increases in a tapered shape from the inside to the outside.

Although the case where silane gas was used as organosilane gas was demonstrated in the above embodiment, organosilane gas is not limited to silane gas. As a result of intensive studies by the inventors, it has been found that, for example, when disilane (Si ₂ H ₆ ) gas is used, the step coverage of the silicon nitride film 23 is further improved as compared with the case where silane gas is used.

  In the plasma film forming apparatus 16 of the above embodiment, the plasma is generated by the microwave from the radial line slot antenna 42. However, the generation of the plasma is not limited to this embodiment. As the plasma, for example, CCP (capacitively coupled plasma), ICP (inductively coupled plasma), ECRP (electron cyclotron resonance plasma), HWP (helicon wave excited plasma) or the like may be used. In any case, since the silicon nitride film 23 is formed in a low temperature environment where the temperature of the glass substrate G is 100 ° C. or lower, it is preferable to use high-density plasma.

  Furthermore, although the above embodiment demonstrated the case where the silicon nitride film 23 was formed as a sealing film on the glass substrate G, and the organic EL device A was manufactured, this invention manufactures another organic electronic device. It can also be applied to For example, also when manufacturing an organic transistor, an organic solar cell, organic FET (Field Effect Transistor) etc. as an organic electronic device, the film-forming method of the silicon nitride film of this invention is applicable. Furthermore, the present invention can be widely applied to the case where a silicon nitride film is formed on a substrate in a low temperature environment where the temperature of the substrate is 100 ° C. or lower, besides the manufacture of such an organic electronic device.

  The preferred embodiments of the present invention have been described above with reference to the accompanying drawings, but the present invention is not limited to such examples. It is obvious for those skilled in the art that various modifications or modifications can be conceived within the scope of the idea described in the claims, and these naturally belong to the technical scope of the present invention. It is understood.

DESCRIPTION OF SYMBOLS 1 Substrate processing system 16 Plasma film-forming apparatus 20 Anode layer 21 Light emitting layer 22 Cathode layer 23 Silicon nitride film 30 Processing container 31 Mounting stand 42 Radial line slot antenna 60 Raw material gas supply structure 62 Opening 63 Raw material gas supply port 70 1st Plasma excitation gas supply port 80 Plasma excitation gas supply structure 82 Second plasma excitation gas supply port 83 Opening portion 90 Exhaust port 100 Control unit A Organic EL device G Glass substrate R1 Plasma generation region R2 Source gas dissociation region

In order to achieve the above object, according to one aspect of the present invention, there is provided a film forming method for forming a silicon nitride film on a substrate accommodated in a processing container, wherein a silane-based gas is formed in the processing container. Then, a processing gas containing nitrogen (N ₂ ) gas and hydrogen (H ₂ ) gas is supplied, the processing gas is excited to generate plasma, and plasma processing using the plasma is performed to form a silicon nitride film on the substrate. It is characterized by filming.

As a result of intensive studies by the inventors, when a silicon nitride film is formed on a substrate by a plasma film forming method, if a processing gas containing a silane-based gas , a nitrogen gas and a hydrogen gas is used, the wet etching rate of the silicon nitride film It has been found that the etching characteristics of are improved. Specifically, it has been found that by adding hydrogen gas to the processing gas, the wet etching rate is reduced and the step coverage of the silicon nitride film is improved. Further, when the amount of hydrogen gas added to the processing gas is increased, the film stress of the silicon nitride film becomes negative. That is, it was found that the film stress of the silicon nitride film can be appropriately controlled. Therefore, according to the present invention, the controllability of the formation of the silicon nitride film formed on the substrate can be improved even in a low temperature environment where the temperature of the substrate in the processing container is 100 ° C. or less, for example. it can. The fact that the controllability of the film characteristics is improved by adding hydrogen gas to the processing gas will be described in detail later.

The processing gas includes a source gas for forming the silicon nitride film and a plasma excitation gas for generating the plasma, and the supply of the source gas is performed by the plasma excitation gas. It may be performed simultaneously with the generation or before the generation of the plasma. For example, silane-based gas , nitrogen gas, hydrogen gas, or the like is used as the source gas, and argon gas, nitrogen gas, hydrogen gas, or the like is used as the plasma excitation gas.

In the processing gas supplied into the processing container, the ratio of the supply flow rate of the nitrogen gas to the supply flow rate of the silane-based gas is preferably 1 to 1.5.

According to another aspect of the present invention, there is provided a method for manufacturing an organic electronic device, in which an organic element is formed on a substrate, and thereafter, a silane-based gas , a nitrogen gas, and a hydrogen gas are introduced into a processing container containing the substrate. And a plasma treatment is performed by exciting the treatment gas and performing plasma treatment with the plasma to form a silicon nitride film as a sealing film so as to cover the organic element. Yes.

In the processing gas supplied into the processing container, the ratio of the supply flow rate of the nitrogen gas to the supply flow rate of the silane-based gas is preferably 1 to 1.5.

According to another aspect of the present invention, there is provided a film forming apparatus for forming a silicon nitride film on a substrate, a processing container for accommodating and processing the substrate, and a silane-based gas and a nitrogen gas in the processing container. And a processing gas supply unit that supplies a processing gas containing hydrogen gas, a plasma excitation unit that generates plasma by exciting the processing gas, and a plasma process using the plasma to form a silicon nitride film on the substrate Thus, it has the control part which controls the processing gas supply part and the plasma excitation part.

The control unit may control the processing gas supply unit so that a ratio of a supply flow rate of the nitrogen gas to a supply flow rate of the silane-based gas becomes 1 to 1.5.

A large number of source gas supply ports 63 are formed on the lower surface of the source gas supply pipe 61 of the source gas supply structure 60 as shown in FIG. These source gas supply ports 63 are evenly arranged in the surface of the source gas supply structure 60. A gas pipe 65 that communicates with a source gas supply source 64 installed outside the processing container 30 is connected to the source gas supply pipe 61. In the source gas supply source 64, for example, silane (SiH ₄ ) gas and hydrogen (H ₂ ) gas, which are silane-based gases , are individually sealed as source gases. The gas pipe 65 is provided with a valve 66 and a mass flow controller 67. With this configuration, a predetermined flow rate of silane gas and hydrogen gas are respectively introduced from the source gas supply source 64 into the source gas supply pipe 61 through the gas pipe 65. And these silane gas and hydrogen gas are supplied toward each lower raw material gas dissociation area | region R2 from each raw material gas supply port 63. FIG.

The above embodiment has described the case of using a silane gas as a silane-based gas, silane-based gas is not limited to silane gas. As a result of intensive studies by the inventors, it has been found that, for example, when disilane (Si ₂ H ₆ ) gas is used, the step coverage of the silicon nitride film 23 is further improved as compared with the case where silane gas is used.

Claims (27)

A film forming method for forming a silicon nitride film on a substrate housed in a processing container,
Supplying a processing gas containing organosilane gas, nitrogen gas and hydrogen gas into the processing container;
A method of forming a silicon nitride film, wherein the processing gas is excited to generate plasma, and plasma processing is performed with the plasma to form a silicon nitride film on a substrate. 2. The method of forming a silicon nitride film according to claim 1, wherein the silicon nitride film is used as a sealing film for an organic electronic device. 3. The method of forming a silicon nitride film according to claim 1, wherein a pressure in the processing vessel is maintained at 20 Pa to 60 Pa during the plasma processing using the plasma. 4. The method for forming a silicon nitride film according to claim 1, wherein a film stress of the silicon nitride film is controlled by controlling a supply flow rate of the hydrogen gas. The method of forming a silicon nitride film according to claim 1, wherein the plasma is generated by exciting the processing gas with microwaves. 6. The method of forming a silicon nitride film according to claim 5, wherein the film power of the silicon nitride film is controlled by controlling the power of the microwave. The processing gas includes a source gas for forming the silicon nitride film and a plasma excitation gas for generating the plasma,
7. The silicon nitride film according to claim 1, wherein the supply of the source gas is performed simultaneously with the generation of the plasma by the plasma excitation gas or before the generation of the plasma. Membrane method. The ratio of the supply flow rate of the nitrogen gas to the supply flow rate of the organosilane gas in the processing gas supplied into the processing container is 1 to 1.5. A method for forming a silicon nitride film according to claim 1. A method for manufacturing an organic electronic device, comprising:
Forming organic elements on the substrate,
Thereafter, a processing gas containing organosilane gas, nitrogen gas, and hydrogen gas is supplied into a processing container containing the substrate, the processing gas is excited to generate plasma, and plasma processing using the plasma is performed, so that the organic A method of manufacturing an organic electronic device, comprising forming a silicon nitride film as a sealing film so as to cover an element. The method for manufacturing an organic electronic device according to claim 9, wherein the pressure in the processing container is maintained at 20 Pa to 60 Pa during the plasma processing using the plasma. 11. The method of manufacturing an organic electronic device according to claim 9, wherein a film stress of the silicon nitride film is controlled by controlling a supply flow rate of the hydrogen gas. The method of manufacturing an organic electronic device according to claim 9, wherein the plasma is generated by exciting the processing gas with microwaves. The method of manufacturing an organic electronic device according to claim 12, wherein the film power of the silicon nitride film is controlled by controlling the power of the microwave. The processing gas includes a source gas for forming the silicon nitride film and a plasma excitation gas for generating the plasma,
14. The manufacturing of the organic electronic device according to claim 9, wherein the supply of the source gas is performed simultaneously with the generation of the plasma by the plasma excitation gas or before the generation of the plasma. Method. The ratio of the supply flow rate of the nitrogen gas to the supply flow rate of the organosilane gas in the processing gas supplied into the processing container is 1 to 1.5. A method for producing an organic electronic device according to claim 1. A film forming apparatus for forming a silicon nitride film on a substrate,
A processing container for receiving and processing a substrate;
A processing gas supply unit for supplying a processing gas containing organosilane gas, nitrogen gas and hydrogen gas into the processing container;
A plasma excitation unit for generating plasma by exciting the processing gas;
A silicon nitride film comprising: a process gas supply unit; and a control unit that controls the plasma excitation unit so as to form a silicon nitride film on a substrate by performing a plasma process using the plasma. Deposition device. The silicon nitride film forming apparatus according to claim 16, wherein the silicon nitride film is used as a sealing film of an organic electronic device. The said control part controls the said process gas supply part so that the pressure in the said process container may be maintained at 20 Pa-60 Pa during the plasma process by the said plasma, The Claim 16 or 17 characterized by the above-mentioned. Silicon nitride film deposition system. The silicon nitride film deposition apparatus according to claim 16, wherein the control unit controls a film stress of the silicon nitride film by controlling a supply flow rate of the hydrogen gas. . The silicon nitride film forming apparatus according to claim 16, wherein the plasma excitation unit excites the processing gas by supplying a microwave. 21. The silicon nitride film deposition apparatus according to claim 20, wherein the control unit controls a film stress of the silicon nitride film by controlling a power of the microwave. The processing gas includes a source gas for forming the silicon nitride film and a plasma excitation gas for generating the plasma,
The control unit controls the processing gas supply unit and the plasma excitation unit so that the supply of the source gas is performed simultaneously with the generation of the plasma by the plasma excitation gas or before the generation of the plasma. The silicon nitride film forming apparatus according to any one of claims 16 to 21, wherein The control unit controls the processing gas supply unit so that a ratio of a supply flow rate of the nitrogen gas to a supply flow rate of the organosilane gas becomes 1 to 1.5. The silicon nitride film forming apparatus according to any one of the above. The processing gas includes a source gas for forming the silicon nitride film and a plasma excitation gas for generating the plasma,
In the upper part of the processing vessel, the plasma excitation unit is provided,
In the lower part of the processing container, a mounting part for mounting the substrate is provided,
Between the plasma excitation unit and the placement unit, a gas supply structure for plasma excitation and a raw material gas supply structure that partition the inside of the processing container and configure the processing gas supply unit are provided,
The plasma excitation gas supply structure includes a plasma excitation gas supply port for supplying the plasma excitation gas to the region on the plasma excitation unit side, and the plasma generated in the region on the plasma excitation unit side. An opening to be passed through the region on the placement portion side is formed,
The source gas supply structure includes a source gas supply port that supplies the source gas to a region on the placement unit side, and the plasma generated in the region on the plasma excitation unit side. An apparatus for forming a silicon nitride film according to claim 16, wherein an opening to be passed through is formed. 25. The silicon nitride film deposition apparatus according to claim 24, wherein the plasma excitation gas supply structure is disposed at a position within 30 mm from the plasma excitation unit. 26. The silicon nitride film deposition apparatus according to claim 24, wherein the source gas supply port is formed in a horizontal direction. 27. The silicon nitride film forming apparatus according to claim 26, wherein the source gas supply port is formed so that an inner diameter thereof increases in a tapered shape from the inside toward the outside.