JP2006299335A - Film deposition method, film deposition apparatus used for the same, and vaporization device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To expand the selective range of solid substances which can be film-deposited by the CVD method by allowing the solid substances to be vaporized at the temperature lower than that for vaporization thereof. <P>SOLUTION: A vapor deposition apparatus comprises a raw material storage container 3 which stores a solution 5 with particles of a solid substance forming a film deposition raw material of the predetermined amount being mixed in a solvent, and scatters the solution 5 to be atomized, a vaporization chamber 4 in which the inside thereof is evacuated, atomized fine liquid droplets 8 to be transported from the raw material storage container 3 via a first transport pipe 9 are introduced, the thermal energy at the predetermined temperature is applied to the particles contained in the fine liquid droplets 8 by a cylindrical heater 15 to vaporize the particles, and the raw material gas is generated, and a reaction chamber 2 in which the raw material gas to be introduced from the vaporization chamber 4 via a second transport pipe 12 is subjected to plasma treatment, and a film of the solid substance is deposited on a substrate 16 installed inside thereof. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a film forming method for forming a film by a CVD method using a source gas, and more specifically, a solid material capable of vaporizing a solid material at a temperature lower than its vaporization temperature and capable of forming a film by the CVD method. The present invention relates to a film forming method for expanding the selection range, a film forming apparatus used for the method, and a vaporizing apparatus.

  In general, a CVD film forming method uses a CVD film forming apparatus to vaporize a raw material immediately before a reaction chamber to generate a raw material gas, introduce the raw material gas into the reaction chamber, and perform plasma treatment to form a film. It is like that.

  In this case, the conventional vaporizer that vaporizes the raw material has a plurality of heaters that are heated to the highest temperature within a range in which the raw material does not change, and is disposed around the device main body to vaporize the liquid raw material to generate the raw material gas. The liquid raw material is sprayed into particles by a nozzle provided on the upper wall of the chamber, and the liquid raw material particles injected from the nozzle are subjected to high-frequency vibrations by a high-frequency vibration plate disposed opposite to the nozzles to form finer particles. The liquid raw material is vaporized and the vaporized raw material gas is transported to the reaction chamber via the raw material gas transport pipe (see, for example, Patent Document 1).

In addition, another vaporizer includes an evaporating dish that can be heated in an airtight chamber, and an evaporating dish in which a liquid material having a low vapor pressure or a sublimable solid material is heated to a predetermined temperature from a material storage container for storing the material. The raw material gas is vaporized by feeding to the CVD reaction chamber, and the generated raw material gas is transferred to the CVD reaction chamber (see, for example, Patent Document 2).
JP 2001-152343 A JP-A-6-346243

  However, in such a conventional vaporizer, vaporizable raw materials are limited to raw materials having a relatively low vaporization temperature, such as liquid raw materials such as liquid organic metals and organic metal solutions, or raw materials of sublimable solid substances. Further, it has been difficult to form a film by a CVD method using a metal such as a rare metal having a high vaporization temperature.

  Accordingly, the present invention provides a film forming method, a film forming apparatus, and a vaporization apparatus used in the method for addressing such problems and expanding the selection range of solid substances that can be formed by a CVD method. For the purpose.

  In order to achieve the above object, the film forming method according to the first aspect of the present invention is a method of spraying a solution obtained by mixing a predetermined amount of a fine particle material of a solid substance as a film forming raw material in a solvent, and atomizing the solution. The fine droplets are introduced into a vaporized chamber that has been decompressed, and the particulate material contained in the fine droplets is vaporized by applying thermal energy at a predetermined temperature to generate a raw material gas, which reacts with the raw material gas It is introduced into a chamber and subjected to plasma treatment, and a film of the solid material is deposited on a substrate installed in the reaction chamber.

  The atomization of the solution is performed by radiating ultrasonic waves into the solution and utilizing the impact force at the time of generation and disappearance of cavities generated in the solution. Thereby, an ultrasonic wave is radiated into the solution, and the solution is atomized by using an impact force at the time of generation and disappearance of the cavity generated in the solution.

  Further, the atomization of the solution is performed by spraying the solution from a spray nozzle. Thereby, the solution is sprayed from the spray nozzle to be atomized.

  Furthermore, plasma energy is added to the generated source gas before it is transported to the reaction chamber to release the source gas. Thereby, plasma energy is added to the raw material gas before being transported to the reaction chamber to release the raw material gas.

  The solid material particulate material is a metal nanoparticle material. Thus, a raw material gas is generated using a fine particle material made of a metal nanoparticle material to form a film.

  A film forming apparatus according to the second invention stores a solution in which a predetermined amount of a solid material fine particle material as a film forming raw material is mixed in a solvent, and also scatters the solution to form a mist, The fine particle material that is formed so that the inside can be decompressed, introduces the atomized fine droplets transported from the raw material storage container via the first transport pipe, and is contained in the fine droplets A vaporizing chamber for generating a raw material gas by adding thermal energy at a predetermined temperature to the heating means and a raw material gas introduced from the vaporizing chamber through a second transport pipe are plasma-treated and installed inside And a reaction chamber for depositing the solid material film on the substrate.

  With such a configuration, a solution in which a predetermined amount of a solid material fine particle material used as a film forming raw material is mixed in a solvent is stored in a raw material storage container, and the solution is atomized into fine droplets so that the inside can be decompressed. The atomized fine droplets transported from the raw material storage container via the first transport pipe into the vaporization chamber formed in the above are introduced, and the fine particle material contained in the fine droplets in the vaporization chamber The raw material gas is generated by adding heat energy at a predetermined temperature to the gas by heating means, and the raw material gas is introduced into the reaction chamber from the vaporization chamber through the second transport pipe. A film of the solid material is deposited on a substrate placed inside by plasma treatment.

  According to a third aspect of the present invention, there is provided a film forming apparatus comprising: a raw material storage container for storing a solution obtained by mixing a predetermined amount of a solid particulate material as a film forming raw material in a solvent; A spray nozzle that sprays the solution to be sprayed into fine droplets to form a mist, and the mist formed inside the spray chamber so that the pressure can be reduced and transported from the spray chamber via a first transport pipe A vaporization chamber that introduces fine droplets that are shaped and vaporizes the particulate material contained in the fine droplets by applying heat energy at a predetermined temperature by a heating means to generate a raw material gas; and the vaporization A reaction chamber that plasma-treats the source gas introduced from the chamber through a second transport pipe and deposits a film of the solid material on a substrate installed in the chamber.

  With such a configuration, a solution in which a predetermined amount of a solid material particulate material that is a film forming raw material is mixed in a solvent is stored in a raw material storage container, and a solution supplied from the raw material storage container through a supply pipe is injected into the injection nozzle. The atomized fine particles are sprayed into the spray chamber, atomized into fine droplets, and transported from the spray chamber through the first transport pipe into the vaporization chamber formed so that the inside can be decompressed. In the vaporization chamber, a fine gas contained in the fine droplets is vaporized by applying thermal energy at a predetermined temperature by a heating means to generate a raw material gas. The raw material gas is introduced through two transport pipes, the raw material gas is plasma-treated in a reaction chamber, and a film of the solid material is deposited on a substrate installed inside.

  A vaporization apparatus according to a fourth aspect of the present invention stores a solution obtained by mixing a predetermined amount of a solid fine particle material as a film forming raw material in a solvent and scatters the solution to form an atomization, and an internal Is introduced into the fine particle material contained in the fine liquid droplets, and is introduced into the fine liquid droplets that are transported from the raw material storage container via the first transport pipe. And a vaporizing chamber that generates a raw material gas by applying a thermal energy of a predetermined temperature by a heating means to vaporize.

  With such a configuration, a solution in which a predetermined amount of a solid material fine particle material used as a film forming raw material is mixed in a solvent is stored in a raw material storage container, and the solution is sprayed to form a mist so that the inside can be decompressed. The atomized fine droplets transported from the raw material storage container through the first transport pipe into the vaporization chamber are introduced, and the fine particle material contained in the fine droplets is heated in the vaporization chamber. Thus, heat energy at a predetermined temperature is applied and vaporized to generate a raw material gas.

  Further, the raw material storage container includes an ultrasonic vibrator on a bottom surface portion thereof, emits ultrasonic waves generated by driving the ultrasonic vibrator into the solution, and generates a cavity generated in the solution; The solution is atomized using an impact force at the time of extinction. As a result, the ultrasonic vibrator provided on the bottom surface portion of the raw material storage container is driven to generate ultrasonic waves, and the ultrasonic waves are radiated into the solution. The solution is atomized using an impact force.

  The raw material storage container is provided with a plurality of outlets arranged in the vertical direction on the side wall portion between the liquid level and the upper wall surface of the solution stored therein, and one of them is provided in the first transport pipe. Connected. Thus, a plurality of outlets are provided in the side wall portion between the liquid level of the solution stored in the raw material storage container and the upper wall surface of the raw material storage container, and one of them is provided for the first transportation. Connect to the tube.

  A vaporization apparatus according to a fifth aspect of the present invention is supplied from a raw material storage container for storing a solution obtained by mixing a predetermined amount of a solid fine particle material, which is a film forming raw material, in a solvent, and the raw material storage container through a supply pipe. The spray nozzle that sprays the solution into the spray chamber and atomizes it into fine droplets, and the mist that is formed so that the inside can be decompressed and is transported from the spray chamber via the first transport pipe. A vaporization chamber that introduces vaporized fine droplets and vaporizes the fine particle material contained in the fine droplets by applying heat energy at a predetermined temperature by a heating means to generate vapor. Is.

  With such a configuration, a solution obtained by mixing a predetermined amount of a solid fine particle material used as a film forming raw material in a solvent is stored in a raw material storage container, and the solution supplied from the raw material storage container through the supply pipe is stored by an injection nozzle. The atomized fine liquid that is sprayed into the spray chamber, atomized into fine droplets, and transported from the spray chamber through the first transport pipe into the vaporization chamber formed so that the inside can be decompressed. Droplets are introduced, and heat energy at a predetermined temperature is applied to the particulate material contained in the fine droplets in the vaporization chamber by a heating means to vaporize the raw material gas.

  Further, the spray chamber is provided with a plurality of outlets arranged in the vertical direction on the side wall, one of which is connected to the first transport pipe. Thus, a plurality of outlets are provided on the side wall of the spray chamber in the vertical direction, and one of them is connected to the first transport pipe.

  Furthermore, the vaporization chamber is provided with a pair of electrodes opposed to the flow in the direction orthogonal to the flow downstream of the heating means. Thereby, plasma is generated between the pair of electrodes arranged in the direction orthogonal to the flow at the downstream side of the heating means of the vaporization chamber, and plasma energy is added to the source gas to supply the source gas. To release.

  The solid material particulate material is a metal nanoparticle material. Vaporizing fine particles made of metal nanoparticle material.

  According to the invention according to claim 1 or 6, a solution obtained by mixing a predetermined amount of a fine particle material of a solid substance as a film forming raw material in a solvent is sprayed and atomized, and in the atomized fine droplets The raw material gas is generated by applying thermal energy at a predetermined temperature to vaporize the particulate material contained in the material, and this is subjected to plasma treatment to form a film, so that the solid substance is originally lower than the vaporization temperature it has. It can be vaporized at temperature. Therefore, the selection range of the solid substance that can be formed by the CVD method can be expanded. In addition, since the solid substance can be vaporized at a low temperature, the film can be formed at a low temperature. For example, the film can be formed on a film or the like. Therefore, when applied to atmospheric pressure plasma CVD, a large surface emitting organic EL can be manufactured by continuously forming a large film while supplying a large film. Manufacture is possible.

  Further, according to the invention of claim 2, ultrasonic waves are emitted into the solution, and the solution is atomized by using the impact force at the time of generation and disappearance of the cavity generated in the solution. Thus, the solution can be easily atomized.

  Furthermore, according to the invention which concerns on Claim 3, a finer droplet can be produced | generated by having sprayed the solution from the injection nozzle and atomized.

  Furthermore, according to the invention according to claim 4, since the gas is released by adding plasma energy to the raw material gas before being transported to the reaction chamber, the ratio of the released raw material gas in the reaction chamber is increased. The film formation efficiency can be improved.

  And according to the invention which concerns on Claim 5 or 14, since the fine particle material which consists of metal nanoparticle material was used, the selection range of the metal material applicable to a electrically conductive film spreads.

  Further, according to the invention of claim 7, a solution in which a predetermined amount of a solid material of a solid material as a film forming raw material is mixed in a solvent is sprayed from a spray nozzle to be atomized into fine droplets. By applying thermal energy at a predetermined temperature to vaporize the fine particle material contained in the formed fine droplets to generate a raw material gas, this is plasma-processed to form a film. Droplets can be generated, thermal energy can be efficiently applied to the particulate material in the fine droplets, and the particulate material can be efficiently vaporized. Therefore, the utilization efficiency of the raw material used for film formation can be improved.

  Furthermore, according to the invention according to claim 8, a solution obtained by mixing a predetermined amount of a solid material fine particle material, which is a film forming raw material, in a solvent is sprayed to be atomized, and in the atomized fine droplets Since the raw material gas is generated by adding thermal energy at a predetermined temperature to the particulate material contained in the material to vaporize the solid material, the solid material can be vaporized at a temperature lower than the inherent vaporization temperature. Accordingly, the selection range of solid substances that can be formed is widened, and a film forming apparatus that enables low-temperature film formation of solid substances that have been difficult to form by conventional CVD can be easily manufactured.

  According to the ninth aspect of the present invention, an ultrasonic vibrator is provided on the bottom surface of the raw material storage container, and ultrasonic waves generated by driving the ultrasonic vibrator are radiated into the solution. Dispersing the solid particulate material stored in the raw material storage container in the solution uniformly by atomizing the solution by using the impact force at the time of generation and extinction of the generated cavity In addition, the fine particle material can be mixed in the atomized fine droplets.

  According to the invention of claim 10, a plurality of outlets are provided in the vertical direction on the side wall portion between the liquid level of the solution stored in the raw material storage container and the upper wall surface of the raw material storage container, By connecting one of them to the first transport pipe, fine droplets having a uniform particle diameter can be introduced into the vaporization chamber. Therefore, the heat energy acting on the fine particle material contained in the fine droplets can be made uniform, and the fine particle material can be efficiently vaporized.

  Further, according to the invention according to claim 11, a solution obtained by mixing a predetermined amount of a fine particle material of a solid substance as a film forming raw material in a solvent is sprayed from a spray nozzle to be atomized into fine droplets. The fine particles contained in the shaped fine droplets are vaporized by applying thermal energy at a predetermined temperature to produce a raw material gas, so that finer droplets can be produced, The substance can be vaporized efficiently at a temperature lower than the vaporization temperature that it originally has. Therefore, the selection range of solid substances that can be formed is widened, and a film forming apparatus that enables low-temperature film formation of solid substances that have been difficult to form by the conventional CVD method can be easily manufactured. . Further, since finer droplets can be generated, thermal energy can be efficiently applied to the particulate material in the minute droplets, and the particulate material can be efficiently vaporized. . Therefore, a film forming apparatus with high film forming efficiency can be manufactured.

  Furthermore, according to the twelfth aspect of the present invention, a plurality of outlets are provided in the vertical direction on the side wall of the spray chamber in which the solution is sprayed by the spray nozzle to be atomized, and one of them is the first transport. By connecting to the tube, finer droplets with a uniform particle size can be introduced into the vaporization chamber. Therefore, the thermal energy acting on the fine particle material contained in the fine droplets can be made uniform, and the fine particle material can be vaporized more efficiently.

  According to the invention of claim 13, the pair of electrodes are disposed in the vaporizing chamber on the downstream side of the source gas in the direction perpendicular to the flow on the downstream side of the heating means, thereby providing a gap between the electrodes. Plasma energy can be added to the source gas before it is generated and transported to the reaction chamber to release the source gas. Therefore, it is possible to manufacture a film forming apparatus with high film forming efficiency by increasing the ratio of the released source gas in the reaction chamber.

  Embodiments of the present invention will be described below in detail with reference to the accompanying drawings. FIG. 1 is an explanatory view showing, in section, a schematic configuration of a first embodiment of a film forming apparatus according to the present invention. This film forming apparatus forms a film by a CVD method using a raw material gas, and includes a raw material storage container 1, a vaporization chamber 2, and a reaction chamber 3.

The raw material storage container 1 is a solid material as a film forming raw material, for example, metal nanoparticles such as gold, silver, copper, tin and rare metal, and a fine particle material having a particle size of 1 nm to 60 nm is mixed in a predetermined amount in an organic solvent, for example. The solution 5 is stored, and the solution 5 is atomized into fine droplets. The ultrasonic vibrator 6 is oscillated on the bottom surface portion 1a of the container and the ultrasonic vibrator 6 is oscillated at 20 KHz to 10 MHz. And an oscillator 7 to be oscillated. In this case, the raw material storage container 1 drives the oscillator 7 to vibrate the ultrasonic vibrator 6, radiates the ultrasonic wave generated at that time into the solution 5, and generates a cavity generated in the solution 5. The solution 5 containing the nanoparticle fine particles is dispersed as fine droplets 8 having a diameter of 1 μm to 50 μm by utilizing the impact force upon disappearance. The raw material storage container 1 has one end of a first transport pipe 9 to be described later connected to the upper end of one side wall 1b, and, for example, nitrogen gas (N ₂ ) at the upper end of the opposite side wall 1c. A carrier gas introduction pipe 10 for introducing a carrier gas such as an inert gas is connected, and the atomized fine droplets 8 are transferred to the inside of the first transport pipe 9 by the carrier gas by the arrow A shown in FIG. It can be transported in the direction.

  In addition, as shown in FIG. 1, when a rod-like or plate-like member 11 such as metal or ceramic is immersed in the solution 5 of the raw material storage container 1, the standing wave of ultrasonic waves generated in the solution 5 is disrupted, The fine droplets 8 of the solution 5 are more scattered from the liquid surface 5a, and the generation of fog is promoted.

  A vaporization chamber 2 is connected to the raw material storage container 1. The vaporizing chamber 2 is a chamber for generating a raw material gas by adding thermal energy at a predetermined temperature of, for example, 500 ° C. or less to the nanoparticle material contained in the fine droplets 8 to vaporize the material. A first transport pipe 9 is provided on the side wall 2a so that the atomized fine droplets 8 can be introduced from the raw material storage container 1, and one end portion of a second transport pipe 12 described later on the other side wall 2b. Is a quartz or metal hermetic chamber in which the source gas can be transported in the direction of arrow B shown in FIG. 1 and the vacuum pump 13 is connected so that the inside can be decompressed.

The distal end portion 9a of the first transport pipe 9 is introduced into the vaporizing chamber 2, and a plurality of holes 14 are formed in the side wall thereof. Further, for example, a cylindrical heater 15 is provided as a heating means so as to surround the distal end portion 9 a of the first transport pipe 9, and a plurality of the distal end portions 9 a of the first transport pipe 9 are formed by the cylindrical heater 15. The fine droplets 8 discharged from the holes 14 are heated, and heat energy at a predetermined temperature is applied to the fine particle material of the nanoparticles contained therein to vaporize the material to generate a raw material gas. In addition, since the surface area of the fine particle material of the nanoparticle is large, the fine particle material is easily vaporized at a temperature lower than the vaporization temperature inherent to the solid material of the raw material. Accordingly, the set temperature of the cylindrical heater 15 is set lower than the vaporization temperature of the solid substance of the same quality as the fine particle material. For example, in the case of carbon, it may be about 120 ° C. In the case of gold, silver, copper, or the like. May be 300 ° C. or less.
And the vaporizer 4 is comprised from the said raw material storage container 1 and the vaporization chamber 2. FIG.

  A reaction chamber 3 is connected to the vaporization chamber 2 of the vaporizer 4. The reaction chamber 3 is a plasma treatment of the source gas introduced from the vaporization chamber 2 to deposit the solid material film on the substrate 16, and the second transport pipe 12 is provided on the upper wall portion 3a. The material gas can be introduced from the vaporizing chamber 2 and is provided with a pair of counter electrodes (not shown) for generating plasma therein, and a transport belt 17 for transporting the substrate 16 on the lower side of the interior. The film can be made. The reaction chamber 3 is not limited to the one described above, and may be a chamber that can be sealed and connected to a vacuum pump so that a film can be formed under reduced pressure, and a known technique can be applied. . The solid material film includes a film formed by reacting a source gas with a reactive gas.

  In FIG. 1, reference numeral 19 a indicates an opening / closing valve for the carrier gas introduction pipe 10, reference numeral 19 b indicates an opening / closing valve for the suction pipe of the vacuum pump 13, and reference numeral 19 c indicates an opening / closing valve for the second transport pipe 12. Reference numeral 20 denotes a heater that is provided around the first and second transport pipes 8 and 12 and the vaporizing chamber 2 and prevents condensation of the atomized fine droplets 8 and liquefaction of the vaporized source gas. It is.

Next, the operation of the film forming apparatus of the first embodiment configured as described above and the film forming method performed using this film forming apparatus will be described.
First, for example, a solution 5 obtained by mixing a predetermined amount of a fine particle material of metal nanoparticles in an organic solvent is stored in the raw material storage container 1 and the container is sealed. At this time, the opening / closing valve 19a of the carrier gas introduction pipe 10 and the opening / closing valve 19c of the second transport pipe 12 are closed.

  Next, the vacuum pump 13 is driven, the open / close valve 19b is opened, and the inside of the vaporizing chamber 2 is depressurized to a predetermined degree of vacuum to be in a deoxygenated state. Then, the open / close valve 19b is closed. At this time, the inside of the raw material storage container 1 is simultaneously decompressed via the first transport pipe 9. Further, the opening / closing valve 19 a of the carrier gas introduction pipe 10 is opened to introduce the carrier gas from the raw material storage container 1 into the vaporization chamber 2. When the vaporizing chamber 2 is filled with the carrier gas, the opening / closing valve 19c is opened to flow the carrier gas to the reaction chamber 3 side.

  Next, the cylindrical heater 15 in the vaporization chamber 2 is energized to heat the cylindrical heater 15 to an appropriate temperature at which the metal nanoparticle particulate material is vaporized, and the heater 20 is energized to form atomized fine particles. The outer peripheral surfaces of the first and second transport pipes 8 and 12 and the vaporizing chamber 2 are warmed to a desired temperature so that the liquid droplets 8 are not condensed and the raw material gas is not liquefied. Further, the oscillator 7 is driven to vibrate the ultrasonic vibrator 6, and the ultrasonic waves generated thereby are radiated into the solution 5 stored in the raw material storage container 1. At this time, the generation and disappearance of cavities occur in the solution 5, and the fine particle material in the solution 5 is uniformly dispersed by the impact force generated therewith. At the same time, the solution 5 scatters as fine droplets 8 due to the impact force, and a mist of the fine droplets 8 is generated in the space between the liquid surface 5a and the upper wall surface 1d of the raw material storage container 1. .

  The mist of the fine droplets 8 is transported in the direction of the arrow A by the carrier gas in the direction of the arrow A, and from the plurality of holes 14 provided in the distal end portion 9a of the first transport tube 9, the vaporizing chamber 2. Is released inside. The solvent in the discharged fine droplet 8 is vaporized by obtaining thermal energy from the cylindrical heater 15. At the same time, the metal nanoparticle fine particles contained in the fine droplets 8 are vaporized by obtaining the thermal energy to generate a raw material gas.

  This source gas is transported in the second transport pipe 12 in the direction of arrow B by the carrier gas and introduced into the reaction chamber 3 where it is plasma treated. Then, for example, the metal film is deposited on the substrate 16 which is transported in the direction of arrow C by the transport belt 17 and installed in the reaction chamber 3. In this case, for example, indium, tin, zinc, or the like can be formed by reacting the source gas with oxygen under normal pressure. Further, when the reaction chamber 3 can be decompressed, gold, silver, copper, or the like can be formed in a deoxygenated state.

  FIG. 2 is a sectional view showing another configuration example of the raw material storage container 1. This raw material storage container 1 is provided with three outlets 21a, 21b, 21c arranged vertically in the side wall 1b portion between the liquid surface 5a of the stored solution 5 and the upper wall surface 1d, one of which is a first one. 1 is connected to one transport pipe 9. As a result, among the fine droplets 8, a light droplet 8 a having a small particle diameter and light can be taken out from the upper take-out port 21 a, and a large droplet having a large particle size 8 c can be taken out from the lower take-out port 21 c. The medium-sized droplet 8b can be taken out from the middle outlet 21b. Accordingly, fine droplets 8 having a uniform particle diameter can be introduced into the vaporizing chamber 2, and the thermal energy acting on the fine particle material contained in the fine droplets 8 can be made uniform to efficiently vaporize the fine particle material. It can be carried out. It should be noted that the fine droplets 8 taken out from the outlets not connected to the vaporizing chamber 2, for example, the outlets 21b and 21c shown in the figure, may be exhausted or returned to the raw material storage container 1 side.

  FIG. 3 is an explanatory view showing in cross section the main part of a second embodiment of the film forming apparatus according to the present invention. In the second embodiment, a raw material storage container 1 for storing a solution 5 in which a predetermined amount of a solid material nanoparticle fine particle material, which is used as a film forming raw material by the vaporizer 4, is mixed in a solvent. The solution 5 supplied through the supply pipe 22 is sprayed into the spray chamber 23 to be atomized into fine droplets 8, and the inside is formed so that the pressure can be reduced. The atomized fine droplet 8 transported through one transport pipe 9 is introduced, and the particulate material contained in the fine droplet 8 is vaporized by applying thermal energy at a predetermined temperature. And a vaporizing chamber 2 for generating a raw material gas. The raw material gas is introduced from the vaporizing chamber 2 into the reaction chamber 3 (not shown) via the second transport pipe 12 (see FIG. 1). The raw material gas is plasma-treated, and the solid material is placed on the substrate 16 installed inside. It has a membrane so as to deposit.

With such a configuration, an inert gas such as nitrogen gas (N ₂ ) whose flow rate is adjusted to about 1 cc to 20 cc by the mass flow controller 25 is introduced into the raw material storage container 1 through the gas pipe 26, and the above solution is supplied by this gas. The liquid surface 5 a of 5 is pressurized and the solution 5 having the fine particle material as a raw material uniformly dispersed is supplied to the injection nozzle 24 through the supply pipe 22. Further, an injection gas made of an inert gas such as nitrogen gas (N ₂ ) whose flow rate is adjusted to about 5 L to 10 L by the mass flow controller 27 is supplied to the injection nozzle 24 via the gas pipe 28 and is supplied from the injection nozzle 24. Be injected. As a result, the solution 5 supplied to the injection nozzle 24 is injected as fine droplets 29 together with the injection gas injected from the injection nozzle 24.

  The fine droplets 29 collide with the wall surface 23a of the spray chamber 23 facing the spray nozzle 24 to be made into finer droplets 8, and are dispersed in the spray chamber 23 and atomized. Then, the atomized fine droplets 8 are brought into the vaporizing chamber 2 in which the inside of the first transport pipe 9 is depressurized in the direction of arrow A shown in the figure by the inert gas ejected from the ejection nozzle 24. It is transported towards.

  The atomized fine droplet 8 transported through the first transport pipe 9 is discharged from the hole 14 provided in the tip end portion 9 a of the first transport pipe 9 and is then generated in the vaporization chamber 2. Thermal energy is obtained from the cylindrical heater 15. Due to this thermal energy, the nanoparticle particulate material contained in the fine droplets 8 is vaporized to become a raw material gas. This source gas is transported in the direction of arrow B shown in the figure by the second transport pipe 12 and introduced into the reaction chamber 3 where it is plasma-treated. Thereby, the film of the solid material is deposited on the substrate 16 (see FIG. 1) installed in the reaction chamber 3.

  FIG. 4 is a cross-sectional view showing another configuration example of the spray chamber 23. The spray chamber 23 is provided with a plurality of outlets 30 a, 30 b, 30 c, 30 d arranged in the vertical direction on the side wall 23 b, and one of them, for example, the outlet 30 a is connected to the first transport pipe 9. . Also in this case, the particle size of the fine droplets 8 can be selected and taken out as in the raw material storage container 1 shown in FIG. Further, the flow rate of the gas flowing into the vaporizing chamber 2 can be adjusted by dividing the pressure of the sprayed gas injected from the spray nozzle 24 into the spray chamber 23 by the plurality of outlets 30a to 30d. In addition, the fine droplet 8 taken out from the taking-out port not connected to the vaporizing chamber 2, for example, the taking-out ports 30b to 30d shown in the figure, may be exhausted or returned to the raw material storage container 1 side.

  FIG. 5 is an explanatory view showing in cross section the main part of a third embodiment of the film forming apparatus according to the present invention. In the third embodiment, a pair of side walls 2c and 2d are opposed to the flow in the direction orthogonal to the flow downstream of the cylindrical heater 15 in the vaporization chamber 2 (in the direction of arrow D shown in the figure). The electrode 31 is disposed, a high frequency of, for example, 13.58 MHz is applied between the electrodes 31 to generate plasma, and plasma energy is applied to the source gas to release the source gas.

  With such a configuration, the thermal energy of the cylindrical heater 15 is caused to act on the fine droplets 8 to vaporize the particulate material contained therein, and plasma energy is added to the raw material gas thus obtained to release the gas, This is transported in the direction of arrow B shown in the figure and introduced into the reaction chamber 3. Thereby, the ratio of the released source gas in the reaction chamber 3 is increased, and the film formation efficiency can be improved. In FIG. 5, the atomization of the solution 5 is performed by driving the ultrasonic vibrator 6 provided in the raw material storage container 1 shown in FIG. 1 to emit ultrasonic waves into the solution 5 in the raw material storage container 1. However, the present invention is not limited to this, and the solution 5 may be sprayed using the spray nozzle 24 as shown in FIG.

  In the above description, the case where metal nanoparticles are used as the fine particle material of the solid substance has been described. However, the present invention is not limited to this, and any solid substance that can be generated as nanoparticles can be used.

It is explanatory drawing which shows schematic structure of 1st Embodiment of the film-forming apparatus by this invention in a cross section. It is sectional drawing which shows the other structural example of the raw material storage container of the said 1st Embodiment. It is explanatory drawing which shows the principal part of 2nd Embodiment of the film-forming apparatus by this invention in a cross section. It is sectional drawing which shows the other structural example of the spray chamber of the said 2nd Embodiment. It is explanatory drawing which shows the principal part of 3rd Embodiment of the film-forming apparatus by this invention in a cross section.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Raw material storage container 1a ... Bottom part 1b ... Side wall 1d ... Upper wall surface 2 ... Vaporization chamber 2a-2d ... Side wall 3 ... Reaction chamber 4 ... Vaporizer 5 ... Solution 5a ... Liquid surface 6 ... Ultrasonic vibrator 8 ... Droplet DESCRIPTION OF SYMBOLS 9 ... 1st transport pipe 12 ... 2nd transport pipe 15 ... Cylindrical heater (heating means)
16 ... Substrate 21a-21c, 30a-309d ... Extraction port 22 ... Supply pipe 23 ... Spraying chamber 23b ... Side wall 24 ... Injection nozzle 31 ... Electrode

Claims (14)

A solution in which a predetermined amount of a solid material of a solid material as a film forming raw material is mixed in a solvent is sprayed to be atomized,
Introducing the atomized fine droplets into a reduced-pressure vaporization chamber, adding thermal energy at a predetermined temperature to the fine particle material contained in the fine droplets to vaporize to generate a raw material gas,
Introducing the source gas into a reaction chamber and performing plasma treatment, and depositing a film of the solid substance on a substrate installed in the reaction chamber;
A film forming method characterized by the above.   The atomization of the solution is performed by radiating ultrasonic waves into the solution and utilizing an impact force at the time of generation and disappearance of a cavity generated in the solution. Membrane method.   The film forming method according to claim 1, wherein the atomization of the solution is performed by spraying the solution from a spray nozzle.   The film forming method according to claim 1, wherein plasma energy is applied to the generated source gas before being transported to a reaction chamber to release the source gas.   The film forming method according to claim 1, wherein the solid material particulate material is a metal nanoparticle material. A raw material storage container for storing a solution obtained by mixing a predetermined amount of a solid material fine particle material used as a film forming raw material in a solvent and spraying the solution into a mist,
The fine particle material that is formed so that the inside can be decompressed, introduces the atomized fine droplets transported from the raw material storage container via the first transport pipe, and is contained in the fine droplets A vaporizing chamber for generating a raw material gas by adding heat energy at a predetermined temperature to the gas by heating means;
A reaction chamber for plasma-treating the source gas introduced from the vaporization chamber via a second transport pipe and depositing a film of the solid material on a substrate installed inside;
A film forming apparatus comprising: A raw material storage container for storing a solution obtained by mixing a predetermined amount of a solid material particulate material as a film forming raw material in a solvent;
An injection nozzle for injecting the solution supplied from the raw material storage container through a supply pipe into a spray chamber to form fine droplets;
The inside of the spray chamber is formed so that the pressure can be reduced, and the atomized fine droplets transported from the spray chamber through the first transport pipe are introduced, and the fine particle material contained in the fine droplets is introduced. A vaporizing chamber for generating a raw material gas by adding heat energy at a predetermined temperature by a heating means to vaporize;
A reaction chamber for plasma-treating the source gas introduced from the vaporization chamber via a second transport pipe and depositing a film of the solid material on a substrate installed inside;
A film forming apparatus comprising: A raw material storage container for storing a solution obtained by mixing a predetermined amount of a solid material fine particle material used as a film forming raw material in a solvent and spraying the solution into a mist,
The fine particle material that is formed so that the inside can be decompressed, introduces the atomized fine droplets transported from the raw material storage container via the first transport pipe, and is contained in the fine droplets A vaporizing chamber for generating a raw material gas by adding heat energy at a predetermined temperature to the gas by heating means;
A vaporizer characterized by comprising.   The raw material storage container includes an ultrasonic vibrator on a bottom surface thereof, radiates ultrasonic waves generated by driving the ultrasonic vibrator into the solution, and generates and disappears cavities generated in the solution. The vaporizing apparatus according to claim 8, wherein the solution is atomized by using an impact force of the liquid.   The raw material storage container is provided with a plurality of outlets arranged vertically in the side wall portion between the liquid level and the upper wall surface of the solution stored therein, and one of them is connected to the first transport pipe. The vaporizer according to claim 8 or 9, characterized by the above. A raw material storage container for storing a solution obtained by mixing a predetermined amount of a solid material particulate material as a film forming raw material in a solvent;
An injection nozzle for injecting the solution supplied from the raw material storage container through a supply pipe into a spray chamber to form fine droplets;
The inside of the spray chamber is formed so that the pressure can be reduced, and the atomized fine droplets transported from the spray chamber through the first transport pipe are introduced, and the fine particle material contained in the fine droplets is introduced. A vaporizing chamber for generating a raw material gas by adding heat energy at a predetermined temperature by a heating means to vaporize;
A vaporizer characterized by comprising.   The vaporizer according to claim 11, wherein the spray chamber is provided with a plurality of outlets arranged in a vertical direction on a side wall, one of which is connected to the first transport pipe.   The said vaporization chamber has arrange | positioned a pair of electrode facing the orthogonal | vertical direction with respect to the flow in the downstream of the source gas rather than the said heating means. The vaporizer described in 1. The vaporizer according to any one of claims 8 to 13, wherein the solid material particulate material is a metal nanoparticle material.

Images