WO2008026242A1

WO2008026242A1 - Cvd apparatus and method for thin film formation using the same

Info

Publication number: WO2008026242A1
Application number: PCT/JP2006/316885
Authority: WO
Inventors: Hisayoshi Yamoto; Masashi Tanaka; Tomoyuki Araki
Original assignee: Youtec Co., Ltd.
Priority date: 2006-08-28
Filing date: 2006-08-28
Publication date: 2008-03-06
Also published as: TW200817531A; JPWO2008026242A1

Abstract

This invention provides a CVD apparatus, which can solve all of problems raised by adopting vapor deposition or sputtering and further can efficiently form a thin film on both sides of a member to be film-deposited without waste of time, and a method for thin film formation using the CVD apparatus. A CVD apparatus (1) comprises a reaction chamber (2), a CVD part (4) for supplying a starting material gas into the reaction chamber (2), and exhaust means (3) for discharging gas within the reaction chamber (2). The reaction chamber (2) comprises a travel path (R) through which a tape (16) to be film-deposited is traveled from a first winding roller (17) to a second winding roller (18), and a double side film formation mechanism (19) for forming a thin film on both sides of the tape (16) being traveled along the travel path (R).

Description

Specification

CVD apparatus and thin film forming method using the same

Technical field

TECHNICAL FIELD [0001] The present invention relates to a CVD apparatus and a thin film forming method using the same, and more particularly to a CVD apparatus for efficiently forming a thin film on a film-forming tape and a thin film forming method using the same.

[0002] Holographic recording and playback technology, which is said to be the ultimate optical memory, is, for example, NIKKEI EL

ECTRONICS 2005. 1.17 “Holographic media near take-off f¾ 2006 [Realizing this 200G noise”, pages 105-114, etc.

[0003] By the way, it is no exaggeration to say that the key to the practical use is based on whether or not it is possible to achieve a low production cost for recording and reproducing media such as optical disks.

That is, a wavelength selective film is indispensable for the recording / reproducing medium of the holographic recording / reproducing technology. For example, the silicon oxide film SiO and the niobium oxide film Nb are used as the wavelength selective film.

twenty two

O (or tantalum oxide film) are alternately laminated, and the number of layers is, for example, 5 to: L00

Five

Become a layer.

[0005] Conventionally, the film has generally been formed by vapor deposition or sputtering.

Non-Patent Document 1: NIKKEI ELECTRONICS 2005. 1.17 “Holographic Media Near Takeoff Realized 200GB in 2006” pages 105-114

Disclosure of the invention

Problems to be solved by the invention

[0006] Incidentally, when a multilayer film is formed by a vapor deposition method or a sputtering method, there are the following problems.

[0007] First, according to the vapor deposition method or the sputtering method, there is a problem that an oxide is deposited on the reaction chamber wall and peels off and adheres to the product.

[0008] Secondly, according to the vapor deposition method or the sputtering method, the film is formed at a high vacuum, a low !, and a deposition temperature, so that an oxide thin film having different physical properties due to insufficient oxygen compared to the stoichiometry. Formed If the characteristics as designed easily are not obtained, problems will easily occur!

[0009] Thirdly, according to the vapor deposition method or the sputtering method, the deposition rate is remarkably lower than that by the CVD method, so that there is a tendency that the productivity is low and it is difficult to reduce the production cost.

[0010] The recording / reproducing medium requires various films in addition to the wavelength selection film, but only for forming the wavelength selection film, a silicon oxide film and a niobium oxide film or Tantalum oxide films need to be stacked alternately, and the number of stacking steps is 5 to 1 000 times (for example, 20 times), which is a major factor that hinders manufacturing cost reduction.

[0011] When a silicon oxide film is formed, for example, a niobium oxide film is then formed, and then a silicon oxide film is formed, and then the niobium oxide film is formed. Repeating film formation 10 times is because it takes time to switch the thin film to be formed.

[0012] For example, when a film forming apparatus is switched each time the film to be formed is changed, such as forming a silicon oxide film with one CVD apparatus and forming a niobium oxide film with another CVD apparatus, This is a great waste of time.

[0013] Furthermore, in order to form a multilayer film on both surfaces of a film forming member, it is necessary to form a film again by turning the film forming member upside down after forming one surface. Therefore, the film formation time is at least twice as large as that of the single-sided case, and time waste becomes significant.

[0014] The present invention has been made to solve such problems, solves all of the above-mentioned problems caused by vapor deposition and sputtering, and further wastes time. Accordingly, it is an object of the present invention to provide a CVD apparatus capable of efficiently forming a thin film on both surfaces of a film forming member and a thin film forming method using the CVD apparatus.

Means for solving the problem

[0015] In order to solve the above-described problem, the invention according to claim 1 includes a reaction chamber, a CVD unit that supplies a source gas into the reaction chamber, and an exhaust unit that exhausts the gas in the reaction chamber. In the apparatus, in the reaction chamber, the film forming tape includes a travel path leading to the first scraping roller force and the second scraping roller, and the CVD unit, and travels in one direction along the travel path. A double-sided film forming mechanism that forms a thin film on both sides of the film-deposited tape is provided. [0016] In the invention according to claim 2, the double-sided film-forming mechanism includes a first film-forming mechanism that forms a thin film on one surface of the film-forming tape, and a thin film on the other surface of the film-forming tape. And a reversing means for reversing the front and back of the film-forming tape in a travel path between the first film-forming mechanism and the second film-forming mechanism. Features.

[0017] Further, the invention according to claim 3 is characterized in that the CVD unit includes the orifice tube that disperses the raw material solution in a fine particle shape or a mist shape in a carrier gas, and the raw material solution that is communicated with the gas passage of the orifice tube. A raw material solution passage for supplying gas, a carrier gas flow path for supplying the carrier gas to the orifice pipe, a vaporization pipe for vaporizing the raw material solution dispersed in the orifice pipe, and the gas passage inserted into the vaporization pipe It has the pore which ejects the gas of an orifice pipe | tube, and the heating means which heats the said vaporization pipe | tube.

[0018] Further, the invention according to claim 4 is characterized in that the CVD unit includes RF plasma generating means for forming plasma by applying an RF voltage in the reaction chamber, and the adjacent CVD unit is disposed in the reaction chamber. It is characterized by providing isolation members that are separated from each other.

[0019] The invention according to claim 5 is characterized in that the first scraping roller and the second scraping roller can rotate in both forward and reverse directions.

[0020] The invention according to claim 6 includes an exhaust step of exhausting the gas in the reaction chamber by an exhaust means, a source gas supply step of supplying a source gas to the reaction chamber, and a cover in the reaction chamber. A film forming step including a film forming step for forming a thin film on the film forming tape, wherein the film forming step includes a traveling path from the film forming tape to the first scraping roller force and the first scraping roller force. And a double-sided film-forming step of forming a thin film on both surfaces of the film-forming tape that travels in one direction along the traveling path.

[0021] In the invention according to claim 7, the double-sided film-forming step includes a first film-forming step of forming a thin film on one surface of the film-forming tape by a first film-forming mechanism; A second film-forming step of forming a thin film on the other surface of the film-forming tape by a film mechanism; and the film-forming film in a travel path between the first film-forming mechanism and the second film-forming mechanism. And a reversing step for reversing the front and back of the tape.

[0022] In the invention according to claim 8, the carrier gas pipe force supplies the carrier gas to the orifice pipe. Carrier gas supply step, a raw material solution supply step for supplying the raw material solution from the raw material solution passage to the orifice pipe, and the raw material solution is dispersed in the carrier gas in the form of fine particles or mist by the orifice pipe. A vaporization pipe supply step for supplying to a vaporization pipe provided at an outlet of the orifice pipe, and a vaporization step for heating and vaporizing the raw material solution by a heating means of the vaporization pipe in the vaporization pipe. It is characterized by.

[0023] The invention according to claim 9 is characterized in that it includes an RF plasma generation step of generating RF plasma in the reaction chamber to form a thin film.

[0024] The invention according to claim 10 includes a thin film forming step of forming the thin film by running the film-forming tape in both forward and reverse directions.

The invention's effect

[0025] According to the inventions according to claims 1 and 6, since the double-sided film forming mechanism is provided, a thin film can be formed on both surfaces of the film-forming tape traveling in one direction. A thin film can be efficiently formed on both sides of the film-deposited tape without any waste.

[0026] According to the inventions according to Claims 2 and 7, since the front and back of the film-forming tape are reversed in the travel path between the first film-forming mechanism and the second film-forming mechanism, it is more reliable. The efficiency can be improved.

[0027] According to the inventions according to claims 3 and 8, various raw material solutions can be dispersed in the form of fine particles or mist in the carrier gas while simplifying the structure of the vaporizer for CVD. Since clogging is less likely to occur, the flow rate of the raw material solution can be accurately controlled over a long period of time.

[0028] According to the inventions according to claims 4 and 9, since the film forming temperature can be lowered, a thin film can be easily formed even on a film forming tape having a low heat resistance temperature.

[0029] According to the inventions according to claims 5 and 10, a multilayer film having an arbitrary laminated structure can be formed.

Brief Description of Drawings

FIG. 1 is a diagram showing an overall configuration of a CVD apparatus according to a first embodiment of the present invention.

FIG. 2 is a diagram showing a configuration of a reaction chamber according to the first embodiment of the present invention.

FIG. 3 is a diagram showing a configuration of a CVD vaporizer according to the first embodiment of the present invention. FIG. 4 is a diagram showing a configuration of a gas shower electrode according to the first embodiment of the present invention.

FIG. 5 is a diagram showing a configuration of a reaction chamber according to a second embodiment of the present invention.

FIG. 6 is a diagram showing a configuration of a reaction chamber according to a third embodiment of the present invention.

FIG. 7 is a diagram showing a configuration of a reaction chamber according to a fourth embodiment of the present invention.

FIG. 8 is a view showing a configuration of a CVD vaporizer according to a fifth embodiment of the present invention.

FIG. 9 shows TG-DTA chart of trisdimethylaminosilane in 760 Torr argon atmosphere.

FIG. 10 shows the results of measuring the vapor pressure characteristics of trisdimethylaminosilane with respect to temperature.

[Fig. 11] Shows the results of measuring the vapor pressure characteristics of hexamethyldisilazane with respect to temperature.

BEST MODE FOR CARRYING OUT THE INVENTION

In the present invention, the best example of the multilayer film to be formed is a diffusion prevention film (usually a silicon nitride film) formed on a PET resin film-deposited tape for a flexible organic EL display. is there.

In addition, the film formation tape is, for example, a plastic (material PET) having a length of 5000 m and a width of 0.3 m, and necessary thin films including the above-described wavelength selection film are formed on both surfaces of the film formation tape. Then, by punching, a large number of media discs of a size according to the standard are obtained.

[0033] The CVD unit of the CVD apparatus may be one in which a normal CVD method is performed, but one having a vaporizing tube for vaporizing a liquid compound or a solid compound having a boiling point of about 25 ° C or higher. Is preferred. Specifically, a solution obtained by dissolving a solid in a solvent, proposed in Japanese Patent Application No. 2004-290087, is vaporized (gasified) by a vaporizer and used as a gas for forming a thin film to form a thin film. You may make full use of technology. In the examples described later, CVD technology using a vaporizer is also used. The details of the vaporization mechanism using this vaporizer will be described later.

[0034] Each CVD unit may perform plasma CVD by forming a plasma by applying an RF (Radio Frequency) voltage between the RF electrode and the film forming roller. In particular, the film deposition table When the heat resistance of the film is low, a multilayer film can be formed at a relatively low temperature by performing plasma CVD, so that the heat resistance required for the film-forming tape is low.

[0035] Incidentally, in that case, there is an embodiment in which an RF power source is provided for each CVD unit. When such a configuration is adopted, a plurality of RF power sources are provided relatively close to each other. May cause interference between other RF power supplies. Therefore, in order to eliminate this possibility, the power and phase may be shifted from each other when the frequencies of the multiple RF power supplies are changed from each other.

[0036] Further, a gas for forming a thin film may be supplied vertically to a film formation area like a shower and supplied with a large number of ejection hole forces (shower method). By doing so, it is possible to easily obtain a multilayer film having a uniform and uniform thickness over the entire surface of the tape.

[0037] Furthermore, it is possible to use a shower plate method and a plasma method together, in which a gas for forming a CVD is supplied to the film formation area like a shower and plasma is formed. In the embodiments described later, this is used together.

[0038] In addition, the number of CVD units provided in one CVD apparatus is not necessarily limited to the force to explain the case of two in the embodiment described later. For example, five or ten, and the like. If you have many, you can make it a number.

[0039] Control and management of CVD temperature is extremely important for the formation of thin films. In order to improve the temperature controllability and controllability, the film forming roller is used with a heat medium (for example, oil). The temperature may be controlled to several tens of degrees Celsius (for example, 50 degrees Celsius or 60 degrees Celsius).

(1) First embodiment

(1—1) Overall configuration

A CVD apparatus 1 shown in FIG. 1 includes a reaction chamber 2, an exhaust means 3, and a plurality of CVD sections 4 (4a, 4b). As a whole, the gas in the reaction chamber 2 is exhausted by the exhaust means 3, and the CVD section 4 The raw material gas generated by vaporizing the raw material solution is introduced into the reaction chamber 2 so that a thin film can be formed on the film formation member V in the reaction chamber 2! RU

[0040] The exhaust means 3 is provided in the main vacuum pipe 6 communicated with the reaction chamber 2 through the vacuum exhaust port 5, the vacuum pipe 8 connecting the main vacuum pipe 6 and the exhaust vacuum pump 7, and the vacuum pipe 8 It consists of a water-cooled trap 9 and a vacuum valve 10. Further, N 2 is introduced into the reaction chamber 2 through the gas supply pipe 11. Gas

2 Configured to be supplied.

[0041] As shown in FIG. 2, the reaction chamber 2 includes a sealed reaction chamber main body 15 and a film forming tape 16 that is a film forming member from the first scraping roller 17 to the second scraping roller 17 A thin film is formed on both surfaces of the film-forming tape 16 while the film-forming tape 16 reaches the second scraping roller 18 from the first scraping roller 17 and the traveling path R to 18. A double-sided film forming mechanism 19 is provided, and a thin film can be efficiently formed on both sides of the film-forming tape 16.

(1 2) Structure of double-sided film formation mechanism

Next, the structure of the double-sided film-forming mechanism 19 that forms a thin film on both sides of the film-forming tape 16, which is a characteristic part of the present invention, will be described in detail with reference to FIG.

The double-sided film forming mechanism 19 includes a first film forming mechanism 21 that forms a thin film on one surface of the film-forming tape 16 and a second film forming mechanism that forms a thin film on the other surface of the film-forming tape 16. A film forming mechanism 22; and a guide roller 23 as a reversing means for reversing the front and back of the film forming tape 16 in the travel path R from the first film forming mechanism 21 to the second film forming mechanism 22. .

[0043] The first film formation mechanism 21 includes a first film formation roller 24 that winds the film formation tape 16, and a first CVD unit provided corresponding to the first film formation roller 24. 4a. The first CVD unit 4a is installed on the lower left side of the reaction chamber 2 so as to supply the source gas upward. On the other hand, the second film forming mechanism 22 includes a second film forming roller 25 for winding the film forming tape 16, and a second CVD unit 4b provided corresponding to the second film forming roller 25. With. The second CVD unit 4b is installed on the upper right side of the reaction chamber 2 so as to supply the raw material gas downward. The guide roller 23 guides the film formation tape 16 from the first film formation roller 24 to the second film formation roller 25 so that the front and back of the film formation tape 16 can be reversed. The guide roller 23 includes a first guide roller 23a disposed above the film forming rollers 24 and 25 and a second guide roller 23b disposed below the film forming rollers 24 and 25.

[0044] The first scraping roller 17 and the second scraper so that the film-forming tape 16 can be continuously supplied to the first deposition mechanism 21 and the second deposition mechanism 22. The roller 18, the first film forming roller 24, the second film forming roller 25, the guide roller 23, and the plurality of feed rollers 26 are installed in the reaction chamber 2, and the film forming tape 16 is the first scraping roller. A travel route R from 17 to the second scraping roller 18 is formed. [0045] The first scraping roller 17 and the second scraping roller 18 are respectively arranged below the left and right sides of the reaction chamber 2, and are connected to driving means (not shown) to drive the driving It is configured to be able to rotate in the positive direction by the driving force transmitted from the means (in the direction of the arrow in the figure). A first film forming roller 24 and a second film forming roller 25 are pivotally supported between the first scraping roller 17 and the second scraping roller 18. The first film formation roller 24 and the second film formation roller 25 are arranged on the same horizontal line. Further, a guide roller 23 is pivotally supported between the first film forming roller 24 and the second film forming roller 25. Further, a feeding roller 26 is pivotally supported between the first scraping roller 17 and the first deposition roller 24, and between the second deposition roller 25 and the second scraping roller 18, respectively. Te!

Note that reference numeral 27 denotes an isolation member that separates the first CVD unit 4a and the second CVD unit 4b from other CVD unit forces. The isolation member 27 is configured by standing a plate-like member on the inner wall of the reaction chamber 2 where the CVD units 4a and 4b are provided, with the first film forming roller 24 and the second film forming roller 25 interposed therebetween. Is done. The isolation member 27 covers the range of the inner wall force of the reaction chamber 2 up to the central axis of the film forming roller, and the tip is folded back inward. The reaction chamber 2 includes a vacuum exhaust port 5 on the inner side covered with the isolation member 27.

[0047] The film-forming tape 16 is guided at one end to the upper side in the reaction chamber 2 by the feed roller 26, and is wound around the first film-forming roller 24 counterclockwise. When wound around the first film-forming roller 24, the surface of the film-forming tape 16 exposed to the plasma generation region A formed between the first CVD unit 4a and the film-forming tape One side of 16.

[0048] The guide roller 23 avoids the separating member 27, and the second film is formed clockwise by the film-forming tape 16 wound around the first film forming roller 24 so as to draw an S-shape. Guide the roller 25 so that it can be wound. In other words, the film-forming tape 16 that has been delivered by the lower force of the first film-forming roller 24 is guided upward by the first guide roller 23a and then lowered by the second guide roller 23b. It is guided and wound around the second film forming roller 25 clockwise. As a result, the front and back of the film-forming tape 16 are reversed between the first film-forming roller 24 and the second film-forming roller 25, and the one surface wound by the first film-forming roller 24 is The other opposite surface is exposed to the plasma generation region A by the second film forming roller 25. The film-forming tape 16 is guided to the lower side of the reaction chamber 2 by the feed roller 26 and reaches the second scraping roller 18. [0049] As described above, the travel path R from the first scraping roller 17 to the second scraping roller 18 is formed. In the traveling path R from the first film forming roller 24 to the second film forming roller 25, the front and back are reversed, and the surface on which the first film forming roller 24 forms the film in the second film forming roller 25. A thin film is formed on the other surface. Further, the film-forming tape 16 is pressed against the film-forming rollers 24 and 25 by a guide roller 23 and a feed roller 26 with a predetermined force!

[0050] The film-forming tape 16 has, for example, a length force of OOOm and a width of 0.3m to 2m, and the material is a resin such as PET (polyethylene terephthalate), PEN (polyethylene naphthalate), polyimide, etc. Or metal power such as copper or aluminum.

(1 3) Structure of CVD section

The first CVD unit 4a and the second CVD unit 4b are capable of forming a thin film on the film forming tape 16 wound around the first film forming roller 24 and the second film forming roller 25, respectively. The first film forming roller 24 and the second film forming roller 25 are provided correspondingly. The first CVD unit 4a and the second CVD unit 4b are respectively provided between a CVD vaporizer 31 for supplying a raw material gas obtained by vaporizing a raw material solution into the reaction chamber 2 and the film forming rollers 24 and 25. A gas shower electrode 32 is provided as an RF plasma generating means for generating plasma in the plasma generation region A and forming a thin film on the film forming tape 16 wound around the film forming rollers 24 and 25.

[0051] The first CVD unit 4a is provided on the lower side of the reaction chamber 2 so that a gas shower electrode 32 faces the first film-forming roller 24 with a downward force. On the other hand, the second CVD unit 4b is provided on the upper side of the reaction chamber 2 so that the gas shower electrode 32 faces the second film forming roller 25 with an upward force.

[0052] In addition, the first CVD unit 4a and the second CVD unit 4b are configured so that film-forming conditions such as the type of raw material solution and temperature can be individually set. Each desired thin film can be formed in the CVD section. In addition, the CVD apparatus 1 can start or stop the film forming operation of each CVD unit individually while the film forming tape 16 is running. .

[0053] The first CVD unit 4a and the second CVD unit 4b have the same configuration except for the positions where they are installed in the reaction chamber 2. Therefore, hereinafter, the first CVD unit 4a and the second CVD unit 4b are the same. Part 4a explain.

The CVD gas vessel 31 introduces a raw material gas into the gas shower electrode 32 through the gas supply pipe 33, so that a large number of jetted loca is also showered on the first film forming roller 24 in the reaction chamber 2. In this way, the raw material gas can be supplied.

(1-3-1) Composition of vaporizer for CVD

As shown in FIG. 3, the CVD vaporizer 31 includes a vaporization mechanism 41 and a raw material solution supply mechanism 42 provided in the vaporization mechanism 41, and the vaporization mechanism 41 is connected to the gas supply pipe 33 of the reaction chamber. It has been.

[0055] In the vaporization mechanism 41, a carrier gas flow path 43 for supplying a carrier gas such as nitrogen gas or argon to the reaction chamber 2 is formed by a carrier gas pipe 44 and an orifice pipe 45. A vaporization tube 47 is formed at the outlet 46) of the carrier gas channel 43.

The vaporization mechanism 41 includes a carrier gas supply mechanism (not shown) connected to the base end of the carrier gas pipe 44 (that is, the inlet of the carrier gas flow path 43), and a carrier gas supply mechanism (not shown). The distal end 48 of the gas pipe ₄₄ is connected to the proximal end 49 of the orifice pipe 45 so that the carrier gas pipe 44 can also supply a high-speed carrier gas to the orifice pipe 45.

[0057] Incidentally, between the proximal end of the carrier gas pipe 44 and the supply mechanism, there are an N supply valve and a mass flow.

2

A row controller (not shown) is provided. The carrier gas pipe 44 has a pressure transducer 50 attached!

It should be noted that the pressure transducer 50 accurately measures the carrier gas pressure in the carrier gas pipe 44 and its fluctuation and constantly monitors it while recording it. The pressure transducer 50 transmits an output signal having a signal level corresponding to the pressure level of the carrier gas to a control unit (not shown).

In this way, the pressure result of the carrier gas can be displayed on the display unit (not shown) based on the output signal so that the operator can monitor it. Thus, the operator can monitor the clogging of the carrier gas channel 43 based on the pressure result.

Here, the carrier gas pipe 44 is selected so that the inner diameter thereof is larger than the inner diameter of the orifice pipe 45, and the carrier gas pipe 44 force is configured to further increase the flow velocity of the carrier gas supplied to the orifice pipe 45. ing. [0061] The orifice tube 45 is arranged in a vertical direction, and a tip portion 46 having a trapezoidal conical shape is provided at the tip 46, and a pore 52 is provided at the top of the convex portion 51. . Thus, in the orifice tube 45, the inclined surface 51a is formed around the outer periphery of the spray port 53, which is the tip of the pore 52, by providing the convex portion 51 at the tip. This makes it difficult for the residue to collect in the spray port 53, and prevents the spray port 53 from being clogged!

Incidentally, in the case of this embodiment, it is preferable that the apex angle Θ of the convex portion 51 is formed at an acute angle of 45 ° to 135 °, particularly 30 ° to 45 °. This prevents the spray port 53 from being clogged with the compound.

[0063] The pore 52 of the spray port 53 is selected so that its inner diameter is smaller than the inner diameter of the orifice tube 45, whereby the pressure of the carrier gas in the orifice tube 45 is increased. Here, the tip of the pore 52 is arranged so as to protrude into the internal space 55 of the vaporization tube 47 by inserting the convex portion 51 of the orifice tube 45 into the proximal end 54 of the vaporization tube 47.

[0064] In connection with the powerful configuration, the orifice pipe 45 has a plurality of (in this case, for example, five) connecting pipes 56a to 56e communicating with each other from the base end 49 to the convex portion 51. Each of the connection pipes 56a to 56e is provided with a raw material solution supply mechanism 42. Thereby, the orifice pipe 45 is configured such that a predetermined raw material solution can be supplied from the raw material solution supply mechanism 42 via the connecting pipes 56a to 56e. In the raw material solution supply mechanism 42, a raw material solution stored in a raw material solution tank (not shown) is routed through a predetermined raw material solution flow path 58, whereby a liquid mass flow controller (LMFC) 57, a block valve are provided. It is configured to supply the orifice pipe 45 through 59 in order. The liquid mass flow controller 57 controls the flow rate of the raw material solution flowing through the raw material solution channel 58.

In this case, in the orifice tube 45, for example, the carrier gas flowing at high speed joins the raw material solution supplied from the connection tube 56a, and the raw material solution is dispersed in the carrier gas in the form of fine particles or mist. Then, it is sprayed at a high speed (230 mZ seconds to 350 mZ seconds) into the vaporization tube 47 through the pores 52.

[0066] In the case of this embodiment, the orifice tube 45 is selected to have an inner diameter of, for example, Φ 1. Omm or less, and the length in the longitudinal direction extending in the vertical direction is selected to be about 100 mm. Thus, a cylindrical gas passage is formed. Furthermore, the inner diameter of the pore 52 is Φ Ο. 2 ~ 0.7 It is selected to be about mm, and the carrier gas inside it can be made high-speed. As described above, since the orifice pipe 45 includes the cylindrical gas passage, the raw material solution can be stably dispersed in the carrier gas and supplied to the vaporization pipe 47.

Here, the vaporization pipe 47 connected to the orifice pipe 45 is tubular and is arranged in the vertical direction in the same manner as the orifice pipe 45, and its inner diameter is selected to be significantly larger than the inner diameter of the orifice pipe 45. Therefore, the pressure in the vaporization pipe 47 is formed to be smaller than the pressure in the orifice pipe 45.

As described above, the vaporizing pipe 47 is provided with a large pressure difference between the orifice pipe 45 and the orifice pipe 45 due to the provision of the pores 52. As a result, the raw material solution and the carrier gas are ejected from the pores 52 at a high speed (for example, 230 mZ seconds to 350 mZ seconds) and can be expanded in the internal space.

[0069] In the case of this embodiment, the pressure in the vaporization pipe 47 is selected to be about lOTorr, for example, whereas the pressure in the orifice pipe 45 is selected to be about 500 to 1000 Torr, for example. A large pressure difference is provided between the orifice tube 45.

[0070] Incidentally, the pressure of the carrier gas after the flow rate control is a force that increases or decreases depending on the carrier gas flow rate, the solution flow rate, and the size of the pore 52. Finally, the size of the spray port 53 is selected and the pressure of the carrier gas is increased. It is preferable to control to 500 to 1000 Torr.

[0071] In addition, a vaporization tube heater 60 as a heating means is attached to the outer periphery of the vaporization tube 47 between the base end 54 and the distal end (that is, the connection portion with the reaction chamber). The vaporizing tube 47 can be heated to, for example, about 270 ° C. by the tube heater 60. In the case of this embodiment, the base end 54 of the vaporization tube 47 is formed in a substantially hemispherical shape so that the vaporization tube heater 60 can uniformly heat the base end 54 side. Has been made.

[0072] In the vaporization tube 47, the raw material solution dispersed and atomized by the high-speed carrier gas flow in the orifice tube 45 is instantaneously heated by the vaporization tube heater 60 and vaporized instantaneously. It is configured. At this time, the time from when the raw material solution is mixed in the orifice tube 45 until it is sprayed into the vaporization tube 47 is preferably extremely short (preferably within 0.1 to 0.002 seconds). . The raw material solution is injected into the orifice by a high-speed carrier gas flow. Immediately after being dispersed in the tube 45, it becomes fine and instantly vaporizes in the high-temperature vaporizing tube 47. In addition, the phenomenon of vaporizing only the solvent is suppressed.

[0073] By spraying the raw material solution and the carrier gas onto the vaporization tube 47 at a high speed, the mist size is reduced (the mist diameter is 1 IX m or less), and the evaporation area and the evaporation rate are increased. Can. If the fog size is reduced by an order of magnitude, the evaporation area will increase by an order of magnitude. It is preferable to design the angle of the spraying port 53 and the dimensions of the vaporizing tube 47 so that the mist ejected from the spraying port 53 does not collide with the inner wall of the vaporizing tube 47. This is because when the mist collides with the inner wall of the vaporization tube 47, it adheres to the wall surface, the evaporation area decreases by an order of magnitude, and the evaporation rate decreases. In addition, if the mist is attached to the wall of the vaporization tube 47 for a long time, there is an example in which it changes into a compound that does not evaporate due to thermal decomposition.

[0074] Further, in this case, the vaporization tube 47 can reduce the sublimation temperature of the raw material mixture contained in each of the raw material solutions by reducing the pressure inside, and as a result, the vaporization tube can be added. The heat from the heat heater 60 can easily vaporize the raw material solution!

In this way, the vaporizing tube 47 vaporizes the raw material solution, supplies it to the reaction chamber 2 as a raw material gas as a thin film forming gas, and can form a thin film by the CVD method in this reaction chamber 2 It is made like that.

It should be noted that the proximal end 54 of the vaporization pipe 47 has a heat insulating material 61 between the vaporization pipe 47 and the heat insulation material 61 so that heat from the vaporization pipe 47 is hardly transmitted to the orifice pipe 45. It is composed! Incidentally, the proximal end 54 of the vaporizing tube 47 is hermetically sealed by an O-ring 62. The fastening member 63 that connects the orifice pipe 45 and the vaporization pipe 47 is provided with a heat insulating material 64.

Incidentally, it is preferable that the mist sprayed from the pores 52 does not wet the inner wall of the vaporizing tube 47.

The reason is that the evaporation area is reduced by orders of magnitude on wet walls compared to fog. That is, a structure in which the inner wall of the vaporizing tube 47 is not soiled at all is preferable. In addition, the wall of the vaporization tube 47 is preferably mirror-finished so that the dirt on the inner wall of the vaporization tube 47 can be easily evaluated.

[0078] In the above configuration, in the CVD unit, the raw material solution is supplied into the carrier gas flow that always flows at high speed toward the reaction chamber 2 in the orifice tube 45, so that the raw material solution is in the form of fine particles or mist. Then, it is dispersed in a carrier gas and vaporized in the vaporization tube 47 as it is and supplied to the reaction chamber 2 as a raw material gas. In this way, the vaporization mechanism 41 instantaneously atomizes the raw material solution by the high-speed carrier gas flow so that the raw material solution can be easily vaporized by the heat of the vaporizing tube heater 60. Because it is difficult to vaporize, it is easy to vaporize even a raw material solution obtained by dissolving a raw material compound in a solvent.

In the vaporization mechanism 41, the carrier gas pressurized in the carrier gas pipe 44 is introduced into the orifice pipe 45 at high speed (for example, the carrier gas is 500 to 1000 Torr, 200 ml Zmin to 2 LZmin). The temperature rise of the raw material solution can be suppressed.

Therefore, in this vaporization mechanism 41, it is possible to prevent only the solvent in the raw material solution from evaporating in the orifice tube 45, so that it is possible to prevent the raw material solution from being highly concentrated in the orifice tube 45, and to force As a result, an increase in viscosity can be suppressed and precipitation of the raw material compound can be prevented.

[0082] Furthermore, in the vaporization mechanism 41, since the raw material solution dispersed in the carrier gas can be instantaneously vaporized by the vaporization tube 47, only the solvent in the raw material solution vaporizes in the pore 52 and in the vicinity of the pore 52. Therefore, clogging of the pores 52 can be suppressed. The continuous use time of the vaporizer for CVD 31 can be increased.

(1-3-2) Configuration of gas shower electrode

As shown in FIG. 4, the gas shower electrode 32 has one end of an RF power supply 71 electrically connected thereto. The other end of the RF power source 71 is grounded, and the film forming rollers 24 and 25 are grounded. As a result, a plasma generation region A in which plasma discharge occurs is formed between the portion of the first film formation roller 24 (second film formation roller 25) on the film formation tape 16 and the gas shower electrode 32.

[0083] 72 is a bottom plate of the reaction chamber 2, 73 is a shield electrode that forms the outermost shell portion of the gas shower electrode 32, and 74 is an RF electrode that is formed inside the shield electrode 73 and insulated from it. Further, one end of the RF power source 71 is electrically connected. A gas supply pipe 33 for supplying the gas from the vaporization pipe 47 into the reaction chamber 2 is provided inside the RF electrode 74 so that a supply space 75 for oxidizing gas etc. is formed therebetween. Speak. Reference numeral 76 denotes an oxidizing gas supply pipe for supplying an oxidizing gas or the like to the supply space 75 for the acid gas. [0084] A gas shower plate 77 provided substantially horizontally so that a space 78 is formed between the lower side of the RF electrode 74 was supplied from the gas supply pipe 33 into the space 78. Vaporized material injection holes (outlet holes) for jetting gas (vaporized raw material) downward 79, 79, ..., and the above-mentioned acid gas supplied space 75, etc. 80, 80, ... are arranged in the lower side, and the vaporized raw material reacts with the oxygen gas in the space 78. In this case, the film is supplied onto the film forming tape 16 on the first film forming roller 24 through paths separated from each other.

[0085] 81 is a heater provided in the RF electrode 74, 82 is a heater power source for supplying power to the heater 81, and 83 is a noise cut filter. Reference numeral 84 denotes a vaporized raw material supply valve.

(1 4) Actions and effects

Next, the operation and effect of the CVD apparatus 1 will be described.

[0086] The CVD apparatus 1 causes the film-forming tape 16 to move in the forward direction along the travel path R formed in the reaction chamber 2 by the rotation of the first scraping roller 17 and the second scraping roller 18. Let it run. The CVD apparatus 1 is provided with a guide roller 23 and configured to reverse the front and back between the first film formation roller 24 and the second film formation roller 25 while the film formation tape 16 is running. did. As a result, in the CVD apparatus 1, a thin film can be formed on the front and back surfaces of the film-forming tape 16 while the film-forming tape 16 is traveling in the forward direction. Thin films can be formed on both sides of the tape 16.

In addition, the CVD apparatus 1 includes an orifice tube 45 in which the CVD gas vessel 31 sprays the vaporizing tube 47 against the carrier gas flowing the raw material solution at a high speed. A thin film can be formed even with downward force. Therefore, in the CVD apparatus 1, the first CVD unit 4 a installed on the lower surface of the reaction chamber 2 reliably forms a thin film on one surface of the film-forming tape 16, so the second CVD unit 4 b By forming a thin film on the surface, the thin film can be reliably formed on both surfaces of the film-forming tape 16.

[0088] Further, the CVD apparatus 1 is configured such that the first and second CVD units 4a and 4b can individually set various CVD conditions, and the thin film to be formed can also be set individually. In addition, it is possible to individually control the film forming operation or stop the film forming operation. It is.

Accordingly, it is possible to form the first thin film in the first CVD unit 4a and the second thin film in the second CVD unit 4b. Furthermore, the first and second CVD portions 4a and 4b can be made to form a similar thin film.

Further, the CVD apparatus 1 may be configured such that the first scraping roller 17 and the second scraping roller 18 can rotate both forward and backward. That is, the film-forming tape 16 is moved from the first scraping roller 17 to the first scraping roller 17 along the travel path R by the first and second scraping rollers 17 and 18 rotating in both forward and reverse directions. It can travel in the direction of the force (forward direction) to the second scraping roller 18, or conversely, it can travel in the direction of direction (reverse direction) from the second scraping roller 18 to the first scraping roller 17. As a result, the front and back surfaces of the film-forming tape 16 are also reversed when reaching the first scraping roller 17 from the second scraping roller 18. Therefore, by setting the film forming conditions of the first CVD unit 4a and the second CVD unit 4b individually, it is possible to form a multilayer film having an arbitrary laminated structural force.

[0091] In addition, the CVD apparatus 1 provides the first CVD unit 4a and the second CVD unit 4b to another CVD by providing the isolation member 27 in the first CVD unit 4a and the second CVD unit 4b. Can be isolated from the department. Thereby, since one CVD part can form a thin film in the film-forming tape 16 without being influenced by the other CVD part, the quality of the formed thin film can be improved. Further, the CVD apparatus 1 can more reliably prevent the source gas from flowing out by folding the tip of the separating member 27 inward.

In addition, the CVD apparatus 1 is configured to smoothly exhaust the treated gas by forming the vacuum exhaust port 5 in the portion covered with the isolation member 27. Therefore, the CVD apparatus 1 can prevent the treated gas from flowing out of the reaction chamber 2 beyond the isolation member 27. Thus, the CVD apparatus 1 is formed because the first CVD unit 4a and the second CVD unit 4b can form a thin film on the film forming tape 16 without being affected by other CVD units. The quality of the thin film can be further improved.

[0093] Further, the CVD apparatus 1 is provided with a gas-sharing electrode 32 in each of the first CVD unit 4a and the second CVD unit 4b, so that the entire surface of the film-forming tape 16 is uniform and uniform in thickness. A thin film can be formed. [0094] Further, the CVD apparatus 1 can easily suppress the temperature change of the inner wall of the reaction chamber 2.

4 By plasma cleaning, the thin film attached to the inner wall of the reaction chamber 2 can be removed by etching, so that a thin film with less dust can be formed. If a thin film of an inorganic material such as SiN, SiOx, Si, C, or DLC is formed, the thin film adhering to the reaction chamber 2 may be peeled off immediately after deposition by sputtering or sputtering. However, according to the CVD apparatus 1 of the present invention, since the thin film is formed by the CVD method, the quality can be improved.

(2) Second embodiment

In FIG. 5, in which parts corresponding to those in FIG. 1 are assigned the same reference numerals, the CVD apparatus 101 is different from the first embodiment described above in that the first CVD unit 4a and the second CVD unit 4b are reaction chambers. It differs in that it is provided so as to face the two side surfaces.

[0095] The first film forming roller 24 is disposed on the left side of the reaction chamber 2, and the second film forming roller 25 is disposed on the right side of the reaction chamber 2, and is supported on the same horizontal line. The first scraping roller 17 is provided on the left side of the reaction chamber 2 and on the right side of the first film forming roller 24. The second scraping roller 18 is disposed on the lower right side in the reaction chamber 2. Therefore, the second film forming roller 25 is provided on the vertical axis. The first CVD unit 4a corresponds to the first film formation roller 24 and corresponds to the left side surface of the reaction chamber 2, and the second CVD unit 4b corresponds to the second film formation roller 25 and reacts. Each is provided on the right side of chamber 2.

The film-forming tape 16 hangs vertically downward from the first scraping roller 17 and is sent to the left at a right angle by the feed roller 26 and wound around the first film-forming roller 24 counterclockwise. Is done. The guide roller 23 guides the film forming tape 16 to which the lower force of the first film forming roller 24 is also sent to the upper side of the reaction chamber 2 so as to draw an S-shape, and the second film forming roller 25 Turn clockwise. As a result, the film-deposited tape 16 has one surface that is reversed by the first film-forming roller 24 between the first film-forming roller 24 and the second film-forming roller 25. The other side opposite to that appears in the plasma generation region A at the second film formation roller 25. The film forming tape 16 delivered from the second film forming roller 25 is guided leftward from the second film forming roller 25 by the feed roller 26 and reaches the second scraping roller 18.

[0097] As described above, the CVD apparatus 101 includes the first CVD unit 4a and the second CVD unit 4b in the reaction chamber 2. By providing on the side surface, the plasma generation region A can be formed on the side of the film forming rollers 24 and 25 in the first CVD unit 4a and the second CVD unit 4b. Thus, the CVD apparatus 101 can supply the source gas in the same horizontal direction in each plasma generation region A, so that the film forming conditions can be made uniform. Accordingly, a stable quality thin film can be formed in any plasma generation region A.

In addition, the CVD apparatus 101 includes the first CVD unit 4a and the second CVD unit 4b including the CVD vaporizer 31 and the gas shower electrode 32, so that the same as in the first embodiment described above. It is possible to obtain the effects of

(3) Third embodiment

In FIG. 6 in which the same reference numerals are assigned to the parts corresponding to FIG. 5, the CVD apparatus 111 is different from the second embodiment described above in that the first film-forming roller 24, the second film-forming roller 25, It is different in that it is provided in the vertical direction.

[0099] The first film formation roller 24 is disposed on the lower left side, and the second film formation roller 25 is disposed on the upper right side. The first scraping roller 17 is provided on the left side of the reaction chamber 2 and on the vertical axis of the first film-forming roller 24. The second scraping roller 18 is disposed in the reaction chamber 2. The lower right side is provided on the vertical axis of the second film forming roller 25.

[0100] The film-forming tape 16 is guided to the right of the reaction chamber 2 from the first scraping roller 17 at one end by the feed roller 26, and is wound counterclockwise by the first film-forming roller 24. . The guide roller 23 guides the film-forming tape 16 sent from the lower force of the first film-forming roller 24 vertically upward to the height of the second film-forming roller 25. The film forming tape 16 is wound around the second film forming roller 25 clockwise so as to draw an S-shape. The film-forming tape 16 to be delivered is fed to the inside of the reaction chamber 2 and then reaches the second scraping roller 18.

[0101] As described above, the CVD apparatus 111 reduces the height dimension of the reaction chamber 2 by providing the first film-forming roller 24 and the second film-forming roller 25 while being shifted upward and downward. Can do. Therefore, the CVD apparatus 111 sets the position where the scraping rollers 17 and 18, the film forming rollers 24 and 25, the feed roller 26, the guide roller 23, and the CVD units 4 a and 4 b are placed at a position where the lower force of the reaction chamber 2 is low. be able to . As a result, the CVD apparatus 111 facilitates the installation and replacement of the film-forming tape 16. And can save space.

[0102] In addition, CVD apparatus 111 has the same effect as that of the second embodiment described above by providing first CVD section 4a and second CVD section 4b on the side surface of reaction chamber 2. Can do.

[0103] Furthermore, the CVD apparatus 111 includes the first CVD unit 4a and the second CVD unit 4b provided with a CVD vaporizer 31 and a gas shower electrode 32, so that the same as in the first embodiment described above. An effect can be obtained.

(4) Fourth embodiment

In FIG. 7 where the same reference numerals are assigned to the parts corresponding to FIG. 5, the CVD apparatus 121 is different from the second embodiment described above in that the first film forming roller 24, the second film forming roller 25, Are different in that they are arranged vertically.

[0104] The first film formation roller 24 is disposed on the upper side in the reaction chamber 2, and the second film formation roller 25 is disposed on the lower side in the reaction chamber 2. The membrane roller 25 is supported on the center axis in the reaction chamber 2. The first scraping roller 17 is provided on the left side in the reaction chamber 2, and the second scraping roller 18 is provided on the left side in the reaction chamber 2.

The film-forming tape 16 is guided at one end by the feed roller 26 from the first scraping roller 17 to the right side of the reaction chamber 2 and wound counterclockwise by the first film-forming roller 24. The guide roller 23 guides the film-forming tape sent from the first film-forming roller 24 so as to avoid the isolation member 27 and to be wound around the second film-forming roller 25 clockwise. The film forming tape 16 wound around the second film forming roller 25 from the upper side is guided to the left side of the reaction chamber 2 and then reaches the second picking roller 18.

As described above, the CVD apparatus 121 reduces the width dimension of the reaction chamber 2 by providing the first film-forming roller 24 and the second film-forming roller 25 in the vertical direction on the central axis. be able to. Therefore, the CVD apparatus 121 can be installed even when the place where the CVD apparatus 121 can be installed is narrow.

[0107] Further, CVD apparatus 121 has the same effects as those of the second embodiment described above by providing first CVD section 4a and second CVD section 4b on the side surface of reaction chamber 2. Can do.

Furthermore, the CVD apparatus 121 includes the first CVD unit 4a and the second CVD unit 4b, which are provided with a CVD vaporizer 31 and a gas shower electrode 32, so that the same as in the first embodiment described above. Effect It can be done.

(5) Fifth embodiment

In FIG. 8, which is described by attaching the same reference numerals to the parts corresponding to FIG. 3, the CVD vaporizer 131 always supplies the carrier gas to the reaction chamber 2 by the vaporization mechanism 132 and is supplied from the raw material solution supply mechanism 42. The raw material solution is configured to be surely vaporized by the vaporization mechanism 132 and supplied to the reaction chamber 2. In the raw material solution supply mechanism 42, the raw material solution stored in the raw material solution tank (not shown) is supplied to the raw material supply pipe 136 sequentially through the liquid mass flow controller (LMFC) 133, the raw material solution flow path 134, and the block valve 59. It is made to do.

[0109] Further, in the raw material solution supply mechanism 42 in addition to the cover structure, when the raw material solution is not supplied from the block valve 59 to the raw material supply pipe 136, the solvent stored in the solvent tank (not shown) Is supplied to the raw material supply pipe 136 via the liquid mass flow controller (L MFC) 138 and the block valve 59 by passing through a predetermined solvent flow path 137.

The vaporization mechanism 132 includes a vaporization mechanism main body 139, a carrier gas pipe 44, a raw material supply pipe 136, and a spray flange 142 having pores 141, and a vaporization pipe 47 is formed at the tip of the pore 141. The vaporizing mechanism 132 is configured such that the vaporizing mechanism main body 139 holds the raw material supply pipe 136 in the vertical direction and can supply a carrier gas to the outside near the tip of the raw material supply pipe 136. Thus, the raw material solution supplied from the raw material supply pipe 136 and the carrier gas supplied from the carrier gas pipe 44 can be mixed in the dispersion part 143 formed on the proximal end side of the pore 141. It is configured.

Incidentally, for example, the raw material supply pipe 136 has an inner diameter of about Φ 1. Omm and a length of about 100 mm.

[0112] The raw material solution supply mechanism 42 communicates with the proximal end of the raw material supply pipe 136 via the raw material solution flow path 134, thereby supplying the raw material solution to the distal end of the raw material supply pipe 136. It is structured to obtain.

[0113] The vaporization mechanism main body 139 forms a gap with the distal end portion of the raw material supply pipe 136, and is provided with a spray flange 142 on the distal end side of the raw material supply pipe 136 via a dispersion portion 143, and also with a carrier gas. An inlet 144 for connecting the tip 44a of the pipe 44 to the tip of the raw material supply pipe 136 is provided. In this way, the dispersion unit 143 is configured to join the raw material solution and the carrier gas so as to disperse the raw material solution in the carrier gas.

[0114] In the above-described configuration, in the CVD vaporizer 131, the raw material solution flowing in the vertical direction from the raw material supply pipe 136 and the carrier gas pipe 44 toward the front end of the raw material supply pipe 136 via the inlet 144 are provided. The carrier gas flowing in the dispersion is mixed in the dispersion part 143. As a result, the CVD vaporizer 131 makes the raw material solution into fine particles or mist, disperses it in the carrier gas, and introduces it into the vaporizer 47. Incidentally, it is preferably within 1 second (more preferably within 0.1 second) from when the raw material solution is mixed in the dispersion part 143 until it is sprayed in the form of a mist.

Next, the raw material solution dispersed in the carrier gas by the dispersion unit 143 passes through the pores 141 and is introduced into the vaporization tube 47. Here, since the pressure in the vaporization pipe 47 is much lower than that in the dispersion part 143, the raw material solution dispersed in the carrier gas is ejected into the vaporization pipe 47 at a high speed and expands. As a result, the sublimation temperature of the compound contained in the raw material solution is lowered, so that the raw material solution is vaporized by the heat of the vaporizing tube heater 60 and supplied to the reaction chamber 2 as a raw material gas.

In this way, in the CVD apparatus 1, the raw material solution can be supplied as a raw material gas into the reaction chamber 2, whereby the raw material gas is uniformly sprayed onto the film forming tape 16 and is covered by RF plasma. A predetermined thin film can be formed by causing a chemical reaction on the film forming tape 16. (6) Example 1

By using the CVD vaporizer 31 according to the first embodiment, a silicon nitride film can be formed from a compound containing silicon and nitrogen in the molecule. As an example of such a compound, trisdimethylaminosilane (hereinafter referred to as TDMAS) is shown in FIG. 1, and hexamethyldisilazane (hereinafter referred to as HMDS) is shown in Chemical Formula 2.

[0117] [Chemical 1]

CH ₃ ,

[0118] [Chemical 2] CH ₃ CH ₃

I I

H ₃ C— Si— N— Si- CH ₃

III CH ₃ H CH ₃

[0119] Fig. 9 shows the TG-DTA chart of TDMAS against temperature, that is, the results of thermogravimetric analysis (TG) and differential thermal analysis. The thermogravimetric analysis characteristics shown in Fig. 9A are data under a 760 Torr argon atmosphere. As is clear from this figure, a temperature of about 100 ° C is required to completely evaporate TDMAS!

[0120] Fig. 10 shows the change in vapor pressure with respect to the temperature of TDMAS, and Fig. 11 shows the change in vapor pressure with respect to the temperature of HMDS. This figure also confirms that TDMAS and HMDS have high vapor pressure and temperature dependence.

(7) Example 2

Table 1 shows the conditions when a silicon nitride film is formed by plasma CVD using TDMAS.

[0121] [Table 1]

Hydrogen introduction calculated at 1000 A in 5 minutes vaporization tube

Upper electrode 120 ° C Pressure 300Pa Evaporation tube temperature 120 ° C Raw material compound 0.2ccm (TDMAS) Others 120 ° C H2 1500sccm

N2 1500sccm

RF 1000w

[0122] Table 2 shows the results of measuring the thickness of the formed silicon nitride film. [0123] [Table 2]

[0124] It was found that the silicon nitride film can be formed at a deposition rate of about lOOnm / min. The composition of the silicon nitride film was Si: 34 at%, N: 7 at%, C: 34 at%, and 0: 25 at%. The high oxygen content is thought to be due to the lack of exhaust in the reaction chamber 2 before the thin film formation.

[0125] When a silicon nitride film is formed by decomposing a compound containing silicon and nitrogen in the molecule with plasma, TDMAS or HMDS can be used. However, since TDMAS and HMDS lack nitrogen, it is effective to set the RF plasma frequency to 13.56 MHz and use ammonia gas.

[0126] Further, by reacting the organic silicon compound with nitrogen gas and ammonia (NH 2),

Three

Alternatively, a silicon nitride film can be formed. In this case, organic silicon compounds include tetraethylsilane (hereinafter 4ES, melting point ≤0 ° C, boiling point 154 to 155 ° C), triethylsilane (hereinafter 3ES, boiling point 107 to 108 ° C), trimethylvinylsilane (hereinafter TMVS). Melting point ≤0 ° C, boiling point 55-57 ° C), phenol silane (hereinafter PhS, boiling point 119-121 ° C), diphenylsilane (hereinafter DPS, boiling point 113-114 ° C [9mmHg]), In either case, materials that are inexpensive and non-hazardous can be used.

[0127] However, when the frequency of the RF plasma is 50KHz to 380KHz, nitrogen gas cannot be decomposed sufficiently. • Since it cannot be radicalized, even if TDMAS, 4ES, 3ES, TMVS, PhS and nitrogen gas are reacted, The formed thin film does not contain sufficient nitrogen.

On the other hand, by increasing the frequency of the RF plasma to 13.56 MHz, the nitrogen gas can be sufficiently decomposed and radicalized. Thereby, a silicon nitride film containing sufficient nitrogen can be formed. In addition, by using ammonia gas, the nitrogen content of the formed silicon nitride film can be increased even when the frequency of the RF plasma is 50 KHz to 380 KHz.

(8) Other The present invention is not limited to the above-described embodiments, and various modifications can be made within the scope of the gist of the present invention. For example, in order to reverse the front and back of the film-forming tape 16, the CVD apparatus guides the film-forming tape 16 from the first film-forming roller 24 to the second film-forming roller 25 so as to draw an S-shape. Although the present invention has been described, the present invention is not limited to this, and it is appropriate to reverse the front and back by twisting the film-forming tape 16 in the direction of travel.

[0129] In the CVD apparatus, the case where each of the first film formation mechanism 21 and the second film formation mechanism 22 is one has been described. However, the present invention is not limited to this, and the first film formation mechanism 21 is provided. In addition, a plurality of (two, three, four, etc.) second film forming mechanisms 22 may be provided. By so doing, it is possible to more efficiently form a multilayer film having an arbitrary laminated structural force. In this case, the film forming tape 16 may be reversed at least once between the first scraping roller 17 and the second scraping roller 18.

[0130] Further, the case where the film-forming tape 16 is reversed once between the first scraping roller 17 and the second scraping roller 18 has been described. Not limited to this, the number of film forming rollers may be reversed any number of times according to the number.

[0131] In the above-described CVD apparatus, the plasma CVD apparatus in which the CVD unit includes the plasma generating means has been described. However, the present invention is not limited to this and may be a thermal CVD apparatus.

Claims

The scope of the claims

[1] In a CVD apparatus comprising: a reaction chamber; a CVD unit that supplies a source gas into the reaction chamber; and an exhaust unit that exhausts the gas in the reaction chamber.

In the reaction chamber,

A thin film is formed on both surfaces of the film-forming tape, which includes a traveling path where the film-forming tape reaches the first scoring roller force and a second scoring roller, and travels in one direction along the traveling path. And a double-sided film forming mechanism to form

A CVD apparatus characterized by that.

[2] The double-sided film forming mechanism includes:

A first film forming mechanism for forming a thin film on one surface of the film-forming tape;

A second film-forming mechanism for forming a thin film on the other surface of the film-forming tape;

Reversing means for reversing the front and back of the film-deposited tape in a travel path between the first film-forming mechanism and the second film-forming mechanism.

The CVD apparatus according to claim 1, wherein:

[3] The CVD unit

An orifice pipe for dispersing the raw material solution in a fine particle or mist form in a carrier gas; a raw material solution passage for supplying the raw material solution communicated with a gas passage of the orifice pipe;

A carrier gas pipe for supplying the carrier gas to the orifice pipe;

A vaporizing tube for vaporizing the raw material solution dispersed in the orifice tube;

Pores inserted into the vaporization pipe and ejecting gas from the orifice pipe;

Heating means for heating the vaporizing tube

The CVD apparatus according to claim 1 or 2, wherein:

[4] The CVD unit includes RF plasma generating means for forming plasma by applying an RF voltage in the reaction chamber,

The CVD apparatus according to any one of claims 1 to 3, wherein an isolation member that separates adjacent CVD parts from each other is provided in the reaction chamber.

[5] The first scraping roller and the second scraping roller can be rotated in both forward and reverse directions. 5. The CVD apparatus according to claim 1, wherein the force is any one of claims 1 to 4.

[6] An exhaust step for exhausting the gas in the reaction chamber by an exhaust means, a source gas supply step for supplying source gas to the reaction chamber, and a film formation step for forming a thin film on the film-forming tape in the reaction chamber; In a thin film forming method comprising:

The film forming step includes

A travel path forming step for forming a travel path for the film-forming tape to reach the first scraping roller force and the second scraping roller;

A double-sided film forming step of forming a thin film on both surfaces of the film-forming tape that travels in one direction along the travel path.

A method for forming a thin film.

[7] The double-sided film forming step includes

A first film-forming step of forming a thin film on one surface of the film-forming tape by a first film-forming mechanism;

A second film-forming step of forming a thin film on the other surface of the film-forming tape by a second film-forming mechanism;

A reversing step of reversing the front and back of the film-deposited tape in a travel path between the first film-forming mechanism and the second film-forming mechanism.

The thin film forming method according to claim 6.

[8] A carrier gas supply step for supplying a carrier gas to the orifice pipe, a raw material solution supply step for supplying the raw material solution from the raw material solution passage to the orifice pipe,

A vaporization pipe supply step for supplying the raw material solution to a vaporization pipe provided at an outlet of the orifice pipe by dispersing the raw material solution into a carrier gas in the form of fine particles or mist in the orifice pipe;

A vaporizing step in which the raw material solution is heated by the heating means of the vaporizing tube and vaporized in the vaporizing tube.

8. The thin film forming method according to claim 6 or 7, wherein:

[9] The method of forming a thin film according to any one of [6] to [8], further comprising an RF plasma generation step of forming a thin film by generating RF plasma in the reaction chamber.

[10] The thin film forming method according to any one of [6] to [9], further comprising a thin film forming step of forming the thin film by running the film-forming tape in both forward and reverse directions.