JP2006028578A - Thin film deposition apparatus and thin film deposition method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thin film deposition apparatus and a thin film deposition method for depositing a thin film of excellent quality by preventing a raw material before activation from being deposited on a base material. <P>SOLUTION: The thin film deposition apparatus has a pair of electrodes which are arranged to form a discharge space with discharge surfaces facing each other to generate the high frequency electric field in the discharge space, and a retaining mechanism to tightly attach a base material to the electrodes and retain them so as to be along at least one electrode in the discharge space. The thin film deposition apparatus also has a gas feed unit which feeds gas into the discharge space so that gas containing thin film deposition gas is activated by the high frequency electric field and deposits a thin film on the surface of the base material by exposing the base material with the activated gas. The gas feed unit has a guide means to guide gas to the discharge space so that gas before activated is not brought into contact with the base material. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a thin film forming apparatus and a thin film forming method, and more particularly to a thin film forming apparatus and a thin film forming method for forming a thin film on a substrate using atmospheric pressure plasma discharge treatment.

  Conventionally, various products such as LSIs, semiconductors, display devices, magnetic recording devices, photoelectric conversion devices, solar cells, Josephson devices, and photothermal conversion devices have been made of materials with high-performance thin films on substrates. ing. Methods for forming a thin film on a substrate include wet film forming methods represented by coating, dry film forming methods represented by sputtering, vacuum deposition, ion plating, etc., or atmospheric pressure plasma discharge treatment. In recent years, the use of an atmospheric pressure plasma film forming method capable of forming a high-quality thin film while maintaining high productivity is particularly desired.

In the atmospheric pressure plasma film forming method, a thin film forming gas is supplied in a state where a base material is disposed between opposing electrodes, and an electric field is applied to both electrodes. Thereby, discharge plasma is generated, and a thin film is formed by exposing the substrate to the discharge plasma. As a thin film forming apparatus that realizes the atmospheric pressure plasma film forming method, for example, a thin film forming apparatus described in Patent Document 1 can be cited. The thin film forming apparatus includes two opposing electrodes, a power source that applies an electric field to these electrodes, and a film transport device that transports the base material in close contact with the discharge surfaces of the two electrodes. And a thin film forming gas supply unit for supplying a thin film forming gas between the electrodes. In this thin film forming apparatus, after a thin film forming gas is supplied between the electrodes, an electric field is applied to generate discharge plasma to form a thin film on a substrate that is in close contact with the two electrodes. Yes.
JP 2000-212753 A

  Here, since there is a considerable gap between the thin film forming gas supply unit and the electrode, all of the thin film forming gas ejected from the thin film forming gas supply unit enters between the electrodes and is exposed to the discharge plasma. Rather than being leaked, there are also those that touch the substrate before leaking out of the gap and being exposed to the discharge plasma. The thin film forming gas contains the raw material for the thin film. If the raw material in the thin film forming gas is activated and adheres to the base material, a thin film is formed on the base material. If it adheres to the substrate before activation, even if the material activated thereafter adheres to the substrate, it is difficult to form a good film.

  The subject of this invention is preventing the raw material before activation adhering to a base material, and enabling formation of a good quality thin film.

The thin film forming apparatus according to the invention of claim 1
A pair of electrodes arranged to form a discharge space with the discharge surfaces facing each other, and generating a high-frequency electric field in the discharge space;
A holding mechanism for holding the substrate in the discharge space;
A thin film is formed on the surface of the base material by supplying the gas to the discharge space so that the gas containing the thin film forming gas is activated by a high-frequency electric field, and exposing the base material with the activated gas. And a gas supply part for forming
The gas supply unit includes guide means for guiding the gas to the discharge space so that the gas before activation does not contact the base material.

  According to the first aspect of the present invention, when the gas containing the thin film forming gas is guided to the discharge space by the guide means, the guide means guides the gas so that the gas before activation does not contact the substrate. Therefore, before the gas after activation touches the substrate, it is possible to prevent the gas before activation from coming into contact with the substrate. Thereby, it can prevent that the raw material contained in thin film formation gas adheres to a base material before activating, As a result, formation of a high quality thin film is attained.

The invention described in claim 2 is the thin film forming apparatus according to claim 1,
The holding mechanism is characterized in that the substrate is held in close contact with the electrodes so as to follow each of the pair of electrodes in the discharge space.

  According to the second aspect of the present invention, since the holding mechanism holds the base material in close contact with the electrodes so as to follow each of the pair of electrodes in the discharge space, two layers of thin films are formed in one discharge space. Therefore, it is possible to form a thin film more efficiently.

The invention according to claim 3 is the thin film forming apparatus according to claim 1 or 2,
The holding mechanism is a transport device that transports the base material.

  According to the third aspect of the invention, since the holding mechanism is a transport device that transports the base material, a thin film can be formed over a wide range.

Invention of Claim 4 is a thin film formation apparatus as described in any one of Claims 1-3,
The guide means has a first gas jet port for jetting the gas, and a pair of second gas jet ports for jetting a raw material gas not containing the thin film forming gas,
The pair of second gas outlets is arranged along the axial direction of the pair of electrodes so as to sandwich the first gas outlet.

  According to invention of Claim 4, since a pair of 2nd gas ejection port is arrange | positioned so that a 1st gas ejection port may be pinched | interposed along the axial direction of a pair of electrode, gas containing thin film formation gas Can be guided from the gas supply unit to the discharge space in a state of being sandwiched between the raw material gases. Thus, if the gas is sandwiched between the raw material gases, it is possible to prevent the gas from being blocked by the raw material gases and flowing out of the raw material gases. In particular, if the interval between the pair of second gas outlets is narrower than the interval between the discharge spaces, the gas is less likely to flow out of the discharge space, and is reliably guided into the discharge space.

The invention according to claim 5 is the thin film forming apparatus according to claim 4,
The guiding means includes
A pair of third gas outlets for jetting the raw material gas;
The pair of third gas outlets are respectively arranged outside both end portions of the first gas outlet in the axial direction.

  According to invention of Claim 5, since each of a pair of 3rd gas jet nozzle is arrange | positioned outside the both ends of a 1st gas jet nozzle, it contains thin film formation gas also to an axial direction The gas to be supplied can be guided from the gas supply unit to the discharge space in a state where the raw material gas is sandwiched. Accordingly, it is possible to reduce the gas flowing out of the discharge space from both ends of the first gas ejection port.

A sixth aspect of the present invention is the thin film forming apparatus according to the fifth aspect,
The pair of second gas outlets and the pair of third gas outlets are continuous so as to surround the first gas outlet.

  According to the sixth aspect of the present invention, the pair of second gas outlets and the pair of third gas outlets are continuous so as to surround the first gas outlet, so that they are ejected from the first gas outlet. The gas can be guided to the discharge space in a state surrounded by the raw material gas. Therefore, the gas containing the thin film forming gas can be guided to the discharge space without leaking out of the discharge space.

The invention according to claim 7 is the thin film forming apparatus according to any one of claims 4 to 6,
The ejection directions of the gas and the raw material gas are parallel to each other and perpendicular to the axial direction.

According to the invention of claim 7, since the jet directions of the gas and the raw material gas are parallel to each other, the flow of the gas containing the thin film forming gas is prevented from being disturbed by the flow of the raw material gas, It is possible to more reliably prevent the gas from flowing out of the raw material gas.
In addition, since the discharge space extends along the axial direction of the pair of electrodes, the direction in which the gas containing the thin film forming gas and the raw material gas are ejected is orthogonal to the axial direction as described above. If so, the gas containing the thin film forming gas can be reliably guided over the entire length of the discharge space.

Invention of Claim 8 is a thin film formation apparatus as described in any one of Claims 4-7,
The Reynolds numbers at the time of ejection of the gas and the raw material gas are substantially equal.

  According to the invention described in claim 8, since the Reynolds number at the time of ejection of the gas containing the thin film forming gas and the raw material gas is substantially the same, the flow of the gas containing the thin film forming gas depends on the flow of the raw material gas. Disturbance can be suppressed.

The invention according to claim 9 is the thin film forming apparatus according to any one of claims 4 to 8,
The pair of electrodes are arranged so that the discharge space is open in the vertical direction,
The gas supply unit is arranged so that the gas and the raw material gas are guided to the discharge space along the vertical direction.

  Here, for example, if the flow path of the gas containing the thin film forming gas and the raw material gas is inclined with respect to the vertical direction, the flow of the gas and the raw material gas is caused by the influence of gravity before reaching the discharge space. It will be disturbed. However, if the gas containing the thin film forming gas and the raw material gas are guided to the discharge space along the vertical direction as in the invention described in claim 9, the influence of gravity can be reduced, and the gas and the raw material gas can be reduced. The flow of turbulence can be suppressed.

The invention according to claim 10 is the thin film forming apparatus according to any one of claims 1 to 9,
A suction unit that is disposed on the opposite side of the gas supply unit across the pair of electrodes and sucks the gas that has passed through the discharge space;
The suction amount of the suction part is set larger than the ejection amount of the gas supply part.

  According to the tenth aspect of the present invention, since the suction portion sucks the gas that has passed through the discharge space, the inside of the apparatus can be prevented from being contaminated by the gas that has passed through the discharge space. In particular, if the suction amount of the suction portion is set to be larger than the ejection amount of the gas supply portion, the gas that has passed through the discharge space can always be sucked and the gas can be reliably prevented from flowing out of the discharge space. be able to.

Invention of Claim 11 is a thin film formation apparatus as described in any one of Claims 1-10,
An interval between the gas supply unit and the pair of electrodes is narrower than an interval between the pair of electrodes.

  According to the eleventh aspect of the present invention, since the distance between the gas supply unit and the pair of electrodes is narrower than the distance between the pair of electrodes, the distance from the gas supply unit to the discharge space can be shortened. Even if the flow of the gas ejected from the supply section is disturbed, the gas can be contained in the discharge space before the influence becomes large.

Invention of Claim 12 is the thin film formation apparatus as described in any one of Claims 1-11,
The guide means is characterized in that at least the surface has an insulating property.

  Here, when a high-frequency electric field is generated in the discharge space by the pair of electrodes, the discharge plasma is generated so as to protrude outside the discharge space. Depending on the position of the guide means, it may enter the discharge plasma generation region. However, if the guide means is a conductor, it serves as a ground, making it difficult to stabilize the discharge plasma. For this reason, if at least the surface of the guide means has an insulating property as in the invention described in claim 12, the discharge plasma can be stabilized without conducting the discharge plasma to the guide means.

The invention according to claim 13 is the thin film forming apparatus according to any one of claims 1 to 12,
The high-frequency electric field is a superposition of a first high-frequency electric field by one of the pair of electrodes and a second high-frequency electric field by the other electrode,
The frequency ω2 of the second high frequency electric field is higher than the frequency ω1 of the first high frequency electric field,
The relationship among the electric field strength V1 of the first high-frequency electric field, the electric field strength V2 of the second high-frequency electric field, and the discharge starting electric field strength IV is:
V1 ≧ IV> V2 or V1> IV ≧ V2 is satisfied.

  According to the invention of claim 13, the high-frequency electric field is a superposition of the first high-frequency electric field and the second high-frequency electric field, and the frequency ω2 of the second high-frequency electric field is higher than the frequency ω1 of the first high-frequency electric field. Since the relationship between the electric field intensity V1 of the high-frequency electric field, the electric field intensity V2 of the second high-frequency electric field, and the discharge starting electric field intensity IV satisfies V1 ≧ IV> V2 or V1> IV ≧ V2, an inexpensive gas such as nitrogen is used. Even in such a case, discharge capable of forming a thin film is caused, and high-density plasma necessary for forming a high-quality thin film can be generated.

Invention of Claim 14 is a thin film forming apparatus as described in any one of Claims 1-13,
The gas contains 50% or more of nitrogen.

  According to the fourteenth aspect of the present invention, since the gas containing the thin film forming gas contains 50% or more of nitrogen, the gas can be made relatively cheaper than when other gases are used.

The invention according to claim 15 is the thin film forming apparatus according to any one of claims 1 to 14,
The pair of electrodes generate a high-frequency electric field in the discharge space under atmospheric pressure or pressure near atmospheric pressure.

  According to the invention described in claim 15, since film formation can be performed under atmospheric pressure or a pressure near atmospheric pressure, high-speed film formation is possible and continuous production is possible as compared with the case where film formation is performed in a vacuum. Is possible. And since the apparatus for making a vacuum is not required, an installation cost can be reduced.

The thin film forming method according to the invention of claim 16 comprises:
A gas containing a thin film forming gas is supplied from a gas supply unit to a discharge space composed of a pair of electrodes whose discharge surfaces face each other, and the gas is activated by generating a high-frequency electric field in the discharge space. The thin film is formed on the substrate by exposing the substrate to the activated gas by holding the substrate in close contact with the electrode along at least one of the pair of electrodes. When doing
The gas is guided to the discharge space so that the gas before activation does not contact the substrate.

  According to the invention of the sixteenth aspect, the same operation and effect as the invention of the first aspect can be obtained.

The invention described in claim 17 is the thin film forming method according to claim 16,
The substrate is held in close contact with the electrodes so as to be along each of the pair of electrodes in the discharge space.

  According to the seventeenth aspect of the invention, it is possible to obtain the same operation and effect as the second aspect of the invention.

The invention according to claim 18 is the method for forming a thin film according to claim 16 or 17,
The base material is transported so as to pass through the discharge space.

  According to the eighteenth aspect of the invention, the same operation and effect as the third aspect of the invention can be obtained.

The invention according to claim 19 is the thin film forming method according to any one of claims 16 to 18,
The raw material gas not containing the thin film forming gas is ejected along each of the pair of electrodes, and the gas is sandwiched and guided.

  According to the nineteenth aspect of the invention, it is possible to obtain the same operation and effect as the fourth aspect of the invention.

The invention according to claim 20 is the thin film forming method according to claim 19,
The raw material gas is ejected so as to sandwich the gas with respect to the axial direction of the pair of electrodes.

  According to the twentieth aspect of the invention, the same operation and effect as the fifth aspect of the invention can be obtained.

The invention according to claim 21 is the thin film forming method according to claim 19,
The raw material gas is ejected so as to surround the gas.

  According to the twenty-first aspect of the invention, it is possible to obtain the same operation and effect as the sixth aspect of the invention.

Invention of Claim 22 is the thin film formation method as described in any one of Claims 19-21,
The ejection directions of the gas and the raw material gas are parallel to each other and perpendicular to the axial direction.

  According to the invention described in claim 22, it is possible to obtain the same operation and effect as the invention described in claim 7.

The invention according to claim 23 is the thin film forming method according to any one of claims 19 to 22,
The Reynolds numbers at the time of ejection of the gas and the raw material gas are substantially equal.

  According to the twenty-third aspect of the invention, it is possible to obtain the same operation and effect as the eighth aspect of the invention.

Invention of Claim 24 is the thin film formation method as described in any one of Claims 19-23,
The pair of electrodes are arranged so that the discharge space is open in the vertical direction,
The gas supply unit is arranged so that the gas and the raw material gas are guided to the discharge space along the vertical direction.

  According to the twenty-fourth aspect of the invention, it is possible to obtain the same operation and effect as the ninth aspect of the invention.

The invention according to claim 25 is the thin film forming method according to any one of claims 16 to 24,
A suction part that sucks the gas that has passed through the discharge space is disposed on the opposite side of the gas supply part across the pair of electrodes,
The suction amount of the suction part is set larger than the ejection amount of the gas supply part.

  According to the twenty-fifth aspect of the invention, the same operation and effect as the tenth aspect of the invention can be obtained.

Invention of Claim 26 is the thin film formation method as described in any one of Claims 16-25,
An interval between the gas supply unit and the pair of electrodes is narrower than an interval between the pair of electrodes.

  According to the twenty-sixth aspect of the invention, the same operation and effect as the eleventh aspect of the invention can be obtained.

The invention according to claim 27 is the thin film formation method according to any one of claims 16 to 26,
The gas supply unit is characterized in that at least a surface of a portion for guiding the gas has an insulating property.

  According to the twenty-seventh aspect, actions and effects equivalent to those of the twelfth aspect can be obtained.

The invention according to claim 28 is the thin film forming method according to any one of claims 16 to 27,
The high-frequency electric field is a superposition of a first high-frequency electric field by one of the pair of electrodes and a second high-frequency electric field by the other electrode,
The frequency ω2 of the second high frequency electric field is higher than the frequency ω1 of the first high frequency electric field,
The relationship among the electric field strength V1 of the first high-frequency electric field, the electric field strength V2 of the second high-frequency electric field, and the discharge starting electric field strength IV is:
V1 ≧ IV> V2 or V1> IV ≧ V2 is satisfied.

  According to the 28th aspect of the invention, the same operation and effect as the 13th aspect of the invention can be obtained.

The invention according to claim 29 is the thin film forming method according to any one of claims 16 to 28,
The gas contains 50% or more of nitrogen.

  According to the twenty-ninth aspect of the present invention, it is possible to obtain the same operation and effect as the fourteenth aspect of the present invention.

The invention according to claim 30 is the thin film formation method according to any one of claims 16 to 29,
The pair of electrodes generate a high-frequency electric field in the discharge space under atmospheric pressure or pressure near atmospheric pressure.

  According to the invention of claim 30, the same operation and effect as those of the invention of claim 15 can be obtained.

  According to the present invention, it is possible to prevent the gas before activation from coming into contact with the substrate before the gas after activation touches the substrate. Thereby, it can prevent that the raw material contained in thin film formation gas adheres to a base material before activating, As a result, formation of a high quality thin film is attained.

[First Embodiment]
Hereinafter, a first embodiment of the present invention will be described with reference to the accompanying drawings. FIG. 1 is a front view illustrating a schematic configuration of the thin film forming apparatus 1.

  The thin film forming apparatus 1 is a thin film forming apparatus that forms a thin film on a substrate by generating discharge plasma under atmospheric pressure or a pressure near atmospheric pressure. As shown in FIG. 1, a pair of electrodes 2 and 3 for generating discharge plasma are fixed to the thin film forming apparatus 1 along the front-rear direction so as to face each other with a gap therebetween. This interval becomes the discharge space H opened in the vertical direction, and the opposing surfaces of the electrodes 2 and 3 forming the discharge space H are defined as discharge surfaces 2a and 3a, respectively.

  FIG. 2 is a perspective view illustrating a schematic configuration of the electrodes 2 and 3. As shown in FIG. 2, the electrodes 2 and 3 are rod-shaped electrodes in which the surfaces of conductive metallic base materials 21 and 31 are covered with dielectrics 22 and 32. The corners 23 and 33 of the electrodes 2 and 3 are formed in an arc shape so that the surfaces of the electrodes 2 and 3 are smoothly continuous. That is, the discharge surfaces 2a and 3a of the electrodes 2 and 3 and the surfaces other than the discharge surfaces 2a and 3a connected to the discharge surfaces 2a and 3a are smoothly continued by the corner portions 23 and 33. A power source 4 is connected to the electrodes 2 and 3 as shown in FIG.

As shown in FIG. 1, the thin film forming apparatus 1 has a transport device (holding) that transports the base material 5 and the support 6 that supports the base material 5 so as to be held in at least the discharge space H. Mechanism) 7 is provided.
The conveying device 7 will be described in detail. A holding roller 71 for a base material that rotatably holds the original winding of the base material 5 is provided above the outer side of the one electrode 2 (left side in FIG. 1). Are arranged in parallel with each other. Between the base material holding roller 71 and the electrode 2 in the vertical direction, the support body holding roller 72 that rotatably holds the original winding of the support body 6 is parallel to the base material holding roller 71. Are arranged as follows. The support 6 held by the support holding roller 72 is coated with an adhesive 61 (see FIG. 3) having removability on the surface thereof.
A first guide roller 73 that guides the substrate 5 and the support 6 to the one electrode 2 is provided between the substrate holding roller 71 and the support holding roller 72 and the one electrode 2. 2 is arranged below a line (auxiliary line S1 in FIG. 1) connecting the upper right end portion of 2 and a portion where the support 6 is pulled out from the support holding roller 72. As a result, the support 6 drawn from the support holding roller 72 is brought into close contact with the back surface of the substrate 5 drawn from the substrate holding roller 71 via the adhesive 61, and then the upper surface ( It will contact point P1) in FIG.

  Further, below the pair of electrodes 2 and 3, a guide path (illustrated) that guides the other electrode 3 while the base material 5 and the support 6 that have passed through the discharge space H along the one electrode 2 are in close contact with each other. (Omitted) is formed. The guide path is formed such that, of the base material 5 and the support body 6, the support body 6 contacts the lower surface of the other electrode 3 (point P <b> 2 in FIG. 1).

  A substrate take-up roller 74 for winding the substrate 5 is disposed above the other electrode 3 (on the right side in FIG. 1) so as to be parallel to the electrodes 2 and 3. Between the substrate take-up roller 74 and the electrode 3 in the vertical direction, the support take-up roller 75 for taking up the support 6 is arranged in parallel with the take-up roller 74 for the substrate. Has been. Between the base material take-up roller 74 and the support take-up roller 75 and the other electrode 3, the base material 5 and the support 6 are respectively connected to the base take-up roller 74 and the support take-up roller. From the line (auxiliary line S2 in FIG. 1) connecting the left end portion of the other electrode 3 to the portion where the support 6 starts to be wound around the substrate winding roller 74. Is also arranged below.

  That is, the transport device 7 rotates the base material take-up roller 74 and the support take-up roller 75 to rotate the base material 5 and the support body 6 with the base material holding roller 71 and the support body hold roller, respectively. 72 is pulled out. The drawn substrate 5 and support 6 are in close contact with the adhesive 61 by the first guide roller 73, along the electrode 2 in the order of the upper surface of one electrode 2, the discharge surface 2a, and the lower surface, via the guide path, The lower surface of the other electrode 3, the discharge surface 3 a, and the upper surface are arranged along the electrode 3, separated from the electrode 3, and separated from each other by the second guide roller 76. It is wound around a winding roller 75.

  3 is a cross-sectional view taken along the line AA in FIG. 1 and shows the positional relationship between the electrodes 2 and 3, the base material 5, and the support 6 in the discharge space H. FIG. As shown in FIG. 3, in the discharge space H, the support 6 is interposed between the electrodes 2, 3 and the base 5, and the support 6 and the base 5 hold the adhesive 61. It will be stuck and fixed via.

  As shown in FIG. 1, a gas supply unit 8 that supplies a gas containing a thin film forming gas to the discharge space H is provided above the discharge space H. A first gas tank 9 for storing a gas containing a thin film forming gas is connected to the gas supply unit 8 via a pipe 91 and a gas adjusting unit 92 (see FIG. 6), and includes a thin film forming gas. The 2nd gas tank 10 which stores no raw material gas is connected via the piping 11 and the raw material gas adjustment part 12 (refer FIG. 6). Here, the gas adjusting unit 92 and the non-source gas adjusting unit 12 adjust the flow rate, flow rate, gas composition, concentration, and the like of the gas flowing in the pipes 91 and 11 and the non-source gas.

  FIG. 4 is a perspective view showing the gas supply unit 8, and FIG. 5 is a cross-sectional view of the gas supply unit 8. As shown in FIG. 4, a gas pipe 81 to which a pipe 91 is connected is provided at the center of the rear end portion of the gas supply unit 8. In addition, at the rear end portion of the gas supply unit 8, four raw material gas gas pipes 82 to which the pipe 11 is connected are arranged on the front, rear, left and right of the gas pipe 81, respectively.

  Further, inside the gas supply unit 8, four partition plates 83 are provided that form a flow path for the gas flowing in from the gas pipe 81 and the gas pipes 82 for each raw material gas and the raw material gas. Of the four partition plates 83, the two partition plates 83 are disposed between the raw material gas gas pipe 82 located in the front and rear, and the raw material gas gas pipe 82 and the gas pipe 81 located in the left and right, It is arranged along the vertical and horizontal directions. Between these two partition plates 83, the remaining two partition plates 83 are arranged between the gas pipe 82 for raw material gas located on the left and right and the gas pipe 81 along the up and down front and rear direction. (See FIG. 5). These partition plates 83 divide the opening at the tip of the gas supply unit 8.

FIG. 6 is a bottom view showing the front end surface of the gas supply unit 8. As shown in FIG. 6, of the divided openings, if the opening for ejecting gas is the first gas outlet 84 and the opening for ejecting the non-source gas is the non-source gas outlet 85, the first gas outlet 84 is surrounded by front and rear, right and left by each raw material gas ejection port 85. Among the plurality of raw material gas outlets 85, the raw material gas outlet 85 arranged along the front-rear direction (the axial direction of the pair of electrodes 2 and 3) so as to sandwich the first gas outlet 84 is the present invention. The raw material gas jet 85 arranged outside the first gas jet 84 in the front-rear direction is the third gas jet 85b according to the present invention. Thereby, the gas and the raw material gas which flowed in from the gas pipe 81 and each of the raw material gas gas pipes 82 are individually ejected.
Since the first gas outlet 84 and the second gas outlet 85a are arranged so as to be parallel to the left-right direction, the ejection direction of the gas ejected from the first gas outlet 84, and the second The ejection direction of the raw material gas ejected from the gas ejection port 85a is parallel to the ejection direction. In addition, since the first gas outlet 84 and the third gas outlet 85b are arranged so as to be parallel to the front-rear direction, the ejection direction of the gas ejected from the first gas outlet 84, The ejection direction of the raw material gas ejected from the second gas ejection port 85a is parallel to the ejection direction.

  Then, as shown in FIG. 5, in the gas supply unit 8, the flow paths of the gas and the raw material gas are along a direction (vertical direction) orthogonal to the axial direction (front-rear direction) of the electrodes 2 and 3. Therefore, the ejection direction of the gas and the raw material gas is along the vertical direction. As described above, the gas ejected from the first gas ejection port 84 is guided to the discharge space H along the vertical direction in a state where the front, rear, left and right are blocked by the raw material gas. That is, the first gas outlet 84, the second gas outlet 85a, and the third gas outlet 85b are the guiding means according to the present invention. Here, if the flow paths of the gas and the raw material gas are inclined with respect to the vertical direction, the flow of the gas and the raw material gas is disturbed by the influence of gravity before reaching the discharge space H. However, as described above, if the gas and the raw material gas are guided to the discharge space H along the vertical direction by the guide means, the influence of gravity can be reduced, and the flow of the gas and the raw material gas can be prevented from being disturbed. be able to.

  The gas supply unit 8 is configured such that the gap between the gas supply unit 8 and the pair of electrodes 2 and 3 (T1 in FIG. 5) is narrower than the gap between the pair of electrodes 2 and 3 (T2 in FIG. 5). Have been placed.

  Further, as shown in FIG. 1, below the discharge space H, a suction part 13 for sucking the gas flowing out from the discharge space H and the raw material gas is provided. The suction portion 13 is provided with a suction port portion 14 extending over the discharge space H, and a suction pump 16 is connected to the suction port portion 14 via a pipe 15.

  On the opposite side of the discharge surfaces 2a and 3a of the pair of electrodes 2 and 3, a plurality of waste suction portions 17 for sucking the scraps generated when the support 6 contacts the electrodes 2 and 3 are supported. It arrange | positions so that the contact vicinity of the body 6 and the electrodes 2 and 3 may be attracted | sucked.

  FIG. 7 is a block diagram showing a main control configuration in the thin film forming apparatus 1. As shown in FIG. 7, the thin film forming apparatus 1 is provided with a control device 40 that controls each drive unit. The control device 40 includes a temperature adjustment device 44 that adjusts the temperature of the electrodes 2 and 3, a storage unit 41, a power supply 4, a gas adjustment unit 92, a raw material gas adjustment unit 12, a suction pump 16, a waste suction unit 17, The drive source 42 of the material take-up roller 74 and the drive source 43 of the support take-up roller 75 are electrically connected. In addition to the above, each drive unit of the thin film forming apparatus 1 is connected to the control device 40. And the control apparatus 40 controls various apparatuses according to the control program and control data which are written in the memory | storage part 41. FIG.

The gas supply unit 8 supplies a gas containing a thin film forming gas and a raw material gas not containing the thin film forming gas.
The gas is a mixture of a discharge gas capable of causing glow discharge capable of forming a thin film and a thin film forming gas containing a raw material for the thin film.
Examples of the discharge gas include nitrogen, rare gas, air, hydrogen gas, oxygen, and the like. These may be used alone as a discharge gas or may be mixed. In this embodiment, relatively inexpensive nitrogen is used. Here, the nitrogen concentration is preferably 50% or more when mixed with the thin film forming gas. Further, when a rare gas is used as a gas to be mixed with nitrogen, it is preferable to contain less than 50% of the discharge gas.

Examples of the raw material contained in the thin film forming gas include organic metal compounds, halogen metal compounds, and metal hydrogen compounds.
As the organometallic compound, those represented by the following general formula (I) are preferable.
General formula (I) R1xMR2yR3z In the formula, M is a metal, R1 is an alkyl group, R2 is an alkoxy group, R3 is a β-diketone complex group, a β-ketocarboxylic acid ester complex group, a β-ketocarboxylic acid complex group, and a ketooxy group (ketooxy group) Complex group), and when the valence of the metal M is m, x + y + z = m, x = 0 to m, or x = 0 to m−1, y = 0 to m, z = 0 to m, each of which is 0 or a positive integer. Examples of the alkyl group for R1 include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the alkoxy group for R2 include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a 3,3,3-trifluoropropoxy group. Further, a hydrogen atom in the alkyl group may be substituted with a fluorine atom. Examples of the group selected from the β-diketone complex group, the β-ketocarboxylic acid ester complex group, the β-ketocarboxylic acid complex group, and the ketooxy group (ketooxy complex group) of R3 include a β-diketone complex group such as 2,4- Pentanedione (also referred to as acetylacetone or acetoacetone), 1,1,1,5,5,5-hexamethyl-2,4-pentanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1,1,1-trifluoro-2,4-pentanedione and the like, and β-ketocarboxylic acid ester complex groups include, for example, acetoacetic acid methyl ester, acetoacetic acid ethyl ester, acetoacetic acid propyl ester, trimethylacetoacetic acid ethyl , Methyl trifluoroacetoacetate and the like, and as β-ketocarboxylic acid, for example, acetoacetate , And triethylene methyl acetoacetate and the like, and as Ketookishi, for example, acetoxy group (or an acetoxy group), a propionyloxy group, Buchirirokishi group, acryloyloxy group, methacryloyloxy group, and the like. The number of carbon atoms of these groups is preferably 18 or less, including the above-mentioned organometallic compounds. Further, as illustrated, it may be linear or branched, or a hydrogen atom substituted with a fluorine atom.

  In the present invention, an organometallic compound having a low risk of explosion is preferred from the viewpoint of handling, and an organometallic compound having at least one oxygen in the molecule is preferred. As such, an organometallic compound containing at least one alkoxy group of R2, a β-diketone complex group, a β-ketocarboxylic acid ester complex group, a β-ketocarboxylic acid complex group and a ketooxy group (ketooxy complex group) of R3 An organometallic compound having at least one group selected from:

  Further, as the metal of the organometallic compound, halogen metal compound, and metal hydride compound used for the thin film forming gas, for example, Li, Be, B, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr , Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Rb, Sr, Y, Zr, Nb, Mo, Cd, In, Ir, Sn, Sb, Cs, Ba, La, Hf, Ta, W , Tl, Pb, Bi, Ce, Pr, Nd, Pm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and the like.

  As the raw material gas, a gas not containing a compound contained in a thin film forming gas that is a raw material of the thin film is used. Specifically, the above-described discharge gas, oxygen, carbon monoxide, air, and the like can be given. When a discharge gas is used as the raw material gas, the discharge plasma generated in the discharge space H can be made uniform.

  Next, the base material 5 will be described. The substrate 5 is not particularly limited as long as a thin film such as a plate shape, a sheet shape, or a film-like planar shape can be formed on the surface thereof. There is no limitation on the form or material of the base material 5 as long as the base material 5 is exposed to a plasma state gas in a stationary state or a transported state to form a uniform thin film. For example, various materials such as glass, resin, ceramics, metal, and nonmetal can be used. Specifically, a glass plate, a resin film, a resin sheet, a resin plate, etc. are mentioned.

  Since the resin film can form a transparent conductive film by continuously transferring between or in the vicinity of the electrodes of the thin film forming apparatus 1 according to the present invention, it is not a batch system of a vacuum system such as sputtering, for mass production. It is suitable as a production method with high orientation and continuous productivity.

  Examples of the material of the substrate 5 made of resin include cellulose esters such as cellulose triacetate, cellulose diacetate, cellulose acetate propionate or cellulose acetate butyrate, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyethylene and polypropylene, and the like. Polyolefin, polyvinylidene chloride, polyvinyl chloride, polyvinyl alcohol, ethylene vinyl alcohol copolymer, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyether ketone, polyimide, polyether sulfone, polysulfone, polyether Imido, polyamide, fluororesin, polymethyl acrylate, acrylate copolymer, etc. It is below.

  Moreover, the base material 5 used in the present invention is a film having a thickness of 10 to 100 μm, more preferably 20 to 50 μm.

Next, the support 6 will be described. As the support 6, a support formed in a film shape so as to be interposed between the substrate 5 and the electrodes 2 and 3 is used. Here, in order to perform uniform film formation on the surface of the base material 5, it is preferable that at least the entire base material 5 is within the discharge space H, but if this is done, a thin film is also formed on the outside of the base material 5. Therefore, if the width of the support 6 is made longer than the width of the base 5 as shown in FIG. 3, the support 6 covers the electrodes 2 and 3 to the outside of the base 5. Therefore, it is possible to prevent the raw material from adhering to the electrodes 2 and 3, which is preferable.
Moreover, it is preferable that the material of the support body 6 is the same material as the base material 5 or has the same thermal physical properties. Thereby, the heat deformation amount of the base material 5 and the support body 6 becomes equivalent, and the generation | occurrence | production of the wrinkles and the slip by the difference in heat deformation amount can also be reduced.

  Next, the adhesive 61 having removability will be described. Even if the base material 5 and the support 6 are exposed to the discharge plasma in the discharge space H, the adhesive 61 is preferably excellent in heat resistance that does not deteriorate its adhesiveness and removability. As such an adhesive 61, an acrylic adhesive is mentioned, for example. In general, since the support 6 previously coated with the adhesive 61 is commercially available, for example, the support 6 made of PET is coated with an acrylic adhesive as the adhesive 61 (Nitto Denko ( It is preferable to use “Heat Resistant Surface Protective Adhesive Tape (Model No. E-MASK TP300)”.

Next, the metal base materials 21 and 31 and the dielectrics 22 and 32 forming the electrodes 2 and 3 will be described.
As a combination of the metallic base materials 21 and 31 and the dielectrics 22 and 32, those in which the characteristics match between them are preferable. As one of the characteristics, the metallic base materials 21 and 31 and the dielectrics 22 and 32 are combined. The combination is such that the difference in linear thermal expansion coefficient is 10 × 10 ⁻⁶ / ° C. or less. It is preferably 8 × 10 ⁻⁶ / ° C. or less, more preferably 5 × 10 ⁻⁶ / ° C. or less, and further preferably 2 × 10 ⁻⁶ / ° C. or less. The linear thermal expansion coefficient is a well-known physical property value of a material.

  Examples of combinations of a conductive metallic base material and a dielectric that have a difference in linear thermal expansion coefficient within this range include, for example, 1) the metallic base material is pure titanium or a titanium alloy, and the dielectric is a ceramic spray coating. 2) Metal base material is pure titanium or titanium alloy, dielectric is glass lining, 3) metal base material is stainless steel, dielectric is ceramic spray coating, 4) metal base material is stainless steel, Dielectric is glass lining, 5) Metal base material is ceramic and iron composite material, dielectric is ceramic spray coating, 6) Metal base material is ceramic and iron composite material, dielectric is glass lining, 7 ) Metallic base material is a composite material of ceramics and aluminum, dielectric is a ceramic sprayed coating, 8) Metallic base material is a composite material of ceramics and aluminum, Glass-lined collector is, and the like. From the viewpoint of the difference in linear thermal expansion coefficient, the above 1) or 2) and 5) to 8) are preferable, and 1) is particularly preferable.

  As the metallic base materials 21 and 31, titanium or a titanium alloy is particularly useful. By making the metal base materials 21 and 31 titanium or a titanium alloy and using the dielectrics 22 and 32 as materials corresponding to the above combination, there is no deterioration of the electrode in use, particularly cracking, peeling, dropping off, etc. It will be possible to withstand long-term use.

  The metal base materials 21 and 31 of the electrode useful for the present invention are a titanium alloy or titanium metal containing 70% by mass or more of titanium. In the present invention, if the titanium content in the titanium alloy or titanium metal is 70% by mass or more, it can be used without any problem, but preferably contains 80% by mass or more of titanium. As the titanium alloy or titanium metal useful in the present invention, those generally used as industrial pure titanium, corrosion resistant titanium, high strength titanium and the like can be used. Examples of the pure titanium for industrial use include TIA, TIB, TIC, TID, etc., all of which contain very few iron atoms, carbon atoms, nitrogen atoms, oxygen atoms, hydrogen atoms, etc. Content has 99 mass% or more. As the corrosion-resistant titanium alloy, T15PB can be preferably used, and it contains lead in addition to the above-mentioned contained atoms, and the titanium content is 98% by mass or more. Further, as the titanium alloy, in addition to the above-mentioned atoms excluding lead, for example, T64, T325, T525, TA3, etc. containing aluminum and containing vanadium or tin can be preferably used. As titanium content, 85 mass% or more is contained. These titanium alloys or titanium metals have a coefficient of thermal expansion that is about ½ smaller than that of stainless steel, such as AISI 316, and dielectric materials 22 and 31 applied on the titanium alloy or titanium metal as metallic base materials 21 and 31. The combination with 32 is good and can endure use at high temperature for a long time.

  On the other hand, examples of the dielectrics 22 and 32 include ceramics such as alumina and silicon nitride, or glass lining materials such as silicate glass and borate glass. Among these, ceramic sprayed ones and those provided by glass lining are preferable. In particular, dielectrics 22 and 32 provided by spraying alumina are preferable.

  Alternatively, as one of the specifications that can withstand high power, the porosity of the dielectrics 22 and 32 is 10% by volume or less, preferably 8% by volume or less, preferably more than 0% by volume and 5% by volume or less. It is. Another preferable specification that can withstand high power is that the thickness of the dielectrics 22 and 32 is 0.5 to 2 mm. The film thickness variation is desirably 5% or less, preferably 3% or less, and more preferably 1% or less.

Next, the operation of the thin film forming apparatus 1 of this embodiment will be described.
First, with the start of thin film formation, the control device 40 drives the suction pump 16 and the waste suction unit 17, and then controls the gas adjustment unit 92 and the non-source gas adjustment unit 12, from the gas supply unit 8. A gas and a raw material gas are supplied to the discharge space H. The gas ejected from the first gas ejection port 84 is guided to the discharge space H along the vertical direction in a state where the front, rear, left and right are blocked by the raw material gas. At this time, the control device 40 controls the gas adjusting unit 92 and the non-source gas adjusting unit 12 so that the Reynolds numbers at the time of ejection of the gas and the non-source gas are substantially equal. The Reynolds number is a function of the representative velocity, the representative length, and the kinematic viscosity coefficient, but the representative lengths of the gas and the raw material gas (the first gas outlet 84, the second gas outlet 85a, and the third gas outlet 85b). The control device 40 controls the gas adjusting unit 92 and the non-source gas adjusting unit 12 to adjust the flow rate, flow rate, gas composition, concentration, etc. of the gas and non-source gas. Thus, the representative speed and the kinematic viscosity coefficient are changed to make the Reynolds numbers of the gas and the raw material gas substantially the same. Here, the Reynolds number is substantially equal is a value that does not disturb the flow of the gas by the flow of the raw material gas when the gas is guided to the discharge space H by the raw material gas. It is preferable that an optimum range is obtained.

  Further, the control device 40 calculates the ejection amount of the gas supply unit 8 from the flow rate and flow velocity at which the Reynolds numbers of the gas and the raw material gas are equal, and the suction amount of the suction unit 13 is larger than the ejection amount. It is set.

  When the gas is supplied to the discharge space H, the control device 40 controls the drive source 42 of the substrate winding roller 74 and the drive source 43 of the support winding roller 75 to control the substrate 5 and the support 6 are conveyed.

  When the conveyance of the base material 5 and the support 6 is started, the control device 40 turns on the power supply 4. Thus, a first high frequency electric field having a frequency ω1, an electric field strength V1, and a current I1 is applied to one electrode 2, and a second high frequency electric field having a frequency ω2, an electric field strength V2, and a current I2 is applied to the other electrode 3. Applied. Here, the frequency ω2 is set higher than the frequency ω1.

  Specifically, the frequency ω1 is preferably 200 kHz or less, and the lower limit is 1 kHz. The electric field waveform may be a continuous wave or a pulse wave. On the other hand, the frequency ω2 is preferably 800 kHz or more, and the higher the frequency, the higher the plasma density, but the upper limit is about 200 MHz.

  Further, when a discharge gas is supplied between the electrodes to increase the electric field strength between the electrodes, and the electric field strength at which the discharge starts is defined as the discharge starting electric field strength IV, the electric field strengths V1 and V2 and the discharge starting electric field strength IV are The relationship is set so as to satisfy V1 ≧ IV> V2 or V1> IV ≧ V2. For example, when the discharge gas is nitrogen, the discharge starting electric field strength IV is about 3.7 kV / mm. Therefore, the electric field strength V1 is set to V1 ≧ 3.7 kV / mm and the electric field strength V2 is set according to the above relationship. When applied as V2 <3.7 kV / mm, the nitrogen gas can be excited to be in a plasma state.

The relationship between the currents I1 and I2 is preferably I1 <I2. Current I1 of the first high-frequency electric field is preferably ^{0.3mA / cm 2 ~20mA / cm 2} , more preferably at ^{1.0mA / cm 2 ~20mA / cm 2} . Furthermore, current I2 of the second high frequency electric field is preferably ^{10mA / cm 2 ~100mA / cm 2} , more preferably ^{20mA / cm 2 ~100mA / cm 2} .

  As described above, when the first high-frequency electric field generated by one electrode 2 and the second high-frequency electric field generated by the other electrode 3 are generated, the high-frequency electric field in which the first high-frequency electrolysis and the second high-frequency electric field are superimposed in the discharge space H. An electric field is generated and reacts with the gas to generate discharge plasma. Prior to entering the discharge space H, the base material 5 and the support 6 are in close contact with the adhesive 61, and further surfaces other than the discharge surfaces 2a and 3a continuous with the discharge surfaces 2a and 3a of the electrodes 2 and 3 ( In order to be in close contact with the upper surface of one electrode 2 and the lower surface of the other electrode 3, it enters the plasma space while being supported by a surface other than the discharge surfaces 2 a and 3 a. Thereby, even if the base material 5 and the support body 6 are affected by heat, they are leveled, so that wrinkles and slippage can be prevented.

Further, since the surface temperature of each of the pair of electrodes 2 and 3 is controlled by the temperature adjusting device 44, before the base material 5 and the support 6 enter the discharge space H, the electrodes other than the discharge surfaces 2a and 3a. It will be preheated by the surface of. For this reason, even if the base material 5 and the support body 6 enter the discharge space H, it can be prevented from being suddenly and excessively affected by heat, and shrinkage due to the heat of the discharge plasma can be suppressed. Therefore, it is possible to further prevent the substrate 5 and the support 6 from being wrinkled or distorted. In particular, in the electrodes 2 and 3, the surfaces other than the discharge surfaces 2 a and 3 a that contact the base material 5 and the support 6 before entering the discharge space H ensure a predetermined area. , 3a, the base material 5 and the support 6 can be heated, rapid heating due to entering the discharge space H can be mitigated, and generation of wrinkles and creases can be further suppressed.
The base material 5 on which the thin film is formed is taken up by the base take-up roller 74, and the support 6 is also peeled off from the base 5 and taken up by the support take-up roller 75.

As described above, according to the thin film forming apparatus 1 of the first embodiment, the pair of second gas outlets 85 a is connected to the first gas outlet 84 along the axial direction of the pair of electrodes 2 and 3. Since they are arranged so as to be sandwiched, the gas can be guided from the gas supply unit 8 to the discharge space H in a state where the gas is sandwiched between the raw material gases. Thus, if the gas is sandwiched between the raw material gases, it is possible to prevent the gas from being blocked by the raw material gases and flowing out of the raw material gases. In particular, if the interval (T3 in FIG. 5) between the pair of second gas ejection ports 84 is narrower than the interval (T2 in FIG. 5) of the discharge space H, the gas is less likely to flow out of the discharge space H. It is surely guided into the discharge space H.
In addition, since each of the pair of third gas ejection ports 85b is disposed outside both ends of the first gas ejection port 84, the gas is sandwiched between the raw material gases in the front-rear direction. It is possible to guide from the supply unit 8 to the discharge space H. Therefore, the gas flowing out of the discharge space H from both ends of the first gas outlet 84 can be reduced.
As described above, when the gas containing the thin film forming gas is guided to the discharge space H by the guide means including the first gas outlet 84, the second gas outlet 85a, and the third gas outlet 85b, before the activation. This gas is blocked by the raw material gas and does not contact the substrate 5. That is, it is possible to prevent the gas before activation from coming into contact with the substrate 5 before the activated gas touches the substrate 5. Therefore, it is possible to prevent the raw material contained in the thin film forming gas from adhering to the base material 5 before being activated, and as a result, a uniform and high quality thin film can be formed.

In addition, since the ejection directions of the gas and the raw material gas are parallel to each other, it is possible to suppress the gas flow from being disturbed by the flow of the raw material gas, and to more reliably prevent the gas from flowing out of the raw material gas. Can be prevented. Since the discharge space H extends along the axial direction of the pair of electrodes 2 and 3, as described above, the ejection direction of the gas and the raw material gas may be a direction orthogonal to the axial direction. Thus, the gas can be reliably guided over the entire length of the discharge space H.
Further, since the suction unit 13 sucks the gas that has passed through the discharge space H, the inside of the apparatus can be prevented from being contaminated by the gas that has passed through the discharge space H. In particular, if the suction amount of the suction unit 13 is set larger than the ejection amount of the gas supply unit 8, the gas that has passed through the discharge space H can always be sucked and the gas flows out of the discharge space H. It can be surely prevented.
Furthermore, since the distance (T1 in FIG. 5) between the gas supply unit 8 and the pair of electrodes 2 and 3 is narrower than the distance between the pair of electrodes 2 and 3 (T2 in FIG. 5), the discharge from the gas supply unit 8 The distance to the space H can be shortened, and even if the flow of the gas ejected from the gas supply unit 8 is disturbed, the gas can be contained in the discharge space H before the influence becomes large.

The high-frequency electric field is a superposition of the first high-frequency electric field and the second high-frequency electric field. The frequency ω2 of the second high-frequency electric field is higher than the frequency ω1 of the first high-frequency electric field. 2 Since the relationship between the electric field intensity V2 of the high frequency electric field and the discharge starting electric field intensity IV satisfies V1 ≧ IV> V2 or V1> IV ≧ V2, a thin film can be formed even when an inexpensive gas such as nitrogen is used. It is possible to generate a high-density plasma necessary for forming a high-quality thin film.
Further, according to the present embodiment, since film formation is performed under atmospheric pressure or a pressure near atmospheric pressure, high-speed film formation is possible and continuous production is possible as compared with the case where film formation is performed in a vacuum. It becomes possible. And since the apparatus for making a vacuum is not required, an installation cost can be reduced.

Of course, the present invention is not limited to the first embodiment but can be modified as appropriate. In the following description, the same parts as those in the first embodiment are denoted by the same reference numerals, and the description thereof is omitted.
For example, in the thin film forming apparatus 1 according to the first embodiment, a case where a substantially prismatic rod-like electrode is used as the pair of electrodes 2 and 3 has been described as an example. For example, as shown in FIG. The electrodes may be roll electrodes 25 and 35, respectively. Since the pair of roll electrodes 25 and 35 are rotatable, the pair of roll electrodes 25 and 35 are rotated as the support 6 is conveyed.

  For example, as shown in FIG. 9, the pair of electrodes may be annular belt electrodes 26 and 36, respectively. Specifically, with reference to FIG. 9, the pair of belt electrodes 26 and 36 are stretched with a pair of rollers 50 and 51 so that the discharge space H is spaced apart from each other. Of these rollers 50 and 51, one roller 50 is rotationally driven and the other roller 51 is rotatably provided. If one roller 50 rotates, the belt electrodes 26 and 36 and the other roller 51 also It is designed to rotate. If the belt electrodes 26 and 36 rotate, the support 6 and the base material 5 are transported along the discharge space H side surfaces (discharge surfaces 26a and 36a) of the belt electrodes 26 and 36. A thin film will be formed on the surface.

  Furthermore, as shown in FIG. 10, for example, even if the pair of electrodes 2 and 3 are substantially prismatic rod-shaped electrodes, the support 6 and the base material are in contact with the discharge surfaces 2a and 3a of the electrodes 2 and 3, respectively. An annular conveying belt 52 that conveys 5 may be provided. Specifically, with reference to FIG. 10, the annular transport belt 52 is formed by a pair of rollers 50, 51 arranged in the vertical direction of the electrodes 2, 3, so that the discharge surfaces 2 a, It is stretched so as to come into contact with 3a. That is, if one roller 50 rotates, the conveyance belt 52 and the other roller 51 also rotate. When the transport belt 52 rotates, the support 6 and the base material 5 pass through the pair of electrodes 2 and 3 while being transported along the surface of the transport belt 52 on the discharge space H side. As a result, a thin film is formed on the surface of the substrate 5.

[Second Embodiment]
The thin film forming apparatus according to the second embodiment will be described below with reference to FIG. FIG. 11 is a front view illustrating a schematic configuration of a thin film forming apparatus according to the second embodiment. In the thin film forming apparatus 1 according to the first embodiment described above, the case where film formation is performed on the film-like base material 5 has been described as an example, but in the second embodiment, a plate shape is used. A case where film formation is performed on the base material will be described. In the following description, the same parts as those in the first embodiment are denoted by the same reference numerals, and the description thereof is omitted.

  In the thin film forming apparatus 100 according to the second embodiment, as shown in FIG. 11, a pair of electrodes 2 and 3 that move up and down relatively with respect to the gas supply unit 8 are arranged at a predetermined interval. Has been. A suction unit 13 is disposed on the opposite side of the gas supply unit 8 across the pair of electrodes 2 and 3. The thin film forming apparatus 100 also holds, for example, a plate-like base material 5A made of glass so as to be along at least one of the electrodes 2 and 3 in the discharge space H1 made of a pair of electrodes 2 and 3. A mechanism (not shown) is provided.

  The holding mechanism includes, for example, a plate-like support 6B made of a curing sheet interposed between the base 5A and the electrodes 2 and 3 so as to be in close contact with the base 5A and the electrodes 2 and 3, together with the base 5A. It is supposed to hold on. Since the adhesive 61B is applied on the surface of the support 6B, the support 6B and the substrate 5A are in close contact with each other by the adhesive 61B. Here, the holding mechanism holds the base 5 </ b> A and the support 6 </ b> B so as not to move relative to the gas supply unit 8. That is, when the pair of electrodes 2 and 3 are moved up and down in contact with the support 6B, they move up and down relatively with respect to the base 5A and the support 6B, and the discharge space H1 also moves up and down accordingly. To do. If an electric field is applied to the pair of electrodes 2 and 3 while the gas is supplied from the gas supply unit 8 and the pair of electrodes 2 and 3 are moved from the upper end to the lower end of the substrate 5, the entire surface of the substrate 5 </ b> A is covered. A thin film can be formed. Even if the discharge space H1 is moved up and down in this way, the support 6B and the base material 5A in the discharge space H1 are fixed by the adhesive 61B. Further, it can be prevented.

[Third Embodiment]
Hereinafter, a thin film forming apparatus according to a third embodiment will be described with reference to FIG. FIG. 12 is a perspective view showing a schematic configuration of a thin film forming apparatus according to the third embodiment. In the thin film forming apparatuses 1 and 100 according to the first and second embodiments described above, the case where the gas supply unit 8 ejects the gas and the raw material gas downward is described as an example. In the third embodiment, a case will be described in which the gas supply unit ejects the gas and the raw material gas upward. In the following description, the same parts as those in the first embodiment are denoted by the same reference numerals, and the description thereof is omitted.

  In the thin film forming apparatus 200 according to the third embodiment, as shown in FIG. 12, the gas supply unit 18 is disposed below the discharge space H so as to eject the gas and the raw material gas upward. ing. Formed on the upper surface of the gas supply unit 18 are a first gas outlet 184 that ejects gas and a raw material gas outlet 185 that ejects a raw material gas parallel to the first gas outlet 184. . FIG. 13 is a top view illustrating an arrangement example of the first gas outlet 184 and the non-source gas outlet 185. As shown in FIG. 13, the pair of raw material gas outlets 185 are arranged along the front-rear direction so as to sandwich the first gas outlet 184. That is, in this embodiment, since the raw material gas jet port 185 is the second gas jet port according to the present invention, the gas is sandwiched between the raw material gases and is directed upward from the gas supply unit 18 to the discharge space H. (G1 in FIG. 12 is a gas path, and G2 is a raw material gas path).

  Note that, in the gas supply unit 8 exemplified in the first embodiment and the gas supply unit 18 exemplified in the third embodiment, the entire circumference of the first gas ejection ports 84, 184 is the raw material gas ejection port 85, Although not surrounded by 185, for example, as shown in the gas supply unit 28 shown in FIG. 14, the raw material gas ejection port 285 may be disposed so as to surround the first gas ejection port 284. Here, the portion extending along the front-rear direction of the raw material gas jet 285 is the second gas jet 285a according to the present invention, and the portion extending along the left-right direction is the second according to the present invention. This is a three gas outlet 285b. In this way, the pair of second gas outlets 285a and the pair of third gas outlets 285b are continuous so as to surround the first gas outlet 284, so that they are ejected from the first gas outlet 284. The gas can be guided to the discharge space H while being surrounded by the raw material gas. Therefore, the gas can be guided to the discharge space H without leaking out of the discharge space H.

[Fourth Embodiment]
Hereinafter, a thin film forming apparatus according to a fourth embodiment will be described with reference to FIG. FIG. 15 is a side sectional view showing a schematic configuration of a thin film forming apparatus according to the fourth embodiment. In the thin film forming apparatus 1 according to the first embodiment described above, the gas supply unit 8 ejects the gas and the raw material gas from the outside of the gap between the pair of electrodes 2 and 3 toward the discharge space H. Although illustrated and described, in the fourth embodiment, the case where the gas supply unit ejects the gas and the raw material gas from the inside of the gap between the pair of electrodes toward the discharge space H will be described as an example. . In the following description, the same parts as those in the first embodiment are denoted by the same reference numerals, and the description thereof is omitted.

  As shown in FIG. 15, the gas supply unit 38 provided in the thin film forming apparatus 300 of the fourth embodiment extends so that the front end 381 becomes narrower toward the inside of the gap between the pair of electrodes 2 and 3. ing. A first gas outlet 84 and a raw material gas outlet 85 are formed at the distal end surface of the distal end portion 381. And since the surface of this front-end | tip part 381 is coated with the insulating material, the surface of the front-end | tip part 381 has insulation. As a result, even if the tip 381 enters the region where the discharge plasma is generated, the discharge plasma can be stabilized without conducting the discharge plasma to the gas supply unit 38.

Here, in this embodiment, although the base material 5 and the support body 6 are conveyed so that the base material 5 may contact the gas supply part 38 with the conveying apparatus 7, the damage | wound of the base material 5 by this contact is prevented. Therefore, a rotatable guide roller 382 is provided at a portion of the gas supply unit 38 that contacts the base material 5. The guide roller 382 suppresses rubbing against the base material 5 and prevents the base material 5 from being scratched by rotation accompanying the conveyance and contact of the base material 5.
In addition, since the gas supply unit 38 and the base material 5 are in contact with each other, the gas supply unit 38 and the gap between the pair of electrodes 2 and 3 are closed by the base material 5 and ejected from the gas supply unit 38. Gas and raw material gas are prevented from leaking outside.

[Fifth Embodiment]
Hereinafter, a thin film forming apparatus according to a fifth embodiment will be described with reference to FIG. FIG. 16 is a side sectional view showing a schematic configuration of a thin film forming apparatus according to the fifth embodiment. In the above-described thin film forming apparatuses 1, 100, 200, and 300 according to the first to fourth embodiments, the gas is guided by a non-source gas to prevent the gas from flowing out of the discharge space H. As described above, in the fifth embodiment, a case will be described in which the gas is guided not by the raw material gas but by the guide member to prevent the gas from flowing out of the discharge space H. In the following description, the same parts as those in the first embodiment are denoted by the same reference numerals, and the description thereof is omitted.

As shown in FIG. 16, in the thin film forming apparatus 400 of the fifth embodiment, a pair of electrodes 402 and 403 made of roll electrodes are arranged so as to face each other with a gap therebetween. Above this interval, a gas supply unit 48 that ejects gas toward the interval is disposed.
A first gas ejection port 481 for ejecting gas is formed at the front end of the gas supply unit 48 so as to extend in the front-rear direction. In addition, a pair of guide members 410 and 411 extending in the vertical direction are disposed at the distal end portion of the gas supply unit 48 so as to sandwich the first gas jet port 481 over the entire length of the first gas jet port 481. . The guide members 410 and 411 are formed such that the tips of the guide members 410 and 411 enter at least the discharge space H2 generated by the pair of electrodes 402 and 403. That is, when gas is ejected from the first gas ejection port 481 by the gas supply unit 48, the gas is guided by the pair of guide members 410 and 411 and reaches the discharge space H2. Until the discharge space H2 is reached, the gas is blocked from flowing out to the outside by the guide members 410 and 411. Therefore, before the activated gas touches the substrate 5, the gas before activation is based on the gas. It is possible to prevent contact with the material 5. Therefore, it is possible to prevent the raw material contained in the thin film forming gas from adhering to the base material 5 before being activated, and as a result, a uniform and high quality thin film can be formed.

Of course, the present invention is not limited to the above-described embodiment and can be modified as appropriate.
For example, in the first to fifth embodiments, the case where the transport device 7 transports the support body 6 and the base material 5 in close contact with each other has been described as an example. It may be configured to be conveyed. In such a case, the substrate 5 and the electrodes 2 and 3 may be rubbed at the time of conveyance, and the substrate 5 may be scratched, but the corners 23 and 33 of the electrodes 2 and 3 are formed in an arc shape. Therefore, the generation of scratches can be suppressed. Furthermore, it is preferable to coat the electrodes 2 and 3 with a substance that improves surface slippage to prevent the scratches. Examples of substances that improve surface slip include Teflon (registered trademark) and fluorine compounds.

It is a front view showing schematic structure of the thin film forming apparatus which concerns on 1st Embodiment. It is a perspective view showing schematic structure of the electrode with which the thin film forming apparatus of FIG. 1 is equipped. It is AA sectional drawing in FIG. It is a perspective view showing the gas supply part with which the thin film forming apparatus of FIG. 1 is equipped. It is sectional drawing of the gas supply part of FIG. It is a bottom view showing the front end surface of the gas supply part of FIG. It is a block diagram showing the main control structure in the thin film forming apparatus of FIG. It is a front view showing the modification of the electrode of the thin film forming apparatus of FIG. It is a front view showing the modification of the electrode of FIG. It is a front view showing the modification of the electrode of FIG. It is a front view showing the schematic structure of the thin film forming apparatus which concerns on 2nd Embodiment. It is a perspective view showing schematic structure of the thin film forming apparatus which concerns on 3rd Embodiment. It is a top view showing the example of arrangement | positioning of the 1st gas ejection opening with which the gas supply part of FIG. It is an upper view showing the example of arrangement | positioning of the 1st gas jet nozzle of FIG. 14, and a raw material gas jet nozzle. It is a sectional side view showing schematic structure of the thin film forming apparatus which concerns on 4th Embodiment. It is a sectional side view showing the schematic structure of the thin film forming apparatus which concerns on 5th Embodiment.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Thin film formation apparatus 2 Electrode 3 Electrode 5 Base material 6 Support body 7 Conveyance apparatus (holding mechanism)
8 Gas supply unit 13 Suction unit 84 First gas outlet 85 Non-source gas outlet 85a Second gas outlet 85b Third gas outlet H Discharge space

Claims (30)

A pair of electrodes arranged to form a discharge space with the discharge surfaces facing each other, and generating a high-frequency electric field in the discharge space;
A holding mechanism for holding the substrate in the discharge space;
A thin film is formed on the surface of the base material by supplying the gas to the discharge space so that the gas containing the thin film forming gas is activated by a high-frequency electric field, and exposing the base material with the activated gas. And a gas supply part for forming
The thin film forming apparatus according to claim 1, wherein the gas supply unit includes guide means for guiding the gas to the discharge space so that the gas before activation does not contact the base material. The thin film forming apparatus according to claim 1,
The holding mechanism holds the base material in close contact with the electrodes so as to follow each of the pair of electrodes in the discharge space. The thin film forming apparatus according to claim 1 or 2,
The thin film forming apparatus, wherein the holding mechanism is a transport device that transports the base material. In the thin film formation apparatus as described in any one of Claims 1-3,
The guide means has a first gas jet port for jetting the gas, and a pair of second gas jet ports for jetting a raw material gas not containing the thin film forming gas,
The pair of second gas ejection ports are arranged along the axial direction of the pair of electrodes so as to sandwich the first gas ejection port. The thin film forming apparatus according to claim 4.
The guiding means includes
A pair of third gas outlets for jetting the raw material gas;
The pair of third gas ejection ports are respectively disposed on the outer sides of both end portions of the first gas ejection port in the axial direction. The thin film forming apparatus according to claim 5, wherein
The pair of second gas ejection ports and the pair of third gas ejection ports are continuous so as to surround the first gas ejection port. In the thin film formation apparatus as described in any one of Claims 4-6,
The thin film forming apparatus, wherein the gas and the raw material gas are ejected in directions parallel to each other and perpendicular to the axial direction. In the thin film formation apparatus as described in any one of Claims 4-7,
A thin film forming apparatus, wherein Reynolds numbers at the time of ejection of the gas and the raw material gas are substantially equal. In the thin film forming apparatus according to any one of claims 4 to 8,
The pair of electrodes are arranged so that the discharge space is open in the vertical direction,
The thin film forming apparatus, wherein the gas supply unit is arranged so that the gas and the raw material gas are guided to the discharge space along the vertical direction. In the thin film forming apparatus according to any one of claims 1 to 9,
A suction unit that is disposed on the opposite side of the gas supply unit across the pair of electrodes and sucks the gas that has passed through the discharge space;
The suction amount of the suction part is set to be larger than the ejection amount of the gas supply part. In the thin film forming apparatus according to any one of claims 1 to 10,
The thin film forming apparatus, wherein an interval between the gas supply unit and the pair of electrodes is narrower than an interval between the pair of electrodes. In the thin film formation apparatus as described in any one of Claims 1-11,
A thin film forming apparatus, wherein at least the surface of the guiding means has an insulating property. In the thin film forming apparatus according to any one of claims 1 to 12,
The high-frequency electric field is a superposition of a first high-frequency electric field by one of the pair of electrodes and a second high-frequency electric field by the other electrode,
The frequency ω2 of the second high frequency electric field is higher than the frequency ω1 of the first high frequency electric field,
The relationship among the electric field strength V1 of the first high-frequency electric field, the electric field strength V2 of the second high-frequency electric field, and the discharge starting electric field strength IV is:
A thin film forming apparatus characterized by satisfying V1 ≧ IV> V2 or V1> IV ≧ V2. In the thin film forming apparatus according to any one of claims 1 to 13,
A thin film forming apparatus, wherein the gas contains 50% or more of nitrogen. In the thin film formation apparatus as described in any one of Claims 1-14,
The thin film forming apparatus, wherein the pair of electrodes generate a high-frequency electric field in the discharge space under atmospheric pressure or pressure near atmospheric pressure. A gas containing a thin film forming gas is supplied from a gas supply unit to a discharge space composed of a pair of electrodes whose discharge surfaces face each other, and the gas is activated by generating a high-frequency electric field in the discharge space. The thin film is formed on the substrate by exposing the substrate to the activated gas by holding the substrate in close contact with the electrode along at least one of the pair of electrodes. When doing
A thin film forming method, wherein the gas is guided to the discharge space so that the gas before activation does not contact the substrate. The thin film forming method according to claim 16, wherein
The method of forming a thin film, wherein the substrate is held in close contact with the electrodes so as to follow each of the pair of electrodes in the discharge space. The thin film forming method according to claim 16 or 17,
The thin film forming method, wherein the substrate is conveyed so as to pass through the discharge space. In the thin film formation method as described in any one of Claims 16-18,
A method of forming a thin film, characterized in that a raw material gas not containing the thin film forming gas is ejected along each of the pair of electrodes, and the gas is sandwiched and guided. The thin film forming method according to claim 19,
The method of forming a thin film, wherein the raw material gas is ejected so as to sandwich the gas with respect to the axial direction of the pair of electrodes. The thin film forming method according to claim 19,
The thin film forming method, wherein the raw material gas is ejected so as to surround the gas. In the thin film formation method as described in any one of Claims 19-21,
A method of forming a thin film, wherein the gas and the raw material gas are ejected in directions parallel to each other and perpendicular to the axial direction. In the thin film formation method as described in any one of Claims 19-22,
A thin film forming method, wherein Reynolds numbers at the time of ejection of the gas and the raw material gas are substantially equal. In the thin film formation method as described in any one of Claims 19-23,
The pair of electrodes are arranged so that the discharge space is open in the vertical direction,
The method of forming a thin film, wherein the gas supply unit is arranged so that the gas and the raw material gas are guided to the discharge space along the vertical direction. In the thin film formation method as described in any one of Claims 16-24,
A suction part that sucks the gas that has passed through the discharge space is disposed on the opposite side of the gas supply part across the pair of electrodes,
The method for forming a thin film according to claim 1, wherein the suction amount of the suction portion is set larger than the ejection amount of the gas supply portion. In the thin film formation method as described in any one of Claims 16-25,
The method of forming a thin film, wherein a distance between the gas supply unit and the pair of electrodes is narrower than a distance between the pair of electrodes. In the thin film formation method as described in any one of Claims 16-26,
In the thin film forming method, the gas supply unit has an insulating property at least on a surface of a portion that guides the gas. In the thin film formation method according to any one of claims 16 to 27,
The high-frequency electric field is a superposition of a first high-frequency electric field by one of the pair of electrodes and a second high-frequency electric field by the other electrode,
The frequency ω2 of the second high frequency electric field is higher than the frequency ω1 of the first high frequency electric field,
The relationship among the electric field strength V1 of the first high-frequency electric field, the electric field strength V2 of the second high-frequency electric field, and the discharge starting electric field strength IV is:
A thin film forming method characterized by satisfying V1 ≧ IV> V2 or V1> IV ≧ V2. In the thin film formation method according to any one of claims 16 to 28,
A thin film forming method, wherein the gas contains 50% or more of nitrogen. The thin film formation method according to any one of claims 16 to 29,
A method of forming a thin film, wherein the pair of electrodes generate a high-frequency electric field in the discharge space under atmospheric pressure or pressure near atmospheric pressure.

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