JP2013214452A - Method and apparatus for producing barrier film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a barrier film, which is capable of uniformly polymerizing and curing the whole of an organic film formed on one main surface of a substrate to be treated and laminating an inorganic film on the polymerized and cured organic film in one chamber.SOLUTION: The method for producing a barrier film sequentially includes: a first step in which an organic film 103A formed on one main surface 102a of a substrate 102 to be treated is arranged in a pressure-reduced space and is polymerized and cured using light L emitted from plasma P; and a second step of laminating an inorganic film made of a silicon compound on the organic film polymerized and cured by the first step, in the pressure-reduced space.

Description

  The present invention relates to a barrier film manufacturing method and a manufacturing apparatus.

  In the field of display devices in recent years, display panels using organic EL elements (organic EL displays) that enable realization of high quality and low price on a large screen are widely used. In an organic EL display, peripheral portions of two flat glass substrates are bonded together via a sealing film made of an adhesive material, and an organic EL element is arranged in a hollow part surrounded by the sealing film. Configured as follows.

  Since the organic EL element is vulnerable to moisture, the sealing film surrounding the entire element is required to have a function as a barrier film having high waterproofness and moisture resistance. As a sealing film (barrier film), an organic film based on an ultraviolet curable resin that can be polymerized and cured by irradiation with ultraviolet rays (ultraviolet light) at a relatively low temperature of 100 ° C. or lower and in a short time. Are mainly used (Patent Document 1). In addition, a composite film in which barrier properties are further improved by laminating an inorganic film on an organic film may be used as a sealing film. Irradiation of the organic film with ultraviolet rays is generally performed using a light source such as a halogen lamp (lamp) having a function as a heating means.

  By the way, when the area of the irradiated region of the organic film exceeds the ultraviolet irradiation range by the lamp, the organic film cannot be cured by simultaneously irradiating the entire irradiated region with ultraviolet light. Therefore, in order to irradiate the entire irradiated region with ultraviolet rays, it is necessary to move the lamp relative to the organic film and scan the irradiated region.

  However, when performing ultraviolet ray irradiation with lamp scanning, there is a difference in standby time after irradiation between the previously irradiated region and the subsequently irradiated region. Therefore, there is a possibility that the degree of cure of the organic film differs between remote irradiated areas. That is, when a light source such as a lamp is used, it is difficult to uniformly cure a large-area organic film. As the area of the irradiated region is larger, the ratio of the time consumed for lamp scanning in the irradiation time increases, and the reduction of the tact time is prevented.

  In addition, when forming a composite film in which an inorganic film is laminated on an organic film as a sealing film, in order to form this composite film, in addition to the treatment of curing the organic film by irradiating ultraviolet rays, It is necessary to perform a process of laminating an inorganic film, and two chambers are used. Since the organic film is exposed to an atmosphere under atmospheric pressure while the object to be processed is transported from the chamber in which the organic film is cured to the chamber in which the inorganic film is laminated, impurities contained in the atmosphere are exposed to the organic film. There is a risk of sticking to. Impurities adhering to the cured organic film are likely to be a factor of reducing the barrier property of the sealing film when an inorganic film is laminated on the organic film to form a sealing film.

JP 2004-79231 A

  The present invention has been made in consideration of the above points. In one chamber, the entire organic film formed on one main surface of the substrate to be processed is uniformly polymerized and cured, and polymerization is performed. Provided is a barrier film manufacturing method that enables an inorganic film to be laminated on a cured organic film.

  Further, the present invention provides a barrier capable of irradiating an organic film formed on one main surface of a substrate to be processed with ultraviolet rays contained in radiation emitted from plasma without damaging the plasma. An apparatus for manufacturing a membrane is provided.

  In the method for manufacturing a barrier film according to claim 1 of the present invention, an organic film formed on one main surface of a substrate to be processed is placed in a reduced pressure space and polymerized and cured using radiation light from plasma. One step and a second step of laminating an inorganic film made of a silicon compound on the organic film polymerized and cured in the first step in the reduced pressure space are sequentially included.

  According to a second aspect of the present invention, there is provided a barrier film manufacturing method according to the first aspect, wherein the first step shields the plasma between the plasma and the organic film and emits the plasma from the plasma. Of the light, at least a member that transmits ultraviolet rays is arranged, and the organic film is irradiated with light that has passed through the member.

  The method for producing a barrier film according to claim 3 of the present invention is characterized in that in claim 1 or 2, the method further comprises a third step of forming an organic film on the inorganic film.

  A method for producing a barrier film according to a fourth aspect of the present invention is the method for producing a barrier film according to the third aspect, wherein the first step, the second step, and the third step are repeated, and one of the substrates to be processed is provided. A stacked structure is formed such that the organic film and the inorganic film overlap with the main surface in order N times (N is a natural number).

  According to a fifth aspect of the present invention, there is provided an apparatus for manufacturing a barrier film, comprising: a chamber in which the inside can be decompressed; a supporting means for placing a substrate to be processed disposed in the chamber; and plasma in the chamber. In the chamber, the generator is disposed between the plasma and the substrate to be processed, shields the plasma from the substrate to be processed, and emits at least ultraviolet rays from the radiated light from the plasma. And a transparent member. The member is movable from a position where the plasma is shielded with respect to the substrate to be processed.

  According to the barrier film manufacturing method of the present invention, the organic film is polymerized and cured by irradiation with radiation from plasma. Since this plasma can be generated uniformly in a wide range, the emitted light generated by the generation of the plasma can be simultaneously irradiated to the organic film formed in a wide range. Therefore, unlike the case where the conventional method using lamp irradiation is used, there is no possibility that the degree of curing of the organic film differs between the different irradiated areas, and the entire organic film can be uniformly cured. Further, unlike the case where the conventional method is used, the lamp is moved relative to the organic film, and the time for scanning the irradiated area is not required, so that the tact time can be shortened.

  In addition, according to the method for producing a barrier film according to the present invention, as a barrier film (sealing film), an organic film that is required when forming a composite film in which an inorganic film is laminated on an organic film is used. The process of curing by irradiating with ultraviolet rays and the process of laminating the inorganic film can be performed in one chamber. Therefore, since the organic film is not exposed to the atmosphere under atmospheric pressure between the time when the organic film is cured and the time when the inorganic film is laminated, impurities such as those contained in the atmosphere adhere to the organic film. There is no fear of doing it. And when an inorganic film is laminated | stacked on the hardened organic film and a barrier film is formed, the barrier property fall of this sealing film resulting from an impurity can be prevented.

  Further, according to the barrier film manufacturing apparatus of the present invention, the plasma is shielded against the substrate to be processed between the plasma generated in the chamber and the substrate to be processed, and among the radiated light from the plasma, And a member that transmits at least ultraviolet rays. Therefore, it is possible to irradiate the organic film formed on one main surface of the substrate to be processed facing the plasma with the ultraviolet rays contained in the radiation emitted by the plasma without damaging the plasma.

It is sectional drawing explaining the structure of the manufacturing apparatus of a barrier film in this invention. It is a process flow explaining the manufacturing method of a barrier film in the present invention. (A) It is sectional drawing of a to-be-processed object in the 1st process process of this invention. (B) It is a perspective view of a to-be-processed object in the 1st process of this invention. (A) It is sectional drawing of the to-be-processed object which passed through the 2nd process of this invention. (B) It is sectional drawing of the to-be-processed object which passed through the 1st process and 2nd process of this invention in multiple times.

  Hereinafter, based on a preferred embodiment, the present invention will be described with reference to the drawings.

<First embodiment>
[Barrier film production equipment]
FIG. 1 is a cross-sectional view illustrating the configuration of a barrier film manufacturing apparatus 100 according to the first embodiment of the present invention. The barrier film manufacturing apparatus 100 includes a chamber (decompressed space) 101 that can be depressurized inside, and an object to be processed in which an organic film 103A is formed on one main surface 102a of the substrate to be processed 102 in the chamber 101. A supporting means 104 for placing M1 and means (plasma generating means) E for generating plasma P are provided. Further, the barrier film manufacturing apparatus 100 is disposed in the chamber 101 between the generated plasma P and the substrate to be processed 102, shields the plasma P spreading toward the substrate to be processed 102, and emits radiation from the plasma P. Of the light L, a member 105 that transmits at least ultraviolet rays is provided. The member 105 is assumed to be movable between a position where the plasma P is shielded with respect to the substrate to be processed 102 and another position.

  It is assumed that the object to be processed M1 is placed on the support means 104 so that one main surface 102a of the substrate to be processed is opposed to the plasma P generated in the chamber 101. The support means 104 is electrically grounded and serves as a lower electrode when the plasma P is generated. Further, the support means 104 includes means T for controlling the temperature of the substrate 102 to be processed.

  The organic film 103A is preferably based on an ultraviolet curable resin that can be polymerized and cured by irradiation with ultraviolet rays (ultraviolet light) at a relatively low temperature of 100 ° C. or lower and in a short time. For example, an acrylic monomer solution (acrylic solution) is used. The organic film 103A made of an acrylic solution is formed on one main surface 102a of the substrate to be processed using a method such as vapor deposition, coating, dropping, or ink jet.

  The plasma generating means E forms means 106 for evacuating the inside of the chamber 101 and an upper electrode when generating the plasma P, and means for introducing a reactive gas G such as nitrogen or argon into the chamber 101 (gas introducing means). 107 and a power supply 108 for applying a voltage to the gas introduction means (upper electrode) 107 at least. By applying a voltage to the upper electrode 107 using the power source 108 and generating a potential difference between the upper electrode 107 and the supporting means 104 forming the lower electrode, the reaction gas G can be brought into a plasma state.

[Method for producing barrier film]
Two process flows A (dotted line) and process flow B (solid line) that realize the manufacture of the barrier film according to the first embodiment of the present invention will be described with reference to FIG. FIG. 2 schematically shows a state in which the chambers (C1 to C4) used for the processing of each process flow are arranged in the order of use (in the order indicated by the arrows).

  In both the process flow A and the process flow B, the process of curing the organic film 103A formed on the one main surface 102a of the substrate to be processed (first process) and the inorganic film 109 on the cured organic film 103B are performed. The step of forming (second step) is sequentially included at least once.

  In addition, the process flow A and the process flow B are both newly performed on the inorganic film formed through the second process after the first process and the second process are sequentially performed once. The step (third step) for forming the first step, the first step to be newly performed, and the second step may be sequentially repeated a plurality of times.

  Process flow A corresponds to the case of manufacturing a barrier film by a conventional method. The above-described three process processes included in the process flow A are performed in individual chambers. That is, a process of forming the organic film 103A on the one main surface 102a of the substrate to be processed, a process of curing the formed organic film 103A, and a process of forming the inorganic film 109 on the cured organic film 103B, Performed in chambers C1, C2, and C3, respectively. Therefore, it is necessary to use at least three chambers in order to perform the process flow A.

  On the other hand, the process flow B corresponds to the case where a barrier film is manufactured by the method according to the first embodiment of the present invention. Of the above-described three process processes included in the process flow B, at least the process process for curing the organic film 103A and the process process for forming the inorganic film 109 on the cured organic film 103B are performed in the same chamber. Done in That is, the process for forming the organic film 103A on one main surface 102a of the substrate to be processed is performed in the chamber C1, the process for curing the formed organic film 103A, and the formation of the inorganic film 109 on the cured organic film 103B. Is performed in the same chamber C4. Therefore, it is necessary to use at least two chambers in order to perform the process flow B.

  A method for processing the organic film 103A formed on one main surface 102a of the substrate to be processed will be described using the barrier film manufacturing apparatus 100 shown in FIG. First, the first step of polymerizing and curing the organic film 103A will be described.

  First, the inside of the chamber 101 is evacuated, and the object to be processed M1 is placed on the support means 104. At this time, a liquid organic film 103A is formed on one main surface 102a of the substrate to be processed, which is a surface to be processed, by a method such as vapor deposition, coating, dropping, or ink jetting.

  Next, the member 105 is moved so as to overlap the substrate to be processed M1 at a position where the plasma P is shielded from the substrate to be processed M1, that is, a position on the side where the organic film 103A of the object to be processed M1 is formed. Arrange.

  Then, a reaction gas G containing nitrogen element or argon element is introduced into a space between the gas introduction means 107 and the member 105 in the chamber 101, and an upper electrode (gas introduction means) is formed by using the plasma generation means E. ) A voltage is applied between 107 and the lower electrode (support means) 104. Thereby, the atmosphere in the chamber 101 is in a state (plasma state) in which the elements constituting the reaction gas G are ionized and the plasma P is generated.

  FIG. 3A is an enlarged view of the region R in the cross section of the barrier film manufacturing apparatus 100 shown in FIG. As shown in FIG. 3A, the barrier film manufacturing apparatus 100 has a configuration in which the plasma atmosphere (plasma) P generated in the chamber 101 is shielded by the member 105 and cannot reach the organic film 103A. ing. Then, the ultraviolet rays contained in the radiated light L generated together with the plasma P are transmitted through the member 105 and irradiated to the organic film 103A, and the organic film 103A is polymerized and cured from the liquid state to the solid state by a photopolymerization reaction. The member 105 has transparency that allows ultraviolet rays having a wavelength range of 0.2 to 1 [μm] to pass therethrough.

  In order to uniformly polymerize and cure the entire organic film 103A formed on one main surface 102a of the substrate to be processed, it is necessary to uniformly irradiate the entire organic film 103A with ultraviolet rays. Therefore, one main surface 105a of the member facing the substrate to be processed 102 and the other main surface 105b of the member facing the plasma P may be arranged in parallel with the one main surface 102a of the substrate to be processed. desirable.

  Further, in order to prevent the organic film 103A formed on the one main surface 102a of the substrate to be processed from being damaged by the plasma P, the object to be processed M1 is prevented from being exposed to the plasma P. It is necessary to have a shape that shields the plasma P that is about to spread. That is, the area of both main surfaces 105a and 105b of the member is required to be a shape that covers at least the region where the organic film 103A is formed on one main surface 102a of the substrate to be processed. The member 105 preferably has a thickness that does not allow at least the plasma P to pass between the other main surface 105b of the member 105 and the one main surface 105a.

  FIG. 3B is an enlarged perspective view showing the configuration of the region R shown in FIG. 1 so that the other main surface 105b side of the member can be seen. The emitted light L from the plasma is transmitted through the member 105 in the thickness direction, and is simultaneously irradiated onto the entire organic film 103A constituting the surface to be processed of the object to be processed M1. If the area within the chamber 101 is within the range, even if the area of the surface to be processed is large, the member 105 having an area larger than that is selected and used, so that radiated light including ultraviolet rays can be emitted to the entire organic film 103A. Can be uniformly and simultaneously irradiated.

  In order to prevent the organic film 103A from being exposed to the plasma P, the member 105 may have such a size that the plasma P does not go around from the other main surface 105b side to the one main surface 105a side. desirable. Further, even if the plasma P wraps around the one main surface 105a side of the member, the object to be processed M1 is disposed at a position close enough not to contact the member 105 in order to prevent reaching the organic film 103A. It is desirable.

  Subsequently, the second step of forming a film made of an inorganic material containing a desired silicon compound on the organic film 103B cured in the first step will be described. The processing in the second step is performed in the chamber 101 used in the first step. This eliminates the need for operations such as opening the atmosphere and evacuating the process chamber.

  First, the inside of the chamber 101 is evacuated together with the process gas (reactive gas) used in the process of the first step. Then, in the chamber 101, a reactive gas containing a silicon compound is introduced into a region near the object to be processed M1. Further, the support means is heated using the temperature control means, and the target object M1 (organic film 103B) is controlled to have a desired temperature via the support means. Thus, the reactive gas thermally reacts with the organic film 103B, and a film (inorganic film) made of a silicon compound is formed on the organic film 103B.

  FIG. 4 shows a cross-sectional configuration of the object M2 that has undergone the second step. The object to be processed M2 includes a barrier film in which an organic film 103B and an inorganic film 109 are sequentially stacked on one main surface 102a of the substrate to be processed. When the barrier film is formed by stacking the inorganic films 109, the barrier property can be improved as compared with the case where the barrier film is formed of a single organic film.

  In addition, with respect to the to-be-processed object M2 shown to Fig.4 (a), the process (3rd process) of forming a new organic film on the inorganic film 109, the 1st process mentioned above, the 2nd process mentioned above. 4 is repeated N times (N is a natural number) to obtain a target object M3 in which a plurality of layers made of an organic film and an inorganic film are stacked as shown in FIG. 4B. The laminated portion of the object to be processed M3 has a laminated structure (103L1, 109L1, 103L2, 109L2,... 103LN, so that the organic film and the inorganic film are sequentially overlapped N times on one main surface 102a of the substrate to be processed. 109LN) and has a higher barrier property than the laminated portion of the object to be processed M2 shown in FIG.

  As described above, according to the method for manufacturing a barrier film according to the first embodiment, the organic film 103A is polymerized and cured by irradiation with the radiation light L from the plasma P. Since the plasma P can be generated uniformly over a wide range, the emitted light generated with the generation of the plasma P can be simultaneously applied to the organic film 103A formed over a wide range. Therefore, unlike the case where the conventional method using lamp irradiation is used, there is no possibility that the degree of curing of the organic film 103A differs between the different irradiated regions, and the entire organic film 103A can be uniformly cured. . Further, as in the case of using the conventional method, the lamp is moved relative to the organic film 103A, and it does not require time for scanning over the irradiated region, so that the tact time can be shortened.

  Further, according to the barrier film manufacturing method according to the first embodiment, it is necessary when forming a composite film in which the inorganic film 109 is laminated on the organic film 103B as the barrier film (sealing film). The process of irradiating the organic film 103 </ b> A by irradiating it with ultraviolet rays and the process of laminating the inorganic film 109 can be performed in one chamber 101. Therefore, since the organic film 103A is not exposed to an atmosphere under atmospheric pressure between the time when the organic film 103A is cured and the time when the inorganic film 109 is stacked, impurities such as those contained in the atmosphere are organic. There is no risk of adhering to the film 103A. Then, when the barrier film is formed by laminating the inorganic film 109 on the cured organic film 103B, it is possible to prevent the barrier property of the barrier film from being deteriorated due to impurities.

  Moreover, according to the barrier film manufacturing apparatus according to the first embodiment, the plasma P is shielded from the substrate to be processed 102 between the plasma P generated in the chamber 101 and the substrate to be processed 102. A member 105 that transmits at least ultraviolet light out of the radiated light L from plasma is provided. Therefore, the organic film 103A formed on the one main surface 102a of the substrate to be processed facing the plasma P is irradiated with ultraviolet rays contained in the radiated light L without being damaged by the plasma P. Can do.

  In the chamber 101, when the substrate to be processed 102 can be disposed at a position away from the plasma P to the extent that the plasma P does not affect the organic film 103A, the member 105 is not disposed. The same effects as those of the first embodiment described above can be obtained.

  The present invention can be widely applied to the case where the barrier property of a sealing film constituting a display device such as an organic EL display or a plasma display is increased.

DESCRIPTION OF SYMBOLS 100 ... Manufacturing apparatus, 101 ... Chamber, 102 ... Substrate to be processed,
102a ... main surface, 103A, 103B ... organic film, 104 ... support means,
105: member, 109: inorganic film, E: plasma generating means, L: emitted light, P: plasma.

Claims (5)

A first step of placing an organic film formed on one main surface of the substrate to be processed in a reduced pressure space and polymerizing and curing using radiation from the plasma;
A method for producing a barrier film, comprising: a second step of sequentially laminating an inorganic film made of a silicon compound on the organic film polymerized and cured in the first step in the reduced pressure space.   In the first step, the plasma is shielded between the plasma and the organic film, and a member that transmits at least ultraviolet light out of the radiated light from the plasma is disposed and passed through the member. The method for producing a barrier film according to claim 1, wherein the organic film is irradiated with light.   The organic film processing method according to claim 1, further comprising a third step of forming an organic film on the inorganic film. Repeat the first step, the second step, and the third step,
4. The barrier film according to claim 3, wherein the laminated structure is formed so that the organic film and the inorganic film overlap N times (N is a natural number) in order on one main surface of the substrate to be processed. Method. A chamber capable of depressurizing the interior;
A supporting means for placing a substrate to be processed disposed in the chamber;
Means for generating plasma in the chamber;
A member that is disposed between the plasma and the substrate to be processed in the chamber, shields the plasma from the substrate to be processed, and transmits at least ultraviolet light among the emitted light from the plasma; At least,
The apparatus for manufacturing a barrier film, wherein the member is movable from a position where the plasma is shielded with respect to the substrate to be processed.

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