TW201238768A - Gas barrier film, production device therefor, and production program therefor - Google Patents

Abstract

The objective of the present invention is to provide a technology regarding a gas barrier film capable of obtaining a favorable balance among transmittance of visible light, coatability, and flexibility. A gas barrier film (1) comprises a buffer layer (2) containing a silicon compound, and a barrier layer (3) laminated on the buffer layer (2) and containing silicon oxide and/or silicon nitride, wherein, with respect to the Fourier transform infrared absorption spectrum of the buffer layer (2), AR and t satisfy ARR=3 and the formula (2), wherein AR (AR=A1/A2) is a ratio between the infrared absorbance (A1) at the wave number of 900 cm-1 and the infrared absorbance (A2) at the wave number of 1260 cm-1, and t (nm) is the total thickness of the buffer layers contained in the gas barrier film.

Description

201238768 VI. Description of the Invention: [Technical Field of the Invention] [The present invention relates to a gas barrier that can be used for protection of an electronic device such as an organic electroluminescence (organic electroluminescence) or the like. Membrane (gas barHer_ iilm) and its manufacturing apparatus and its manufacturing process. [Prior Art] Conventionally, various types of articles such as foods, medicines, chemicals, enamels, and miscellaneous goods are required to have a plastic film having a high gas barrier (gas barr_ier property). Since the plastic film is generally inferior in gas barrier properties to glass, various methods for applying various gas barrier films to the plastic film have been proposed. In recent years, it has been proposed to use a plastic thin plate or a plastic film as a substrate for a display device using an organic EL or a liquid crystal, from the viewpoint of weight reduction, thin film formation, and flexibilization. . From the viewpoint of maintaining the visibility of the display portion and preventing oxidative degradation of the element portion formed on the surface of the substrate, it is required to be transparent and have a gas barrier property which is extremely high in oxygen barrier property and water vapor barrier property. Gas barrier film. In addition, the solar cell (solar cel 1) is also required to have a gas barrier film having high gas barrier properties from the viewpoint of preventing deterioration of the power generation layer or the electrodes and the like.

For example, Patent Document 1 discloses that it is formed on a plastic substrate and formed by chemical vapor deposition of an organic cerium compound, and 8 丨 (^3 of the wave number 845 to 833 cin_1) The characteristic absorption is substantially zero, and the infrared absorption ratio of Si〇H/SiO rat io)(A) 1013085717-0 (infra red absorbance 101101411^ single number application page 4 / total 45 pages 201238768 is 0.25 or less oxidized stone On the other hand, in the case of the above-mentioned patent document 2, it is described that the organic compound layer is disposed on the substrate to flatten the unevenness of the surface for forming the oxide layer. A fine coating film of an organic bismuth compound polymer is formed on the surface of a plastic substrate by a low-temperature electropolymerization method, and then a ruthenium oxide film is coated on the coating film of the organic bismuth compound polymer of the substrate to produce a gas barrier plastic material. [Patent Document 1] Japanese Unexamined Patent Publication No. Hei No. Hei No. Hei. No. Hei. No. Hei. The bismuth coating film itself exhibits excellent gas barrier properties, but has low flexibility. Therefore, when it is formed on a soft substrate such as plastic, the adhesion between the film and the substrate is low, and the film is easy. There is a problem that the gas barrier property cannot be sufficiently exerted as a result. The gas barrier film in which the layer of the organic germanium compound polymer and the tantalum oxide layer are laminated has the following problems. The layer functions as a buffer layer, that is, a stress relaxation layer, but generally, the organic ruthenium compound polymer has low transparency. Therefore, as a gas barrier film having high transparency, it is necessary to reduce an organic ruthenium compound. As a result, the thickness of the layer is lowered, and the effect of stress relaxation is lowered, and the flexibility is lowered to cause cracking. The object of the present invention is to provide a good visibility of light transmittance and coverage and flexibility in the gas barrier film. The gas barrier film according to the first aspect of the present invention comprises: a buffer layer containing a silicon compound; and is laminated on the aforementioned 10110141!^, single number A0101, page 5 / Total 45 pages 1013085717-0 201238768 Punch layer, containing a barrier layer of oxidized stone and/or silicon nitride, Fourier transform infrared absorption spectrum for the aforementioned buffer layer (Fourier transform infrared absorption spectrum) In the spectrum, the ratio of the infrared absorbance A1 of the wave number 900 cm_1 to the infrared absorbance A2 of the wave number 1 260 (^-1 (AR = A1/A2), and the buffer included in the above gas barrier film The total thickness t(nra) of the layers satisfies AR < 3 and formula (1), 哎 SAR 23 and formula (2), [Formula 1] [0004] 15656

A 3.313 (1)

R

[Formula 2] (2) 837 a 0.648 ΆΚ ΙΟΠΟΗ ^单单 Α 0101 Page 6 / Total 45 pages 1013085717-0 201238768 Further, the buffer layer thickness calculating device according to the second aspect of the present invention includes: at least accepting The regu 1 ar transmission factor of the visible light in the gas barrier film and the infrared absorption A1 of the wave number of 90 0 cm-1 in the Fourier transform infrared absorption spectrum for the buffer layer The input receiving unit of the input of the ratio AD (AD = A1/A2) of the infrared ray absorbance A2 of the wave number of 12 60 cm 1 ; the content of the acceptance of the input accepting unit satisfies AD < 3 and formula (1), or satisfies AD 23 Calculating the thickness of the buffer layer included in the gas barrier film by the formula (2)

K Ο [0005] [0006]

A buffer layer thickness calculation unit of t (nm). [Effects of the Invention] According to the present invention, it is possible to maintain good transmittance of visible light in a gas barrier film with a moderate thickness. [Embodiment] [1. Gas barrier film] The gas barrier film 1 of the present embodiment will be described with reference to Fig. 1. As shown in Fig. 1, the gas barrier film 1 of the present embodiment is disposed so as to be placed over the substrate. The electronic component 42 such as an organic EL element on the substrate 4 is used. The gas barrier film 1 is also referred to as a sealing film to protect the electronic component 42 from water, oxygen, and the like. The thickness of the entire gas barrier film 1 may be about 1/m. The outermost surface of the gas barrier film 1 is covered by the barrier layer 3. In the present embodiment, the buffer layer 2 and the barrier layer 3 are alternately laminated. Further, the gas barrier film 1 may have two or more buffer layers directly laminated, for example, including different compositions, and may include two or more barrier layers directly laminated with different compositions. 1011014#单号 A_ Page 7 of 45 1013085717-0 201238768 In Figure 1, there are shown n buffer layers 2 and n barrier layers 3. Each of the buffer layers 2 is referred to as a first buffer layer 2-1, a second buffer layer 2-2, and an n-th buffer layer 2-n. Further, each of the barrier layers 3 is referred to as a first barrier layer 3-1, a second barrier layer 3-2, ..., an n barrier layer 3-n. When the respective buffer layers are not particularly distinguished, the buffer layers are integrated only as the buffer layer 2. When the respective barrier layers are not particularly distinguished, the barrier layers are integrated only as the barrier layer 3. In the following, η is sometimes referred to as [number of layers], and the number of layers η may be 2 or more, for example, 5 or more, and 10 or less. Further, the thickness of each of the barrier layer 3 and the buffer layer 2 is not particularly limited, and may be from 1 to 11111 to several hundreds of 11111. In particular, the thickness of the barrier layer 3 is preferably 20 nm or more. The buffer layer 2, also referred to as a stress relaxation layer, contains a broken compound. The buffer layer 2 may contain a compound of the stone compound as a main component. The term "containing a component as a main component" may be 60% by weight or more, and may be 70% by weight or more, and may be 80% by weight or more, and may be 90% by weight or more, meaning that only Its composition is also ok. For example, the buffer layer 2 may be a lanthanide film, and may be a lanthanoid film containing lanthanum, C, and Si. Specifically, the buffer layer 2 may be a lanthanoid film containing Si (CH3). The composition of each of the buffer layers 2 may be the same or different. The range of the density of the buffer layer 2 is 1. 3~1. The range of 7g/cm3 is preferred. In the Fourier transform infrared absorption spectrum for the buffer layer 2, the ratio of the infrared absorbance A1 of the wave number 900 cm_1 to the infrared absorbance A2 of the wave number of 1260 cm 1 is AD (AD = A1/A2), and is included in the gas barrier film 1 The total thickness t (nm) of the buffer layer 2 satisfies AD < 3 and formula (1), or satisfies Ar23 and formula (2) [formula 3] Xie leg ^ single number A_ 1013085717-0 page 8 / total 45 pages (1) 201238768 15656λ 3.313 Ar [0007] ❹ [Formula 4] 837 Δ 0.648 XJL*p

t< (2) The total thickness t of the buffer layer 2 is preferably 10 nm or more, and more preferably 4,000 nm or less. When the gas barrier film 1 satisfies this condition, the positive transmittance (for example, 70% or more) of visible light can be kept in good balance with at least one of flexibility and coverage. The barrier layer 3 may contain cerium oxide and/or cerium nitride as a main component. Moreover, when the barrier layer 3 contains yttrium oxide and tantalum nitride as a main component, the composition of the first barrier layer 31 and the composition of the second barrier layer 32 may be the same or different, and the barrier layer 3 has a buffer ratio. Layer 2 has a high density. Although the size of the barrier layer 3, A0101, page 9 / page 45, 1013085717-0, 201238768 is limited to a specific value, if it is to prevent water or oxygen from reaching the electronic component 4 2 Just fine. For example, the density of the barrier layer 3 is preferably about 1. 8 to 2. 5 g / cm 3 or so. Further, the configuration of the gas barrier film 1 may be changed to include a layer containing an organic substance in addition to the buffer layer 2 and the barrier layer 3. Further, the configuration of the gas barrier film 1 may be changed so that the buffer layer 2 and the barrier layer 3 may be arranged upside down. That is, the substrate 4, the barrier layer 3, the buffer layer 2, the barrier layer 3, the buffer layer 2, ... may be arranged in this order. Further, it is preferable to provide at least one barrier layer 3 on the outer side of the buffer layer 2 located on the outermost side (upper side) of all the buffer layers 2. [2. Manufacturing Apparatus] A manufacturing apparatus of the gas barrier film will be described with reference to FIG. As shown in Fig. 2, the manufacturing unit 1 includes an input receiving unit, a control device 102, and a film forming apparatus 1A. The input accepting unit 101 receives an input of a desired condition such as a positive transmittance of visible light from the operator, an infrared ray absorbance ratio of the buffer layer, a thickness of the entire gas barrier film, a thickness of the buffer layer, and a number of buffer layers. The input accepting unit 101 is realized by a hard key, a touch panel, or the like. The control device 102 performs various calculations and controls the operations of the respective units of the manufacturing apparatus 100. The functional block included in the control device 1〇2 can be obtained by cpu (Central)

Processing Unit: Central Processing Unit) and R〇M (Read 〇nly

Memory media such as Memory: Read Only Memory, RAM (Random Access Memory), and FLASH (Flash Memory). It can also be executed by the CPU by reading the program stored in the recording medium of the ROM or the like, such as 10110141#single number Α01〇ι 1 page/45 pages 1013085717-0 201238768, to realize various functions. The RAM functions as a work area of the CPU. Further, it is also possible to record, on a recording medium such as R〇M, a calibration curve showing the correlation between the infrared absorbance ratio AR and the film forming conditions, and the sum of the thicknesses of the buffer layers in the gas barrier film. The correlation curve between the infrared absorption ratio and the correlation between the infrared absorption ratio and the positive transmittance of the visible light. Specifically, the control device 102 includes an infrared ray absorbance ratio calculating unit 103, a film forming condition determining unit 104, a buffer layer thickness calculating unit 〇5, and a film forming apparatus control unit 106. The functions for each block will be described later. As shown in FIGS. 3 and 4, the film forming apparatus 1A includes a load-lock chamber 5, a robot chamber 6 coupled to the load lock chamber 5, and a machine attached to the machine. The first film forming chamber 7 and the second film forming chamber 8 of the arm chamber 6. The film forming apparatus 1 can form a laminated film of the buffer layer 2 and the barrier layer 3 (i.e., a gas barrier film).设置 A gate valve 51 is disposed between the load lock chamber 5 and the arm chamber 6. The load lock chamber 5 can be isolated from the robot arm chamber 6 by the gate valve 51. The load lock chamber 5 is connected to a vacuum pump 52 and has a substrate holder 53 therein. The substrate storage rack 53 is provided with a support pin 54 that supports the peripheral edge portion of the substrate 4. The electronic component a is formed on one surface of the substrate 4 on one surface, and the size of the substrate 4 is, for example, about 370 mm x 470 mm. The robot arm chamber 6 is provided with a substrate transport robot 61 therein. The substrate transport robot 61 includes a motor 62, an arm 63, and a movable support table 64. The movable support table 64 is configured to be movable in the respective directions of the χ, y&z section_production number by the driving of the motor 62 and through the arm 63. The movable support table 64 and the substrate storage rack 53 Α 0101 Page 11 of 45 1013085717-0 201238768 The support pin 54 is provided with a support pin 65. Further, a vacuum pump 67 is connected to the arm chamber 6 via the first flow rate control valve 66. A gate valve 68 is disposed between the robot arm chamber 6 and the first film forming chamber 7, and a gate valve 69 is disposed between the robot arm chamber 6 and the second film forming chamber 8. The substrate transport robot 61 moves the movable support table 64 and moves the substrate 4 to the first film forming chamber 7 and the second film forming chamber 8 by the switch gate valves 68 and 69. The first film forming chamber 7 communicates with the robot arm chamber 6, is connected to the vacuum pump 71 via the second flow rate control valve 761, and is connected to the HMDS (hexamethyldisi lazane) supply tank via the third flow rate control valve 762. 72 is connected to the H2 supply tank 73 and the Ar supply tank 74 via the fourth flow rate control valve 763. A loop antenna 77 is disposed inside the first film forming chamber 7. The loop antenna 77 is a means for generating plasma, and is constituted by an insulating tube 78 and a conductive electrode 79. The two insulating tubes 78 are arranged in parallel in the first film forming chamber 7. The conductive electrode 79 is inserted into the two insulating tubes 78, as shown in FIG. 4, and has a substantially U-shape in plan view and penetrates the opposite side walls of the first film forming chamber 7, and is connected to a power source for supplying a high frequency current. 771. The frequency of the high frequency current is preferably about 13.56 MHz. In addition, the structure of the loop antenna 77 is a structure of ICP (Inductive Coupled Plasma) discharge, and the electrodes of the other structure are CCP (Capacitive Coupled Plasma), barrier, An electrode such as a hollow may be electrically discharged. The second film forming chamber 8 communicates with the robot arm chamber 6, is connected to the vacuum pump 81 via the fifth flow control valve 861, and is connected via the sixth flow control valve 862. The leg #单编号施 01 page 12 / total 45 pages 1013085717-0 201238768 is connected to the 〇 supply tank 83 via the seventh flow control valve 863 in the HMDS supply tank 82. 2 A loop antenna 87 is disposed in the second film forming chamber 8. The loop antenna is constructed by an insulating officer 88 and a conductive electrode 89. The detailed description of the loop antenna 87 is omitted because it overlaps with the loop antenna 77 of the first film forming chamber 7. The conductive electrode 89 is connected to a power source 871 that supplies a high-frequency current. [3. Manufacturing method] Next, a method of manufacturing a gas barrier film using the manufacturing apparatus 1 and the operation of the manufacturing apparatus 100 will be described with reference to Figs. 2 and 5 to 8 . Further, the film formation is automatically controlled in the present embodiment, but the start and end of some or all of the film formation may be manually controlled. In the present embodiment, the target value of the positive transmittance of visible light of the gas barrier film 1 is set to 70% or more. Further, the number of laminations 11 is also set to a constant value '. However, the present invention is not limited thereto, and for example, the positive transmittance of the visible light of the gas barrier film 1 and the number of layers η may be specified by the operator. & As shown in Fig. 5, when the input accepting unit 1〇1 receives input from the operator, the film forming conditions are set in accordance with the contents. For example, when the infrared absorption ratio of the input buffer layer 2 or the value corresponding to the infrared absorption ratio AD is correlated (Yes in step S31), the sum of the thicknesses of the buffer layers 2 is determined (step S32). Here, since the number of layers η is fixed as described above, it can be said that step S32 is a step of determining the thickness of each of the buffer layers 2. The absorbance ratio AD, as already explained, refers to the ratio AR (AR = A1/A2) of the infrared absorbance A1 at a wave number of 900 cm_1 to the infrared absorbance A2 at a wavenumber of 1260 cm_1. In addition, a value that has a correlation with the infrared absorbance ratio AD means

R 10110141^Single number A〇101 Page 13 of 45 1013085717-0 201238768 Positive transmittance of visible light including buffer layer 2 and [film formation pressure xHMDS flow rate / input power (Pa*sccm/kW)]. As will be described later, the positive transmittance of visible light of the buffer layer 2 has a correlation with the infrared ray absorbance ratio, and the infrared ray absorbance &AR has a correlation with the film forming pressure xHMDS flow rate/input power (Pa*sccra/kW). Therefore, the control device 1〇2 can determine the infrared absorption ratio Ar from the [values having a mutual relationship] based on the mutual relations. The transmission layer thickness calculation unit 105 calculates the total thickness of the buffer layer 2 from the infrared ray absorbance ratio 〜 which is input or obtained as described above. That is, the target value of the total t (nm) of the thickness of the buffer layer 2 included in the gas barrier film 1 is set so as to satisfy AR < 3 and the formula (1), or satisfy the formula (2). The graphs of these equations are shown in Figure 9. [Formula 5] 15656

Ar 3.313 (1) [0008] [Formula 6] [0009] Page 14 of 45 10110141^Single Number A0101 1013085717-0 837 201238768 t A 0.648Ar (2) If the target value of the positive transmittance of visible light is 70 %, the inequality in equations (1) and (2) may be changed to an equal sign. That is, the input receiving unit 101 and the buffer layer thickness calculating unit 105 function as a buffer layer thickness calculating means. Further, when the operator does not input the infrared ray absorbance ratio ad (including a value related to the infrared ray absorbance ratio AR) (No at step S31), the total value t of the thickness of the buffer layer 2 is obtained (at step S33). In the case of Yes, the infrared ray absorbance ratio calculating unit 103 calculates the infrared ray absorbance ratio AD as the target based on the above formula (1) or (2) (step S34). In this case, if 1 is larger than 411 nm, the formula (1) is used, and when t is 411 nm 0 or less, the formula (2) is applied. Next, the film forming conditions are determined (step S35). In this step, the film forming condition determining unit 104 sets the film forming time of each buffer layer from the total value of the thickness determined in step S32 or input by the operator, or based on the operation determined in step S34 or by operation. The infrared ray absorbance input is set to a target value of 8%, and the film forming pressure xHMDS flow rate/input power (Pa*sccm/kW) is set. When the information necessary for determining the film forming conditions is not input (No in steps S31 and S33), the processing is terminated without determining the film forming conditions. At this time, the display of the urging information is displayed to the operator in a display device (not shown). 1) 1111^单单 A0101 Page 15 of 45 1013085717-0 201238768 The incoming message is also available. The film forming apparatus control unit m controls the operation of the film forming apparatus 10 based on the conditions determined as described above. The film forming apparatus 10 will be described in an initial state as shown below. That is, the load lock chamber 5 is in a state in which the gate valve 51 is closed, and the internal pressure of the load lock chamber 5 is atmospheric. In the substrate storage rack, the unsealed substrate 4 on which the electronic component 42 is disposed is held in a state where the oil is directly under one side of the substrate. First, in the state where the closing valve 69' gate valve 68 is opened, as shown in Fig. 6, the first film forming chamber 7 and the robot arm chamber 6 are decompressed by the vacuum pump 71 (step si). At this time, the second film forming chamber 8 is decompressed by the fact (step S1). The human real work 52 starts to operate, and the load lock vacuum chamber 5 is depressurized (step S2). The internal pressure of the load lock vacuum chamber 5 is substantially the same as the internal pressure of the first film forming chamber 7 and the robot arm chamber 6. The point in time to open the question is 51. Next, a buffer layer 形成 is formed (the step substrate transport robot arm 61 extends the arm 63 to the load lock vacuum chamber 5, and is held in the substrate storage rack even in the same posture even if its one side faces the wrong straight side. The unsealed substrate 4 of 53 is delivered to the movable gantry 64. After receiving the substrate 4, the substrate transport robot 61 contracts the arm 63. After the arm 63 is retracted, the gate valve 51 is closed. The substrate transport robot 61 rotates the arm 63 to the first The direction of the film forming chamber 7. Next, the mixed gas of the gas and the Ar gas is introduced into the first film forming chamber 7 by opening the fourth flow rate control valve 763*Η2 (step S10 of Fig. 7). The third flow rate control valve 762 introduces the HMDS gas into the first film forming chamber 7 (step S10 of Fig. 7). At this time, the introduction flow rate of each gas, 1011014ΐί^ early number A0101 page 16 / total 45 pages 1013085717-0 201238768 In particular, the flow rate of the HMDS gas is determined in step S35. For example, the mixed gas for the H2 gas and the Ar gas may be set to 20 sccm to 40 sccm, and the HDMS gas may be set to 3 sccm to 5 sccm by being used in step S35. The determined flow introduces each gas The first film forming chamber 7 is adjusted to the first pressure by adjusting the opening degree of the second flow rate control valve 761 (step S11 of Fig. 7). The first pressure means the film forming condition determined in step S35. Next, the high-frequency current is supplied to the loop antenna 77 by the power source 771. The plasma power at this time, that is, the input power is set to, for example, about 0. lkW to 10 kW. Accordingly, around the loop antenna 77. The plasma is generated (step S12 of Fig. 7). Then, the arm 63 is extended to the first film forming chamber 7, and the substrate 4 is placed above the loop antenna 77 (step S13 of Fig. 7). The surface is made on the surface of the substrate 4. The surface layer forms a buffer layer 2-1 so as to cover the electronic component 42. Since the chemical formula of HMDS is (CH3)3SiNHSi(CH3)3, the HMDS supply tank 72 functions as a supply source of C (carbon). By containing carbon, the density of the formed film can be made lower, and cracks and the like due to stress can be effectively suppressed. After the lapse of a prescribed time, the third flow control valve 762 is closed by the third flow rate control valve 762. And a fourth flow control valve 763, stopping the HMDS gas, the H2 gas, and Introduction of Ar gas (step S14 of Fig. 7) The buffer layer 2-1 is formed, and the formation process of the barrier layer 3-1 is started in step S4. First, the substrate transport robot 61 causes the substrate 4 to be first. The film forming chamber 7 is retracted to the robot arm chamber 6. When the retraction is completed, the gate valve 68 is closed. Next, as shown in Fig. 8, the vacuum pump 67 and the first flow rate control valve 66 1〇11〇141 are produced, the order number A_ page 17/ A total of 45 pages 1013085717-0 201238768 act and decompress the robot arm chamber 6 (step S20). When the internal pressure of the robot arm chamber 6 is substantially the same as the internal pressure of the second film forming chamber 8, the gate valve 69 is opened to stop the vacuum pump 67. Further, the vacuum pump 81 is in a state of being operated. Next, the helium gas is introduced into the second film forming chamber 8 by opening the seventh flow rate control valve 863 (step S21). At the same time, the HMDS gas is introduced into the second film forming chamber 8 by opening the sixth flow rate control valve 862 (step S21). At this time, the introduction flow rate of each gas can be set to 20 sccm to 1000 sccm, and HDMS gas can be set to 3 sccm to 20 sccm. The second pressure is adjusted by adjusting the opening degree of the fifth flow rate control valve 861 (step S22). Next, the high frequency current is caused to flow to the loop antenna 87 by the power source 871. The plasma power at this time, that is, the input power is set to, for example, about 0.1 kW to 10 kW. According to this, plasma is generated around the loop antenna 87 (step S23). Then, the arm 63 is extended to the second film forming chamber 8, and the substrate 4 is placed above the loop antenna 87 (step S24). Surface reaction is performed on the surface of the substrate 4 to form a barrier layer 3-1, that is, a ruthenium oxide layer so as to cover the buffer layer 2-1. After the lapse of the predetermined time, the introduction of the HMDS gas and the 〇2 gas is stopped by closing the sixth flow control valve 862 and the seventh flow control valve 863 (step S25). Further, a nitrogen-containing gas (N2 gas or NH3 gas) is used. Alternatively, a mixed gas of 〇2 gas and a nitrogen-containing gas may be substituted for 〇2 gas. The processing of the above-described step S3 and step S4 (step S5) is repeated a predetermined number of times (N times). When the number of times of processing is less than N (No in step S5), when the buffer layer is formed after the formation of the barrier layer, step S3 is performed. Further, when the plurality of buffer layers 2 are formed, the film forming conditions (the composition of the material gas, the flow rate of the material gas, the pressure, and the like) of the respective buffer layers 2 may be the same or different. The same applies to the film formation of the barrier layer 3. ΗΠ1 with 1*single number A_ page 18/total 45 pages 1013085717-0 201238768 The specified number of layers is formed (Yes in step S5), and the substrate transport robot 61 rotates the arm 63 to the load-locking vacuum chamber 5 The direction. The gate valve 51 is opened and the substrate transport robot 61 extends the arm 63 to the load lock vacuum chamber 5. Then, the sealed substrate 4 is transferred to the substrate storage rack 53, and the substrate transport robot 61 contracts the arm 63. After the arm 63 is contracted, the gate valve 51 is closed, the vacuum pump 52 is stopped in step S6, the outside air is allowed to enter, and the load lock vacuum chamber 5 is returned and released to atmospheric pressure, and the sealing film can be formed in the substrate 4 in step S7. Further, in the present embodiment, the buffer layer 2 is formed first and then the barrier layer 3 is formed, and the steps are repeated to form the buffer layer 2, the barrier layer 3, and the buffer layer 2 on the substrate 4. The barrier layer 3 is a repetitive structure laminated in this order. However, the present invention is not limited thereto, and the barrier layer 3 may be formed first and then the buffer layer 2 may be formed. That is, the barrier layer 3, the buffer layer 2, the barrier layer 3, ... may be formed in this order on the substrate 4. Further, in the manufacturing method shown in the flowcharts of FIGS. 5 to 8, in the state in which the mask is disposed opposite to the substrate 4, by the CVD (plasma chemical Vapour) under the first pressure. Deposit ion: a buffer layer forming process for depositing an inorganic substance to form the buffer layer 2 (step S3), and after the buffer layer forming process, the substrate 4 having the mask disposed is lower than the first pressure The barrier layer forming process (step S4) of forming the barrier layer 3 by depositing inorganic substances by plasma CVD is performed under the second pressure (step S4). The mask is an area defining the formation of the gas barrier film 1. Further, in the present embodiment, since the gas barrier film is used as a gas barrier film for protecting the electronic component 10110141, the order number A 〇 101 page 19 / page 45 1013085717-0 201238768, the gas barrier film is formed. The substrate 4' is exemplified as the substrate 4'. However, the production method and the production apparatus of the present invention are not limited thereto, and it is possible to produce a gas barrier film for various objects (substrates). [4] Other Embodiments of the Manufacturing Apparatus The film forming apparatus 1 shown in FIGS. 3 and 4 includes an example in which the first film forming chamber 7 (including various connected grooves and a vacuum pump) is used as a buffer layer forming portion. An example in which the second film forming chamber 8 (including various grooves and vacuum systems to be connected) is provided as a barrier layer forming portion is provided. Further, the robot arm chamber 6 can also be regarded as a part of the buffer layer forming portion and the barrier layer forming portion. In other words, in the above embodiment, the mechanical arm 6 is transported through the substrate to move between the two film forming chambers, and the first house force and the second pressure are switched. However, the present invention is not limited thereto, and the gas damper manufacturing apparatus may switch between the first pressure and the second pressure by changing the internal pressure of one of the film forming chambers. Further, the substrate 4 may be a long film such as plastic. The sheet can be continuously subjected to the formation of a gas barrier film by a roller-to-roller (rG11t. rQ(1) method. Further, HDMS is merely an example of a material gas, and the material gas can be changed to another gas. The material gas is particularly contained. The gas of Si and C is preferable. Further, the material gas forming the buffer layer 2 may be different from the composition of the gas forming the barrier layer 3. [5. Infrared absorbance ratio, film formation conditions, and positive transmittance of visible light. Relationship between the thickness of the buffer layer] In the following experimental procedure, the infrared absorbance is determined by Fourier transform infrared absorption method. Specifically, it is made by Bruker 101101411^Single number A0101 Page 20/45 pages 1013085717-0 201238768 FT-IRIFS The transmission method of -66 V / S was measured. Moreover, the positive transmittance in the visible light region was measured by a spectrophotometer (Model V-670). As shown in Fig. 10, the Fourier of the buffer layer 2 The converted infrared absorption spectrum shows a peak of stretching vibration originating from Si-C and Si-N at a wave number of 900 cm_1, and is derived from a shape vibration at a wave number of 1260 cm 1 ( The peak of the wave number of 900 cm 1 shows the sum of the amounts of Si-C and Si-N, and the amount of peaks of the wave number of 1260 cm 1 shows the amount of Si-CH3. The inventors have found The infrared ray absorbance A1 of the wave layer 900CHT1 of the buffer layer 2 and the &AD (AD = A1/A2) of the infrared ray absorbance A2 of the wave number of 1260 cm_1, and the film formation pressure xHMDS flow rate/input of the buffer layer 2 at the time of film formation The power (Pa*sccm/kW) has the correlation shown in Fig. 11. Further, the positive transmittance of visible light in the gas barrier film (i.e., the minimum value of the positive transmittance measured in the visible light region of 400 to 800 nm) was found. The film formation pressure xHMDS flow rate/input power (Pa*sccm/kW) with the buffer layer 2 has a correlation relationship as shown in Fig. 12. Further, the measurement target of the positive transmittance in Fig. 12 is the entire gas barrier film, and the resistance is In the gas film, the total thickness t of the buffer layer is 42 Onm. Since the positive transmittance of the barrier layer is high, the influence of the barrier layer on the positive transmittance of the entire gas barrier film can be ignored. The formation of the barrier layer is implemented. Example - the sample was carried out. That is, the inventors found that the infrared absorbance is better than that of the human Light

The positive transmittance of K has a correlation. By changing the input power at the time of film formation, the flow rate or pressure of the material gas, etc., the buffer layer can be changed without changing the type of the material gas. The number of the buffer layer is A11101, page 21, page 45, 1013085717-0 201238768 Infrared light absorption button. Its _ can be as follows. In the case where the raw material gas uses HMDS and changes the power of the input, for example, when the power is small, the dissociation of the c_h bond which is small in the bond energy (bGnd(4)(4)) of the HMDS is not caused, and the amount of Si-% is present. More state. On the other hand, when the input power is large, the dissociation of the C-Η bond is increased, the amount of Μ-% is also decreased, and conversely, the amount of Si_c is increased in addition to Si. Therefore, in the case where the power of the investment is large, the value of the infrared absorption ratio is larger than the value of the amount of Si, which is the amount of Si-C/Si-CH3. Actually, if the power of the input is lowered, it becomes smaller, and ar is made smaller by increasing the film forming pressure, and A R is lowered by increasing the flow rate of the raw material (e.g., HMDS) gas. The illustration is omitted, and even if the thickness of the buffer layer in the gas barrier film is changed in total, the correlation between the positive transmittance of visible light and the infrared absorption ratio AR is observed. The relationship between the infrared absorption ratio AR and the thickness of the buffer layer in the case where the positive transmittance of visible light is 70% is shown in Fig. 9 is shown. As shown in Fig. 9, the equations (1,) and (2,) are satisfied with an infrared absorption ratio AR = 3, that is, a total thickness of the buffer layer of 4 iinra. [Formula 7]

15656

A 3313 (1,)

R 10110141^单编号A〇101 Page 22/45 pages 1013085717-0 201238768 LUUIUJ [Formula 8] [0011] (2,) 837 λ 0.648 xTLti 亦 That is, by setting the infrared absorbance ratio and the thickness of the buffer layer In order to satisfy this formula, the positive transmittance can be satisfied by 70%. Further, by substituting the formula (Γ) and the formula (2') for the above formulas (1) and (2), a condition satisfying a positive transmittance of 70% or more can be obtained. [Examples] (Example 1) A gas barrier film was produced in accordance with the above procedure. Specifically, seven layers of buffer layer and barrier layer are alternately laminated on a PET (polyethylene terephthalate) sheet having a thickness of 100/m. In the film formation of the buffer layer, HMDS gas was used as a material gas, and H2 gas and Ar gas were used as a plasma generating gas, and plasma CVD was performed. The infrared absorption of the buffer layer 2 is eight. The total thickness of the buffer layer is 2.0 Onm. In addition, in the present specification, the infrared absorbance in the wave number 900cin_1 at the time of the infrared absorbance ratio is calculated and the infrared wave in the wave number 1260CHT1 is calculated. The single-number A0101 page 23/45 page 1013085717-0 201238768 absorbance is 530~1 320CDT1, respectively. A range of 1 225 to 1 300 cm_1 was subjected to baseline correction. The barrier layer is formed by using HMDS gas as a material gas and 〇2 gas as a plasma generating gas by plasma CVD. The barrier layer 3 is made of a material having high transparency and high gas barrier properties. 0%。 In the visible light region, the visible light region was 91.0% as a result of measuring the positive transmittance of the visible film of the gas barrier film (in which the value after the substrate was subtracted). It was confirmed that the positive transmittance of visible light in the visible light region of the barrier layer of cerium oxide used in the present embodiment was extremely high, and the positive transmittance of the gas barrier film was not imparted. When the maximum value of the total thickness of the buffer layer 2 is calculated from the relationship (1) of the infrared ray absorbance ratio AD and the thickness t of the buffer layer, it is 1452 nm. That is, the total thickness of the buffer layer described above sufficiently satisfies the equation. (Example 2) A gas barrier film 1 was produced by laminating three layers of the buffer layer 2 and the barrier layer 3 on a PET sheet having a thickness of 100 // in. The conditions for providing the barrier layer 3 are the same as those of the first embodiment. The infrared ray absorbance ratio AD of the buffer layer 2 was 5.86, and the total thickness of the buffer layer included in the gas barrier film was 180 nm. 9%。 In the visible light region, the visible light transmittance was 83.9%. Further, when the maximum value of the total thickness of the buffer layer is calculated from the relation (2) of the infrared ray absorbance ratio AD and the thickness t of the buffer layer 2, it is 266 nm. Therefore, the total value of the thickness of the buffer layer of the present embodiment sufficiently satisfies the formula (2). (Comparative Example 1) Seven layers of the buffer layer and the barrier layer were alternately laminated on a PET sheet having a thickness of 100/zra to form a gas barrier film. The conditions for providing the barrier layer 3 are the same as those of the first embodiment. 1〇11〇14#单号 A_ 1013085717-0 Page 24 of 45 201238768 The infrared absorption ratio of the buffer layer is 3.90, and the total thickness of the buffer layer contained in the gas barrier film is 420 nra. The result of the positive transmittance of the visible light in the gas barrier film was 63.9% in the visible light region. If the infrared absorbance is greater than the thickness of the AD and the buffer layer

The relation (2) of the total value of K is calculated as the maximum thickness of the buffer layer, which is 347 nm. Therefore, the actual thickness does not satisfy the formula. [Table 1] Infrared Absorbance Ratio Total Thickness of ar Buffer Layer (nm) Actual Measurement Value (%) of Positive Conductance of Gas Barrier Film Calculation of Maximum Value of Thickness of Buffer Layer with Positive Transmittance of 70% or More Value (nm) Example 1 2. 05 810 91. 0 1452 Example 2 5. 86 180 83. 9 266 Comparative Example 1 3.90 420 63. 9 347 (Examples 3 and 4 and Comparative Example 3)

From the viewpoint of improving the coverage of the unevenness on the surface of the substrate, the thickness of the buffer layer is such that a thick film is formed as much as possible within a range satisfying the required positive transmittance, and a gas barrier film having few defects can be formed. A buffer layer having an infrared absorption ratio of 2.79 was used as the third embodiment, and seven buffer layers and a barrier layer were alternately laminated on the glass substrate, and a gas barrier film was produced as the third embodiment. Set the thickness of the buffer layer contained in the gas barrier film. 10110141 Production No. A0101 Page 25 of 45 1013085717-0 201238768 Degree is 480nm. The result of the positive transmittance of the light-shielding film was determined to be 73.2% in the visible light region. If the relationship between the infrared absorbance ratio AD and the thickness of the buffer layer is t

K Formula (1) calculates the maximum thickness of the buffer layer and becomes 523 nm. That is, the total thickness t of the buffer layer is in the range represented by the formula (1). For the third embodiment, the water vapor transmission rate of the gas barrier film was measured by a calcium etching me thod, and it was 3x10_3 g/m2/day in an environment of 85 ° C x 85% RH. Good gas barrier properties were exhibited while maintaining high transparency. Further, the same buffer layer as in the third embodiment was used as the fourth embodiment, and the total thickness t of the buffer layer was set to 350 nm. This value t is within the range expressed by the formula (1). Actually, the results of the positive transmittance were measured for the fourth embodiment, and a high value was obtained. Moreover, the use of infrared absorbance is better than that of people. Used as a buffer layer of 4.09

K Comparative Example 3, a gas barrier film was produced. The maximum value of the total thickness t of the buffer layer allowed by the infrared ray absorbance ratio ar is 336 nm, but in this comparative example, it is set to 504 nm exceeding the value. As a result, the measured value of the positive transmission of the gas barrier film of Comparative Example 3 showed a low value of 63.8%. Comparing Examples 3 and 4 and Comparative Example 3, particularly in the gas barrier film of Example 3, high barrier properties and high positive transmittance can be achieved. [Table 2] Infrared buffer layer positive transmission The water vaporization ratio of the true transmission rate of the thickness of the gas barrier film absorbance is measured and the total value (%) is 70%. The rate of gas transmission (nm) or more is 101101411^^^^ A〇101 ^ 26 1 / * 45 I 1013085717-0 Calculated value of the maximum value of the total thickness of the buffer layer (nm) / day ) Example 2. 79 480 73. 2 523 3xl0~3 Example 4 2.79 350 81.0 523 lxlO-2 Comparative Example 3 4. 09 540 63. 8 336 2xl0-3 201238768 Ο [Industrial Applicability] The gas barrier film of the present invention can be used as a light-emitting material for an organic EL display or a power generation material for a solar battery. It is applied to a gas barrier film of a material that is very weak to oxygen or water. Further, it can also be used as a gas barrier film (functionally added) attached to a sheet or a film. BRIEF DESCRIPTION OF THE DRAWINGS [0013] Fig. 1 is a cross-sectional view showing the configuration of a gas barrier film 1 according to an embodiment of the present invention. 2 is a block diagram showing an example of a device for manufacturing a gas barrier film. 3 is a front view showing an example of a device for manufacturing a gas barrier film. Fig. 4 is a plan view of the manufacturing apparatus shown in Fig. 3. Fig. 5 is a flow chart for determining the conditions at the time of production of the gas barrier film. Fig. 6 is a flow chart showing an example of a method of producing a gas barrier film. Fig. 7 is a flow chart showing an example of a method of forming a buffer layer. 10110141 Production Order No. Α0101 Page 27 of 45 1013085717-0 201238768 FIG. 8 is a flow chart showing an example of a method of forming a barrier layer. Fig. 9 is a graph showing the relationship between the infrared ray absorbance ratio in the gas barrier film showing the positive transmittance of visible light of 7 〇% and the thickness of the buffer layer. Fig. 10 is an example of an infrared absorption spectrum of a buffer layer. Fig. 11 is a graph showing the relationship between the film forming conditions and the infrared ray absorbance ratio. Fig. 12 is a graph showing the relationship between the condition and the positive transmittance of visible light. [Description of Main Element Symbols] [0014] 1 : Gas barrier film 2: Buffer layer 2-1: First buffer layer 2-2: Second buffer layer 2-n: nth buffer layer 3: barrier layer 3- 1 : First barrier layer 3-2: Second barrier layer 3 - η: nth barrier layer 4: Substrate 5: Load interlocking vacuum chamber 6: Robot arm chamber 7: First film forming chamber 8: Second Film making chamber 10: Film forming apparatus 31: First barrier layer 32: Second barrier layer 10110141 Production order number Α〇 101 Page 28 / Total 45 pages 1013085717-0 201238768 42: Electronic component 51: Gate valve 52, 67 81: vacuum pump 53: substrate storage rack 54, 65: support pin 61: substrate transport robot 62: motor 63: arm 64: movable support table 66: first flow control valve 68: mechanical arm chamber and first film making chamber Gate valve 69 between 7: Gate valve 72 between the arm chamber and the second film forming chamber 8, 8LHMDS supply tank 73: H2 supply tank 74: Ar supply tank 77, 87: Loop antenna 78: Insulation tube 79: Conductive electrode 83: 〇2 supply tank 88: insulating tube 89: conductive electrode 100: manufacturing apparatus 1 01: input receiving unit 102. control device 103: infrared absorbing ratio calculation unit 104: film forming condition determining unit 匪 hidden production number A 〇m 10130 85717-0 Page 29 of 45 201238768 105: Buffer layer thickness calculation unit 106: Film formation apparatus control unit 761: Second flow rate control valve 762: Third flow rate control valve 763: Fourth flow rate control valve 771: Power source 105 : Buffer layer thickness calculation unit 8 61 : Fifth flow rate control valve 862 : Sixth flow rate control valve 863 : Seventh flow rate control valve 8 71 : Power supply AD: Infrared absorbance ratio

K 10U0141 Production Order No. A〇101 No. 3. Page / Total 45 Stomach 1013085717-0

Claims (1)

201238768 VII. A patent scope: 1. A gas barrier film comprising: a buffer layer containing a ruthenium compound, and a barrier layer layered on the buffer layer containing ruthenium oxide and/or tantalum nitride, In the Fourier transform infrared absorption spectrum of the buffer layer, the ratio of the infrared absorbance A1 of the wave number 900 CHT1 to the infrared absorbance A2 of the wave number of 1 260 cm_1 (AD = A1/A2), and the buffer contained in the gas barrier film The total thickness t(nm) of the layers satisfies Ad<3 and formula (1), or satisfies Ad KK 23 and formula (2), eight [formula 1] 15656 ix 3.313 (1) [formula 2] (2) 1013085717- 0 837 Δ 0.648 JLJLT% lOllOMlf single number A〇1〇l Page 31 of 45 201238768 • The gas barrier film of claim 1 of the patent scope, wherein the positive transmittance of light in the visible light region is 70% or more. In the gas barrier film of the first or second aspect of the patent application, the total thickness t of the buffer layer included in the gas barrier film is from 10 nm to 4000 nm. A gas barrier film>} includes a gas barrier film of any of the scope of the patent application. A buffer layer thickness calculation device comprising: at least a positive transmittance of visible light that is targeted as a gas barrier film, and an infrared absorption of a wave number of 900 CDT1 in a Fourier transform infrared absorption spectrum for a buffer layer Accepting the input of the ratio AR (AR=A1/A2) of the infrared ray absorbance A2 of the wave; and satisfying \<3 and formula (丨) according to the accepted content of the input accepting unit, or satisfying AR 2 3 and In the formula (2), the buffer layer thickness calculation unit of the total thickness t (nm) of the buffer layer of the gas barrier film is calculated, [Formula 3] 15656 Ar 3.313 (1) [Formula 4] Page 32 of 45 1013085717-0 (2) 837201238768 O 101101411^单号 A0101 jAl 0.648 Page 33 of 45 1013085717-0