[go: up one dir, main page]

WO2018034179A1 - Film barrière au gaz ainsi que procédé de fabrication de celui-ci, et dispositif électronique muni de ce film barrière au gaz - Google Patents

Film barrière au gaz ainsi que procédé de fabrication de celui-ci, et dispositif électronique muni de ce film barrière au gaz Download PDF

Info

Publication number
WO2018034179A1
WO2018034179A1 PCT/JP2017/028535 JP2017028535W WO2018034179A1 WO 2018034179 A1 WO2018034179 A1 WO 2018034179A1 JP 2017028535 W JP2017028535 W JP 2017028535W WO 2018034179 A1 WO2018034179 A1 WO 2018034179A1
Authority
WO
WIPO (PCT)
Prior art keywords
film
gas barrier
barrier film
gas
sputtering
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2017/028535
Other languages
English (en)
Japanese (ja)
Inventor
森　孝博
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Konica Minolta Inc
Original Assignee
Konica Minolta Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Konica Minolta Inc filed Critical Konica Minolta Inc
Priority to JP2018534349A priority Critical patent/JPWO2018034179A1/ja
Publication of WO2018034179A1 publication Critical patent/WO2018034179A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering

Definitions

  • the present invention relates to a gas barrier film, a method for producing the same, and an electronic device having the gas barrier film. More specifically, the present invention relates to a gas per unit thickness rather than a gas barrier film when a silicon (Si) simple compound is used. The present invention relates to a gas barrier film having improved barrier properties, a method for producing the same, and an electronic device including the same.
  • Gas barrier laminated films having a gas barrier film as a substrate film or a sealing film are used in flexible electronic devices, particularly flexible organic electroluminescence (EL) devices.
  • the gas barrier laminate film used for these is required to have high gas barrier properties.
  • a bottom emission type organic EL device using a gas barrier laminated film as a substrate is used for a long time even in durability evaluation performed under extremely severe conditions of high temperature and high humidity such as 85 ° C. and 85% RH.
  • An extremely high gas barrier property at the glass substrate level that does not substantially cause dark spots is required.
  • a silicon oxide film or a silicon nitride film formed by sputtering or CVD is used for the gas barrier film.
  • These silicon oxide films and silicon nitride films have insufficient gas barrier properties per unit thickness, and even if the film thickness is simply increased, cracks are generated and gas barrier properties are not improved.
  • studies have been made to improve gas barrier properties by forming multiple layers by alternating lamination with organic layers. However, since the organic layer itself does not have a gas barrier property, even in this configuration, there is a concern that side leakage may occur from the organic layer portion, and it has not reached a level applicable to an organic EL device.
  • Patent Document 1 a gas barrier film having a concentration gradient in the layer by mixing silicon oxide and aluminum oxide has been studied.
  • gas barrier films containing zinc-tin oxide (ZnSnO x ) see, for example, Patent Document 2
  • mixed thin film layers mainly composed of a mixture containing ZnS and SiO 2 are studied.
  • Patent Document 3 Although improvement of gas barrier property is seen in any case, it has not reached a high level of gas barrier property applicable to organic EL devices.
  • the present invention has been made in view of the above-mentioned problems and situations, and its solution is a gas barrier with improved gas barrier properties per unit thickness as compared to a gas barrier film when using a silicon compound. It is providing a conductive film, its manufacturing method, and an electronic device provided with the same.
  • the present inventor is a gas barrier film containing silicon (Si) and an element M of Group 5 of the long-period periodic table in the process of examining the cause of the above-described problems.
  • the gas barrier film has a Si-M bond
  • the gas barrier film has an improved gas barrier property per unit thickness compared to the gas barrier film when a silicon compound is used, It has been found that a method for producing an electronic device and a gas barrier film comprising the same can be obtained.
  • gas barrier film detects a fragment having a Si-M bond when a mass spectrum is measured by time-of-flight secondary ion mass spectrometry (TOF-SIMS). film.
  • TOF-SIMS time-of-flight secondary ion mass spectrometry
  • a gas barrier film manufacturing method for manufacturing a gas barrier film containing silicon (Si) and an element M of Group 5 of the periodic table and having a Si-M bond A method for producing a gas barrier film, comprising a step of forming a silicon (Si) -containing film, and a step of depositing a compound containing the element M on the silicon (Si) -containing film.
  • Item 7 The method for producing a gas barrier film according to Item 5 or 6, wherein reverse sputtering treatment is performed on the silicon (Si) -containing film.
  • An electronic device comprising the gas barrier film according to any one of items 1 to 4.
  • a gas barrier film having improved gas barrier property per unit thickness over gas barrier property when a silicon compound is used, a method for producing the same, and an electronic device including the same. be able to.
  • an oxygen-deficient composition film containing a compound containing silicon (Si) (for example, an oxide) alone is formed as a gas barrier film, or a group 5 element M is included.
  • Si silicon
  • a compound containing a compound for example, an oxide
  • the gas barrier property tends to improve as the degree of oxygen deficiency increases.
  • the gas barrier property is remarkably improved. It was not connected.
  • the direct bonding between the silicon (Si) and the Group 5 element M was performed by measuring the mass spectrum of the gas barrier film using the time-of-flight secondary ion mass spectrometry (TOF-SIMS) according to the present invention. Occasionally, since a fragment having a Si-M bond is detected, the presence of the bond can be confirmed.
  • TOF-SIMS time-of-flight secondary ion mass spectrometry
  • Sectional drawing which shows an example of the gas barrier film of this invention Mass spectrum by TOF-SIMS showing Si-Nb bond Graph showing the ratio of the number of atoms to the depth of the gas barrier film in the thickness direction
  • Schematic diagram showing an example of a vacuum plasma CVD apparatus used in the present invention.
  • Schematic sectional view showing an example of vacuum ultraviolet light irradiation apparatus applicable to polysilazane reforming treatment
  • the gas barrier film of the present invention is a gas barrier film containing silicon (Si) and an element M of Group 5 of the long-period periodic table, and the gas barrier film has Si—M bonds. It is characterized by having. This feature is a technical feature common to or corresponding to the claimed invention.
  • the gas barrier film measures mass spectrum using time-of-flight secondary ion mass spectrometry (TOF-SIMS), By detecting a fragment having -M bond, its mass number (m / z) indicates the presence of the Si-M bond.
  • TOF-SIMS time-of-flight secondary ion mass spectrometry
  • the method for producing a gas barrier film of the present invention includes a step of forming a silicon (Si) -containing film and a step of depositing a compound containing element M on the silicon (Si) -containing film.
  • the film formation of the compound containing the element M is preferably performed by a sputtering method because the gas barrier film having the Si-M bond can be efficiently produced.
  • performing reverse sputtering treatment on the silicon (Si) -containing film can roughen the surface of the silicon (Si) -containing film and promote the formation of a gas barrier film by Si-M bonding, From the viewpoint of further improving gas barrier properties, it is preferable.
  • a compound containing the element M is formed on the silicon (Si) -containing film by a sputtering method. It is preferable from the viewpoint of roughening the surface of the containing film and promoting the formation of a gas barrier film by Si—M bonding to further improve the gas barrier property.
  • the gas barrier film according to the present invention is suitably provided for an electronic device and can prevent the device from being damaged by humidity or gas outside the device.
  • ⁇ is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
  • the gas barrier film of the present invention is a gas barrier film containing silicon (Si) and an element M of Group 5 of the long-period periodic table, and the gas barrier film has Si—M bonds.
  • Si silicon
  • M element M of Group 5 of the long-period periodic table
  • the gas barrier film has Si—M bonds.
  • Si silicon
  • FIG. 1 shows a schematic diagram of a gas barrier film of the present invention.
  • the gas barrier film 1 of the present invention is a gas barrier film containing Si and a Group 5 element M of the long-period periodic table, and mainly contains a region 2 containing Si and a Group 5 element. Between the region 4 mainly containing M, a mixed region 3 having an Si—M bond, which will be described later, is provided. In FIG. 1, the mixed region 3 exists in a part in the film thickness direction of the gas barrier film 1, but all of the gas barrier film 1 may be the mixed region 3.
  • the gas barrier film 1 is preferably provided in an electronic device as it is, or the gas barrier film 1 is formed on a film-like substrate, and is provided in a flexible electronic device as a gas barrier laminated film. .
  • the gas barrier property of the gas barrier film of the present invention is based on JIS K 7126-1987 when calculated with a laminate in which the gas barrier film is formed on a substrate (for example, a film substrate).
  • the oxygen permeability measured by the method was 1 ⁇ 10 ⁇ 3 mL / (m 2 ⁇ 24 h ⁇ atm) or less, and the water vapor permeability (25 ⁇ 0.5 measured by a method according to JIS K 7129-1992) C. and relative humidity (90 ⁇ 2)%) are preferably high gas barrier properties of 1 ⁇ 10 ⁇ 3 g / (m 2 ⁇ 24 h) or less.
  • the Si—M bond may be present in all or part of the gas barrier film of the present invention, and when it is present in part, a plane (region) parallel to the outermost surface of the gas barrier film. ) In the film thickness direction.
  • the region where Si and the Group M element M of the long-period periodic table are bonded by Si—M is referred to as “mixed region” in the present invention.
  • the “mixed region” in the present invention is an oxygen deficient region of an oxide of Si and an oxide of Group 5 element M in the long-period periodic table, and is an atom of Group 5 element M with respect to Si.
  • the region where the number ratio value (M / Si) is in the range of 0.02 to 49 is a thickness that is not less than a predetermined value (specifically, 5 nm or more) continuously in the thickness direction of the gas barrier film. An area that is configured to exist.
  • the “region” is a plane that is substantially perpendicular to the thickness direction of the gas barrier film (that is, a plane parallel to the outermost surface of the gas barrier film), or the gas barrier film is fixed or arbitrary.
  • the region is a plane that is substantially perpendicular to the thickness direction of the gas barrier film (that is, a plane parallel to the outermost surface of the gas barrier film), or the gas barrier film is fixed or arbitrary.
  • TOF-SIMS time-of-flight secondary ion mass spectrometry
  • Time-of-flight secondary ion mass spectrometry is generally called TOF-SIMS (Time-Of-Flight Secondary Ion Spectrometry).
  • TOF-SIMS Time-Of-Flight Secondary Ion Spectrometry
  • the sample is irradiated with pulsed ions in a high vacuum, and the ions removed from the surface by the sputtering phenomenon are detected by dividing them by mass (atomic weight, molecular weight). Then, the chemical species (atoms, molecules) existing in the gas barrier film can be estimated from the pattern of mass and the detected amount (mass spectrum).
  • TFS-2100 manufactured by Physical Electronics can be used, and measurement can be performed at a temperature of 23 ° C. and a humidity of 55% RH.
  • Secondary ion release Various particles are released from the surface of the gas barrier film irradiated with ions (primary ions) by irradiating the surface of the gas barrier film with a pulse, due to the sputtering phenomenon.
  • the primary ion current density is kept low (static mode), and sputtering is performed without destroying the gas barrier film surface as much as possible.
  • Mass separation and detection A method for analyzing the composition of the gas barrier film surface to the inside by taking out ions (secondary ions) present in the particles released by sputtering and separating them by their mass. Is secondary ion mass spectrometry.
  • TOF-SIMS uses a time-of-flight analyzer for mass separation.
  • the ions that are drawn into the flight tube by the electric field fly faster in the lighter and slower in the flight tube and reach the detector.
  • the element composition analysis in the depth direction becomes possible by repeating the measurement by scraping the surface with an ion beam.
  • the relative abundance of the detected chemical species can also be determined.
  • “detected” means, for example, the mass number (m / z) relative to the detected intensity of an oxygen atom (O) having a mass number (m / z) of 16.
  • / Z) is a strength ratio of Si—Nb with 121 (adopting 120.9919 as the exact mass) or Si—Ta with a mass number (m / z) of 209 (adopting 209.0334 as the exact mass).
  • the intensity ratio is preferably 0.0002 or more, more preferably 0.0003 or more, and further preferably 0.0005 or more.
  • the “intensity ratio” is a value obtained by the following equation 1.
  • Intensity ratio detection intensity of target fragment / detection intensity of oxygen atom (O)
  • Measurement in the depth direction of the gas barrier film is performed by repeating sputtering and measurement at regular intervals until the gas barrier film and the base material are exposed, with the outermost surface in a state where no dirt or foreign matter is attached as a base point. .
  • the measurement interval is 30 seconds to 3 minutes in terms of sputtering time, but is preferably as short as possible, and therefore preferably 30 seconds to 1 minute.
  • the interior of the sample chamber is set to a predetermined degree of vacuum, the surface of the sample is irradiated with primary ions, the secondary ions emitted from the surface of the sample are given a constant kinetic energy, and are guided to a time-of-flight mass spectrometer.
  • Each of the secondary ions accelerated with the same energy passes through the analyzer at a speed depending on the mass. Since the distance to the detector is constant, the time to reach it is a function of mass, and by accurately measuring this time-of-flight distribution, the mass number of secondary ion species released from the sample surface And the intensity ratio was determined from the peak intensity of the designated fragment (for example, SiNb ⁇ ).
  • FIG. 2 shows a mass spectrum by TOF-SIMS showing Si—Nb bonds.
  • the horizontal axis represents the mass number (m / z), and the vertical axis represents the detected intensity.
  • Gas barrier film [2.1] Mixed region In the present invention, a part of the composition contained in the mixed region having a Si-M bond has a non-stoichiometric composition (oxygen-deficient composition) in which oxygen is lost. )
  • the oxygen deficient composition means that when the composition of the mixed region is represented by the following chemical composition formula (1), at least a part of the composition of the mixed region is defined by the following relational expression (2). It is defined as satisfying the condition. Further, as an oxygen deficiency index indicating the degree of oxygen deficiency in the mixed region, the minimum value obtained by calculating (2y + 3z) / (a + bx) in the mixed region is used. In the following chemical composition formula (1), the Group 5 element M is simply M.
  • the composition of the mixed region of Si and the Group 5 element M according to the present invention is represented by (Si) (M) x O y N z which is the chemical composition formula (1).
  • the composition of the mixed region may partially include a nitride structure, and it is more preferable to include a nitride structure from the viewpoint of gas barrier properties.
  • the maximum valence of Si is a
  • the maximum valence of group 5 element M is b
  • the valence of O is 2
  • the valence of N is 3.
  • This formula means that the total number of bonds of Si and Group 5 element M and the total number of bonds of O and N are the same, and in this case, both Si and Group 5 element M, It is combined with either O or N.
  • the composite valence calculated by weighted averaging the maximum valence of each element according to the abundance ratio of each element It shall be adopted as the value of each “maximum valence” b.
  • Si and the Group 5 element M are directly bonded, and when Si and the Group 5 element M are directly bonded to each other, the case where the metals are bonded through O or N is more than that. It is considered that a dense and high-density structure is formed, and as a result, the gas barrier property is improved.
  • the mixed region is a region where the value of x satisfies 0.02 ⁇ x ⁇ 49 (0 ⁇ y, 0 ⁇ z). This is the same as defining the region where the value of the atomic ratio of the Group 5 element M / Si is in the range of 0.02 to 49 and the thickness is 5 nm or more. Is the definition of
  • the mixed region satisfying this condition exists in a thickness of a predetermined value or more (5 nm), thereby providing a gas barrier. It is thought that it contributes to the improvement of property. Since the closer the abundance ratio of Si and the Group 5 element M is, the more likely it is to contribute to the improvement of gas barrier properties, the mixed region is a region satisfying 0.1 ⁇ x ⁇ 10 with a thickness of 5 nm or more. Preferably, the region satisfying 0.2 ⁇ x ⁇ 5 is included with a thickness of 5 nm or more, and the region satisfying 0.3 ⁇ x ⁇ 4 is included with a thickness of 5 nm or more. Further preferred.
  • (2y + 3z) / (a + bx) ⁇ 0.85 is more preferably satisfied, and (2y + 3z) / (a + bx) ⁇ 0.8 is still more preferable.
  • the smaller the value of (2y + 3z) / (a + bx) in the mixed region the higher the gas barrier property, but the greater the absorption in visible light. Therefore, in the case of a gas barrier film used for applications where transparency is desired, 0.2 ⁇ (2y + 3z) / (a + bx) is preferable, and 0.3 ⁇ (2y + 3z) / (a + bx). It is more preferable that 0.4 ⁇ (2y + 3z) / (a + bx).
  • the thickness of the mixed region that provides good gas barrier properties is 5 nm or more as the sputtering thickness in terms of SiO 2 in the XPS analysis method, and this thickness is preferably 8 nm or more. It is more preferably 10 nm or more, and further preferably 20 nm or more.
  • the thickness of the mixed region is not particularly limited from the viewpoint of gas barrier properties, but is preferably 100 nm or less, more preferably 50 nm or less, and further preferably 30 nm or less from the viewpoint of optical characteristics. preferable.
  • the element concentration distribution in the thickness direction of the gas barrier film of the present invention is specifically a Si distribution curve (silicon distribution curve), a Group 5 element M distribution curve (for example, Niobium (Nb) distribution curve), oxygen (O), nitrogen (N), carbon (C) distribution curve, etc. are measured by X-ray photoelectron spectroscopy (XPS) and rare gas ion sputtering such as argon.
  • XPS X-ray photoelectron spectroscopy
  • rare gas ion sputtering such as argon.
  • a distribution curve obtained by such XPS depth profile measurement can be created, for example, with the vertical axis as the atomic ratio of each element (unit: atom%) and the horizontal axis as the etching time (sputtering time).
  • the etching time generally correlates with the distance from the surface of the gas barrier film in the thickness direction of the gas barrier film in the film thickness direction. From “the distance from the surface of the gas barrier film in the thickness direction of the gas barrier film”, the gas barrier film calculated from the relationship between the etching rate and the etching time employed in the XPS depth profile measurement. The distance from the surface can be employed.
  • etching rate is 0.05 nm / It is preferable to set to sec (SiO 2 thermal oxide film conversion value).
  • ⁇ Analyzer QUANTERA SXM manufactured by ULVAC-PHI ⁇ X-ray source: Monochromatic Al-K ⁇ ⁇ Sputtering ion: Ar (2 keV)
  • Depth profile Measurement is repeated at a predetermined thickness interval with a SiO 2 equivalent sputtering thickness to obtain a depth profile in the depth direction. The thickness interval was 1 nm (data every 1 nm is obtained in the depth direction).
  • the background was determined by the Shirley method, and quantified using the relative sensitivity coefficient method from the obtained peak area.
  • Data processing uses MultiPak manufactured by ULVAC-PHI.
  • the analyzed elements are silicon (Si), Group 5 element M (for example, niobium (Nb)), oxygen (O), nitrogen (N), and carbon (C).
  • the composition ratio is calculated from the obtained data, Si and the Group 5 element M coexist, and the value of the atomic ratio of the Group 5 element M / Si is 0.02 to 49.
  • the range was determined, this was defined as the mixed region, and the thickness was determined.
  • the thickness of the mixed region represents the sputter depth in XPS analysis in terms of SiO 2 .
  • FIG. 3 shows a schematic graph of the element profile when the composition distribution of Si and the Group 5 element M in the thickness direction of the gas barrier film including the mixed region is analyzed by the XPS method.
  • FIG. 3 shows the elemental analysis of Si, Group 5 elements M, O, N, and C in the depth direction from the surface of the gas barrier film (the left end of the graph), and the horizontal axis represents the sputter depth ( (Film thickness: nm) is a graph in which the vertical axis represents the content (atom%) of Si and the Group 5 element M.
  • the elemental composition of the second gas barrier film containing the oxide of the group 5 element M is a region where the value of the atomic ratio of the Group 5 element M / Si is in the range of 0.02 to 49 and the thickness is 5 nm or more.
  • a gas barrier film having a mixed region having a specific configuration as described above exhibits a very high gas barrier property that can be used as a gas barrier film for an electronic device such as an organic EL element.
  • the gas barrier film of the present invention is characterized by having a mixed region having Si—M bonds between Si and Group 5 element M as described above.
  • a laminated body of a first gas barrier film mainly containing Si and a second gas barrier film mainly containing a Group 5 element M is preferable, and the order of layers may be reversed. It is also preferable that the entire gas barrier film is a mixed region of Si and the Group 5 element M.
  • the “mainly contained” means that the content of the metal of the kind in the film is 50% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more, particularly preferably. It means containing 90 mass% or more.
  • the group 5 element M of the long-period periodic table according to the present invention is not particularly limited, and any metal selected from niobium (Nb), tantalum (Ta), and vanadium (V) may be used alone or in combination. Can be used. Of these, Nb and Ta can be preferably used because of various examination results, and it is considered that bonding to Si contained in the gas barrier film is likely to occur, and Nb is particularly preferable.
  • the formation of the gas barrier film and the mixed region includes a region containing Si (corresponding to the first gas barrier film) and a region containing the metal selected from Group 5 element M (second gas).
  • a mixed region is formed between the Si-containing region and the Group 5 element M-containing region by appropriately adjusting the respective forming conditions. preferable.
  • the Si-containing region is formed by the vapor phase growth method
  • the ratio of Si and oxygen in the film forming raw material, the ratio of the inert gas and the reactive gas during the film formation, and the gas supply amount during the film formation can be formed by adjusting one or more conditions selected from the group consisting of the degree of vacuum during film formation, the magnetic force during film formation, and the power during film formation.
  • a Si-containing region When forming a Si-containing region by a coating method, for example, a film-forming raw material species containing Si (polysilazane species, etc.), a catalyst species, a catalyst content, a coating film thickness, a drying temperature / time, a modification method, a modification
  • the mixed region can be formed by adjusting one or more conditions selected from the group consisting of conditions.
  • the Si-containing region is preferably subjected to a modification treatment after forming a Si-containing film by a coating method using a polysilazane species.
  • the ratio of the Group 5 element M to oxygen in the film forming raw material, the inert gas and the reactive gas at the time of film formation Adjusting one or more conditions selected from the group consisting of ratio, gas supply amount during film formation, degree of vacuum during film formation, magnetic force during film formation, and power during film formation A mixed region can be formed.
  • co-evaporation method As a method for directly forming the mixed region, it is preferable to use a known co-evaporation method. As such a co-evaporation method, a co-sputtering method is preferable.
  • the co-sputtering method employed in the present invention includes, for example, a composite target made of an alloy containing both Si and a Group 5 element M, a composite oxide of Si and a Group 5 element M (hereinafter, a plurality of metals).
  • the oxide composed of the above-mentioned oxide is referred to as “composite oxide”).
  • the co-sputtering method in the present invention may be multi-source simultaneous sputtering using a plurality of sputtering targets including a simple substance of Si or its oxide and a simple substance of Group 5 element M or its oxide.
  • the film forming conditions for carrying out the co-evaporation method include the ratio of the group 5 element M and oxygen in the film forming raw material, the ratio of the inert gas to the reactive gas during the film forming, and the film forming time.
  • One or two or more conditions selected from the group consisting of the gas supply amount, the degree of vacuum during film formation, and the power during film formation are exemplified, and these film formation conditions (preferably oxygen content)
  • these film formation conditions preferably oxygen content
  • a desired gas barrier property can be realized by an extremely simple operation of controlling the thickness of the mixed region.
  • what is necessary is just to adjust the film-forming time at the time of implementing a co-evaporation method in order to control the thickness of a mixing area
  • the method for producing a gas barrier film of the present invention includes a gas for producing a gas barrier film containing silicon (Si) and an element M of Group 5 of the long-period periodic table and having a Si-M bond.
  • a method for producing a barrier film which includes a step of forming a silicon (Si) -containing film and a step of depositing a compound containing element M on the silicon (Si) -containing film.
  • the compound containing the Group 5 element M is deposited by a sputtering method, reverse sputtering treatment is performed on the Si-containing film, and reversely applied to the Si-containing film. After performing the sputtering treatment, it is preferable to deposit a compound containing the Group 5 element M on the Si-containing film by a sputtering method.
  • the gas barrier film containing Si and the Group 5 element M is preferably formed by vapor deposition from the viewpoint of accurately forming the mixed region having Si-M bonds according to the present invention.
  • Examples of the method for forming the deposited film include physical vapor deposition and chemical vapor deposition.
  • PVD Physical Vapor Deposition
  • a target substance for example, a carbon film
  • Examples thereof include vapor deposition methods (resistance heating method, electron beam vapor deposition method, molecular beam epitaxy method), ion plating method, sputtering method and the like.
  • a chemical vapor deposition method (chemical vapor deposition, CVD (Chemical Vapor Deposition)) is supplied to a substrate surface in a gas phase mixed with an excited discharge gas containing a target thin film component.
  • CVD Chemical Vapor Deposition
  • a thin film is deposited on the surface of the substrate or on the substrate by a chemical reaction in the gas phase.
  • CVD methods such as thermal CVD method, catalytic chemical vapor deposition method, photo CVD method, plasma CVD method, atmospheric pressure plasma CVD method, etc. Etc.
  • the film thickness of the first gas barrier film containing Si varies depending on the composition, formation method, and the like, but is preferably in the range of 10 to 1000 nm, for example.
  • the thickness of the second gas barrier film containing the Group 5 element M varies depending on the composition, formation method, etc., but is preferably in the range of 2 to 50 nm, for example, 4 to 25 nm. Is more preferable, and a range of 5 to 15 nm is even more preferable.
  • each of the first gas barrier film and the second gas barrier film may be a plurality of films, and both may have the same configuration / formation method, and at least of these One may be a different configuration / formation method.
  • a preferred method for forming the deposited film is a sputtering method which is one of vacuum film forming methods.
  • Sputtering is a method in which an inert gas such as argon gas is ionized (plasmaized) using an electric field or magnetic field, and the target atoms are knocked out by the kinetic energy obtained by accelerating the ionized ions. It is a physical process for depositing on a substrate to form a target film.
  • a sputtering gas such as argon is ionized (plasmaized) using an electric field or a magnetic field and accelerated to collide with the target surface.
  • target atoms are ejected from the target with which the plasma particles collide, and the ejected atoms are deposited on the object to be processed to form a sputtered film.
  • Film formation by sputtering can be performed by using bipolar sputtering, magnetron sputtering, dual magnetron sputtering (DMS) using an intermediate frequency region, ion beam sputtering, ECR sputtering, or the like alone or in combination of two or more.
  • the target application method is appropriately selected according to the target type, and any of DC (direct current) sputtering, DC pulse sputtering, AC (alternating current) sputtering, and RF (high frequency) sputtering may be used.
  • a reactive sputtering method using a transition mode that is intermediate between the metal mode and the oxide mode can also be used.
  • a metal oxide film can be formed at a high film formation speed, which is preferable.
  • the inert gas used for the process gas He, Ne, Ar, Kr, Xe or the like can be used, and Ar is preferably used. Furthermore, by introducing oxygen, nitrogen, carbon dioxide, and carbon monoxide into the process gas, a thin film of a complex oxide, nitride oxide, oxycarbide, or the like of Si and Group 5 element M can be formed. .
  • film formation conditions in the sputtering method include applied power, discharge current, discharge voltage, time, and the like, which can be appropriately selected according to the sputtering apparatus, film material, film thickness, and the like.
  • the sputtering method may be a multi-source simultaneous sputtering method using a plurality of sputtering targets including Si or its oxide, a group 5 element M alone or its oxide.
  • a method for producing these sputtering targets and a method for producing a thin film made of a composite oxide using these sputtering targets for example, JP 2000-160331 A, JP 2004-068109 A, JP
  • JP The methods and conditions described in JP 2013-047361 A can be referred to as appropriate.
  • a sputtering target containing a simple substance of Group 5 element M or an oxide thereof after performing reverse sputtering treatment on the Si-containing film.
  • Etching the surface of the Si-containing film by reverse sputtering can facilitate the formation of the mixed region having Si-M bonds according to the present invention.
  • a known method can be used without limitation.
  • plasma excitation power is supplied to the electrode while sputter gas is introduced between the surface of the Si-containing film and the electrode while the inside of the processing unit and the surface of the Si-containing film are maintained at a predetermined pressure by the vacuum exhaust means, and generated by the sputter gas.
  • the positive ions that collide with the surface of the Si-containing film are etched. At this time, the surface may be roughened.
  • the sputtering gas (sputtering gas) to be used is not particularly limited, but one or more gases selected from Ar gas, He gas, Ne gas, Kr gas, Xe gas, Rn gas, and N 2 gas may be used. Preferably exemplified.
  • the supply amount of the sputtering gas is not particularly limited, and may be appropriately set according to the etching amount of the Si-containing film.
  • the target etching process can be performed stably. And preferably 10 to 50 mL / min.
  • the processing pressure in the reverse sputtering process is not particularly limited, and may be set as appropriate according to the gas used, the etching amount of the target Si-containing film, etc., but the target Si-containing film is stable. In view of being able to perform the roughening treatment, the pressure is preferably 0.3 to 10 Pa, particularly 0.5 to 2 Pa.
  • the plasma excitation power in the reverse sputtering process is not particularly limited, and may be appropriately set according to the type of gas used and the etching amount of the target Si-containing film. In view of being able to perform the treatment, the power is preferably set to 10 to 100 W.
  • a DC pulse power source When a DC pulse power source is used as the power source, it is preferable to apply a potential of ⁇ 200 to ⁇ 10 V to the shower electrode (electrode for performing sputtering) in order to increase the collision of sputtering gas ions.
  • the surface of the Si-containing film is preferably etched in the range of 0.01 to 10 nm.
  • a film containing the Group 5 element M on the Si-containing film by sputtering.
  • the etching process impurities in the Si-containing film are removed, and an effect of promoting Si-M bonding is obtained.
  • the roughening obtained accompanying the etching treatment increases the area of the interface between the Si-containing film and the film containing the Group 5 element M formed by the sputtering method, and promotes Si-M bonding.
  • a very good anchor effect can be obtained, and the adhesion between the Si-containing film and the film containing the Group 5 element M can be made stronger.
  • the average surface roughness Ra of the Si-containing film obtained as a result of the roughening of the Si-containing film accompanying the reverse sputtering treatment is 1 to 50 nm.
  • Vasma CVD method As a method of forming a vapor deposition film as a gas barrier film, it is also preferable to use a vacuum or atmospheric pressure plasma CVD method from the viewpoint of film formation speed and processing area.
  • the excited gas as used in the present invention means that at least part of the molecules in the gas move from the existing state to a higher energy state by obtaining energy, and the excited gas molecules, radicalized gas This includes molecules and gas containing ionized gas molecules.
  • a metal element such as Si is contained in the discharge space in which a high-frequency electric field is generated.
  • a plasma CVD method is preferred in which a source gas is mixed with an excited discharge gas to form a secondary excitation gas, and the substrate is exposed to the secondary excitation gas to form an inorganic film (ceramic film) on the substrate. .
  • a discharge gas is introduced between the counter electrodes (discharge space), a high-frequency voltage is applied between the counter electrodes to bring the discharge gas into a plasma state, and then the discharge gas and the raw material gas that are in the plasma state are moved outside the discharge space.
  • the substrate is exposed to the mixed gas (secondary excitation gas) to form a deposited film on the substrate.
  • the deposited film containing metal oxide, metal nitride, or metal oxynitride formed by plasma CVD in the present invention includes at least one of metal oxide, metal nitride, and metal oxynitride.
  • the deposited film may be a composite compound such as a metal oxide, metal nitride, metal oxynitride, or metal carbide.
  • a raw material for such an inorganic film may be in a gas, liquid, or solid state at room temperature and normal pressure as long as it contains Si or a Group 5 element M.
  • gas it can be introduced into the discharge space as it is, but in the case of liquid or solid, it is used after being vaporized by means such as heating, bubbling, decompression or ultrasonic irradiation.
  • solvent an organic solvent such as methanol, ethanol, n-hexane or a mixed solvent thereof can be used. Since these diluted solvents are decomposed into molecular and atomic forms during the plasma discharge treatment, the influence on the film formation can be almost ignored.
  • a decomposition gas for decomposing a raw material gas containing a metal element to obtain an inorganic compound for example, hydrogen gas, methane gas, acetylene gas, carbon monoxide gas, carbon dioxide gas, nitrogen gas, ammonia gas, suboxide
  • examples thereof include nitrogen gas, nitrogen oxide gas, nitrogen dioxide gas, oxygen gas, water vapor, fluorine gas, hydrogen fluoride, trifluoroalcohol, trifluorotoluene, hydrogen sulfide, sulfur dioxide, carbon disulfide, and chlorine gas.
  • a ceramic film of a mixture of a metal oxide, a metal oxide and a metal carbide, a metal nitride, a metal oxynitride, a metal halide, a metal sulfide, etc., by appropriately selecting a source gas containing a metal element and a decomposition gas can be obtained.
  • a discharge gas that tends to be in a plasma state can be mixed with the reactive gas of the source gas and the decomposition gas, and the mixed gas can be sent to the plasma discharge treatment apparatus.
  • nitrogen gas and / or Group 18 atom of the periodic table specifically helium, neon, argon, krypton, xenon, radon, etc. are used.
  • nitrogen, helium, and argon are preferably used, and nitrogen is particularly preferable because of low cost.
  • a vapor deposition film is formed by supplying a mixed gas obtained by mixing a discharge gas and a reactive gas to a plasma discharge treatment apparatus.
  • the ratio of the discharge gas and the reactive gas varies depending on the properties of the film to be obtained, it is preferable to supply the reactive gas with the ratio of the discharge gas being 50% by volume or more with respect to the entire mixed gas.
  • FIG. 4 is a schematic view showing an example of a vacuum plasma CVD apparatus used in the present invention.
  • the vacuum plasma CVD apparatus 101 has a vacuum chamber 102, and a susceptor 105 is disposed on the bottom surface inside the vacuum chamber 102. Further, a cathode electrode 103 is disposed on the ceiling side inside the vacuum chamber 102 at a position facing the susceptor 105.
  • a heat medium circulation system 106, a vacuum exhaust system 107, a gas introduction system 108, and a high-frequency power source 109 are disposed outside the vacuum chamber 102.
  • a heat medium is disposed in the heat medium circulation system 106.
  • the heat medium circulation system 106 stores a pump for moving the heat medium, a heating device for heating the heat medium, a cooling device for cooling, a temperature sensor for measuring the temperature of the heat medium, and a set temperature of the heat medium.
  • a heating / cooling device 160 having a storage device is provided.
  • the heating / cooling device 160 is configured to measure the temperature of the heat medium, heat or cool the heat medium to a stored set temperature, and supply the heat medium to the susceptor 105.
  • the supplied heat medium flows inside the susceptor 105, heats or cools the susceptor 105, and returns to the heating / cooling device 160.
  • the temperature of the heat medium is higher or lower than the set temperature, and the heating and cooling device 160 heats or cools the heat medium to the set temperature and supplies the heat medium to the susceptor 105.
  • the cooling medium circulates between the susceptor and the heating / cooling device 160, and the susceptor 105 is heated or cooled by the supplied heating medium having the set temperature.
  • the vacuum chamber 102 is connected to an evacuation system 107, and before the film forming process is started by the vacuum plasma CVD apparatus 101, the inside of the vacuum chamber 102 is evacuated in advance and the heat medium is heated to start from room temperature.
  • the temperature is raised to a set temperature, and a heat medium having the set temperature is supplied to the susceptor 105.
  • the susceptor 105 is at room temperature at the start of use, and when a heat medium having a set temperature is supplied, the susceptor 105 is heated.
  • the substrate 110 to be deposited is carried into the vacuum chamber 102 while maintaining the vacuum atmosphere in the vacuum chamber 102 and placed on the susceptor 105.
  • a large number of nozzles (holes) are formed on the surface of the cathode electrode 103 facing the susceptor 105.
  • the cathode electrode 103 is connected to a gas introduction system 108.
  • a CVD gas is introduced from the gas introduction system 108 to the cathode electrode 103, the CVD gas is ejected from the nozzle of the cathode electrode 103 into the vacuum chamber 102 in a vacuum atmosphere.
  • the cathode electrode 103 is connected to a high frequency power source 109, and the susceptor 105 and the vacuum chamber 102 are connected to a ground potential.
  • a CVD gas is supplied from the gas introduction system 108 into the vacuum chamber 102, a high-frequency power source 109 is activated while a heating medium having a constant temperature is supplied from the heating / cooling device 160 to the susceptor 105, and a high-frequency voltage is applied to the cathode electrode 103, Plasma of the introduced CVD gas is formed.
  • a gas barrier layer (B) which is a thin film grows on the surface of the substrate 110. At this time, the distance between the susceptor 105 and the cathode electrode 103 is set as appropriate.
  • the flow rates of the raw material gas and the cracked gas are appropriately set in consideration of the raw material gas, the cracked gas type and the like.
  • the flow rate of the source gas is 30 to 300 sccm
  • the flow rate of the decomposition gas is 100 to 1000 sccm.
  • a heating medium having a constant temperature is supplied from the heating / cooling device 160 to the susceptor 105, and the susceptor 105 is heated or cooled by the heating medium, and a thin film is formed while being maintained at a constant temperature.
  • the lower limit temperature of the growth temperature when forming a thin film is determined by the film quality of the thin film
  • the upper limit temperature is determined by the allowable range of damage to the thin film already formed on the substrate 110.
  • the minimum temperature and maximum temperature vary depending on the material of the thin film to be formed and the material of the thin film that has already been formed, but the minimum temperature is 50 ° C. or higher in order to ensure a film quality with high gas barrier properties. It is preferable that it is below the heat-resistant temperature of a material.
  • the correlation between the film quality and deposition temperature of the thin film formed by the vacuum plasma CVD method and the correlation between the damage to the deposition object (substrate 110) and the deposition temperature are obtained in advance, and the lower limit temperature and the upper limit temperature are determined. Is done.
  • the temperature of the substrate 110 during the vacuum plasma CVD process is preferably 50 to 250 ° C.
  • the relationship between the temperature of the heat medium supplied to the susceptor 105 and the temperature of the substrate 110 when plasma is formed by applying a high frequency voltage of 13.56 MHz or more to the cathode electrode 103 is measured in advance, and vacuum plasma CVD is performed.
  • the temperature of the heat medium supplied to the susceptor 105 is required.
  • a lower limit temperature here, 50 ° C.
  • a heat medium whose temperature is controlled to a temperature equal to or higher than the lower limit temperature is set to be supplied to the susceptor 105.
  • the heat medium refluxed from the susceptor 105 is heated or cooled, and a heat medium having a set temperature of 50 ° C. is supplied to the susceptor 105.
  • a gas composed of silicon nitride (SiN) is supplied by supplying a mixed gas of silane gas, ammonia gas, and nitrogen gas as a CVD gas and maintaining the substrate 110 at a temperature condition not lower than the lower limit temperature and not higher than the upper limit temperature.
  • a barrier layer is formed.
  • the susceptor 105 Immediately after the startup of the vacuum plasma CVD apparatus 101, the susceptor 105 is at room temperature, and the temperature of the heat medium returned from the susceptor 105 to the heating / cooling apparatus 160 is lower than the set temperature. Therefore, immediately after the activation, the heating / cooling device 160 heats the refluxed heat medium to raise the temperature to the set temperature, and supplies it to the susceptor 105. In this case, the susceptor 105 and the substrate 110 are heated and heated by the heat medium, and the substrate 110 is maintained in a range between the lower limit temperature and the upper limit temperature.
  • the susceptor 105 When a thin film is continuously formed on a plurality of substrates 110, the susceptor 105 is heated by heat flowing from the plasma. In this case, since the heat medium recirculated from the susceptor 105 to the heating / cooling device 160 is higher than the lower limit temperature (50 ° C.), the heating / cooling device 160 cools the heat medium and converts the heat medium at the set temperature into the susceptor. It supplies to 105. Thereby, it is possible to form a thin film while maintaining the substrate 110 in a range between the lower limit temperature and the upper limit temperature. Thus, the heating / cooling device 160 heats the heating medium when the temperature of the refluxed heating medium is lower than the set temperature, and cools the heating medium when the temperature is higher than the set temperature.
  • the lower limit temperature 50 ° C.
  • a heat medium having a set temperature is supplied to the susceptor, and as a result, the substrate 110 is maintained in a temperature range between the lower limit temperature and the upper limit temperature.
  • the first gas barrier film is preferably subjected to a modification treatment by forming a coating film containing Si-containing polysilazane or a modified polysilazane.
  • the precursor-containing film is baked and modified, or modified by vacuum ultraviolet light. Or a method of forming a gas barrier film.
  • any appropriate wet coating method can be applied as a coating method for applying a gas barrier region forming coating solution containing a polysilazane compound.
  • a roller coating method a flow coating method, an ink jet method, a spray coating method, a printing method, a dip coating method, a casting film forming method, a bar coating method, and a gravure printing method.
  • the thickness of the coating film can be set according to the purpose of use of the gas barrier film, and is not particularly limited.
  • the thickness of the coating film is in the range of 10 to 1000 nm as the thickness after drying. Preferably, it is in the range of 20 to 500 nm, more preferably in the range of 50 to 300 nm.
  • the “polysilazane compound” preferably used in the present invention is a polymer having a silicon-nitrogen bond in the structure, and is composed of Si—N, Si—H, N—H, etc., SiO 2 , Si 3 N 4, and an intermediate between them. It is a ceramic precursor inorganic polymer such as solid solution SiO x N y .
  • polysilazane compound those having the following structure are preferably used.
  • R 1 , R 2 and R 3 each represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group or an alkoxy group.
  • perhydropolysilazane (abbreviation: PHPS) in which all of R 1 , R 2 and R 3 are hydrogen atoms is particularly preferable from the viewpoint of the denseness of the obtained gas barrier film.
  • organic solvent for preparing a coating solution containing a polysilazane compound, it is preferable to avoid using an alcohol or water-containing one that easily reacts with polysilazane.
  • organic solvent include hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbon solvents, or ethers such as aliphatic ethers or alicyclic ethers. Can be used.
  • the concentration of the polysilazane compound in the polysilazane compound-containing coating solution is about 0.2 to 35% by mass, although it varies depending on the thickness of the target gas barrier region and the pot life of the coating solution.
  • An amine or metal catalyst can be added to the coating solution in order to promote modification to the silicon oxide compound.
  • Specific examples include Aquamica NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL150A, NP110, NP140, and SP140 manufactured by AZ Electronic Materials Co., Ltd.
  • the addition amount of these catalysts is preferably adjusted to 2% by mass or less with respect to the polysilazane compound in order to avoid excessive silanol formation by the catalyst, decrease in film density, increase in film defects, and the like.
  • the coating liquid containing the polysilazane compound can contain an inorganic precursor compound.
  • the inorganic precursor compound other than the polysilazane compound is not particularly limited as long as a coating solution can be prepared.
  • paragraphs 0140 to 0142 of International Publication No. 2012/090644, paragraphs of International Publication No. 2013/002026 Examples thereof include silicon-containing compounds and polysilsesquioxanes described in 0112 to 0114 and paragraphs 0072 to 0074 of JP-A-2015-33764.
  • the modification treatment of polysilazane in the present invention refers to a reaction in which part or all of the polysilazane compound is converted into silicon oxide or silicon oxynitride.
  • a known method based on the conversion reaction of polysilazane can be selected. Formation of a silicon oxide film or a silicon oxynitride film by a substitution reaction of a polysilazane compound requires baking modification at 450 ° C. or higher, and is difficult to adapt to a flexible substrate using a resin film as a base material. Therefore, when using a film substrate, a method using ultraviolet light capable of performing a conversion reaction at a lower temperature is preferable. Ozone and active oxygen atoms generated by ultraviolet light (synonymous with ultraviolet light) have high oxidation ability, and can form silicon oxide films or silicon oxynitride films with high density and insulation at low temperatures. It is.
  • the ultraviolet light referred to in the present invention refers to ultraviolet light containing electromagnetic waves having a wavelength of 10 to 200 nm, generally called vacuum ultraviolet light.
  • irradiation intensity and irradiation time within the range where the base material carrying the pre-modified polysilazane film and other areas constituting the gas barrier unit are not damaged. It is preferable to do.
  • ultraviolet ray generating means examples include, but are not particularly limited to, metal halide lamps, high pressure mercury lamps, low pressure mercury lamps, xenon arc lamps, carbon arc lamps, excimer lamps, and UV light lasers.
  • metal halide lamps high pressure mercury lamps, low pressure mercury lamps, xenon arc lamps, carbon arc lamps, excimer lamps, and UV light lasers.
  • the ultraviolet light from the source is reflected by the reflector and then before modification. It is desirable to apply to a polysilazane-containing film.
  • UV irradiation can be applied to both batch processing and continuous processing, and can be appropriately selected depending on the shape of the substrate used.
  • the substrate having the polysilazane modified film is a long film, it is converted into ceramics by continuously irradiating ultraviolet rays in the drying zone equipped with the ultraviolet ray generation source as described above while being conveyed. Can do.
  • the time required for ultraviolet irradiation is generally 0.1 seconds to 10 minutes, preferably 0.5 seconds to 3 minutes, depending on the substrate used and the composition and concentration of the polysilazane modified film.
  • the oxygen concentration at the time of irradiation with vacuum ultraviolet light (VUV) is preferably 300 to 10000 volume ppm (1 volume%), more preferably 500 to 5000 volume ppm. By adjusting to such an oxygen concentration range, it is possible to prevent the generation of a gas-barrier region with excessive oxygen and to prevent the deterioration of the gas barrier property.
  • dry inert gas is preferably used, and dry nitrogen gas is particularly preferable from the viewpoint of cost.
  • the gas barrier film can be formed by a wet method using a vacuum ultraviolet irradiation apparatus 200 shown in FIG.
  • an apparatus chamber 201 supplies nitrogen and oxygen in appropriate amounts from a gas supply port (not shown) and exhausts gas from a gas discharge port (not shown), thereby substantially removing water vapor from the inside of the chamber. Can be maintained at a predetermined concentration.
  • an Xe excimer lamp (excimer lamp light intensity: 130 mW / cm 2 ) 202 having a double tube structure that irradiates vacuum ultraviolet rays of 172 nm, an excimer lamp holder 203 also serving as an external electrode, a sample stage 204, and A light shielding plate 206 and the like are provided.
  • the sample stage 204 is configured to be able to move horizontally (in the V direction in FIG.
  • the sample stage 204 can be maintained at a predetermined temperature by a heating means (not shown).
  • a sample 205 on which a polysilazane compound coating layer is formed is placed on the sample stage 204.
  • the height of the sample stage is adjusted so that the shortest distance between the coating layer surface of the sample 205 and the excimer lamp tube surface is 3 mm.
  • the light shielding plate 206 prevents the application layer of the sample 205 from being irradiated with vacuum ultraviolet rays while the Xe excimer lamp 202 is aged.
  • the amount of irradiation energy irradiated to the coating layer surface of the sample 205 with the vacuum ultraviolet irradiation apparatus 200 is measured using a 172 nm sensor head using an ultraviolet integrated light meter (C8026 / H8025 UV POWER METER) manufactured by Hamamatsu Photonics Co., Ltd. can do.
  • the sensor head is installed in the center of the sample stage 204 so that the shortest distance between the Xe excimer lamp tube surface and the measurement surface of the sensor head is 3 mm, and the atmosphere in the apparatus chamber 201 is irradiated with vacuum ultraviolet rays.
  • Nitrogen and oxygen are supplied so that the oxygen concentration is the same as the time, and the sample stage 204 is moved at a speed of 0.5 m / min to perform measurement.
  • an aging time of 10 minutes is provided after the Xe excimer lamp is turned on, and then the sample stage is moved to start the measurement. Based on the irradiation energy obtained by this measurement, the amount of irradiation energy can be adjusted by adjusting the moving speed of the sample stage.
  • gas barrier laminated film The gas barrier film of the present invention may be provided in an electronic device as it is, but it is formed on a film-like substrate and is provided in a flexible electronic device as a gas barrier laminated film. It is preferable.
  • Preferred resins include polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide, fluorinated polyimide resin, polyamide resin, polyamideimide resin, polyetherimide resin, and cellulose acylate resin.
  • the base material is preferably made of a material having heat resistance. Specifically, a base material having a linear expansion coefficient of 15 ppm / K or more and 100 ppm / K or less and a glass transition temperature (Tg) of 100 to 300 ° C. is used.
  • the base material satisfies the requirements for use as a laminated film for electronic parts and displays. That is, when using a gas barrier laminate film for these applications, the substrate may be exposed to a process of 150 ° C. or higher. In this case, when the linear expansion coefficient of the base material exceeds 100 ppm / K, the substrate dimensions are not stable when flowing through the temperature process as described above, and the barrier performance deteriorates due to thermal expansion and contraction. Or, the problem that it cannot withstand the thermal process is likely to occur. If it is less than 15 ppm / K, the film may break like glass and the flexibility may deteriorate.
  • Polyolefin for example, ZEONOR (registered trademark) 1600: 160 ° C, manufactured by Nippon Zeon Co., Ltd.
  • polyarylate PAr: 210 ° C
  • polyethersulfone PES: 220 ° C
  • polysulfone PSF: 190 ° C
  • COC cycloolefin copolymer
  • the glass transition temperature (Tg) can be measured according to JIS K7121 (1987). Specifically, it can be measured using a DSC 6220 manufactured by Seiko Instruments Inc. as a measuring device under the conditions of a thermoplastic resin sample of 10 mg and a heating rate of 20 ° C./min.
  • the substrate is preferably transparent. That is, the light transmittance is usually 80% or more, preferably 85% or more, and more preferably 90% or more.
  • the light transmittance is calculated by measuring the total light transmittance and the amount of scattered light using the method described in JIS K7105: 1981, that is, using an integrating sphere light transmittance measuring device, and subtracting the diffuse transmittance from the total light transmittance. can do.
  • the substrate may be an unstretched film or a stretched film.
  • the said base material can be manufactured by a conventionally well-known general method. Regarding the method for producing these base materials, the items described in paragraphs “0051” to “0055” of International Publication No. 2013/002026 can be appropriately employed.
  • the surface of the substrate may be subjected to various known treatments for improving adhesion, such as corona discharge treatment, flame treatment, oxidation treatment, or plasma treatment, and the above treatments are performed in combination as necessary. It may be. Moreover, you may perform an easily bonding process to a base material.
  • the base material may be a single layer or a laminated structure of two or more layers.
  • the respective substrates may be the same type or different types.
  • the thickness of the substrate according to the present invention (the total thickness in the case of a laminated structure of two or more layers) is preferably 10 to 200 ⁇ m, more preferably 20 to 150 ⁇ m.
  • the gas barrier film of the present invention depends on chemical components (oxygen, water, nitrogen oxide, sulfur oxide, ozone, etc.) in the air. It can be preferably applied to a device whose performance deteriorates. That is, the gas barrier film of the present invention or the gas barrier laminated film having the gas barrier film can be applied to an electronic device including an electronic device body.
  • an electronic device body in which the gas barrier film of the present invention is suitably used examples include, for example, an organic electroluminescence element (organic EL element), a liquid crystal display element (LCD), a thin film transistor, a touch panel, electronic paper, a solar cell (PV And the like.
  • organic EL element organic electroluminescence element
  • LCD liquid crystal display element
  • PV solar cell
  • the electronic device body is preferably an organic EL element or a solar cell, and more preferably an organic EL element.
  • the gas barrier laminate film is preferably applied to an organic EL element.
  • the prepared sample was cut out about 5 mm square, paying attention to contamination, and set in the TOF-SIMS sample chamber so that the primary ion was irradiated onto the surface to be measured.
  • the interior of the sample chamber is set to a predetermined degree of vacuum, the surface of the sample is irradiated with primary ions, the secondary ions emitted from the surface of the sample are given a constant kinetic energy, and are guided to a time-of-flight mass spectrometer.
  • the mass number of the secondary ion species released from the sample surface is identified, and each intensity-designated fragment with respect to the peak intensity of oxygen (O) (120.9919 for Si—Nb, 209.0334 for Si—Ta) The intensity ratios were determined from the detected intensities.
  • thermosetting sheet-like adhesive epoxy resin
  • a sample using a quartz glass plate having a thickness of 0.2 mm instead of the gas barrier laminate film was used as a comparative sample. It was stored under high temperature and high humidity at 40 ° C. and 90% RH, and it was confirmed that no metallic calcium corrosion occurred even after 500 hours.
  • the gas barrier property was evaluated by the ratio (%) of the decrease in permeation density from the initial permeation density when the evaluation cell was stored in an environment of 85 ° C. and 85% RH for 100 hours.
  • a black and white transmission density meter TM-5 manufactured by Konica Minolta Co., Ltd. was used, and measurement was performed at any four points in the cell, and the average value was calculated.
  • the concentration reduction of 100% represents the transmission concentration when a Ca evaluation cell is produced without performing Ca deposition.
  • a UV curable resin manufactured by Aika Kogyo Co., Ltd., product number: Z731L was applied on a substrate so that the dry layer thickness was 0.5 ⁇ m, dried at 80 ° C., and then high-pressure mercury in air. Curing was performed using a lamp under the condition of an irradiation energy amount of 0.5 J / cm 2 .
  • a clear hard coat layer having a thickness of 2 ⁇ m was formed as follows on the surface of the substrate on which the gas barrier film was to be formed.
  • UV curable resin OPSTAR (registered trademark) Z7527 manufactured by JSR Corporation
  • OPSTAR registered trademark
  • Z7527 manufactured by JSR Corporation
  • curing was performed under the condition of an irradiation energy amount of 0.5 J / cm 2 .
  • this base material with a clear hard coat layer is simply used as a base material for convenience.
  • Condition 1 Silicon oxide (Si) film by sputtering method A silicon oxide film was formed on the substrate using a magnetron sputtering apparatus manufactured by Osaka Vacuum Co., Ltd. This apparatus can install a plurality of types of magnetron targets, and can continuously form a plurality of layers having different metal types while maintaining a predetermined vacuum state.
  • the power supply is equipped with two DC / RF cathodes, the DC power supply is equipped with a maximum of 6 kW for sputtering, the RF power supply is equipped with a maximum of 2 kW for sputtering, a substrate reverse sputtering, and a substrate bias application of 500 W.
  • the substrate is placed above the target and is in a sputter-up arrangement, and the substrate can be heated, cooled, and rotated.
  • a commercially available polycrystalline Si target was used as a target, Ar and oxygen were used as process gases, and a 100 nm thick film was formed by RF sputtering.
  • the sputtering power source power was 150 W
  • the oxygen partial pressure was 50%
  • the film formation pressure was 0.5 Pa.
  • the film thickness change data with respect to the film formation time is taken, the film thickness formed per unit time is calculated, and then the film formation time is set so that the set film thickness is obtained. It was adjusted.
  • the adjustment of the film thickness the following conditions were also adjusted using the same method.
  • Niobium Oxide (Nb) Film by Sputtering Method A niobium oxide film was formed using a magnetron sputtering apparatus manufactured by Osaka Vacuum. A commercially available niobium oxide target was used as the target. The sputtering power source power was 150 W and the film forming pressure was 0.5 Pa. A film having a thickness of 10 nm was formed by RF sputtering using Ar as the process gas.
  • Niobium oxide (Nb) film by sputtering method (including 50 W reverse sputtering treatment)
  • a niobium oxide film was formed using a magnetron sputtering apparatus manufactured by Osaka Vacuum. Before the niobium oxide film was formed, the film formation surface was etched by reverse sputtering. The power supply for reverse sputtering was 50 W, and the treatment was for 2 minutes. Thereafter, a film having a thickness of 10 nm was formed in the same manner as in Condition 2.
  • Condition 4 Niobium oxide film by sputtering method (including 100 W reverse sputtering treatment) A film having a thickness of 10 nm was formed in the same manner as in Condition 3 except that the power supply for reverse sputtering was set to 100 W.
  • Condition 5 Tantalum Oxide Film by Sputtering Method A film having a thickness of 10 nm was formed in the same manner as in Condition 2 except that tantalum oxide was used as a target.
  • Tantalum oxide film by sputtering (including reverse sputtering treatment of 100 W) A film having a thickness of 10 nm was formed in the same manner as condition 4 except that tantalum oxide was used as a target.
  • the Nb 2 O 5 powder was mixed at 50% by mass and the SiO 2 powder was mixed at 50% by mass using distilled water as a dispersant in a ball mill, and the resulting slurry was granulated using a spray dryer.
  • An oxide mixed powder having a particle size of 20 to 100 ⁇ m was obtained.
  • a copper backing plate having a diameter of 6 inches was used as a target holder. Then, the oxide mixed powder is a backing plate surface portion to be sprayed, roughened by sandblasting using Al 2 O 3 abrasive grains was in a state of the rough surface.
  • Ni—Al (mass ratio 8: 2) alloy powder is plasma sprayed in a reducing atmosphere (using a Metco sprayer) to form a 50 ⁇ m thick Ni—Al (mass ratio 8: 2) undercoat.
  • the above oxide mixed powder was plasma sprayed on the undercoat in a reducing atmosphere to prepare a target.
  • the obtained target was a target containing Si at 40 atomic% and Nb at 60 atomic%.
  • a silicon oxide / niobium oxide mixed film was formed using this target.
  • a film having a thickness of 50 nm was formed by RF sputtering using Ar and oxygen as process gases.
  • the sputtering power source power was 150 W
  • the oxygen partial pressure was 20%
  • the film formation pressure was 0.5 Pa.
  • Condition 8 Sputtered silicon oxide / niobium oxide mixed film (no oxygen supply) A silicon oxide / niobium oxide mixed film was formed in the same manner as in Condition 7 except that only Ar was used as the process gas.
  • Silicon nitride film by CVD A silicon nitride film was formed using a vacuum plasma CVD apparatus 101 shown in FIG.
  • the high frequency power source used at this time was a 27.12 MHz high frequency power source, and the distance between the electrodes was 20 mm.
  • the source gas was introduced into the vacuum chamber at a silane gas flow rate of 7.5 sccm, an ammonia gas flow rate of 50 sccm, and a hydrogen gas flow rate of 200 sccm (sccm is cm 3 / min at 133.322 Pa). Further, the substrate temperature was set to 100 ° C. at the start of film formation, and a silicon nitride film was formed with a film thickness of 50 nm.
  • Silicon oxynitride film by polysilazane coating A silicon oxynitride film was formed by a coating method as follows.
  • a dibutyl ether solution containing 20% by mass of perhydropolysilazane (manufactured by AZ Electronic Materials Co., Ltd., NN120-20) and an amine catalyst (N, N, N ′, N′-tetramethyl-1,6-diaminohexane (TMDAH) ))
  • a dibutyl ether solution of 20% by mass of perhydropolysilazane manufactured by AZ Electronic Materials Co., Ltd., NAX120-20
  • a ratio of 4: 1 (mass ratio) was diluted to 3% by mass to prepare a coating solution containing Si.
  • the coating solution was prepared in a glove box.
  • the coating solution was applied onto the substrate by spin coating so that the dry film thickness was 100 nm, and dried at 80 ° C. for 2 minutes.
  • Condition 11 Silicon Oxynitride Film by Polysilazane Application / Modification
  • the silicon oxynitride film obtained under Condition 10 was subjected to a modification treatment as described below to form a silicon oxynitride film.
  • the dried coating film was subjected to a vacuum ultraviolet ray irradiation treatment using the vacuum ultraviolet ray irradiation apparatus of FIG. 5 having a Xe excimer lamp with a wavelength of 172 nm under the condition that the irradiation energy amount was 6.0 J / cm 2 .
  • the irradiation atmosphere was replaced with nitrogen, and the oxygen concentration was set to 0.1% by volume.
  • the stage temperature for installing the sample was set to 80 ° C.
  • the gas barrier laminated film having the gas barrier film of the present invention in which the presence of Si-M was confirmed by analyzing the fragments by TOF-SIMS, has a gas barrier property remarkably different from that of the comparative example. I found it excellent.
  • the gas barrier film of the present invention is obtained by subjecting the first gas barrier film to reverse sputtering treatment (deposition conditions 3, 4, and 6).
  • the gas barrier film of the present invention is a gas barrier film having an improved gas barrier property per unit thickness as compared with a gas barrier film when a silicon compound is used.
  • EL devices liquid crystal display devices (LCD), thin film transistors, touch panels, electronic paper, solar cells (PV), and other electronic devices can be suitably used.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Physical Vapour Deposition (AREA)
  • Chemical Vapour Deposition (AREA)
  • Formation Of Insulating Films (AREA)

Abstract

L'invention a pour objet de fournir un film barrière au gaz ainsi qu'un procédé de fabrication de celui-ci, et un dispositif électronique muni de ce film barrière au gaz dont les propriétés de barrière au gaz par unité d'épaisseur sont améliorées, en comparaison avec un film barrière au gaz lorsqu'un composé de silicium est mis en œuvre. Le film barrière au gaz de l'invention comprend un silicium (Si), et un élément M du cinquième groupe du tableau périodique des éléments sous sa forme complète, et est caractéristique en ce qu'il possède une liaison Si-M.
PCT/JP2017/028535 2016-08-18 2017-08-07 Film barrière au gaz ainsi que procédé de fabrication de celui-ci, et dispositif électronique muni de ce film barrière au gaz Ceased WO2018034179A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2018534349A JPWO2018034179A1 (ja) 2016-08-18 2017-08-07 ガスバリアー性膜、その製造方法及びそれを具備した電子デバイス

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016160277 2016-08-18
JP2016-160277 2016-08-18

Publications (1)

Publication Number Publication Date
WO2018034179A1 true WO2018034179A1 (fr) 2018-02-22

Family

ID=61197180

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2017/028535 Ceased WO2018034179A1 (fr) 2016-08-18 2017-08-07 Film barrière au gaz ainsi que procédé de fabrication de celui-ci, et dispositif électronique muni de ce film barrière au gaz

Country Status (2)

Country Link
JP (1) JPWO2018034179A1 (fr)
WO (1) WO2018034179A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024100886A1 (fr) * 2022-11-11 2024-05-16 株式会社シンクロン Film mince contenant du silicium et de l'oxygène

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0470330A (ja) * 1990-02-16 1992-03-05 Nitto Denko Corp 透明耐透湿性フィルム及びｅｌ発光装置
JP2005035128A (ja) * 2003-07-18 2005-02-10 Sumitomo Bakelite Co Ltd 透明ガスバリアフィルムおよびそれを用いた表示装置
JP2010247369A (ja) * 2009-04-13 2010-11-04 Fujifilm Corp ガスバリア積層体の製造方法およびガスバリア積層体
JP2013226757A (ja) * 2012-04-26 2013-11-07 Konica Minolta Inc ガスバリア性フィルム
WO2016039060A1 (fr) * 2014-09-10 2016-03-17 コニカミノルタ株式会社 Film barrière aux gaz et élément électroluminescent organique

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0470330A (ja) * 1990-02-16 1992-03-05 Nitto Denko Corp 透明耐透湿性フィルム及びｅｌ発光装置
JP2005035128A (ja) * 2003-07-18 2005-02-10 Sumitomo Bakelite Co Ltd 透明ガスバリアフィルムおよびそれを用いた表示装置
JP2010247369A (ja) * 2009-04-13 2010-11-04 Fujifilm Corp ガスバリア積層体の製造方法およびガスバリア積層体
JP2013226757A (ja) * 2012-04-26 2013-11-07 Konica Minolta Inc ガスバリア性フィルム
WO2016039060A1 (fr) * 2014-09-10 2016-03-17 コニカミノルタ株式会社 Film barrière aux gaz et élément électroluminescent organique

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024100886A1 (fr) * 2022-11-11 2024-05-16 株式会社シンクロン Film mince contenant du silicium et de l'oxygène

Also Published As

Publication number Publication date
JPWO2018034179A1 (ja) 2019-06-13

Similar Documents

Publication Publication Date Title
US7740917B2 (en) Method for forming thin film and base and having thin film formed by such method
JP5136114B2 (ja) ガスバリア膜の作製方法及び作製装置
JP5958346B2 (ja) ガスバリア積層体の製造方法
JP5626308B2 (ja) ガスバリア積層体の製造方法及びガスバリア積層体
JP2008235165A (ja) 透明導電膜を有するロール状樹脂フィルムの製造方法
JP2010247369A (ja) ガスバリア積層体の製造方法およびガスバリア積層体
JP2013226757A (ja) ガスバリア性フィルム
JP5798747B2 (ja) 積層体の製造方法
JP4876918B2 (ja) 透明導電膜
JP2012131194A (ja) ガスバリア性フィルム
WO2014178332A1 (fr) Film de barrière aux gaz et son procédé de production
WO2017047346A1 (fr) Dispositif électronique et procédé d'étanchéification de dispositif électronique
JPWO2008102868A1 (ja) 透明導電膜を有するロール状樹脂フィルムの製造方法及びこれを用いる有機エレクトロルミネッセンス素子
JP2018052041A (ja) 積層体
WO2018034179A1 (fr) Film barrière au gaz ainsi que procédé de fabrication de celui-ci, et dispositif électronique muni de ce film barrière au gaz
JP4686956B2 (ja) 機能体の形成方法
JP2018012234A (ja) ガスバリアー性フィルム及び電子デバイス
WO2016194559A1 (fr) Film étanche aux gaz
JP4984367B2 (ja) 基材、及び表示装置
WO2005108055A1 (fr) Pellicule pour panneau d'affichage et procédé pour la fabrication d’une pellicule mince d’un élément organique el et d’oxyde d'aluminium
WO2005061757A1 (fr) Procede de production d'une couche mince de fluorure de magnesium, couche mince de fluorure de magnesium, film multicouche, film plastique transparent et dispositif organique el
CN113366141A (zh) 用于金属涂层的方法
JP2014065259A (ja) フィルム部材およびその製造方法
JP2005076099A (ja) 薄膜の製造方法とそれにより造られた薄膜、積層薄膜、透明プラスチックフィルム、及び積層薄膜付き有機ｅｌ素子
JP2008266682A (ja) 酸化マグネシウム膜の成膜方法

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2018534349

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17841404

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17841404

Country of ref document: EP

Kind code of ref document: A1