Silicon metal oxide encapsulation film and preparation method thereof

Abstract

The present invention relates to a silicon metal oxide packaging film and a preparation method thereof. The silicon metal oxide packaging film of the present invention has a high film growth rate and low water and oxygen permeability. Although the thickness is very thin, the sealing effect is very good, and the stress intensity and refractive index can be adjusted. Therefore, a high-quality silicon metal oxide packaging film for use in flexible displays can be effectively prepared.

Description

Technical Field

[0001] The present invention relates to a silicon oxide encapsulation film containing metal or metal oxide in the film and a preparation method thereof, and more particularly, to a silicon metal oxide encapsulation film formed by using a silicon precursor and a metal precursor and a preparation method thereof. Background Art

[0002] Generally, organic semiconductor devices are vulnerable to moisture or oxygen and are easily oxidized by moisture or oxygen in the air, which deteriorates their electrical properties. Therefore, the core of the device packaging process is to isolate it from moisture and oxygen, which can be said to be an important technology that determines the life of the panel. The above packaging technology can be roughly divided into three types: a method using a glass / metal container (Can, glassencapsulation), a thin film encapsulation method (TFE, thin film encapsulation) and a hybrid encapsulation method (hybridencapsulation) that uses both thin film and glass containers. The various methods can be described as follows: a method using a metal with gas insulation or a container with a cover and a getter made of glass; a thin film packaging method called face sealing that uses an organic or inorganic multilayer film on the upper layer of the device to achieve barrier properties; and a hybrid method that uses a plastic barrier film as a cover and configures an adhesive layer between it and the passivation film.

[0003] The currently widely used method of using a glass / metal container (Can, glass encap) exhibits the best packaging characteristics by placing an organic semiconductor device between two glasses consisting of a substrate and a cover, then using a laser to melt glass powder for sealing, or using ultraviolet (UV) adhesive for sealing. However, it has the disadvantages of poor thermal conductivity due to the inert gas in the device and increased costs due to large-area glass processing. It also has problems in being applied to flexible panels that require flexibility.

[0004] In order to make up for the shortcomings of the above-mentioned glass encapsulation technology (Can, glass encapsulation), inorganic layers such as Al2O3 with high barrier properties to oxygen or moisture and organic layers of polymers are used as thin films and alternately stacked on the overall organic semiconductor device. This thin film encapsulation method (TFE, thin film encapsulation) of forming a multi-layer encapsulation film is being studied in full swing.

[0005] Although a thin film encapsulation technology with high film density and excellent permeability has been developed in recent research, the components of the organic layer of the multi-layer encapsulation film are mostly UV-curable substances. Since the organic encapsulation film using UV curing uses a solution process, it has the disadvantages of reduced electrical properties and flexibility due to the reduction of properties through the solvent and shortened life. In addition, although the encapsulation film formed by the inorganic layer can ensure good properties due to its thick thickness, it has the disadvantage of reduced flexibility.

[0006] In order to solve the above problems, it is necessary to develop a method for producing a packaging film having excellent sealing properties that can prevent the penetration of moisture or oxygen in the atmosphere even if the thickness is thin and has high flexibility. Summary of the invention

[0007] Technical issues

[0008] In order to solve the above problems in the prior art, an object of the present invention is to provide a silicon metal oxide encapsulation film doped with metal and metal oxide.

[0009] Furthermore, an object of the present invention is to provide a method for preparing the silicon metal oxide encapsulation film of the present invention.

[0010] Technical Solution

[0011] In order to solve the above problems, the present invention provides a metal oxide encapsulation film represented by the following Chemical Formula 1.

[0012] Chemical formula 1: Si x M y O z

[0013] (In the above chemical formula 1, M is a metal, 0.1<x<1, 0<y<2, 1≤z≤3, 1 <x+y<3,1.5<x+y+z<6)。

[0014] The packaging film according to an embodiment of the present invention may be a packaging film for an organic light emitting diode (OLED) of a display.

[0015] In the packaging film of an embodiment of the present invention, M in the chemical formula 1 may be one or more metals selected from the group consisting of Group IB to Group VB and Group IIIA to Group IVA in the periodic table.

[0016] In the silicon metal oxide encapsulation film according to an embodiment of the present invention, the content of metal atoms may be within a range of 1 atomic percent to 50 atomic percent (at%) relative to the total content of the silicon metal oxide.

[0017] In one embodiment of the present invention, the moisture permeability of the silicon metal oxide encapsulation film can be 1.0×10 -2 g / m2 -day to 1.0×10 -6 g / m 2 -day.

[0018] In one embodiment of the present invention, the stress of the silicon metal oxide encapsulation film may be -700 MPa to +700 MPa.

[0019] In one embodiment of the present invention, the refractive index of the silicon metal oxide encapsulation film may be in the range of 1.0 to 10.

[0020] The silicon metal oxide encapsulation film according to an embodiment of the present invention may be dry-etched by using one or more etching gases selected from fluorine-containing compounds, NF3 and BCl3.

[0021] In the silicon metal oxide encapsulation film of one embodiment of the present invention, the thickness of the film can be to

[0022] The present invention provides a method for preparing a silicon metal oxide encapsulation film represented by Chemical Formula 1 using an atomic layer deposition method (ALD).

[0023] Chemical formula 1: Si x M y O z

[0024] (In the above chemical formula 1, M is a metal, 0.1<x<1, 0<y<2, 1≤z≤3, 1 <x+y<3,1.5<x+y+z<6)。

[0025] The method for preparing a silicon metal oxide encapsulation film according to an embodiment of the present invention can be prepared by allowing a metal precursor and a silicon precursor to enter a reactor at the same time.

[0026] In the method for preparing a silicon metal oxide encapsulation film according to an embodiment of the present invention, the silicon precursor may be an organic aminosilane compound containing a Si—N bond.

[0027] In the method for preparing a silicon metal oxide encapsulation film according to an embodiment of the present invention, the metal precursor may be an organic metal compound containing one or more metal elements selected from Group IB to Group VB and Group IIIA to Group IVA of the periodic table as a central metal.

[0028] The method for preparing a silicon metal oxide encapsulation film according to an embodiment of the present invention may include: allowing a metal precursor and a silicon precursor to simultaneously enter a reactor to contact a substrate; and allowing a reaction gas to contact the substrate to prepare a silicon metal oxide encapsulation film on the substrate.

[0029] In the method for preparing a silicon metal oxide encapsulation film according to an embodiment of the present invention, the atomic layer deposition (ALD) method may be a plasma enhanced atomic layer deposition (PEALD) method.

[0030] The reaction gas in one embodiment of the present invention may be one or more selected from O2, N2O, NO2, H2O, H2O2 and O3.

[0031] The present invention provides a multilayer film for an organic light emitting diode, comprising: a substrate; a first layer comprising a first silicon metal oxide represented by the following chemical formula 1; a second layer located on the first layer and comprising a cross-linked polymer; and a third layer located on the second layer and comprising a second silicon metal oxide represented by chemical formula 1.

[0032] Chemical formula 1: Si x M y O z

[0033] (In the above chemical formula 1, M is a metal, 0.1<x<1, 0<y<2, 1≤z≤3, 1 <x+y<3,1.5<x+y+z<6)。

[0034] The multi-layer thin film for an organic light emitting diode according to an embodiment of the present invention may be a flexible transparent substrate.

[0035] According to an embodiment of the present invention, the curvature radius of the multilayer film for an organic light emitting diode may be less than 2R.

[0036] The present invention provides an organic light emitting diode device comprising the encapsulation film.

[0037] Effects of the Invention

[0038] Since the density of the silicon metal oxide encapsulation film of the present invention is very high, even at a very thin thickness, it has excellent sealing properties for blocking moisture and oxygen penetrating from the outside.

[0039] Furthermore, the silicon metal oxide encapsulating film of the present invention has the advantage of being able to adjust optical characteristics because the refractive index can be easily adjusted, and has the advantage of being applicable to a flexible display substrate because the stress can be easily adjusted.

[0040] Furthermore, the method for preparing the silicon metal oxide encapsulation film of the present invention has a very high film growth rate and contains metal or metal oxide, so it is easy to remove particles and dry clean by adjusting the dry etching speed during deposition, which has the advantage of improving productivity by shortening the process time. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1Graphs showing the permeabilities of the silicon oxide encapsulating films and the metal oxide encapsulating films of Comparative Examples 1 to 3 and the silicon metal oxide encapsulating films prepared in Examples 1 to 3.

[0042] Figure 2 Graph showing the permeability of the silicon metal oxide encapsulation films prepared in Examples 4 to 9.

[0043] Figure 3 is a graph showing the permeability of the silicon metal oxide encapsulation films prepared in Examples 10 to 12.

[0044] Figure 4 Graphs showing moisture permeability of the silicon oxide encapsulation films and metal oxide encapsulation films of Comparative Examples 1 to 3 and the silicon metal oxide encapsulation films prepared in Examples 1 to 3.

[0045] Figure 5 Graph showing the moisture permeability of the silicon metal oxide encapsulation films prepared in Examples 4 to 9.

[0046] Figure 6 Graph showing the moisture permeability of the silicon metal oxide encapsulation films prepared in Examples 10 to 12.

[0047] Figure 7 Graph showing the metal content related to the refractive index of the silicon metal oxide encapsulation films prepared in Examples 7 to 12 of the present invention. DETAILED DESCRIPTION

[0048] The following is a detailed description of the silicon metal oxide encapsulation film doped with metal or metal oxide of the present invention. Unless otherwise defined, all terms used in this specification, including technical terms or scientific terms, may have the same meanings as those generally understood by ordinary technicians in the technical field to which the present invention belongs. In the following description and drawings, the description of well-known functions and structures that may confuse the main purpose of the present invention will be omitted.

[0049] The present invention provides a metal oxide encapsulation film represented by the following Chemical Formula 1.

[0050] Chemical formula 1: Si x M y O z

[0051] (In the above chemical formula 1, M is a metal, 0.1<x<1, 0<y<2, 1≤z≤3, 1 <x+y<3,1.5<x+y+z<6)。

[0052] The silicon metal oxide encapsulation film represented by Chemical Formula 1 above is a silicon oxide encapsulation film containing a metal or a metal oxide. Preferably, the silicon oxide encapsulation film may be doped with a metal or a metal oxide.

[0053] Preferably, Chemical Formula 1 above may meet the following conditions: M is a metal, 0.3 < x < 1, 0.05 < y < 2, 1.6 ≤ z ≤ 2.7, 1 < x + y < 2, 2.5 < x + y + z < 5. The silicon metal oxide encapsulation film of the present invention contains a metal or a metal oxide. Therefore, it not only has excellent moisture permeability, but also has excellent permeability, refractive index, and flexibility, and has improved physical properties compared to existing silicon oxide encapsulation films.

[0054] In the silicon metal oxide of an embodiment of the present invention, M in Chemical Formula 1 may be one or more metals selected from the group consisting of Group IB to Group VB and Group IIIA to Group IVA in the periodic table of elements. Preferably, it may be one or two or more selected from Ti, Zr, Hf, Al, Ga, In, Sn, Pb, V, Cu, Ag, Nb, Zn, and Cd. More preferably, it may be one or two or more metals selected from Zr, Hf, Al, Sn, and Zn.

[0055] According to a preferred embodiment of the silicon metal oxide encapsulation film of the present invention, in order to make the silicon metal oxide encapsulation film in which the above metal element is doped in the silicon oxide have a better effect, preferably, the content of metal atoms may be within 1 atomic percentage to 50 atomic percentages based on the total content of the silicon metal oxide. More preferably, it may be 1 atomic percentage to 40 atomic percentages. Even more preferably, it may be 3 atomic percentages to 40 atomic percentages. As described above, if the range of the metal content doped in the silicon oxide is satisfied, the above silicon metal oxide encapsulation film can achieve excellent water vapor transmission rate (WVTR, Water Vapor Transmission Rate) even at a very thin thickness. Since the non-crystallinity of the silicon oxide is maintained, no grain boundary is formed when applied to a substrate. And, since the encapsulation film has a very thin thickness and the encapsulation film does not contain grain boundaries, even if the flexible substrate is repeatedly bent, the encapsulation film formed on the flexible substrate will not be damaged, so it has excellent durability.

[0056] The silicon metal oxide encapsulation film according to a preferred embodiment of the present invention can be dry-etched using one or more etching gases selected from fluorine-containing compounds, NF3, and BCl3.

[0057] In the etching of the silicon metal oxide encapsulation film according to a preferred embodiment of the present invention, the gas can be used alone as C x F yType (x is an integer from 1 to 5, y is an integer from 4 to 12) gas, C x H y F z The gas used in the etching may be a single gas selected from fluorine-containing compounds, especially perfluorinated compounds (perfluorocycloalkanes), NF3 and BCl3, or a mixed gas thereof. In the case of using the above-mentioned etching gas, the dry etching speed can be adjusted in the silicon metal oxide encapsulation film, so that not only dry cleaning is possible, but also particles can be easily removed.

[0058] The silicon metal oxide of one embodiment of the present invention changes the metal content according to the metal precursor, thereby adjusting the viewing angle, preventing diffuse reflection and optical properties such as the color rendering index, and the refractive index can be adjusted to the range of 1.0 to 10. Preferably, the refractive index can be in the range of 1.0 to 5.0, more preferably, it can be in the range of 1.0 to 2.0, and most preferably, it can be in the range of 1.4 to 1.9.

[0059] The thickness of the silicon metal oxide encapsulation film according to an embodiment of the present invention may be to Preferably, it can be to In this case, the moisture permeability can be 1.0×10 -2 g / m 2 -day to 1.0×10 -6 g / m 2 -day, preferably, it can be 1.0×10 -2 g / m 2 -day to 1.0×10 -5 g / m 2 -day.

[0060] The stress intensity of the silicon metal oxide encapsulation film of one embodiment of the present invention may be -700MPa to +700MPa, which may include compressive or tensile forms, preferably, -500MPa to +500MPa, and more preferably, -200MPa to +200MPa. By adjusting the stress within the above range, the flexibility that can prevent the flexible substrate from being damaged due to folding or bending can be ensured in the soft display.

[0061] According to a preferred embodiment of the present invention, the silicon metal oxide encapsulation film can be applied to a flexible display device, and preferably, can be an encapsulation film for an organic light emitting diode of a display.

[0062] According to a preferred embodiment of the present invention, in the case of the silicon metal oxide encapsulation film, since the stress intensity and refractive index can be easily adjusted according to the metal content range, it can replace the existing organic-inorganic multilayer thin film formed by repeated overlapping of organic and inorganic substances. That is, by using a silicon metal oxide layer of the present invention to replace the multilayer thin film, not only can the thin film encapsulation process be shortened epoch-makingly, but also optical properties and flexibility can be ensured in a very thin state, and as an encapsulation technology that is very suitable for soft displays such as flexible organic light-emitting diodes, it has a very high application possibility.

[0063] The present invention provides a method for preparing a silicon metal oxide encapsulation film represented by the following chemical formula 1 using atomic layer deposition. Preferably, as a specific example, the atomic layer deposition method may be plasma enhanced atomic layer deposition method, which is easier than thin film deposition and has better properties than thin film deposition.

[0064] Chemical formula 1: Si x M y O z

[0065] (In the above chemical formula 1, M is a metal, 0.1<x<1, 0<y<2, 1≤z≤3, 1 <x+y<3,1.5<x+y+z<6)。

[0066] In the preparation method according to an embodiment of the present invention, the silicon metal oxide represented by Chemical Formula 1 can be prepared by introducing a metal precursor and a silicon precursor into a reactor at the same time.

[0067] The silicon precursor is an organic aminosilane compound containing a Si-N bond, preferably, a (C1-C10) alkylaminosilane, more preferably, a (C1-C6) alkylaminosilane, and even more preferably, a (C1-C3) alkylaminosilane. The alkyl group of the present invention may be a linear or branched type. In addition, the alkylaminosilane of the present invention includes a trialkylaminosilane, a dialkylaminosilane or a monoalkylaminosilane, preferably, a di(C1-C6) alkylaminosilane, and more preferably, a di(C1-C3) alkylaminosilane. Furthermore, the above-mentioned metal precursor is an organic metal compound containing one or more metals selected from Group IB to Group VB and Group IIIA to Group IVA of the periodic table, preferably, it is an organic metal compound containing one or more metal elements selected from Ti, Zr, Hf, Al, Ga, In, Sn, Pb, V, Cu, Ag, Nb, Zn and Cd, and more preferably, it is an organic metal precursor containing one or more metal elements selected from Zr, Hf, Al, Sn and Zn as the central element.

[0068] The metal precursor according to an embodiment of the present invention can be represented by the following Chemical Formula 2.

[0069] Chemical formula 2:

[0070] (In Chemical Formula 2, R1 to R5 are each independently hydrogen or (C1-C3) alkyl; R 11 To R 13 Each is independently cyclopentadienyl, carbonyl, (C1-C4) alkyl, (C3-C5) aryl, or (C2-C4) alkenyl).

[0071] In a method for preparing a silicon metal oxide encapsulating film according to an embodiment of the present invention, before, during or after supplying a metal precursor and a silicon precursor to a chamber in which a substrate to be deposited exists, an oxygen-containing gas, a nitrogen-containing gas, a carbon-containing gas or a mixed gas thereof as a reaction gas may be supplied to the chamber. Any reaction gas may be used as long as it is a gas that is usually used together with a metal precursor and a silicon precursor when considering the material of the silicon metal oxide encapsulating film to be prepared. As a specific example, the oxygen-containing gas may be oxygen (O2), ozone (O3), distilled water (H2O) or hydrogen peroxide (H2O2), and the nitrogen-containing gas may be nitric oxide (NO), nitrous oxide (N2O), nitrogen dioxide (NO2), ammonia (NH3), nitrogen (N2), hydrazine (N2H4) or tert-butylhydrazine (C4H 12 N2) and other hydrazine derivatives, the carbon-containing gas may be carbon monoxide (CO), carbon dioxide (CO2), C1 to C12 saturated or unsaturated hydrocarbons, etc., but are not limited thereto. In addition, the above-mentioned reaction gas may be mixed with an inert gas such as nitrogen, helium or argon, and hydrogen may be used as other reaction gas.

[0072] In the method for preparing a silicon metal oxide encapsulation film according to an embodiment of the present invention, the plasma enhanced atomic layer deposition method includes four steps of adding a precursor, removing the precursor, adding plasma and a reaction gas, and removing the reaction gas as a cycle. The deposition time of the above cycle can be less than 0.5 seconds to 5.0 seconds, and the temperature of the substrate to be deposited can be less than 20°C to 150°C.

[0073] In the preparation method of the silicon metal oxide encapsulation film of one embodiment of the present invention, the metal precursor and the silicon precursor are supplied at the same time, and the reaction gas can be supplied simultaneously with the precursor, or can be supplied into the chamber relatively independently of the supply of the precursor. In addition, the reaction gas can be supplied into the chamber continuously or discontinuously, and the discontinuous supply can include a pulse form. In addition, the reaction gas can be in the form of activated plasma. In this case, as described above, the reaction gas activated into plasma can be a gas that activates an oxygen-containing gas, a nitrogen-containing gas, or a mixed gas thereof into plasma, specifically, it can be selected from oxygen (O2), ozone (O3), distilled water (H2O), hydrogen peroxide (H2O2), nitric oxide (NO), nitrous oxide (N2O) and nitrogen dioxide (NO2) One or more activated mixed gases of the gas, but not limited to this.

[0074] Specifically, a method for preparing a silicon metal oxide encapsulation film according to an embodiment of the present invention may include: step a), heating a deposition target substrate (substrate) located in a chamber to a deposition temperature and maintaining the temperature; step b), adding a metal precursor and a silicon precursor into a reactor at the same time; step c), bringing the metal precursor and the silicon precursor entering the reactor into contact with the substrate so that they are adsorbed on the above-mentioned deposition target substrate (substrate); and step d), injecting a reaction gas into the deposition target substrate on which silicon containing metal or metal oxide is adsorbed to form a silicon metal oxide encapsulation film.

[0075] More specifically, in the above step b), the metal precursor and the silicon precursor may be supplied simultaneously. In this case, after step b) or step c), a purging step of supplying an inert gas into the chamber may be performed.

[0076] The method for preparing a silicon metal oxide encapsulation film according to an embodiment of the present invention can adjust the deposition conditions according to the structure or thermal mode of the target film. Specifically, the deposition conditions can include the addition flow rate of the metal precursor and the silicon precursor, the addition flow rate of the reaction gas and the transport gas, the pressure, the temperature of the substrate to be deposited, etc. As a non-limiting example of the above-mentioned deposition conditions, the addition flow rate of the metal precursor can be 10 cubic centimeters per minute (cc / min) to 1000 cubic centimeters per minute, the flow rate of the transport gas can be 10 cubic centimeters per minute to 1000 cubic centimeters per minute, the flow rate of the reaction gas can be 1 cubic centimeter per minute to 1500 cubic centimeters per minute, the pressure can be 0.5 torr to 10 torr, and the temperature of the substrate to be deposited can be in the range of 10°C to 200°C, specifically, it can be adjusted in the range of less than 20°C to 150°C, but it is not limited thereto. Furthermore, according to an advantageous example, when the reaction gas is activated to a plasma state, that is, when deposition is performed using plasma enhanced atomic layer deposition, the radio frequency (RF) power may be 50 W to 1000 W, but is not limited thereto.

[0077] The deposition object substrate used in the preparation method of the silicon metal oxide encapsulation film of one embodiment of the present invention can be a semiconductor substrate containing one or more semiconductor materials selected from Si, Ge, SiGe, GaP, GaAs, SiC, SiGeC, InAs and InP; SOI (Silicon On Insulator) substrate; quartz substrate or glass substrate for display; polyimide, polyethylene terephthalate (PET, PolyEthyleneTerephthalate), polyethylene naphthalate (PEN, PolyEthyleneNaphthalate), polymethyl methacrylate (PMMA, PolyMethylMethAcrylate), polycarbonate (PC, PolyCarbonate), polyethersulfone (PES), polyester fiber (Polyester) and other flexible plastic substrates, but not limited thereto. Specifically, as an example of a preferred substrate, it can be a foldable substrate that can have folding characteristics, and more specifically, it can be a polymer film with an appropriate thickness. The polymer may be a polymer such as polyimide, polyethylene terephthalate, polyethylene naphthalate, polymethyl methacrylate, polycarbonate, polyether sulfone, polyester fiber, or the like.

[0078] Furthermore, the silicon metal oxide may be directly contacted with a substrate to be deposited to form a thin film, and a plurality of conductive layers, dielectric layers or insulating layers may be interposed between the substrate to be deposited and the silicon metal oxide thin film.

[0079] Furthermore, the present invention provides a multilayer film for an organic light-emitting diode, wherein the multilayer film for an organic light-emitting diode comprises: a substrate; a first layer comprising a first silicon metal oxide represented by the following chemical formula 1; a second layer located on the first layer and comprising a polymer; and a third layer located on the second layer and comprising a second silicon metal oxide represented by chemical formula 1.

[0080] Chemical formula 1: Si x M y O z

[0081] (In the above chemical formula 1, M is a metal, 0.1<x<1, 0<y<2, 1≤z≤3, 1 <x+y<3,1.5<x+y+z<6)。

[0082] The first silicon metal oxide and the second silicon metal oxide may be the same or different. The first silicon metal oxide and the second silicon metal oxide are different from each other, which means that the values ​​of x, y, and z in the chemical formula 1 are different from each other.

[0083] The polymer of the second layer may be a cross-linked polymer, and the multi-layer film may be a cross-linked polymer that cross-links and cures the cross-linkable polymer of the second layer under known curing conditions.

[0084] The polymer of the second layer of one embodiment of the present invention can be a polyimide block copolymer, but is not limited thereto, and the polyimide block copolymer can have a weight average molecular weight of 100000g / mol to 5000000g / mol, preferably, it can have a weight average molecular weight of 200000g / mol to 1000000g / mol, more preferably, it can have a weight average molecular weight of 300000g / mol to 750000g / mol, and more preferably, it can have a weight average molecular weight of 500000g / mol to 650000g / mol. The polyimide block copolymer film of one embodiment of the present invention can be prepared by conventional methods such as dry method and wet method using the above-mentioned polyimide block copolymer. As an example, the polyimide block copolymer film can be obtained by the following method: after the solution containing the above-mentioned copolymer is applied to any support to form a film, the solvent is evaporated from the above-mentioned film to dry. It can be stretched and heat treated as needed.

[0085] If the polymer of the second layer of one embodiment of the present invention is a polyimide block copolymer film, it can exhibit excellent mechanical properties in a colorless and transparent state. The multilayer film for an organic light emitting diode according to a preferred embodiment of the present invention can be a flexible multilayer film, and as a preferred embodiment, can be a foldable multilayer film. When the multilayer film for an organic light emitting diode has a foldable property, the curvature radius of the multilayer film for an organic light emitting diode can be less than 3R, preferably, can be less than 2R, preferably, can be greater than R and less than or equal to 2R.

[0086] Also, the present invention provides an organic light emitting diode device including the silicon metal oxide encapsulation film represented by the above Chemical Formula 1.

[0087] Hereinafter, the present invention will be described in more detail by the following examples. It should be noted that the terms or words used in this specification and the scope of protection of the invention should not be limited to the usual or dictionary meanings for interpretation, and the inventors can interpret the meanings and concepts that conform to the technical ideas of the present invention based on the principle of appropriately defining the concepts of the terms for the purpose of describing in the best way.

[0088] Therefore, the embodiments described in this specification and the structures shown in the accompanying drawings are merely the best embodiments of the present invention and do not represent the entire technical concept of the present invention. It should be understood that when the present application is filed, there may be a variety of equivalents and modifications that can replace these.

[0089] Furthermore, all the following embodiments are performed by using a commercial showerhead-type 200 mm single wafer type atomic layer deposition device (CN1, Atomic Premium) through a known plasma enhanced atomic layer deposition method. Furthermore, a commercial showerhead-type 200 mm single wafer type atomic layer deposition device (CN1, Atomic Premium) can be used to perform the deposition by chemical vapor deposition (CVD) (plasma enhanced chemical vapor deposition (PECVD)).

[0090] The thickness of the deposited silicon metal oxide encapsulation film was measured using an ellipsometer (Ellipsometer, OPTI-PROBE 2600, THERMA-WAVE), and an infrared spectrometer (Infrared Spectroscopy, IFS66V / S & Hyperion 3000, Bruker Optics), an X-ray photoelectron spectrometer (X-ray photoelectronspectroscopy), and a water vapor transmission rate (WVTR, MOCON, Aquatran 2) were used. The amount of nitrogen used in the measurement was 20 ml / min·Air, and the water vapor transmission rate detection area was set to 50 cm 2 . After forming the silicon metal oxide film, dry etching was performed. The dry etching speed was performed using a plasma etching device (ExelanHPT, Lam research) using a conventional plasma etching method. In this case, the etching gas was a mixed gas containing C4F8 (perfluorocyclobutane), the temperature was 20°C, the driving pressure was 70 mTorr, and the plasma output power was set to 250W at the upper end / 250W at the lower end. Stress detection used a stress detector (Frontier Semiconductor, FSM500TC model) with a detection area of ​​160mm and a silicon wafer thickness of 0.725μm to analyze the film characteristics.

[0091] Example 1. Preparation of silicon metal oxide encapsulation film by plasma enhanced atomic layer deposition

[0092] In order to form a silicon metal oxide encapsulation film in a conventional plasma enhanced atomic layer deposition apparatus using a known plasma enhanced atomic layer deposition method, diisopropylaminosilane was used as a silicon precursor, cyclopentadienyl tris(dimethylamino)zirconium was used as a metal precursor, and the concentration of 1.84×10 -4 The silicon precursor was added at a rate of 9.09×10 -7 The zirconium precursor was added at a rate of 100 mol / sec to prepare the silicon zirconium oxide encapsulation film and the film formation was evaluated. Plasma and nitrous oxide (N2O) were used as reaction gases, and argon gas was used as an inert gas for purging purposes. The number of deposition cycles was 136, and the specific deposition method of the silicon metal oxide encapsulation film is shown in Table 1.

[0093] As shown in Table 2, the thickness of the deposited packaging film was measured by an ellipsometer, the formation of the silicon metal oxide packaging film was analyzed by an infrared spectrometer, and the composition of the silicon metal oxide packaging film was analyzed by an X-ray photoelectron spectrometer. In addition, the dry etching rate of the silicon metal oxide packaging film was measured by a plasma etching device, the stress of the silicon metal oxide packaging film was analyzed by a stress detector, and the moisture permeability was detected by a moisture permeation evaluation device in order to detect the moisture permeability of the packaging film. The specific analysis results of the silicon metal oxide packaging film are shown in the following Table 3, Figure 1 The permeability of the deposited film measured by infrared spectroscopy is shown. Figure 4 The results of analysis of water vapor permeability measured using a moisture permeability tester are shown.

[0094] Example 2. Preparation of silicon metal oxide encapsulation film by plasma enhanced atomic layer deposition

[0095] In order to form a silicon metal oxide encapsulation film in a conventional plasma enhanced atomic layer deposition apparatus using a known plasma enhanced atomic layer deposition method, diisopropylaminosilane was used as a silicon precursor, cyclopentadienyl tris(dimethylamino)zirconium was used as a metal precursor, and the concentration of 1.84×10 -4 The silicon precursor was added at a rate of 1.82×10 -6 The zirconium precursor was added at a rate of 100 mol / sec to prepare the silicon zirconium oxide encapsulation film and the film formation was evaluated. Plasma and nitrous oxide (N2O) were used as reaction gases, and argon gas was used as an inert gas for purging purposes. The number of deposition cycles was 116, and the specific deposition method of the silicon metal oxide encapsulation film is shown in Table 1.

[0096] The deposited encapsulation film was analyzed using the same analysis method as in Example 1. The specific analysis results of the silicon metal oxide encapsulation film are shown in Tables 2 and 3. Figure 1 The permeability of the deposited film measured by infrared spectroscopy is shown. Figure 4 The results of analysis of water vapor permeability measured using a moisture permeability tester are shown.

[0097] Example 3. Preparation of silicon metal oxide encapsulation film by plasma enhanced atomic layer deposition

[0098] In order to form a silicon metal oxide encapsulation film in a conventional plasma enhanced atomic layer deposition apparatus using a known plasma enhanced atomic layer deposition method, diisopropylaminosilane was used as a silicon precursor, cyclopentadienyl tris(dimethylamino)zirconium was used as a metal precursor, and the concentration of 1.84×10 -4 The silicon precursor was added at a rate of 3.64×10 -6The zirconium precursor was added at a rate of 100 mol / sec to prepare the silicon zirconium oxide encapsulation film and the film formation was evaluated. Plasma and nitrous oxide (N2O) were used as reaction gases, and argon gas was used as an inert gas for purging purposes. The number of deposition cycles was 112, and the specific deposition method of the silicon metal oxide encapsulation film is shown in Table 1.

[0099] The deposited encapsulation film was analyzed using the same analysis method as in Example 1. The specific analysis results of the silicon metal oxide encapsulation film are shown in Tables 2 and 3. Figure 1 The permeability of the deposited film measured by infrared spectroscopy is shown. Figure 4 The results of analysis of water vapor permeability measured using a moisture permeability tester are shown.

[0100] Example 4. Preparation of silicon metal oxide encapsulation film by plasma enhanced atomic layer deposition

[0101] In order to form a silicon metal oxide encapsulation film in a conventional plasma enhanced atomic layer deposition apparatus using a known plasma enhanced atomic layer deposition method, diisopropylaminosilane was used as a silicon precursor and trimethylaluminum was used as a metal precursor at a concentration of 1.84×10 -4 The silicon precursor was added at a rate of 3.83×10 -5 The aluminum precursor was added at a rate of mol / sec to prepare the silicon aluminum oxide encapsulation film and the film formation was evaluated. Plasma and nitrous oxide (N2O) were used as reaction gases, and argon gas was used as an inert gas for purging purposes. The number of depositions was 125 cycles, and the specific deposition method of the silicon metal oxide encapsulation film is shown in Table 1.

[0102] The deposited encapsulation film was analyzed using the same analysis method as in Example 1. The specific analysis results of the silicon metal oxide encapsulation film are shown in Tables 2 and 3. Figure 2 The permeability of the deposited film measured by infrared spectroscopy is shown. Figure 5 The results of analysis of water vapor permeability measured using a moisture permeability tester are shown.

[0103] Example 5. Preparation of silicon metal oxide encapsulation film by plasma enhanced atomic layer deposition

[0104] In order to form a silicon metal oxide encapsulation film in a conventional plasma enhanced atomic layer deposition apparatus using a known plasma enhanced atomic layer deposition method, diisopropylaminosilane was used as a silicon precursor and trimethylaluminum was used as a metal precursor at a concentration of 1.84×10 -4 The silicon precursor was added at a rate of 5.1×10 -5The aluminum precursor was added at a rate of mol / sec to prepare the silicon aluminum oxide encapsulation film and the film formation was evaluated. Plasma and nitrous oxide (N2O) were used as reaction gases, and argon gas was used as an inert gas for purging purposes. The number of depositions was 125 cycles, and the specific deposition method of the silicon metal oxide encapsulation film is shown in Table 1.

[0105] The deposited encapsulation film was analyzed using the same analysis method as in Example 1. The specific analysis results of the silicon metal oxide encapsulation film are shown in Tables 2 and 3. Figure 2 The permeability of the deposited film measured by infrared spectroscopy is shown. Figure 5 The results of analysis of water vapor permeability measured using a moisture permeability tester are shown.

[0106] Example 6. Preparation of silicon metal oxide encapsulation film by plasma enhanced atomic layer deposition

[0107] In order to form a silicon metal oxide encapsulation film in a conventional plasma enhanced atomic layer deposition apparatus using a known plasma enhanced atomic layer deposition method, diisopropylaminosilane was used as a silicon precursor and trimethylaluminum was used as a metal precursor at a concentration of 1.84×10 -4 The silicon precursor was added at a rate of 6.38×10 -5 The aluminum precursor was added at a rate of mol / sec to prepare the silicon aluminum oxide encapsulation film and the film formation was evaluated. Plasma and nitrous oxide (N2O) were used as reaction gases, and argon gas was used as an inert gas for the purpose of purging. The number of depositions was 105 cycles, and the specific deposition method of the silicon metal oxide encapsulation film is shown in Table 1.

[0108] The deposited encapsulation film was analyzed using the same analysis method as in Example 1. The specific analysis results of the silicon metal oxide encapsulation film are shown in Tables 2 and 3. Figure 2 The permeability of the deposited film measured by infrared spectroscopy is shown. Figure 5 The results of analysis of water vapor permeability measured using a moisture permeability tester are shown.

[0109] Example 7. Preparation of silicon metal oxide encapsulation film by plasma enhanced atomic layer deposition

[0110] In order to form a silicon metal oxide encapsulation film in a conventional plasma enhanced atomic layer deposition apparatus using a known plasma enhanced atomic layer deposition method, diisopropylaminosilane was used as a silicon precursor and dimethylbis(dimethylamino)tin was used as a metal precursor at a concentration of 1.84×10 -4 The silicon precursor was added at a rate of 5.23×10 -7Tin precursor was added at a rate of mol / sec to prepare silicon tin oxide encapsulation film and film formation evaluation was performed. Plasma and nitrous oxide (N2O) were used as reaction gases, and argon gas was used as an inert gas for purging purposes. The number of depositions was 140 cycles, and the specific deposition method of the silicon metal oxide encapsulation film is shown in Table 1.

[0111] The deposited encapsulation film was analyzed using the same analysis method as in Example 1. The specific analysis results of the silicon metal oxide encapsulation film are shown in Tables 2 and 3. Figure 2 The permeability of the deposited film measured by infrared spectroscopy is shown. Figure 5 The results of analysis of water vapor permeability measured using a moisture permeability tester are shown.

[0112] Example 8. Preparation of silicon metal oxide encapsulation film by plasma enhanced atomic layer deposition

[0113] In order to form a silicon metal oxide encapsulation film in a conventional plasma enhanced atomic layer deposition apparatus using a known plasma enhanced atomic layer deposition method, diisopropylaminosilane was used as a silicon precursor and dimethylbis(dimethylamino)tin was used as a metal precursor at a concentration of 1.84×10 -4 The silicon precursor was added at a rate of 3.38×10 -6 Tin precursor was added at a rate of mol / sec to prepare silicon tin oxide encapsulation film and film formation evaluation was performed. Plasma and nitrous oxide (N2O) were used as reaction gases, and argon gas was used as an inert gas for purging purposes. The number of deposition cycles was 133, and the specific deposition method of the silicon metal oxide encapsulation film is shown in Table 1.

[0114] The deposited encapsulation film was analyzed using the same analysis method as in Example 1. The specific analysis results of the silicon metal oxide encapsulation film are shown in Tables 2 and 3. Figure 2 The permeability of the deposited film measured by infrared spectroscopy is shown. Figure 5 The results of analysis of water vapor permeability measured using a moisture permeability tester are shown.

[0115] Example 9. Preparation of silicon metal oxide encapsulation film by plasma enhanced atomic layer deposition

[0116] In order to form a silicon metal oxide encapsulation film in a conventional plasma enhanced atomic layer deposition apparatus using a known plasma enhanced atomic layer deposition method, diisopropylaminosilane was used as a silicon precursor and dimethylbis(dimethylamino)tin was used as a metal precursor at a concentration of 1.84×10 -4 The silicon precursor was added at a rate of 6.75 × 10 -6Tin precursor was added at a rate of mol / sec to prepare silicon tin oxide encapsulation film and film formation evaluation was performed. Plasma and nitrous oxide (N2O) were used as reaction gases, and argon gas was used as an inert gas for purging purposes. The number of deposition cycles was 133, and the specific deposition method of the silicon metal oxide encapsulation film is shown in Table 1.

[0117] The deposited encapsulation film was analyzed using the same analysis method as in Example 1. The specific analysis results of the silicon metal oxide encapsulation film are shown in Tables 2 and 3. Figure 2 The permeability of the deposited film measured by infrared spectroscopy is shown. Figure 5 The results of analysis of water vapor permeability measured using a moisture permeability tester are shown.

[0118] Example 10. Preparation of silicon metal oxide encapsulation film by plasma enhanced atomic layer deposition

[0119] In order to form a silicon metal oxide encapsulation film in a conventional plasma enhanced atomic layer deposition apparatus using a known plasma enhanced atomic layer deposition method, diisopropylaminosilane was used as a silicon precursor and dimethylbis(dimethylamino)tin was used as a metal precursor at a concentration of 1.84×10 -4 The silicon precursor was added at a rate of 9.15×10 -6 Tin precursor was added at a rate of mol / sec to prepare silicon tin oxide encapsulation film and film formation evaluation was performed. Plasma and nitrous oxide (N2O) were used as reaction gases, and argon gas was used as an inert gas for purging purposes. The number of deposition cycles was 130, and the specific deposition method of the silicon metal oxide encapsulation film is shown in Table 1.

[0120] The deposited encapsulation film was analyzed using the same analysis method as in Example 1. The specific analysis results of the silicon metal oxide encapsulation film are shown in Tables 2 and 3. Figure 3 The permeability of the deposited film measured by infrared spectroscopy is shown. Figure 6 The results of analysis of water vapor permeability measured using a moisture permeability tester are shown.

[0121] Example 11. Preparation of silicon metal oxide encapsulation film by plasma enhanced atomic layer deposition

[0122] In order to form a silicon metal oxide encapsulation film in a conventional plasma enhanced atomic layer deposition apparatus using a known plasma enhanced atomic layer deposition method, diisopropylaminosilane was used as a silicon precursor and dimethylbis(dimethylamino)tin was used as a metal precursor at a concentration of 5.52×10 -5 The silicon precursor was added at a rate of 9.15×10 -6Tin precursor was added at a rate of mol / sec to prepare silicon tin oxide encapsulation film and film formation evaluation was performed. Plasma and nitrous oxide (N2O) were used as reaction gases, and argon gas was used as an inert gas for purging purposes. The number of depositions was 125 cycles, and the specific deposition method of the silicon metal oxide encapsulation film is shown in Table 1.

[0123] The deposited encapsulation film was analyzed using the same analysis method as in Example 1. The specific analysis results of the silicon metal oxide encapsulation film are shown in Tables 2 and 3. Figure 3 The permeability of the deposited film measured by infrared spectroscopy is shown. Figure 6 The results of analysis of water vapor permeability measured using a moisture permeability tester are shown.

[0124] Example 12 Preparation of silicon metal oxide encapsulation film by plasma enhanced atomic layer deposition

[0125] In order to form a silicon metal oxide encapsulation film in a conventional plasma enhanced atomic layer deposition apparatus using a known plasma enhanced atomic layer deposition method, diisopropylaminosilane was used as a silicon precursor and dimethylbis(dimethylamino)tin was used as a metal precursor at a concentration of 1.97×10 -5 The silicon precursor was added at a rate of 1.31×10 -5 Tin precursor was added at a rate of mol / sec to prepare silicon tin oxide encapsulation film and film formation evaluation was performed. Plasma and nitrous oxide (N2O) were used as reaction gases, and argon gas was used as an inert gas for purging purposes. The number of depositions was 125 cycles, and the specific deposition method of the silicon metal oxide encapsulation film is shown in Table 1.

[0126] The deposited encapsulation film was analyzed using the same analysis method as in Example 1. The specific analysis results of the silicon metal oxide encapsulation film are shown in Tables 2 and 3. Figure 3 The permeability of the deposited film measured by infrared spectroscopy is shown. Figure 6 The results of analysis of water vapor permeability measured using a moisture permeability tester are shown.

[0127] Comparative Example 1. Preparation of silicon oxide encapsulation film by plasma enhanced atomic layer deposition

[0128] In order to form a silicon oxide encapsulation film in a conventional plasma enhanced atomic layer deposition apparatus using a known plasma enhanced atomic layer deposition method, bis(dimethylaminomethylsilyl)amine was used as a silicon precursor at a concentration of 1.84×10 - 4The silicon oxide encapsulation film was prepared by adding silicon precursor at a rate of mol / sec and the film formation was evaluated. Plasma and nitrous oxide (N2O) were used as reaction gases, and argon gas was used as an inert gas for the purpose of purging. The number of deposition cycles was 370, and the specific deposition method of the silicon oxide encapsulation film is shown in Table 1.

[0129] The deposited encapsulation film was analyzed using the same analysis method as in Example 1. The specific analysis results of the silicon oxide encapsulation film are shown in Tables 2 and 3. Figure 1 The permeability of the deposited film measured by infrared spectroscopy is shown. Figure 4 Show the use Figure 1 The analysis results of moisture permeability measured by the moisture permeability tester.

[0130] Comparative Example 2. Preparation of silicon oxide encapsulation film by plasma enhanced atomic layer deposition

[0131] In order to form a silicon oxide encapsulation film in a conventional plasma enhanced atomic layer deposition apparatus using a known plasma enhanced atomic layer deposition method, diisopropylaminosilane was used as a silicon precursor at a concentration of 5.66×10 -4 The silicon oxide encapsulation film was prepared by adding silicon precursor at a rate of mol / sec and the film formation was evaluated. Plasma and nitrous oxide (N2O) were used as reaction gases, and argon gas was used as an inert gas for the purpose of purging. The number of deposition cycles was 608, and the specific deposition method of the silicon oxide encapsulation film is shown in Table 1.

[0132] The deposited encapsulation film was analyzed using the same analysis method as in Example 1. The specific analysis results of the silicon oxide encapsulation film are shown in Tables 2 and 3. Figure 1 The permeability of the deposited film measured by infrared spectroscopy is shown. Figure 4 The results of analysis of water vapor permeability measured using a moisture permeability tester are shown.

[0133] Comparative Example 3. Preparation of Metal Oxide Encapsulation Film by Plasma Enhanced Atomic Layer Deposition

[0134] In order to form a metal oxide encapsulation film in a conventional plasma enhanced atomic layer deposition apparatus using a known plasma enhanced atomic layer deposition method, dimethylbis(dimethylamino)tin was used as a metal precursor at a concentration of 3.38×10 - 6 Tin oxide encapsulation film was prepared by adding tin precursor at a rate of mol / sec and film formation was evaluated. Plasma and nitrous oxide (N2O) were used as reaction gases, and argon gas was used as an inert gas for purging purposes. The number of deposition cycles was 241, and the specific deposition method of the metal oxide encapsulation film is shown in Table 1.

[0135] The deposited encapsulation film was analyzed using the same analysis method as in Example 1. The specific analysis results of the metal oxide encapsulation film are shown in Tables 2 and 3. Figure 1 The permeability of the deposited film measured by infrared spectroscopy is shown. Figure 4 The results of analysis of water vapor permeability measured using a moisture permeability tester are shown.

[0136] Table 1

[0137] Deposition conditions of silicon metal oxide encapsulation films

[0138]

[0139]

[0140] Table 2

[0141] Results of X-ray Photoelectron Spectroscopy Analysis of Silicon Metal Oxide Encapsulation Films

[0142] Si Metal O ％ ％ ％ Example 1 31.2 2.8 66 Example 2 29.1 4.9 66 Example 3 226.9 7.1 66 Example 4 26.5 7.4 66.1 Example 5 23.9 9.9 66.2 Example 6 23.8 10.1 66.1 Example 7 33.7 4.6 61.7 Example 8 26.7 8.5 64.8 Example 9 25.5 12.9 61.6 Example 10 24.8 16.1 59.1 Embodiment 11 14.3 27.1 58.6 Example 12 6.7 35.0 58.3 Comparative Example 1 33.8 0 66.2 Comparative Example 2 33.9 0 66.1 Comparative Example 3 0.0 33.3 66.7

[0143] Table 3

[0144] Characteristic evaluation of silicon metal oxide encapsulation films

[0145]

[0146]

[0147]

[0148] It can be seen from Table 1 and Table 2 that, based on the total deposition time, the deposition rates of Examples 1 to 12 are to Based on the sedimentation cycle, to In the range of, based on the total deposition time, the deposition rate of Comparative Examples 1 to 3 is to The range, based on the sedimentation cycle, is to From the above, it can be seen that Examples 1 to 12 deposit thin films at an excellent speed of at least 1.1 times faster and at most 2.5 times faster than Comparative Examples 1 to 3. It can be confirmed that compared with Example 6 as the maximum value, the deposition speed of Comparative Example 1 is lower than that of Example 6 as the maximum value. Based on the deposition cycle, the deposition rate is low above.

[0149] Furthermore, the refractive indexes of Examples 1 to 3 are 1.49, 1.51, and 1.53, respectively; the refractive indexes of Examples 4 to 6 are all 1.49; the refractive indexes of Examples 7 to 12 are 1.52 and 1.88, and the refractive indexes of Comparative Examples 1 to 3 are 1.48, 1.48, and 2.20, respectively. Figure 5 As shown, through the ratio of the refractive index to the metal content in Examples 7 to 12, it can be seen that when the same metal is contained, the higher the metal content, the higher the refractive index formed. It can be confirmed that the refractive index can be adjusted not only by changing the type of metal, but also by changing the metal content.

[0150] Furthermore, it can be confirmed that the film thickness in Examples 1 to 12 is to When the film thickness is , the stress of the film ranges from -662MPa to 192MPa. When, it has 7.05×10- 4 g / [m 2 -day] has a significantly low moisture permeability.

[0151] At the same time, through Figures 1 to 4 It can be seen that compared with Comparative Examples 1 to 3, Examples 1 to 12 have better sealing properties. Figure 1 and Figure 2 It can be confirmed that the silicon metal oxide encapsulation films of Examples 1 to 12 have higher visible light transmittance than those of Comparative Examples 1 to 3. Figure 3 and Figure 4 As shown, it can be confirmed that compared with the film thickness of Comparative Example 1 to Comparative Example 2, having a thinner thickness Example 8 has a moisture permeability that is more than 14 times lower.

[0152] The above contents confirm that the silicon metal oxide packaging films of Examples 1 to 8 are not only significantly superior to those of Comparative Examples 1 to 3 or metal oxide packaging films in terms of film growth rate and low moisture permeability, but also capable of adjusting the refractive index and etching rate, and are easy to ensure flexibility by adjusting stress. As packaging films for displays using flexible substrates, they have very excellent properties.

[0153] That is, it can be seen that in the case of the silicon metal oxide encapsulation film represented by Chemical Formula 1 of the present invention, a high-quality silicon metal oxide encapsulation film with very low moisture permeability at a very thin thickness is formed at an astonishing speed. Since the dry etching speed is excellent, it is easy to remove the particles generated during the deposition of silicon oxide, which can overcome the problem of difficulty in cleaning that occurs during the deposition of existing metal oxides, and can significantly improve the process productivity.

[0154] Furthermore, since the silicon metal oxide encapsulation film of the present invention can adjust the stress strength and refractive index according to the metal content, it can not only epoch-makingly shorten the existing thin film encapsulation process of forming a very thick thickness by repeated overlapping of organic and inorganic substances, but also ensure optical properties and flexibility at a very thin thickness, thereby confirming that it has very high application potential as a packaging technology suitable for flexible displays.

[0155] Experiment 1. Folding endurance test

[0156] According to the D2176-16 standard of the American Society for Testing and Materials (ASTM), an MIT-type folding endurance tester was used to evaluate the folding endurance of the packaging films of Examples 1 to 12 and Comparative Examples 1 to 3.

[0157] After loading a film test piece (1 cm×7 cm) on a folding endurance tester, the test piece was bent at a speed of 175 rpm on the left and right sides, at an angle of 135°, a radius of curvature of 0.8 mm, and a load of 250 g until it broke to measure the number of reciprocating bending cycles, as shown in Table 4 below.

[0158] Table 4

[0159]

[0160]

[0161] As shown in Table 4, it can be seen that compared with Comparative Examples 1 to 3, the silicon metal oxide encapsulation film of the present invention has significantly improved folding resistance.

[0162] As described above, although the present invention is described through specific matters and limited embodiments and drawings, these are only provided to help to more fully understand the present invention. The present invention is not limited to the above-mentioned embodiments, and ordinary technicians in the technical field to which the present invention belongs can make various modifications and variations through the above description.

[0163] Therefore, the idea of ​​the present invention should not be limited to the illustrated embodiments, and all modifications equivalent to or equivalent to the accompanying claims should fall within the scope of the present invention.

Claims

1. A silicon metal oxide encapsulation film, characterized in that: It is represented by the following chemical formula 1: Chemical formula 1: Si x M y O z , In the above chemical formula 1, M is one or more metals selected from Ti, Zr, Hf, Al, Ga, In, Sn, Pb, V, Cu, Ag, Nb, Zn and Cd, 0.1 <x<1,0<y<2,1≤z≤3,1<x+y<3, 1.5 <x+y+z<6; The content of metal atoms is within a range of 1 atomic percent to 50 atomic percent relative to the total content of the silicon metal oxide; The stress of the silicon metal oxide encapsulation film is -700Mpa to +700Mpa.

2. The silicon metal oxide encapsulation film according to claim 1, characterized in that: The above-mentioned packaging film is a packaging film for organic light emitting diodes of displays.

3. The silicon metal oxide encapsulation film according to claim 1, characterized in that: The moisture permeability of silicon metal oxide encapsulation film is 1.0×10 -2 g / m 2 -day to 1.0×10 -6 g / m 2 -day.

4. The silicon metal oxide encapsulation film according to claim 1, characterized in that: The refractive index is 1.0 to 10.

5. The silicon metal oxide encapsulation film according to claim 1, characterized in that: The silicon metal oxide encapsulation film can be dry-etched by using one or more etching gases selected from fluorine-containing compounds and BCl 3 .

6. The silicon metal oxide encapsulation film according to claim 1, characterized in that: The thickness of the silicon metal oxide encapsulation film is to 7. A method for preparing a silicon metal oxide encapsulation film, characterized in that: The silicon metal oxide encapsulation film is prepared by atomic layer deposition and is represented by chemical formula 1: Chemical formula 1: Si x M y O z , In the above chemical formula 1, M is one or more metals selected from Ti, Zr, Hf, Al, Ga, In, Sn, Pb, V, Cu, Ag, Nb, Zn and Cd, 0.1 <x<1,0<y<2,1≤z≤3,1<x+y<3, 1.5 <x+y+z<6; The content of metal atoms is within a range of 1 atomic percent to 50 atomic percent relative to the total content of the silicon metal oxide; The stress of the silicon metal oxide encapsulation film is -700Mpa to +700Mpa.

8. The method for preparing a silicon metal oxide encapsulation film according to claim 7, characterized in that: The silicon metal oxide represented by Chemical Formula 1 is prepared by simultaneously introducing a metal precursor of an organic metal compound having one or more metal elements selected from Ti, Zr, Hf, Al, Ga, In, Sn, Pb, V, Cu, Ag, Nb, Zn and Cd as a central metal and a silicon precursor into a reactor.

9. The method for preparing a silicon metal oxide encapsulation film according to claim 8, characterized in that: The silicon precursor is an organic aminosilane compound containing a Si-N bond.

10. The method for preparing a silicon metal oxide encapsulation film according to claim 7, characterized in that: include: A step of simultaneously introducing a metal precursor of an organometallic compound having one or more metal elements selected from Ti, Zr, Hf, Al, Ga, In, Sn, Pb, V, Cu, Ag, Nb, Zn and Cd as a central metal and a silicon precursor into a reactor to contact the substrate; as well as The step of making the reaction gas contact with the substrate to prepare a silicon metal oxide encapsulation film on the substrate.

11. The method for preparing a silicon metal oxide encapsulation film according to claim 7, characterized in that: The above atomic layer deposition method is a plasma enhanced atomic layer deposition method.

12. The method for preparing a silicon metal oxide encapsulation film according to claim 10, characterized in that: The reaction gas is one or more selected from O2, N2O, NO2, H2O, H2O2 and O3.

13. A multilayer film for an organic light emitting diode, characterized in that: include: substrate; A first layer comprising a first silicon metal oxide represented by the following chemical formula 1; wherein the stress of the first layer is -700Mpa to +700Mpa; A second layer, located on the first layer, comprising a cross-linked polymer; and A third layer, located on the second layer, comprises a second silicon metal oxide represented by the following chemical formula 1, wherein the stress of the second layer is -700Mpa to +700Mpa; The first silicon metal oxide and the second silicon metal oxide are the same or different, Chemical formula 1: Si x M y O z , In the above chemical formula 1, M is one or more metals selected from Ti, Zr, Hf, Al, Ga, In, Sn, Pb, V, Cu, Ag, Nb, Zn and Cd, 0.1 <x<1,0<y<2,1≤z≤3,1<x+y<3, 1.5 <x+y+z<6; wherein the content of the metal atoms is within a range of 1 atomic percent to 50 atomic percent relative to the total content of the first silicon metal oxide; The content of the metal atoms is within a range of 1 atomic % to 50 atomic % relative to the total content of the second silicon metal oxide.

14. The multilayer film for an organic light emitting diode according to claim 13, characterized in that: The substrate is a flexible transparent substrate.

15. The multilayer film for an organic light emitting diode according to claim 13, characterized in that: The multilayer film has a curvature radius of 2R or less.

16. An organic light emitting diode device, characterized in that: The encapsulation film comprises the encapsulation film according to any one of claims 1 to 6.

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