A composition for silicon-containing encapsulation films containing a silazane compound, and a method for producing a silicon-containing encapsulation film using the same.

Abstract

The present invention provides a silicon-containing encapsulation film composition containing a silazane compound and a method for producing a silicon-containing encapsulation film using the same, which prevents degradation of organic light-emitting devices by blocking moisture and oxygen. [Solution] The silicon-containing encapsulation film composition exhibits a high vapor pressure and excellent deposition rate, enabling the production of high-quality silicon-containing encapsulation films with high purity and high durability.

Description

[Technical Field]

[0001] The present invention relates to a composition for silicon-containing encapsulation films containing a silazane compound, and a method for producing a silicon-containing encapsulation film using the same. [Background technology]

[0002] Organic light-emitting diodes (OLEDs) have advantages such as low power consumption, light weight, ease of use, a wide field of view, and fast response time, enabling flexible displays and are applied to smart devices such as smartphones and tablet PCs.

[0003] Currently, some problems still exist in the technological development of OLED devices, limiting the progress of their industrialization. Among these, device lifespan is the most important issue. The lifespan of an OLED device is related, on the one hand, to the performance and lifespan of the selected organic material, and on the other hand, to the packaging method of the OLED device. This is because the organic material and negative electrode in the OLED device react easily with moisture and oxygen. In particular, since the device uses an active metal with a thickness of several tens of nanometers as the negative electrode, even a minute amount of water vapor or oxygen will cause the metal to react completely, resulting in the deterioration or loss of the physical properties and performance of such materials, and as a result, the function of the device is lost. Therefore, improving the packaging effect of the device to separate each functional layer of the device from moisture and oxygen in the surrounding environment is extremely important for the device's lifespan.

[0004] Traditional OLED packaging involves fabricating electrodes and functional layers on a substrate, and then protecting the element with a substrate possessing good chemical stability, density, and electrical insulation. However, the glass substrates used in conventional methods are prone to cracking or adhesive failure and fail to meet the requirements for flexibility. Furthermore, the relatively large space occupied by glass substrates makes them inadequate to meet the trend towards slimmer OLED elements.

[0005] Thin-film encapsulation (TFE) technology is being applied as a new packaging process. This technology is a type of gapless encapsulation method that enables physical protection of the elements in the encapsulated area by forming a dense thin film. Conventional inorganic layer thin film encapsulation structures can have pinholes due to impurities, which can allow moisture and oxygen to penetrate. Organic layer thin films, including polymer films with high flexibility, do not have good moisture and oxygen barrier properties. Therefore, research is being conducted on encapsulation films that can solve the above problems, have low impurity levels, and have excellent moisture and oxygen barrier properties. [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] The object of the present invention is to provide a silicon-containing encapsulation film composition containing a silazane compound, and a method for producing a silicon-containing encapsulation film using the same that blocks moisture and oxygen and prevents degradation of an organic light-emitting element. [Means for solving the problem]

[0007] The present invention provides a silicon-containing encapsulation film composition comprising a silazane compound represented by the following chemical formula 1.

[0008] [ka] [In the above chemical formula 1, R 1 These are C1-C7 alkyl, C2-C7 alkenyl, C2-C7 alkynyl, C3-C10 cycloalkyl, or C6-C12 aryl. R 2 and R 3 These are, independently of each other, hydrogen, C1-C7 alkyl, C2-C7 alkenyl, C2-C7 alkynyl, C3-C10 cycloalkyl, C6-C12 aryl, C1-C7 haloalkyl, or halogen. X is a halogen.

[0009] Preferably, R of the chemical formula 1.1 may be C1-C5 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C3-C6 cycloalkyl, or C6-C12 aryl, and R 2 and R 3 may each independently be hydrogen, C1-C5 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C3-C6 cycloalkyl, C6-C12 aryl, C1-C5 haloalkyl or halogen.

[0010] The silazane compound according to an embodiment of the present invention may be represented by the following Chemical Formula 2.

[0011]

化

[0012] In an embodiment, X in Chemical Formula 1 may be Cl.

[0013] Further, in an embodiment, the silazane compound may be selected from the following compounds.

化

[0014] The present invention provides a silazane compound represented by the following Chemical Formula 1, or a silicon-containing sealing film composition comprising the same, and a method for producing a silicon-containing sealing film, comprising the step of depositing a silicon-containing sealing film using a reaction gas.

[0015]

Chemical Formula

[0016] The method for producing a silicon-containing sealing film is characterized by comprising: a step of adsorbing the silazane compound represented by Chemical Formula 1 or the silicon-containing sealing film composition comprising the same onto a substrate; and a step of injecting a reaction gas into the substrate to form a silicon-containing sealing film.

[0017] Further, the method for producing a silicon-containing sealing film may comprise a step of simultaneously injecting the silazane compound represented by Chemical Formula 1 or the silicon-containing sealing film composition comprising the same and a reaction gas to form a silicon-containing sealing film.

[0018] Further, in the method for producing a silicon-containing sealing film, the temperature of the substrate may be 200°C or lower, and the reaction gas may be any one or two or more selected from the group consisting of oxygen (O<s1>2< / s1>), ozone (O<s1>3< / s1>), distilled water (H<s1>2< / s1>O), hydrogen peroxide (H<s1>2< / s1>O<s1>2< / s1>), nitric oxide (NO), nitrous oxide (N<s1>2< / s1>O), nitrogen dioxide (NO<s1>2< / s1>), ammonia (NH<s1>3< / s1>), nitrogen (N<s1>2< / s1>), hydrazine (N<s1>2< / s1>H<s1>4< / s1>), amine, diamine, carbon monoxide (CO), carbon dioxide (CO<s1>2< / s1>), C<s1>1< / s1> to C<s1>12< / s1> saturated or unsaturated hydrocarbons, hydrogen (H<s1>2< / s1>), argon (Ar), and helium (He).

[0019] The silicon-containing sealing film produced by the method for producing a silicon-containing sealing film according to an embodiment of the present invention is characterized by being a silicon oxide film or a silicon nitride film, and has a water vapor transmission rate of 0.1g / [m 2 -day] or less. [Effects of the Invention]

[0020] By using the silicon-containing encapsulation film composition containing the silazane compound of the present invention, it is possible to produce a high-purity encapsulation film with significantly low levels of carbon and other impurities, even in low-temperature processes.

[0021] Furthermore, the method for producing a silicon-containing encapsulating film according to the present invention, by using an encapsulating film composition containing the silazane compound of the present invention, can produce an encapsulating film with a fast deposition rate and a low impurity content.

[0022] Therefore, the silicon-containing encapsulation film produced by the manufacturing method of the present invention has excellent properties, such as blocking moisture and oxygen and preventing the degradation of organic light-emitting elements. [Modes for carrying out the invention]

[0023] The following describes in detail the silicon-containing encapsulation film composition containing the silazane compound of the present invention, and a method for producing a silicon-containing encapsulation film using the same.

[0024] In this invention, the singular form is intended to include multiple forms unless otherwise specified in the context.

[0025] Furthermore, the numerical ranges used herein include lower and upper limits, all values ​​within those limits, increments logically derived from the form and width of the defined range, all double-limited values, and all possible combinations of upper and lower limits of numerical ranges limited in different forms. Unless otherwise defined in the specification of the present invention, values ​​outside the numerical range that may arise due to experimental error or rounding of values ​​are also included in the defined numerical range.

[0026] The term "includes" as used in this invention is an open-ended statement equivalent to expressions such as "equipped with," "contains," "possesses," or "characterizes," and does not exclude any elements, materials, or processes not listed.

[0027] In this invention, "alkyl" means a linear or branched acyclic hydrocarbon, which may have 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms. In yet another embodiment, the alkyl may have 1 to 3 carbon atoms.

[0028] The term "alkenyl" as used in this invention means a saturated linear or branched acyclic hydrocarbon containing at least one carbon-carbon double bond, and includes, but is not limited to, -vinyl, -allyl, -1-butenyl, -2-butenyl, -isobutyrenyl, -1-pentenyl, -2-pentenyl, -3-methyl-1-butenyl, -2-methyl-2-butenyl, -2,3-dimethyl-2-butenyl, -1-hexenyl, -2-hexenyl, -3-hexenyl, -1-heptenyl, -2-heptenyl, -3-heptenyl, -1-octenyl, -2-octenyl, -3-octenyl, -1-nonenyl, -2-nonenyl, -3-nonenyl, -1-decenyl, -2-decenyl, and -3-decenyl. Such alkenyl groups may be selectively substituted. The alkenyls include radicals having cis and trans orientations, or alternatively, E and Z orientations.

[0029] The term "alkynyl" as used in this invention means a saturated linear or branched acyclic hydrocarbon having at least one carbon-carbon triple bond, and includes, but is not limited to, ethynyl, propynyl, butynyl, butadiinyl, pentynyl, pentadinyl, hexynyl, hexadinyl, and their isomers.

[0030] The term "cycloalkyl" as used in this invention refers to a monocyclic or polycyclic saturated ring containing carbon and hydrogen atoms and lacking carbon-carbon multiple bonds. This includes, but is not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl. The cycloalkyl group may be selectively substituted.

[0031] In this invention, "halogen" means fluorine, chlorine, bromine, or iodine.

[0032] In this invention, "haloalkyl" means an alkyl group in which one or more hydrogen atoms are substituted with halogen atoms. For example, haloalkyls include -CF3, -CHF2, -CH2F, -CBr3, -CHBr2, -CH2Br, -CCl3, -CHCl2, -CH2CI, -CI3, -CHI2, -CH2I, -CH2-CF3, -CH2-CHF2, -CH2-CH2F, -CH2-CBr3, -CH2-CHBr2, -CH2-CH2Br, -CH2-CCl3, -CH2-CHCl2, -CH2-CH2CI, -CH2-CI3, -CH2-CHI2, -CH2-CH2I, and similar groups. Here, alkyl and halogen are as defined above.

[0033] The term "aryl" as used in this invention refers to a carbocyclic aromatic group containing 5 to 10 ring atoms. Typical examples include phenyl, tolyl, xylyl, naphthyl, tetrahydronaphthyl, and anthracenyl. This includes, but is not limited to, fluorenyl, indenyl, and azulenyl. Furthermore, aryls also include those in which a carbocyclic aromatic group is linked to an alkylene or alkenylene, or to one or more heteroatoms selected from B, O, N, C(=O), P, P(=O), S, S(=O)2, and Si atoms.

[0034] The carbon number described in this invention does not include the carbon number of substituents. For example, C1-C7 alkyl means an alkyl group with 1 to 7 carbon atoms, excluding the carbon number of alkyl substituents.

[0035] The present invention provides a silicon-containing encapsulation film composition comprising a silazane compound represented by the following chemical formula 1.

[0036] [ka] [In the above chemical formula 1, R 1 These are C1-C7 alkyl, C2-C7 alkenyl, C2-C7 alkynyl, C3-C10 cycloalkyl, or C6-C12 aryl. R 2 and R 3 These are, independently of each other, hydrogen, C1-C7 alkyl, C2-C7 alkenyl, C2-C7 alkynyl, C3-C10 cycloalkyl, C6-C12 aryl, C1-C7 haloalkyl, or halogen. X is a halogen.

[0037] Because the silazane compound represented by chemical formula 1 has a high vapor pressure, using a silicon-containing encapsulation film composition containing it allows for the production of encapsulation films at low temperatures with significantly improved deposition rates. Furthermore, due to the low content of carbon and other impurities, high-quality silicon-containing encapsulation films with high purity and durability can be obtained.

[0038] In detail, the silazane compound represented by chemical formula 1, in which two silicon atoms are bonded to a central nitrogen atom, forms a stable liquid compound at room temperature and atmospheric pressure, has a vapor pressure of 30 torr or more at 70°C and exhibits excellent volatility, and has a very fast deposition rate even when deposited at low temperatures below 100°C, and in practical examples as low as 90°C.

[0039] Furthermore, when a silicon-containing encapsulation film is formed using the silazane compound of chemical formula 1, it can have excellent cohesive force and excellent step coverage. Moreover, because the silazane compound has the structure of chemical formula 1, it has high thermal stability and low activation energy, excellent reactivity, and does not produce non-volatile by-products, so a silicon-containing encapsulation film with high purity and excellent stress strength can be easily formed.

[0040] In one embodiment, the R of chemical formula 1 1R may be a C1-C5 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C3-C6 cycloalkyl, or C6-C12 aryl, 2 and R 3 These elements may be, independently of each other, hydrogen, C1-C5 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C3-C6 cycloalkyl, C6-C12 aryl, C1-C5 haloalkyl, or halogen.

[0041] The silazane compound according to one embodiment of the present invention may be represented by the following chemical formula 2.

[0042] [ka] [In the above chemical formula 2, R 11 These are C1-C7 alkyl, C2-C7 alkenyl, C2-C7 alkynyl, C3-C10 cycloalkyl, or C6-C12 aryl. R 12 These are hydrogen, C1-C7 alkyl, C2-C7 alkenyl, C2-C7 alkynyl, C3-C10 cycloalkyl, C6-C12 aryl, C1-C7 haloalkyl, or halogen. X is a halogen.

[0043] In the embodiment of the present invention, X in chemical formula 1 may be Cl.

[0044] The silazane compound according to one embodiment of the present invention may be selected from the following compounds. [ka] JPEG2026149663000009.jpg226170

[0045] The silazane compound represented by the following chemical formula 1 according to one embodiment of the present invention can be produced by any method possible in the field of organic synthesis. For example, the compound of the following chemical formula 1 is produced by reacting the compound represented by the following chemical formula 11 with the compound represented by the following chemical formula 12. It is possible.

[0046] [ka]

[0047] [ka]

[0048] [ka] [In the above chemical formulas 1, 11, and 12, R 1 These are C1-C7 alkyl, C2-C7 alkenyl, C2-C7 alkynyl, C3-C10 cycloalkyl, or C6-C12 aryl. R 2 and R 3 These are, independently of each other, hydrogen, C1-C7 alkyl, C2-C7 alkenyl, C2-C7 alkynyl, C3-C10 cycloalkyl, C6-C12 aryl, C1-C7 haloalkyl, or halogen. X is a halogen.

[0049] The method for synthesizing a silazane compound according to one embodiment of the present invention may be carried out at -70 to 10°C for 1 to 10 hours, preferably at -50 to 0°C for 2 to 6 hours.

[0050] The present invention provides a method for producing a silicon-containing encapsulation film, comprising the steps of: a silazane compound represented by the following chemical formula 1 or a silicon-containing encapsulation film composition containing the same; and a reaction gas used to deposit the silicon-containing encapsulation film.

[0051] [ka] (In the above chemical formula 1, R1-R3 and X are as defined in Claim 1.

[0052] Specifically, the method for manufacturing a silicon-containing encapsulating film according to one embodiment of the present invention is the chemical formula 1 The method for producing the silicon-containing encapsulation film is characterized by comprising the steps of: adsorbing a silazane compound represented by chemical formula 1 or a silicon-containing encapsulation film composition containing the same onto a substrate; and injecting a reaction gas into the substrate on which the silazane compound or silicon-containing encapsulation film composition has been adsorbed to form a silicon-containing encapsulation film. In this case, the method for producing the silicon-containing encapsulation film may specifically include the steps of: adsorbing a silazane compound represented by chemical formula 1 or a silicon-containing encapsulation film composition containing the same onto a substrate; purging residual silazane compound or composition containing the same and by-products; injecting a reaction gas into the substrate to form a silicon-containing encapsulation film; and purging residual reaction gas and by-products.

[0053] Furthermore, the silicon-containing encapsulation film according to one embodiment may be manufactured by simultaneously injecting a silazane compound represented by chemical formula 1 or a silicon-containing encapsulation film composition containing the same with a reaction gas.

[0054] The method for producing a silicon-containing encapsulating film according to the present invention uses a silazane compound represented by chemical formula 1, which is liquid at room temperature, highly volatile, and has excellent thermal stability. This makes it easy to handle and allows for the production of high-purity silicon-containing encapsulating films with a high deposition rate even at low temperatures and / or low power. Furthermore, the silicon-containing encapsulating film produced by the production method of the present invention has excellent durability and electrical properties and can prevent the penetration of moisture and oxygen.

[0055] In a method for manufacturing a silicon-containing encapsulating film according to one embodiment of the present invention, the method for depositing the encapsulating film can be any method that is possible within the scope recognized by those skilled in the art, but preferably it may be formed by atomic layer deposition (ALD), chemical vapor deposition (CVD), metal-organic chemical vapor deposition (MOCVD), low-pressure vapor deposition (LPCVD), plasma-enhanced vapor deposition (PECVD), or plasma-enhanced atomic layer deposition (PEALD), and more specifically, plasma-enhanced atomic layer deposition (PEALD) may be used because the deposition of the encapsulating film is easy and the manufactured encapsulating film has excellent properties, but it is not limited thereto.

[0056] Furthermore, in the method for manufacturing a silicon-containing encapsulation film according to one embodiment of the present invention, the temperature of the substrate may be 200°C or lower, and more specifically, the deposition may be carried out at 50 to 200°C. Due to the excellent low-temperature volatility and high reactivity of the silazane compound according to chemical formula 1 of the present invention, and other extremely excellent properties as a silicon precursor for deposition, the temperature of the substrate to be deposited located inside the chamber may be less than 120°C, and more specifically, 100°C or lower. The deposition of the silicon-containing encapsulation film, which includes the step of supplying the silazane compound according to one embodiment to the chamber in which the substrate to be deposited is located, may be carried out at a low temperature of less than 100°C, more specifically 95°C or lower.

[0057] In one embodiment of the present invention, the reaction gas used in the method for producing a silicon-containing sealing film is oxygen (O2), ozone (O3), distilled water (H2O), hydrogen peroxide (H2O2), nitric oxide (NO), nitrous oxide (N2O), nitrogen dioxide (NO2), ammonia (NH3), nitrogen (N2), hydrazine (N2H4), amines, diamines, carbon monoxide (CO), carbon dioxide (CO2), saturated or unsaturated hydrocarbons of C1-C12, hydrogen (H2), argon (Ar), and helium (He). It may be one or more selected from the following, more specifically, one or more selected from oxygen (O2), nitric oxide (NO), nitrous oxide (N2O), nitrogen dioxide (NO2), ammonia (NH3), and nitrogen (N2), and more specifically, one or more selected from nitrous oxide (N2O), nitrogen dioxide (NO2), ammonia (NH3), hydrogen (H2), and nitrogen (N2), but not limited to these.

[0058] In a method for producing a silicon-containing encapsulating film according to one embodiment of the present invention, a silazane compound The silazane compound and the reaction gas may be supplied organically or independently of each other. Furthermore, the silazane compound and the reaction gas may be supplied continuously or discontinuously, and the discontinuous supply may include pulses.

[0059] In a method for manufacturing a silicon-containing encapsulating film according to one embodiment, the deposition conditions may be adjusted according to the structure or thermal properties of the target encapsulating film. Examples of deposition conditions include the flow rate of the silicon-containing encapsulating film composition containing a silazane compound, the flow rate of the reaction gas, the flow rate of the transport gas, pressure, and the temperature of the substrate to be deposited. A non-limiting example of such deposition conditions is that the flow rate of the composition containing the silazane compound is 10 to 1000 cc / min, the reaction gas is 1 to 10000 cc / min, the transport gas is 10 to 10000 cc / min, the pressure is 0.5 to 10 torr, and the temperature of the substrate to be deposited is 200°C or lower, specifically 50 to 200°C, more specifically 50 to 120°C, and characteristically 60 to 100°C, but is not limited to these. Furthermore, when using plasma-enhanced atomic layer deposition (PEALD), in which the reaction gas is activated by plasma, the RF power may be 50 to 1000 W, but is not limited to this.

[0060] The silicon-containing encapsulating film produced by the method for producing a silicon-containing encapsulating film according to one embodiment of the present invention is characterized by being a silicon oxide film or a silicon nitride film, and in addition, various other high-quality encapsulating films containing silicon within a range recognizable to those skilled in the art can be produced.

[0061] The silicon-containing encapsulating film produced by the method for producing a silicon-containing encapsulating film of the present invention may be used to protect an organic light-emitting element from moisture and oxygen.

[0062] The silicon-containing encapsulated film produced by the method for producing silicon-containing encapsulated films of the present invention has a moisture permeability of 0.1 g / m². 2 It is characterized by being less than or equal to -day, preferably 0.05g / [m 2 -day] or less, more preferably 0.015g / [m 2 The present invention is characterized by having a lifespan of -day or less. As a result, the silicon-containing encapsulating film produced using the manufacturing method of the present invention has significantly improved moisture and oxygen barrier performance, and can prevent a decrease in the lifespan of organic light-emitting devices that employ it.

[0063] The water vapor permeability of the silicon-containing encapsulating film was measured using a water vapor transmission rate (WVTR, MOCON, Aquatran2) meter, using nitrogen, with a measurement area of ​​50 cm². 2 I set it to that.

[0064] The structure of the encapsulation film produced by the method for producing a silicon-containing encapsulation film according to one embodiment of the present invention can cover the surface and / or sides of an organic light-emitting element, depending on the demand. The thickness of such encapsulation film may be 5 to 2000 nm, preferably 200 to 1000 nm, and more preferably 500 to 800 nm.

[0065] The following describes in more detail, with reference to specific examples, the silicon-containing encapsulation film composition containing the silazane compound according to the present invention and the method for producing a silicon-containing encapsulation film using the same.

[0066] However, the following embodiments are merely references to illustrate the present invention in detail, and the invention is not limited thereto, but can be realized in various forms. Furthermore, the terms used in this description are for the purpose of effectively describing specific embodiments and are not intended to limit the invention.

[0067] [Manufacturing Example 1] After vacuum drying a 5 L high-pressure reactor containing a stirrer and reflux condenser, 2 L of n-pentane was added, and 40 g (1.29 mol) of methylamine was added while maintaining the internal temperature at -40°C. After stirring for 30 minutes, 86.8 g (0.86 mol) of dichlorosilane was slowly added while maintaining the temperature. After the addition was complete, the mixture was stirred for 4 hours while maintaining the internal temperature at -10°C. By removing the salt and solvent by vacuum filtration and vacuum distillation, 38 g of MeN(SiH2Cl)2 was obtained (yield 55%). 1 H NMR(400 MHz, C6D6) δ 2.7(s, 3H), 5.07(s, 4H)

[0068] [Example 1] Silicon oxide film for sealing film The encapsulation film was evaluated using a conventional plasma-enhanced atomic layer deposition apparatus employing a known plasma-enhanced atomic layer deposition method, with the silazane compound produced in Production Example 1.

[0069] Nitrous oxide was used as the reaction gas along with plasma, and argon, an inert gas, was used as the transport gas. The silicon wafer on which the silicon oxide film was to be formed was transported into the deposition chamber and maintained at 90°C. The silazane compound of Production Example 1, which was filled in a bubbler-type stainless steel container, was vaporized at a vapor pressure of 20 Torr, transported onto the substrate with 50 sccm of argon gas as the transport gas, and then adsorbed. Unreacted compounds were then removed using 500 sccm of argon gas. After forming a silicon oxide film using 800 sccm of nitrous oxide gas and an 800 W plasma as the reaction gas, unreacted compounds were removed using 500 sccm of argon gas.

[0070] The above process constituted one cycle, and the cycle was repeated to form a silicon oxide film. The thickness of the formed silicon oxide film was measured using an ellipsometer. The deposition thickness of the silicon oxide film per unit cycle was confirmed to be 2.01 Å, and the refractive index was confirmed to be 1.47 at 633 nm. Furthermore, compositional analysis using an X-ray photoelectron spectrometer confirmed that the proportions of silicon and oxygen were 33.5% and 66.5%, respectively.

[0071] To evaluate the water vapor permeability, the thin film was deposited at 700 Å onto a polyethylene naphthalate (PEN) film, and the water vapor permeability was analyzed, resulting in a reading of 1.5 x 10⁻⁶. -3 g / [m 2 An excellent result, [-day], was confirmed.

[0072] [Example 2] Silicon nitride film for encapsulation film The encapsulation film was evaluated using the silazane compound from Production Example 1 in a conventional plasma-enhanced atomic layer deposition apparatus employing a known plasma-enhanced atomic layer deposition method.

[0073] Ammonia was used as the reaction gas along with plasma, and nitrogen, an inert gas, was used as the transport gas. The silicon wafer on which the silicon nitride film was to be formed was transported into the deposition chamber and maintained at 90°C. The silazane compound of Production Example 1, which was filled in a bubbler-type stainless steel container, was vaporized at a vapor pressure of 20 Torr, transported onto the substrate with 50 sccm of nitrogen gas as the transport gas, and then adsorbed. Unreacted compounds were then removed using 500 sccm of nitrogen gas. A silicon nitride film was formed using 1000 sccm of ammonia gas and an 800 W plasma as the reaction gas, and then unreacted compounds were removed using 500 sccm of nitrogen gas. Next, the surface of the silicon nitride film was treated using 1000 sccm of nitrogen gas and an 800 W plasma, and then unreacted compounds were removed using 500 sccm of nitrogen gas.

[0074] The above process constituted one cycle, and the cycle was repeated to form a silicon nitride film. The thickness of the formed silicon nitride film was measured using an ellipsometer. The deposition thickness of the silicon nitride film per unit cycle was confirmed to be 0.82 Å, and the refractive index at 633 nm was confirmed to be 1.97. This was confirmed. Furthermore, compositional analysis using an X-ray photoelectron spectrometer confirmed that the proportions of silicon and nitrogen were 43.1% and 56.8%, respectively.

[0075] To evaluate the water vapor permeability, the thin film was deposited at 700 Å onto a polyethylene naphthalate (PEN) film, and the water vapor permeability was analyzed. The result was 1 x 10 -4 g / [m 2 An excellent result, [-day], was confirmed.

[0076] [Example 3] Silicon nitride film for encapsulation film The encapsulation film was evaluated using the silazane compound from Production Example 1 in a conventional plasma-enhanced chemical vapor deposition apparatus employing a known plasma-enhanced chemical vapor deposition method.

[0077] The silicon wafer on which the silicon nitride film was to be formed was transported into a deposition chamber and maintained at 90°C. The silazane compound of Production Example 1, which was filled in a bubbler-type stainless steel container, was vaporized at a vapor pressure of 0.1 Torr, and 5 sccm of nitrogen gas was transported into the chamber as the transport gas. Simultaneously, nitrogen, hydrogen, and ammonia were used as reaction gases, and a silicon nitride film was formed using an 800 W plasma. Detailed process conditions and results are shown in Table 1. Furthermore, compositional analysis using an X-ray photoelectron spectrometer confirmed that the proportions of silicon and nitrogen were approximately 43% and 57%, respectively.

[0078] [Examples 4-7] Except for changing the gas ratio in Example 3, the silicon nitride film was deposited in the same manner as in Example 3, and the process conditions and results are shown in Table 1.

[0079] [Table 1]

[0080] From the above results, the silicon-containing encapsulating film composition containing the silazane compound of Production Example 1 of the present invention can exhibit a high vapor pressure and excellent deposition rate, and the content of carbon and other impurities It is possible to manufacture high-quality silicon-containing encapsulating films with low volatility, high purity, and high durability. A silicon-containing encapsulating film composition containing a silazane compound, which is a specific compound according to one embodiment of the present invention, exhibits excellent volatility and high reactivity, can be deposited even at low temperatures, and can manufacture encapsulating films that are more uniform and of improved quality.

[0081] The silicon-containing encapsulating film produced using the manufacturing method of the present invention has been found to have improved moisture permeability and excellent moisture and oxygen barrier properties. It is expected that when this film is used in organic light-emitting devices, it will be an excellent material that can prevent moisture and oxygen penetration and thus prevent a decrease in lifespan.

[0082] As described above, the present invention has been explained with specific details and limited examples and comparative examples, but these are provided only for a more general understanding of the present invention, and the present invention is not limited to the above examples. A person with ordinary skill in the art to which the present invention belongs can make various modifications and variations from these descriptions.

[0083] Therefore, the concept of the present invention should not be limited to the embodiments described above. Not only the claims attached, but also anything equivalent to these claims, or equivalent variations thereof, can all be said to fall within the scope of the concept of the present invention.

Claims

1. A composition for silicon-containing encapsulation films, comprising a silazane compound represented by the following chemical formula 1. 【Chemistry 1】 [In the above chemical formula 1, R １ These are C1-C7 alkyl, C2-C7 alkenyl, C2-C7 alkynyl, C3-C10 cycloalkyl, or C6-C12 aryl. R ２ and R ３ These are independently hydrogen, C1-C7 alkyl, C2-C7 alkenyl, C2-C7 alkynyl, C3-C10 cycloalkyl, C6-C12 aryl, or C1-C7 haloalkyl. X is fluorine, chlorine, bromine, or iodine.

2. In the aforementioned chemical formula 1, R １ These are C1-C5 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C3-C6 cycloalkyl, or C6-C12 aryl. R ２ and R ３ These are independently hydrogen, C1-C5 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C3-C6 cycloalkyl, C6-C12 aryl, or C1-C5 haloalkyl. The silicon-containing encapsulating film composition according to claim 1, wherein X is fluorine, chlorine, bromine, or iodine.

3. The silicon-containing encapsulating film composition according to claim 1, wherein the silazane compound is represented by the following chemical formula 2. 【Chemistry 2】 [In the above chemical formula 2, R １１ These are C1-C7 alkyl, C2-C7 alkenyl, C2-C7 alkynyl, C3-C10 cycloalkyl, or C6-C12 aryl. R １２ These are hydrogen, C1-C7 alkyl, C2-C7 alkenyl, C2-C7 alkynyl, C3-C10 cycloalkyl, C6-C12 aryl, or C1-C7 haloalkyl. X is fluorine, chlorine, bromine, or iodine.

4. The silicon-containing encapsulating film composition according to claim 1, wherein X in the chemical formula 1 is chlorine.

5. The silicon-containing encapsulation film composition according to claim 1, wherein the silazane compound is selected from the following compounds. 【Transformation 3】 【change】 【change】 【change】 【change】

6. A silazane compound represented by the following chemical formula 1 or a silicon-containing encapsulation film composition containing the same, and A method for producing a silicon-containing encapsulation film, comprising the step of depositing the silicon-containing encapsulation film using a reaction gas. 【Chemistry 4】 (In the above chemical formula 1, R １ ~R ３ and X are as defined in claim 1.)

7. The steps include adsorbing a precursor containing a silazane compound represented by the chemical formula 1 or a silicon-containing encapsulation film composition onto a substrate, A method for producing a silicon-containing encapsulation film according to claim 6, characterized by comprising the step of injecting a reaction gas into a substrate on which the silazane compound or silicon-containing encapsulation film composition is adsorbed to form a silicon-containing encapsulation film.

8. A method for producing a silicon-containing encapsulation film according to claim 6, characterized by comprising the step of injecting a silazane compound represented by the chemical formula 1 or a silicon-containing encapsulation film composition containing the same simultaneously with a reaction gas to form a silicon-containing encapsulation film.

9. The reaction gas is oxygen (O ２ ), ozone (O ３ ), distilled water (H ２ O), hydrogen peroxide (H ２ O ２ ), nitric oxide (NO), nitrous oxide (N ２ O), Nitrogen dioxide (NO) ２ ), ammonia (NH ３ ), nitrogen (N ２ ), hydrazine (N ２ H ４ ), amines, diamines, carbon monoxide (CO), carbon dioxide (CO) ２ ), saturated or unsaturated hydrocarbons of C1 to C12, hydrogen (H ２ A method for producing a silicon-containing encapsulation film according to claim 6, wherein the silicon is one or more selected from ), argon (Ar), and helium (He).

10. The method for producing a silicon-containing encapsulating film according to claim 7, wherein the substrate has a temperature of 200°C or less.

11. The method for producing a silicon-containing encapsulation film according to claim 6, characterized in that the silicon-containing encapsulation film is a silicon oxide film or a silicon nitride film.

12. The aforementioned silicon-containing encapsulating film has a moisture permeability of 0.1 g / m². ２ A method for producing a silicon-containing encapsulation film according to claim 6, characterized in that the date is less than or equal to -day.

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