Composition for silicon-containing sealing film containing silazane compound, and method for producing silicon-containing sealing film using the same

Abstract

The present invention provides a composition for a silicon-containing sealing film containing a silazane compound, and a method for manufacturing a silicon-containing sealing film using the composition, which can block moisture and oxygen and prevent deterioration of an organic light-emitting device. The composition for a silicon-containing sealing film according to the present invention has a high vapor pressure and can exhibit an excellent deposition rate, and can provide a high-quality silicon-containing sealing film having high purity and high durability.

Description

[Technical field]

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

[0002] Organic light emitting devices (OLEDs) have the advantages of low power consumption, light weight, and ease of use, as well as a wide viewing angle and fast response. They also enable flexible displays, and are therefore used in smart devices such as smartphones and tablet PCs.

[0003] At present, some problems still exist in the technical development process of OLED elements, which restrict the industrialization of OLED elements. Among them, the life of the element is the most important issue. The life of an OLED element is related to the performance and life of the selected organic material on the one hand, and to the packaging method of the OLED element on the other hand. This is because the organic matter and the negative electrode in the OLED element are easily reacted with moisture and oxygen. In particular, since the element uses an active metal with a thickness of several tens of nanometers as the negative electrode, the metal will react completely even with a very small amount of water vapor or oxygen, and the physical properties and performance of such materials will degenerate or be lost, and as a result, the function of the element will be lost. Therefore, it is very important for the life of the element to improve the packaging effect of the element and isolate each functional layer of the element from the moisture and oxygen in the surrounding environment.

[0004] Traditional packaging of OLED devices involves fabricating electrodes and functional layers on a substrate, and then using a substrate with good chemical stability, density, and electrical insulation to cover the device to protect it. The glass substrate used in the traditional method is not only prone to cracks or adhesive breakage, but also does not meet the requirements for flexibility. In addition, the glass substrate occupies a relatively large space, making it difficult to meet the trend of slimming OLED devices.

[0005] Thin film encapsulation (TFE) technology is being applied as a new packaging process, which is a kind of gapless encapsulation method that forms a dense thin film to provide physical protection for devices in the encapsulated area. Conventional inorganic thin film encapsulation structures can have pinholes caused by impurities, which can allow moisture and oxygen to penetrate, and organic thin films, including polymer films with high flexibility, have poor moisture and oxygen blocking properties. Therefore, research is being conducted on encapsulation films that have low impurities and excellent moisture and oxygen blocking properties to solve the above problems. Summary of the Invention [Problem to be solved by the invention]

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

[0007] The present invention provides a composition for a silicon-containing sealing film, which contains a silazane compound represented by the following chemical formula 1.

[0008] [ka] [In the above Chemical Formula 1, R 1 is C1-C7 alkyl, C2-C7 alkenyl, C2-C7 alkynyl, C3-C10 cycloalkyl, or C6-C12 aryl; R 2 and R 3 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, R1 may be C1-C5 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C3-C6 cycloalkyl, or C6-C12 aryl; R 2 and R 3 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.

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

[0011] [ka] [In the above Chemical Formula 2, R 11 is C1-C7 alkyl, C2-C7 alkenyl, C2-C7 alkynyl, C3-C10 cycloalkyl, or C6-C12 aryl; R 12 is 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.

[0012] According to an embodiment, X in Formula 1 may be Cl.

[0013] Moreover, the silazane compound according to one embodiment may be selected from the following compounds: [ka] JPEG2025513797000004.jpg226170

[0014] The present invention provides a method for producing a silicon-containing sealing film, comprising the steps of depositing a silicon-containing sealing film using a silazane compound represented by the following chemical formula 1, or a composition for a silicon-containing sealing film containing the same, and a reactive gas:

[0015] [ka] (In the above Chemical Formula 1, R 1 ~R 3 and X is as defined above.

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

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

[0018] In the method for producing a silicon-containing sealing film, the temperature of the substrate may be 200° C. or less, and the reaction gas may be 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 from C1 to C12, hydrogen (H 2), argon (Ar), and helium (He).

[0019] The silicon-containing sealing film manufactured by the method for manufacturing a silicon-containing sealing film according to one embodiment of the present invention is characterized in that it is a silicon oxide film or a silicon nitride film, and has a moisture permeability of 0.1 g / [m 2 -day] or less. Effect of the Invention

[0020] By using the composition for a silicon-containing sealing film containing the silazane compound of the present invention, a high-purity sealing film with extremely low carbon and other impurities can be produced even in a low-temperature process.

[0021] In addition, the method for producing a silicon-containing sealing film of the present invention can produce a sealing film having a high deposition rate and a low impurity content by using a composition for a sealing film containing the silazane compound of the present invention.

[0022] Therefore, the silicon-containing sealing film produced by the production method of the present invention has excellent performance of blocking moisture and oxygen and preventing deterioration of the organic light-emitting device. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0023] The composition for a silicon-containing sealing film containing the silazane compound of the present invention and the method for producing a silicon-containing sealing film using the composition will be described in detail below.

[0024] As used herein, the singular forms are intended to include the plural forms as well, unless the context clearly indicates otherwise.

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

[0026] "Comprising" as used herein is an open-ended term having the same meaning as terms such as "comprising," "containing," "having," or "characterized by," and does not exclude further unrecited elements, materials, or steps.

[0027] "Alkyl" according to the present invention means a straight or branched acyclic hydrocarbon, which may have 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, and in yet another embodiment, the alkyl may have 1 to 3 carbon atoms.

[0028] According to the present invention, "alkenyl" refers to a saturated, straight or branched, acyclic hydrocarbon containing at least one carbon-carbon double bond, including, but not limited to, -vinyl, -allyl, -1-butenyl, -2-butenyl, -isobutylenyl, -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 optionally substituted. Alkenyl includes radicals having cis and trans orientations, or, alternatively, E and Z orientations.

[0029] According to the present invention, "alkynyl" means a saturated, straight or branched, acyclic hydrocarbon having at least one carbon-carbon triple bond, including, but not limited to, ethynyl, propynyl, butynyl, butadiynyl, pentynyl, pentadiynyl, hexynyl, hexadiynyl, and isomers thereof.

[0030] According to the present invention, "cycloalkyl" refers to a monocyclic or polycyclic saturated ring containing carbon and hydrogen atoms and no carbon-carbon multiple bonds. It includes, but is not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl. Cycloalkyl groups may be optionally substituted.

[0031] "Halogen" according to the present invention means fluorine, chlorine, bromine or iodine.

[0032] According to the present invention, "haloalkyl" refers to an alkyl group in which one or more hydrogen atoms are replaced by halogen atoms. For example, haloalkyl is -CF 3 , -CHF 2 , -CH 2 F, -CBr 3 , -CHBr 2 , -CH 2 Br, -CCl 3 , -CHCl 2 , -CH 2 CI, -CI 3 , -CHI 2 , -CH 2 I, -CH 2 -CF 3 , -CH 2 -CHF 2 , -CH 2 -CH 2 F, -CH 2 -CBr 3 , -CH 2 -CHBr 2 , -CH 2 -CH 2 Br, -CH 2 -CCl 3 , -CH 2-CHCl 2 , -CH 2 -CH 2 CI, -CH 2 -CI 3 , -CH 2 -CHI 2 , -CH 2 -CH 2 I, and the like, where alkyl and halogen are as defined above.

[0033] "Aryl" according to the present invention means a carbocyclic aromatic group containing 5-10 ring atoms. Representative examples include, but are not limited to, phenyl, tolyl, xylyl, naphthyl, tetrahydronaphthyl, anthracenyl, fluorenyl, indenyl, azulenyl, etc. In addition, aryl also includes carbocyclic aromatic groups linked to the group by alkylene or alkenylene, or by one or more heteroatoms selected from B, O, N, C(=O), P, P(=O), S, S(=O)2, and Si atoms.

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

[0035] The present invention provides a composition for a silicon-containing sealing film, which contains a silazane compound represented by the following chemical formula 1.

[0036] [ka] [In the above Chemical Formula 1, R 1 is C1-C7 alkyl, C2-C7 alkenyl, C2-C7 alkynyl, C3-C10 cycloalkyl, or C6-C12 aryl; R 2 and R 3are, 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] The silazane compound represented by Chemical Formula 1 has a high vapor pressure, and therefore, when a composition for a silicon-containing sealing film containing the silazane compound is used, a sealing film can be produced at a significantly improved deposition rate at a low temperature. Also, since the content of carbon and other impurities is low, a high-quality silicon-containing sealing film having high purity and high durability can be obtained.

[0038] In detail, the silazane compound represented by Chemical Formula 1 has a form in which two silicon atoms are bonded to a central nitrogen atom, and forms a stable liquid compound at room temperature and pressure. It has excellent volatility with a vapor pressure of 30 torr or more at 70°C, and has a very fast deposition rate even when deposited at a low temperature of less than 100°C, for example, only 90°C.

[0039] In addition, when a silicon-containing sealing film is formed using the silazane compound of Chemical Formula 1, it can have excellent cohesion and step coverage. Furthermore, since the silazane compound has the structure of Chemical Formula 1, it has high thermal stability, low activation energy, excellent reactivity, and does not generate non-volatile by-products, so that a silicon-containing sealing film having high purity and excellent stress strength can be easily formed.

[0040] In one embodiment, R 1 may be C1-C5 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C3-C6 cycloalkyl, or C6-C12 aryl; R 2 and R 3 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 is C1-C7 alkyl, C2-C7 alkenyl, C2-C7 alkynyl, C3-C10 cycloalkyl, or C6-C12 aryl; R 12 is 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] According to an embodiment of the present invention, X in 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] JPEG2025513797000009.jpg226170

[0045] The silazane compound represented by the following formula 1 according to one embodiment of the present invention can be produced by any method available in the field of organic synthesis. As an example, the compound represented by the following formula 1 can be produced by reacting a compound represented by the following formula 11 with a compound represented by the following formula 12.

[0046] [ka]

[0047] [ka]

[0048] [ka] [In the above Chemical Formulas 1, 11, and 12, R 1 is C1-C7 alkyl, C2-C7 alkenyl, C2-C7 alkynyl, C3-C10 cycloalkyl, or C6-C12 aryl; R 2 and R 3 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, and preferably at −50 to 0° C. for 2 to 6 hours.

[0050] The present invention provides a method for producing a silicon-containing sealing film, comprising the steps of depositing a silicon-containing sealing film using a silazane compound represented by the following chemical formula 1 or a composition for a silicon-containing sealing film containing the same, and a reactive gas.

[0051] [ka] (In the above Chemical Formula 1, R 1 ~R 3 and X are as defined in claim 1.

[0052] Specifically, the method for producing a silicon-containing sealing film according to one embodiment of the present invention is characterized by comprising the steps of: adsorbing the silazane compound represented by the chemical formula 1 or a composition for silicon-containing sealing film containing the silazane compound on a substrate; and injecting a reactive gas into the substrate on which the silazane compound or the composition for silicon-containing sealing film is adsorbed, thereby forming a silicon-containing sealing film. At this time, the method for producing a silicon-containing sealing film may specifically comprise the steps of adsorbing the silazane compound represented by the chemical formula 1 or a composition for silicon-containing sealing film containing the silazane compound on a substrate; purging the residual silazane compound or a composition containing the silazane compound and by-products; injecting a reactive gas into the substrate to form a silicon-containing sealing film; and purging the residual reactive gas and by-products.

[0053] In addition, the silicon-containing sealing film according to an embodiment may be prepared by simultaneously injecting the silazane compound represented by Formula 1 or a composition for a silicon-containing sealing film containing the silazane compound and a reaction gas.

[0054] The method for producing a silicon-containing sealing 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, and is easy to handle, and can produce a high-purity silicon-containing sealing film at a high deposition rate even at low temperature and / or low power. Furthermore, the silicon-containing sealing 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 the method for manufacturing a silicon-containing sealing film according to an embodiment of the present invention, the deposition method of the sealing film may be any method that is possible within the scope of what a person skilled in the art can recognize in this technical field, but is preferably formed by atomic layer deposition (ALD), chemical vapor deposition (CVD), metalorganic chemical vapor deposition (MOCVD), low pressure vapor deposition (LPCVD), plasma enhanced vapor deposition (PECVD), plasma enhanced atomic layer deposition (PEALD), or the like. More specifically, the deposition method of the sealing film may be plasma enhanced atomic layer deposition (PEALD) because the deposition of the sealing film is easy and the manufactured sealing film has excellent properties, but is not limited thereto.

[0056] In addition, in the method for producing a silicon-containing sealing film according to an embodiment of the present invention, the temperature of the substrate may be 200° C. or less, and specifically, deposition may be performed at 50 to 200° C. Due to the excellent properties of the silazane compound according to Chemical Formula 1 of the present invention as a silicon precursor for deposition, such as excellent low-temperature volatility and high reactivity, the temperature of the deposition target substrate located inside the chamber may be less than 120° C., typically less than 100° C., and the deposition of the silicon-containing sealing film, which is performed by supplying the silazane compound according to an embodiment to the chamber in which the deposition target substrate is located, may be performed at a low temperature of less than 100° C., more specifically, less than 95° C.

[0057] In one embodiment of the present invention, the reaction gas used in the method for producing the silicon-containing sealing film 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 from C1 to C12, hydrogen (H2 ), argon (Ar), and helium (He). Specifically, oxygen (O 2 ), nitric oxide (NO), nitrous oxide (N 2 O), nitrogen dioxide (NO 2 ), ammonia (NH 3 ), and nitrogen (N 2 ), more specifically, nitrous oxide (N 2 O), nitrogen dioxide (NO 2 ), ammonia (NH 3 ), hydrogen (H 2 ), and nitrogen (N 2 ) may be any one or more selected from, but is not limited to, these.

[0058] In the method for producing a silicon-containing sealing film according to an embodiment of the present invention, the silazane compound and the reaction gas may be supplied organically or independently. The silazane compound and the reaction gas may be supplied continuously or discontinuously, and the discontinuous supply may include a pulse form.

[0059] In the method for producing a silicon-containing sealing film according to an embodiment, the deposition conditions may be adjusted according to the structure or thermal properties of the target sealing film, and the deposition conditions include the feed flow rate of the composition for silicon-containing sealing film containing a silazane compound, the feed flow rate of the reactive gas, the feed flow rate of the carrier gas, the pressure, and the temperature of the deposition target substrate. Non-limiting examples of such deposition conditions include the feed flow rate of the composition containing a silazane compound of 10 to 1000 cc / min, the feed flow rate of the reactive gas of 1 to 10000 cc / min, the feed flow rate of the carrier gas of 10 to 10000 cc / min, the pressure of 0.5 to 10 torr, and the temperature of the deposition target substrate of 200°C or less, specifically 50 to 200°C, more specifically 50 to 120°C, and characteristically 60 to 100°C, but are not limited thereto. In addition, when using plasma-enhanced atomic layer deposition (PEALD), which is a case in which the reactive gas is in a state activated by plasma, the RF power may be 50 to 1000W, but is not limited thereto.

[0060] The silicon-containing sealing film manufactured by the method for manufacturing a silicon-containing sealing film according to one embodiment of the present invention is characterized in that it is a silicon oxide film or a silicon nitride film. In addition, various high-quality sealing films containing silicon can be manufactured within a range that can be recognized by a person skilled in the art.

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

[0062] The silicon-containing sealing film produced by the method for producing a silicon-containing sealing film of the present invention has a moisture permeability of 0.1 g / [m 2 -day] or less, and preferably 0.05 g / [m 2 -day] or less, and more preferably 0.015g / [m 2 As a result, the silicon-containing sealing film manufactured by the manufacturing method of the present invention has a significantly improved moisture and oxygen blocking performance, and can prevent a decrease in the life span of an organic light-emitting device employing the silicon-containing sealing film.

[0063] The moisture permeability of the silicon-containing sealing film was measured using a moisture permeability measuring device (Water Vapor Transmission Rate (WVTR, MOCON, Aquatran2)). Nitrogen was used and the moisture permeability measurement area was 50 cm 2 was set to.

[0064] The structure of the sealing film manufactured by the method for manufacturing a silicon-containing sealing film according to one embodiment of the present invention can cover the surface and / or side of the organic light-emitting device according to demand. The thickness of the sealing film may be 5 to 2000 nm, preferably 200 to 1000 nm, and more preferably 500 to 800 nm.

[0065] The composition for a silicon-containing sealing film containing a silazane compound according to the present invention and the method for producing a silicon-containing sealing film using the composition will be described in more detail below with reference to specific examples.

[0066] However, the following examples are merely one reference for describing the present invention in detail, and the present invention is not limited thereto, and may be realized in various forms. Furthermore, the terms used in the description of the present invention are for effectively describing specific examples, and are not intended to limit the present invention.

[0067] [Production Example 1] After vacuum drying a 5 L high-pressure reactor equipped with a stirrer and a 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 completed, the internal temperature was maintained at -10°C and stirring was continued for 4 hours. Salts and solvents were removed by vacuum filtration and vacuum distillation to obtain MeN(SiH 2 Cl) 2 38 g 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 The silazane compound produced in Production Example 1 was used in a conventional plasma-enhanced atomic layer deposition apparatus using a known plasma-enhanced atomic layer deposition method to evaluate the sealing film.

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

[0070] The above process constitutes 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. In addition, composition analysis using an X-ray photoelectron spectroscope confirmed that the proportions of silicon and oxygen were 33.5% and 66.5%, respectively.

[0071] To evaluate the moisture permeability, the thin film was deposited to a thickness of 700 Å on a polyethylene naphthalate (PEN) film, and the moisture permeability was analyzed, which was found to be 1.5x10 -3 g / [m 2 -day] was an excellent result.

[0072] [Example 2] Silicon nitride film for sealing The silazane compound of Production Example 1 was used to evaluate a sealing film in a conventional plasma-enhanced atomic layer deposition apparatus using a known plasma-enhanced atomic layer deposition method.

[0073] Ammonia was used as the reactive gas together with plasma, and nitrogen, an inert gas, was used as the carrier gas. 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 Preparation Example 1, which was filled in a bubbler-type stainless steel container, was vaporized at a vapor pressure of 20 Torr, transported to the substrate using 50 sccm of nitrogen gas as a carrier gas and adsorbed thereon, and then unreacted compounds were removed using 500 sccm of nitrogen gas. A silicon nitride film was formed using 1000 sccm of ammonia gas and 800 W plasma as reactive gases, 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 800 W plasma, and then unreacted compounds were removed using 500 sccm of nitrogen gas.

[0074] The above process constitutes 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 was confirmed to be 1.97 at 633 nm. In addition, composition analysis using an X-ray photoelectron spectroscope confirmed that the proportions of silicon and nitrogen were 43.1% and 56.8%, respectively.

[0075] To evaluate the moisture permeability, the thin film was deposited to a thickness of 700 Å on a polyethylene naphthalate (PEN) film, and the moisture permeability was analyzed. -4 g / [m 2 -day] was an excellent result.

[0076] [Example 3] Silicon nitride film for sealing The silazane compound of Preparation Example 1 was used to evaluate a sealing film in a conventional plasma-enhanced chemical vapor deposition apparatus using a known plasma-enhanced chemical vapor deposition method.

[0077] The silicon wafer on which the silicon nitride film was to be formed was transferred into a deposition chamber and maintained at 90°C. The silazane compound of Preparation Example 1, which was filled in a bubbler-type stainless steel container, was vaporized at a vapor pressure of 0.1 Torr and transferred into the chamber with 5 sccm of nitrogen gas as a carrier gas. At the same time, nitrogen, hydrogen, and ammonia were used as reactive gases, and a silicon nitride film was formed using 800 W plasma. The detailed process conditions and results are shown in Table 1. Furthermore, as a result of composition analysis using an X-ray photoelectron spectroscope, the ratios of silicon and nitrogen were confirmed to be approximately 43% and 57%, respectively.

[0078] [Examples 4 to 7] The silicon nitride film was deposited in the same manner as in Example 3, except that the gas ratio was changed. The process conditions and results are shown in Table 1.

[0079] [Table 1]

[0080] From the above results, the composition for silicon-containing sealing film containing the silazane compound of Preparation Example 1 of the present invention has a high vapor pressure and can exhibit an excellent deposition rate, and has a low content of carbon and other impurities, making it possible to produce a high-quality silicon-containing sealing film having high purity and high durability. The composition for silicon-containing sealing film containing the 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 a low temperature, and can produce a sealing film with more uniform and improved quality.

[0081] It has been found that the silicon-containing sealing film produced by the production method of the present invention has improved moisture permeability and is extremely excellent in terms of blocking moisture and oxygen. When this film is employed in an organic light-emitting element, it is expected to be used as an excellent material that can prevent the penetration of moisture and oxygen and prevent a decrease in the element's lifespan.

[0082] As described above, the present invention has been described using specific and limited examples and comparative examples. However, these are merely provided for a more general understanding of the present invention, and the present invention is not limited to the above examples. A person having ordinary knowledge in the field to which the present invention belongs can make various modifications and variations from such descriptions.

[0083] Therefore, the idea of ​​the present invention should not be limited to the above-mentioned embodiments, and it can be said that not only the scope of the attached claims, but also equivalents to the scope of the claims or equivalent variations all fall within the scope of the idea of ​​the present invention.

Claims

1. A composition for a silicon-containing sealing film, comprising a silazane compound represented by the following chemical formula 1: 【Chemistry 1】 [In the above Chemical Formula 1, R １ is C1-C7 alkyl, C2-C7 alkenyl, C2-C7 alkynyl, C3-C10 cycloalkyl, or C6-C12 aryl; R ２ and R ３ are each independently 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.

2. In the above Chemical Formula 1, R １ is C1-C5 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C3-C6 cycloalkyl, or C6-C12 aryl; R ２ and R ３ are each independently hydrogen, C1-C5 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C3-C6 cycloalkyl, C6-C12 aryl, C1-C5 haloalkyl or halogen; The silicon-containing sealing film composition according to claim 1 , wherein X is a halogen.

3. The composition for a silicon-containing sealing film 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 is C1-C7 alkyl, C2-C7 alkenyl, C2-C7 alkynyl, C3-C10 cycloalkyl, or C6-C12 aryl; R １２ is 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.

4. The composition for a silicon-containing sealing film according to claim 1 , wherein X in Formula 1 is Cl.

5. The composition for a silicon-containing sealing film according to claim 1 , wherein the silazane compound is selected from the following compounds: 【Chemistry 3】 【change】

6. A silazane compound represented by the following chemical formula 1 or a composition for a silicon-containing sealing film containing the same, A method for making a silicon-containing encapsulating film, comprising depositing a silicon-containing encapsulating film using a reactive gas. 【Chemistry 4】 (In the above Chemical Formula 1, R １ ~R ３ and X are as defined in claim 1.

7. A step of adsorbing a precursor including the silazane compound represented by the formula 1 or a composition for a silicon-containing sealing film onto a substrate; and injecting a reactive gas into the substrate on which the silazane compound or the composition for a silicon-containing sealing film is adsorbed to form a silicon-containing sealing film.

8. 7. The method for producing a silicon-containing sealing film according to claim 6, further comprising the step of simultaneously injecting the silazane compound represented by Chemical Formula 1 or a composition for a silicon-containing sealing film containing the same with a reactive gas to form a silicon-containing sealing 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 ), C1-C12 saturated or unsaturated hydrocarbons, hydrogen (H ２ 7. The method for producing a silicon-containing sealing film according to claim 6, wherein the oxygen is at least one selected from the group consisting of argon (Ar) and helium (He).

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

11. 7. The method for producing a silicon-containing sealing film according to claim 6, wherein the silicon-containing sealing film is a silicon oxide film or a silicon nitride film.

12. The silicon-containing sealing film has a moisture permeability of 0.1 g / [m ２ 7. The method for producing a silicon-containing sealing film according to claim 6, wherein the time required for the formation of the silicon-containing sealing film is equal to or less than [-day].

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