KR20210117677A - Encapsulation film and fabricating method of the same - Google Patents

Abstract

A manufacturing method of an encapsulation film is provided. The manufacturing method of the encapsulation film comprises the following steps of: preparing a substrate; providing a first precursor comprising a first element and a second precursor comprising a second element onto the substrate; and providing a reaction source onto the substrate, onto which the first precursor and the second precursor are provided, to form a material film in which the first precursor, the second precursor, and the reaction source are reacted.

Description

Encapsulation film and manufacturing method thereof {Encapsulation film and fabricating method of the same}

The present invention relates to an encapsulation film and a method for manufacturing the same, and more particularly, to an encapsulation film formed by providing a precursor and a reaction source on a substrate and a method for manufacturing the same.

Demand for the flat panel display device is explosively increasing as the performance of the flat panel display device is improved, such as the size of the screen of the flat panel display device is increased and the weight thereof is reduced thanks to the rapidly developing semiconductor technology.

Such flat panel displays include a liquid crystal display (LCD), a plasma display device (PDP), a field emission display device (FED), and an electroluminescence display device (ELD). ), an electrophoresis display device (EPD), and an organic light emitting display device (OLED).

These flat panel display devices are lighter and thinner than CRTs, and have advantages in enlargement, so their use is increasing day by day.

In addition, a flexible display device capable of maintaining display performance even when bent like paper using a substrate formed using a flexible material is rapidly emerging as a flat panel display device. Such a flat panel display device may be provided with an encapsulation film for sealing the display element so that external oxygen and moisture do not penetrate into the display element. is being applied

For example, Korean Patent Publication No. 10-2016-0060988 (Application No.: 10-2014-0163293, Applicant: LG Chem Co., Ltd.) includes a polymer having a water reaction site capable of forming an adhesive functional group by reacting with water. As an encapsulation film including an organic layer and an inorganic layer formed on the organic layer, it not only prevents a gas generation problem that may occur during the coating process of the organic layer, but also reduces the frequency of pinholes in the inorganic layer, and An encapsulant capable of effectively protecting a device sensitive to a factor is disclosed.

Korean Patent Publication No. 10-2016-0060988

One technical problem to be solved by the present invention is to provide an encapsulation film with easy composition control and a method for manufacturing the same.

Another technical problem to be solved by the present invention is to provide an encapsulation film having improved moisture permeation prevention properties and oxygen permeation prevention properties, and a method for manufacturing the same.

Another technical problem to be solved by the present invention is to provide an encapsulation film having improved mechanical stability and a method for manufacturing the same.

Another technical problem to be solved by the present invention is to provide an encapsulation film for improving reliability of a flexible device and a method for manufacturing the same.

The technical problem to be solved by the present invention is not limited to the above.

In order to solve the above-described technical problems, the present invention provides a method of manufacturing an encapsulation film.

According to an embodiment, the method of manufacturing the encapsulation film includes preparing a substrate, providing a first precursor including a first element and a second precursor including a second element on the substrate; A first precursor and a reaction source provided on the substrate provided with the second precursor to form a material film in which the first precursor, the second precursor, and the reaction source are reacted, the composition of the material film Silver may include controlling according to the process conditions of the step of providing the first precursor and the second precursor.

According to an embodiment, the providing of the first precursor and the second precursor may include providing the first precursor on the substrate, purging the substrate provided with the first precursor for a first time. ), providing a second precursor on the substrate provided with the first precursor, and purging the substrate provided with the second precursor for a second time period shorter than the first time. can do.

According to an embodiment, as the provision time of the first precursor increases, the content of the metal in the material layer may increase.

According to an embodiment, the step of purging the substrate provided with the first precursor for a first time may include increasing the content of the metal in the material layer as the first time increases. have.

According to an embodiment, the providing of the first precursor and the second precursor may include providing the second precursor on the substrate, purging the substrate provided with the second precursor for a first time. ), providing a first precursor on the substrate provided with the second precursor, and purging the substrate provided with the first precursor for a second time shorter than the first time. can do.

According to an embodiment, the provision time of the first precursor may include longer than the provision time of the second precursor.

According to an embodiment, the providing of the first precursor and the second precursor may include providing the first precursor and the second precursor together on the substrate, and the first precursor and the second precursor. may include purging the provided substrate.

According to an embodiment, the reaction source may include an oxygen plasma (O ₂ plasma).

In order to solve the above-described technical problems, the present invention provides an encapsulation film.

According to an embodiment, the encapsulation layer may include a substrate and a material layer disposed on the substrate, in which a first element, a second element, and oxygen (O) are mixed.

According to an embodiment, the material layer further includes carbon (C) and nitrogen (N), wherein the content of the first element and the second element in the material layer is, the carbon (C) and the nitrogen (N) ) may contain higher than the content of.

According to an embodiment, the first element may include tin (Sn), and the second element may include silicon (Si).

According to an embodiment, the substrate may include a flexible one.

A method of manufacturing an encapsulation film according to an embodiment of the present invention includes the steps of preparing a substrate, providing a first precursor including a first element and a second precursor including a second element on the substrate; providing a reaction source on the substrate provided with a first precursor and the second precursor to form a material film in which the first precursor, the second precursor, and the reaction source are reacted; The composition may include being controlled according to process conditions of the step of providing the first precursor and the second precursor. Accordingly, an encapsulation film having improved moisture permeation prevention properties and oxygen permeation prevention properties may be provided.

1 is a flowchart illustrating a method of manufacturing an encapsulation film according to an embodiment of the present invention.
2 is a view showing an encapsulation film according to an embodiment of the present invention.
3 to 5 are graphs specifically illustrating a manufacturing process of an encapsulation film according to an embodiment of the present invention.
6 is a graph comparing compositions of encapsulation films according to Examples 1 to 4 and Comparative Example 1 of the present invention.
7 is a graph comparing compositions of encapsulation films according to Example 7 and Comparative Example 2 of the present invention.
8 is a diagram illustrating an apparatus for measuring moisture permeability of an encapsulation film according to Examples and Comparative Examples of the present invention.
9 is a graph comparing moisture permeability of encapsulation films according to Examples and Comparative Examples of the present invention.
10 is a graph comparing mechanical properties of encapsulation films according to Comparative Example 1 and Comparative Example 2 of the present invention.
11 is a graph comparing mechanical properties of an encapsulation film according to Comparative Example 3 of the present invention.
12 is a graph comparing mechanical properties of an encapsulation film according to Comparative Example 4 of the present invention.
13 is a graph comparing mechanical properties of an encapsulation film according to Example 7 of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the technical spirit of the present invention is not limited to the embodiments described herein and may be embodied in other forms. Rather, the embodiments introduced herein are provided so that the disclosed content may be thorough and complete, and the spirit of the present invention may be sufficiently conveyed to those skilled in the art.

In this specification, when a component is referred to as being on another component, it may be directly formed on the other component or a third component may be interposed therebetween. In addition, in the drawings, thicknesses of films and regions are exaggerated for effective description of technical content.

In addition, in various embodiments of the present specification, terms such as first, second, third, etc. are used to describe various components, but these components should not be limited by these terms. These terms are only used to distinguish one component from another. Accordingly, what is referred to as a first component in one embodiment may be referred to as a second component in another embodiment. Each embodiment described and illustrated herein also includes a complementary embodiment thereof. In addition, in the present specification, 'and/or' is used to mean including at least one of the elements listed before and after.

In the specification, the singular expression includes the plural expression unless the context clearly dictates otherwise. In addition, terms such as "comprise" or "have" are intended to designate that a feature, number, step, element, or a combination thereof described in the specification is present, and one or more other features, numbers, steps, configuration It should not be construed as excluding the possibility of the presence or addition of elements or combinations thereof. Also, in the present specification, the term “connection” is used to include both indirectly connecting a plurality of components and directly connecting a plurality of components.

In addition, in the following description of the present invention, if it is determined that a detailed description of a related well-known function or configuration may unnecessarily obscure the gist of the present invention, the detailed description thereof will be omitted.

1 is a flowchart illustrating a method of manufacturing an encapsulation film according to an embodiment of the present invention, FIG. 2 is a view showing an encapsulation film according to an embodiment of the present invention, and FIGS. 3 to 5 are encapsulation films according to an embodiment of the present invention These are graphs specifically showing the manufacturing process of the membrane.

1 to 5 , the substrate 10 is prepared (S100). According to an embodiment, the substrate 10 may be a flexible substrate. For example, the substrate 10 may include polyethylene naphthalate (PEN). Alternatively, according to another embodiment, the substrate 10 may be a glass substrate, a semiconductor substrate, a metal substrate, or a plastic substrate. The type of the substrate 10 is not limited.

A first precursor and a second precursor may be provided on the substrate 10 ( S200 ). According to an embodiment, the first precursor may include a first element. For example, the first element may include tin (Sn). For example, the first precursor may be TDMASn (Tetrakis(Dimethylamino)Tin). Alternatively, the second precursor may include a second element. For example, the second element may include silicon (Si). For example, the second precursor may be Diisopropylaminosilane (DIPAS).

A reaction source may be provided on the substrate 10 provided with the first precursor and the second precursor. For example, the reaction source may be oxygen plasma (O ₂ Plasma). Accordingly, a material film 20 in which the first precursor, the second precursor, and the reaction source are reacted may be formed on the substrate 10 ( S300 ). In this case, the material layer 20 may include the first element (eg, tin), the second element (eg, silicon), and oxygen (O).

According to an embodiment, the step of providing the first precursor and the second precursor ( S200 ) includes providing the first precursor on the substrate 10 , and the substrate 10 on which the first precursor is provided. ), providing a second precursor on the substrate 10 provided with the first precursor, and purging the substrate 10 provided with the second precursor may include In addition, the step of forming the material film 20 ( S300 ) may include providing the reaction source on the substrate 10 , and purging the substrate 10 .

That is, the material film 20 is an atomic layer deposition method in which, as shown in FIG. 3 , a first precursor providing step - a purge step - a second precursor providing step - a purge step - a reaction source provision step - a purge step are sequentially performed. (Atomic Layer Deposition, ALD) may be formed.

The first precursor providing step - purge step - second precursor providing step - purge step - reaction source providing step - purge step may be defined as a cycle process. In this case, the thickness of the material layer 20 may be controlled according to the number of repetitions of the cycle process. For example, as the number of repetitions of the cycle process increases, the thickness of the material layer 20 may increase.

As a more specific process condition, the provision time of the first precursor may be longer than the provision time of the second precursor. For example, the first precursor may be provided for a time of 0.5 s, 0.7, or 1 s. Alternatively, the second precursor may be provided for a time of 0.2 s. In addition, a time for purging the substrate 10 provided with the second precursor may be shorter than a time for purging the substrate 10 provided with the first precursor. For example, the time for purging the substrate 10 provided with the first precursor may be 60 s. Alternatively, the time for purging the substrate 10 provided with the second precursor may be 25 s.

The composition of the material layer 20 may be controlled according to a time of providing the first precursor and a time of purging the substrate 10 provided with the first precursor. More specifically, as the supply time of the first precursor increases, the content of the metal (eg, tin) in the material layer 20 may increase. For example, as the supply time of the first precursor increases to 0.1 s, 0.5 s, 0.7 s, and 1 s, the content of the metal (eg, tin) in the material layer 20 is 5.5 at %, 10.9 at%, 18.5 at%, and 20.8 at%. Also, as the time for purging the substrate 10 provided with the first precursor increases, the content of the metal (eg, tin) in the material layer 20 may increase.

Unlike the above, according to another embodiment, the step of providing the first precursor and the second precursor ( S200 ) may include providing the second precursor on the substrate 10 , the second precursor is purging the provided substrate 10 , providing the first precursor on the substrate 10 provided with the second precursor, and purging the substrate 10 provided with the first precursor (purge) may include a step. In addition, the step of forming the material film 20 ( S300 ) may include providing the reaction source on the substrate 10 , and purging the substrate 10 .

That is, the material layer 20 is an atomic layer deposition method in which the second precursor providing step - purge step - first precursor providing step - purge step - reaction source provision step - purge step are sequentially performed as shown in FIG. 4 . (ALD) may be formed. The material film 20 formed in the above-described order (the second precursor is provided before the first precursor) is the material film 20 formed in the order described in FIG. 3 (the first precursor is provided before the second precursor) ) can be higher than

The second precursor providing step-purge step-first precursor providing step-purge step-reaction source provision step-purge step may be defined as a cycle process. In this case, the thickness of the material layer 20 may be controlled according to the number of repetitions of the cycle process. For example, as the number of repetitions of the cycle process increases, the thickness of the material layer 20 may increase.

As a more specific process condition, the provision time of the first precursor may be longer than the provision time of the second precursor. For example, the first precursor may be provided for a time of 1 s. Alternatively, the second precursor may be provided for a time of 0.2 s. In addition, a time for purging the substrate 10 provided with the first precursor may be shorter than a time for purging the substrate 10 provided with the second precursor. For example, the time for purging the substrate 10 provided with the second precursor may be 60 s. Alternatively, the time for purging the substrate 10 provided with the first precursor may be 25 s.

According to another embodiment, the step of providing the first precursor and the second precursor ( S200 ) includes providing the first precursor and the second precursor together on the substrate 10 , the first It may include purging the substrate provided with the precursor and the second precursor together. In addition, the step of forming the material film 20 ( S300 ) may include providing the reaction source on the substrate 10 , and purging the substrate 10 .

That is, as shown in FIG. 5 , the material layer 20 is formed by an atomic layer deposition (ALD) method in which a step of providing a first precursor and a second precursor together - a purge step - a reaction source provision step - a purge step are sequentially performed. ) can be formed.

The step of providing the first precursor and the second precursor together - the purge step - the reaction source providing step - the purge step may be defined as a cycle process. In this case, the thickness of the material layer 20 may be controlled according to the number of repetitions of the cycle process. For example, as the number of repetitions of the cycle process increases, the thickness of the material layer 20 may increase.

As a result, the material film 20 includes the first element (eg, tin), the second element (eg, silicon), and oxygen (O) as described above, but the atomic layer deposition method As it is formed of (ALD), it may further include carbon (C) and nitrogen (N). In this case, the content of the first element (eg, tin) and the second element (eg, silicon) in the material layer 20 is the content of the carbon (C) and the nitrogen (N) can be higher.

Accordingly, the material layer 20 may have improved moisture permeation prevention properties and oxygen permeation prevention properties as compared to a single layer including any one of the first element or the second element. For this reason, when the material layer 20 is used as an encapsulation layer of an organic thin film included in devices such as an organic light emitting device display, an organic transistor display, and an organic solar cell, reliability of the above-described devices can be improved.

In addition, the material layer 20 may have improved mechanical stability compared to a single layer including either the first element or the second element. As a specific example, in spite of a plurality of bending tests, deterioration of the moisture permeation prevention property and the oxygen permeation prevention property can be prevented. For this reason, when the material layer 20 is applied to a flexible device, the reliability of the flexible device can be improved.

In addition, the thickness of the material film 20 may be reduced as compared to a material film formed through a process such as PECVD. In the case of a material film formed through a process such as PECVD, since the thickness in μm is thick, the residual stress of the film itself is large. may occur. However, in the case of the material layer 20 formed by atomic layer deposition (ALD), as it is formed to a relatively thin thickness, the above-described problems can be solved.

As described above, an encapsulation film and a manufacturing method thereof according to an embodiment of the present invention have been described. Hereinafter, specific experimental examples and characteristic evaluation results of an encapsulation film and a manufacturing method thereof according to an embodiment of the present invention will be described.

Preparation of encapsulation film according to Example 1

The encapsulation film according to Example 1 was prepared by sequentially performing TDMASn (Tetrakis (Dimethylamino) Tin) provision-first purge-DIPAS (Diisopropylaminosilane) provision-second purge-O _{2 plasma provision-third purge process on the substrate.} .

As more specific process conditions, TDMASn was provided for 0.1 s and DIPAS was provided for 0.2 s. In addition, the first purge was performed for 60 seconds, the second purge was performed for 25 seconds, and the third purge was performed for 10 seconds.

Preparation of encapsulation film according to Example 2

An encapsulation film according to Example 2 was manufactured by the method of manufacturing the encapsulation film according to Example 1 described above, but by providing TDMASn for 0.5 seconds.

Preparation of encapsulation film according to Example 3

An encapsulation film according to Example 3 was manufactured by the method of manufacturing the encapsulation film according to Example 1 described above, but by providing TDMASn for 0.7 seconds.

Encapsulation film manufacturing according to Example 4

An encapsulation film according to Example 4 was manufactured by the method of manufacturing the encapsulation film according to Example 1 described above, but by providing TDMASn for 1 second.

Encapsulation film manufacturing according to Example 5

An encapsulation film according to Example 5 was manufactured by the method of manufacturing the encapsulation film according to Example 4 described above, but the first purge step was performed for 35 seconds.

Encapsulation film manufacturing according to Example 6

An encapsulation film according to Example 6 was manufactured by the method of manufacturing the encapsulation film according to Example 4 described above, but the first purge step was performed for 45 seconds.

Encapsulation film manufacturing according to Example 7

An encapsulation film according to Example 7 was prepared by sequentially performing the DIPAS (Diisopropylaminosilane) provision-first purge-TDMASn(Tetrakis(Dimethylamino)Tin) provision-second purge O _{2 plasma provision-third purge process on the substrate.}

As more specific process conditions, DIPAS was applied for 0.2 sec and TDMASn was applied for 1 sec. In addition, the first purge was performed for 60 seconds, the second purge was performed for 25 seconds, and the third purge was performed for 10 seconds.

Preparation of encapsulation film according to Comparative Example 1

An encapsulation film according to Comparative Example 1 composed of a _{SiO 2 single film was prepared.}

Preparation of encapsulation film according to Comparative Example 2

An encapsulation film according to Comparative Example 2 composed of a _{SnO x single film was prepared.}

Preparation of encapsulation film according to Comparative Example 3

An encapsulation film according to Comparative Example 3 having a total thickness of 60 nm was prepared by alternately and repeatedly stacking a 10 nm thick SiO ₂ single film and a 10 nm thick SnO _{x single film on a substrate.}

Preparation of the encapsulation film according to Comparative Example 4

A 1 nm-thick SiO ₂ single layer and a 1 nm-thick SnO _x single layer were alternately and repeatedly laminated on a substrate to prepare an encapsulation layer according to Comparative Example 4 having a total thickness of 60 nm.

The manufacturing process of the encapsulation film according to the above-described embodiments and comparative examples is summarized in <Table 1> below.

division encapsulant structure Process order TDMASn serving time (S) DIPAS service time(s) first purge time (s) Second purge time (s) Example 1 SnSi _x O _y mixed film TDMASn-DIPAS 0.1 0.2 60 25 Example 2 SnSi _x O _y mixed film TDMASn-DIPAS 0.5 0.2 60 25 Example 3 SnSi _x O _y mixed film TDMASn-DIPAS 0.7 0.2 60 25 Example 4 SnSi _x O _y mixed film TDMASn-DIPAS One 0.2 60 25 Example 5 SnSi _x O _y mixed film TDMASn-DIPAS One 0.2 35 25 Example 6 SnSi _x O _y mixed film TDMASn-DIPAS One 0.2 45 25 Example 7 SnSi _x O _y mixed film DIPAS-TDMASn One 0.2 60 25 Comparative Example 1 SiO ₂ single film - - - - - Comparative Example 2 SnO _x single film - - - - - Comparative Example 3 SiO ₂ (10 nm)-SnO _x (10 nm) alternating stacking DIPAS-TDMASn - - - - Comparative Example 4 SnO _x (1 nm)-SiO ₂ (1 nm) alternating stacking TDMASn-DIPAS - - - -

6 is a graph comparing compositions of the encapsulation films according to Examples 1 to 4 and Comparative Example 1 of the present invention, and FIG. 7 is a graph comparing the compositions of the encapsulation films according to Example 7 and Comparative Example 2 of the present invention.

6, the composition of the encapsulation film according to Examples 1 to 4 and the ratio (at%) of Sn and Si in the encapsulation film (thickness 30-40 nm) according to Comparative Example 1 were measured and shown, Referring to FIG. 7 , the ratio (at%) of Sn and Si in the encapsulation film (thickness of 50 nm) according to Example 7 and Comparative Example 2 was measured and shown.

The results of FIG. 6 are summarized in Table 2 below, and the results of FIG. 7 are summarized in Table 3 below.

division Si, Sn (at%) O (at%) Si+Sn/O Sn/Si C, N impurity (at%) Si Sn C N Example 1 26.8 5.5 63.1 2.0 0.21 2.9 < detection limit Example 2 20.1 10.9 64.5 2.1 0.54 2.1 < detection limit Example 3 12.8 18.5 64.2 2.1 1.44 1.9 2.6 Example 4 9.8 20.8 64.9 2.1 2.12 < detection limit 2.3 Comparative Example 1 - 34.3 59.7 1.7 - < detection limit < detection limit

division Si, Sn (at%) O (at%) Si+Sn/O Sn/Si C, N impurity (at%) Si Sn C N Example 7 21.2 9.0 64.8 2.1 0.42 2.9 2.1 Comparative Example 2 35.9 - 63.1 1.8 - < detection limit < detection limit

As can be seen in FIGS. 6 and <Table 2>, when comparing Examples 1 to 4, as the TDMASn provision time increased to 0.1 second, 0.5 second, 0.7 second, and 1 second, the amount of Sn in the encapsulation film It was confirmed that the ratio gradually increased to 5.5 at%, 10.9 at%, 18.5 at%, and 20.8 at%. In addition, as can be seen in <Table 2> and <Table 3>, the encapsulation film according to the embodiments includes silicon (Si), tin (Sn), and oxygen (O) as it is formed by an atomic layer deposition method. As well as, it was confirmed that it further contains carbon (C) and nitrogen (N).

In addition, the growth rate and refractive index of the encapsulation films according to Examples 1 to 4, Example 7, Comparative Example 1, and Comparative Example 2 were measured, which are summarized in Table 4 below.

division Growth rate (A/cycle) refractive index Example 1 1.02±0.14 1.51±0.04 Example 2 0.95±0.18 1.55±0.06 Example 3 1.30±0.28 1.62±0.09 Example 4 1.16±0.24 1.71±0.06 Example 7 1.83±0.20 1.62±0.03 Comparative Example 1 1.09±0.10 1.87±0.04 Comparative Example 2 1.19±0.02 1.46±0.01

As can be seen from <Table 4>, it was confirmed that the encapsulation film according to Example 7 had a higher growth rate than that of the encapsulation films according to Examples 1 to 4. That is, when the DIPAS precursor is provided before the TDMASn precursor, it can be seen that the growth rate of the _{SnSi x} O _{y mixed film is higher.}

In addition, the thickness, growth rate (GPC), and refractive index (RI) of the encapsulation films according to Examples 4 to 6 were measured, which are summarized in <Table 5> to <Table 7> below.

Example 5 thickness Cycle Growth rate (GPC) refractive index (RI) Average 43.38 300.00 1.55 1.64 Diviation 8.48 0.00 0.16 0.10 Uniformity 0.29 0.00 0.12 0.06

Example 6 thickness Cycle Growth rate (GPC) refractive index (RI) Average 43.30 300.00 1.54 1.72 Diviation 7.51 0.00 0.07 0.02 Uniformity 0.30 0.00 0.05 0.01

Example 4 thickness Cycle Growth rate (GPC) refractive index (RI) Average 41.50 300.00 1.50 1.74 Diviation 8.44 0.00 0.06 0.02 Uniformity 0.35 0.00 0.05 0.01

As can be seen in <Table 5> to <Table 7>, when comparing the encapsulation films according to Examples 4 to 6, as the purge time increased to 35 seconds, 45 seconds, and 60 seconds, the refractive index was 1.64, It was confirmed that it increases to 1.72, and 1.74. As a result, it can be seen that as the purge time of the substrate provided with TDMASn increases, the content of tin (Sn) in the encapsulation layer increases.

8 is a diagram illustrating an apparatus for measuring moisture permeability of an encapsulation film according to Examples and Comparative Examples of the present invention.

Referring to FIG. 8 , Al/Ti electrodes 210 and 220 spaced apart from each other are disposed on a glass substrate 100 , and a Ca thin film 300 having a thickness of 500 nm is disposed between the Al/Ti electrodes. In addition, a 125 μm thick PEN substrate 500 is disposed to be spaced apart from the upper surface of the Al/Ti electrodes 210 and 220 and the Ca thin film 300 , and on the PEN substrate 500 in the above embodiments and comparative examples. An encapsulation film 600 was disposed. Thereafter, a moisture permeability measuring device having a structure in which the PEN substrate 500 on which the encapsulation film 600 is disposed and the Ca thin film 300 is surrounded by the epoxy resin 400 was prepared. The above-described moisture permeability measuring apparatus, when the Ca thin film is changed to CaO as it is oxidized by moisture and oxygen in the outside air, a change in resistance occurs, so it is possible to measure the moisture permeability by measuring the changed resistance.

More specific water permeability (WVTR, water vapor transition ratio) was calculated through <Equation 1> below.

<Equation 1>

9 is a graph comparing moisture permeability of encapsulation films according to Examples and Comparative Examples of the present invention.

Referring to FIG. 9 , the moisture permeability measuring apparatus described with reference to FIG. 8 is prepared, and the encapsulation film 600 according to Example 7, Comparative Example 1, and Comparative Example 2 is disposed on the PEN substrate 500 . After that, the moisture permeability was measured for each. As can be seen in FIG. 9 , the encapsulation film according to Example 7 showed higher water permeability than the encapsulation film according to Comparative Example 1, but lower water permeability than the encapsulation film according to Comparative Example 2.

10 is a graph comparing mechanical properties of encapsulation films according to Comparative Example 1 and Comparative Example 2 of the present invention.

Referring to FIG. 10 , the moisture permeability of the encapsulation membrane (Bare) according to Comparative Example 1, the moisture permeability of the encapsulation membrane (5mm, 5k) according to Comparative Example 1 bent 5,000 times with a 5mm bending radius, 5 with a 3mm bending radius Differential transmittance of the encapsulation film (3mm, 5k) according to Comparative Example 1 bent 1,000 times, moisture permeability of the encapsulation film (Bare) according to Comparative Example 2, and the encapsulation film according to Comparative Example 2 bent 5,000 times with a bending radius of 5 mm ( Water permeability of 5mm, 5k), water permeability of the encapsulation membrane (3mm, 5k) according to Comparative Example 2 bent 5,000 times with a 3mm bending radius, and the encapsulation membrane according to Comparative Example 2 bent 10,000 times with a 1mm bending radius (1mm, 10k) was measured and shown.

As can be seen in FIG. 10 , it was confirmed that, in the encapsulation film according to Comparative Example 1, the moisture permeability was significantly increased from the case of bending 5,000 times with a bending radius of 5 mm. In addition, it was confirmed that the water permeability of the encapsulation film according to Comparative Example 2 was significantly increased from the case of bending 10,000 times with a bending radius of 1 mm.

11 is a graph comparing the mechanical properties of the encapsulation film according to Comparative Example 3 of the present invention, and FIG. 12 is a graph comparing the mechanical properties of the encapsulation film according to Comparative Example 4 of the present invention.

Referring to FIG. 11 , the moisture permeability of the encapsulation membrane (Bare) according to Comparative Example 3, the moisture permeability of the encapsulation membrane (3mm, 10k) according to Comparative Example 3 bent 10,000 times with a 3mm bending radius, 5 with a 1mm bending radius The moisture permeability of the encapsulation membrane (1mm, 5k) according to Comparative Example 3 bent 1,000 times, and the moisture permeability of the encapsulation membrane (1mm, 10k) according to Comparative Example 3 bent 10,000 times with a 1 mm bending radius were measured and shown.

As can be seen in FIG. 11 , it was confirmed that, in the encapsulation film according to Comparative Example 3, the moisture permeability was significantly increased from the case of bending 10,000 times with a bending radius of 3 mm.

12 , the moisture permeability of the encapsulation membrane (Bare) according to Comparative Example 4, the moisture permeability of the encapsulation membrane (3mm, 10k) according to Comparative Example 4 bent 10,000 times with a 3 mm bending radius, 5 with a 1 mm bending radius The moisture permeability of the encapsulant membrane (1mm, 5k) according to Comparative Example 4 bent 1,000 times, and the moisture permeability of the encapsulation membrane (1mm, 10k) according to Comparative Example 4 bent 10,000 times with a 1 mm bending radius were measured and shown.

As can be seen in FIG. 12 , it was confirmed that the encapsulation film according to Comparative Example 4 also significantly increased water permeability from the case of bending 10,000 times with a bending radius of 3 mm.

13 is a graph comparing mechanical properties of an encapsulation film according to Example 7 of the present invention.

Referring to FIG. 13 , the moisture permeability of the encapsulation membrane (Bare) according to Example 7, the moisture permeability of the encapsulation membrane (3mm, 10k) according to Example 7 bent 10,000 times with a 3mm bending radius, 5 with a 1mm bending radius The water permeability of the encapsulation film (1mm, 5k) according to Example 7 bent 1,000 times, and the water permeability of the encapsulation film (1mm, 10k) according to Example 7 bent 10,000 times with a 1 mm bending radius were measured and shown.

As can be seen in FIG. 13 , in the case of the encapsulation film according to Example 7, it was confirmed that the water permeability was substantially constant in various bending tests.

As a result, as can be seen in FIGS. 10 to 13 , compared to an encapsulation film composed of a single film of Sn or Si, and an encapsulation film _{having a structure in which a SnO x} single film-SiO ₂ single film is alternately stacked, SnSi _x O _y It was found that the mechanical properties of the encapsulation film according to the embodiment of the mixed film structure were remarkably improved. Accordingly, it can be seen that, when the encapsulation film according to the embodiment is applied to a flexible device, the reliability of the flexible device can be remarkably improved.

As mentioned above, although the present invention has been described in detail using preferred embodiments, the scope of the present invention is not limited to specific embodiments and should be construed according to the appended claims. In addition, those skilled in the art should understand that many modifications and variations are possible without departing from the scope of the present invention.

10: substrate
20: material film

Claims (12)

preparing a substrate;
providing a first precursor including a first element and a second precursor including a second element on the substrate; and
providing a reaction source on the substrate provided with the first precursor and the second precursor to form a material film in which the first precursor, the second precursor, and the reaction source are reacted;
The composition of the material layer is controlled according to the process conditions of the step of providing the first precursor and the second precursor.
According to claim 1,
The step of providing the first precursor and the second precursor,
providing the first precursor on the substrate;
purging the substrate provided with the first precursor for a first time;
providing a second precursor on the substrate provided with the first precursor; and
and purging the substrate provided with the second precursor for a second time period shorter than the first time period.
3. The method of claim 2,
and an increase in a content of the metal in the material layer as the supply time of the first precursor increases.
3. The method of claim 2,
In the step of purging the substrate provided with the first precursor for a first time,
and increasing the content of the metal in the material layer as the first time increases.
According to claim 1,
The step of providing the first precursor and the second precursor,
providing the second precursor on the substrate;
purging the substrate provided with the second precursor for a first time;
providing a first precursor on the substrate provided with the second precursor; and
and purging the substrate provided with the first precursor for a second time period shorter than the first time period.
6. The method of claim 5,
A method of manufacturing an encapsulation film comprising a time period for providing the first precursor is longer than a time period for providing the second precursor.
According to claim 1,
The step of providing the first precursor and the second precursor,
providing the first precursor and the second precursor together on the substrate; and
and purging the substrate provided with the first precursor and the second precursor.
According to claim 1,
The reaction source is a method of manufacturing an encapsulation film including _{oxygen plasma (O 2 plasma).}
Board; and
An encapsulation film disposed on the substrate and including a material film in which a first element, a second element, and oxygen (O) are mixed.
10. The method of claim 9,
The material film further comprises carbon (C) and nitrogen (N),
Contents of the first element and the second element in the material layer are higher than contents of the carbon (C) and the nitrogen (N).
10. The method of claim 9,
The first element includes tin (Sn), and the second element includes silicon (Si).
10. The method of claim 9,
The substrate is an encapsulation film including a flexible (flexible).

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