KR102139077B1 - Gas barrier film and method for manufacturing the same - Google Patents

Abstract

A gas barrier film and a method for manufacturing the same, comprising: a substrate; And located on the substrate, including silicon (Si), nitrogen (N), and hydrogen (H), when the content relationship of the silicon, nitrogen, and hydrogen represented by the following equation 1, satisfying the following equation 2 It may provide a gas barrier film comprising a silicon nitride film; and a method for manufacturing the same.
[Equation 1]
Si _x N _y H _z
[Equation 2]
1.0 ≤ z/y ≤ 1.4

Description

Gas barrier film and manufacturing method therefor{GAS BARRIER FILM AND METHOD FOR MANUFACTURING THE SAME}

The present invention relates to a gas barrier film and a method for manufacturing the same.

Recently, in the field of display devices such as organic light emitting diodes (OLEDs), semiconductor devices, and various devices such as solar cells, development of a flexible device using a lightweight and flexible plastic film as a substrate instead of a conventionally used plate glass has been actively developed. Is being made.

Since the plastic film substrate has a lower gas barrier performance than an inorganic substrate such as a glass substrate, research on a high performance gas barrier film for suppressing the incorporation of air or water vapor on the plastic film substrate has been actively conducted.

Various methods have been developed to satisfy such high performance, and among them, a method of cross-laminating organic and inorganic thin films on a base film is most frequently applied.

Inorganic thin films, such as aluminum oxide, silicon oxide, and silicon nitride, are used as important materials to block the gas, and by forming organic layers on one or both sides of the inorganic thin film to protect these inorganic thin films and to prevent pinholes or As such, the gas barrier performance is partially improved.

Among these, a gas barrier film including a silicon nitride film is mainly formed by a thin film encapsulation (TFE) process through an in-line deposition method of organic and inorganic materials in a manufacturing process such as OLED. When the silicon nitride film is formed, batch type sputtering or PECVD (Plasma Enhanced Chemical Vapor De position) equipment is used.

However, the conventional method of forming an encapsulation film by the TFE process is applicable to devices of a glass substrate, but is not applicable to a continuous roll-to-roll process using a flexible substrate such as a plastic film substrate, and physical properties of a thin film at low temperature film formation. Not only does this change significantly, but there is also a problem of reduced flexibility.

Accordingly, it is necessary to develop a technology capable of forming a film by a low-temperature process that does not overwhelm the plastic film substrate, and at the same time, the film-forming silicon nitride film has excellent gas barrier properties.

One aspect of the present invention is to provide a gas barrier film having excellent gas barrier properties as well as excellent optical properties such as flexibility and transparency.

One aspect of the present invention, it is possible to form a stable film without changing the physical properties of the silicon nitride film and the plastic substrate at a low temperature, by using a roll-to-roll process on the plastic film substrate to form a silicon nitride film of excellent performance as described above in large area It is intended to provide a method for manufacturing a gas barrier film.

One aspect of the invention, the substrate; And located on the substrate, and includes silicon (Si), nitrogen (N), and hydrogen (H), when the content relationship of the silicon, nitrogen, and hydrogen represented by the following equation 1, satisfying the following equation 2 It provides a gas barrier film comprising a; silicon nitride film.

[Equation 1]

Si _x N _y H _z

[Equation 2]

1.0 ≤ z/y ≤ 1.4

In Formula 1 and Formula 2, x, y, and z are ratios depending on the number of atoms of silicon, nitrogen, and hydrogen, respectively, and x+y+z=1.

The substrate may be a plastic substrate.

The silicon nitride film may further satisfy Equation 3 below.

[Equation 3]

2 ≤ [Si-H] / [N-H] ≤ 6

In the formula 3, [Si-H] is a peak area due to the Si-H bond has a peak between 2100cm ^-1 and 2200cm ^-1 of the spectrum of the silicon nitride film observed by infrared absorption spectroscopy, [NH] is Refers to the peak area due to NH bonding having the highest point between 3250 cm ^-1 and 3500 cm ^-1 .

In Equation 1, 0.3≤z≤0.4.

The silicon nitride film may have a thickness of 30 to 300 nm.

An aspect of the present invention, a plasma-enhanced chemical vapor deposition (PECVD) using silane gas (SiH ₄ ) and ammonia gas (NH ₃ ) as raw materials and microwaves as an energy source. Using a silicon nitride film to form a film on the substrate; In the step of forming the silicon nitride film, the ratio of the flow rate of the ammonia gas to the flow rate of the silane gas is 2.0 to 5.0, a method for manufacturing a gas barrier film. to provide.

The substrate may be a plastic substrate.

Hydrogen gas (H ₂ ) may not be included in the raw material.

The step of forming the silicon nitride film may be performed while transferring the substrate in a roll-to-roll manner.

In the gas barrier film manufacturing method of one aspect of the present invention, the gas barrier film produced is a substrate; And located on the substrate, and includes silicon (Si), nitrogen (N), and hydrogen (H), when the content relationship of the silicon, nitrogen, and hydrogen represented by the following equation 1, satisfying the following equation 2 It may be a gas barrier film containing a silicon nitride film;.

[Equation 1]

Si _x N _y H _z

[Equation 2]

1.0 ≤ z/y ≤ 1.4

In Formula 1 and Formula 2, x, y, and z are ratios depending on the number of atoms of silicon, nitrogen, and hydrogen, respectively, and x+y+z=1.

An aspect of the present invention provides a flexible device including the gas barrier film of the above aspect of the present invention.

One aspect of the present invention provides a gas barrier film having excellent gas barrier properties as well as excellent optical properties such as flexibility and transparency.

In one aspect of the present invention, stable film formation is possible without changing the properties of the silicon nitride film and the plastic substrate at a low temperature, and a large area roll-to-roll process can be used on the plastic film substrate to form a silicon nitride film having excellent performance as described above. Provided is a method for manufacturing a gas barrier film.

1 is FTIR measurement data of the silicon nitride film of Example 1.
2 is a gas barrier measurement data according to the ratio of hydrogen atoms and nitrogen atoms in the silicon nitride film of Examples and Comparative Examples.

Unless otherwise defined, all terms (including technical and scientific terms) used in the present specification may be used as meanings commonly understood by a person having ordinary skill in the art to which the present invention pertains. When a part of the specification "includes" a certain component, this means that other components may be further included instead of excluding other components, unless otherwise stated. Also, the singular form includes the plural form unless otherwise specified in the phrase.

In this specification, when a part such as a layer, film, region, plate, or the like is said to be “on” or “on” another part, this is not only when the other part is “directly above” but also when there is another part in the middle. Includes.

Throughout this specification, "A to B" means A to B, unless otherwise defined.

One aspect of the present invention provides a gas barrier film having excellent gas barrier properties as well as excellent mechanical properties and optical properties such as transparency.

Specifically, an aspect of the present invention, the substrate; And located on the substrate, and includes silicon (Si), nitrogen (N), and hydrogen (H), when the content relationship of the silicon, nitrogen, and hydrogen represented by the following equation 1, satisfying the following equation 2 It provides a gas barrier film comprising a; silicon nitride film.

[Equation 1]

Si _x N _y H _z

[Equation 2]

1.0 ≤ z/y ≤ 1.4

In Formula 1 and Formula 2, x, y, and z are ratios depending on the number of atoms of silicon, nitrogen, and hydrogen, respectively, and x+y+z=1.

Equation 1 shows only silicon, nitrogen, and hydrogen atoms included in the silicon nitride film, and the silicon nitride film included in the gas barrier film of one aspect of the present invention may further include unavoidable impurities mixed in the film forming process.

In Formulas 1 and 2, x, y, and z are silicon, nitrogen, and when the total amount of silicon, nitrogen, and hydrogen atoms in the silicon nitride film is 1 (ie, x+y+z=1), and It means the content of each hydrogen atom.

ckel, R. L

demann, Detailed study of the composition of hydrogenated SiNx layers for high-quality silicon surface passivation, J. Appl. Phys. 92 (2002) 2602-2609.)을 통해 계산될 수 있다. In addition, the atomic content ratio of silicon, nitrogen, and hydrogen in the silicon nitride film is, for example, [Si-H] and [Si-N] measured using FTIR (equipment name: IFS-66/S, manufacturer: Bruker), From the binding concentration of [NH], the'material balance equation' (H. M

ckel, R. L

demann, Detailed study of the composition of hydrogenated SiNx layers for high-quality silicon surface passivation, J. Appl. Phys. 92 (2002) 2602-2609.).

In the gas barrier film of one aspect of the present invention, the ratio (hydrogen atom/nitrogen atom) of the hydrogen atom content to the nitrogen atom content in the silicon nitride film deposited on the substrate satisfies 1.0 to 1.4.

By satisfying the above relationship, the content of the hydrogen atom and the nitrogen atom, gas barrier properties, mechanical flexibility, and transparency within the above range can be realized.

This was also confirmed from the examples described below, and when the content ratio of the hydrogen atom and the nitrogen atom is too small or too large, gas barrier properties and transparency may be rapidly deteriorated compared to cases in which the above range is satisfied. have.

The upper and lower limits of Equation 2 above are closer to the specific examples identified as experimental examples, and the lower limit may be more specifically 1.05, and the upper limit may be more specifically 1.35, or 1.32.

Meanwhile, in Equation 1, 25≤x≤35, 25≤y≤40, and 30≤z≤40 may be satisfied, but the present invention is not limited thereto.

In addition, as in the above numerical range, the hydrogen atom may be included in 30 to 40 atomic%, but the present invention is not necessarily limited thereto, and excellent gas barrier properties and mechanical flexibility in this range may be implemented and may be good.

In the gas barrier film of one aspect of the present invention, the substrate may be a plastic substrate. Specific and exemplary polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethylene (polyethylene, PE), polypropylene (polypropylene, PP), polystyrene (polystyrene, PS), polymethyl Methacrylic (poly(methyl methacrylate), PMMA), polyvinyl alcohol (PVA), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), polyamide (PA) , Polycarbonate (PC), polysulfone (PSF), polyether sulfone (PES), polyarylate (PAR), polyimide (PI), cyclic polyolefin (cyclic polyolefin) ), ethylene vinyl alcohol copolymer (EVAL), or a combination thereof.

The gas barrier film of one aspect of the present invention can be imparted with excellent mechanical flexibility, including a plastic substrate as a substrate.

Furthermore, since the gas barrier film of one aspect of the present invention described above can be formed on a plastic substrate in a large area through a roll-to-roll process, as in the method of manufacturing the gas barrier film of one aspect of the present invention described below. , It has the advantage of being able to produce a large area of the gas barrier film applicable to the flexible device.

In the gas barrier film of one embodiment of the present invention, the silicon nitride film may further satisfy the following equation (3).

[Equation 3]

2 ≤ [Si-H] / [N-H] ≤ 6

And in the formula 3, [Si-H] is the area of the peak due to Si-H bonds having a peak between of the spectrum of the silicon nitride film observed by infrared absorption spectrometry (FTIR) 2100cm ^-1 and 2200cm ^-1, [ NH] means the peak area by NH bonds having a peak between 3250 cm ^-1 and 3500 cm ^-1 .

The ratio of Si-H bond to NH bond in the silicon nitride film also seems to be related to the gas barrier properties, mechanical flexibility, and transparency of the gas barrier film, and the Si-H bond having the highest point between 2100 cm ^-1 and 2200 cm ^-1 When the peak area satisfies the above range compared to the NH bond peak area having the highest point between 3250 cm ^-1 and 3500 cm ^-1 , excellent gas barrier properties, mechanical flexibility, and transparency can be realized.

This was also confirmed from the examples described below, and when the ratio of the Si-H bond peak area and NH bond peak area of Equation 3 satisfies Equation 3, excellent gas barrier properties, mechanical flexibility, and transparency are implemented, but the above range When it deviated from, it was confirmed that the gas barrier properties deteriorated or the mechanical flexibility deteriorated.

The upper limit of Equation 3 may be more specifically 5.12, and the lower limit may be more specifically 2.05.

In the gas barrier film of one aspect of the present invention, the thickness of the silicon nitride film may be 30 to 300 nm, more specifically 30 to 200 nm, 30 to 150 nm, 30 to 100 nm, or 50 to 100 nm. However, the present invention is not limited thereto.

In the gas barrier film of one aspect of the present invention, the thickness of the substrate may be, for example, 50 to 1000 μm, more specifically 50 to 500 μm, or 50 to 300 μm, but the present invention is not limited thereto. The thickness may be generally employed in the art depending on the type of flexible device.

Hereinafter, a method for manufacturing a gas barrier film of one aspect of the present invention will be described.

One aspect of the present invention uses a plasma enhanced chemical vapor deposition (PECVD) using silane gas (SiH ₄ ) and ammonia gas (NH ₃ ) as raw materials and microwaves as an energy source. The step of forming a silicon nitride film on the substrate by; a ratio of the flow rate of the ammonia gas to the flow rate of the silane gas in the step of forming the silicon nitride film (ammonia gas flow rate / flow rate of the silane gas) is 2 to 5 Provided is a method of manufacturing a film for blocking phosphorus and gas.

The method for producing a gas barrier film of one aspect of the present invention, for example, 100 ℃ or less, 70 ℃ or less, more specifically 40 to 100 ℃, or excellent gas barrier on the substrate at a low temperature of 40 to 70 ℃ It is a manufacturing method that can form a silicon nitride film that exhibits properties.

Specifically, through a plasma-enhanced chemical vapor deposition method using a microwave capable of applying high energy as an energy source, a high-quality silicon nitride film can be stably formed at a low temperature without a rapid change in a silicon nitride film or a change in the properties of a plastic substrate. Can.

In the manufacturing method of the gas barrier film of one aspect of the present invention, the substrate may be a plastic substrate. Specific and exemplary polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethylene (polyethylene, PE), polypropylene (polypropylene, PP), polystyrene (polystyrene, PS), polymethyl Methacrylic (poly(methyl methacrylate), PMMA), polyvinyl alcohol (PVA), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), polyamide (PA) , Polycarbonate (PC), polysulfone (PSF), polyether sulfone (PES), polyarylate (PAR), polyimide (PI), cyclic polyolefin (cyclic polyolefin) ), ethylene vinyl alcohol copolymer (EVAL), or a combination thereof.

By forming a silicon nitride film on a plastic substrate, excellent gas barrier properties, mechanical flexibility, and transparency can be realized.

In addition, the method for manufacturing a gas barrier film of one aspect of the present invention, by employing a plasma-enhanced chemical vapor deposition method using microwaves as an energy source, enables low-temperature film formation, and when employing a plastic substrate, roll-to-roll was difficult to adopt conventionally. It is possible to adopt a process, and by forming a silicon nitride film while transferring the substrate in a roll-to-roll manner, it is possible to manufacture a gas barrier film having excellent performance in a large area.

In addition, in the method for manufacturing a gas barrier film of one aspect of the present invention, hydrogen gas (H ₂ ) may not be included in the source gas of the step of forming the silicon nitride film.

Through plasma-enhanced chemical vapor deposition employing a microwave energy source that applies high energy, it is possible to form a silicon nitride film without injecting a separate hydrogen gas. Accordingly, the content of hydrogen gas in the deposited silicon nitride film is increased unnecessarily. It is possible to prevent the problem of deterioration of gas barrier properties and flexibility.

On the other hand, in the method for producing a gas barrier film of one aspect of the present invention, the ratio of the flow rate of the ammonia gas to the flow rate of the silane gas in the step of forming the silicon nitride film (ammonia gas flow rate / flow rate of the silane gas) is 2 It may be from 5.

By adjusting the flow rate ratio of the silane gas and the ammonia gas, the hydrogen atom and nitrogen atom content ratio in the silicon nitride film to be formed and the ratio of the above-described Si-H bond peak area and N-H bond peak area can be adjusted.

In the manufacturing method of the gas barrier film of one aspect of the present invention, when the ratio of the flow rate of the ammonia gas to the flow rate of the silane gas satisfies the above range, the above gas barrier properties, mechanical flexibility, and excellent gas barrier properties for transparency Films can be produced.

If it is outside the above range, it is preferable to satisfy the above range because the gas barrier properties, mechanical flexibility, and transparency of the gas barrier film to be produced may be poor.

When the method for manufacturing the gas barrier film of one aspect of the present invention is further elaborated, argon gas may be further injected as an excitation gas for plasma excitation of silane gas and ammonia gas as raw material gases. However, the present invention is not limited thereto.

The injection flow rates of the silane gas and the ammonia gas may be adjusted in a range that satisfies the above-described bilateral flow rate ratio in the range of 1 to 1000 sccm, respectively, but this is not limited thereto as an example.

The injection flow rate of the gas for excitation may also be 1 to 1000 sccm, but this is only an example and the present invention is not limited thereto.

An aspect of the present invention provides a flexible device including the gas barrier film of one aspect of the present invention described above. The flexible device may be, for example, a flexible display such as a flexible OLED, but is not limited thereto.

Hereinafter, preferred examples and comparative examples of the present invention will be described. However, the following examples are only preferred examples of the present invention, and the present invention is not limited to the following examples.

[ Example One]

Roll-to-roll ECR-PECVD equipment using microwave power (device name: pilot roll-to-roll PECVD Roll coat 500 system, manufacturer: Roth and Rau AG) was used. It is divided into a load lock) chamber and a process chamber for forming a thin film. As a base film, an optical polyethylene terephthalate (PET) film (SKC Co., Ltd.) having a thickness of 100 μm was used. Roll-to-roll process to meet the plasma as it passes through the drum roll of PET film, the process chamber from unwinder of the load lock chamber, having a structure into the rewinder of the load lock chamber again, the film forming process pressure in the process chamber is 8x10 ^{- It} is precisely maintained at ² mbar. A uniform silicon nitride thin film was formed on the PET film through a reaction by applying a microwave power of 2.46 GHz to form a high-density plasma and introducing raw materials gases. More specific film formation conditions are as follows.

Process pressure: 8*10 ^-2 mbar

Power source: 2.46GHz microwave generator

Process power: 1.5 kW

Carrier gas flow rate: Ar= 900 sccm

Total process reaction gas flow rate: SiH ₄ + NH ₃ = 930 sccm

Reaction gas flow rate ratio: R = NH ₃ /SiH ₄ = 3.0

Film thickness: 100 nm

Process temperature: 40℃

[ Example 2]

A silicon nitride film was formed in the same manner as in Example 1, except that the flow rate of the processing gas was as follows.

Reaction gas flow rate ratio: R = NH ₃ /SiH ₄ = 2.0

[ Example 3]

A silicon nitride film was formed in the same manner as in Example 1, except that the flow rate of the processing gas was as follows.

Reaction gas flow rate ratio: R = NH ₃ /SiH ₄ = 2.5

[ Example 4]

A silicon nitride film was formed in the same manner as in Example 1, except that the flow rate of the processing gas was as follows.

Reaction gas flow rate ratio: R = NH ₃ /SiH ₄ = 5.0

[ Comparative example One]

A silicon nitride film was formed in the same manner as in Example 1, except that the flow rate of the processing gas was as follows.

Reaction gas flow rate ratio: R = NH ₃ /SiH ₄ = 7.0

[ Comparative example 2]

A silicon nitride film was formed in the same manner as in Example 1, except that the flow rate of the processing gas was as follows.

Reaction gas flow rate ratio: R = NH ₃ /SiH ₄ = 9.0

[ Comparative example 3]

A silicon nitride film was formed in the same manner as in Example 1, except that the flow rate of the processing gas was as follows.

Reaction gas flow rate ratio: R = NH ₃ /SiH ₄ = 1.0

[ Comparative example 4]

A silicon nitride film was formed in the same manner as in Example 1, except that the flow rate of the processing gas was as follows.

Reaction gas flow rate ratio: R = NH ₃ /SiH ₄ = 1.5

[ Experimental Example 1]-atomic concentration analysis and gas permeability measurement

For the silicon nitride films of the gas barrier films prepared in Examples 1 to 4 and Comparative Examples 1 to 4, FTIR (equipment name: IFS-66/S, manufacturer: Bruker) spectroscopy was performed, and silicon from each binding concentration was used. The ratio of hydrogen and nitrogen atom content in the nitride film was determined. The FTIR spectrum was analyzed with the background of the substrate removed and normalized to the thickness measured by ellipsometry.

1 shows the results of FTIR analysis for Example 1. In Examples 2 to 4 and Comparative Examples 1 to 4, peaks of the same shape were also observed.

In atomic concentration analysis, N-N and H-H bonds were neglected because they existed in very small amounts in the amorphous silicon nitride film.

In addition, for the gas barrier films prepared in Examples 1 to 4 and Comparative Examples 1 to 4, water vapor transmission rate (WVTR) was measured.

WVTR was performed using TECHNOLOX's DELTAPERM-2 (condition: 40° C., relative humidity 90%, effective sample area 100 cm ² ), and was calculated by detecting a change in minute pressure due to gas permeation.

The ratio of hydrogen and nitrogen atom content (H/N) in the silicon nitride film measured above and WVTR measurement results are shown in FIG. 2.

As shown in Figure 2, in the case of Examples 1 to 4 in which the content ratio (H/N) of hydrogen and nitrogen atoms in the silicon nitride film was 1 to 1.4, the WVTR value was very small, showing excellent gas barrier properties, and hydrogen and nitrogen. In the case of comparative examples in which the content ratio of atoms was less than 1 or greater than 1.4, the WVTR value increased more than 4 times sharply compared to the examples.

[ Experimental Example 2] - FTIR [ Si -H]/[N-H] Peak area Ratio analysis

The silicon nitride film of the gas barrier film prepared in Examples 1 to 4 and Comparative Examples 1 to 4, based on the results of FTIR analysis measured in Experimental Example 1, has a peak between 2100cm ^-1 and 2200cm ^-1 Si- Table 1 summarizes the ratio ([Si-H]/[NH]) of the peak area due to the NH bond having the highest point between the area of the peak by H bond and 3250cm ^-1 and 3500cm ^-1 .

In the case of Examples 1 to 4 showing very good gas barrier performance, the peak area ratio was about 2 to 6.

On the other hand, in the case of Comparative Examples 1 and 2, the peak area ratio was less than 2, but in this case, as shown in FIG. 2, the WVTR increased rapidly, and thus the gas barrier performance as a thin film was hardly realized.

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 [Si-H]/[N-H] 2.71 4.09 5.12 2.05 1.05 0.932 8.53 6.34

[ Experimental Example 3]-Mechanical flexibility evaluation

The gas barrier films of Examples 1 to 4 and Comparative Examples 1 to 4 were repeated 10,000 times in the inward direction at a small radius of curvature of 10 mm, and then measured for WVTR in the same manner as in Experimental Example 1, to bend. Before and after WVTR increase rate was measured, and it is shown in Table 2.

In the case of Examples, the increase rate of WVTR was about 100% or less (ie, 2 times or less), but in the case of Comparative Examples 3 and 4 in which the ratio of the [Si-H]/[NH] peak area was greater than 6, the WVTR was 500 after the bending experiment. The mechanical flexibility was not very good due to the sharp rise of more than% (ie, 6 times or more).

Comparative Examples 3 and 4 have relatively good gas barrier properties compared to Comparative Examples 1 and 2, but when the ratio of the [Si-H]/[NH] peak area is too large, mechanical flexibility deteriorates, and performance is poor in terms of mechanical flexibility. It is confirmed to be.

Thus, when the content ratio (H/N) of hydrogen and nitrogen atoms in the silicon nitride film satisfies 1 to 1.4, and at the same time the ratio of the peak area of [Si-H]/[NH] is 2 to 6, excellent gas barrier It can be seen that performance and mechanical flexibility are realized simultaneously.

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 WVTR growth rate (%) 73 92 85 70 68 102 730 540

[ Experimental Example 4]-Transparency evaluation

The average transmittance (including the PET substrate) at a wavelength of 380 to 780 nm was measured using a spectrophotometer (device name: U4100, manufacturer: Hitachi), and haze was measured using a haze meter (device name: .NDH5000, manufacturer: Nippon Denshoku). It was measured.

The transmittance was measured by JIS K7361 method, haze was measured by JIS K7136 method, and the measurement results are summarized in Table 3.

In the case of Examples, the light transmittance was excellent compared to Comparative Examples.

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Transmittance (%) 87.9 88.9 88.3 87.2 86.1 86.0 84.8 86.3 Haze (%) 1.15 1.05 1.14 1.13 1.14 1.10 1.2 1.08

Claims (11)

Board; And
Located on the substrate, including silicon (Si), nitrogen (N), and hydrogen (H), when the relationship between the content of the silicon, nitrogen, and hydrogen is represented by the following Equation 1, Equations 2 and 3 Satisfactory silicon nitride film; containing gas barrier film.
[Equation 1]
Si _x N _y H _z
[Equation 2]
1.0 ≤ z/y ≤ 1.4
(In Equations 1 and 2, x, y, and z are ratios depending on the number of atoms of silicon, nitrogen, and hydrogen, respectively, and x+y+z=1.)
[Equation 3]
2 ≤ [Si-H] / [NH] ≤ 6
(And in the formula 3, [Si-H] is the area of the peak due to Si-H bonds having a peak between the spectrum of 2100cm ^-1 and 2200cm ^-1 of the silicon nitride film observed by infrared absorption spectroscopy, [NH] Is the peak area due to NH bonds having the highest point between 3250 cm ^-1 and 3500 cm ^-1 .) In claim 1,
The substrate is a plastic substrate, a gas barrier film. delete In claim 1,
In the formula 1, 0.3≤z≤0.4 gas barrier film. In claim 1,
A gas barrier film having a thickness of 30 to 300 nm of the silicon nitride film. Silicon nitride film on the substrate using plasma enhanced chemical vapor deposition (PECVD) using silane gas (SiH ₄ ) and ammonia gas (NH ₃ ) as raw materials and microwaves as an energy source The step of forming a; includes,
The method for producing a gas barrier film according to claim 1, wherein a ratio of a flow rate of silane gas to a flow rate of ammonia gas is 2 to 5 in the step of forming the silicon nitride film. In claim 6,
The substrate is a plastic substrate, a method for manufacturing a gas barrier film. In claim 6,
Method for producing a gas barrier film that does not contain hydrogen gas (H ₂ ) in the raw material. In claim 6,
The method of forming the silicon nitride film is performed while transferring the substrate in a roll-to-roll manner. delete A flexible device comprising the gas barrier film of claim 1.

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