BARRIER FILM

Abstract

Provided is a barrier film comprising a base layer, and an inorganic layer including Si, N, and O, and including a first region and a second region, which have different elemental contents (atomic %) of Si, N, and O from each other as measured by XPS, wherein the film has a water vapor transmission rate of 5.0×10.sup.−4 g/m.sup.2.Math.day or less as measured under conditions of a temperature of 38° C. and 100% relative humidity after being stored at 85° C. and 85% relative humidity conditions for 250 hours, or wherein the inorganic layer has a compactness expressed through an etching rate of 0.17 nm/s in the thickness direction for an Ar ion etching condition to etch Ta.sub.2O.sub.5 at a rate of 0.09 nm/s. The barrier film has excellent barrier properties and optical properties and can be used for electronic products that are sensitive to moisture and the like.

Claims

1. A barrier film, comprising: a base layer; and an inorganic layer including Si, N, and O, and including a first region and a second region, which have different elemental contents (atomic %) of Si, N, and O from each other as measured by XPS, wherein the film has a water vapor transmission rate of 5.0×10.sup.−4 g/m.sup.2.Math.day or less as measured under conditions of a temperature of 38° C. and 100% relative humidity after being stored at 85° C. and 85% relative humidity conditions for 250 hours.

2. The barrier film according to claim 1, wherein the inorganic layer has a compactness expressed through an etching rate of 0.17 nm/s or less in the thickness direction for an Ar ion etching condition to etch Ta.sub.2O.sub.5 at a rate of 0.09 nm/s.

3. A barrier film, comprising: a base layer; and an inorganic layer including Si, N, and O, and including a first region and a second region, which have different elemental contents (atomic %) of Si, N, and O from each other as measured by XPS, wherein the inorganic layer has a compactness expressed through an etching rate of 0.17 nm/s or less in the thickness direction for an Ar ion etching condition to etch Ta.sub.2O.sub.5 at a rate of 0.09 nm/s.

4. The barrier film according to claim 2, wherein the first region is in a position closer to the base layer than the second region.

5. The barrier film according to claim 2, wherein the first region satisfies the relationship: O content>Si content>N content.

6. The barrier film according to claim 5, wherein the O content of the first region is in a range of 50 to 65 atomic %, the Si content of the first region is in a range of 35 to 45 atomic %, and the N content of the first region is in a range of 1 to 15 atomic %.

7. The barrier film according to claim 6, wherein the first region has a ratio (a/b) of the O content (a) to the Si content (b) in a range of 1.1 to 1.9.

8. The barrier film according to claim 6, wherein the second region satisfies the relationship: Si content>N content>O content.

9. The barrier film according to claim 8, wherein the Si content of the second region is in a range of 45 to 60 atomic %, the N content of the second region is in a range of 20 to 35 atomic %, and the O content of the second region is in a range of 10 to 30 atomic %.

10. The barrier film according to claim 9, wherein the N content in the second region is greater than the N content in the first region.

11. The barrier film according to claim 9, wherein the difference between the highest value of the Si content in the second region and the highest value of the O content in the first region is 15 atomic % or less.

12. The barrier film according to claim 1, wherein the inorganic layer is obtained by plasma-treating polysilazane having a unit of Formula 1 below: ##STR00004## wherein, R.sup.1, R.sup.2 and R.sup.3 are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkylsilyl group, an alkylamino group or an alkoxy group.

13. The barrier film according to claim 2, comprising: the base layer; a planarizing layer; and the inorganic layer sequentially, wherein the planarizing layer has an average surface roughness (Rt) of the surface facing the inorganic layer in a range of 15 to 45 nm.

14. The barrier film according to claim 13, wherein the first region has a thickness of twice or more the average surface roughness (Rt) of the planarizing layer.

15. An electrical or electronic element comprising the barrier film according to claim 1.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0103] FIG. 1 shows the XPS analysis results for the inorganic layer of Example 4.

[0104] FIG. 2 is a view obtained by TEM analyzing the cross section of the barrier film of Example 4.

[0105] FIG. 3 shows, in connection with Experimental Example 2, the relationship between the thickness of the first region and the water vapor transmission rate measured under Condition 2.

EXAMPLES

[0106] Hereinafter, the barrier film of the present application will be described through examples according to the present application and comparative examples, but the scope of the present application is not limited by the following examples.

[0107] Measuring Method [0108] Water vapor transmission rate: Using MOCON Aquatron II, the water vapor transmission rate of the produced barrier film was measured at 38° C. and 100% relative humidity conditions (water vapor transmission rate in Condition 1). Separately, the barrier film was stored at 85° C. and 85% relative humidity conditions for 250 hours, and the water vapor transmission rate of the barrier film was again measured at 38° C. and 100% relative humidity conditions (water vapor transmission rate in Condition 2). [0109] Etching rate and elemental content analysis: The element distribution analysis in the depth (thickness) direction from the surface of the inorganic material layer to the base material direction was performed while gradually removing the inorganic layer using Ar ions. As the etching conditions, an Ar ion setting with an etching rate of 0.09 nm/s for Ta.sub.2O.sub.5 as the reference material was used. In addition, the elemental contents of the inorganic layer were analyzed using XPS (X-ray photoelectron spectroscopy) (C can be detected as an impurity derived from the base material).

Experimental Example 1

[0110] The thickness, etching rate, and water vapor transmission rate (Condition 1) of the barrier film produced as described below were measured, and the results were described in Table 1.

Example 1

[0111] A planarizing layer having a thickness of 1 μm was laminated on a PET (poly(ethylene terephthalate)) film (a product from Teijin Co., Ltd.) having a thickness of about 50 μm, and an inorganic material layer was formed on the planarizing layer. The specific process is as follows. [0112] Formation of planarizing layer: A composition comprising 2 ratios by weight of a photocuring initiator to a mixture of fluorine-based acrylate HR6060:PETA (pentaerythritol triacrylate):DPHA (dipentaerythritol hexaacrylate) in a content (weight) ratio of 80:10:10 was diluted in PGME (propylene glycol methyl ether) to 25% to prepare a coating liquid for a planarizing layer. The coating liquid was applied onto a PET film as a base material using a Mayer bar, and dried at 100° C. for 5 minutes. Subsequently, the coating layer was irradiated with ultraviolet rays at 0.6 J/cm.sup.2 by a mercury lamp, and cured to form a planarizing layer.

[0113] Formation of inorganic coating layer (1): Polysilazane was diluted to 3.7% with Merck's NL grade dibutylether, coated on the planarizing layer using a Mayer bar, and then dried at 100° C. for 5 minutes. A plasma treatment was performed on the polysilazane coating layer under the following conditions, and an inorganic coating layer was formed. Regarding the concentration of the diluted polysilazane, % means the weight ratio of the total solid content. [0114] Pressure 250 mTorr (flow rate on the basis of sccm atmosphere of Ar:O.sub.2:H.sub.2O=1.5:1:1) [0115] Distance between polysilazane coated surface and electrode 25 mm [0116] Power density: supply of DC power 0.8 W/cm.sup.2 for 25 seconds

Example 2

[0117] On the inorganic coating layer (1) manufactured in Example 1, a polysilazane layer was further formed by using a coating liquid having a silazane concentration of 1%, and the plasma treatment was performed under the same conditions as in Example 1 to further laminate an inorganic coating layer (2).

Example 3

[0118] On the inorganic coating layer (1) manufactured in Example 1, a polysilazane layer was further formed by using a coating liquid having a silazane concentration of 2.4%, and the plasma treatment was performed under the same conditions as in Example 1 to further laminate an inorganic coating layer (2-1).

Example 4

[0119] On the inorganic coating layer (1) manufactured in Example 1, a polysilazane layer was further formed by using a coating liquid having a silazane concentration of 3.7%, and the plasma treatment was performed under the same conditions as in Example 1 to further laminate an inorganic coating layer (2-2).

Example 5

[0120] A barrier film comprising a base layer/a planarizing layer/an inorganic coating layer (1-1) was produced in the same method as in Example 1, except that upon producing the inorganic coating layer, a coating liquid having a silazane concentration of 2.4% was applied on the planarizing layer and the plasma treatment conditions were changed as follows. Thereafter, a coating liquid having a silazane concentration of 2.4% was applied onto the inorganic coating layer (1-1), and the plasma treatment was performed under the following conditions to produce a barrier film comprising the base layer/the planarizing layer/the inorganic coating layer (1-1)/the inorganic coating layer (2-3). [0121] Pressure 150 mTorr (flow rate on the basis of sccm atmosphere of Ar:O.sub.2:H.sub.2O=1.5:1:1) [0122] Distance between polysilazane coated surface and electrode 40 mm [0123] Power density: supply of DC power 0.45 W/cm.sup.2 for 45 seconds

Comparative Example 1

[0124] A barrier film was produced in the same manner as in Example 1, except that the polysilazane solution diluted to 4.5% was used and the plasma conditions were changed as follows. [0125] Pressure 100 mTorr (flow rate on the basis of sccm atmosphere of Ar: 02=1:1) [0126] Distance between polysilazane coated surface and electrode 10 mm [0127] Power density: supply of DC power 0.3 W/cm.sup.2 for 65 seconds

Comparative Example 2

[0128] A barrier film was produced in the same method as in Comparative Example 1, except that the polysilazane solution diluted to 4.9% was used and the distance from the electrode was 175 mm.

TABLE-US-00001 TABLE 1 Inorganic layer (first Water vapor region + second region) Second region transmission rate Thickness Etching Etching Etching Thickness under Condition 1 (nm) time (s) rate (nm/s) time (s) (nm) (×10.sup.−4 g/m.sup.2 .Math. day) Example 1 150 925 0.162 105 17 7.0 2 185 1,180 0.157 380 57 2.3 3 215 1,310 0.164 540 86 <0.5 4 250 1,600 0.156 800 125 <0.5 5 165 1,000 0.165 630 100 <0.5 Comparative 1 180 700 0.257 180 46 23.9 Example 2 200 760 0.263 130 34 12.0 * The thickness of the second region was obtained by multiplying ‘the etching time for the second region distinguished through the XPS analyses’ and ‘the etching rate for the inorganic layer.’

[0129] As in Table 1, it can be seen that Examples comprising the inorganic layer satisfying an etching rate of 0.17 nm/s or less have very low water vapor transmission rates relative to Comparative Examples which do not satisfy the etching rate. In particular, in can be confirmed that in the case of Example 1 of the present application, the thickness of the inorganic layer is thinner than those of Comparative Examples, but the excellent water vapor transmission rate can be ensured. This means that the inorganic layers of the barrier films in Examples are denser than the inorganic layers of the barrier films in Comparative Examples. In addition, the 4.9% silazane solution was used when forming the barrier film of Comparative Example 2 and the 2.4% silazane solution was used twice when forming the barrier film of Example 5, whereby the concentrations of the silazane solutions were almost similar (the concentration of Comparative Example was higher), but it can be seen that the difference in water vapor transmission rate occurred. This suggests that the compactness of the film is not due to the concentration of the coating solution.

[0130] Under the premise that they have similar compactness degrees, it is common that if the thickness of the layer increases, the barrier properties to gas or moisture increase (see water vapor transmission rates of Comparative Examples 1 and 2). In this regard, comparing Example 2 with Example 5, it can be seen that the water vapor transmission rate of Example 5 having a lower thickness is lower. This is because the thickness of the second region, which is a high nitrogen concentration region, is larger in the film of Example 5. This is also confirmed when comparing the thicknesses of the second regions of Examples 1 to 5. That is, like the etching rate for the reference conditions is 0.17 nm/s or less, it can be confirmed that under the premise that the compactness of the inorganic layer identified through the etching rate is ensured, the thicker the second region, which is a high nitrogen concentration region, the water vapor transmission rate is improved.

[0131] On the other hand, the second regions of the films in Examples 3 and 5 have been formed equally from the 2.4% silazane solution, but the second regions have different thicknesses. That is, by appropriately adjusting the above-mentioned conditions upon the plasma treatment, the thickness of the second region, which is a high nitrogen concentration region, can be increased and the water vapor transmission rate of the barrier film can be more improved.

Experimental Example 2

[0132] The thickness, etching rate, and water vapor transmission rate (Condition 1 and Condition 2) of the barrier film prepared as produced below were measured, and the results were described in Tables 2 and 3.

Example 6

[0133] A planarizing layer having a thickness of 1 μm was laminated on a PET (poly(ethylene terephthalate)) film (a product from Teijin Co., Ltd.) having a thickness of about 50 and an inorganic material layer was formed on the planarizing layer. The specific process is as follows.

[0134] Formation of planarizing layer: A composition comprising 2 ratios by weight of a photocuring initiator to a mixture of fluorine-based acrylate HR6060:PETA (pentaerythritol triacrylate):DPHA (dipentaerythritol hexaacrylate) in a content (weight) ratio of 80:10:10 was diluted in PGME (propylene glycol methyl ether) to 25% to prepare a coating liquid for a planarizing layer. The coating liquid was applied onto a PET film as a base material using a Mayer bar, and dried at 100° C. for 5 minutes. Subsequently, the coating layer was irradiated with ultraviolet rays at 0.6 J/cm.sup.2 by a metal lamp, and cured to form a planarizing layer. 10 different regions having an area of about 100 μm.sup.2 of the surface of the planarizing layer were designated, and the height difference between the highest part and the lowest part in each region was obtained by using Optical Profiler, and an average surface roughness value (Rt) of 34 nm (standard deviation 5.8 nm) was obtained.

[0135] Formation of inorganic coating layer (1′): Polysilazane was diluted to 3.7% with Merck's NL grade dibutylether, coated on the planarizing layer using a Mayer bar, and then dried at 100° C. for 5 minutes. A plasma treatment was performed on the polysilazane coating layer under the following conditions, and an inorganic coating layer was formed. [0136] Pressure 250 mTorr (flow rate on the basis of sccm atmosphere of Ar:O.sub.2:H.sub.2O=1.5:1:1) [0137] Distance between polysilazane coated surface and electrode 25 mm [0138] Power density: supply of DC power 0.8 W/cm.sup.2 for 25 seconds

[0139] Formation of inorganic coating layer (2′): On the inorganic layer (1′), a polysilazane layer was further formed by using a coating liquid having a silazane concentration of 3.7%, and the plasma treatment was performed under the same conditions as in the formation of the inorganic coating layer (1′) to further laminate an inorganic coating layer (2′).

Example 7

[0140] A barrier film was produced in the same method as in Example 6, except that the concentrations of silazane used upon forming the inorganic coating layer (1′-1) and the inorganic coating layer (2′-1) were both 2.4%.

Reference Example 1

[0141] A barrier film was produced in the same method as in Example 6, except that the concentrations of silazane used upon forming the inorganic layer (1′-2) and the inorganic layer (2′-2) were 1.1% and 3.7%, respectively.

Reference Example 2

[0142] A barrier film was produced in the same method as in Example 6, except that the concentrations of silazane used upon forming the inorganic layer (1′-3) and the inorganic layer (2′-3) were 1.8% and 3.1%, respectively.

TABLE-US-00002 TABLE 2 Inorganic layer (first Water vapor region + second region) First region transmission rate Thickness Etching Etching Etching Thickness (×10.sup.−4 g/m.sup.2 .Math. day) (nm) time (s) rate (nm/s) time (s) (nm) Condition 1 Condition 2 Example 6 250 1,600 0.156 800 125 <0.5 <0.5 Reference Example 1 150 950 0.158 220 35 0.8 44 * The thickness of the first region was obtained by multiplying ‘the etching time performed until the interface between the first region and the second region distinguished through the XPS analyses appeared’ and ‘the etching rate for the inorganic layer.’

TABLE-US-00003 TABLE 3 Inorganic layer (first Water vapor region + second region) First region transmission rate Thickness Etching rate Thickness (×10.sup.−4 g/m.sup.2 .Math. day) (nm) (nm/s) (nm) Condition 1 Condition 2 Example 7 170 <0.17 nm/s 78 <0.5 4.4 Reference Example 2 160 <0.17 nm/s 50 1.1 53

[0143] The barrier films of Examples 6 and 7 have each a first region having a thickness of twice or more relative to 34 nm which is the surface roughness of the planarizing layer. On the other hand, Reference Example 1 is a barrier film, in which the surface roughness of the planarizing layer and the thickness of the first region are almost similar. Then, the first region of the barrier film in Reference Example 2 has a larger thickness than the surface roughness of the planarizing layer, but its size is less than twice. Inferred from the results of Tables 2 and 3, it is believed that when the first region does not have a thickness of about twice or more the surface roughness of the planarizing layer, the inorganic layer cannot be stably formed even under the plasma treatment, and upon the storage, some of the inorganic layer are damaged and simultaneously, the water vapor transmission rate under Condition 2 becomes poor, as confirmed in Table 2.

[0144] Particularly, it can be seen from Example 7 and Reference Example 2 that the total concentrations of the silazane solutions used in forming the inorganic layers are 4.8% and 4.9%, respectively, which are similar, but the difference in water vapor transmission rates (Condition 2) after high temperature/high humidity storage is very large. This means that considering the surface roughness of the planarizing layer, the thickness of the first region formed on the planarizing layer should be sufficiently secured.