TWI681870B - Method for manufacturing water-vapor barrier structure, water-vapor barrier structure - Google Patents

Abstract

A method for manufacturing a water-vapor barrier structure, comprising the following steps：(a) forming a light-transmitting zinc tin oxide film having a thickness ranging from 25 to 100 nm on a light- transmitting substrate to obtain a first laminate； (b) forming a light-transmitting metal oxide film on the surface of said light- transmitting zinc tin oxide film of said first laminate to obtain a second laminate, and causing the chromaticity of said light-transmitting metal oxide and the chromaticity of a first laminate is complementary color to each other, wherein said light-transmitting metal oxide film is selected from zinc oxide or tin oxide and has a thickness ranging from 10 to 180 nm; and (c) forming a parylene film having a thickness ranging from 40 to 550 nm on the surface of said light-transmitting metal oxide film of said second laminate. The present invention also provides a water-vapor barrier structure.

Description

Method for manufacturing water vapor barrier structure, water vapor barrier structure

The invention relates to a laminate, in particular to a method for manufacturing a water vapor barrier structure and a water vapor barrier structure.

An organic light-emitting display device (organic light-emitting display device) is a self-luminous display device including an organic light-emitting diode (OLED). The organic light-emitting display device has self-luminous properties, a wide viewing angle, and high contrast The advantages of low power consumption, high reaction rate, full colorization and simple manufacturing process are the main development of today's display device products. However, the stability and longevity of organic light-emitting display devices are the biggest challenges of technological development. The key to determining the life span of an organic light-emitting display device is to prevent the organic light-emitting materials and metal electrodes therein from being deteriorated by the influence of oxygen and moisture.

On the other hand, display device products are changing with each passing day. Thick glass substrates are gradually replaced by plastic substrates that are light, thin, flexible and highly plastic. Flexible organic light-emitting display devices are the mainstream development today. However, the disadvantage of the plastic substrate is that it has a high oxygen permeability and water vapor transmission rate, which easily causes moisture and oxygen in the air to penetrate into the interior of the organic light-emitting display device through the plastic substrate, resulting in organic light-emitting materials and metal electrodes Degradation and aging, thereby reducing the stability and product life of the flexible organic light-emitting display device.

In order to improve the stability and product life of the flexible organic light-emitting display device, a water vapor barrier element will be provided on the plastic substrate of the flexible organic light-emitting display device, thereby blocking the penetration of external moisture and oxygen to the flexible Of the organic light-emitting display device. Generally, the water vapor barrier element is designed as a composite membrane structure with multiple layers of thin films of different materials stacked on top of each other to achieve the effect of blocking moisture and oxygen. However, these films have colors due to their material properties. Therefore, when the water vapor barrier element is disposed on the path of white light emitted by the organic light-emitting diode, the color of the white light emitted by the organic light-emitting diode will be affected. The interference of the color of the water vapor barrier element causes the white light passing through the water vapor barrier element to bear the color of the water vapor barrier element.

Therefore, in addition to the good water vapor barrier effect, the water vapor barrier element needs to further have the characteristic of not disturbing the color of the white light emitted by the organic light emitting diode.

Therefore, the first object of the present invention is to provide a method for manufacturing a water vapor barrier structure, the prepared water vapor barrier structure has light permeability and white light emitted from an organic light emitting diode Will not interfere with the color of the white light when on the road.

Therefore, the manufacturing method of the water vapor barrier structure of the present invention includes the following steps: (a) forming a layer of light-transmitting zinc-tin oxide film on a light-transmitting substrate to obtain a first laminate, and the light-transmitting The thickness of the zinc-tin oxide film is in the range of 25 to 100 nm; (b) A light-transmitting metal oxide film is formed on the surface of the light-transmissive zinc-tin oxide film of the first laminate to obtain a second laminate, and The chromaticity of the light penetrating metal oxide film and the chromaticity of the first laminate are complementary colors, wherein the light penetrating metal oxide film is selected from zinc oxide or tin oxide, and the light penetrating metal oxide The thickness of the film is in the range of 10 to 180 nm; and (c) a parylene-based film is formed on the surface of the second laminate in the light penetrating metal oxide film, and the thickness of the parylene-based film is in the range 40 to 550 nm.

Therefore, the second object of the present invention is to provide a water vapor barrier structure.

Therefore, the water vapor barrier structure of the present invention includes: a light penetrating substrate; and at least one water vapor barrier element, disposed on the light penetrating substrate and including: a layer of light penetrating zinc tin oxide film, and the The thickness of the light penetrating zinc tin oxide film is 25 to 100 nm. A layer of light penetrating metal oxide film is disposed on the light penetrating zinc tin oxide film and is selected from zinc oxide or tin oxide, and the light penetrating The thickness of the metal oxide film ranges from 10 to 180 nm, and a parylene-based film is provided on the light-transmitting zinc-tin oxide film, and the thickness of the parylene-based film ranges from 40 to 550 nm, Wherein, the chromaticity formed by the light penetrating substrate and the light penetrating zinc-tin oxide film and the chromaticity of the light penetrating metal oxide film are complementary colors to each other.

The effect of the present invention lies in: in the manufacturing method of the water vapor barrier structure of the present invention, by forming a light-transmitting zinc-tin oxide film, a light-transmitting metal oxide film and a parylene-based film having a specific thickness range, and making The chromaticity of the light penetrating metal oxide film and the chromaticity of the first laminate are complementary to each other. The formed water vapor barrier structure has light penetrability and the white light emitted by the organic light emitting diode During the course, the water vapor barrier structure will not interfere with the color of the white light, while avoiding the white light with the color of the water vapor barrier structure.

The content of the present invention will be described in detail below:

The manufacturing method of the water vapor barrier structure of the present invention includes the following steps: (a) forming a layer of light penetrating zinc-tin oxide film on a flexible substrate to obtain a first laminate; (b) in the first The light penetrating through the surface of the zinc-tin oxide film of the laminate forms a light penetrating metal oxide film to obtain a second laminate, and the chromaticity of the light penetrating metal oxide film and the chromaticity of the first laminate Complementing each other, the light penetrating metal oxide film is selected from zinc oxide or tin oxide; and (c) forming a parylene film on the surface of the light penetrating metal oxide film of the second laminate.

In the manufacturing method of the water vapor barrier structure, for example, when the chromaticity of the first laminate is blue, and the complementary color of blue is yellow, zinc oxide with a yellow color is selected to form the light Through metal oxide film. When the chromaticity of the first laminate is yellow, and the complementary color of yellow is blue, tin oxide with a blue color is selected to form the light penetrating metal oxide film. When the water vapor barrier structure is disposed on the path of the white light emitted by the organic light-emitting diode, the white light contacts the first lamination member that is blue, and part of the yellow light in the white light is absorbed so that it passes through the The white light of the first laminate is slightly bluish, and then, the light that touches yellow passes through the metal oxide film, and part of the blue light in the bluish white light is absorbed, so that the white light passing through the metal oxide film through the light Does not carry the color of the water vapor barrier structure. In another aspect, the white light is in contact with the yellow first laminate, and part of the blue light in the white light is absorbed, so that the white light passing through the first laminate is slightly yellow, and then, in contact with the blue When the light penetrates the metal oxide film, part of the yellow light in the yellowish white light will be absorbed, so that the white light passing through the metal oxide film through the light will not have the color of the water vapor barrier structure. Therefore, as a whole, after the white light passes through the water vapor barrier structure, it is still substantially white light without being disturbed by the color of the water vapor barrier structure.

The material of the light penetrating substrate is not particularly limited, such as but not limited to: polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyvinylidene chloride (PVDC), polyimide resin (polyimide resin), ethylene-vinyl alcohol copolymer (EVOH), polyamide (PA), etc. Preferably, the light-transmitting substrate is selected from polyethylene terephthalate, polyethylene naphthalate or a combination thereof. The surface of the light penetrating substrate can be selectively modified. The specific method of the modification is, for example, but not limited to, modifying the surface of the light penetrating substrate with oxygen plasma. The thickness of the light penetrating substrate is not particularly limited, such as but not limited to 50 to 200 mm. The light penetrating substrate is, for example but not limited to, the light penetrating flexible substrate.

In some embodiments of the present invention, in this step (a), a tin target and a zinc target are subjected to reactive sputtering in the presence of a reactive gas to form the light penetrating zinc tin oxide film, The reaction gas is oxygen. The physical vapor deposition technique for performing the reactive sputtering is, for example but not limited to, RF sputtering, DC sputtering, magnetron sputtering, or any combination thereof. In order to make the light penetrating zinc tin oxide film have better flatness and density, so that the water vapor barrier structure has better water vapor barrier capability, preferably, in this step (a), The sputtering power range of the tin target and the zinc target is 20 to 30 watts, respectively, and the flow rate of the oxygen is 20 to 50 sccm.

In some embodiments of the present invention, the arithmetic mean deviation Ra of the surface roughness distribution of the light penetrating zinc tin oxide film is in the range of 1.48 to 2.18 nm; the maximum height of the surface roughness of the light penetrating zinc tin oxide film The range of Rz is 13.45 to 21.14 nm.

In order to make the water vapor barrier structure have a lower thickness, so that the water vapor barrier structure has a higher light penetration and does not interfere with the color of the white light emitted by the organic light-emitting diode, the light penetrates the oxidation The thickness of the zinc tin film ranges from 25 to 100 nm; preferably, the thickness of the light penetrating zinc tin film is 25 nm.

In order for the water vapor barrier structure to have a better water vapor barrier capability, preferably, the tin content of the light penetrating zinc tin oxide film ranges from 15 to 58 at%.

In some embodiments of the present invention, in this step (b), a metal target is subjected to reactive sputtering in the presence of a reactive gas to form the light penetrating metal oxide film, and the metal target is selected Since zinc or tin, and the reaction gas is oxygen. The physical vapor deposition technique for performing the reactive sputtering is, for example but not limited to, RF sputtering, DC sputtering, magnetron sputtering, or any combination thereof. In order to make the light penetrating the metal oxide film have better flatness and density, so that the water vapor barrier structure has better water vapor barrier capability and less interference with the white light emitted by the organic light emitting diode Color, preferably, in this step (b), the sputtering power of the metal target ranges from 20 to 30 watts, and the oxygen flow rate ranges from 20 to 50 sccm.

In some embodiments of the present invention, the arithmetic mean deviation Ra of the surface roughness distribution of the light penetrating metal oxide film ranges from 2.51 to 5.34 nm; the maximum height of the surface roughness of the light penetrating metal oxide film Rz The range is from 27.09 to 66.89 nm. .

In order to make the water vapor barrier structure have a lower thickness, so that the water vapor barrier structure has a higher light penetration and does not interfere with the color of the white light emitted by the organic light-emitting diode, the light penetrates the oxidation The thickness of the metal film ranges from 10 to 180 nm; more preferably, the thickness of the light penetrating metal oxide film ranges from 10 to 100 nm.

In some embodiments of the present invention, in this step (c), the paraxylene-based dimer is subjected to gasification, cracking, chemical vapor deposition (CVD), and polymerization to form the polypair A xylene-based membrane, and the p-xylene-based dimer is selected from monochlorop-xylene dimer, p-xylene dimer, or any combination of the above. In order to further provide the water vapor barrier structure with better water vapor barrier capability, preferably, in the step (c), the paraxylene-based dimer is selected from monochloroparaxylylene Aggregate. In order to further make the water vapor barrier structure have a lower thickness, so that the water vapor barrier structure has a higher light penetration, preferably, in this step (c), the light penetrates the substrate The area is 10 cm ² , and the amount of the paraxylene dimer used ranges from 0.15 to 1 gram.

In order to make the water vapor barrier structure have a lower thickness, so that the water vapor barrier structure has a higher light penetration and does not interfere with the color of the white light emitted by the organic light-emitting diode, the parylene The thickness of the system membrane ranges from 40 to 550 nm; preferably, the thickness of the parylene system membrane ranges from 60 to 75 nm.

In some embodiments of the present invention, the arithmetic mean deviation Ra of the surface roughness distribution of the parylene-based film ranges from 2.81 to 3.50 nm; the maximum height of the surface roughness of the parylene-based film Rz The range is 24.52 to 28.62nm.

The water vapor barrier structure of the present invention is made by the manufacturing method described above. The water vapor barrier structure includes a light penetrating substrate, and at least one water vapor barrier element disposed on the light penetrating substrate. Wherein, the water vapor barrier element includes a layer of light penetrating zinc tin oxide film disposed on the light penetrating substrate, and a layer of light penetrating zinc oxide or tin oxide disposed on the light penetrating zinc tin film A metal oxide penetrating film and a parylene film disposed on the light penetrating metal oxide film, and the chromaticity formed by the light penetrating substrate and the light penetrating zinc tin film and the light penetrating together The chromaticity of the metal oxide film is complementary to each other.

The formation method and properties of the light penetrating substrate, the light penetrating zinc-tin oxide film, the light penetrating metal oxide film, and the parylene film are as described above, so they will not be repeated here.

Preferably, the wavelength of the light penetrating through the zinc-tin oxide film is 400 to 800 nm and the transmittance of each wavelength is more than 65%. Preferably, when the light penetrating metal oxide film is zinc oxide, the penetrating light wavelength of the light penetrating metal oxide film is 400 to 800 nm and the transmittance of each wavelength is more than 65%. Preferably, when the light penetrating metal oxide film is tin oxide, the penetrating light wavelength of the light penetrating metal oxide film is 400 to 800 nm and the transmittance of each wavelength is more than 80%. Preferably, the parylene film has a transmission light wavelength of 400 to 800 nm and the transmission rate of each wavelength is 75% or more.

In some embodiments of the present invention, the water vapor barrier structure includes two water vapor barrier elements stacked on each other on the light-transmitting substrate.

In some embodiments of the present invention, the water vapor barrier structure includes three water vapor barrier elements that are stacked on each other on the light-transmitting substrate.

The present invention will be further described in the following embodiments, but it should be understood that this embodiment is for illustrative purposes only, and should not be construed as a limitation of the implementation of the present invention.

Before the present invention is described in detail, it should be noted that in the following description, similar elements are denoted by the same numbers.

〈Materials and equipment〉 1. Light penetrating flexible substrate: purchased from Nanya Plastic Co., Ltd., made of polyethylene terephthalate (Polyethylene terephthalate, PET), area 10×12 cm ² , thickness It is 125μm. One surface of the light penetrating the flexible substrate undergoes corona treatment, and the other surface opposite to the surface undergoes antistatic treatment. 2. Zn Target: purchased from Bangjie Material Technology Co., Ltd., with a purity of 99.999%, a target diameter of 2 inches, and a thickness of 6 mm. 3. Tin target (Zn Target): purchased from Bangjie Material Technology Co., Ltd., with a purity of 99.999%, a target diameter of 2 inches, and a thickness of 6 mm. 4. Reactive gas: the type is oxygen, and the purity is 99.999%. 5. Para-xylene dimer: purchased from Laki Corporation. 6. Monochlorop-xylene dimer: purchased from Laki Corporation. 7. Magnetron sputtering equipment: purchased from Kao Duen Technology Corporation, model R-24K08-SPUTTERING. 8. Chemical vapor deposition equipment: purchased from Laki Corporation, model LH300.

<Cleaning the light-transmissive flexible substrate> Immerse the light-transmissive flexible substrate in 75% ethanol and wash it with ultrasonic vibration for 3 to 5 minutes to remove the light-transmitting flexible substrate Dust and grease on the surface of the substrate. Next, the cleaned light-transmitting flexible substrate was placed in an oven and dried at 80°C for 5 minutes. Finally, the dried light is passed through the flexible substrate and cleaned with high-pressure air. The light transmission rate of the light penetrating flexible substrate is 88.63%, the chromaticity value a*=-0.021, b*=0.4467, and the water vapor transmission rate is 6.773 g/m ² . day.

<Preparation Examples A1 to A10: Zinc-Tin Oxide Laminates> The common manufacturing method for the zinc oxide tin-layer laminates of Preparations A1 to A10 is to fix the cleaned light-transmitting flexible substrate in the magnetron sputtering equipment cavity On the turntable in the body, the background pressure of the chamber was first pumped to 3×10 ^-6 torr, and then argon gas with a flow rate of 30 sccm was introduced to control the working pressure of the chamber to 1 mtorr. The sputtering conditions are set as follows: the sputtering power of the zinc target is 30W, the sputtering power of the tin target is 20 to 30W, and the rotation speed of the turntable is 20 rpm. Next, clean the surface of the zinc target and the tin target for 15 to 20 minutes until the voltage no longer floats. Then pass in oxygen with a flow rate of 20 to 50 sccm. After the working pressure in the chamber and no longer float, open the shutter and start reactive sputtering. The sputtering time is 10 to 60 minutes. After the light penetrates A layer of light penetrating zinc tin oxide is formed on the surface of the flexible substrate to obtain a zinc tin oxide laminate. Preparation Examples A1 to A10 form the sputtering power and oxygen flow rate of the light penetrating zinc oxide film by reactive sputtering, and the properties of the prepared zinc oxide tin laminate are shown in Table 1.

<Preparation Examples B1 to B11: Metal Oxide Laminates> Using the same sputtering method as Preparation Examples A1 to A10, the metal oxide laminates of Preparation Examples B1 to B11 were produced, except that only zinc targets were used for light penetration during sputtering A zinc oxide film, or only a tin target is used to form a light penetrating tin oxide film. Preparation Examples B1 to B11 form the sputtering power and oxygen flow rate of the light penetrating metal oxide film by reactive sputtering, and the properties of the prepared metal oxide laminate are shown in Table 2.

<Preparation Examples C1 to C7: Parylene-based laminates> Place the cleaned light-permeable flexible substrate on the mesh carrier in the chamber of the chemical vapor deposition equipment, and the amount is from 0.15 to One gram of parachloroxylene dimer or paraxylene dimer is placed in the boat-shaped vehicle in the cavity of the chemical vapor deposition equipment. Start to evacuate the cavity until the pressure of the suction line reaches 30 mtorr and the pressure of the cavity reaches 10 mtorr, the temperature in the cavity is increased to 120°C (sublimation temperature of the material) through eight stages of temperature rise, and then continues to rise to 650 ℃ (material cracking temperature). Then press the system process button. At this time, the process light turns on and the coating starts. After the process lights are extinguished, the coating is completed for a total of 3 hours, and a parylene-based film of the type of polychloropylene or parylene is formed on the surface of the light-transmissive flexible substrate To obtain a parylene-based laminate. Preparation Examples C1 to C7 The amount of the parachloroxylene dimer or p-xylene dimer used in forming the parylene-based film, and the properties of the prepared parylene-based laminate are as follows Table 3 shows.

<Nature Test>

The properties of each of the above preparation examples were measured using the property evaluation methods described below. The results of the property tests are summarized in Tables 1 to 3.

1. Film thickness The optical transmission of the zinc tin oxide film of the preparation examples A1 to A10, and the light transmission of the zinc oxide tin film of the preparation examples B1 to B11 were measured using an optical film thickness meter (manufacturer model BTC111E). The thickness of the metal oxide film and the parylene-based film of the parylene-based laminate of Preparation Examples C1 to C7. First select the optical film thickness gauge to measure the preparation example to be tested under the conditions of penetration or reflection, then input the estimated refractive index of the film of the preparation example, and then adjust the parameters to make the actual wave mode and software calculation According to the ideal wave mode, the thickness of the film of this preparation example can be calculated.

2. Elemental analysis Using a total reflection fluorescence spectrometer (Total Reflection X-Ray Fluorescence, referred to as TXRF, manufacturer model S2 PICOFOX), the elemental analysis of the light penetrating zinc-tin oxide films of the preparation examples A1 to A10 zinc-tin oxide laminates To obtain the elemental composition and atomic percentage (at%) of the film of the preparation example to be tested.

3. The surface roughness was measured using an atomic force microscope (AFM for short, Park System XE-100). The light penetration of the zinc tin oxide films of preparation examples A1 to A10, and the preparation examples B1 to The light of the B11 metal oxide laminate passes through the metal oxide film, and the surface roughness of the parylene-based film of the parylene-based laminate of Preparation Examples C1 to C7. Using the non-contact mode of the atomic force microscope, the scanning range was 1 × 1 µm, and the microstructure distribution and surface roughness of the thin film of the preparation example to be measured were observed. The surface roughness includes two types: Arithmetical Mean Deviation (Ra) and Maximum Height of Profile (Rz).

4. Light transmittance

A UV-VIS spectrometer (Agilent cary 5000 model) was used to measure the light penetration through the flexible substrate, preparation examples A1 to A10 zinc tin oxide laminates, preparation examples B1 to B11 metal oxide laminates, and preparation examples C1 to C7 The light transmittance (transmittance, T%) of the parylene-based laminate. First, the air is used as the background for correction, and then the preparation example to be measured is placed in the UV-VIS spectrometer for measurement. The measurement wavelength range is 300 to 800 nm. The measured light transmittance spectrum is shown in Figure 5 To 7. The light transmittance of each wavelength is averaged to obtain the average light transmittance. The average light transmittance is shown in Tables 1 to 3.

5. Chromaticity: Use UV-VIS spectrometer (Agilent cary 5000 model) and expansion software (the software name is Color) to measure the light penetration through the flexible substrate, preparation examples A1 to A10, zinc-tin oxide laminate, preparation The chromaticity values of the metal oxide laminates of Examples B1 to B11 and the parylene laminates of Preparation Examples C1 to C7 in the CIE LAB color space. The value of a* is positive, indicating that the color is biased toward red; the value is negative, indicating that the color is biased toward green; if the absolute value of a* is between 0 and 1, it indicates that its color cannot be recognized by the human eye. The value of b* is positive, indicating that the color is biased toward yellow; the value is negative, indicating that the color is biased toward blue; if the absolute value of b* is between 0 and 1, it indicates that its color cannot be recognized by the human eye.

6. Water vapor permeability

Use a water vapor permeability measuring instrument (the manufacturer's model is Mocon AQUATRAN ^® Model 2 G, the detection limit is 5×10 ^-5 g/m ² .day) to measure the light penetration through the flexible substrate, Preparation Examples A1 to A10 Water Vapor Transmission Rate (abbreviated as WVTR) of the zinc oxide tin laminate, the preparation examples B1 to B11 metal oxide laminates, and the preparation examples C1 to C7 parylene-based laminates. During the measurement, the preparation example to be measured is placed in the sample tank, and the humidity is controlled by a hygrometer (built into the water vapor permeability measuring instrument) on one side of the sample tank and nitrogen is introduced. When nitrogen carries water vapor through When the sample to be tested reaches the other side, it will enter the coulometric phosphorus pentoxide sensor to detect the content of permeated water vapor, thereby analyzing the water vapor permeability of the preparation example to be tested. Among them, the measurement conditions are: temperature is 37.8 ℃, relative humidity is 100%, and the flow rate of the sample tank is set to 20 sccm.

7. Sputtering rate The sputtering rates in Preparation Examples A1 to A10, Preparation Examples B1 to B11, and Preparation Examples C1 to C7 are obtained by the following calculation method: Sputtering rate (nm/min) = thickness of the film formed by sputtering ÷Sputtering time.

Table 1 Preparation Example A Zinc-Tin Oxide Laminate A1 A2 A3 A4 A5 A6 Sputtering power (W) Zn 30 30 30 30 30 30 Sn 30 30 30 30 20 25 Oxygen flow (sccm) 20 30 40 50 40 40 Film thickness (nm) 100 100 100 100 100 100 Sputtering rate (nm/min) 7.87 4.62 3.78 3.73 2.87 3.51 Elemental analysis (at%) Zn 42 42 42 42 85 75 Sn 58 58 58 58 15 25 Surface roughness (nm) Ra 2.99 4.33 1.48 3.52 2.18 1.53 Rz 31.57 57.88 13.45 47.73 21.14 16.50 Average light transmittance (%) 78 77 84.44 80 83.76 84.06 Chroma a* 0.2736 0.3059 1.1076 0.1673 0.2850 0.4068 b* -2.324 3.0548 -2.387 4.5881 4.6502 4.1998 WVTR (g/m ² .day) 0.2276 0.2497 0.2506 0.2879 0.3848 0.2706 Table 1 (continued) Preparation Example A Zinc-Tin Oxide Laminate A7 A8 A9 A10 Sputtering power (W) Zn 30 30 30 30 Sn 30 30 30 30 Oxygen flow (sccm) 40 30 40 40 Film thickness (nm) 25 25 30 40 Sputtering rate (nm/min) 3.78 4.62 3.78 3.78 Elemental analysis (at%) Zn 42 42 42 42 Sn 58 58 58 58 Surface roughness (nm) Ra 1.48 2.07 1.63 1.58 Rz 16.38 25.8 15.74 15.61 Average light transmittance (%) 87.63 87.92 86.35 86.07 Chroma a* -0.015 -0.023 0.106 0.257 b* -1.536 -1.875 -1.843 -2.337 WVTR (g/m ² .day) 2.4767 2.3018 1.4522 0.6853

From the preparation examples A3, A5 and A6 of Table 1, it can be seen that the higher the sputtering power of tin, the higher the light transmittance of the obtained zinc oxide tin laminate, and the better the water vapor barrier ability. Furthermore, as can be seen from Preparation Examples A1 to A4, the lower the oxygen flow rate, the better the water vapor barrier effect of the obtained zinc-tin oxide laminate. Compared with the light transmittances of Preparation Examples A1, A2, and A4, the zinc-tin oxide laminates of Preparation Examples A3, A5, and A10 also have higher light transmittances. In addition, the zinc-tin oxide laminates of Preparation Examples A1, A3, and A7 to A10 appear blue to the human eye, and the zinc-tin oxide laminates of Preparation Examples A2, A4 to A6 appear yellow to the human eye.

Table 2 Preparation Example B Oxide metal laminate B1 B2 B3 B4 B5 B6 Sputtering power (W) Zn 50 40 30 --- --- --- Sn --- --- --- 30 25 20 Oxygen flow (sccm) 40 40 40 40 40 40 Film thickness (nm) 100 100 100 100 100 100 Sputtering rate (nm/min) 3.34 2.67 2.15 4.75 4.23 4.15 Surface roughness (nm) Ra 5.34 4.02 2.90 2.51 2.97 2.75 Rz 66.89 34.18 27.09 31.51 31.13 35.02 Average light transmittance (%) 76.96 77.58 77.08 85.04 85.66 85.34 Chroma a* 0.5141 0.4781 0.4372 0.7067 -0.098 -0.313 b* 4.2117 4.2508 4.2601 -2.042 -2.176 -1.365 WVTR (g/m ² .day) 0.3168 0.3562 0.3748 4.8432 5.0893 4.9215 Table 2 (continued) Preparation Example B Oxide metal laminate B7 B8 B9 B10 B11 Sputtering power (W) Zn --- 30 30 30 30 Sn 30 --- --- --- --- Oxygen flow (sccm) 40 40 40 40 40 Film thickness (nm) 20 80 25 20 10 Sputtering rate (nm/min) 4.75 2.15 2.15 2.15 2.15 Surface roughness (nm) Ra 2.36 2.84 2.61 2.66 1.97 Rz 29.57 26.67 25.89 25.97 25.86 Average light transmittance (%) 87.71 86.18 86.62 87.08 87.93 Chroma a* 0.1508 0.302 0.205 0.164 -0.028 b* -0.047 4.088 3.126 2.465 2.576 WVTR (g/m ² .day) 5.2186 0.4451 1.8985 2.3635 4.5047

It can be seen from Table 2 that the transparent metal oxide laminates of Preparation Examples B1 to B3 and B8 to B11 appear yellow in the human eye, and the transparent metal oxide laminates of Preparation Examples B4 to B7 appear blue in the human eye. Moreover, the metal oxide laminates of Preparation Examples B4 to B11 also have a higher light transmittance, and the metal oxide films of the metal oxide laminates of Preparation Examples B4, B7, and B11 also have better flatness and density ( Ra value is lower).

table 3 Preparation Example C Parylene-based laminate C1 C2 C3 C4 C5 C6 C7 Paraxylene dimer (g) 1 0.4 0.15 --- --- --- --- Dichlorop-xylene dimer (g) --- --- --- 0.15 0.4 1 0.08 Film thickness (nm) 440 134 41 72 216 550 25 Surface roughness (nm) Ra 7.18 6.61 5.06 3.50 2.79 2.81 2.36 Rz 64.39 56.86 49.08 24.52 29.23 28.62 28.81 Average light transmittance (%) 84.02 85.82 88.98 89.27 85.44 84.67 89.74 Chroma a* -5.1069 1.0807 -0.2503 -0.2257 1.0771 -4.8123 -0.0357 b* 3.0843 -1.1453 3.3528 3.2537 -1.2287 2.3125 1.2642 WVTR (g/m ² .day) 5.432 6.089 6.221 5.804 5.268 4.731 6.218

As can be seen from Table 3, although the parylene-based laminates of Preparation Examples C1 to C7 have a water vapor barrier capability comparable to PET, they can still maintain good light transmittance even at high film thicknesses.

<Examples 1 to 9 Water vapor barrier structure> The water vapor barrier structures of Examples 1 to 7 have a common structure, as shown in FIG. 1; the structure of the water vapor barrier structure of Example 8 is as follows Figure 2; the structure of the water vapor barrier structure of Example 9 is shown in Figure 3. And the materials and properties used in the various examples are shown in Table 4. The manufacturing method of the water vapor barrier structure of each embodiment is further described below.

[Example 1] The manufacturing method of the water vapor barrier structure of Example 1 is as follows: (a): Using the same reactive sputtering method as Preparation Example A5, the cleaned light penetrates the flexible substrate 1 A layer of light penetrating zinc-tin oxide film 21 is formed on the surface of the surface to obtain a first laminate. And measure the chromaticity value of the first laminate (a*=0.2850, b*=4.6502). Wherein, the absolute value of the chromaticity value a* of the first layered component is less than 1, indicating that human eyes cannot recognize the red-green color of the first layered component; the chromaticity value b* of the first layered component is 4.6502, indicating human The first layered product is yellow to the naked eye. (b): Since the human naked eye sees the first laminate as yellow and the complementary color of yellow is blue, and because the human naked eye sees the metal oxide laminate of the preparation example B7 as blue, and the oxidation of the preparation example B7 The metal oxide film of the metal laminate has a fine degree of detail. Therefore, with the sputtering power and oxygen flow rate used in Preparation Example B7, a layer of light selected from tin oxide is formed on the surface of the light penetrating zinc tin oxide film 21 Through the metal oxide film 22, a second laminate is obtained. And measure the chromaticity value of the second laminate (a* = 1.1023, b* = 0.4188) (c) Because the parylene laminate of Preparation C5 has better water vapor barrier ability, it is used The same chemical vapor deposition method as in Preparation Example C5 forms a parylene-based film 23 selected from polychlorop-xylene on the surface of the metal oxide film 22.

[Example 2] The water vapor barrier structure of Example 2 was produced using the same method of manufacturing the water vapor barrier structure as in Example 1, except that in step (a), the same as in Preparation Example A6 was used The light penetrating zinc tin oxide film 21 is formed by a reactive sputtering method, and the light penetrating metal oxide film 22 is formed using the same reactive sputtering method as in Preparation Example B4.

[Example 3] The water vapor barrier structure of Example 3 was produced using the same method of manufacturing the water vapor barrier structure as in Example 1, except that in step (a), the same reaction as in Preparation Example A4 was used The light penetrating zinc-tin oxide film 21 is formed by a sputtering method to obtain the first laminate, the chromaticity value of the first laminate is a*=1.1076, b*=-2.387, indicating that the human eye sees the first A laminate 21 is blue. And, in step (b), since the first laminate exhibits blue and the complementary color of blue is yellow, and since the metal oxide laminate of Preparation Example B3 exhibits yellow, and the metal oxide laminate of Preparation Example B8 The light penetrating metal oxide film is more detailed, so with the sputtering power and oxygen flow rate used in Preparation Example B8, a layer of light penetrating selected from tin oxide is formed on the surface of the light penetrating zinc tin oxide film 21 The metal film 22 is oxidized to obtain a second laminate.

[Examples 4 to 7, 8 to 9] The manufacturing method of the water vapor barrier structure of Examples 4 to 7 is similar to the manufacturing method of the water vapor barrier structure of Examples 1 to 3, except that it is used according to Table 4. The light penetrating zinc-tin oxide film 21, the light penetrating metal oxide film 22, and the parylene film 23 are prepared under different conditions. The manufacturing method of the water vapor barrier structure of the embodiment 8 is further based on the embodiment 5 and stacks two water vapor barrier elements 2. The manufacturing method of the water vapor barrier structure of the embodiment 9 is further based on the embodiment 5 and stacks three water vapor barrier elements 2.

<Comparative Examples 1 and 2 Water vapor barrier structure> The water vapor barrier structures of Comparative Examples 1 and 2 have a common structure, as shown in FIG. 4. Table 4 summarizes the materials and properties used in each comparative example. The method for manufacturing the water vapor barrier structure of each comparative example will be further described below.

[Comparative Example 1] The manufacturing method of the water vapor barrier structure of Comparative Example 1 is as follows: (a): Using the same reactive sputtering method as Preparation Example A3, on the cleaned surface of the flexible substrate 1 A layer of light penetrating zinc tin oxide film 21 is formed. (b) Using the same chemical vapor deposition method as in Preparation Example C5, a parylene-based film 23 selected from polychlorop-xylene was formed on the surface of the light-transmissive zinc-tin oxide film 21.

[Comparative Example 2] The water vapor barrier structure of Comparative Example 2 was produced using the same method for manufacturing the water vapor barrier structure as in Comparative Example 1, except that in step (b), the same chemistry as in Preparation Example C2 was used In the vapor deposition method, a parylene-based film 23 selected from parylene is formed on the surface of the light-transmissive zinc-tin oxide film 21.

<Nature Evaluation>

The properties of the above examples and comparative examples were measured using the property evaluation methods described below. Table 4 summarizes the results of the property evaluation.

1. Film thickness: Optical penetration gauge (manufacturer model BTC111E) was used to measure the light-transmitting zinc-tin oxide film, light-transmitting metal oxide film, and parylene film of the water vapor barrier structure of each embodiment. thickness of. The detailed measurement method is as described above, so it will not be repeated here.

2. Light transmittance The UV-VIS spectrometer (Agilent cary 5000 model) was used to measure the light transmittance (T%) of the water vapor barrier structure of each example and comparative example. The detailed measurement method is as described above, so it will not be repeated here. The measured light transmittance profiles are shown in Figures 8 to 10. The light transmittance of each wavelength is averaged to obtain the average light transmittance. The average light transmittance is shown in Table 4.

3. For colorimetry, use UV-VIS spectrometer (Agilent cary 5000 model) and expansion software (the software name is Color) to measure the first laminate, the second laminate, and the water vapor resistance of each embodiment and comparative example. The chromaticity value of the barrier structure in the CIE LAB color space. The detailed measurement method is as described above, so it will not be repeated here. At present, the industry's requirements for the properties of organic light-emitting display devices are: the chromaticity value a* of the water vapor barrier structure needs to be in the range of 0~±5, and b* needs to be in the range of 0~±5.

4. The water vapor permeability is measured with a water vapor permeability measuring instrument (the manufacturer's model is Mocon AQUATRAN ^® Model 2 G, the detection limit is 5×10 ^-5 g/m ² .day). The water vapor barrier rate (Water Vapor Transmission Rate, abbreviated as WVTR) of the water vapor barrier structure. The detailed measurement method is as described above, so it will not be repeated here.

Table 4 Water vapor barrier structure Examples 1 2 3 4 5 Number of water vapor barrier elements 2 1 1 1 1 1 Light penetrating zinc tin oxide film 21 Preparation Example A A5 A6 A4 A3 A3 Film thickness (nm) 100 100 100 100 100 Light penetrating metal oxide film 22 Preparation Example B B7 B4 B8 B9 B9 species SnO SnO ZnO ZnO ZnO Film thickness (nm) 20 100 80 25 25 Parylene 23 Preparation Example C C5 C5 C5 --- C4 species C C C C C Film thickness (nm) 216 216 216 150 72 The first laminate Chroma a* 0.2850 0.4068 1.1076 --- --- b* 4.6502 4.1998 -2.387 --- --- Second buildup Chroma a* 1.1023 -4.4751 -3.3984 --- --- b* 0.4188 3.2669 -0.2621 --- --- Water vapor barrier structure Chroma a* 1.6478 -1.5482 0.9445 -1.9748 0.7065 b* -0.8513 1.2453 -3.4364 5.8122 1.7416 WVTR (g/m ² .day) 0.2571 0.2509 0.0155 0.0577 0.0312 Average light transmittance (%) 74.93 81.38 82.42 84.8 82.5 Table 4 (continued) Water vapor barrier structure Examples 6 7 8 9 Number of water vapor barrier elements 2 1 1 2 3 Light penetrating zinc tin oxide film 21 Preparation Example A A9 A10 A3 A3 Film thickness (nm) 30 40 100 100 Light penetrating metal oxide film 22 Preparation Example B B10 B11 B9 B9 species ZnO ZnO ZnO ZnO Film thickness (nm) 20 10 25 25 Parylene 23 Preparation Example C C4 C4 C4 C4 species C C C C Film thickness (nm) 72 72 72 72 The first laminate Chroma a* --- --- --- --- b* --- --- --- --- Second buildup Chroma a* --- --- --- --- b* --- --- --- --- Water vapor barrier structure Chroma a* 0.5913 0.6983 -1.3182 -1.8835 b* 2.3897 2.1228 2.9668 8.6665 WVTR (g/m ² .day) 0.0295 0.0537 0.00622 5×10 ^-5 Average light transmittance (%) 81.56 81.2 83.53 81.84 Table 4 (continued) Water vapor barrier structure Comparative example 1 2 Number of water vapor barrier elements 2 1 1 Light penetrating zinc tin oxide film 21 Preparation Example A A3 A3 Film thickness (nm) 100 100 Light penetrating metal oxide film 22 species no no Film thickness (nm) --- --- Parylene 23 Preparation Example C C5 C2 species C N Film thickness (nm) 216 134 Water vapor barrier structure Chroma a* 0.9445 0.8752 b* -4.336 -3.842 WVTR (g/m ² .day) 0.0264 0.2957 Average light transmittance (%) 82.36 84.07 Note: In Table 4, "C" for the type of parylene-based membrane means "Parylene C" and "N" means "Parylene N".

Embodiments 8 and 9 further increase the number of water vapor barrier elements so that the water vapor barrier structure has better water vapor barrier capabilities.

However, the above are only examples of the present invention, and should not be used to limit the scope of the present invention. Any simple equivalent changes and modifications made according to the scope of the patent application of the present invention and the content of the patent specification are still classified as This invention covers the patent.

1‧‧‧Light penetrating substrate 2‧‧‧Water vapor barrier element 21‧‧‧Light penetrating zinc tin oxide film 22‧‧‧Light penetrating metal oxide film 23‧‧‧Parylene film

Other features and effects of the present invention will be clearly presented in the embodiment with reference to the drawings, in which: FIG. 1 is a schematic diagram illustrating the water vapor barrier structure of Examples 1 to 7 of the present invention; FIG. 2 is A schematic diagram illustrating the water vapor barrier structure of Example 8 of the present invention; FIG. 3 is a schematic diagram illustrating the water vapor barrier structure of Example 9 of the present invention; FIG. 4 is a schematic diagram illustrating Comparative Example 1 and Water vapor barrier structure of 2; FIG. 5 is a data diagram illustrating the light transmittance of Preparation Examples A1 to A4 of the invention; FIG. 6 is a data diagram illustrating the light transmission substrate of the invention and Preparation Examples B1 to B6 FIG. 7 is a data graph illustrating the light transmittances of Preparation Examples C1 to C6 of the present invention; FIG. 8 is a data graph illustrating the light transmittances of Examples 1 to 3 of the present invention; FIG. 9 Is a data graph illustrating the light transmittances of Examples 3 to 7 of the present invention; and FIG. 10 is a data graph illustrating the light transmittances of Examples 5, 8 and 9 of the present invention.

1‧‧‧Light penetrating substrate

2‧‧‧Water vapor barrier element

21‧‧‧Light penetrating zinc tin oxide film

22‧‧‧Light penetrating metal oxide film

23‧‧‧Parylene film

Claims (9)

A method for manufacturing a water vapor barrier structure includes the following steps: (a) forming a layer of light-transmitting zinc-tin oxide film on a light-transmitting substrate to obtain a first laminate, and the light penetrating zinc-tin oxide The thickness of the film is in the range of 25 to 100 nm; (b) A light penetrating metal oxide film is formed on the surface of the light penetrating zinc oxide film of the first laminate to obtain a second laminate, and the light The chromaticity of the penetrating metal oxide film and the chromaticity of the first laminate are complementary colors, wherein the light penetrating metal oxide film is selected from zinc oxide or tin oxide, and the light penetrating the thickness of the metal oxide film A range of 10 to 180 nm; and (c) a parylene-based film is formed on the surface of the second laminate in the light penetrating metal oxide film, and the thickness of the parylene-based film is in the range of 40 to 550nm. The method for manufacturing a water vapor barrier structure according to claim 1, wherein in this step (a), the tin target and the zinc target are subjected to reactive sputtering in the presence of a reactive gas to form the light penetration In the zinc-tin-oxide film, the reaction gas is oxygen, and the sputtering power of the tin target and the zinc target ranges from 20 to 30 watts, respectively, and the flow rate of the oxygen ranges from 20 to 50 sccm. The method for manufacturing a water vapor barrier structure according to claim 1, wherein the tin content of the light penetrating zinc tin oxide film ranges from 15 to 58 at %. The method for manufacturing a water vapor barrier structure according to claim 1, wherein in the step (b), a metal target is subjected to reactive sputtering in the presence of a reactive gas to form the light penetrating metal oxide For the film, the metal target is selected from zinc or tin, and the reaction gas is oxygen, and the sputtering power of the metal target ranges from 20 to 30 watts, and the flow rate of the oxygen ranges from 20 to 50 sccm. The method for manufacturing a water vapor barrier structure according to claim 1, wherein the thickness of the light penetrating metal oxide film ranges from 10 to 100 nm. The method for manufacturing a water vapor barrier structure according to claim 1, wherein in this step (c), p-xylene-based dimer is formed by gasification, cracking, chemical vapor deposition and polymerization reaction In the parylene-based film, the paraxylene-based dimer is selected from monochlorop-xylene dimer, p-xylene dimer, or any combination thereof. A water vapor barrier structure, comprising: a light penetrating substrate; and at least one water vapor barrier element, disposed on the light penetrating substrate and comprising: a layer of light penetrating zinc tin oxide film, and the light penetrating The thickness of the zinc-tin oxide film is in the range of 25 to 100 nm, a layer of light penetrating metal oxide film is disposed on the light penetrating zinc oxide film and is selected from zinc oxide or tin oxide, and the light penetrating metal oxide film The thickness range is 10 to 180 nm, and a parylene film is provided on the light penetrating metal oxide film, and the thickness of the parylene film is 40 to 550 nm, wherein the light The chromaticity formed by the transparent substrate and the light penetrating zinc-tin oxide film and the chromaticity of the light penetrating metal oxide film are complementary colors to each other. The water vapor barrier structure according to claim 7, comprising two water vapor barrier elements arranged on the light-transmitting substrate on top of each other. The water vapor barrier structure according to claim 7, comprising three water vapor barrier elements arranged on the light-transmitting substrate on top of each other.

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