TW201342141A - Manufacturing method for polymer substrate having transparent conductive oxide layer - Google Patents

Abstract

A manufacturing method for a polymer substrate having a transparent conductive oxide (TCO) layer is provided and includes steps of: providing a polymer substrate having a primer layer, a silicon dioxide film and a TCO layer in turn; and placing the polymer substrate into an oxygen-free environment followed by heating the polymer substrate under 120-180 DEG C about 60-90 minutes, in order to reduce the amount and the particle diameter of white microparticles in the primer layer generated due to heating. Thus, the entire light transmittance can be enhanced, and the impedance of the TCO layer can be efficiently lowered, so as to relatively enhance the film quality and the manufacture yield of the polymer substrate.

Description

Method for producing polymer substrate with transparent conductive oxide layer

The present invention relates to a method for producing a polymer substrate having a transparent conductive oxide layer, and more particularly to a method for producing a polymer substrate having a transparent conductive oxide layer capable of reducing white particles generated by heating of a base layer.

In recent years, more and more consumer electronic products (such as mobile phones or tablets) use a transparent touch panel to provide touch operation functions. The transparent touch panel is usually configured on the display screen so that The user can directly perform interactive input operation with finger touch and improve input operation efficiency. Generally, the mechanism of the transparent touch panel mainly includes a sensor and a controller chip, wherein the sensor can be roughly classified into a resistive type, a capacitive type, an infrared type, and an ultrasonic type according to the operation principle and the structure. Most of the current mainstream consumer electronics products are gradually adopting capacitive sensors with multi-signal sensing performance to enhance the touch operation function and avoid the previous single-point sensor being vulnerable to scratching and cracking. Missing use.

In the structure of a general capacitive inductor, two transparent conductive films, such as indium tin oxide (ITO) materials, are usually provided, and a desired electrode pattern is provided on each layer of the conductive film, for example, a plurality of X-axis sensing. The line (X-Trace) and the Y-axis sensing line (Y-Trace), and each of the sensing lines maintain a gap of appropriate width between each other for the purpose of insulation setting. Furthermore, the transparent conductive film of the inductor can be formed on the glass substrate or the transparent polymer substrate, and in order to reduce the thickness of the product and reduce the manufacturing cost, the manufacturing of the touch panel has a tendency to gradually replace the glass substrate with a transparent polymer substrate. .

For example, referring to FIG. 1 , a cross-sectional view of a touch substrate of a conventional touch sensor is disclosed. A touch substrate 10 includes a polymer substrate 11 and a substrate layer from bottom to top. (primer) 12, a layer of cerium oxide (SiO ₂ ) film 13 and a transparent conductive oxide (TCO) layer 14. The polymer substrate 11 is generally obtained from a polyethylene terephthalate (PET) substrate. When the polymer substrate 11 is commercially available, the surface thereof is coated with the base layer 12 to increase the surface thereof. Adhesion. The ruthenium dioxide film 13 is further plated on the base layer 12 by chemical vapor deposition (CVD) or physical vapor deposition (PVD). The ruthenium dioxide film 13 is used to prevent Water vapor intrudes into the transparent conductive oxide layer 14 from the side of the polymer substrate 1, thereby ensuring electrical stability of the transparent conductive oxide layer 14.

Further, the transparent conductive oxide layer 14 is further plated on the ceria film 13 by physical vapor deposition. The transparent conductive oxide layer 14 is usually selected from indium tin oxide (ITO). In order to improve the conductivity of indium tin oxide, it is usually baked at 120 to 180 ° C for about 60 to 90 minutes to recrystallize the indium tin oxide film. In this way, the impedance can be lowered and the adhesion between the laminates can be improved. However, during the high-temperature baking, the polymer substrate 11 and the base layer 12 are also easily reacted with oxygen to generate a plurality of white particles 121 which substantially belong to the material of the polymer substrate 11 and the base layer 12 itself. Tinted oxide particles that block the passing light and thus greatly reduce the overall light transmittance.

In order to solve the problem, please refer to FIG. 2 , which illustrates a cross-sectional view of another touch sensor of the prior art. The touch substrate 20 includes a polymer substrate 21 and a bottom layer. The base layer 22, a hard coat 23, a thin film of ruthenium dioxide 24, and a transparent conductive oxide layer 25. The hard coat layer 23 is coated on the base layer 22 for preventing the polymer substrate 21 and the base layer 22 from reacting with oxygen during high temperature baking to reduce the white particles 221 produced thereby. The amount, thereby ensuring that the number of white particles 221 is below a predetermined value, to avoid excessively affecting the overall light transmittance. However, the problem of adding the hard coat layer 23 is that the hard coat layer 23 not only increases the overall thickness, but also has a problem of poor adhesion between the material and the ceria film 24, so that it is easy to cause obvious peeling. (peel off) defects, and will seriously affect the structural reliability, manufacturing yield and service life of the touch substrate 20, so the product of the hard coating 23 is not easily applied to the market of touch sensors.

Therefore, it is necessary to provide a method for producing a polymer substrate having a transparent conductive oxide layer to solve the problems of the conventional technology.

The main object of the present invention is to provide a method for manufacturing a polymer substrate having a transparent conductive oxide layer by placing the polymer substrate in an oxygen-free environment for high-temperature heating baking to avoid the base layer (and the polymer substrate). The white particles are generated by the influence of oxygen during heating, thereby significantly reducing the amount of white particles, and controlling the particle size of the white particles to the nanometer level, thereby ensuring the overall light transmittance and effectively reducing the transparent conductive oxide layer. The impedance, therefore, can improve film quality and manufacturing yield.

A secondary object of the present invention is to provide a method for manufacturing a polymer substrate having a transparent conductive oxide layer, which is directly subjected to a high-temperature heat baking treatment in an oxygen-free environment to reduce the amount of white particles generated in the substrate layer. The particle size, therefore, does not need to be coated with any hard coating, so the adhesion between the film and the substrate is not affected by the provision of the hard coating, so that structural reliability, manufacturing yield and service life can be ensured.

In order to achieve the above object, the present invention provides a method for manufacturing a polymer substrate having a transparent conductive oxide layer, comprising the steps of: providing a polymer substrate on which a base layer is previously coated; and the base layer Forming a thin film of ruthenium dioxide; forming a transparent conductive oxide layer on the ruthenium dioxide film; and heating the polymer substrate to 120 to 180 ° C in an anaerobic environment for 60 to 90 minutes, The number and particle diameter of white particles generated by heating in the underlayer are reduced.

In an embodiment of the invention, the ratio of the white particles to the total surface area of the substrate layer is controlled to be between 1.0% and 0.0001%, and the particle size of the white particles is controlled between 1000 and 1 nanometer. Between meters (nm).

In one embodiment of the invention, the anaerobic environment is a vacuum chamber.

In one embodiment of the invention, the oxygen-free environment is a chamber filled with an inert gas; the inert gas is selected from the group consisting of nitrogen (N ₂ ) or argon (Ar).

In an embodiment of the invention, the material of the polymer substrate is selected from the group consisting of polyethylene terephthalate (PET).

In one embodiment of the invention, the material of the transparent conductive oxide layer is selected from the group consisting of indium tin oxide (ITO), zinc oxide (ZnO), or aluminum doped zinc oxide (AZO).

In an embodiment of the invention, the material of the base layer is selected from the group consisting of an acrylic resin, a polyester, a silicone acrylic resin, a methacrylic resin or Polysiloxane resin.

In an embodiment of the present invention, before the step of heating the polymer substrate, the method further comprises: forming a protective layer on a lower surface of the polymer substrate.

In an embodiment of the invention, the material of the protective layer is selected from the group consisting of an acrylic resin, a polyester resin, a decyl acrylate resin, a methacrylic resin or a polyoxyalkylene resin.

In an embodiment of the present invention, after the step of heating the polymer substrate, the method further comprises: forming a touch substrate of a touch sensor by using the polymer substrate.

Furthermore, the present invention provides a method for fabricating a polymer substrate having a transparent conductive oxide layer, comprising the steps of: providing a polymer substrate having a substrate layer pre-coated thereon, and at least the substrate layer Having a transparent conductive oxide layer; and heating the polymer substrate to 120 to 180 ° C in an oxygen-free environment for 60 to 90 minutes to reduce the amount of white particles generated by heating in the substrate layer and Particle size.

The above and other objects, features and advantages of the present invention will become more <RTIgt; Furthermore, the directional terms mentioned in the present invention, such as "upper", "lower", "before", "after", "left", "right", "inside", "outside" or "side", etc. Just refer to the direction of the additional schema. Therefore, the directional terminology used is for the purpose of illustration and understanding of the invention.

The method for manufacturing a polymer substrate with a transparent conductive oxide layer according to a preferred embodiment of the present invention is mainly applied to a touch substrate for manufacturing a touch sensor of a touch panel, and the manufacturing method thereof The method includes the following steps: providing a polymer substrate 31 having a primer layer 32 pre-coated thereon; forming a thin film of cerium oxide (SiO ₂ ) 33 on the substrate layer 32; Forming a transparent conductive oxide (TCO) layer 34 on the yttria film 33; and heating the polymer substrate 31 to 120 to 180 ° C in an oxygen-free environment for 60 to 90 minutes to reduce the substrate layer 32 The number and particle diameter of the white particles 321 which are generated by heating. The invention will be described in detail below with reference to Figures 3 and 4 in detail detailing the implementation of the above-described steps of the preferred embodiment and its principles.

Referring to FIG. 3, a method for manufacturing a polymer substrate having a transparent conductive oxide layer according to a preferred embodiment of the present invention first provides a polymer substrate 31. In this step, the material of the polymer substrate may be selected from polyethylene terephthalate (PET), triacetyl cellulose (TAC) or polycarbonate (PC). A sheet made of a polymer material, but is not limited thereto. In the present embodiment, the polymer substrate 31 is, for example, a PET substrate. The thickness of the polymer substrate 31 is between about 80 and 250 micrometers (μm), for example, 125, 150 or 180 μm, etc., but is not limited thereto. Further, when the polymer substrate 31 is commercially available, the upper surface thereof is previously coated with the base layer 32 by spin coating or the like to increase the adhesion of the surface. The material of the base layer 32 may be selected from the group consisting of an acrylic resin, a polyester, a silicone acrylic resin, a methacrylic resin or a polydecane resin. Polysiloxane resin), etc., but is not limited thereto. In the present embodiment, the base layer 32 is, for example, a coating of poly(methyl methacrylate) (PMMA). The thickness of the base layer 32 is between about 5 nanometers (nm) and 10 micrometers (μm), for example, 50 nm, 250 nm, 500 nm, 1 μm, 5 μm or 10 μm, etc., but is not limited thereto. .

Referring to FIG. 3, a method for manufacturing a polymer substrate having a transparent conductive oxide layer according to a preferred embodiment of the present invention is followed by forming a thin film of germanium oxide 33 on the base layer 32. In this step, the present invention can be deposited on the substrate layer 32 by chemical vapor deposition (CVD), physical vapor deposition (PVD) or other existing deposition methods. The ruthenium dioxide layer 33 is for preventing moisture from intruding into the transparent conductive oxide layer 34 from the side of the polymer substrate 31, thereby ensuring electrical stability and use of the transparent conductive oxide layer 34. life. The thickness of the ruthenium dioxide film 33 is between about 10 and 100 nanometers (nm), for example, 10, 15, 50, 85 or 100 nm, etc., but is not limited thereto.

Referring to FIG. 3, a method for manufacturing a polymer substrate having a transparent conductive oxide layer according to a preferred embodiment of the present invention is followed by forming a transparent conductive oxide layer 34 on the ceria film 33. In this step, the material of the transparent conductive oxide layer 34 may be selected from indium tin oxide (ITO), zinc oxide (ZnO) or aluminum doped zinc oxide (AZO), but Not limited to this. In this embodiment, the material of the transparent conductive oxide layer 34 is, for example, indium tin oxide. The present invention can deposit the transparent conductive oxide layer 34 on the ceria film 33 by physical vapor deposition or other conventional deposition methods. The thickness of the transparent conductive oxide layer 34 is between about 15 and 150 nanometers (nm), such as 15, 50, 75, 100, 125 or 150 nm, etc., but is not limited thereto. Furthermore, the transparent conductive oxide layer 34 can be deposited by physical vapor deposition or other existing deposition methods to form a copper film or other metal film (not shown), and fabricated into an electrode by a lithography process. The circuit can be used to initially form a touch substrate 30 of a touch sensor.

In addition, before the step of heating the polymer substrate 31, the present invention may optionally include: forming a protective layer 35 on the lower surface of the polymer substrate 31 to protect the polymer substrate. The surface below 31 is not worn. The timing of coating the protective layer 35 may be before the first step or after any step. The material of the protective layer 35 may be selected from the group consisting of acrylic resin, polyester resin, decyl acrylate resin, methacryl resin or polyoxyalkylene resin, but is not limited thereto. In the present embodiment, the protective layer 35 is, for example, a coating of polymethyl methacrylate. The thickness of the base layer 32 is between about 5 nanometers (nm) and 10 micrometers (μm), such as 50 nm, 250 nm, 500 nm, 1 μm, 5 μm, or 10 μm.

In another embodiment of the present invention, the above three steps may be integrated into the same step, that is, a polymer substrate 31 is provided, and the base substrate 32 is pre-coated on the polymer substrate 31, and at least the base layer 32 is coated thereon. There is a transparent conductive oxide layer 34. This step means that the base layer 32 and the transparent conductive oxide layer 34 are formed in advance on the polymer substrate 31 when the polymer substrate 31 is provided, wherein the base layer 32 and the transparent conductive oxide layer 34 are further The ruthenium dioxide film 33 is selected; and the protective layer 35 is selectively formed on the lower surface of the polymer substrate 31.

Referring to FIG. 3, a method for manufacturing a polymer substrate having a transparent conductive oxide layer according to a preferred embodiment of the present invention is followed by heating the polymer substrate 31 to 120 to 180 ° C in an oxygen-free environment. And continuing for 60 to 90 minutes to reduce the number and particle diameter of the white particles 321 generated by the heating in the base layer 32. In this step, the polymer substrate 31 is first placed on a carrier 41, or is clamped to form a suspended state by a plurality of clamping members (not shown). Then, a chamber 42 is used to cover the carrier 41 and the polymer substrate 31 to be insulated from the outside atmosphere. Next, the chamber 42 is evacuated to 3 x 10 ^-4 torr or below to form a closed vacuum chamber as the oxygen-free environment 40. Alternatively, if necessary, an inert gas may be further injected after evacuation to form a chamber filled with an inert gas as the oxygen-free environment 40. The above inert gas may be selected, for example, from nitrogen (N ₂ ) or argon (Ar). In this embodiment, the inert gas system is selected from argon.

Furthermore, at least one heater 43 is provided in the chamber 42, for example, a plurality of heating lamps, but is not limited thereto. The heater 43 is configured to increase the space temperature in the oxygen-free environment 40 to 120 to 180 ° C for 60 to 90 minutes, for example, to 120, 140, 150, 160 or 180 ° C, and continue for 60, 65, 70, 75, 80, 85 or 90 minutes. The purpose of heating the polymer substrate 31 in the oxygen-free environment 40 is to reduce the number and particle diameter of the white particles 321 generated by heating in the base layer 32, and to ensure that the number and particle diameter of the white particles 321 are Below a predetermined value to avoid excessively affecting the overall light transmittance. For example, the present invention controls the ratio of the white particles 321 to the total surface area of the base layer 32 between 1.0% and 0.0001%, for example, 1.0%, 0.5%, 0.1%, 0.05%, 0.01%, 0.005. %, 0.001%, 0.0005% or 0.0001%, etc., but is not limited thereto. And, the present invention controls the particle size of the white particles 321 to be between 1000 and 1 nanometer (nm), for example, 1000, 800, 750, 500, 250, 150, 100, 75, 50, 25 or 1 nm, etc., but is not limited to this.

Please refer to the figures 5A and 5B, which respectively disclose the electronic scanning of the existing polymer substrate with the basal layer after heating in the general atmosphere and in the whole oxygen (O ₂ ) environment to 150 ° C for 30 minutes. Microphotograph (magnification 1000x). As can be seen from FIGS. 5A and 5B, after heating the conventional polymer substrate 11 as shown in FIG. 1, the white particles 121 generated by the base layer 12 (and the polymer substrate 11) due to heating account for the total of the base layer 12. The ratio of surface area is significantly greater than 1.0%; and the particle size of most white particles 121 is significantly greater than 1 micrometer (μm). Therefore, a large amount of white particles 121 will severely block the light passing through, and thus greatly reduce the overall light transmittance. In particular, the higher the oxygen content in the heating environment, the greater the proportion of the total surface area of the white particles 121 due to heating, and the larger the particle size of the white particles 121.

In contrast, please refer to FIGS. 6A and 6B, which respectively disclose that the polymer substrate of the present invention having a base layer is heated to 150 ° C for 30 minutes in an oxygen-free environment filled with argon (Ar). Electron scanning photomicrographs (magnifications 1000x, 5000x, respectively). 6A and 6B, after heating the polymer substrate 31 of the present invention as shown in FIG. 3, the white particles 321 which are generated by the heating of the base layer 32 (and the polymer substrate 31) occupy the base layer 32. The ratio of total surface area is significantly less than 1.0%; and the particle size of most white particles 321 is significantly less than 1 micron (i.e., 1000 nm). Therefore, when the number of the white particles 321 is reduced and the particle diameter is reduced, the probability that the white particles 321 block the passing light can be significantly reduced, and thus the overall light transmittance is greatly improved and improved.

As described above, the present invention in the third and fourth embodiments places the polymer substrate 31 in an anaerobic environment 40 as compared with the conventional polymer substrates 11 and 21 which cannot simultaneously reduce white particles and take into account the adhesion between the films. The high-temperature heating baking is performed to prevent the base layer 32 (and the polymer substrate 31) from being affected by oxygen during heating to generate white particles 321 , thereby significantly reducing the number of the white particles 321 and facilitating control of the white particles 321 Since the particle size is up to the nanometer level, the overall light transmittance can be ensured and the impedance of the transparent conductive oxide layer 34 can be effectively reduced, so that the film quality and the manufacturing yield can be relatively improved. Furthermore, the present invention directly heats and bakes the process in the oxygen-free environment 40 to reduce the amount and particle size of the white particles 321 produced by the base layer 32, thereby eliminating the need to apply any hard coating. Therefore, the adhesion between the film and the substrate is not affected by the provision of the hard coating, so that structural reliability, manufacturing yield and service life can be ensured.

The present invention has been disclosed in its preferred embodiments, and is not intended to limit the invention, and the present invention may be modified and modified without departing from the spirit and scope of the invention. The scope of protection is subject to the definition of the scope of the patent application.

10. . . Touch substrate

11. . . Polymer substrate

12. . . Base layer

121. . . White particles

13. . . Cerium oxide film

14. . . Transparent conductive oxide layer

20. . . Touch substrate

twenty one. . . Polymer substrate

twenty two. . . Base layer

221. . . White particles

twenty three. . . Hard coating

twenty four. . . Cerium oxide film

25. . . Transparent conductive oxide layer

30. . . Touch substrate

31. . . Polymer substrate

32. . . Base layer

321. . . White particles

33. . . Cerium oxide film

34. . . Transparent conductive oxide layer

35. . . The protective layer

40. . . Anaerobic environment

41. . . Carrier

42. . . Chamber

43. . . Heater

FIG. 1 is a cross-sectional view of a touch substrate of a conventional touch sensor.

Figure 2: A cross-sectional view of another touch substrate of a conventional touch sensor.

Figure 3 is a cross-sectional view showing a polymer substrate having a transparent conductive oxide layer in accordance with a preferred embodiment of the present invention.

Fig. 4 is a view showing the heating of a polymer substrate having a transparent conductive oxide layer in an oxygen-free environment according to a preferred embodiment of the present invention.

5A and 5B: Electron scanning photomicrographs (magnification: 1000x) of a conventional polymer substrate having a basal layer after being baked in an atmospheric environment and under an oxygen (O ₂ ) atmosphere for 30 minutes at 150 ° C.

6A and 6B: Electron scanning photomicrographs of the polymer substrate of the present invention having a basal layer heated to 150 ° C for 30 minutes in an oxygen-free environment filled with argon (Ar) (magnification of 1000x, respectively) 5000x).

Claims (10)

A method for manufacturing a polymer substrate having a transparent conductive oxide layer, comprising the steps of: providing a polymer substrate on which a base layer is preliminarily coated; and forming a thin film of ruthenium dioxide on the base layer; Forming a transparent conductive oxide layer on the ceria film; and heating the polymer substrate to 120 to 180 ° C in an oxygen-free environment for 60 to 90 minutes to reduce heat generation in the substrate layer The number and particle size of the white particles. The method for producing a polymer substrate having a transparent conductive oxide layer according to claim 1, wherein the ratio of the white particles to the total surface area of the base layer is controlled to be between 1.0% and 0.0001%. And the particle size of the white particles is controlled between 1000 and 1 nm. The method for producing a polymer substrate having a transparent conductive oxide layer according to claim 1, wherein the oxygen-free environment is a vacuum chamber. The method for producing a polymer substrate having a transparent conductive oxide layer according to claim 1, wherein the oxygen-free environment is a chamber filled with an inert gas; and the inert gas is selected from nitrogen or argon. The method for producing a polymer substrate having a transparent conductive oxide layer according to claim 1, wherein the material of the polymer substrate is selected from the group consisting of polyethylene terephthalate; and the material of the transparent conductive oxide layer It is selected from the group consisting of indium tin oxide, zinc oxide or aluminum-doped zinc oxide; and the material of the base layer is selected from the group consisting of an acrylic resin, a polyester resin, a decyl acrylate resin, a methacrylic resin or a polyoxyalkylene resin. The method for producing a polymer substrate having a transparent conductive oxide layer according to claim 1, wherein before the step of heating the polymer substrate, the method further comprises: coating a lower surface of the polymer substrate to form a polymer substrate The protective layer. The method for producing a polymer substrate having a transparent conductive oxide layer according to claim 1, wherein the material of the protective layer is selected from the group consisting of an acrylic resin, a polyester resin, a decyl acrylate resin, a methacryl resin or Polyoxyalkylene resin. The method for manufacturing a polymer substrate having a transparent conductive oxide layer according to the first aspect of the invention, wherein after the step of heating the polymer substrate, the method further comprises: fabricating a touch sensor with the polymer substrate A touch substrate. A method for manufacturing a polymer substrate having a transparent conductive oxide layer, comprising the steps of: providing a polymer substrate having a base layer pre-coated thereon, and having at least one transparent conductive oxide layer on the base layer And heating the polymer substrate to an oxygen-free environment to 120 to 180 ° C for 60 to 90 minutes to reduce the amount and particle size of the white particles generated by heating in the substrate layer. The method for producing a polymer substrate having a transparent conductive oxide layer according to claim 9, wherein the ratio of the white particles to the total surface area of the base layer is controlled to be between 1.0% and 0.0001%. And the particle size of the white particles is controlled between 1 micrometer and 1 nanometer.