TW200535261A - Transparent conductive thin film and method of manufacturing thereof - Google Patents

Abstract

A transparent conductive thin film and method of manufacturing thereof are provided. The method is to deposit a transparent conductive thin film on a flexible transparent substrate by performing an intermittent low temperature sputtering process. The resulting transparent conductive thin film is amorphous or lower crystallinity and its sheet resistance is less than that formed by continuous process.

Description

200535261 V. Description of the invention (1) [Technical field to which the invention belongs] The present invention relates to a transparent conductive thin film and a manufacturing method thereof ', and particularly to a flexible substrate with a low temperature process The formed transparent conductive film and its manufacturing method. [Previous technology] With the development of high technology, video products, especially digital video or imaging devices, have become common products in ordinary life. In these digitized video or image devices, the display is an important component for displaying related information so that the user can read the information from the display or control the operation of the device. Most current displays use temperature-resistant glass as the substrate to meet process requirements. However, in the future, computer, communication and consumer electronic products will become thinner, lighter, shorter and more functional. In recent years, the focus of research in various circles has shifted to how to use flexible plastic substrates. Deposit a transparent conductive film. However, because the plastic substrate is a material that is not resistant to temperature, a high-temperature process above 350 degrees Celsius cannot be used to deposit a highly conductive transparent conductive film. The low-temperature process will cause poor crystallinity of the conductive film, which will lead to the increase in resistance of the transparent conductive film. Therefore, the development of the low-temperature sputtering process to deposit conductive films with high light transmission and low resistance has become the focus of research and development in various countries. In national patent No. 48 9 0 1 9 5 it has been proposed that the partial pressure ratio of water to inert gas is in the range of 2.5 x 10-6 to 7 x 10-4, and to control the substrate during film formation Μ

200535261 V. Description of the invention (2) Method for maintaining temperature. Under the oxygen atmosphere, the transparent conductive technology is finally processed. In addition, the formula is close to the source, where after mixing, the target and the membrane. Among them are US patents. [Summary of the Invention] Therefore, the manufacturing method is transparent and low-power. The present invention has high light transmittance. According to the present invention, the aforementioned intermittent section is plated intermittently, each of which is f80, and after the transparent conductive film is formed on the transparent substrate, the layered body forming the transparent conductive film on the substrate 含有 is contained and heat-treated at 80 ~ 150 C. 0 · 5 ~ 12 hours to obtain the most electric film 1 t. The above-mentioned patent does not disclose "intermittent" sputtering. The technology of this patent does not need to heat the geothermally-coated geodesic substrate after the film is formed. Base temperature 6, 383 The present invention is another low-current method for imparting resistance characteristics. A sputtering process is proposed at sputtering stage 6, 383'345. Ion beam annihilation method is proposed. Ί t a mixture as an initial The money mine ion beam provides a chlorine between the monthly gas and the low electron affinity, to obtain the final transparent conductivity from the actinide Luo Luoxie milk, and maintain it between 25 t ~ 100. However,… also does not disclose the "intermittent" technology to provide a transparent, electrically thin film substrate, such as acrylic substrates, which are both high in purpose, is to provide a kind of transmission resistance and amorphous or蚨 7 Shou Dian Lian Bing has negative characteristics such as low crystallinity, a method for manufacturing a conductive thin film, deposition of a conductive material on a substrate, and a conductive material. The characteristics of the conductive film are described by 々 红 奴 π, I ... The process includes several stages of sputtering and several stages of interruption. When the substrate is sputtered, the container is white τ ", and the system reaches its thermal deformation temperature.

200535261 V. Invention description (3) Stop before heat distortion temperature (HDT), and each interruption phase is arranged between the sputtering phases. The present invention also proposes a transparent conductive film prepared by using the foregoing manufacturing method, which is characterized in that the transparent conductive film is amorphous, the light transmittance is between 70-90%, and the sheet resistance is 10-500 Ω / 匚] . Because the present invention adopts an intermittent sputtering process to deposit a transparent conductive film such as an indium tin oxide (IT0) film, it can form a substrate with high light transmission / low temperature on a substrate that is not resistant to high temperatures (below the substrate temperature). / Resistance and amorphous or low crystallinity characteristics-to avoid high temperature resistant substrate deformation and cracking. / 、 'The traditional continuous sputtering process will have a ττ target because of the escape of oxygen in it, which affects the system's atmosphere ratio, so the long-term bombardment results in a systematic atmosphere configuration which is relatively unaffected. Intermittent time is used to release the bombardment stress, so as to provide the available space between the atom and the reactor, and to reach an equilibrium state, leading to the wrong light transmittance required for the second movement. The transparent conductive phase has both low sheet resistance and non-a. In addition to the effect of stone 4 i ΐ ΐ Λ, such as acrylic materials, the present invention needs to be changed from high temperature to two: high temperature substrate = ί material (resistant Temperature-resistant glass and non-temperature-resistant plastic materials: The pieces can be made of different minerals and have a different degree of whiteness. In addition, the intermittent splashing speed or reciprocating rate of the present invention: make === Other items & special 1 man points can be more obvious

200535261 V. Description of the invention (4) It is easy to understand. A preferred embodiment is given below, and it will be described in detail with the accompanying drawings. [Embodiment] Fig. 1 is a flowchart of steps of a transparent conductive film according to a preferred embodiment of the present invention. Please refer to FIG. 1. In this embodiment, an intermittent sputtering process (step 100) is used to deposit a conductive film on a substrate, wherein the temperature of the substrate needs to be maintained at room temperature to the heat distortion temperature of the substrate (heat distortion temperature (HDT): For example, when the substrate is an acrylic substrate, the thermal deformation temperature of the acrylic substrate is about 80 ° c. To avoid substrate deformation and cracking, acrylic The temperature of the force substrate needs to be controlled and maintained below 800 ° C. The foregoing intermittent sputtering process 100 includes, for example, a multi-stage sputtering stage (step 102) and a multi-stage interruption stage (step 104). Among them, each interruption stage 104 is arranged between the sputtering stages 102, and each sputtering stage 102 needs to consider the total time required for the overall thickness of the money deposit film, and the time required for each cheap money stage Less than the time required for the substrate temperature to rise to the thermal deformation temperature during sputtering, and the time for each interruption period is 104, the balance time and mass production efficiency need to be considered, for example, between 0.55 ~ 90 minutes. Although only one interruption phase (step 〇 04) is shown in step 丨 00 in FIG. 1, this is not intended to limit the number of interruption phases 104 and sputtering phase 102 of the present invention; that is, Anyone who forms a transparent conductive film based on the concept of "% intermittent base plating process" is the scope of the present invention, and the present invention can use the rotation or reciprocating method, use the rotation or reciprocating rate control, or supplement the intermittent Time to achieve. In addition, the intermittent sputtering process of the present invention can use a money mining equipment.

Page 14 200535261 V. Description of the invention (5) For implementation, such as pulsed DC plasma magnetron basement equipment or RF AC plasma magnetron sputtering equipment, but it is also applicable to all types of coating equipment. Moreover, because the present invention can be applied to all sputtering processes and substrates that require high temperature to low temperature conditions, the process of FIG. 1 can be applied to general transparent plastic substrates or glass substrates, where the transparent plastic substrate includes Acrylic substrates such as polymethylmethacrylate (PMMA), polyester, polycarbonate, PC, polyimide (PI), and ART0N® The glass substrate includes heat-resistant glass and the like. In addition, the conductive film formed by the present invention includes, for example, an indium tin oxide (ITO) film commonly used in displays. In addition, the transparent conductive film prepared by the intermittent sputtering process of the present invention has an amorphous or low crystallinity, a light transmittance between 70-90%, and a sheet resistance between 10-50. 0 Ω / □ characteristic. The following is an experimental example using this embodiment, which also includes a conventional continuous sputtering process as a comparative example. Experimental example 1. Coating conditions: The substrates of each group in the experimental examples are acrylic substrates, and the target material is indium tin oxide (I T 0). The sputtering atmosphere was argon (99%) and oxygen (丨%), and no water or radon gas was added. The mining equipment is a pulse-type magnetic lightning hard-sputtering machine (manufactured by Taiwan Double Strong Co., Ltd.) with a sputtering power of 30 $.工 ’2. Changing conditions: The comparative example's continuous money-reduction process has a cheap time of 3,000 seconds.

13259twf.ptd Page 15 200535261 V. Description of the invention (6) (Vacuum degree 5-7mtorr), the deposition of transparent conductive film is completed in one time. The intermittent sputtering process of the present invention is divided into (1) a sputtering time of 100 seconds (vacuum degree 5-7 mt 〇rr) 'resting adjustment time 0 seconds' cycle-by-cycle twice (that is, the total time of ore destruction 3 0 0 0 seconds, completed three times), and (2) sputtering time 1000 seconds (vacuity 5-7mtorr), rest time 1 hour (vacuity 5 X 10-3mtorr), three cycles (ie, sputtering The total time is 30000 seconds, and the rest adjustment time is 3 hours, which is completed three times) Two examples. Among them, the time of each interruption phase (see step 104 of Fig. 1) refers to the time of each "resting adjustment time". The results of the transparent conductive indium tin oxide thin film obtained by the above processes after measuring the film thickness, the sheet resistance, and the X-ray diffraction (X-r a y d i f f r a c t i ο η, X R D) are shown in Table 1 below. Table 1. Flail-type intermittent (1) · intermittent (2) sheet resistance (Ω / CD 74.4 + 9.6 44.3 ± 16.6 24_6 soil 1_1 film thickness (nm) 768 ± 13 770 + 19 7454: 15 crystalline structure partly crystallized As can be seen from Table 1, the sheet resistance of the transparent conductive film produced by the intermittent sputtering process of the present invention is significantly lower than the conventional continuous process, and the thickness is also thinner. In addition, please refer to the figure 2, which are XRD diagrams of transparent conductive films made according to the preferred embodiment of the present invention and the comparative example, respectively, which include only XRD for acrylic substrates and conventional ("continuous" / Expression) and the present invention (represented by "intermittent (1)" and "intermittent (2)")

13259twf.ptd Page 16 200535261 V. Description of Invention (7) The transparent conductive film made by (7) is X R D. As can be seen from Fig. 2, the transparent conductive film formed by the method of the present invention is amorphous. The transparent conductive film produced by the conventional continuous sputtering process has a diffraction peak (440) in the XRD pattern, which indicates that it has crystals. In addition, the measured transmittances of the transparent conductive films represented by "intermittent (1)" and "intermittent (2)" were 87.0 and 85.9, respectively. Therefore, it was confirmed that the transparent conductive film prepared according to the preferred embodiment of the present invention can also obtain good light transmittance. In summary, the features of the present invention are: (1). The present invention successfully deposits the I T0 film on a substrate that is not resistant to temperature by using an intermittent, low-temperature sputtering process to avoid such substrates from being deformed by high temperatures. With cracking. The obtained transparent conductive film has good photoelectric properties and does not affect the performance of the substrate. (2). The high-transmittance, low-resistance transparent conductive film formed by the present invention is amorphous or has a low crystallinity structure, and the 'South crystallinity, South-transmittance, and low resistance obtained by the traditional high-temperature sputtering process IT 0 film is 'extremely different' and therefore has easy #etching characteristics. (3) The present invention not only has the advantage that the atmosphere distribution of the system is relatively unaffected, but also the film stack can use the intermittent time to release the bombardment stress to provide the time required for the movement of atoms and vacancies to reach an equilibrium state. (4). In addition to the unique effect on acrylic materials, the present invention is different for all sputtering processes and substrates (temperature-resistant glass and non-temperature-resistant plastic materials) that need to be changed from high temperature to low temperature conditions. The degree of effectiveness. (5). The intermittent sputtering process of the present invention can actually be performed by rotating or

13259twf.ptd Page 17 200535261 V. Description of the invention (8) The reciprocating method is achieved by using rotation or reciprocating rate control or supplemented by intermittent time control. Although the present invention has been disclosed in the preferred embodiment as above, it is not intended to limit the present invention. Any person skilled in the art can make some modifications and retouching without departing from the spirit and scope of the present invention. Therefore, the present invention The scope of protection shall be determined by the scope of the attached patent application.

13259twf.ptd Page 18 200535261 Brief description of the drawings Figure 1 is a flowchart of the steps of a transparent conductive film according to a preferred embodiment of the present invention. Fig. 2 is an XRD pattern of a transparent conductive film prepared according to an embodiment of the present invention and a transparent conductive film of a comparative example, respectively. [Schematic description] 100, 102, 104: Step ill 13259twf.ptd Page 19

Claims (1)

200535261 6. Application Patent Scope 1. A method for manufacturing a transparent conductive film, which deposits a conductive film on a substrate by an intermittent sputtering process, which is characterized in that the intermittent sputtering process includes: most stages of sputtering Phase, wherein each of the sputtering phases is stopped before the thermal accumulation temperature of the substrate reaches the thermal deformation temperature of the substrate when the substrate is sputtered; and most of the interruption phases are arranged between the sputtering phases. 2. The method for manufacturing a transparent conductive film according to item 1 of the scope of patent application, wherein the time of each of these interrupted phases is between 0.5 and 90 minutes. 3. The method for manufacturing a transparent conductive film according to item 1 of the scope of patent application, wherein the temperature of the substrate is maintained between room temperature and a heat distortion temperature of the substrate to avoid the substrate Wood deformation and cracking. 4. The method for manufacturing a transparent conductive film according to item 1 of the scope of patent application, wherein the intermittent sputtering process uses a sputtering equipment. 5. The method for manufacturing a transparent conductive film according to item 4 of the scope of patent application, wherein the sputtering equipment includes a pulsed DC plasma magnetron sputtering device or a radio frequency AC plasma magnetron sputtering device. 6. The method for manufacturing a transparent conductive film according to item 1 of the patent application scope, wherein the substrate comprises a transparent plastic substrate or a glass substrate. 7. The method for manufacturing a transparent conductive film according to item 6 of the scope of the patent application, wherein the transparent plastic substrate includes acrylic, polyester, polycarbonate (PC), and polycarbonate 13259twf.ptd Page 20 200535261 6. Scope of Patent Application One of amine (polyimide, PI). 8. The method for manufacturing a transparent conductive film according to item 6 of the patent application scope, wherein the glass substrate comprises heat-resistant glass. 9 β The method for manufacturing a transparent conductive film according to item 1 of the scope of patent application, wherein the conductive film includes an indium tin oxide (ITO) film. 10. The method for manufacturing a transparent conductive film according to item 1 of the scope of patent application, wherein the conductive film includes an amorphous film. 1 1. A transparent conductive film made by using the manufacturing method of any one of claims 1 to 10, wherein the transparent conductive film is amorphous and has a light transmittance of 70-9 Between 0% and the sheet resistance is 10 ~ 50 0 Ω / □. 1 2. The transparent conductive film according to item 11 of the scope of patent application, wherein the material of the conductive film includes an indium tin oxide film. 13259twf.ptd Page 21