The present application claims priority to U.S. patent application Ser. No. 18/076,458, titled “Stretchable composite electrode and fabricating method thereof” and filed on Dec. 7, 2022, which is incorporated herein by reference.
The present disclosure relates to a stretchable composite electrode and a manufacturing method of a stretchable composite electrode.
With the development of science and technology, many electronic devices on the market are gradually evolving towards a thin, short, and wearable form. However, a sensing electrode in a wearable electronic device is often unable to withstand the large stretching deformation caused by limb movements of a user and is prone to local cracks or whole fracture during use, which limits its application as a stretchable electrode.
Silver nanowires have the potential to replace existing materials as electrode materials in wearable electronic devices due to their high electrical conductivity, high ductility, and excellent optical properties. A conventional technique is to coat a solution containing silver nanowires on a soft substrate. However, due to poor adhesion of silver nanowires and when the selected soft substrate is a material with low surface tension, the silver nanowire solution often condenses into water droplets on the surface of the substrate, thus the silver nanowire layer cannot be stably formed. It is mentioned in China patent of publication patent number CN107655598B that by using a solvent to treat the surface of a polydimethylsiloxane (PDMS) substrate, the adhesion between the PDMS substrate and the silver nanowire is increased. However, the experiment of the present disclosure proves that a surface treatment by plasma has a better improvement than a surface treatment by solvent. On the other hand, it is mentioned in China patent of publication patent number CN112428699B that by using plasma to treat the surface of the PDMS substrate, the adhesion between the PDMS substrate and the silver nanowire is increased. However, China patent of publication patent number CN112428699B only discloses the formation of the silver nanowire layer on the surface of the PDMS substrate and does not disclose the technical features of the silver nanowire layer partially embedded in the PDMS film of the present disclosure. Although these methods can improve the hydrophobicity of the PDMS material and form the silver nanowire layer on the PDMS substrate, it is difficult to prevent the silver nanowire layer from being broken or peeled off when stretched by external force.
Based on the above, how to provide a stretchable electrode that can be well and stably applied to wearable electronic devices is an important issue for those skilled in the art.
According to some embodiments of the present disclosure, a stretchable composite electrode includes a film and a silver nanowire layer. The film has a surface that is substantially flat, and the film is a polymer film with a Young's modulus between 1.25 MPa and 3 MPa. The silver nanowire layer is partially embedded in the surface of the film. When a stretching length variation of the stretchable composite electrode is 47%, a resistance recovery of the stretchable composite electrode is between 94% and 98%.
In some embodiments of the present disclosure, the polymer film is polydimethylsiloxane.
In some embodiments of the present disclosure, when the stretching length variation of the stretchable composite electrode is 18%, the resistance recovery of the stretchable composite electrode is between 97% and 98%.
In some embodiments of the present disclosure, a thickness of a portion of the silver nanowire layer that is embedded in the film is 0.027% to 0.048% of a thickness of the film.
In some embodiments of the present disclosure, the silver nanowire layer includes a plurality of silver nanowires, and at least a portion of the silver nanowires are embedded in the surface of the film.
In some embodiments of the present disclosure, a thickness of the film is between 200 μm and 400 μm.
According to some other embodiments of the present disclosure, a manufacturing method of a stretchable composite electrode includes: forming a silver nanowire layer on a carrier, in which the silver nanowire layer has a first surface in contact with the carrier and a second surface facing away from the first surface; forming a coating on the second surface of the silver nanowire layer, and allowing a portion of the coating to penetrate into the silver nanowire layer; curing the coating to form a film, in which the coating that penetrates into the silver nanowire layer forms a surface of the film that is substantially flat, and a portion of the silver nanowire layer is embedded in the surface of the film; and removing the carrier, thereby exposing the first surface of the silver nanowire layer.
In some embodiments of the present disclosure, the manufacturing method of the stretchable composite further includes: performing a surface plasma treatment on the silver nanowire layer and the film from the first surface of the silver nanowire layer.
In some embodiments of the present disclosure, forming the silver nanowire layer on the carrier includes: coating a silver nanowire solution on the carrier in which the silver nanowire solution includes a plurality of silver nanowires, and a weight percentage concentration of the silver nanowires in the silver nanowire solution is between 0.01 wt. % and 0.2 wt. %.
In some embodiments of the present disclosure, the manufacturing method of the stretchable composite further includes: performing a heating treatment on the
According to the aforementioned embodiments of the present disclosure, since the silver nanowire layer is partially embedded in the film, the silver nanowire layer can be firmly combined with the film. Therefore, when the stretchable composite electrode is stretched by external force, the silver nanowire layer will not produce local cracks or even fracture the whole piece while being stretched, and thus the stretchable composite electrode can be well applied in wearable electronic devices.
The disclosure can be more fully understood by reading the following detailed description of the embodiments, with reference made to the accompanying drawings as follows:
Reference will now be made in detail to the present embodiments of the disclosure, examples of which are illustrated in the accompanying drawings. Wherever possible, the same reference numbers are used in the drawings and the description to refer to the same or like parts.
It should be understood that, relative terms such as “lower” or “bottom” and “upper” or “top” can be used herein to describe the relationship between one element and another element, as shown in the figure. It should be understood that relative terms are intended to include different orientations of the device other than those shown in the figures. For example, if the device in one figure is turned over, elements described as being on the “lower” side of other elements will be oriented on the “upper” side of the other elements. Therefore, the exemplary term “lower” may include an orientation of “lower” and “upper”, depending on the specific orientation of the drawing. Similarly, if the device in one figure is turned over, elements described as “below” other elements will be oriented “above” the other elements. Therefore, the exemplary term “below” can include an orientation of “above” and “below”.
Reference is made to
Reference is made to
In some embodiments, a thickness T2 of the film 110 may be between 200 μm and 400 μm. In some embodiments, a thickness T1 of the silver nanowire layer 120 embedded in the film 110 can be 0.027% to 0.048% of the thickness T2 of the film 110, such that the silver nanowire layer 120 can be stably disposed on the film 110. Hence, the stretchable composite electrode 100 can withstand relatively large stretching deformation without electrical failure. For details, reference is made to
In some embodiments, the stretchable composite electrode 100 may further include a conductive layer 130 disposed on a surface 121 (also referred to as the first surface 121 hereinafter) of the silver nanowire layer 120 facing away from the film 110. The conductive layer 130 can be disposed at a suitable position (for example, at both ends of the stretchable composite electrode 100) to form a signal line of the stretchable composite electrode 100 for transmitting signals to external electronic components such as a controller. In some preferred embodiments, the material of the conductive layer 130 may include metallic silver. In some embodiments, when the silver nanowire layer 120 does not include the matrix 122, the silver nanowire 124 can also be at least partially embedded in the conductive layer 130 (not shown). That is, the conductive layer 130 can cover a portion of the silver nanowires 124.
In some embodiments, the stretchable composite electrode 100 may further include a protective layer 140 disposed on the surface 111 of the film 110 and completely covering the silver nanowire layer 120 and the conductive layer 130. The protective layer 140 can be, for example, pressure sensitive adhesive (PSA), and when the stretchable composite electrode 100 has optical requirements, the protective layer 140 can be, for example, optical clear adhesive (OCA). More specifically, the protective layer 140 may include rubber-based pressure sensitive adhesive, silicon-based material, and acrylic-based material. In some preferred embodiments, the material of the protective layer 140 may be an acrylic-based material.
The aforementioned structural features of the stretchable composite electrode 100 of the present disclosure will be more clearly illustrated through the description of the manufacturing steps below.
Reference is made to
First, reference is made to
In some embodiments, before forming the silver nanowire layer 120 on the carrier 50, annealing may be performed on the carrier 50, such that the carrier 50 has better stability, and the residual stress of the carrier 50 is eliminated, in which the annealing temperature may be between 140° C. and 160ºC, and the annealing time may be between 2 minutes and 5 minutes. In some embodiments, after the silver nanowire layer 120 is formed on the surface 51 of the carrier 50, a curing process is performed to cure the formed silver nanowire layer 120 and to lower the junction resistance of the silver nanowire layer 120, in order to improve the electrical performance of the silver nanowire layer 120, in which the curing temperature can be between 140° ° C. to 160ºC, and the curing time can be between 2 minutes to between 5 minutes. In some embodiments, heating treatment may be performed before and after forming the silver nanowire layer 120 on the carrier 50. In some embodiments, the heating treatment includes an annealing process, a curing process, and the like. In some embodiments, the heating treatment is performed by using an infrared (IR) sinter oven.
In some embodiments, the silver nanowire layer 120 can be formed by coating the silver nanowire solution on the surface 51 of the carrier 50, and the silver nanowire solution can be coated at a temperature between 110° C. and 130° C. In some embodiments, the stage heat of the carrier 50 can be set at 120° C. to perform the operation of coating the silver nanowire solution. After the silver nanowire layer 120 is formed, the silver nanowire layer 120 can be soft-baked at a temperature between 110° C. and 130° C. for 3 minutes, and then cured (hard-baked) to make the silver nanowire layer 120 have a low and stable resistance. In some embodiments, the hard baking temperature can be between 140° C. and 160ºC, and the baking time can be between 2 minutes and 5 minutes. In some embodiments, the hard baking can be performed at 150° C. for 3 minutes. In some embodiments, the soft baking and hard baking can be done in an infrared sintering furnace. After step S10 is completed, the silver nanowire layer 120 including at least the silver nanowire 124 can be obtained, and the silver nanowire layer 120 has a first surface 121 in contact with the carrier 50 and a second surface 123 facing away from the first surface 121.
Next, reference is made to
During step S20, a portion of the coating 80 will infiltrate into the silver nanowire layer 120, more specifically, a portion of the coating 80 will penetrate between the silver nanowires 124. In this way, the silver nanowires 124 in the silver nanowire layer 120 adjacent to the second surface 123 of the silver nanowire layer 120 can be partially embedded in the coating 80. On the other hand, the process of forming the coating 80 can make a depth d of the coating 80 that penetrated into the silver nanowire layer 120 at each position be substantially the same through a suitable method. That is, the coating 80 penetrating into the silver nanowire layer 120 can form a surface 81 that is substantially flat.
Subsequently, reference is made to
Next, reference is made to
Subsequently, reference is made to
In some embodiments, before forming the conductive layer 130, the silver nanowire layer 120 and the film 110 can be subjected to a surface plasma treatment, so as to facilitate the coating of the conductive layer 130 and the disposition of other subsequent layers (e.g., the protective layer 140). In detail, the silver nanowire layer 120 and the film 110 can be subjected to a surface plasma treatment from the side of the first surface 121 of the silver nanowire layer 120 to remove the residue attached to the surface of the silver nanowire 124, such that the silver nanowires 124 can be directly exposed to form contact with the conductive layer 130, and the adhesion between the film 110 and the conductive layer 130 and other subsequent layers (e.g., the protective layer 140) can be improved. In some embodiments, the surface plasma treatment can be carried out on the silver nanowire layer 120 and the film 110 simultaneously for 5 minutes with argon plasma at a power of 0.2 KW to 0.6 KW and a flow rate of 40 ML/min to 120 ML/min under vacuum for 10 minutes to achieve better results. It is worth noting that, compared with using oxygen plasma for surface plasma treatment, the use of argon plasma can reduce the possibility of oxidation of the silver nanowires 124 which leads to electrical failure. In some embodiments, the silver nanowire layer 120 and the film 110 may be subjected to solvent treating before or after the surface plasma treatment. In some embodiments, the solvent treating is performed by using a silicon-based surface treatment solvent.
In some embodiments, after the conductive layer 130 is formed, the slurry containing the silver material can be cured to form the conductive layer 130, in which the curing temperature can be between 100° C. and 120° C., and the curing time can be between 15 minutes and 25 minutes. In some embodiments, after the silver material is cured to form the conductive layer 130, the stretchable composite electrode 100 can further be pre-cut to a suitable size.
Next, reference is made to
Reference is made to
In the following description, a variety of experiments will be used to illustrate how the implementation details (for example, the selection of materials and the implementation methods of each step) are obtained when manufacturing the stretchable composite electrode 100 of the present disclosure, and features and effects of the present disclosure are verified through various experiments. It is noted that without exceeding the scope of the present disclosure, the materials used, their amount and ratio, processing details, processing flow, etc. can be appropriately alternated. Therefore, the present disclosure should not be limited by the embodiments provided below.
Regarding the step of forming the silver nanowire layer 120 on the carrier plate (i.e., step S10), the concentration of the silver nanowire 124 in the silver nanowire solution, the spraying times, and the direction of spraying can affect the overall coating uniformity of the silver nanowire layer 120, which further affects the electrical performance of the silver nanowire layer 120. Reference is made to Table 2, which shows the effects of the dilution concentration of the silver nanowire solution and the spraying conditions on the electrical performance of the silver nanowire layer 120 of Comparative Example 1. In Comparative Example 1, sample was formed by diluting the silver nanowire ink with isopropanol (solvent) to obtain a silver nanowire solution, then spraying the silver nanowire solution on the surface of the glass and baking the silver nanowire solution on the surface of the glass at a temperature of 120° C. for 3 minutes to form the silver nanowire layer 120, and then covering the silver nanowire layer 120 with a protective film RF (of which the material is polyethylene). The resistance was measured by eddy current. The parameters of the spraying machine are: atomization pressure of 0.1 MPa, valve pressure of 0.4 MPa, nozzle spacing of 8 mm, nozzle height of 40 mm, and valve speed of 75 mm/s.
It can be seen from the results shown in Table 2 that when the silver nanowire ink is diluted with isopropanol at a volume ratio of 1:5, the resulting silver nanowire solution has better sprayability, thereby improving the uniformity of the resistance. In addition, more spraying times (spraying multiple times in the X direction and Y direction) and more baking times can improve the uniformity of the resistance. Furthermore, smaller fluid velocity (smaller valve scale) is helpful to improve the uniformity of resistance. Based on the above results, the present disclosure can use any parameter in Table 2 to spray the silver nanowire solution.
When the silver nanowire layer 120 is disposed on the film 110 that is made by a material of PDMS and is partially embedded in the PDMS film 110, the stretchable composite electrode 100 can withstand greater stress (larger stretching deformation) without causing a sharp increase in resistance while being stretched. Specifically, reference is made to
Furthermore, reference is made to
Regarding the effect of the step of carrying out a surface plasma treatment on the silver nanowire layer 120 and the film 110 on the adhesion of the conductive layer 130, in this experiment, a PDMS material was coated on the PET film and cured to form the PDMS film 110, then a vacuum oxygen plasma treatment and/or solvent surface treatment were carried out on the PDMS film 110, then a silver paste (brand/model: Phoenix AW02A) was coated on the PDMS film 110 that had undergone a surface treatment, and then the silver paste was sintered to form the conductive layer 130. Next, the conductive layer 130 is subjected to a tape test (100-grid test) to verify the effect of the surface plasma treatment on the adhesion of the conductive layer 130. Reference is made to Table 3 for the test results.
As can be seen from the results of Table 3, when no surface treatment is carried out on the silver nanowire layer 120 and the film 110, the test sample cannot pass the 100-grid test; when the silver nanowire layer 120 and the film 110 are treated with solvent surface treatment, but not treated with surface plasma treatment, the test sample cannot pass the 100-grid test; when the silver nanowire layer 120 and the film 110 are treated with surface plasma treatment, the test sample can pass the 100-grid test. It can be seen that the surface plasma treatment on the silver nanowire layer 120 and the film 110 has a positive impact on the adhesion of the conductive layer 130.
However, in another experiment, it was found that oxygen plasma would cause the silver nanowires 124 to oxidize and negatively affect the electrical function, while argon plasma could maintain the electrical function of the silver nanowires 124. Specifically, reference is made to
Regarding the effect of the step of carrying out surface plasma treatment on the PDMS film 110 on the adhesion between the protective layer 140 and the PDMS film 110, please refer to
As can be seen from Comparative Example 7 of
In this experiment, through the measurement of the water contact angle (WCA) (test 1) and the measurement of the resistance (test 2), the effect of embedding the silver nanowires 124 in the film 110 on the electrical performance of the stretchable composite electrode 100 is reflected. In Test 1, a PDMS material was coated on the PET film and cured to form the PDMS film 110, then the PDMS film 110 was selectively treated by a vacuum surface treatment with oxygen plasma, then the silver nanowire solution containing the silver nanowires 124 was sprayed onto the PDMS film 110, and then three measurement points (No. #1-#3) were randomly selected to measure the water contact angle between the silver nanowire solution and the PDMS film 110. In Test 2, a PDMS material was coated on the PET film and cured to form a PDMS film 110, then the PDMS film 110 was subjected to a vacuum surface treatment with oxygen plasma, then the silver nanowire solution containing the silver nanowires 124 was sprayed onto the PDMS film 110 and cured to form a silver nanowire layer 120, then a pressure-sensitive adhesive was formed on the silver nanowire layer 120, and then nine measurement points (No. #1-#9) of the entire stacked structure were randomly selected to measure the resistance. The result of each test is shown in Table 4.
As can be seen from the water contact angle measurement results in Table 4, the vacuum surface treatment to the PDMS film 110 can greatly reduce the water contact angle between the silver nanowire solution and the PDMS film 110. However, even if the vacuum surface treatment is performed, it is still impossible to completely prevent the silver nanowire solution from agglomerating into water droplets on the surface of the PDMS film 110, and it is impossible to improve the film-forming properties of the silver nanowire solution. In addition, it can be seen from the resistance measurement results in Table 4 that even if the PDMS film 110 is subjected to vacuum surface treatment, the silver nanowire layer 120 formed on the PDMS film 110 still has a relatively large resistance. It can be seen that it is difficult to form the silver nanowire layer 120 by directly spraying the silver nanowire solution on the surface of the PDMS film 110 in practice. Based on the above results, the present disclosure forms the silver nanowire layer 120 on the PDMS film 110 by transferring, such that the silver nanowire layer 120 can be partially embedded in the PDMS film 110, which is beneficial for the silver nanowire layer 120 to be firmly disposed on the film 110, such that the silver nanowire layer 120 can have a relatively small resistance when subjected to tensile stress.
In this experiment, the electrode of Comparative Example 9 and the stretchable composite electrode of Example 6 were stretched multiple times (using multiple test samples to stretch once), and the electrical tests were carried out during multiple stretches. The measurement method was to stretch the test samples by Instron tensile testing machine at a speed of 5 mm/min with an initial setting position of 50 mm, and at the initial stage where the test samples were in a tight state, the tensile applied was 0.08 N. The resistance variation of each test sample during stretching and the strain at the time of open circuit was measured. More specifically, reference is made to
For Comparative Example 9, it can be seen from
In this experiment, the stretchable composite electrode of Embodiment 7 was stretched multiple times (using a same test sample to stretch multiple times), and the resistance recovery test was carried out during multiple (six times) stretching. The measurement method was to stretch the test sample by Instron tensile testing machine at a speed of 100 mm/min with an initial setting position of 50 mm, and at the initial stage where the test sample was in a tight state, the tensile applied was 0.08 N. The resistance recovery of the test sample before and after multiple stretches was measured. More specifically, reference is made to
Reference is made to
On the other hand, although not shown in the drawings, under the premise that the stretching resistance recovery of the stretchable composite electrode of Embodiment 7 falls within the aforementioned range, the number of stretching recovery times of the stretchable composite electrode of Embodiment 7 is between 1 and 20 times.
In order to highlight the characteristics and effects of the present disclosure, the present disclosure further tests the stretching resistance recovery of the electrode of Comparative Example 10 by the same method as that of the stretchable composite electrode of Embodiment 7, in which the manufacturing method of the electrode of Comparative Example 10 was to form the PET film first, then the PET film was subjected to a vacuum surface treatment with oxygen plasma, then the silver nanowire solution at least containing the silver nanowires 124 was sprayed on the PET film and cured to form the silver nanowire layer 120 on an entire surface of the PET film, and then the conductive layer (silver layer) 130 was disposed on the silver nanowire layer 120. When performing the stretching resistance recovery test on Comparative Example 10, the stacked structure included the PET film, the silver nanowire layer 120, the conductive layer 130, and the conductive cloth 150 sequentially disposed from bottom to top, and the stack was clamped with clamps C to assist in the measurement, in which the stretching direction was the direction of the arrow as shown
According to the aforementioned embodiments of the present disclosure, since the silver nanowire layer is partially embedded in the film, the silver nanowire layer can be firmly combined with the film, and thus the stretchable composite electrode can be well applied to wearable electronic devices.
Although the present disclosure has been described in considerable detail with reference to certain embodiments thereof, other embodiments are possible. Therefore, the spirit and scope of the appended claims should not be limited to the description of the embodiments contained herein.
It will be apparent to those skilled in the art that various modifications and variations can be made to the structure of the present disclosure without departing from the scope or spirit of the disclosure. In view of the foregoing, it is intended that the present disclosure covers modifications and variations of this disclosure provided they fall within the scope of the following claims.
Number | Date | Country | |
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Parent | 18076458 | Dec 2022 | US |
Child | 18602520 | US |