KR101679144B1 - Composition for forming conductive copper pattern by light sintering including carbon nanostructures, method for preparing conductive copper pattern by light sintering, and electronic device including the conductive copper pattern prepared therefrom - Google Patents
Composition for forming conductive copper pattern by light sintering including carbon nanostructures, method for preparing conductive copper pattern by light sintering, and electronic device including the conductive copper pattern prepared therefrom Download PDFInfo
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- KR101679144B1 KR101679144B1 KR1020150048367A KR20150048367A KR101679144B1 KR 101679144 B1 KR101679144 B1 KR 101679144B1 KR 1020150048367 A KR1020150048367 A KR 1020150048367A KR 20150048367 A KR20150048367 A KR 20150048367A KR 101679144 B1 KR101679144 B1 KR 101679144B1
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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
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- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
Abstract
The present invention relates to a composition for forming a conductive copper pattern by photo-sintering, a method for producing a conductive copper pattern by photo-sintering, and an electronic device comprising the conductive copper pattern produced therefrom. More particularly, A composition for forming a conductive copper pattern by photo-sintering comprising the activated carbon nanostructure, copper nanoparticles, a binder and a solvent, a method for producing a conductive copper pattern by photo-sintering, and an electron Device.
INDUSTRIAL APPLICABILITY According to the present invention, a conductive copper pattern having excellent electrical conductivity and high reliability can be produced by a simple and economical process, and by using it, RFID, flexible electronic products, wearable electronic products, large area displays, , And thin-plate type batteries can be manufactured inexpensively in a large amount.
Description
The present invention relates to a composition for forming a conductive copper pattern by photo-sintering, a method for producing a conductive copper pattern by photo-sintering, and an electronic device including the conductive copper pattern produced therefrom.
Recently, as electronic and information technologies have been developed, the use of various electronic products is steadily increasing. Most of the conductive patterns in such electronic products are manufactured by photolithography process. However, the photolithography process has 12 or more steps, which is very complicated, has a high process cost, takes a long time to manufacture, and uses many toxic chemicals, which can cause environmental pollution. In addition, it has a disadvantage that it is difficult to manufacture on flexible polymer substrates such as PET, photo paper and PI.
Therefore, research on printed electronic devices has been actively conducted to replace the photolithography process described above. A printed electronic element means an electronic element in which a pattern is formed by a printing technique such as screen printing, gravure printing, and the like. The printing technique consists of three simple steps including printing, drying, and sintering. The printing method has advantages such as low cost, environment friendly, flexibility, large area mass production and low temperature / simple process compared with the conventional photolithography process This is the technology that is currently popular. Therefore, the printing technique can be applied to various electronic products such as flexible displays, solar cells, Radio Frequency Identification Devices (RFID), flexible electronic products, wearable electronic products, thin plate solar batteries, and thin plate batteries.
Currently, conductive inks using gold, silver, or copper nanoparticles are mainly used as inks used for printing electronic patterns of devices. As a core technology of the printed electronic device, sintering is a very important factor that determines the damage of the substrate, the electric conductivity of the pattern after sintering and the quality of the pattern depending on the sintering method and conditions. Conventional conventional conductive nano ink sintering methods include a thermal sintering method but are not applicable to a flexible substrate which is a next generation substrate because sintering is performed at a high temperature of 300 ° C or higher. Therefore, the laser sintering method, the plasma sintering method, and the microwave sintering method have been proposed as new sintering methods. However, the laser sintering method can only be sintered to a very small area and the practicality is poor. The microwave sintering method is unsuitable because of its shallow depth, Has the problem that it is not suitable for industrialization because it requires sophisticated and expensive equipments.
Korean Patent Laid-Open Publication No. 10-2012-0132424 discloses a photo-sintering method of conductive copper nano ink, specifically, a method of mixing a copper nanoparticle or a copper precursor with a polymer dispersant, coating and drying the substrate, Discloses a method of photo-sintering a conductive copper nano ink through a process of irradiating white light or the like. Korean Patent Laid-Open Publication No. 10-2014-0044743 discloses a conductive hybrid copper ink and a light sintering method using the same, and more specifically, a copper nanoparticle, a copper precursor, and / or a metal precursor other than copper having a predetermined solubility Discloses a method of photo-sintering a conductive hybrid copper ink through a process such as mixing and drying a polymer binder resin, coating and drying on a substrate, and extreme ultraviolet-white light irradiation.
Therefore, when the above white light irradiation method or the like is used, various problems caused by the above-described conventional sintering methods can be solved to some extent. However, in order to commercialize a flexible substrate, It is necessary to improve the quality of the pattern, and to secure durability and reliability against repetitive bending.
Therefore, the present invention solves the problems of the prior art, and it is possible to produce large-area and large-scale production at low cost through a simple process without expensive equipments in a short time at room temperature and atmospheric conditions, And an electronic device including the conductive copper pattern.
In order to solve the above problems,
There is provided a composition for forming a conductive copper pattern by photo-sintering comprising a carbon nanostructure, a copper nanoparticle, a binder and a solvent, the surface of which has been pretreated with an acid.
According to an embodiment of the present invention, the pretreatment may be performed by adding carbon nanotubes, graphene or a mixture thereof to a solution of hydrochloric acid, sulfuric acid, nitric acid or a mixture thereof, stirring and reacting the mixture, and then washing.
According to another embodiment of the present invention, the solvent is selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, hexylene glycol, glycerin, isopropyl alcohol, And may be selected from the group consisting of alcohol, hexyl alcohol, butyl alcohol, octyl alcohol, formamide, methyl ethyl ketone, ethyl alcohol, methyl alcohol, acetone or a mixture thereof.
According to another embodiment of the present invention, the binder is selected from the group consisting of polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyvinyl butyral, polyethylene glycol, polymethyl methacrylate, dextran, azobis, Sodium benzene sulphate, sodium silbenzene sulphate, and mixtures thereof.
According to another embodiment of the present invention, the carbon nanostructure may be carbon nanotubes having an average length of 1 μm to 500 μm.
According to another embodiment of the present invention, the carbon nanostructure may be contained in an amount of 0.05 wt% to 2.5 wt% based on the total weight of the composition.
According to another embodiment of the present invention, the weight average molecular weight of the binder is 10,000 to 500,000, and the content thereof may be 1 wt% to 50 wt% based on the total weight of the composition.
On the other hand,
Pretreating the carbon nanostructure with an acid to activate the surface;
Preparing a composition for forming a conductive copper pattern by light sintering by dispersing the carbon nanostructure, the binder and the copper nanoparticles in a solvent;
Coating and drying the composition for forming a conductive copper pattern on a substrate; And
And photo-sintering the resultant coating using white light emitted from a xenon flash lamp.
According to an embodiment of the present invention, the step of dispersing the carbon nanostructure, the binder and the copper nanoparticles in a solvent may be performed for 5 to 60 minutes using an ultrasonic disperser, a mechanical stirrer, a ball mill or a 3-roll mill.
According to another embodiment of the present invention, the step of coating the composition for forming a conductive copper pattern may be performed by any one of a screen printing method, an ink jet printing method, a micro-contact printing method, an imprinting method, a gravure printing method, It can be carried out by gravure-offset printing, flexography printing or spin coating.
According to another embodiment of the present invention, the substrate may be at least one selected from the group consisting of photo paper, PET, paper, glass, polybutylene terephthalate, polyethylene terephthalate, polysulfone, polyether, polyetherimide, polyethylene naphthalate (PEN) A substrate made of a material selected from the group consisting of resin, heat-resistant epoxy, BT epoxy / glass fiber, vinyl acetate resin (EVA), butyl rubber resin, polyarylate, polyimide, silicone, ferrite, ceramic and FR- Lt; / RTI >
According to another embodiment of the present invention, the light sintering step may further include preheating at a temperature of 80 ° C to 110 ° C for 5 minutes to 60 minutes before irradiating the white light.
According to another embodiment of the present invention, the light irradiation time of the xenon flash lamp is 0.1 ms to 10 ms, the pulse gap is 0.01 ms to 20 ms, 100 times.
According to another embodiment of the present invention, the intensity of the xenon flash lamp may be 7.5 J / cm2 to 15.0 J / cm2.
Meanwhile, the present invention provides an electronic device including a conductive copper pattern manufactured by the above method.
INDUSTRIAL APPLICABILITY According to the present invention, a conductive copper pattern having excellent electrical conductivity and high reliability can be produced by a simple and economical process, and by using it, RFID, flexible electronic products, wearable electronic products, large area displays, , And thin-plate type batteries can be manufactured inexpensively in a large amount.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic process diagram of a method of manufacturing a conductive copper pattern according to the present invention; FIG.
2 is a view schematically showing a light sintering apparatus and a light sintering condition used in the method according to the present invention.
3 is a graph showing a change in resistance value according to irradiation energy in the method according to the present invention.
4 is a graph showing the results of X-ray diffraction analysis of the composition for forming a conductive copper pattern according to the present invention before and after photo-sintering.
FIG. 5 is a scanning electron microscope (SEM) photograph of a composition for forming a copper pattern having a content of CNTs of 0.1 wt.%, 0.5 wt.% And 1.0 wt.%, Respectively.
6A and 6B are graphs showing fatigue characteristics test results after sintering according to the content of CNTs and results thereof.
FIGS. 7A to 7C are graphs showing a scanning electron microscope photograph, a graph showing a change in resistance value, and a graph of a fatigue characteristic test result after sintering according to the CNT length, respectively.
Hereinafter, the present invention will be described in more detail.
In the present invention, an electrode pattern is manufactured by using a sintering method through white light irradiation which can solve problems such as conventional thermal sintering method, laser sintering method, plasma sintering method, or microwave sintering method, To produce a reliable conductive copper pattern.
Accordingly, the present invention provides a composition for forming a conductive copper pattern by photo-sintering. Specifically, the composition includes a carbon nanostructure, copper nanoparticles, a binder, and a solvent, the surface of which is pretreated with an acid and activated.
The carbon nanostructure may be graphene, carbon nanotube (CNT), or a mixture thereof. On the other hand, when a carbon nanostructure such as CNT or graphene is added during the production of a conductive ink, carbon nanostructures cohere with each other in the ink, so that it is difficult to produce an ink having a high dispersibility as a general method for producing a conductive ink . Accordingly, in the present invention, the carbon nanostructure is pretreated with an acid to activate the surface. As the pretreatment method, the carbon nanostructure is added to and stirred with hydrochloric acid, sulfuric acid, nitric acid, or a mixture thereof, Method may be used. By this pretreatment, the surface of the carbon nanostructure contains a hydroxyl group and is readily activated for dispersion. The activated carbon nanostructure is dispersed in a solvent through a dispersing device such as a sonicator. Examples of the solvent include, but are not limited to, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol , Dipropylene glycol, hexylene glycol, glycerin, isopropyl alcohol, 2-methoxyethanol, pentyl alcohol, hexyl alcohol, butyl alcohol, octyl alcohol, formamide, methyl ethyl ketone, ethyl alcohol, methyl alcohol, And the like. The kind of the specific solvent can be appropriately selected in consideration of the viscosity of the other components to be added and the composition to be produced such as a binder and the like.
Meanwhile, the composition according to the present invention includes a binder for enhancing the dispersibility and reducing property of the ink, but the binder is not limited to polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyvinyl butyrate A binder selected from the group consisting of polyethylene glycol, polyethylene glycol, polymethylmethacrylate, dextran, azobis, sodium dodecylbenzenesulfate, and mixtures thereof. The weight average molecular weight of the binder is preferably from 10,000 to 500,000, and the content thereof is preferably from 1 to 50% by weight based on the total weight of the composition. When the weight average molecular weight of the binder is less than 10,000, If it exceeds 500,000, there is a possibility of forming an aggregate, which is not preferable. In addition, even when the content of the binder in the composition is less than 1% by weight, sufficient dispersing or reducing effect can not be obtained, and when it exceeds 50% by weight, aggregation is likely to be formed.
On the other hand, as can be seen from the results of Examples to be described later, the average length and content of the carbon nanotubes, for example, carbon nanotubes contained in the composition according to the present invention are important for the resistance value of the pattern It affects. In the present invention, the carbon nanostructure may include carbon nanotubes having an average length of 1 μm to 500 μm in an amount of 0.05 wt% to 2.5 wt% based on the total weight of the composition. When the average length of the carbon nanotubes is less than 1 占 퐉 or less than 0.05% by weight, the effect of improving the electrode characteristics between the carbon nanotubes sintered copper nanoparticles can not be sufficiently exhibited. When the average length is more than 500 탆 or more than 2.5% by weight, the carbon nanotubes interfere with the sintering between the copper nanoparticles during the light sintering, which may deteriorate the electrical conductivity.
The present invention also provides a method for producing a conductive copper pattern using the composition,
Pretreating the carbon nanostructure with an acid to activate the surface;
Preparing a composition for forming a conductive copper pattern by light sintering by dispersing the carbon nanostructure, the binder and the copper nanoparticles in a solvent;
Coating and drying the composition for forming a conductive copper pattern on a substrate; And
And photo-sintering the resultant coating using white light emitted from a xenon flash lamp.
FIG. 1 is a schematic process diagram of a method for manufacturing a conductive copper pattern according to the present invention. Referring to FIG. 1, the carbon nanostructure is pretreated with an acid as described above, and a composition for forming a conductive copper pattern is prepared by dispersing the carbon nanostructure, the binder and the copper nanoparticles thus prepared in a solvent do. Such dispersion can be carried out by a conventional dispersion method, and can be performed for 5 minutes to 60 minutes, for example, using an ultrasonic disperser, a mechanical stirrer, a ball mill or a 3-roll mill, although not limited thereto.
After the composition for pattern formation is prepared by the above process, it is coated and dried on the substrate. Substrates that may be used herein include but are not limited to photographic paper, PET, paper, glass, polybutylene terephthalate, polyethylene terephthalate, polysulfone, polyether, polyetherimide, polyethylene naphthalate (PEN) A substrate made of a material selected from the group consisting of resin, heat-resistant epoxy, BT epoxy / glass fiber, vinyl acetate resin (EVA), butyl rubber resin, polyarylate, polyimide, silicone, ferrite, ceramic and FR- Can be used.
In view of the fact that the coating step is advantageous in that the present invention can be manufactured by an inexpensive method which does not require a high temperature and a vacuum condition, although various coating methods used in conventional electrode pattern formation can be used, Printing, ink-jet printing, micro-contact printing, imprinting, gravure printing, gravure-offset printing, flexography printing or spin coating spin coating, and the like.
Following the coating step, a preliminary step of preheating or drying the solvent may be further included to enhance the effect of the photoresist to be performed in subsequent steps and to make the texture densified. This preliminary step can be carried out by preheating at a temperature of 80 [deg.] C to 110 [deg.] C for 5 minutes to 60 minutes.
Next, in the present invention, a photo-sintering step is performed to produce a conductive copper pattern, which is performed using a xenon flash lamp that emits white light. In the present invention, complete drying and sintering can be accomplished in a very short time of about 0.1 ms to 100 ms by such white light irradiation. FIG. 2 shows the light sintering apparatus and light sintering conditions used in the method according to the present invention Respectively.
Through the photo-sintering process, a copper oxide film reduction reaction occurs between the copper nanoparticles and the binder coated on the surface of the carbon nanostructure, whereby most of the copper oxide is reduced to pure copper and can be sintered. FIG. 4 shows the results of X-ray diffraction analysis of the composition for forming a conductive copper pattern according to the present invention before and after photo-sintering. Referring to FIG. 4, it can be seen that the peak corresponding to pure copper which was insignificant before light sintering (the graph in the drawing) increased greatly after the light sintering (the graph in the drawing).
Since the light irradiation time or pulse width, the pulse gap, the number of pulses, and the intensity of light are changed when the white light is irradiated in the light sintering step, the specific light sintering conditions are changed, J / cm 2 . At this time, sintering can be performed only when sufficient light energy is irradiated. However, when excessive light energy is irradiated, the substrate and copper conductive copper pattern are damaged. Therefore, white light of appropriate energy should be irradiated. For example, the optimum energy range may be 5 to 50 J / cm 2 for the PI substrate, 5 to 20 J / cm 2 for the PET substrate, 3 to 15 J / cm 2 for the photopaper substrate, And 10 to 20 J / cm 2 for a BT substrate. In order to enhance the light irradiation effect, a stepwise light sintering method in which light is divided into a preheating step and a densification step may be used.
In addition, as can be seen from the results of the following examples, the light irradiation energy in the present invention has a significant influence on the resistance value of the pattern after sintering. 3, the intensity of the Xenon flash lamp irradiated in the present invention is in the range of 7.5 J / cm 2 to 15.0 J / cm 2 It can be seen that the lowest resistance value can be achieved. In particular, if light sintering is carried out at an irradiation energy of less than 7.5 J / cm 2, sufficient energy for sintering is not sufficient and sufficient sintering can not be achieved. As a result, the resistance value is increased, and 15.0 J / If the photo-sintering is performed with excess irradiation energy, the copper film is damaged due to excessive light energy irradiation, and the electrical conductivity after sintering is rather lowered.
Further, the light irradiation time of the xenon flash lamp may be 0.1 ms to 10 ms, the pulse gap may be 0.01 ms to 20 ms, and the pulse number may be 1 to 100 times have. By optimizing such light irradiation conditions, sintering of the conductive ink having higher conductivity may be possible, or the conductivity may be improved by using other metal nanoparticles such as gold, silver and the like together.
Meanwhile, the present invention provides an electronic device including a conductive copper pattern manufactured by the above method.
As described above, according to the present invention, it is possible to produce a conductive copper pattern having excellent electrical conductivity and high reliability by a simple and economical process. If the conductive copper pattern thus produced is used, High-value-added products such as electronic products, wearable electronic products, large-area displays, thin-plate solar cells, and thin-plate batteries can be mass-produced at a low cost.
EXAMPLES Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are intended to assist the understanding of the present invention and should not be construed as limiting the scope of the present invention.
Example One.
0.01 g of carbon nanotubes (length: 20 탆) was added to 100 ml of the nitric acid solution, and the mixture was sufficiently stirred using a stirrer for 6 hours. The stirred solution was filtered through a filter to remove nitric acid, and then washed with 1 L of distilled water to prepare an acid-pretreated carbon nanotube. Subsequently, the pretreated carbon nanotubes were dispersed in 4.5 g of 2-ethoxyethanol for 1 hour by using a sonicator. PVP (molecular weight: 40,000, Sigma Aldrich Co, Ltd.) (0.9 g) was added to the dispersion and dispersed for 1 hour using a sonicator. To the dispersion was dispersed 11.4 g of copper nanoparticles (diameter 20-50 nm, Quantum Spehere Inc Co. Ltd) using a sonicator and a stirrer. After the dispersion, the copper agglomerates were removed using a filter (pore size: 0.45 mu m) and dispersed again using a mixed deaerator. 1.5 ml of γ-butyrolactone (Wako Pure Chemical Ind., Ltd) was added to 1 g of the copper ink obtained by the above procedure to adjust the viscosity to 2 ml of a silane coupling agent (KBE-603, Shin-Etsu silicones) Roll mill to prepare a conductive copper ink containing the carbon nanostructure according to the present invention. The content of the carbon nanotubes was 0.05 wt% based on the total weight of the conductive copper ink finally prepared.
The conductive copper ink containing the carbon nanostructure produced by the above process was printed on a polyimide (PI) substrate in the form of an electrode using a screen printer. In the present embodiment, the electrode is printed using a screen printer. However, by adjusting the surface tension and viscosity of the ink, if necessary, gravuring, flexography, and the like used in the high-speed roll- ) May be used to perform printing. Then, the pattern printed by the above process was dried using an oven at a temperature of 90 ° C., and the pulsed light was irradiated to the dried pattern to complete the conductive copper pattern according to the present invention. At this time, the light irradiation time was 10 ms, the number of pulses was 1, and the pulse energy was 12.5 J / cm 2.
Example 2 to 4.
(Example 2), 0.114 g (Example 3), and 0.57 g (Example 2) were added to the conductive copper ink containing the carbon nanostructure in the same manner as in Example 1, Example 4), thereby preparing a conductive copper ink containing 0.25 wt%, 0.5 wt%, and 2.5 wt%, respectively, of the carbon nanostructure.
Comparative Example 1. to 3.
(Comparative Example 1), 0.0057 g (Comparative Example 2), and 1.14 g (Comparative Example 1) were prepared in the same manner as in Example 1, except that the amounts of carbon nanotubes to be added were 0 g Comparative Example 3), a conductive copper ink containing 0 wt%, 0.05 wt%, and 10 wt% carbon nanostructures, respectively, was prepared.
Table 1 shows resistance values measured after the conductive copper pattern was finally formed using the conductive copper ink according to Examples 1 to 4 and the conductive copper ink according to Comparative Examples 1 to 3.
number
(weight %)
(Ohm / sq)
Referring to Table 1, when the conductive copper ink according to Examples 1 to 4 having a CNT content of 0.05 wt% to 2.5 wt% was used for producing a pattern, the ink according to Comparative Example 1, to which CNT was not added at all, , The fact that the resistance value after sintering is much lower than that in the case of using the ink according to Comparative Example 2 in which the content of CNT is 0.05 wt% or the ink according to Comparative Example 3 in which the content of CNT is 10 wt% .
5 shows a scanning electron micrograph after sintering when the ink having the CNT content of 0.1 wt%, 0.5 wt% and 1.0 wt%, respectively, is used. Referring to FIG. 5, it can be seen that as the content of CNT added to the ink increases, the pores of the sintered CNT and the copper film after the photo-sintering decrease, and the resistivity value of the sintered pattern also decreases . Thus, it can be seen that higher conductivity can be secured by controlling the content of CNT in the composition.
6A and 6B show the outline of fatigue characteristics after sintering according to the content of CNTs (6a) and the result thereof in a graph (6b). Referring to the graphs, when the CNTs are 0.1 wt% and 0.5 wt% % And 1.0 wt.%, The resistance increase rate is remarkably lower as the fatigue characteristic test is repeated for several cycles as compared with the ink containing no CNT at all. This effect can be obtained by increasing the content of CNT The more it became clear. This shows that the added CNT can enhance the reliability of the pattern by strengthening the structural characteristics of the pattern between the sintered copper nanoparticles.
Example 5. to 10.
(Example 5), 80 占 퐉 (Example 6), 200 占 퐉 (Example 7), and 300 占 퐉 (Example 6), respectively, in the same manner as in Example 1 except that the conductive copper ink containing carbon nanostructure was prepared. (Example 8), 400 占 퐉 (Example 9) and 500 占 퐉 (Example 10) were added.
Comparative Example 4.
A conductive copper ink containing a carbon nanostructure was prepared in the same manner as in Example 1, except that a carbon nanotube having a length of 600 μm was added.
Table 2 shows resistance values measured after the conductive copper pattern was finally formed using the conductive copper ink according to Examples 5 to 10 and the conductive copper ink according to Comparative Example 4, respectively.
number
(탆)
(Ohm / sq)
Referring to Table 2, the case of producing the pattern using the conductive copper ink according to Examples 1 and 5 to 10, in which the length of the CNTs is 1 to 500 탆, 4 shows that the resistance value after sintering is much lower than that in the case of using the ink according to the present invention.
7A to 7C show a scanning electron micrograph (7a), a graph (7b) showing a change in resistance value and a graph (7c) showing a fatigue characteristic test result according to the length of the CNT, respectively, , It can be seen that the longer the length of the CNT is, the lower the resistance increase rate is when the fatigue characteristic test is repeated for several cycles. This shows that as the length of the CNT increases, the bridging effect between the sintered copper nanoparticles increases, thereby further improving conductivity and reliability.
Example 11. to 13.
A conductive copper ink containing a carbon nanostructure was prepared in the same manner as in Example 1 except that the printed and dried patterns were subjected to a photoexcitation with pulse energies of 7.5 J / cm 2 (Example 11) and 10.0 J / cm 2 (Example 12), and 15.0 J / cm 2 (Example 13).
Comparative Example 5 and 6.
A conductive copper ink containing a carbon nano structure was prepared in the same manner as in Example 1 except that the printed and dried patterns were subjected to light sintering in the presence of a photon defect of 5.0 J / cm 2 and 17.5 J / Respectively.
FIG. 3 is a graph showing a resistance value after sintering according to light sintering conditions. 3, the pattern according to Example 11 and Example 12, Example 1 and Example 13, in which the pulse energy is 7.5 J / cm2 to 15.0 J / cm2, has a pulse energy of 5.0 J / cm2 and 17.5 J / Cm < 2 >, the resistance values after sintering are much lower than those of the patterns according to Comparative Examples 5 and 6. [
Claims (15)
Wherein the carbon nanotubes are carbon nanotubes having an average length of 1 μm to 500 μm in an amount of 0.05 wt% to 2.5 wt% based on the total weight of the composition. .
Preparing a composition for forming a conductive copper pattern by light sintering by dispersing the carbon nanostructure, the binder and the copper nanoparticles in a solvent;
Coating and drying the composition for forming a conductive copper pattern on a substrate; And
And photo-sintering the resultant coating using white light emitted from a xenon flash lamp,
Wherein the carbon nano structure is carbon nanotubes having an average length of 1 탆 to 500 탆 and is contained in an amount of 0.05 wt% to 2.5 wt% based on the total weight of the composition. .
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| KR20120132424A (en) | 2011-05-27 | 2012-12-05 | 한양대학교 산학협력단 | Light sintering method of conductive Cu nano ink |
| KR20140044743A (en) | 2012-10-04 | 2014-04-15 | 한양대학교 산학협력단 | Conductive hybrid cu ink and light sintering method using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101350507B1 (en) | 2013-01-09 | 2014-01-17 | (주)쎄미시스코 | Electro-conductive ink comprising metal nano-particle and light sintering method of the same |
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