METHOD FOR 3D PRINTING OF CARBON NANOTUBE MICROSTRUCTURE HAVING HIGH CONDUCTIVITY, AND INK USED THEREIN
20230053799 · 2023-02-23
Inventors
Cpc classification
B29C64/106
PERFORMING OPERATIONS; TRANSPORTING
B33Y10/00
PERFORMING OPERATIONS; TRANSPORTING
B33Y70/00
PERFORMING OPERATIONS; TRANSPORTING
C09D11/03
CHEMISTRY; METALLURGY
B33Y70/10
PERFORMING OPERATIONS; TRANSPORTING
International classification
C09D11/03
CHEMISTRY; METALLURGY
B29C64/106
PERFORMING OPERATIONS; TRANSPORTING
B29C67/00
PERFORMING OPERATIONS; TRANSPORTING
B33Y10/00
PERFORMING OPERATIONS; TRANSPORTING
B33Y70/10
PERFORMING OPERATIONS; TRANSPORTING
Abstract
Carbon nanotube (CNT) ink includes a CNT, a rheological modifier for controlling a flow of the CNT, and a solvent. The CNT ink exhibits a liquid-like behavior under shear stress of 10.sup.−1 to 10 Pa. A loss modulus of the CNT ink may have a larger value than that of storage modulus under shear stress of 10.sup.−1 to 10 Pa. A content of the CNT may be 1 to 20 wt %. A content of the rheological modifier in the CNT ink may be 5 to 40 wt %. A weight ratio of the content of the CNT and the content of the rheological modifier in the CNT ink may be 1:1 to 1:5. The solvent may have a boiling point of 100° C. or less.
Claims
1. Carbon nanotube (CNT) ink, comprising: a CNT; a rheological modifier for controlling a flow of the CNT; and a solvent, wherein the CNT ink exhibits a liquid-like behavior under shear stress of 10.sup.4 to 10 Pa.
2. The CNT ink of claim 1, wherein a loss modulus of the CNT ink has a larger value than that of storage modulus under shear stress of 10.sup.−1 to 10 Pa.
3. The CNT ink of claim 1, wherein a content of the CNT is 1 to 20 wt %.
4. The CNT ink of claim 3, wherein a content of the rheological modifier in the CNT ink is 5 to 40 wt %.
5. The CNT ink of claim 2, wherein a weight ratio of the content of the CNT and the content of the rheological modifier in the CNT ink is 1:1 to 1:5.
6. The CNT ink of claim 1, wherein the solvent has a boiling point of 100° C. or less.
Description
DESCRIPTION OF DRAWINGS
[0028]
[0029]
[0030]
[0031]
[0032]
[0033]
[0034]
[0035]
[0036]
[0037]
[0038]
[0039]
BEST MODE
[0040] In the foregoing, an exemplary embodiment of the present invention has been described, but the exemplary embodiment illustrates the present invention and does not limit the present invention.
[0041] A term used in the specification of the present invention is used as a general meaning of the term. However, a term specially defined in the present specification is used as the definition thereof. In the present invention, a pattern is a structure functioning as an electric and electronic device, and includes a three-dimensional (3D) structure, as well as a two-dimensional (2D) structure, and includes all of the structures, for example, a structure stacked in a direction parallel to a surface of a substrate or a structure in the form of a wire extended in a vertical direction to a substrate.
[0042]
[0043] The ink extruded in the vicinity of nozzle of the leading end of the pen forms a meniscus B by surface tension. A solvent of the ink is momentarily evaporated from a surface of the meniscus, and as a result, a pure CNT/polymer stacked structure A remains on the substrate. According to the movement of the printing pen 110 in an upper direction, the surface tension by the meniscus B formed at the leading end of the nozzle enables the solution to be extruded to the outside of the nozzle without interruption. By the scheme, the solution within the nozzle is continuously extruded according to the movement of the nozzle, and a continuous process, in which the CNT/polymer stacked structure A is printed on an evaporation region close to the substrate, and the meniscus B is formed at the nozzle side, is generated.
[0044] As a result, a predetermined CNT composite material stacked pattern corresponding to a movement trace of the nozzle may be printed on the substrate.
[0045]
[0046]
[0047] As illustrated in
[0048] Next, as illustrated in
[0049] In the present invention, the solvent of the meniscus B has a high specific surface area, so that the solvent voluntarily evaporates even at a room temperature. As a matter of course, the present invention does not exclude an addition of an appropriate heating means to the operation process of the pen depending on the case. In the present invention, the forming of the meniscus and the evaporation of the solvent are generated almost at the same time, and as a result, a shape of the CNT composite material pattern is maintained.
[0050] In the present invention, a width of the meniscus is maintained within an appropriate range so as to provide a high specific surface area for evaporating the solvent. In the present invention, the width of the meniscus depends on an aperture of the nozzle and a movement speed of the nozzle. Further, the CNT flows within the pipe channel of the meniscus, so that a line width of the resultant CNT composite material pattern has the same value as or a smaller value than a value of a width d of the meniscus.
[0051] Referring back to
r=[W(v)/(πv)].sup.1/2
(herein, r is a radius of the meniscus, v is a movement speed of the nozzle, and W is a flow speed of the ink).
[0052] In the meantime, the rheological modifier of the CNT composite material pattern printed by the method of the present invention may be removed by an appropriate scheme. For example, the rheological modifier may be removed by a heat treatment process at a vacuum or non-oxidizing atmosphere. The heat treatment temperature and time may be appropriately designed in consideration of a device printed on the substrate, heat resistance of a neighboring device, and the like.
[0053] In the meantime, the printing method of the present invention is applicable to various forms of pattern.
[0054]
[0055] Referring to
[0056] Further, referring to
[0057] Further, those skilled in the art will appreciate that a wire bonding is available in a 3D space by appropriately combining the two-directional movements.
[0058]
[0059] Referring to
[0060] The printing pen 110 has a storage space containing a CNT composite material ink 20 therein, and extrudes the CNT composite material ink 20 through a nozzle provided at a leading end portion. In the present invention, a cross-section of the nozzle of the printing pen 110 may have various forms, such as a circular shape, a quadrangular shape, and a hexagonal shape.
[0061] In the present invention, the nozzle has a predetermined aperture. As described above, a line width of the pattern printed by the movement of the nozzle depends on a movement speed of the nozzle. Accordingly, in order to obtain a pattern having a nano size, an aperture having the nano size is not required. Preferably, an aperture of the nozzle in the present invention may be 0.1 μm to 50 μm. When the aperture of the nozzle is 50 μm or more, a specific surface area of the formed meniscus is small, so that it is not easy to print a stacked structure. Further, when the aperture of the nozzle is less than 0.1 μm, the nozzle may be clogged.
[0062] An ink supply tank (not illustrated) and an ink supply valve (not illustrated) may be connected to the printing pen 110. The ink supply valve may control a flow of the ink flowing into the printing pen 110. Further, the printing pen 110 may be attached to a feeding mechanism, for example, a feeding arm, for three-axis directional feeding, and the feeding arm may feed the printing pen 110 in the directions of X, Y, and Z axes.
[0063] The substrate stage 110 may be provided with all of the means for maintaining a substrate, which is a printed target. The substrate stage 120 may be provided with a feeding mechanism (not illustrated) movable in the three axial directions.
[0064] Further, the position control unit 140 controls a position of at least one of the printing pen 110 and the substrate stage 120. To this end, the position control unit 140 may control 3D relative positions of the printing pen 110 and the substrate stage 120 by driving the feeding mechanisms of the printing pen 110 and the substrate stage 120.
[0065] Further, the position control unit 140 controls a relative movement speed of the printing pen 110 to the substrate. In the present invention, a movement speed of the nozzle for printing the pattern is designed in consideration of a solution evaporation speed within the meniscus and surface tension of the solution. When water, ethanol, or acetone is used as a solvent, a movement speed of the nozzle may be the range of 0.1 μm/sec to 200 μm/sec. At the movement speed of less than 0.1 μm/sec, the nozzle is clogged due to the rapid evaporation, and at the movement speed of 200 μm/sec or more, the pattern is cut.
[0066] As a matter of course, in the present invention, the position control unit 120 may also control a position of the printing pen 110 and/or a substrate holder 120 by referring to a shape of a unit structure obtained through a CCD camera 142. In this case, the position control unit 140 may adjust a grow direction of the structure by controlling a shape of the meniscus 113 formed between the printing pen 110 and the substrate 120.
[0067] In the present invention, the ink supplied as a raw material of the CNT composite material pattern printing device 100 may have the characteristic below.
[0068] The ink includes a CNT 22, a polymer 23 as the rheological modifier, and a solvent (or a dispersion medium) 24.
[0069] The CNT may be particles or powder of a Single wall CNT (SWNT), a Multi wall CNT (MWNT), or a combination thereof.
[0070] The CNT represents a strong coagulation characteristic by Van der Waals force within the solution. In order to suppress the coagulation characteristic, a functional group, such as a carboxyl group (—COOH) and a hydroxyl group (—OH), may be introduced to a surface of the CNT by an acidic treatment and the like. However, the treatment cannot guarantee a continuous flow of the individual CNT through the nozzle.
[0071] Because of the reason, a rheological modifier is introduced to the ink of the present invention. The rheological modifier suppresses the coagulation of the CNT and induces uniform dispersion. By the rheological modifier, the CNT may flow through the nozzle without interruption.
[0072] In the present invention, the rheological modifier may be a hydrophilic polymer. Further, the hydrophilic polymer may be a hydrophilic polymer. For example, as the rheological modifier, a minimum of one kind of polymer selected from the group consisting of polyvinyl pyrrolidone (PVP), polyacrylic acid (PAA), and polyethylene glycol (PEG) may be used.
[0073] The rheological modifier is stuck to a surface of the CNT to be attached to the surface of the CNT or wrap the surface of the CNT.
[0074]
[0075] In the present invention, it is preferable that the solvent does not generate a residue after evaporation. In the present invention, as the solvent, an inorganic solvent or an organic solvent having polarity may be used. Preferably, water may be used as the inorganic solvent, and alcohol, dichloromethane, and acetone may be used as the organic solvent. Further, in the present invention, the evaporation of the solvent and the printing of the pattern need to be substantially performed in situ. Accordingly, in the present invention, a boiling point of the solvent may be the same as or lower than that of water, and may be 100° C. or lower.
[0076] In the present invention, when a content of rheological modifier is increased, viscosity of the ink is increased. Further, the ink represents a shear thinning characteristic, in which viscosity is decreased according to an increase in shear stress. Further, in the present invention, the ink represents a liquid-like behavior during shear stress. That is, a loss moduli G″ has a larger value than that of a storage moduli G′ under the shear stress.
MODE FOR CARRYING OUT THE INVENTION
[0077] Hereinafter, illustrative Examples of the present invention will be described.
Preparation Example of CNT Composite Material Ink
[0078] MWNT (Iljin Nanotech) and PVP (Aldrich) having molecular weight (Mw) of 10,000 were used as an ink raw material.
[0079] MWNT was dispersed in a mixture of enriched H.sub.2SO.sub.4 and HNO.sub.3 (volume ratio: 3:1) and acidized by performing a heat treatment at 70° C. for 24 hours. The acidized MWNT was washed in heavy water several times and dried by using a dry oven at 100° C. for 24 hours.
[0080] Ink having different compositions was prepared by weighing MWNT and PVP so that MWNT of 7 wt %, and PVP of each concentration of 0 wt %, 7 wt %, 17 wt %, and 25 wt % are included with respect to the total weight of ink, and dispersing the weighed MWNT and PVP in water by using water as a solvent.
[0081] A rheological characteristic of the prepared ink was measured by using a rheometer (MCR102, Anton Paar). In order to measure viscosity of the ink, strain was continuously changed in the range of 10 to 10.sup.2 s.sup.−1 in order to measure viscosity at a changed shear rate. In order to obtain a storage modulus and a loss modulus with a function of stress, stress was continuously changed at a predetermined frequency of 1 Hz.
[0082] Further, in order to measure a decrease in mass of the MWNT and the PVP, a thermo gravimetric analysis was performed by using a thermo gravimetric analysis instrument (TA Instruments Q600, USA). For the thermo gravimetric analysis, a temperature of a sample was increased to 450° C. in an alumina crucible at a temperature increasing speed of 10° C./min, and then was maintained in an Ar atmosphere (a flow rate of 100 ml/min) for 1 hour.
[0083]
[0084] First,
[0085] In the meantime, a small graph illustrated at an inner side of
[0086] Next,
[0087] Referring to
[0088] As described above, by using the ink having the liquid-like behavior, the present invention does not need to use a pressure scheme, so that it is possible to improve space resolution of a 3D structure that may be manufactured. For example, it is possible to implement a 3D structure having a width of less than 10 μm, and further, it is possible to implement a 3D pattern having a width of less than 5 μm or a 3D pattern having a width of sub micrometer.
[0089]
[0090] A 2D wire was formed on a Pt coated Si substrate by using ink of MWNT 7 wt %+PVP (each of 0 wt %, 7 wt %, 17 wt %, and 25 wt %). In this case, a width (Ws) of the wire was set to 24 μm, and a wire was formed at a pulling speed (u) of 75 mm.sup.−1 in a pressureless state by using a nozzle having a diameter of 20 μm. Next, the formed wire was heat treated in a vacuum atmosphere of 450° C. for 1 hour.
[0091] Upper pictures
[0092] Lower pictures of
[0093]
[0094] The thermo gravimetric analysis was performed on the MWNT 7 wt % sample (7-wt % A-MWNT) and the MWNT 7 wt %+17 wt % PVP sample (7-wt % A-MWNT+17-wt % PVP). In the result of the thermo gravimetric analysis of each sample, a decrease in weight at a temperature around 100° C. is caused by the evaporation of a solvent, and a decrease in weight at a temperature of 400° C. or more is mostly caused by the resolution of the PVP. As a matter of course, even in the case of the MWNT 7 wt % sample, a decrease in weight is observed at a high temperature, and this is estimated to be caused by the resolution of the MWNT.
[0095] The final weight of the MWNT 7 wt % sample was about 5 wt %, and the final weight of the MWNT 7 wt %+17 wt % PVP sample was about 6.6 wt %. Accordingly, the content of the MWNT within the MWNT 7 wt %+17 wt % PVP sample is the same as the content of the MWNT 7 wt % sample, so that it can be seen that the sample generates a structure formed of MWNT 75 wt %+PVP 25 wt % by the heat treatment. Accordingly, the MWNT structure prepared by the ink of the present invention uses the MWNT as a main component, so that it is possible to fully utilize an electric and mechanical characteristic of the MWNT.
[0096] In the meantime, it is shown that in the present invention, the structure after the PVP removal operation uses the MWNT as a main component and is capable of firmly maintaining a shape by van der Waals bonding between the MWNT, and does not exhibit a re-soluble property to water.
[0097] <Prepare CNT Composite Material Structure>
[0098] A CNT composite material structure was prepared by using ink including 7 wt % of MWNT and 17 wt % of PVP. As a nozzle, a glass micro-nozzle was used, and an aperture of the nozzle was various from 8 μm to 30 μm. As described in relation to
[0099] By using the device illustrated in
[0100] A printed MWNT structure was heat treated in vacuum at 450° C. for 1 hour. As illustrated in
[0101]
[0102]
[0103]
[0104]
[0105] Referring to
[0106] <Manufacture Functional Element>
[0107] As illustrated in
[0108] As illustrated in
[0109]
[0110]
INDUSTRIAL APPLICABILITY
[0111] The present invention is applicable to a printed electronic technology of a wire of a PCB substrate and the like or a 3D printing technology for implementing an electronic device, such as an active device and a passive device.