KR102678247B1 - Laser painting method and pattern structure formed thereby - Google Patents

Abstract

A laser painting method is provided. The laser painting method includes preparing a substrate, immersing the substrate in a precursor solution containing a base metal, and irradiating a laser to the substrate immersed in the precursor solution to form the precursor solution on the substrate. Forming a base metal pattern hydrothermally grown from the base metal pattern, controlling the thickness of the base metal pattern by controlling the scanning speed of the laser and the irradiation time of the laser, and controlling the thickness of the base metal pattern. A laser painting method comprising controlling the color of the base metal pattern according to the thickness of the metal pattern.

Description

Laser painting method and pattern structure formed thereby}

The present invention relates to a laser painting method and a pattern structure formed thereby, and more specifically, to a laser painting method in which color is realized through a hydrothermally grown base metal pattern and a pattern structure formed thereby.

Microcoloration is not only an important topic for decoration and high-resolution displays, but is also closely related to the properties and performance of optoelectronics. Microscale controlled coloration can be used to determine wavelength-dependent photoelectronic properties, such as the light-harvesting properties of water splitting cells, the responsiveness of photodiodes, and the transmission bandwidth of integrated photonic devices. It has been proven to have a significant effect on the electric field strength within the device causing the reaction. Accordingly, various studies related to microcoloring that can be used in optoelectronic devices are continuously being conducted.

One technical problem to be solved by the present invention is to provide a laser painting method capable of manufacturing pattern structures of various shapes and colors through a simplified process, and a pattern structure formed thereby.

Another technical problem to be solved by the present invention is to provide a laser painting method that can effectively display macroscopic shapes such as symbols, letters, figures, numbers, or logos, and a pattern structure formed thereby.

Another technical problem to be solved by the present invention is to provide a highly reproducible laser painting method and a pattern structure formed thereby.

Another technical problem to be solved by the present invention is to provide a laser painting method and a pattern structure formed thereby that can be variously applied in the field of optoelectronic devices in the future.

The technical problems to be solved by the present invention are not limited to those described above.

In order to solve the above-mentioned technical problems, the present invention provides a laser painting method.

According to one embodiment, the laser painting method includes preparing a substrate, immersing the substrate in a precursor solution containing a base metal, and irradiating a laser to the substrate immersed in the precursor solution, Forming a base metal pattern hydrothermally grown from the precursor solution on the base metal pattern, wherein the thickness of the base metal pattern is increased by adjusting the scanning speed of the laser and the irradiation time of the laser. Control, and may include controlling the color of the base metal pattern according to the thickness of the base metal pattern.

According to one embodiment, as the laser irradiation time increases, the thickness of the base metal pattern may increase, and the color of the base metal pattern may change.

According to one embodiment, the base metal pattern may change from a first color to a second color as the irradiation time of the laser increases, and then change from the second color to the first color again. .

According to one embodiment, the base metal pattern may include different colors depending on the scanning speed of the laser.

According to one embodiment, the intensity of the laser irradiated to the substrate may be inversely proportional to the irradiation time of the laser.

According to one embodiment, after the base metal pattern is formed, the method may include changing the color of the base metal pattern by increasing the crystallinity of the formed base metal pattern.

According to one embodiment, as the crystallinity of the formed base metal pattern increases, the thickness of the base metal pattern may be reduced.

According to one embodiment, the base metal may include iron (Fe).

According to one embodiment, in forming the base metal pattern, the base metal pattern is formed in the first region of the substrate to which the laser is irradiated and the second region of the substrate to which the laser is not irradiated. It may include being selectively formed in a region.

According to one embodiment, the laser painting method includes, after forming the base metal pattern, immersing the substrate on which the base metal pattern is formed in a removal solution containing an alcohol compound, and immersing the substrate in the removal solution. The method may further include removing the base metal pattern by irradiating a laser to the base metal pattern.

According to one embodiment, after removing the base metal pattern, immersing the substrate in the precursor solution, and irradiating a laser to the substrate immersed in the precursor solution to reform the base metal pattern. It may further include that the base metal pattern before being removed and the re-formed base metal pattern may have different colors.

In order to solve the above-mentioned technical problems, the present invention provides a pattern structure.

According to one embodiment, the pattern structure includes a substrate containing platinum (Pt), iron oxide, and a plurality of base metal patterns spaced apart from each other on the substrate, wherein the plurality of base metal patterns include: A first base metal pattern having a first thickness, and a second base metal pattern having a second thickness thinner than the first thickness, wherein the first base metal pattern and the second base metal pattern have different colors. It may include marking.

According to one embodiment, the target pattern may include a first area and a second area with different colors along the length direction.

According to one embodiment, the first base metal pattern and the second base metal pattern may be combined to display at least one of a symbol, letter, figure, number, or logo.

The laser painting method according to an embodiment of the present invention includes preparing a substrate, immersing the substrate in a precursor solution containing a base metal, and irradiating a laser to the substrate immersed in the precursor solution, Forming a base metal pattern hydrothermally grown from the precursor solution on a substrate, wherein the scanning speed of the laser and the irradiation time of the laser are adjusted to control the thickness of the base metal pattern. and may include controlling the color of the base metal pattern according to the thickness of the base metal pattern.

In addition, in the step of forming the base metal pattern, the base metal pattern is selectively applied to the first region of the first region of the substrate to which the laser is irradiated and the second region of the substrate to which the laser is not irradiated. can be formed.

Accordingly, by forming and combining various shapes, numbers, colors, etc. of the base metal patterns, macroscopic shapes such as symbols, letters, figures, numbers, or logos can be effectively displayed. In addition, as described above, various colors can be expressed by a simple method of controlling the conditions of the laser, and the reproducibility of color expression is high, so it can be applied in a variety of ways in the field of optoelectronic devices in the future.

1 is a flowchart explaining a laser painting method according to an embodiment of the present invention.
2 to 4 are diagrams showing the process of the laser painting method according to an embodiment of the present invention.
Figure 5 is a diagram showing the selective formation of a base metal pattern in the laser painting method according to an embodiment of the present invention.
6 and 7 are diagrams showing examples of base metal patterns formed by a laser painting method according to an embodiment of the present invention.
Figure 8 is a photograph of the real-time formation process of a pattern structure formed through a laser painting method according to an embodiment of the present invention.
9 and 10 are images showing the color change of the pattern structure according to the change in the scanning speed of the laser during the laser painting method according to an embodiment of the present invention.
11 and 12 are images showing a large-area pattern structure formed through a laser painting method according to an embodiment of the present invention.
13 to 16 are images showing the color change of the pattern structure according to the change in laser irradiation time during the laser painting method according to an embodiment of the present invention.
Figure 17 is an image and graph showing the surface profile of a patterned structure formed through a laser painting method according to an embodiment of the present invention.
Figure 18 is a graph showing the change in thickness of the pattern structure according to the change in laser irradiation time during the laser painting method according to an embodiment of the present invention.
Figure 19 is an image showing a state in which pattern structures formed through a laser painting method according to an embodiment of the present invention are overlapped.
Figure 20 is an image showing a pattern structure formed in an alphabet shape and removal of the pattern structure through a laser painting method according to an embodiment of the present invention.
21 to 23 are graphs and images showing changes in crystallinity of a pattern structure formed through a laser painting method according to an embodiment of the present invention.
Figure 24 is a graph showing FDTD simulation results according to the thickness of a pattern structure formed through a laser painting method according to an embodiment of the present invention.
Figure 25 is a graph showing temperature data when 450 nm and 650 nm wavelength laser diodes are irradiated with 150 mW.
Figure 26 is an image showing the formation of a pattern structure, removal of the pattern structure, and reformation of the pattern structure through a laser painting method according to an embodiment of the present invention.
FIG. 27 is a graph showing resistance data measured in each state of FIG. 26.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the attached drawings. However, the technical idea of the present invention is not limited to the embodiments described herein and may be embodied in other forms. Rather, the embodiments introduced herein are provided so that the disclosed content will be thorough and complete and so that the spirit of the present invention can be sufficiently conveyed to those skilled in the art.

In this specification, when an element is referred to as being on another element, it means that it may be formed directly on the other element or that a third element may be interposed between them. Additionally, in the drawings, the thicknesses of films and regions are exaggerated for effective explanation of technical content.

Additionally, in various embodiments of the present specification, terms such as first, second, and third are used to describe various components, but these components should not be limited by these terms. These terms are merely used to distinguish one component from another. Accordingly, what is referred to as a first component in one embodiment may be referred to as a second component in another embodiment. Each embodiment described and illustrated herein also includes its complementary embodiment. Additionally, in this specification, 'and/or' is used to mean including at least one of the components listed before and after.

In the specification, singular expressions include plural expressions unless the context clearly dictates otherwise. In addition, terms such as "include" or "have" are intended to designate the presence of features, numbers, steps, components, or a combination thereof described in the specification, but are not intended to indicate the presence of one or more other features, numbers, steps, or components. It should not be understood as excluding the possibility of the presence or addition of elements or combinations thereof. Additionally, in this specification, “connection” is used to mean both indirectly connecting and directly connecting a plurality of components.

In addition, in the following description of the present invention, if a detailed description of a related known function or configuration is judged to unnecessarily obscure the gist of the present invention, the detailed description will be omitted.

Figure 1 is a flowchart explaining a laser painting method according to an embodiment of the present invention, Figures 2 to 4 are diagrams showing the process of the laser painting method according to an embodiment of the present invention, and Figure 5 is an implementation of the present invention. It is a diagram showing the selective formation of a base metal pattern in a laser painting method according to an example, and FIGS. 6 and 7 are diagrams showing examples of base metal patterns formed by a laser painting method according to an embodiment of the present invention.

Referring to FIGS. 1 and 2, a substrate 100 containing metal is prepared (S100). According to one embodiment, the substrate 100 may be prepared by depositing a metal layer 120 on the base substrate 110. For example, the base substrate 110 may include a glass substrate. For example, the metal may include platinum (Pt). More specifically, the substrate 100 can be prepared by coating platinum on a glass substrate through an e-beam evaporator.

Referring to FIGS. 1 and 3 , the substrate 100 may be immersed in the precursor solution 200 (S200). According to one embodiment, the substrate 100 is provided in a chamber C containing the precursor solution 200, as shown in FIG. 3, so that the substrate 100 can be immersed in the precursor solution 200. there is.

According to one embodiment, the precursor solution 200 may include a base metal. For example, the base metal may include iron (Fe). Alternatively, according to another embodiment, the base metal may include zinc (Zn), titanium (Ti), etc. More specifically, the precursor solution 200 is prepared by mixing iron (III) chloride (FeCl ₃ ) at a concentration of 0.15 M, sodium nitrate (NaNO ₃ ) at a concentration of 1 M, and DI water, and then adding hydrochloric acid (HCl). It may be a solution whose pH is controlled to 1.5.

Referring to FIGS. 1 and 4 , a laser L is irradiated to the substrate 100 immersed in the precursor solution 200 to form a base metal pattern 300 on the substrate 100. (S300). More specifically, when the laser L is irradiated to the substrate 100 immersed in the precursor solution 200, platinum (Pt) contained in the substrate 100 causes light to form on the surface of the substrate 100. A photothermal reaction may occur, and hydrothermal growth may occur due to the base metal (eg, Fe) contained in the precursor solution 200. Accordingly, the base metal pattern 300 hydrothermally grown from the precursor solution 200 may be formed on the substrate 100. Since the base metal pattern 300 is hydrothermally grown from the precursor solution 200, it may include an oxide of the base metal included in the precursor solution 200. For example, the oxide of the base metal may include iron(III) oxide (Fe ₂ O ₃ ).

According to one embodiment, a lens (not shown) may be placed at the entrance of the chamber C. Accordingly, the laser L may be focused through the lens (not shown) and then irradiated to the substrate 100.

Referring to FIG. 5, the base metal pattern 300 is formed in a first area 100a of the substrate 100 to which the laser L is irradiated and a second area 100a of the substrate 100 to which the laser L is not irradiated. It may be selectively formed in the first area 100a among 100b. Accordingly, the base metal pattern 300 may be formed to have a specific shape along the path along which the laser L is irradiated. For this reason, by varying the path of the laser L irradiated onto the substrate 100, the base metal pattern 300 can have various shapes.

According to one embodiment, the intensity of the laser (L) irradiated to the substrate 100 may be inversely proportional to the irradiation time of the laser (L) irradiated to the substrate 100. For example, when the laser L with relatively high intensity is irradiated, the laser L may be irradiated for a relatively short time. For another example, when the laser L is irradiated with a relatively low intensity, the laser L may be irradiated for a relatively long time.

In contrast, when the intensity of the laser (L) irradiated to the substrate 100 and the irradiation time of the laser (L) irradiated to the substrate 100 are proportional, the base metal pattern 300 is not formed. Otherwise, a problem may occur in which the reliability of the formed base metal pattern 300 is reduced. Specifically, when the laser L of relatively weak intensity is irradiated for a relatively short time, hydrothermal growth does not occur from the precursor solution 200, and the base metal pattern 300 is not formed. It can happen. In addition, when the laser L of relatively high intensity is irradiated for a relatively long time, the precursor solution 200 boils, and the base metal pattern 300 is not formed, or the base metal pattern 300 is not formed. ) is formed, the reliability of the formed base metal pattern 300 may be reduced.

The base metal pattern 300 formed on the substrate 100 may display a color. Additionally, the color of the base metal pattern 300 can be controlled as the thickness of the base metal pattern 300 is controlled. When the thickness of the base metal pattern 300 changes, the reflection spectrum of the base metal pattern 300 changes, so the color of the base metal pattern 300 may change.

According to one embodiment, the thickness of the base metal pattern 300 is determined by the scanning speed of the laser L irradiated on the substrate 100 in the step of forming the base metal pattern 300. ) and can be controlled by adjusting the irradiation time of the laser (L). For example, as the irradiation time of the laser L increases, the thickness of the base metal pattern 300 may increase.

Specifically, the base metal pattern 300 will change from a first color (eg, red) to a second color (eg, blue) as the irradiation time of the laser (L) increases. You can. Additionally, the base metal pattern 300 may change from the second color back to the first color as the irradiation time of the laser L increases. That is, as the irradiation time of the laser L increases, the base metal pattern 300 changes from the first color to the second color, and then changes again from the second color to the first color. You can.

According to another embodiment, after the base metal pattern 300 is formed, the thickness of the base metal pattern 300 can be controlled by adjusting the crystallinity of the formed base metal pattern 300. Specifically, after the base metal pattern 300 is formed, the thickness of the base metal pattern 300 can be reduced by increasing the crystallinity of the base metal pattern 300 formed. Accordingly, the color of the base metal pattern 300 may change.

For example, when the formed base metal pattern 300 is heat-treated by irradiating a laser, the crystallinity of the base metal pattern 300 may increase. Specifically, the base metal pattern 300 hydrothermally grown from the precursor solution 200 may have an amorphous structure. When a laser is irradiated to the base metal pattern 300 having an amorphous structure, the degree of crystallinity increases and the base metal pattern 300 may be transformed from an amorphous structure to an α-phase structure. As a result, the thickness of the base metal pattern 300 may be reduced, and the color of the base metal pattern 300 may change.

Referring to FIGS. 6 and 7 , the base metal pattern 300 may be formed in various shapes on the substrate 100. According to one embodiment, by irradiating the laser L to different areas on the substrate 100, as shown in FIG. 6, a plurality of base metal patterns spaced apart from each other on the substrate 100 ( 310, 320) may be formed. For example, a first base metal pattern 310 having a first thickness and a second base metal pattern 320 having a second thickness thinner than the first thickness may be formed on the substrate 100 . Accordingly, the first base metal pattern 310 and the second base metal pattern 320 may display different colors.

In addition, by controlling the scan speed and irradiation time of the laser L while irradiating the laser L, as shown in FIG. Different colors can be displayed in the area. For example, the base metal pattern 300 is divided into a first region 300a and a second region 300b along the length direction, and the first region 300a and the second region 300b are connected to each other. Different colors can be displayed.

That is, the base metal pattern 300 formed by the laser painting method according to an embodiment of the present invention may be formed to have various shapes depending on the irradiation method of the laser L, and may be formed in different shapes on the substrate 100. A plurality of regions may be formed by irradiating the laser L to each region. In addition, while the laser L is irradiated, the scan speed and irradiation time of the laser L are controlled, so that different colors can be expressed in the length direction. Accordingly, the laser painting method according to an embodiment of the present invention combines various numbers and colors of the base metal patterns 300 formed on the substrate 100 to create symbols, letters, shapes, numbers, etc. Alternatively, macroscopic shapes such as logos can be effectively displayed.

The laser painting method includes, after forming the base metal pattern 300 (S300), immersing the substrate 100 on which the base metal pattern 300 is formed in a removal solution containing an alcohol compound, And the step of removing the base metal pattern 300 by applying the laser (L) to the base metal pattern 300 immersed in the removal solution. For example, the alcohol compound may include ethylene glycol. That is, after forming the base metal pattern 300 on the substrate 100, the base metal pattern 300 formed on the substrate 100 can be removed.

According to one embodiment, the removal solution may also be accommodated in the chamber (C) like the precursor solution. Thereafter, the substrate 100 is immersed in the chamber C containing the removal solution, and the laser L is irradiated on the substrate 100 to form the base metal pattern on the substrate 100. (300) can be removed. That is, by irradiating the laser L on the substrate 100 immersed in a solution and changing the type of solution in which the substrate 100 is immersed (precursor solution or removal solution), the laser L is immersed in the solution. The base metal pattern 300 may be formed on or the base metal pattern 300 may be removed from the substrate 100 .

The laser painting method includes, after controlling the base metal pattern 300, immersing the substrate 100 in the precursor solution 200, and immersing the substrate 100 in the precursor solution 200. ) may further include reforming the base metal pattern 300 by irradiating the laser (L). That is, after removing the base metal pattern 300 on the substrate 100, the base metal pattern 300 can be reformed on the substrate 100.

In this case, according to one embodiment, the reformed base metal pattern 300 may have a different color from the base metal pattern 300 before removal. In contrast, according to another embodiment, the reformed base metal pattern 300 may have the same color as the base metal pattern 300 before removal. That is, not only can the color of the base metal pattern 300 before removal be diversified, but the color of the re-formed base metal pattern 300 can also be diversified. Additionally, it is obvious to those skilled in the art that the shape of the reformed base metal pattern 300 can also be varied.

Additionally, the laser painting method according to the above embodiment can be performed repeatedly to form a plurality of base metal patterns 300 by overlapping them. In this case, the portion where the plurality of base metal patterns 300 overlap may display a color different from the color of the base metal pattern 300.

As a result, the laser painting method according to an embodiment of the present invention includes preparing the substrate 100, immersing the substrate 100 in the precursor solution 200 containing a base metal, and By irradiating the laser L to the substrate 100 immersed in the precursor solution 200, the base metal pattern 300 is hydrothermally grown from the precursor solution 200 on the substrate 100. ), wherein the thickness of the base metal pattern 300 is controlled by controlling the scanning speed of the laser L and the irradiation time of the laser L, and controlling the thickness of the base metal pattern 300. The color of the base metal pattern 300 may be controlled depending on the thickness of the pattern 300.

In addition, in the step of forming the base metal pattern 300, the base metal pattern 300 is formed on the first region 100a of the substrate 100 to which the laser L is irradiated and the laser L. may be selectively formed in the first region 100a of the second region 100b of the substrate 100 that is not irradiated.

Accordingly, by forming and combining various shapes, numbers, colors, etc. of the base metal patterns 300, macroscopic shapes such as symbols, letters, figures, numbers, or logos can be effectively displayed. In addition, as described above, various colors can be expressed by a simple method of controlling the conditions of the laser L, and the reproducibility of color expression is high, so it can be applied in a variety of ways in the field of optoelectronic devices in the future.

Above, a laser painting method according to an embodiment of the present invention has been described. Hereinafter, specific experimental examples and characteristic evaluation results of the laser painting method according to embodiments of the present invention will be described.

Formation of a pattern structure through a laser painting method according to an embodiment

The substrate was prepared by coating platinum (Pt) on a glass substrate using an e-beam evaporator, and 0.15 M concentration of iron(III) chloride (FeCl ₃ ), 1 M concentration of sodium nitrate (NaNO ₃ ), and After mixing DI water, hydrochloric acid (HCl) was added to prepare a precursor solution whose pH was adjusted to 1.5.

A PDMS (polydimethylsiloxane) chamber is filled with the precursor solution, the substrate is immersed in the precursor solution, and then a 532 nm CW (Continuous Wave Laser) laser is irradiated onto the substrate immersed in the precursor solution through an objective lens. An iron(III) oxide (Fe ₂ O ₃ ) pattern was formed by hydrothermal growth from the precursor solution.

Figure 8 is a photograph of the real-time formation process of a pattern structure formed through a laser painting method according to an embodiment of the present invention.

Referring to (a) of FIG. 8, a pattern structure is photographed and shown after forming it through the laser painting method according to the above embodiment. Referring to (b) of FIG. 8, the laser painting method according to the above embodiment is shown. After forming a plurality of pattern structures through the method, the formed plurality of pattern structures were photographed and shown.

As can be seen through Figures 8 (a) and (b), it was confirmed that a pattern structure having a line shape was formed through the laser painting method according to the above embodiment. Additionally, as can be seen in (b) of FIG. 8, it was confirmed that the plurality of pattern structures had different colors.

9 and 10 are images showing the color change of the pattern structure according to the change in the scanning speed of the laser during the laser painting method according to an embodiment of the present invention.

Referring to FIG. 9, a plurality of pattern structures are formed on a substrate through the laser painting method according to the above embodiment, and each of the plurality of pattern structures is scanned at different scanning speeds of 10 μm/s to 30 μm/s. ), a reflection optical image of the formed pattern structure was shown.

As can be seen in FIG. 9, it was confirmed that pattern structures formed at different scanning speeds showed different colors. In addition, it was confirmed that the pattern structure formed through the laser painting method according to the above embodiment can exhibit a spectrum of various visible regions.

Referring to FIG. 10, a pattern structure is formed on a substrate through the laser painting method according to the above embodiment, and the scanning speed of the laser is changed from 10 μm/s to 20 μm/s along the direction of laser travel, An image of the pattern structure formed through this was shown.

As can be seen in Figure 10, when the scanning speed of the laser changes along the direction of movement of the laser, the color of the pattern structure formed through this changes continuously along the length direction. In other words, it was confirmed that a plurality of regions divided along the length direction of the pattern structure can each display different colors.

11 and 12 are images showing a large-area pattern structure formed through a laser painting method according to an embodiment of the present invention.

Referring to FIGS. 11 and 12 , after forming a large-area pattern structure through the laser painting method according to the above embodiment, an image thereof is shown. As can be seen in FIGS. 11 and 12, it was confirmed that the pattern structure formed through the laser painting method according to the above embodiment can be formed in a large area that can be confirmed with the naked eye.

13 to 16 are images showing the color change of the pattern structure according to the change in laser irradiation time during the laser painting method according to an embodiment of the present invention.

13 to 16, a plurality of pattern structures are formed through the laser painting method according to the above embodiment, and after the plurality of pattern structures are formed at different laser exposure times, the formed pattern structures are formed. An image is shown. The pattern structure was formed in a dot shape.

More specifically, the horizontal axis arrangement in Figures 13 to 15 represents the laser irradiation time, the vertical axis arrangement represents the pattern structure repeatedly formed under the same conditions, and the section where the color of the pattern structure changes from red to blue is 1 ^st. Divided into Order and ^2nd Order. Figure 16 shows a pattern structure formed by gradually increasing the laser irradiation time along the direction of the arrow. In addition, in Figures 13 to 15, the laser was irradiated through an objective lens with a magnification of x 5, and in Figure 16, the laser was irradiated through an objective lens with a magnification of x 50.

As can be seen in Figures 13 to 16, it was confirmed that the color of the pattern structure changed as the laser irradiation time increased. In particular, as can be seen in Figures 13 and 13, as the laser irradiation time increased, it was confirmed that the color changed from red to blue, and then from blue to red again.

In addition, as can be seen in FIGS. 13 to 15, pattern structures repeatedly formed under the same conditions showed the same color. Accordingly, it was confirmed that the laser painting method according to an embodiment of the present invention has high reproducibility.

Figure 17 is an image and graph showing the surface profile of a patterned structure formed through a laser painting method according to an embodiment of the present invention.

Referring to FIG. 17, an AFM (Atomic Force Microscope) image of a pattern structure formed through the laser painting method according to the above embodiment and a cross-sectional profile of a plurality of pattern structures formed according to irradiation times of different lasers are graphically shown. It was.

As can be seen in the AFM image of FIG. 17, the pattern structure formed through the laser painting method according to the above embodiment was confirmed to have a smooth surface profile. In addition, as can be seen in the graph of FIG. 17, it was confirmed that the plurality of pattern structures formed according to different laser irradiation times had different heights and displayed different colors.

Figure 18 is a graph showing the change in thickness of the pattern structure according to the change in laser irradiation time during the laser painting method according to an embodiment of the present invention.

Referring to Figure 18 (a), the theoretical reflectance (Reflection) according to the height (nm) of the pattern structure is calculated and shown, and Figure 18 (b) shows the laser irradiation time (Exposure Time, sec). ) The reflected light voltage (Photovoltage, a.u.) of the pattern structure according to the change was measured and shown, and referring to (c) of FIG. 18, the height (Height, nm) changes were measured and expressed.

As can be seen in (a) to (c) of Figure 18, the reflected light voltage of the patterned structure decreases as the laser irradiation time increases, while the height of the patterned structure increases as the laser irradiation time increases. there was. In other words, it can be seen that the thickness of the pattern structure increases as the laser irradiation time increases.

Figure 19 is an image showing a state in which pattern structures formed through a laser painting method according to an embodiment of the present invention are overlapped.

Referring to FIG. 19, a pattern structure is formed through the laser painting method according to the above embodiment, and the laser painting method is performed again on the formed pattern structure to overlap the pattern structure, and then an AFM image of the formed structure is taken. indicated.

As can be seen in Figure 19, it was confirmed that the height of the part where the line-shaped pattern structure overlaps appears higher than the height of the other parts. In addition, it was confirmed that the parts where the pattern structures overlapped had different colors compared to the parts where the pattern structures did not overlap. Accordingly, it was found that the pattern structure could be formed by overlapping it by repeatedly performing the laser painting method according to the above embodiment. In addition, it was found that various colors can be displayed through overlapping pattern structures.

Figure 20 is an image showing a pattern structure formed in an alphabet shape and removal of the pattern structure through a laser painting method according to an embodiment of the present invention.

Referring to FIG. 20, a pattern structure is formed through the laser painting method according to the above embodiment, and the path of the laser irradiated on the substrate is controlled to form the pattern structure into the letters 'O', 'N', and 'L'. It was formed into a shape. As can be seen in the upper image of FIG. 20, it was confirmed that the pattern structure formed through the laser painting method according to the above embodiment could be formed into the shape intended by the user.

In addition, pattern structures formed in the shapes of the letters 'O', 'N', and 'L' are immersed in a chamber containing ethylene glycol and then irradiated with a laser. Among the pattern structures formed in the shape of the letters 'O', Pattern structures were selectively removed. In order to confirm whether the pattern structure was removed, EDS measurement was performed on the removed substrate to confirm mapping data for ferrite.

As can be seen in the image below in FIG. 20, it was confirmed that the content of Fe element was significantly reduced in the 'O'-shaped pattern structure that was subjected to the pattern structure removal process using ethylene glycol. Accordingly, not only can the pattern structure be removed by immersing the formed pattern structure in a chamber containing ethylene glycol and then irradiating a laser, but also selectively removing a specific pattern structure among a plurality of pattern structures. You can see that it is possible.

21 to 23 are graphs and images showing changes in crystallinity of a pattern structure formed through a laser painting method according to an embodiment of the present invention.

Referring to FIGS. 21 and 22, after preparing the pattern structure formed through the laser painting method according to the above embodiment, the formed pattern structure is irradiated with a laser again (performed in an air atmosphere) to measure the change in crystallinity of the formed pattern structure. It was expressed as follows. Figure 21 is a graph comparing the cross-sectional profile of the patterned structure before the laser was irradiated with the cross-sectional profile of the patterned structure after the laser was irradiated, and Figure 22 is Raman spectroscopy data of the patterned structure before the laser was irradiated. This is a graph comparing Raman spectroscopy data of the patterned structure after irradiation with the laser.

As can be seen in Figure 21, when the laser was irradiated again to the formed pattern structure, it was confirmed that the overall height (nm) was lowered. In addition, as can be seen in FIG. 22, the patterned structure in the state before the laser was irradiated had an amorphous structure, but as the laser was irradiated, the degree of crystallinity increased, confirming that it had an α-phase structure.

Referring to FIG. 23, after forming a pattern structure of the shape shown in FIG. 23 through the laser painting method according to the above embodiment, the laser was irradiated again to a specific area of the formed pattern structure. As can be seen in Figure 23, it was confirmed that the part where the laser was irradiated again and the part where the laser was not irradiated again showed different colors (red and green).

That is, as can be seen in FIGS. 21 to 23, when the laser is irradiated again to the pattern structure formed after the pattern structure is formed, the crystallinity of the formed pattern structure increases and the thickness decreases, which causes a change in color. Could know.

Figure 24 is a graph showing FDTD simulation results according to the thickness of a pattern structure formed through a laser painting method according to an embodiment of the present invention.

Referring to FIG. 24, after preparing pattern structures of different thicknesses (h _low : 70 nm, h _high : 130 nm) formed through the laser painting method according to the above embodiment, when a spectrum of 400 nm to 700 nm is exposed The FDTD (finite difference time domain) simulation results are shown.

As can be seen in FIG. 24, it was confirmed that for pattern structures of different thicknesses, the total amount of absorbed power can be reversed in different wavelength regions (typically, 450 nm and 650 nm).

Figure 25 is a graph showing temperature data when 450 nm and 650 nm wavelength laser diodes are irradiated with 150 mW.

Referring to Figure 25, temperature data when 450 nm and 650 nm wavelength laser diodes are irradiated at 150 mW are shown as measured by an IR camera. The color of each graph represents the color of the substrate surface. As can be seen in Figure 25, it was confirmed that the amount of temperature increase can be reversed depending on the laser wavelength.

Figure 26 is an image showing the formation of a pattern structure, removal of the pattern structure, and reformation of the pattern structure through a laser painting method according to an embodiment of the present invention, and Figure 27 shows resistance data measured in each state of Figure 26. This is a graph that represents

Referring to FIG. 26, different pattern structures are formed on different substrates (R ₁ , R ₂ ) through the laser painting method according to the above embodiment, and then photographed through a CCD camera, as shown in (a) of FIG. 26. After removing the different pattern structures formed, they were photographed through a CCD camera and shown in (b) of FIG. 26, and after reforming the pattern structures on different substrates (R ₁ and R ₂ ), they were captured on a CCD. It was taken using a camera and shown in (c) of Figure 26. As described above, the formation of the patterned structure was performed by immersing the substrate in an iron (Fe) precursor solution and then irradiating a laser, and the removal of the patterned structure was performed by immersing the substrate in ethylene glycol (EG) and then irradiating the laser. It was performed in the following way.

Referring to FIG. 27, resistance (Ω) in each state of FIG. 26 (pattern structure formation state, pattern structure removal state, pattern structure reformation state) is measured and shown. Figures 27 (a) to (c) sequentially show the resistance in the state of forming the pattern structure, removing the pattern structure, and reforming the pattern structure performed on the R ₁ substrate, and Figures 27 (d) to ( f) sequentially shows the resistance in the state of forming the pattern structure, removing the pattern structure, and reforming the pattern structure performed on the R ₂ substrate.

As can be seen in FIGS. 26 and 27, through the laser painting method according to an embodiment of the present invention, the formed pattern structure can be easily removed after forming the pattern structure on the substrate, and the same pattern structure can be removed even after the pattern structure is removed. It was confirmed that the pattern structure could be reformed on the area. In addition, it was confirmed that when the pattern structure is reformed, it can be formed to have a different color from the pattern structure before removal.

Above, the present invention has been described in detail using preferred embodiments, but the scope of the present invention is not limited to the specific embodiments and should be interpreted in accordance with the appended claims. Additionally, those skilled in the art should understand that many modifications and variations are possible without departing from the scope of the present invention.

100: substrate
110: base substrate
120: metal layer
200: precursor solution
300: Base metal pattern

Claims (14)

Preparing a substrate;
Immersing the substrate in a precursor solution containing a base metal; and
Comprising the step of irradiating a laser to the substrate immersed in the precursor solution to form a base metal pattern hydrothermally grown from the precursor solution on the substrate,
By adjusting the scanning speed of the laser and the irradiation time of the laser, the thickness of the base metal pattern is controlled, and the color of the base metal pattern is controlled according to the thickness of the base metal pattern,
The base metal pattern includes a first base metal pattern and a second base metal pattern,
At least a portion of the first base metal pattern and the second base metal pattern overlap each other,
The color of the portion where the first base metal pattern and the second base metal pattern overlap is the color of the first base metal pattern in the non-overlapping portion, and the color of the second base metal pattern in the non-overlapping portion. Laser painting methods including others.
According to claim 1,
A laser painting method comprising: as the laser irradiation time increases, the thickness of the base metal pattern increases, and the color of the base metal pattern changes.
Preparing a substrate;
Immersing the substrate in a precursor solution containing a base metal; and
Comprising the step of irradiating a laser to the substrate immersed in the precursor solution to form a base metal pattern hydrothermally grown from the precursor solution on the substrate,
By adjusting the scanning speed of the laser and the irradiation time of the laser, the thickness of the base metal pattern is controlled, and the color of the base metal pattern is controlled according to the thickness of the base metal pattern,
The base metal pattern changes from a first color to a second color as the laser irradiation time increases, and then changes back from the second color to the first color.
According to claim 1,
The base metal pattern may display different colors depending on the scanning speed of the laser.
According to claim 1,
The intensity of the laser irradiated to the substrate is inversely proportional to the irradiation time of the laser.
According to claim 1,
A laser painting method comprising changing the color of the base metal pattern by increasing the crystallinity of the base metal pattern after the base metal pattern is formed.
According to clause 6,
A laser painting method comprising reducing the thickness of the base metal pattern as the crystallinity of the formed base metal pattern increases.
According to claim 1,
A laser painting method wherein the base metal includes iron (Fe).
According to claim 1,
In forming the base metal pattern,
The base metal pattern is selectively formed on a first region of the substrate to which the laser is irradiated and a second region of the substrate to which the laser is not irradiated.
Preparing a substrate;
Immersing the substrate in a precursor solution containing a base metal;
irradiating a laser to the substrate immersed in the precursor solution to form a base metal pattern hydrothermally grown from the precursor solution on the substrate;
immersing the substrate on which the base metal pattern is formed in a removal solution containing ethylene glycol; and
Removing the base metal pattern by irradiating a laser to the base metal pattern immersed in the removal solution,
By controlling the scanning speed of the laser and the irradiation time of the laser, the thickness of the base metal pattern is controlled, and the color of the base metal pattern is controlled according to the thickness of the base metal pattern. Laser painting method including.
According to claim 10,
After removing the base metal pattern,
It further includes immersing the substrate in the precursor solution, and irradiating a laser to the substrate immersed in the precursor solution to reform the base metal pattern,
A laser painting method, wherein the base metal pattern before removal and the re-formed base metal pattern have different colors.
A substrate containing platinum (Pt);
A plurality of base metal patterns including iron oxide, at least some of which are arranged overlapping each other on the substrate,
The plurality of base metal patterns are,
a first base metal pattern having a first thickness; and
It includes a second base metal pattern having a second thickness thinner than the first thickness,
A pattern structure comprising: the first base metal pattern, the second base metal pattern, and a portion where the first base metal pattern and the second base metal pattern overlap display different colors.
According to claim 12,
The base metal pattern is a pattern structure including a first region and a second region of different colors along the length direction.
According to claim 12,
The first base metal pattern and the second base metal pattern are combined with each other to display at least one of a symbol, letter, figure, number, or logo.

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