KR102114658B1 - Copper oxide thin-film structure with an adjustable color and manufacturing method thereof - Google Patents

Abstract

The present invention relates to a copper oxide thin film structure with an adjustable color and a manufacturing method thereof. In particular, the present structure comprises: a substrate; a single crystal copper layer which is formed on the upper portion of the substrate and has a uniform directivity; and a copper oxide (I) layer which is formed on the upper portion of the single crystal copper layer and has a sudden boundary with the single crystal copper layer. In addition, the present method comprises: a single crystal copper thin film structure forming step that a single crystal copper thin film structure is manufactured after allowing the single crystal copper layer to be deposited on the upper portion of the substrate by using a single crystal copper ingot target and performing sputtering; and a sudden boundary forming step that the single crystal copper thin film structure undergoes thermal treatment to be oxidized into a copper oxide (I) layer and a copper oxide (II) layer while the sudden boundary is formed between the single crystal copper layer and the copper oxide (I) layer. Therefore, various colors can be uniformly embodied.

Description

Copper oxide thin-film structure with an adjustable color and manufacturing method thereof

The present invention relates to a copper oxide thin film structure capable of color control and a method for manufacturing the same, and more specifically, to produce a defect-free single crystal copper thin film layer using a defect-free single crystal copper ingot target, and heat-treating it to produce a copper oxide thin film structure. The present invention relates to a copper oxide thin film structure capable of uniformly realizing color and a method for manufacturing the same.

Recently, with the rapid development of IT technology, the development of electronic devices such as smartphones has been actively conducted, and in particular, as the use of metal materials in electronic devices has increased, various surface treatment technologies are required.

The surface treatment is made for various purposes such as making the surface of the material look beautiful, corrosion resistance, abrasion resistance, and hardening of the surface. For example, electronic devices such as IT products have a form in which electronic components are accommodated in an exterior case made of a metal or an injection material, and the exterior case essentially protects electronic parts from the external environment and incidentally visual aesthetics. In order to provide the function of imparting a surface treatment.

Particularly, in accordance with the leveling of technology, aesthetic functions have been given priority over protection functions of internal parts when consumers purchase electronic devices.

The metallic material that becomes the outer sheath implements color through painting or plating, and representatively, colored steel sheets exist. Conventional color steel sheet is a technology that combines coating process or film bonding process to electro-galvanized steel sheet and hot-dip galvanized steel sheet. It is used for construction materials, household appliances, and automotive steel sheets, but the color is monotonous and the color itself As a result, there is a limit to satisfying aesthetic needs.

Accordingly, in Korean Patent No. 10-1508970 (a street light column having a high strength and high corrosion resistance brass film), a composite film forming body is coated to form a high corrosion resistant basic anti-corrosion film, and a protective paint film is formed on the basic anti-corrosion film to protect the surface. Then, a technique was proposed to provide a street lamp pole that utilizes the unique color of brass and enhances durability by mixing and coating brass powder on a transparent paint over a protective paint film and heating it.

However, the method of forming a film through heat treatment after coating by mixing powder brass with a transparent paint has a problem in that it is difficult to realize various colors according to the type of material to be coated and the oxidation reaction.

In addition, copper having a reddish brown color, which is used as a metal material for the outer shell, exhibits blue color while oxidizing, but there is a problem in that it cannot realize various other colors. Accordingly, an attempt has been made to produce a color by using the degree of oxidation of the copper thin film, but there is a problem in that it is not diverse and has poor color uniformity.

Therefore, a method for solving these problems is required.

Republic of Korea Registered Patent Publication No. 10-1508970

The technical problem of the present invention is to solve the problems mentioned in the background art, and more specifically, to produce a defect-free single crystal copper thin film layer using a defect-free single-crystal copper ingot target, and heat-treating it to achieve homogeneity with little grain. It is to provide a copper oxide thin film structure capable of homogeneously implementing various colors by manufacturing a (homogeneous) copper oxide thin film structure and a method for manufacturing the same.

The technical problems to be achieved by the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned can be clearly understood by those skilled in the art from the following description. There will be.

The copper oxide thin film structure capable of color control according to the present invention devised to solve the technical problem is formed on a substrate, on the substrate, and has a single directional copper layer and a single crystalline copper layer, and is formed on the single crystal copper layer. It may be composed of a copper (I) oxide layer having a sudden boundary.

Here, the thickness of the copper (I) oxide layer is adjusted according to the heat treatment temperature or time, and the color may be determined according to the thickness.

In addition, a copper oxide (II) layer formed on the copper oxide (I) layer and preventing oxidation of the copper oxide (I) layer may be further included.

On the other hand, a method of manufacturing a color-adjustable copper oxide thin film structure uses a single crystal copper ingot target, sputters to deposit a single crystal copper layer on top of the substrate, forming a single crystal copper thin film structure to produce a single crystal copper thin film structure, and the single crystal copper thin film The structure is heat-treated to oxidize to a copper (I) oxide layer and a copper (II) oxide layer, and at the same time, comprises a step of forming a sudden boundary between the single crystal copper layer and the copper (I) oxide layer. Can be.

The step of forming the boundary is characterized in that the single crystal copper layer formed in the step of forming the single crystal copper thin film structure remains, so that a boundary is formed between the single crystal copper layer and the copper (I) oxide layer.

Here, the sputtering is preferably performed for 10 minutes to 150 minutes at 150 ° C to 250 ° C at 30W to 60W.

In addition, the heat treatment is preferably performed for 1 second to 300 minutes at 100 ° C to 450 ° C in an electric furnace on an air atmosphere.

The present invention by the above configuration can expect the following effects.

The copper oxide thin film structure manufactured using a defect-free single crystal copper thin film can realize various colors using only the copper thin film. And, it can exhibit a uniform color as a whole. Therefore, it is possible to provide a copper oxide thin film structure having high manufacturing efficiency and excellent quality.

The effects of the present invention are not limited to the above-mentioned effects, and other effects not mentioned will be clearly understood by those skilled in the art from the description of the claims.

1 and 2 is a schematic configuration of a copper oxide thin film structure capable of color control according to an embodiment of the present invention.
3 is a view showing incident light and reflected light reflected from a thin film.
4 is a flowchart of a method of manufacturing a copper oxide thin film structure capable of color control according to an embodiment of the present invention.
5 is a view showing an XRD pattern and color of a copper oxide thin film structure manufactured by a method of manufacturing a copper oxide thin film structure capable of color control according to an embodiment of the present invention.
6 is a photograph and a TEM photograph of a copper oxide thin film structure manufactured by a method of manufacturing a copper oxide thin film structure capable of color control according to an embodiment of the present invention.
7 is a photograph showing the color of the copper oxide thin film structure manufactured by the method of manufacturing a copper oxide thin film structure capable of color adjustment according to an embodiment of the present invention according to various heat treatment temperatures.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, in describing the present invention, descriptions of already known functions or configurations will be omitted to clarify the gist of the present invention.

In addition, in describing the present invention, terms indicating directions such as forward / backward or upper / lower are described so that those skilled in the art can clearly understand the present invention, and indicate relative directions. It will be said that it is not limited.

The color-adjustable copper oxide thin film structure and its manufacturing method according to the present invention are capable of homogeneously implementing various colors by manufacturing a defect-free single crystal copper thin film layer using a single crystal copper ingot target and heat-treating it to produce a copper oxide thin film structure. It is characteristic.

Hereinafter, a copper oxide thin film structure capable of color control and a method of manufacturing the same according to an embodiment of the present invention will be described in detail with reference to FIGS. 1 to 7.

First, a copper oxide thin film structure capable of color adjustment according to an embodiment of the present invention will be described.

The color-adjustable copper oxide thin film structure according to the present invention may include a substrate 100, a single crystal copper layer 200, and a copper oxide (I) layer, as shown in FIGS. 1 and 2.

The substrate 100 is transparent and has structural or chemical stability, and may be formed of a sapphire substrate or a silicon substrate.

The single crystal copper layer 200 is formed on the substrate 100 and may be formed to have a certain directionality, which can be formed on the substrate 100 through sputtering by using a defect-free single crystal copper ingot as a target. .

In addition, the copper oxide (I) 300 layer may be formed on the single crystal copper layer 200 and may have a single crystal copper layer 200 and a sudden boundary 210.

The copper oxide (I) 300 layer may be homogeneous with little grains having a single crystal copper layer and a sudden boundary.

At this time, the copper oxide (I) layer 300 is preferably formed uniformly in a constant direction so that diffusion of oxygen (diffusion) can be uniformly compared with the conventional polycrystalline copper oxide (I), and the single crystal copper has a [111 ], The copper (I) oxide layer is formed with a cubic structure with a preferred orientation in the [111] direction.

This can be formed by oxidizing the single crystal copper thin film layer 200 formed on the substrate 100 in an electric furnace.

As described above, the copper (I) oxide layer 300 forms a sudden boundary 210 between the single crystal copper layer 200 and the copper (I) oxide layer 300, and the copper (I) oxide layer 300 ) Depending on the thickness, various colors can be implemented. More specifically, the copper (I) oxide layer 300 may be adjusted to various thicknesses by heat treatment, and may exhibit various colors according to the thickness. Accordingly, various colors may be uniformly implemented according to the use of the copper oxide thin film structure.

Referring to FIG. 3, the copper oxide (I) layer 300 having the sudden boundary 210 will be described in more detail with reference to FIG. Here, the first thin film (F1) and the second thin film (F2) may be a thin film or a substrate, in an embodiment of the present invention, the first thin film (F1) is a thin film, the second thin film (F2) is a thin film or a substrate Explain that.

As illustrated in FIG. 3, when the incident light travels through the first thin film F1 and then reflects off the surface of the second thin film F2, the first thin film according to the path of the first thin film F1 The light L11 reflected from the surface of (F2) and the light L12 reflected from the surface of the second thin film (F2) through the first thin film (F1) cancel or interfere. At this time, the wavelength of the offset or reinforced light depends on the path through the first thin film F1, and through this, the thin film structure can exhibit various colors.

Previously, there existed a method of realizing color by generating a new thin film on a substrate or a base film using various deposition techniques. However, the method using heat treatment presented in the present invention has limitations in realizing various colors and the color quality is limited. It wasn't good, so little was tried.

This is due to the control of the interface between the first thin film (F1) and the second thin film (F2.) The light reflected from the second thin film (F2) does not diffuse and has an accurate path difference to obtain a clean color and has various resolutions. Color can be implemented, but the existing heat treatment method does not implement this due to diffuse reflection caused by the failure to form a clean boundary at the interface, but in the present invention, as shown in FIGS. 2 and 6, the first thin film and By forming a boundary between the second thin film, that is, between the single crystal copper layer and the copper (I) layer, light reflected from the copper (I) oxide layer 300 can have an accurate path difference without diffuse reflection, thereby providing various and clean colors. Can be implemented.

Therefore, the color-adjustable copper oxide thin film structure according to the present invention can realize various colors using only one copper thin film, and may have an effect of displaying a uniform color as a whole.

Meanwhile, the copper oxide thin film structure capable of color control according to the present invention is formed on the copper oxide (I) layer 300, and the copper oxide (II) layer prevents oxidation of the copper oxide (I) layer 300. It may be configured to further include 400.

The copper (II) oxide layer 400 prevents peroxidation of the copper (I) oxide layer 300 on top of the copper (I) oxide layer 300 and prevents external damage, thereby improving the mechanical stability of the copper oxide thin film structure. To improve.

This can be formed by oxidizing only the surface of the single crystal copper thin film layer 200 by maintaining a defect-free single crystal copper thin film deposited on the upper portion of the substrate 100 by a high-frequency sputtering or direct current sputtering method at a deposition temperature in a sputtering equipment for a certain period of time. Do.

The configuration of the copper oxide thin film structure capable of color control according to an embodiment of the present invention has been described above, and the method of manufacturing the copper oxide thin film structure capable of color control will be described in detail below.

A method of manufacturing a color-adjustable copper oxide thin film structure according to an embodiment of the present invention may include a single crystal copper thin film structure forming step (S10) and a sudden boundary forming step (S20) as illustrated in FIG. 4.

The copper thin film structure forming step (S10) is a step of manufacturing a single crystal copper thin film structure by using a single crystal copper ingot target and sputtering to deposit a single crystal copper layer on the substrate.

That is, after the substrate is put into the sputtering equipment (not shown), a defect-free single crystal copper ingot is deposited on the top of the substrate 100 by sputtering to form a defect-free single crystal copper thin film layer 200 formed on the top of the substrate 100. A thin film structure can be produced.

At this time, it is preferable to perform sputtering at 150 ° C to 250 ° C at 30W to 60W. If it is higher or lower than the temperature range, the adhesion between copper (I) and the substrate decreases when the copper (I) oxide layer is subsequently formed, and crystallinity decreases according to formation of grain boundaries and dislocations, and is higher than the power range. If it is low or low, the defect-free single crystal copper thin film layer is not uniformly deposited and the electrical and mechanical properties are lowered, so it is preferable to perform sputtering according to the above conditions.

In addition, since the thickness of the single crystal copper thin film layer 200 is determined according to the sputtering time, sputtering is preferably performed for 10 minutes to 180 minutes.

Subsequently, in the step of forming the boundary (S20), the single crystal copper thin film structure is heat-treated to oxidize the copper (I) layer 300 and the copper (II) oxide layer 400, and simultaneously the single crystal copper layer 200 and the copper oxide. (I) This is a step of forming a sudden boundary 210 between the layers 300.

Here, the step of forming a boundary (S20) is processed so that the single crystal copper layer 200 formed in the single crystal copper thin film structure forming step remains, between the single crystal copper layer 200 and the copper oxide (I) layer 300 It is preferable that the sudden boundary 210 is made.

In addition, the heat treatment is preferably performed for 1 second to 300 minutes at 100 ° C to 450 ° C in an electric furnace on an air atmosphere.

As described above, the light reflected from the copper oxide (I) layer does not diffusely and has an accurate path difference to obtain a clean color and realizes a color having various resolutions. In the present invention, by forming a sudden boundary between the single crystal copper layer and the copper (I) layer through heat treatment, the light reflected from the copper (I) layer 300 can have an accurate path difference without diffuse reflection and various and clean colors. You can implement

That is, referring to FIG. 6, it can be confirmed that a sudden boundary is not formed before the heat treatment, and the copper oxide thin film structure according to the present invention is formed with a sudden boundary after the heat treatment, so that various colors can be realized and the overall color is uniform It can be confirmed that can have.

In addition, the light reflected from the surface of the copper oxide (I) layer and the light reflected through the copper oxide (I) layer through the path of the copper oxide (I) layer cancel or reinforce interference. At this time, the wavelength of the offset or reinforced light depends on the path through the copper (I) oxide layer, and through this, the thin film structure can exhibit various colors.

Accordingly, the copper (I) oxide layer may exhibit various colors depending on the thickness, and the thickness may be controlled by the heat treatment temperature and time.

That is, as shown in FIG. 5, it can be seen that the copper oxide thin film structure exhibits various colors when heat-treated in an electric furnace on an air atmosphere at 350 ° C. for various times, and at 330 ° C. 1 as shown in FIG. 6. It can be seen that when the heat treatment was performed for a minute and when the heat treatment was performed at 350 ° C for 20 seconds, a sudden boundary was formed and exhibited different colors. And it can be seen that various colors can be implemented through heat treatment as shown in FIG. 7.

Therefore, as described above, the heat treatment is preferably performed for 1 second to 300 minutes at 100 ° C to 450 ° C in an electric furnace on an air atmosphere.

The copper oxide thin film structure manufactured by the method of manufacturing a copper oxide thin film structure according to the above-described embodiment of the present invention can be seen that the color changes according to the heat treatment time and temperature, substrate, single crystal copper, copper oxide (I, It can be seen that Ⅱ) coexisted and a sudden boundary was formed between the single crystal copper layer and the copper (I) oxide layer.

Accordingly, it is possible to have the effect of uniformly realizing various colors, and thus, it is possible to have an effect of providing a copper oxide thin film structure having high manufacturing efficiency and excellent quality.

As described above, the preferred embodiments according to the present invention have been examined, and the fact that the present invention can be embodied in other specific forms without departing from the spirit or scope of the embodiments described above has ordinary knowledge in the art. It is obvious to them. Therefore, the above-described embodiments should be regarded as illustrative rather than restrictive, and accordingly, the present invention is not limited to the above description and may be changed within the scope of the appended claims and their equivalents.

100: substrate
200: single crystal copper layer
210: sudden boundary
300: copper (I) oxide layer
400: copper (II) oxide layer

Claims (7)

Board;
A single crystal copper layer formed on the substrate and having a certain directivity; And
A copper (I) oxide layer formed on the single crystal copper layer and having a boundary with the single crystal copper layer;
Copper oxide thin film structure capable of color control, characterized in that consisting of. According to claim 1,
A copper oxide thin film structure capable of color control, wherein the copper oxide (I) layer is formed on the copper oxide layer and further comprises a copper (II) oxide layer that prevents oxidation of the copper oxide (I) layer. According to claim 1,
The copper oxide (I) layer is a thickness-controllable copper oxide thin film structure characterized in that the thickness is adjusted according to the heat treatment temperature or time, and the color is determined according to the thickness. A single crystal copper thin film structure forming step of using a single crystal copper ingot target and sputtering to deposit a single crystal copper layer on the substrate to produce a single crystal copper thin film structure; And
Forming a sudden boundary between the single crystal copper layer and the copper oxide (I) layer while heat-treating the single crystal copper thin film structure to oxidize the copper oxide (I) layer and the copper oxide (II) layer;
A method of manufacturing a copper oxide thin film structure capable of color control, comprising: The method of claim 4,
The step of forming the border,
A method of manufacturing a color-controllable copper oxide thin film structure characterized in that the single crystal copper layer formed in the step of forming the single crystal copper thin film structure is left to remain, thereby forming a boundary between the single crystal copper layer and the copper (I) layer. . The method of claim 4,
The sputtering,
A method of manufacturing a copper oxide thin film structure capable of color control, characterized in that it is performed at 150 ° C to 250 ° C at 30W to 60W for 10 minutes to 180 minutes. The method of claim 4,
The heat treatment,
A method for manufacturing a copper oxide thin film structure capable of color control, characterized in that it is carried out for 1 second to 300 minutes at 100 ° C to 450 ° C in an electric furnace on an air atmosphere.

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