KR101558872B1 - heating glass window having thermal conductive pattern and manufacturing method thereof - Google Patents

Abstract

The present invention relates to a heat generating window including a thermally conductive metal pattern. According to the heat generating window of the present invention, a metal oxide film formed by using an electron cyclotron resonance plasma chemical vapor deposition method and a micro-lithography process And a thermally conductive pattern formed on the surface of the metal oxide film, and has high electrical conductivity and low resistance, thus exhibiting excellent heat generation performance even at a low voltage. Therefore, it is possible to prevent the frost and condensation phenomenon caused by the temperature difference between the indoor and the outdoor, and to reduce the energy in the cooling and heating. In addition, it has high visible light transmittance and excellent visibility and can be widely applied to a window of a building or a glass of a vehicle.

Description

TECHNICAL FIELD [0001] The present invention relates to a heating window including a thermal conductive pattern and a manufacturing method thereof,

[0001] The present invention relates to a heat generating window including a thermally conductive metal pattern, and more particularly, to a heat generating window including a first and a second transparent substrate laminated to each other and a metal oxide film arranged between the transparent substrates, And a method of manufacturing the same.

If there is a difference in temperature between the outside and inside, such as during the winter season or during the rainy season, the window will become wet or hot. In order to solve this problem, a heating device (Patent Document 1) in which a heating wire is installed on the rim of the front glass of an automobile or a heating glass which increases the surface temperature of glass by generating heat by attaching a heating wire sheet to the glass or directly heating the glass . However, it is difficult to apply it to a place requiring a large area such as a veranda glass of an apartment and a glass window of a building, and there is a problem in that the time consumed to generate heat and the loss of fuel are large, and visibility is poor.

It is also important that such a heat-resistant glass has low resistance in order to smoothly generate heat in automotive or architectural glass, but it should not be disturbing to the human eye. For this reason, conventional transparent heat generating glasses have been proposed to produce a heating layer by a sputtering method or a chemical vapor deposition method on an oxide thin film material such as indium tin oxide (ITO), but are driven at a low voltage of 40 V or less due to high sheet resistance There is a problem that it is hard.

Although a heat-generating glass for solving the above problem has been developed, there is a problem that it is difficult to control the day-to-day variation because the heat generation rate is low and the inside visible light can not be protected. (Patent Document 2)

(Patent Document 1) Patent Document 1. Korean Utility Model Publication No. 2000-0003151 (Patent Document 2) Patent Document 2: Korean Patent Publication No. 10-2011-0083513

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and it is an object of the present invention to provide a method of manufacturing a metal oxide film by depositing a metal oxide film using an electron cyclotron resonance plasma enhanced chemical vapor deposition Which is excellent in heat generation performance and has a high visible light transmittance, and a method for manufacturing the same.

According to an aspect of the present invention, there is provided a liquid crystal display comprising: a first transparent substrate; A thermally conductive pattern formed on the first transparent substrate; A metal oxide film formed on the surface of the thermally conductive pattern; A heating terminal formed on a part of the metal oxide film to supply power to the metal oxide film; And a second transparent substrate pressed onto the heating terminal.

And the first and second transparent substrates are glass or plastic substrates.

The metal oxide film is deposited by an electron cyclotron resonance plasma chemical vapor deposition method. The metal oxide film is formed of fluorine-doped tin oxide (FTO), indium tin oxide (ITO), and aluminum-doped zinc oxide And the like.

Wherein the thermally conductive pattern is fabricated through a micro-lithographic process, wherein the thermally conductive pattern is characterized by any one selected from the group consisting of copper, silver, nickel, chromium and nickel chromium alloys.

The heat generating terminal is in the form of a bar or tape, and is characterized by including copper.

The thickness of the metal oxide layer is 100 to 300 nm.

Wherein the thermally conductive pattern has a line width of 15 to 50 mu m.

The heat generating window has a calorific value of 10 to 35 W / m 2 at a voltage of 5 to 30 V, a visible light transmittance of 85 to 95% or more, and a sheet resistance value of 10 to 50 Ω / cm.

The present invention also relates to a method of forming a thermally conductive pattern comprising: i) forming a thermally conductive pattern using fine-lithography on a first transparent substrate; Ii) depositing a metal oxide film on the thermally conductive pattern using electron cyclotron resonance plasma enhanced chemical vapor deposition; Iii) forming a heating terminal electrically connected to the metal oxide film; And iv) attaching and pressing a second transparent substrate on the heat generating terminal.

Wherein the transparent substrate is a glass or plastic substrate, and the thermally conductive pattern is any one selected from the group consisting of copper, silver, nickel, chromium and nickel chromium alloys.

The metal oxide film is any one selected from the group consisting of a fluorine-doped tin oxide film (FTO), an indium tin oxide film (ITO), and an aluminum-doped zinc oxide film (AZO).

The heating terminal may be in the form of a bar or a tape, and the heating terminal may include copper.

According to the heat generating window of the present invention, as a transparent heat window including a metal oxide film formed on the surface of a transparent substrate by using electron cyclotron resonance plasma chemical vapor deposition and a metal oxide film formed on the surface of the thermal conductive pattern by a micro-lithography process , Exhibits excellent heat conductivity even at a low voltage due to its high electrical conductivity and low resistance. Therefore, it is possible to prevent the frost and condensation phenomenon caused by the temperature difference between the indoor and the outdoor, and to reduce the energy in the cooling and heating. In addition, since the visible light transmittance is high, it is excellent in visibility and can be widely applied to a glass window of a building or a glass of a vehicle.

1 is a schematic view showing the structure of a heat generating window manufactured according to the present invention.
Fig. 2 shows the thermal conductive patterns of the respective heat generating windows manufactured according to the first to fourth embodiments of the present invention.
FIG. 3 is a graph illustrating the heat generation characteristics of each of the heat generating windows manufactured according to Examples 1 to 4 of the present invention.

Hereinafter, a heat generating window according to the present invention and a method for manufacturing the same will be described in detail with reference to the drawings.

FIG. 1 is a schematic view showing a structure of a heat generating window manufactured according to the present invention. Referring to FIG. 1, the heat generating window according to the present invention includes a first transparent substrate 10; A thermally conductive pattern (20) formed on the first transparent substrate (10); A metal oxide film 30 formed on the surface of the thermally conductive pattern 20; A heating terminal 40 formed on a part of the metal oxide film to supply power to the metal oxide film 30; And a second transparent substrate (50) pressed onto the heating terminal (40).

The heat generating window may include the first and second transparent substrates 10 and 50 to be laminated to each other and the metal oxide film 30 arranged between the first and second transparent substrates 10 and 50, A conductive pattern 20, a heating terminal 40, and the like. The first and second transparent substrates 10 and 50 are not limited to those having a visible light transmittance of 70% or more, but a glass or plastic substrate may be preferably used, and a glass substrate is more preferably used Do.

The heat generating window of the present invention is formed by coating a thermally conductive pattern 20 on one surface of the first transparent substrate 10 by using micro-lithography and coating the first transparent substrate 10 and the metal oxide film 30, And the thermally conductive pattern is not limited to a metal having excellent thermal conductivity, but it is preferable to use any one selected from the group consisting of copper, silver, nickel, chromium and nickel chromium alloys.

The thermally conductive pattern 20 is not limited to a pattern that minimizes diffraction and interference effects of light and does not disturb visibility. Preferably, a thermally conductive pattern of the type shown in Figures 2A-2D can be used. 2A is a pattern of a lattice structure having the same size, and Fig. 2B is a pattern further comprising a circle 21 in the lattice structure of Fig. 2A. In this case, the diameter of the circle 21 Is equal to the length of one of the squares. 2C is characterized in that a diagonal line 22 is further included in the lattice structure of FIG. 2A, and the major line 22 is positioned so as to be in the shape of an X at the center of the four corners of the lattice structure .

Further, FIG. 2D is characterized in that it further includes a rhombus 23 in the lattice structure of FIG. 2A.

The thermal conductive pattern 20 may have a line width of 15 to 50 mu m, more preferably 15 to 35 mu m or less, so as to improve the heat generating temperature and excel in heat generation performance even in a large area, It does not interfere with visibility.

In addition, the thermally conductive pattern 20 is related to the aperture ratio, and when the line width of the thermally conductive pattern is thick and the interval between lines is narrow, the aperture ratio, visible light transmittance and resistance become low. Accordingly, it is possible to manufacture a heat-generating window having excellent heat-generating performance and visible light transmittance by adjusting the line width and pattern shape of the thermally conductive pattern according to the present invention.

The metal oxide film 30 is formed on the surface of the thermally conductive pattern 20 by using the electron cyclotron resonance plasma chemical vapor deposition method. The metal oxide film 30 is positioned between the thermally conductive pattern 20 and the heat generating terminal 40 . As a result, it is suitable for forming a film on the surface of a substrate which has a good adhesion to a substrate and a metal oxide film, exhibits a high electric conductivity, and is weak against heat, compared with a deposition using a sputtering and chemical vapor deposition method.

The metal oxide film 30 may be any one selected from the group consisting of fluorine-doped tin oxide (FTO), indium tin oxide (ITO), and aluminum-doped zinc oxide (AZO). It is more preferable to use fluorine-doped tin oxide. In general, the conventional transparent metal oxide film deteriorates with the lapse of time, so that the sheet resistance generally increases up to 3 to 10 times of the resistance in manufacturing. However, when fluorine-doped tin oxide is used in the deposition process, the degree of deterioration is low.

If the thickness of the metal oxide layer is less than 100 nm, the thickness of the metal oxide layer may not be sufficient. When the thickness of the metal oxide layer is more than 300 nm, the visible light transmittance may decrease .

In addition, in the present invention, the heat conductive pattern 20 is further provided on the surface of the metal oxide film 30 so that the time consumed for power supply and heat generation is shortened and uniform heat transfer can be performed. As a result, the heating window of the present invention has excellent heating rate and performance at low voltage.

A heating terminal 40 may be formed on a part of the surface of the metal oxide film 30 to supply power to the metal oxide film 30. The heating terminal 40 may be in the form of a bar or a tape. Specifically, the heating terminal 40 may include copper.

In addition, the second transparent substrate 50 may be placed on the heat generating terminal 40. Here, the second transparent material 50 is preferably the same size as the first transparent material 10.

The heat generating window manufactured according to the present invention may have a calorific value of 10 to 35 W / m ² and exhibits the same calorific value even at 30 V or less, a sheet resistance of 15 to 50 Ω / m, a visible light transmittance of 85 to 100 Ω / 95%. Therefore, as described above, since it has a high transparency, transparency, and excellent heat generation performance even under a low voltage, it can be used in automobiles and the like.

The present invention also provides a method of depositing a metal oxide film on a transparent substrate, comprising the steps of: i) forming a thermally conductive pattern using fine-lithography on a transparent substrate, ii) depositing a metal oxide film on the thermally conductive pattern using electron cyclotron resonance plasma chemical vapor deposition Forming a heating terminal electrically connected to the metal oxide film; and iv) attaching and pressing a transparent substrate on the heating terminal.

First, in the step i), it is preferable that the thermally conductive pattern is formed on a transparent substrate by photolithography. More specifically, in the photolithography process, a thermally conductive pattern material layer is formed on the entire surface of the transparent substrate, A photoresist layer is patterned through a selective exposure and development process by forming a resist layer, patterning the thermally conductive pattern material layer using the patterned photoresist layer as a mask, and then removing the photoresist layer .

Next, an electron cyclotron resonance plasma chemical vapor deposition having a high ionization rate was used to form a metal oxide film on the thermally conductive pattern produced in the above step, and the electron cyclotron resonance plasma chemical vapor deposition Density plasma ion having a high energy using an electron cyclotron resonance plasma generated when a rotation frequency of the plasma ion is equal to a microwave frequency applied to a power source. When a metal precursor, which is a metal oxide, is supplied and a low-frequency direct current positive or negative voltage is applied, metal ions are generated in the supplied metal precursor. The metal ions collide with plasma ions and organic substances in the metal precursor, and are condensed and deposited on the surface of the substrate by chemical bonding between metal ions to form a transparent conductive metal oxide film. Therefore, the metal precursor supply position is preferably supplied to the microwave introducing portion just above the electron cyclotron forming region. Therefore, it is preferable that the metal precursor supply position is provided to the microwave introducing portion just above the electron cyclotron forming region.

Hereinafter, specific examples will be described in detail.

(Example 1)

Electron cyclotron resonance chemical vapor deposition was used to form a fluorine-doped tin oxide (FTO) layer on the surface of the soda lime glass. The deposition was carried out at a microwave power of 1400 W, an electromagnet current of 165 A, The deposition pressure is 10 mtorr and the amount of the introduced gas is 4,7 sccm of tetramethyltin (TMT), 6 sccm of argon (Ar), 0.2 sccm of fluorine (SF6), 8.4 sccm of hydrogen (H2) and 36.7 sccm of oxygen At this time, the distance between the nozzle to which the tetramethyltin precursor was supplied and the substrate was 5 cm, the distance between the hydrogen nozzle and the substrate was 3 cm, the rotation speed was 15 RPM, and the Bubbler pressure was 43.8 torr of tetramethyltin , And the deposition time was 7 minutes to prepare an oxide layer having a thickness of approximately 400 nm.

Photolithography was used to form a thermally conductive pattern on the surface of the oxide layer. The thermally conductive pattern used was a nickel chromium alloy. After the photoresist layer was formed, a soft bake was performed at 95 ° C for 3 minutes, and the mask was aligned and exposed for 13 seconds. Next, put in the developer solution for 45 seconds, remove the photoresist layer, and rinse with distilled water to remove water from the air gun. Finally, the pattern shape as shown in FIG. 2A was confirmed using a microscope and hard bake was performed at 110 ° C for 3 minutes to produce a heat window.

(Examples 2 to 4)

Examples 2 to 4 produced heat generating windows in the same manner as in Example 1, except that the pattern shapes of Figs. 2B to 2D were used, respectively.

(Experimental Example)

A variable DC voltage source for measurement of various voltages (0 to 100 V) and generated currents (0 to 1 A), a glass substrate having a thickness of 0.7 mm for uniform temperature measurement, an oxide layer comprising a thermally conductive pattern, A heating window composed of a glass substrate formed on the oxide layer was measured.

A variable DC voltage was used to measure the heat and current generated when a constant voltage was applied to the heating window according to the above embodiment. In order to measure the temperature uniformly, a glass substrate was used and both sides were covered and pressed. The surface temperature was measured after the temperature of the glass substrate became constant by using a thermal imaging camera for temperature detection. The results are shown in Fig. 3 and Table 1 below.

Mobility
(cm ² / Vs) Electrical conductivity
(1 /? Cm) Resistivity
(× 10 ^-4 Ω · cm) Sheet resistance
(Ω / cm) Heating temperature
(° C) Visible light transmittance
(550 nm) Example
One 62 740 13.5 45 52 87 Example
2 67 1041 9.6 32 57 88 Example
3 108 1587 6.3 21 78 85 Example
4 124 2380 4.2 14 76 88

FIG. 3 is a mapping image obtained by measuring the heat generating performance of the heat generating window manufactured according to the first to fourth embodiments of the present invention, and the temperature change of the thin film with time at an applied voltage of 5 V is measured. Table 1 compares the performances according to the thermal conductive patterns formed in the heat generating window according to Examples 1 to 4 of the present invention.

In this case, when the voltage is applied at an initial temperature of 24 ° C, when the temperature of the heating window is increased and maintained for 5 minutes, the breakdown temperature is 52 ° C for the pattern a, 57 ° C for the b, 78 ° C for the c, 76 ° C Respectively.

It can be seen that when the applied voltage is 5 V, the temperature uniformity is less than 30%, b is less than 25%, c is less than 13%, and d is less than 10%. As a result, it was confirmed that the heat generating window according to the present invention exhibits excellent heat generating performance even at a low low voltage of 5 V due to an invisible fine thermal conductive pattern.

In addition, it is understood that the visible light transmittance is 80% or more and the resistance value is 50? / Cm or less, which is a significantly lower value than the conventional art.

Claims (19)

A first transparent substrate;
A thermally conductive pattern formed on the first transparent substrate;
A metal oxide film formed on the surface of the thermally conductive pattern;
A heating terminal formed on a part of the metal oxide film to supply power to the metal oxide film; And
And a second transparent substrate pressed onto the heating terminal,
Wherein the metal oxide film is deposited by an electron cyclotron resonance plasma chemical vapor deposition method. The method according to claim 1,
Wherein the first and second transparent substrates are glass or plastic substrates. delete The method according to claim 1,
Wherein the metal oxide film is any one selected from the group consisting of a fluorine-doped tin oxide film (FTO), an indium tin oxide film (ITO), and an aluminum-doped zinc oxide film (AZO). The method according to claim 1,
Characterized in that the thermally conductive pattern is produced through a micro-lithographic process. 6. The method according to claim 1 or 5,
Wherein the thermally conductive pattern is any one selected from the group consisting of copper, silver, nickel, chromium and nickel chromium alloys. The method according to claim 1,
Wherein the heat generating terminal is in the form of a bar or tape. 8. The method of claim 1 or 7,
Wherein the heat generating terminal comprises copper. The method according to claim 1,
Wherein the metal oxide film has a thickness of 100 to 300 nm. The method according to claim 1,
Wherein the thermally conductive pattern has a line width of 15 to 50 占 퐉. 11. The method according to claim 1 or 10,
Wherein the thermally conductive pattern is a cross shape including a cross, an asterisk (*), a cross shape including a rhombus, and a cross shape including a circle. The method according to claim 1,
Wherein the heat generating window has a heating value of 10 to 35 W / m ² at a voltage of 5 to 30 V. The method according to claim 1,
Wherein the heat generating window has a visible light transmittance of 85 to 95% and a sheet resistance value of 50 to 10? / Cm, I) forming a thermally conductive pattern using micro-lithography on a first transparent substrate;
Ii) depositing a metal oxide film on the thermally conductive pattern using electron cyclotron resonance plasma enhanced chemical vapor deposition;
Iii) forming a heating terminal electrically connected to the metal oxide film; And
Iv) attaching and pressing the second transparent substrate on the heating terminal. 15. The method of claim 14,
Wherein the first and second transparent substrates are glass or plastic substrates. 15. The method of claim 14,
Wherein the thermally conductive pattern is any one selected from the group consisting of copper, silver, nickel, chromium and nickel chromium alloys. 15. The method of claim 14,
Wherein the metal oxide film is any one selected from the group consisting of a fluorine-doped tin oxide film (FTO), an indium tin oxide film (ITO), and an aluminum-doped zinc oxide film (AZO). 15. The method of claim 14,
Wherein the heat generating terminal is in the form of a bar or a tape. The method according to claim 14 or 18,
Wherein the heat generating terminal comprises copper.

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