KR101128009B1 - Making method for transparency conductive oxide of thin film solar cell - Google Patents

Abstract

PURPOSE: A method for manufacturing a transparent conductive thin film for a thin film solar cell is provided to improve adhesion between a substrate and a coated transparent conductive thin film by colliding conductive oxide with plasma cations of argon and oxide mixed gas before the conductive oxide is coated on the substrate. CONSTITUTION: A carrier mounting a substrate is transferred to a vacuum chamber(S110). Plasma cations of argon and oxide mixed gas generated from a plasma generating device is collided with the substrate(S120). Aluminum-zinc-oxide thin film layer is formed by sputtering aluminum-zinc-oxide. The plasma cations of the argon and oxide mixed gas are collided with the aluminum-zinc-oxide thin film layer(S130,S140,S150,S160,S170,S180,S190,S200).

Description

Making Method for Transparency Conductive Oxide of Thin Film Solar Cell}

The present invention relates to a method for manufacturing a transparent conductive thin film for a thin film solar cell, and more particularly, before a conductive oxide is coated on a substrate, a plasma cation of argon and an oxygen mixed gas is first impinged on the substrate, and the substrate and the transparent conductive thin film to be coated. Manufacture of transparent conductive thin film for thin film solar cell which improves adhesion and improves thin film density and electro-optical properties by forming plasma transparent cations of argon and oxygen mixed gas while forming transparent conductive thin film layer. It is about a method.

The transparent conductive thin film refers to a material that transmits light and is transparent and exhibits good electrical conductivity, and is generally referred to as an oxide because the material exhibiting such characteristics is an oxide semiconductor material. In general, the term TCO (Transparent Conductive Oxide), in Korean, is used as the term transparent conductive thin film or transparent electrode.

The concept of transparent conductive thin film was first introduced by depositing silver (Ag) and platinum (Pt) on the front electrode of a solar cell using Se in the 1880s, and then during the Second World War, the plane was warned. In use, the need for transparent conductive thin films has been raised for the purpose of eliminating the defrost of airplane windows. Since then, the solar cell market has grown, and since the late 1990s, as the FPD market has exploded, led by LCD and PDP, the demand for transparent conductive thin films has increased, and research and application have been actively conducted to this day.

Transparent conductive thin films are used in flat panel displays and touch panels such as LCD, OLED, and PDP. BACKGROUND OF THE INVENTION In the solar cell and the like, various applications have been used throughout the industry. Recently, as the development of information display devices is rapidly progressed, interest in high-performance transparent conductive thin films is increasing.

Types of transparent conductive thin films include indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO), zinc oxide (ZnO), and the like. The same conductive oxide thin film is typical, and among the materials developed so far, indium-tin-oxide is the most transparent, electrically conductive, and productive product. use.

Indium-tin-oxide is a compound in which indium oxide (In ₂ O ₃ ) and tin oxide (SnO ₂ ) are mixed in a weight ratio of 9 to 1 or 9.7 to 0.3, and indium is a main component. Increasing the use of indium-tin-oxide has led to an increase in demand for indium, and the price of indium ingots has soared since 2003. Among metal materials applied to LCD, indium price has increased more than 1,000% in 2005 compared to 2002 and has fallen to 500% since 2007, but is still trading at a relatively higher price than other metal materials. The price increase of indium is very large compared to other metal materials during the same period, and the price per unit mass is more than 20 times higher. The rising price of indium, the main component of indium-tin-oxide, and the prospect of depletion of indium in the future are increasing the need for securing an indium-tin-oxide substitute.

CdTe thin film solar cells, amorphous silicon thin film solar cells, dye-sensitized thin film solar cells, organic thin film solar cells, etc., manufacture a transparent conductive thin film on a glass substrate. Cu (In _1-x Ga _x ) (Se _1-y Sy) of 5-, 4-, or 3-membered systems consisting of (Cu), indium (In), gallium (Ga), selenium (Se), and sulfur (S) ) _2, a thin film solar cell having a Cu (in _1-x Ga _x) Se _2, CuInS, etc. (hereinafter referred to, CIGS) it is prepared transparent conductive thin film as the last step in a CIGS process.

The transparent conductive thin film used in the thin film solar cell should have not only general electro-optic characteristics but also n-type semiconductor characteristics, and should be a relatively inexpensive material.

Zinc-oxide (ZnO) is a typical n-type semiconductor with an energy band around 3.4 eV, and has many advantages as a transparent conductive material for use as an optoelectronic device. Widely used. Since zinc-oxide has a narrow conduction band due to easy doping, it is easy to control the electro-optic properties according to the doping material. It can be manufactured at low cost and has high light transmittance and conductivity, making it a promising practical transparent conductive thin film material. Since the electrical properties of intrinsic zinc-oxides are close to insulators, a separate process is required to impart conductivity. Doping impurities such as aluminum (Al), gallium (Ga), indium (In), and boron (B) to increase charge concentration and electrical conductivity, and to make n-type zinc-oxide with stable environment. Application is being made.

Currently, substrates used in the manufacture of thin-film solar cells are soda-lime glass, low iron glass, alkali-free glass or tempered glass, and the transparent conductive thin film is formed on the glass such as aluminum-zinc-oxide, indium-zinc-oxide, tin-oxide, etc. Oxides are produced by the sputtering method.

The manufacturing method of the transparent conductive thin film by the prior art is as follows. First, the substrate is charged into a vacuum chamber, and then an initial vacuum state of about 10 ^-7 Torr is made, the temperature is applied to the substrate at about 200 ° C, and a small amount of argon and oxygen mixed gas is injected to vacuum about 10 ^-3 Torr. Make Then, a transparent conductive thin film is manufactured by applying RF (AC) or DC (DC) power to the copper cathode to which the conductive oxide target is attached by magnetron sputtering.

The transparent conductive thin film for thin film solar cell should be thickened more than 1,000 nm because of the thin film solar cell's characteristics that are manufactured and operated in module units to improve electrical characteristics. However, the thicker the transparent conductive thin film has a disadvantage in that the light transmittance is lowered. In addition, when the transparent conductive thin film is manufactured on a substrate such as glass, a peeling phenomenon occurs when the adhesion between the substrate and the thin film is not good. The decrease in light transmittance and the peeling phenomenon have a serious negative effect on the energy conversion efficiency of the thin film solar cell.

In order to solve this problem, that is, conductive oxide is used as a transparent conductive thin film of a thin film solar cell, a new manufacturing method that can be made into a dense thin film having relatively better electro-optic characteristics, and the adhesion property between the substrate and the thin film. There is a need for new manufacturing methods that can be improved.

The present invention has been made to solve the above situation, and before the conductive oxide is coated on the substrate, the plasma cations of the argon and oxygen mixed gas first impinge on the substrate to improve the adhesion between the substrate and the transparent conductive thin film to be coated. The main object of the present invention is to provide a method for manufacturing a transparent conductive thin film for a thin film solar cell.

In addition, the present invention provides a method for manufacturing a transparent conductive thin film for a thin film solar cell to form a transparent conductive thin film to improve the density and electro-optical properties of the thin film by impinging the plasma cation of argon and oxygen mixed gas to the thin film layer while forming a transparent conductive thin film layer. The purpose is to provide.

In order to achieve the above object,

Transferring a carrier on which the substrate is mounted into a vacuum chamber; Colliding the plasma cations of the argon and oxygen mixed gas generated in the plasma generator with the transferred substrate; Sputtering a conductive oxide on the substrate to form a transparent conductive thin film layer and impinge the plasma cations of the argon and oxygen mixed gas on the transparent conductive thin film layer; And continuously sputtering a conductive oxide on the substrate to form a transparent conductive thin film layer and impinging plasma cations of a mixture of argon and oxygen on the transparent conductive thin film layer.

The carrier may be formed in a flat plate shape, and the substrate may be disposed on the carrier.

The substrate may include soda-lime glass, low iron glass, alkali-free glass, or tempered glass having a thickness of 2 to 10 mm.

The substrate has a thickness of 2 to 10 mm, and may include soda-lime glass, low iron glass, alkali-free glass, or tempered glass coated with one or a sequence of high and low refractive oxides. Of course, the high refractive oxide and the low refractive oxide may include soda-lime glass, low iron glass, alkali-free glass or tempered glass coated in succession four or more times.

The high refractive oxide may include Nb ₂ O ₅ , Ti ₂ O ₃ , Ta ₂ O ₅ or ZrO ₂ , but is not limited thereto. The low refractive oxide may be SiO ₂ , MgF ₂ , BaF ₂ or AlF ₃ . It may include, but is not limited to.

In the case of a CIGS thin film solar cell, at least one selected from the group consisting of a back electrode (Mo), a laser type first pattern, a light absorbing layer (CIGS), and a buffer layer has a thickness of 2 to 10 mm coated with a lamination. Soda-lime glass, low iron glass, alkali-free glass or tempered glass may be included, the buffer layer may comprise CdS or ZnO.

The conductive oxide may include a zinc oxide in which any one material selected from the group consisting of aluminum (Al), gallium (Ga), indium (In), and boron (B) is doped with zinc-oxide (ZnO). Aluminum (Al), gallium (Ga), indium (In), or boron (B) doped with zinc oxide (ZnO) may be doped in an amount of 2 to 15 wt% to improve electrical properties.

In addition, the conductive oxide may include indium tin oxide (ITO).

In particular, the conductive oxide is sputtered on the substrate continuously, for example, 2 to 10 times in succession to form a transparent conductive thin film layer, while controlling the thickness of the thin film layer by colliding plasma cations of argon and oxygen mixed gas on the transparent conductive thin film layer. Can be.

According to the manufacturing method of the present invention, the plasma cations of the argon and oxygen mixed gas may first collide with the substrate before the conductive oxide is coated on the substrate, thereby improving adhesion between the substrate and the transparent conductive thin film to be coated. While forming the transparent conductive thin film layer, the plasma cations of the argon and oxygen mixed gas may collide with the thin film layer to improve the density and electro-optical characteristics of the thin film.

1 is a flowchart illustrating a method of manufacturing an aluminum-zinc-oxide thin film as a transparent conductive thin film according to an embodiment of the present invention.
2 is a view schematically showing the configuration of a vacuum coating system for performing a method of manufacturing an aluminum-zinc-oxide thin film, which is a transparent conductive thin film according to an embodiment of the present invention.
3 is a view showing the configuration of a substrate and a carrier used in an embodiment of the present invention.
4 is a cross-sectional view showing the configuration of an aluminum-zinc-oxide thin film as a transparent conductive thin film according to an embodiment of the present invention.
FIG. 5 is a graph showing the rate of change of optical properties when a cation of plasma of argon and oxygen mixed gas collides with a thin film layer while forming an aluminum-zinc-oxide thin film layer which is a transparent conductive thin film according to an embodiment of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

1 is a flowchart illustrating a method of manufacturing an aluminum-zinc-oxide thin film as a transparent conductive thin film according to an embodiment of the present invention.

Referring to FIG. 1, in the method of manufacturing an aluminum-zinc-oxide thin film, which is a transparent conductive thin film, transferring a carrier 100 on which a substrate is mounted into the vacuum coating system 10 (S110) and argon generated in a plasma generator. In step (S120), the plasma cations of the argon and the oxygen mixed gas to form the aluminum-zinc-oxide thin film layer by sputtering the aluminum-zinc-oxide to form the aluminum-zinc-oxide thin film layer. In the step (S130), to increase the thickness of the aluminum-zinc-oxide thin film layer by sputtering aluminum-zinc-oxide continuously to form the aluminum-zinc-oxide thin film layer and plasma-cations of argon and oxygen mixed gas aluminum-zinc -Impinging on the oxide thin film layer (S140, S150, S160, S170, S180, S190, S200).

In addition, Figure 2 is a view schematically showing the configuration of a vacuum coating system for performing the aluminum-zinc-oxide thin film manufacturing method of the transparent conductive thin film according to an embodiment of the present invention.

2, in order to perform the aluminum-zinc-oxide thin film manufacturing method of the transparent conductive thin film according to an embodiment of the present invention, the following manufacturing facilities are prepared.

First, there is prepared a vacuum coating system 10 that provides a space in which a process such as coating by sputtering, impinging a cation of a plasma of argon and oxygen mixed gas on the substrate 300 to the substrate therein is prepared. .

In the vacuum coating system 10, a substrate 300, which is a substrate processing target, is loaded and unloaded.

Here, the vacuum coating system 10 is a load lock chamber (11a) to charge the carrier 100 for transporting the mounted substrate 300 into the vacuum coating system 10, the first and second buffer chamber to make a high vacuum 12a, 12b, a process chamber 30 for coating and an unloading chamber 11b for discharging the substrate 300 out of the vacuum coating system 10.

In addition, the process chamber 30 further includes first and second transfer chambers 13a and 13b installed at the substrate inlet and the substrate outlet to the process chamber 30, respectively.

In addition, the process chamber 30 includes first to ninth process chambers 14a, 14b, 14c, 14d, 14e, 14f, 14g, 14h, 14i.

Here, the carrier 100 and its configuration will be described later.

In addition, a conveyor 19 is installed to continuously reload the carrier 100 with the substrate discharged out of the vacuum coating system 10 into the vacuum coating system 10.

In addition, turbo molecular pumps (TMPs) 20 are installed in the first and second buffer chambers 12a and 12b to make high vacuum. The first to ninth process chambers 14a, 14b, 14c, 14d, 14e, 14f, 14g, 14h, 14i are provided with a gas flow controller (MFC) 16 for injecting argon and oxygen mixed gas. do. By injection of argon gas, the coating process may be performed in the first to ninth process chambers 14a, 14b, 14c, 14d, 14e, 14f, 14g, 14h, 14i.

In order to coat the aluminum-zinc-oxide thin film, which is a transparent conductive thin film, a plasma gun 17 is installed in the first process chamber 14a, and second to ninth process chambers 14b, 14c, 14d, 14e, 14f, 14g, 14h, and 14i are provided with a magnetron sputtering gun 18 and a plasma generator 17 equipped with an aluminum-zinc-oxide target.

Load lock chamber 11a, buffer chamber 12a, first and second transfer chambers 13a, 13b and first through ninth process chambers 14a, 14b, 14c, 14d, 14e, 14f, 14g, 14h, The heaters 15 are respectively provided at 14i so that a predetermined heat can be applied to the substrate 300.

Devices of such a structure are generally referred to as inline magnetron sputtering devices. Such a configuration is well known in the art and thus detailed description thereof will be omitted.

3 is a view showing the configuration of a substrate carrier used in the present invention.

Referring to FIG. 3, the carrier 100 supports the substrate when loading the substrate 300 into the vacuum coating system 10 or unloading the vacuum coating system 10.

The carrier 100 is formed in a flat plate shape having a predetermined area. A plurality of substrate holders 200 are disposed on the carrier 100, and two substrates having a size of 635 mm × 1,245 mm are disposed on one side of the substrate holder 200.

Here, the substrate 300 may include soda-lime glass, low iron glass, alkali-free glass or tempered glass having a thickness of 10 mm or less.

In the case of the CIGS thin film solar cell, the substrate 300 has a thickness of 2 to 10 mm in which a back electrode (Mo), a laser type first pattern, a light absorption layer (CIGS), and buffer layers CdS and ZnO are laminated and coated. Soda-lime glass, low iron glass, alkali-free glass or tempered glass.

Again, a manufacturing method according to the present invention will be described with reference to FIG. 1.

3 illustrates an embodiment of a mounting state of the substrate 300. As illustrated, a plurality of substrates may be disposed on the carrier 100.

Referring to FIG. 3, a substrate holder 200 is disposed on the carrier 100, and two substrates having a size of 635 mm × 1,245 mm are disposed on the substrate holder 200. Here, the size and arrangement number of the substrate can be changed according to the needs of the user.

The carrier 100 on which the substrate 300 is mounted is first loaded into the load lock chamber 11a before charging into the vacuum coating system 10. Thereafter, the turbomolecular pump 20 is used to make the inside of the load lock chamber 11a in a vacuum state of about 10 ⁻³ Torr. The carrier 100 is charged into the vacuum coating system 10 using the load lock chamber 11a.

It is preferable to set the vacuum coating system 10 and the process chamber 30 into which the carrier 100 is loaded as follows.

That is, the heater 15 is operated to heat the inside of the vacuum coating system 10 to about 50 ° C as a whole. The first buffer chamber 12a, the first and second transfer chambers 13a and 13b, and the first to ninth process chambers 14a, 14b, 14c, 14d, 14e, and the like may be formed using the turbomolecular pump 20. 14f, 14g, 14h, 14i) The inside is set to a vacuum of about 10 ^-7 Torr.

Thereafter, the temperature inside the vacuum coating system 10 is heated to about 200 ° C. as a whole, the second buffer chamber 12b is set to a vacuum state of about 10 ⁻⁷ Torr, and the inside of the unloading chamber 11b is about Set the vacuum to 10 ^-3 Torr.

And into the first and second transfer chambers 13a and 13b and the first to ninth process chambers 14a, 14b, 14c, 14d, 14e, 14f, 14g, 14h, 14i to facilitate the coating process. Ar is injected into the mixed gas of argon and oxygen through the gas flow controller 16 is set to a vacuum state of about 10 ^-3 Torr.

The sputtering gun 18 of the second to ninth process chambers 14b, 14c, 14d, 14e, 14f, 14g, 14h, 14i equipped with the aluminum-zinc-oxide target, which is a conductive oxide, is supplied with power to the target surface. Remove any foreign substances by sputtering.

Venting the load lock chamber (11a) and loading the carrier on which the substrate is mounted in the load lock chamber (11a), a vacuum of about 10 ^-3 Torr is made by using a rotary and booster pump, which is a general low vacuum vacuum pump. When the carrier 100 is transferred to the first buffer chamber 12a, the first buffer chamber 12a is set to a vacuum state of about 10 ⁻⁷ Torr using the turbomolecular pump 20, and then a predetermined amount of argon gas is used. Is injected into a vacuum of about 10 ^-3 Torr.

When the setting inside the vacuum coating system 10 is completed as described above, the carrier 100 is transferred to the first transfer chamber 13a, the first to ninth process chambers 14a, 14b, 14c, 14d, 14e, 14f, 14g, 14h, 14i) and an aluminum-zinc-oxide thin film are produced while transferring at a constant speed to the second transfer chamber 13b.

First, the substrate 300 is transferred to the first process chamber 14a included in the vacuum coating system 10 (S110), and then generated in the plasma generating apparatus 17 in the first process chamber 14a. The cations of the plasma of the argon and oxygen mixed gas is impinged on the substrate (S120).

After the step S120 is performed for a predetermined time, the substrate 300 is transferred to the second process chamber 14b. In the second process chamber 14b, sputtering the aluminum-zinc-oxide target using a sputtering gun 18 equipped with an aluminum-zinc-oxide target to form an aluminum-zinc-oxide layer on the surface of the substrate 300. To perform (S130). At the same time, the plasma generator 17 generates a cation of the plasma of the argon and oxygen mixed gas, and collides it with the aluminum-zinc-oxide layer being coated (S130).

The conductive oxide for preparing the transparent conductive thin film is aluminum-zinc-oxide doped with zinc (ZnO) in an amount of 2 to 15 wt% of aluminum (Al).

The conductive oxide for manufacturing the transparent conductive thin film may be one of zinc-oxide (ZnO) doped with gallium (Ga), indium (In), or boron (B).

In this case, the content of the doped gallium (Ga), indium (In) or boron (B) may be 2 to 15% by weight in order to improve the electrical properties.

In addition, the conductive oxide for manufacturing the transparent conductive thin film may include indium tin oxide (ITO).

When the step S130 is completed, in order to increase the thickness of the aluminum-zinc-oxide thin film layer, the substrate 300 may be replaced by a third process chamber 14c, a fourth process chamber 14d, a fifth process chamber 14e, and a third process chamber. The aluminum-zinc-oxide thin film layer was formed by sputtering aluminum-zinc-oxide while continuously transferring to the sixth process chamber 14f, the seventh process chamber 14g, the eighth process chamber 14g, and the ninth process chamber 14i. While forming the plasma cations of the argon and oxygen mixed gas collide with the aluminum-zinc-oxide thin film layer (S140, S150, S160, S170, S180, S190, S200) is performed.

The following aluminum-zinc-oxide thin film was formed by performing the above process.

4 is a cross-sectional view showing the configuration of an aluminum-zinc-oxide thin film produced by the present invention.

Referring to FIG. 4, it can be seen that the aluminum-zinc-oxide thin film layer 310, which is a transparent conductive thin film, is formed as one layer on the substrate 300.

Generally, sputtering a coating of an aluminum-zinc-oxide target, which is a conductive oxide, and simultaneously bombarding the cations of the plasma generated in the plasma generator to the coated aluminum-zinc-oxide thin film layer is called plasma assisted deposition.

Here, the aluminum-zinc-oxide thin film layer 310, which is a transparent conductive thin film, was manufactured to a thickness between 900 and 1,000 nm.

When the transparent conductive thin film is formed on the substrate 300, a small amount of argon and oxygen mixed gas is injected into the second buffer chamber 12b which maintains a vacuum of about 10 ⁻⁷ Torr to about 10 ⁻³ Torr. After the vacuum is established, the carrier 100 is transferred from the second transfer chamber 13b to the second buffer chamber 12b and then to the unloading chamber 111b. After venting the inside of the chamber, the carrier 100 on which the substrate 300 is disposed is discharged out of the vacuum coating system 10.

After removing the substrate 300 disposed on the carrier 100, the carrier 100 is transferred to the load lock chamber 11a using the conveyor 19 to finish the manufacture of one transparent conductive thin film, an aluminum-zinc-oxide thin film. At the same time, by mounting a new substrate on a carrier and repeatedly performing the above steps, the aluminum-zinc-oxide thin film, which is a transparent conductive thin film, may be repeatedly manufactured.

Table 1 is a table showing the rate of change when the cations of the plasma of the argon and oxygen mixed gas collides with the thin film layer while forming the aluminum-zinc-oxide (AZO) thin film layer which is a transparent conductive thin film.

sample fair thickness
[nm] Cotton resistance
[Ω / sq] Average transmittance
[%, at 400-800 nm] Comparative Example 1 Plasma + AZO
(Non-plasma treatment) 1,000 12.70 71.19 Example 1 Plasma + AZO +
Plasma treatment 900 9.70 74.02

5 is a graph showing the rate of change of optical properties when the cations of the plasma of argon and oxygen mixed gas collide with the thin film layer while forming the aluminum-zinc-oxide thin film layer which is a transparent conductive thin film.

In FIG. 5, b performs a step (S120) of colliding the cations of the plasma of the argon and oxygen mixed gas generated in the plasma generator 17 in the first process chamber 14a to the substrate, and in the second process chamber 14b. ), The aluminum-zinc- while continuously transferring to the third process chamber 14c, the fourth process chamber 14d, the fifth process chamber 14e, the sixth process chamber 14f, and the seventh process chamber 14g. Sputtering the oxide to form an aluminum-zinc-oxide thin film layer while colliding the plasma cations of the argon and oxygen mixed gas on the aluminum-zinc-oxide thin film layer (S130, S140, S150, S160, S170, S180), The thin film of aluminum-zinc-oxide had a thickness of 900 nm, a sheet resistance of 9.70 dl / sq, and a transmittance of 74.02%.

In FIG. 5, a is performed without colliding a plasma cation onto the aluminum-zinc-oxide thin film layer while forming the aluminum-zinc-oxide thin film layer, wherein the thickness of the aluminum-zinc-oxide thin film is 1,000 nm, and the sheet resistance is 12.70 Ω / sq, transmittance was 71.19%.

In general, the thicker the thickness of the aluminum-zinc-oxide thin film, the lower the thickness and the higher the light transmittance. When forming the aluminum-zinc-oxide thin film layer as shown in b of FIG. 5 and colliding the plasma cations of the argon and oxygen mixed gas on the aluminum-zinc-oxide thin film layer, the sheet resistance is lower than the thickness of FIG. Got it. It can be seen that the aluminum-zinc-oxide was made into a denser thin film when the plasma cation was impinged on the aluminum-zinc-oxide thin film layer. This means that the aluminum-zinc-oxide thin film has temperature stability in order to be used as the transparent conductive thin film of the thin-film solar cell. The aluminum-zinc-oxide thin film forms an aluminum-zinc-oxide thin film layer and imparts a cation of plasma of argon and oxygen mixed gas to the thin film layer. It can be found that the new manufacturing method results in improved density and electrical properties of the aluminum-zinc-oxide thin film.

Therefore, according to the present invention, as the thickness of the aluminum-zinc-oxide thin film was decreased, the optical properties such that the light transmittance was improved could be obtained.

In addition, before coating the aluminum-zinc-oxide on the substrate, the plasma cations of the argon-oxygen mixed gas are first impinged on the substrate, followed by the formation of the aluminum-zinc-oxide thin film layer while the cations of the plasma collide with the thin film layer. As a result of the adhesion test, the aluminum-zinc-oxide thin film prepared as was found to have no phenomenon that the aluminum-zinc-oxide thin film layer was peeled off from the substrate.

This means that the adhesion between the substrate and the aluminum-zinc-oxide thin film to be coated is improved by first impinging the cation of the plasma of argon and oxygen mixed gas on the substrate before coating the aluminum-zinc-oxide, which is a transparent conductive thin film, onto the substrate. .

Although the present invention has been described with reference to the embodiments shown in the drawings, this is merely exemplary, and it will be understood by those skilled in the art that various modifications and equivalent other embodiments are possible. Therefore, the true technical protection scope of the present invention will be defined by the technical spirit of the appended claims.

10: vacuum coating system
11a: load lock chamber
11b: unloading chamber
12a, 12b: first and second buffer chambers
13a, 13b: first and second transfer chambers
14a: first process chamber
14b, 14c, 14d, 14e: second, third, fourth and fifth process chambers
14f, 14g, 14h, 14i: sixth, seventh, eighth, and ninth process chambers
15: heater
16: gas flow controller
17: plasma generator
18: Magnetron Sputtering Gun
19: conveyor
20: turbomolecular pump
30: process chamber
100: carrier
200: substrate holding
300: substrate
310: aluminum-zinc-oxide thin film layer

Claims (9)

Transferring a carrier on which the substrate is mounted into a vacuum chamber;
Colliding the plasma cations of the argon and oxygen mixed gas generated in the plasma generator with the transferred substrate;
Sputtering a conductive oxide on the substrate to form a first transparent conductive thin film layer while impinging a plasma cation of an argon and oxygen mixed gas on the first transparent conductive thin film layer; And
Continuously sputtering a conductive oxide on the substrate to form a second transparent conductive thin film layer while impinging a plasma cation of an argon and oxygen mixed gas on the second transparent conductive thin film layer.
Transparent conductive thin film manufacturing method for a thin film solar cell comprising a. The method of claim 1,
The carrier is formed in the form of a flat plate, the substrate is disposed on the carrier transparent conductive thin film manufacturing method for thin film solar cells. The method of claim 1,
The substrate is a method for manufacturing a transparent conductive thin film for a thin film solar cell, characterized in that the soda-lime glass, low iron glass, alkali-free glass or tempered glass. The method of claim 1,
The substrate is a method for manufacturing a transparent conductive thin film for a thin film solar cell, characterized in that the high refractive oxide and low refractive oxide is soda-lime glass, low iron glass, alkali-free glass or tempered glass coated in succession or sequentially. The method of claim 4, wherein
The high refractive oxide is Nb ₂ O ₅ , Ti ₂ O ₃ , Ta ₂ O ₅ or ZrO ₂ characterized in that the transparent conductive thin film manufacturing method for thin film solar cells. The method of claim 4, wherein
The low refractive oxide is SiO ₂ , MgF ₂ , BaF ₂ or AlF ₃ Transparent conductive thin film manufacturing method for a thin film solar cell, characterized in that. The method of claim 1,
In the case of CIGS thin film solar cell, at least one selected from the group consisting of a back electrode, a laser type primary pattern, a light absorbing layer, and a buffer layer is a lamination coated soda-lime glass, low iron glass, alkali-free glass or tempered glass. Transparent conductive thin film manufacturing method for thin film solar cells, characterized in that. The method of claim 1,
The conductive oxide is zinc-oxide doped with any one material selected from the group consisting of aluminum (Al), gallium (Ga), indium (In) and boron (B) on zinc-oxide (ZnO). Transparent conductive thin film manufacturing method for thin film solar cell. The method of claim 1,
The conductive oxide is indium-tin-oxide (ITO) characterized in that the transparent conductive thin film manufacturing method for thin film solar cells.

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