KR101264072B1 - Making method for transparency conductive oxide of thin film solar cell - Google Patents

Abstract

PURPOSE: A method for manufacturing a transparent conduction layer for a thin film solar cell is provided to improve the adhesion between a substrate and a transparent conduction layer by the collision of the substrate with the plasma positive ions of the mixed gas of argon and oxygen. CONSTITUTION: A carrier having a substrate is transferred into a process chamber(S110). A pre-heating process is performed in a first buffer and a thermal process chamber(S120). The positive ions of plasma collide with the substrate in a first process chamber(S130). Aluminum-zinc-oxide is sputtered to form a transparent conduction thin film layer in a second process chamber(S140). The aluminum-zinc-oxide is sputtered to form a transparent conduction thin film layer in a third process chamber(S150). The aluminum-zinc-oxide is sputtered to form a transparent conduction thin film layer in a fourth process chamber(S160). The aluminum-zinc-oxide is sputtered to form a transparent conduction thin film layer in a fifth process. A post heating process is performed in a second buffer and a thermal process chamber(S180). [Reference numerals] (S110) Transfer a substrate mounted carrier to a process chamber; (S120) Pre-heating process in a first buffer and a thermal process chamber; (S130) Collide positive ions of plasma with the substrate in a first process chamber; (S140) Form a transparent conduction thin film layer by sputtering aluminum-zinc-oxide in a second process chamber; (S150) Form a transparent conduction thin film layer by sputtering aluminum-zinc-oxide in a third process chamber; (S160) Form a transparent conduction thin film layer by sputtering aluminum-zinc-oxide in a fourth process chamber; (S170) Form a transparent conduction thin film layer by sputtering aluminum-zinc-oxide in a fifth process chamber; (S180) Post heating process in a second buffer and thermal process chamber

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 the conductive oxide is coated on the substrate, the substrate is first heated through a heat treatment process, and a plasma cation of a mixture of argon and oxygen is applied to the substrate. To improve the adhesion between the substrate and the transparent conductive thin film to be coated, to form a transparent conductive thin film layer by sputtering method, to form a transparent conductive thin film layer and then to heat treatment to improve the crystallinity and electro-optical properties of the thin film It relates to a method for manufacturing a transparent conductive thin film for a thin film solar cell to form a conductive thin film.

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 in the 1880s by using thin deposition of silver (Ag) and platinum (Pt) on the front electrode of a solar cell using selenium (Se), and then during the Second World War. As wars were used in warfare, the need for transparent conductive thin films was raised to remove frost on 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 transparent conductive thin films on glass substrates. Cu (In _1-x Ga _x ) (Se _1-y S) of 5-membered, quaternary or ternary system composed of (Cu), indium (In), gallium (Ga), selenium (Se), and sulfur (S) _y ) ₂ , Cu (In _1-x Ga _x ) Se ₂ , CuInS, etc. (hereinafter referred to as CIGS), a thin film solar cell manufactures a transparent conductive thin film as the final process in the 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.

Republic of Korea Patent Publication No. 10-1047941 discloses a method for manufacturing a C (S) solar cell back electrode.

Conventional method of manufacturing a transparent conductive thin film in the process of forming the back electrode on the substrate by DC sputtering in an inert gas atmosphere, the back electrode layer is formed to a thickness of 700 ~ 1500 nm in an argon atmosphere of 2 ~ 10 mTorr, A target for the rear electrode doped with an alkali component at 1 to 3% by weight based on the total weight of the target, and by applying an RF bias on the substrate content of the alkali component to be included in the CI (G) S light absorption layer It is characterized by adjusting by the strength of the RF bias or the application time.

However, the conventional transparent conductive thin film for thin film solar cells has to be thickened to about 1,500 nm due to the characteristics of the thin film solar cell fabricated and operated in a large-area module unit to improve electrical characteristics. The transparent conductive thin film used for the thin film solar cell should have not only general electro-optic characteristics but also n-type semiconductor characteristics, and in particular, electrical characteristics of mobility should be good. When the transparent conductive thin film for the thin film solar cell is thickened to about 1,500 nm thick, the electrical properties of the conductivity (conductivity) is greatly improved, but the electrical properties of the mobility (mobility) are lowered.

In order to solve this problem, namely, in order to use the conductive oxide as a transparent conductive thin film of a thin film solar cell, a new manufacturing method capable of manufacturing a thin film having a relatively better mobility (mobility) electrical characteristics is required.

The present invention has been made in order to solve the above situation, and before the conductive oxide is coated on the substrate, the substrate is first heated through a pre-heat treatment process, and the plasma cations of the mixed gas of argon and oxygen are first impinged on the substrate. To improve adhesion between the transparent conductive thin film and the transparent conductive thin film to be coated, to form a transparent conductive thin film layer by sputtering method, and to form a transparent conductive thin film layer and then heat treatment to form a transparent conductive thin film having improved crystallinity and electro-optic properties of the thin film. An object of the present invention is to provide a method for manufacturing a transparent conductive thin film for a thin film solar cell.

The present invention includes the steps of transferring the carrier on which the substrate is mounted into a vacuum chamber; Preheating the substrate through a pre-thermal treatment at a temperature of 180 to 220 ° C. before coating the conductive oxide onto the substrate; 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; Continuously sputtering a conductive oxide on the substrate to form a transparent conductive thin film layer; And it provides a method for producing a transparent conductive thin film for a thin film solar cell comprising the step of post-heat treatment at a temperature of 180 to 220 ℃ after forming the transparent conductive thin film layer.

In addition, the carrier may be formed in a flat plate shape, and the substrate may be disposed on the carrier, and the substrate may include soda lime glass, low iron glass, alkali free glass, or tempered glass.

In addition, the substrate may include soda-lime glass, low iron glass, alkali-free glass or tempered glass coated with one or a sequence of high refractive oxides and low refractive oxides, wherein the low refractive oxides are SiO ₂ , MgF ₂ , BaF ₂ or AlF ₃ .

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 coated soda-lime glass, low iron glass, alkali-free glass or tempered glass. The conductive oxide may include zinc-doped zinc-oxide (ZnO) doped with any one material selected from the group consisting of aluminum (Al), gallium (Ga), indium (In), and boron (B). An oxide may be included, and the conductive oxide may include indium tin oxide (ITO).

According to the manufacturing method of the present invention, before the conductive oxide is coated on the substrate, the substrate is preheated through a pre-heating process, and a plasma cation of an argon and oxygen mixed gas is first impinged on the substrate, thereby forming a gap between the substrate and the transparent conductive thin film to be coated. The adhesion is improved, and the transparent conductive thin film layer is formed by the sputtering method, and after the transparent conductive thin film layer is formed, there is an effect that the crystallinity and electro-optical characteristics of the thin film can be improved by post-heat treatment.

후의 열처리를 통하여 얻은 전기광학적 특성변화를 나타낸 것이다.
표 2는 투명성 전도박막인 알루미늄-아연-산화물 박막층 형성 전

후의 열처리를 통하여 얻은 결정성 변화를 전자현미경(SEM)의 표면사진과 단면사진으로 나타낸 것이다. 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.
Table 1 forms the aluminum-zinc-oxide thin film layer which is a transparent conductive thin film according to an embodiment of the present invention, before forming the thin film layer.

It shows the change of electro-optic properties obtained through the subsequent heat treatment.
Table 2 shows the aluminum-zinc-oxide thin film layer before the transparent conductive thin film is formed.

The crystallinity change obtained through the post-heat treatment is represented by the surface photograph and the cross-sectional photograph of the electron microscope (SEM).

The present invention includes the steps of transferring the carrier on which the substrate is mounted into a vacuum chamber; Preheating the substrate through a pre-thermal treatment at a temperature of 180 to 220 ° C. before coating the conductive oxide onto the substrate; 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; Continuously sputtering a conductive oxide on the substrate to form a transparent conductive thin film layer; And it provides a method for producing a transparent conductive thin film for a thin film solar cell comprising the step of post-heat treatment at a temperature of 180 to 220 ℃ after forming 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 may be continuously sputtered on the substrate, for example, 4 to 20 times in succession to form a transparent conductive thin film layer, thereby controlling the thickness of the thin film layer.

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 the carrier 100 on which the substrate is mounted into the vacuum coating system 10 (S110) and coating the conductive oxide on the substrate. Before the step of preheating the substrate through a pre-heat treatment step (S120), the step of impinging the cations of the plasma of the argon and oxygen mixed gas generated in the plasma generator to the substrate (S130), aluminum-zinc-oxide sputtered aluminum Forming a zinc-oxide thin film layer (S140), and sputtering aluminum-zinc-oxide continuously to increase the thickness of the aluminum-zinc-oxide thin film layer to form an aluminum-zinc-oxide thin film layer (S150, S160, S170). After the transparent conductive thin film layer is formed, a post-heat treatment step (S180) is included.

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 a vacuum coating system that provides a space for performing a process such as pre-heating of the substrate 300, impingement of plasma of argon and oxygen mixed gas on the substrate, coating by sputtering, and post-heat treatment. Prepare (10).

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

후의 열처리를 할 수 있는 제1 및 제2 버퍼 및 열처리 챔버(12a, 12b), 코팅을 하기 위한 프로세스 챔버(30) 및 기판(300)을 진공코팅시스템(10) 밖으로 배출하는 언로딩 챔버(11b)를 포함한다. Here, the vacuum coating system 10 is a load lock chamber (11a) for charging the carrier 100 for transporting the mounted substrate 300 into the vacuum coating system 10, and also makes a high vacuum

First and second buffer and heat treatment chambers 12a and 12b capable of subsequent heat treatment, the process chamber 30 for coating and the unloading chamber 11b for discharging the substrate 300 out of the vacuum coating system 10. ).

The process chamber 30 further includes first and second transfer chambers 13a and 13b which are respectively installed at the substrate inlet and the substrate outlet to the process chamber 30.

The process chamber 30 also includes first to fifth process chambers 14a, 14b, 14c, 14d, 14e.

Here, the carrier 100 and its related 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, turbomolecular pumps (TMPs) 20 are installed in the first and second buffer and heat treatment chambers 12a and 12b to make high vacuum. The first to fifth process chambers 14a, 14b, 14c, 14d, and 14e are provided with a gas flow controller (MFC) 16 for injecting argon and oxygen mixed gas. By injection of argon gas, the coating process may be performed in the first to fifth process chambers 14a, 14b, 14c, 14d, and 14e.

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 fifth process chambers 14b, 14c, 14d, 14e) is equipped with a magnetron sputtering gun 18 equipped with an aluminum-zinc-oxide target.

Load lock chamber 11a, first and second buffer and heat treatment chambers 12a and 12b, first and second transfer chambers 13a and 13b and first to fifth process chambers 14a, 14b, 14c and 14d. , 14e) are provided with heaters 15 so as to apply heat of about 180 to 220 ° C 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 loads the substrate 300 into the vacuum coating system 10, or in the vacuum coating system, a pre-heat treatment, a plasma collision, a sputtering coating, a post-heat treatment process, and a vacuum coating system 10. Support the substrate when unloading.

The carrier 100 is formed in the form of a flat plate having an area of about 1,700 mm × 2,400 mm. A plurality of substrate holders 200 are disposed on the carrier 100, and two substrates having a size of 650 mm × 1,650 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.

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 650 mm × 1,650 mm are disposed on the substrate holder 200. Here, the size and arrangement number of the substrate may 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 entire inside of the vacuum coating system 10 to 180 to 220 ° C. The first and second buffer and heat treatment chambers 12a and 12b, the first and second transfer chambers 13a and 13b, and the first to fifth process chambers 14a and 14b may be formed using the turbomolecular pump 20. 14c, 14d, 14e) The inside is set to a vacuum of about 10 ^-7 Torr.

Thereafter, the temperature inside the vacuum coating system 10 is heated to 180 to 220 ° C. as a whole, and the first and second buffers and the heat treatment chambers 12a and 12b are set to a vacuum state of about 10 ⁻⁷ Torr, and the load lock The interior of chamber 11a and unloading chamber 11b is set to a vacuum of about 10 ⁻³ Torr.

The gas flow controller 16 is introduced into the first and second transfer chambers 13a and 13b and the first to fifth process chambers 14a, 14b, 14c, 14d, and 14e to facilitate the coating process. Argon and oxygen mixed gas is injected into the vacuum of about 10 ^-3 Torr.

Power is supplied to the sputtering guns 18 of the second to fifth process chambers 14b, 14c, 14d, and 14e equipped with the aluminum-zinc-oxide target, which is a conductive oxide, to sputter and remove foreign substances on the target surface. .

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 substrate 100 is transferred to the first buffer and heat treatment chamber 12a, the carrier 100 sets the vacuum state of about 10 ⁻⁷ Torr to the first buffer and heat treatment chamber 12a using the turbomolecular pump 20. While transferring the carrier 100 at a speed of 300 to 600 mm per minute and simultaneously applying heat to 180 to 220 ° C. to perform a pre-heat treatment step (S120), argon gas is injected to set a vacuum state of about 10 ⁻³ Torr. .

When the setting inside the vacuum coating system 10 is completed as above, the carrier 100 is transferred to the first transfer chamber 13a, the first to fifth process chambers 14a, 14b, 14c, 14d, 14e, and the second transfer. The aluminum-zinc-oxide thin film is manufactured while being transferred to the chamber 13b at a constant speed.

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 (S130).

After performing the step S130 while transferring the carrier 100 at a speed of 300 to 600 mm per minute, 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. Perform (S140).

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 preparing the transparent conductive thin film may include indium tin oxide (ITO).

When the step S140 is completed, the substrate 300 is continuously moved into the third process chamber 14c, the fourth process chamber 14d, and the fifth process chamber 14e to increase the thickness of the aluminum-zinc-oxide thin film layer. Sputtering the aluminum-zinc-oxide while transferring to to form the aluminum-zinc-oxide thin film layer (S150, S160, S170) is performed.

After performing the steps of forming the aluminum-zinc-oxide thin film layer (S150, S160, S170), the carrier 100 is transferred to the second buffer and the heat treatment chamber 12b from the second transfer chamber 13b, the second buffer And argon gas is injected into the heat treatment chamber 12b to a vacuum state of about 10 ⁻³ Torr, and heat is applied at 180 to 220 ° C. while transferring the carrier 100 at a speed of 300 to 600 mm per minute. ).

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.

Here, the aluminum-zinc-oxide thin film layer 310, which is a transparent conductive thin film, was manufactured to a thickness of about 1,500 nm.

When the transparent conductive thin film is formed on the substrate 300 and the post-heat treatment is completed, the carrier 100 is transferred from the second buffer and the heat treatment chamber 12b 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.

후의 열처리를 통하여 얻은 전기광학적 특성변화를 나타낸 것이다.Table 1 below forms the aluminum-zinc-oxide thin film layer, which is a transparent conductive thin film according to an embodiment of the present invention, before forming the thin film layer.

It shows the change of electro-optic properties obtained through the subsequent heat treatment.

Sample classification
Temperature [℃] thickness
[Nm] Sheet resistance
[Ω / ㎠] Transmittance
[%] Mobility
[Cm 2 / Vs] Pre-heat treatment process Plasma pretreatment process Sputtering process After heat treatment process A
100
200
200
100
1450
6.30
546 nm 15.61 83.31% B
200
200
200
200
1480
4.94
543 nm 22.51 84.37%

As shown in Table 1, Sample A performs the step (S130) of impinging the cations of the plasma of the argon and oxygen mixture gas generated in the plasma generating apparatus 17 in the first process chamber 14a to the substrate, and the second The aluminum-zinc-oxide thin film layer is formed by sputtering aluminum-zinc-oxide while continuously transferring to the process chamber 14b, the third process chamber 14c, the fourth process chamber 14d, and the fifth process chamber 14e. (S140, S150, S160, S170), the thickness of the aluminum-zinc-oxide thin film is 1,450nm, sheet resistance is 6.30Ω / cm ² , transmittance is 83.31% at 546nm wavelength, the electrical characteristics mobility Was 15.61 cm ² / Vs. The sample B performs the pre-heat treatment step S120 while applying 180 to 220 ° C. heat in the first buffer and the heat treatment chamber 12a, and argon generated in the plasma generator 17 in the first process chamber 14a. The step (S130) of impinging the cations of the plasma of the oxygen mixed gas and the substrate, the second process chamber 14b, the third process chamber 14c, the fourth process chamber 14d, the fifth process chamber ( 14e) while sputtering the aluminum-zinc-oxide while continuously transferring to 14e) to form the aluminum-zinc-oxide thin film layer (S140, S150, S160, S170), and then performing 180 steps in the second buffer and heat treatment chamber 12b. The heat treatment step (S180) was performed while applying heat to 220 ° C., and the thin film of aluminum-zinc-oxide was 1,480 nm, the sheet resistance was 4.94 Ω / cm ² , and the transmittance was 84.37% at a wavelength of 543 nm. The mobility was 22.51 cm ² / Vs.

후의 열처리 단계(S120, S180)를 수행한 시료 B가 박막층 형성 전

후의 열처리 단계를 100℃에서 수행한 시료 A보다 전기광학적 특성이 향상되었음을 알 수 있다. Before forming the transparent conductive thin film layer while applying heat at 180 to 220 ° C. in the first and second buffer and heat treatment chambers 12a and 12b.

Sample B after the post-heat treatment step (S120, S180) is formed before the thin film layer

It can be seen that the electro-optical properties are improved than the sample A which is subjected to the subsequent heat treatment step at 100 ° C.

후의 열처리를 통하여 얻은 결정성 변화를 전자현미경(SEM)의 표면사진과 단면사진으로 나타낸 것이다. In addition, Table 2 below shows the aluminum-zinc-oxide thin film layer formed as a transparent conductive thin film.

The crystallinity change obtained through the post-heat treatment is represented by the surface photograph and the cross-sectional photograph of the electron microscope (SEM).

As shown in the comparison of the surface and cross-sectional photographs of samples A and B by electron microscopy, it can be seen that the particle size of the aluminum-zinc-oxide thin film coated with sample B is larger. In other words, it can be found that the larger the particle size, the smaller the pores of the aluminum-zinc-oxide thin film, resulting in the improved electro-optical properties of Sample B.

후의 열처리 단계를 수행한 새로운 제조방법에 의해 제조된 투명성 전도박막인 알루미늄-아연-산화물 박막이 전기광학적 특성이 향상된 결과 얻었음을 발견할 수 있다.Therefore, according to the present invention before forming the transparent conductive thin film layer

It can be found that the aluminum-zinc-oxide thin film, which is a transparent conductive thin film manufactured by a new manufacturing method which is subjected to the subsequent heat treatment step, has obtained an improved electro-optical characteristic.

Sample classification Surface photograph of sample by electron microscope Cross section photo of the sample by electron microscope



A

B

While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. 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: first buffer and heat treatment chamber
12b: second buffer and heat treatment chamber
13a, 13b: first and second transfer chambers
14a: first process chamber
14b, 14c, 14d, 14e: second, third, fourth and fifth 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;
Preheating the substrate through a pre-thermal treatment at a temperature of 180 to 220 ° C. before coating the conductive oxide onto the substrate;
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;
Continuously sputtering a conductive oxide on the substrate to form a transparent conductive thin film layer; And
A transparent conductive thin film manufacturing method for a thin film solar cell comprising the step of post-heat treatment at a temperature of 180 to 220 ℃ after forming the transparent conductive thin film layer. 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 transparent conductive thin film manufacturing method for a thin film solar cell comprising soda lime glass, low iron glass, alkali-free glass or tempered glass. The method of claim 1,
The substrate is a method for producing a transparent conductive thin film for a thin film solar cell comprising a high refractive oxide and a low refractive oxide, soda-lime glass, low iron glass, alkali-free glass, or tempered glass coated in succession once or sequentially. 5. The method of claim 4,
The high refractive oxide is a transparent conductive thin film manufacturing method for a thin film solar cell comprising Nb ₂ O ₅ , Ti ₂ O ₃ , Ta ₂ O ₅ or ZrO ₂ . 5. The method of claim 4,
The low refractive oxide is a transparent conductive thin film manufacturing method for a thin film solar cell comprising SiO ₂ , MgF ₂ , BaF ₂ or AlF ₃ . 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 coated with soda-lime glass, low iron glass, alkali-free glass, or tempered glass. Transparent conductive thin film manufacturing method for a thin film solar cell comprising. The method of claim 1,
The conductive oxide is a thin film solar cell including a zinc oxide in which any one material selected from the group consisting of aluminum (Al), gallium (Ga), indium (In), and boron (B) is added to zinc-oxide (ZnO). Transparent conductive thin film manufacturing method for batteries. The method of claim 1,
The conductive oxide is indium-tin-oxide (ITO) comprising a transparent conductive thin film manufacturing method for a thin film solar cell.

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