KR101094315B1 - Manufacturing apparatus of ?-?-?2 compound semiconductor thin film and manufacturing method using the same - Google Patents

Abstract

The present invention relates to an apparatus used when manufacturing the I-III-VI ₂ compound semiconductor thin film by selenization or sulfiding method.

An apparatus for producing an I-III-VI ₂ compound semiconductor thin film of the present invention includes a chamber in which a holder on which a substrate is placed is formed and an upper portion thereof is opened; An upper lamp unit coupled to the upper chamber and including a heating lamp; And a lower lamp unit coupled to a lower portion of the chamber and including a heating lamp.

Accordingly, various lamps can be easily replaced and used in accordance with a desired process. In particular, by using an infrared lamp, it is possible to form a thin film having improved uniformity in the depth direction.

I-III-VI2 compound semiconductor thin film, CIS, CIGS, selenide, selenide, solar cell

Description

Manufacture apparatus of I-III-VI2 compound semiconductor thin film and manufacturing method using same TECHNICAL TECHNICAL FIELD [Manufacturing application of I-III-VI2 COMPOUND SEMICONDUCTOR THIN FILM AND MANUFACTURING METHOD USING THE SAME}

The present invention relates to a device for producing a compound of the I-III-VI ₂ compound semiconductor thin film for use in a solar cell and a method for producing an I-III-VI ₂ compound semiconductor thin film using the same, and more specifically in the selenization or sulfiding method I -III-VI ₂ Compound The present invention relates to a device used when producing a semiconductor thin film and a method of selenization or sulfidation using the device.

Generally, renewable energy using solar energy can be classified into a power generation system using solar heat and a power generation system using solar light. Dual photovoltaic systems use solar cells with the opposite principle to LEDs and laser diodes that convert electrical energy into light energy.

The pn junction solar cell is composed of a combination of n-type semiconductor and p-type semiconductor. The n-type has a large electron density and a small hole density, while the p-type has a small electron density and a large hole density. Have In the p-n junction semiconductor, carrier diffusion does not occur in a general thermal equilibrium state, but electrons are excited to the conduction band in the valence band when light is applied beyond the band gap energy, which is an energy difference between the conduction band and the valence band of the constituent material. Electrons excited by the conduction band move freely, and holes are formed in the valence band where the electrons escape. Electrons excited in the p-type region by light energy and holes made in the n-type region are called minority carriers in comparison to the carrier (main carrier) before bonding. The main carriers do not flow because of the energy barrier created by the electric field, but the minority carriers continue to flow so that they can be connected to external circuits and used as solar cells.

Solar cells are classified into various types according to materials used as light absorption layers, and at present, the most commonly used are silicon solar cells using silicon. However, as prices have soared recently due to a shortage of silicon, interest in thin-film solar cells is increasing. Thin-film solar cells are manufactured with a thin thickness, so the materials are consumed less and the weight is lighter, so the application range is wide. As a material of such a thin-film solar cell, research on amorphous silicon, CdTe, CIS (CuInSe ₂ ) or CIGS (CuIn _1-x Ga _x Se ₂ ) has been actively conducted.

The CIS or CIGS ternary thin film is one of the I-III-VI ₂ compound semiconductors and has the highest conversion efficiency (about 19.9%) among the experimental thin film solar cells. In particular, it can be manufactured to a thickness of less than 10 microns, and has a stable characteristic even in long-term use, and is expected to be a low-cost, high-efficiency solar cell that can replace silicon.

Methods of manufacturing a CIS or CIGS thin film (hereinafter referred to as a 'CIS-based thin film') include a selenization method, a MOCVD method, an evaporation method, an electrodeposition method, and the like.

In the selenization method, a Cu-In or Cu-In-Ga precursor is formed on a soda glass coated with molybdenum electrode by vacuum sputtering or the like, and then heated in a gas atmosphere containing selenium such as H ₂ Se to form a CIS system. It is a method of manufacturing a thin film. The CIS-based thin film forming method of the selenization method has a problem in that the uniformity of the thin film is inferior because the reaction for thin film formation does not occur evenly, and recently, the preference for the simultaneous vacuum evaporation method has increased.

In addition, copper indium sulfide and copper indium gallium sulfide, which are I-III-VI ₂ compound semiconductors, may be manufactured by a sulfation process.

Therefore, there is a growing interest in a device for manufacturing an I-III-VI ₂ compound semiconductor thin film capable of performing a selenization or sulfidation process to improve reactivity and uniformity.

The present invention has been invented based on the above contents, and provides a manufacturing apparatus capable of efficiently forming a uniform I-III-VI ₂ compound semiconductor thin film and a method of manufacturing the I-III-VI ₂ compound semiconductor thin film using the same. The purpose is.

The apparatus for producing an I-III-VI ₂ compound semiconductor thin film of the present invention for achieving the above object has the following configuration.

A chamber in which a holder on which the substrate is placed is formed, and the top of which is open;

An upper lamp unit coupled to the upper chamber and including a heating lamp; And

Apparatus for manufacturing an I-III-VI ₂ compound semiconductor thin film, characterized in that it comprises a lower lamp portion coupled to the lower portion of the chamber and including a heating lamp.

In the present invention, the heating lamp uses a long wavelength lamp, which may be an infrared lamp that emits light in the infrared region in a preferred embodiment. The heating lamp can be detachably coupled, which is easy to maintain and manage.

Meanwhile, a valve cracker cell (VCC) equipped with a valve may be coupled to the side of the chamber to supply pyrolyzed selenium (Se) gas or sulfur (S) gas into the chamber. Such a cracker cell can continuously supply uniform molecular unit selenium beams or sulfur beams. Cracker cell is a device for supplying the flux of the raw material to the deposition equipment. In the present invention, a cracker cell for supplying selenium flux or sulfur flux is combined with an I-III-VI ₂ compound semiconductor thin film manufacturing apparatus.

In addition, the apparatus for producing an I-III-VI ₂ compound semiconductor thin film according to another feature of the present invention has the following constitution.

A chamber including a holder for vertically supporting the substrate and having one side open;

A lamp unit coupled to the open side of the chamber and including a heating lamp; And

And a cracker cell coupled to the chamber for continuously supplying selenium gas or sulfur gas toward the substrate, wherein the I-III-VI ₂ compound semiconductor thin film is manufactured.

According to such a structure, since the continuous and uniform selenium flux or sulfur flux is supplied perpendicularly to the substrate direction from the cracker cell, a product having excellent process efficiency can be obtained.

In addition, the manufacturing method of Ⅰ-Ⅲ-Ⅵ ₂ compound semiconductor thin film using the manufacturing apparatus of the present invention, consists of the following steps.

Mounting a heating lamp suitable for heat treatment conditions;

Positioning the substrate in the chamber;

Supplying Se flux or S flux from the cracker cell into the chamber; And

And operating the heating lamp to heat-treat the substrate, wherein the I-III-VI ₂ compound semiconductor thin film is manufactured.

After this step, the heating lamp can be easily replaced by selecting a heating lamp suitable for the heat treatment conditions according to the characteristics of the I-III-VI ₂ compound semiconductor thin film manufacturing apparatus of the present invention, and also due to Se flux or S flux supplied from the cracker cell. The efficiency of the selenization or sulfiding process is improved.

According to the present invention, as a heating lamp, an infrared lamp can be easily replaced and used in addition to an existing lamp such as a halogen lamp. Therefore, by increasing the depth of heat penetration as an effect of the infrared lamp, it is possible to easily exchange various lamps suitable for the conditions, such as forming a uniform I-III-VI ₂ compound semiconductor thin film in the depth direction.

In addition, by using a cracker cell that can adjust the supply amount of selenium gas or sulfur gas pyrolyzed by the valve, there is an effect that the reactivity is improved.

Furthermore, by vertically positioning the substrate, selenium or sulfur is uniformly supplied to the substrate, thereby further improving the efficiency of the process.

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

1 to 3 is a view showing the manufacturing apparatus of the I-III-VI ₂ compound semiconductor thin film according to the first embodiment of the present invention.

In FIG. 1, an apparatus for manufacturing an I-III-VI ₂ compound semiconductor thin film includes a chamber 110, an upper lamp unit 120, a lower lamp unit 130, and a cracker cell 140.

The chamber 110 is a space where a heat treatment operation is performed, and a holder 112 in which a substrate to be subjected to selenization or sulfidation is placed is formed therein. The holder 112 functions to fix the substrate, rotate the substrate for uniform heat treatment, and the like, and techniques known to date can be used without particular limitation. Since the structure and function of the holder 112 is not the main configuration of the present invention, a detailed description thereof will be omitted.

The upper part of the chamber 110 may be opened, and the substrate 110 may be inserted into the holder 112 through the opened upper part. Conventional apparatuses for manufacturing I-III-VI ₂ compound semiconductor thin films have moved to the inside of the chamber by forming an entrance and exit of the substrate on the side of the chamber and sliding the holder on the side to insert the substrate horizontally. In this case, a separate moving device must be installed, and the entrance is narrow, and there is a problem that damage occurs while the substrate is inserted. In the chamber 110 of the present embodiment, the entire upper surface is opened and the substrate is moved into the chamber 110 through the opened upper portion, so that the process of inserting the substrate is easy and the problem of damage to the substrate does not occur.

Meanwhile, in the present exemplary embodiment, the shape of the inside of the chamber 110 is a rectangular parallelepiped, but the shape of the chamber 110 is not particularly limited and may be manufactured in various shapes. The chamber is connected to a pipe for keeping the inside of the vacuum or for discharging the reaction gas, and has a structure for sealing.

The upper lamp unit 120 is a portion for performing heat treatment by applying heat to the upper portion of the substrate, and includes a plurality of heating lamps 122 for dissipating heat. The heating lamp 122 may use a lamp that emits light in various wavelength ranges. Halogen lamps are widely used, and this embodiment uses an infrared lamp that emits light in the infrared region. Since the light emitted from the infrared lamp penetrates deeply into the thin film formed on the substrate, the reactivity is improved and a uniform selenization or sulfidation reaction occurs in the depth direction.

The upper lamp unit 120 is hinged to the open upper portion of the chamber 110 (124), and also serves as a door for opening and closing the opening of the chamber 110. When the upper lamp unit 120 is closed, the chamber 110 and the upper lamp unit 120 are sealed, and the heating lamp 122 is positioned to face the holder 112. In this structure, the heating lamp 122 is exposed to the outside when the upper lamp unit 120 is opened. Therefore, there is an advantage that the management of the heating lamp 122 is very convenient. For example, the lamp at the end of its life may be simply replaced while the heating lamp 122 is exposed to the outside. In this case, the heating lamp 122 may replace only one lamp at the end of its life, as necessary, or may be configured to replace the module itself by having a structure in which all the lamps are coupled to the lamp unit in a module form. Accordingly, there is an advantage that the lamp of the wavelength suitable for the heat treatment conditions can be easily mounted or removed.

The lower lamp unit 130 is a portion for performing heat treatment by applying heat to a lower portion of the substrate, and includes a plurality of heating lamps 132 for dissipating heat. In the present embodiment, the heating lamp 132 is an infrared lamp like the heating lamp 122 of the upper lamp unit 120.

The lower ramp unit 130 is connected to the lower surface of the chamber 110 in a manner of being inserted and withdrawn while sliding along the guide 134. When performing the selenization or sulfiding process, the lower lamp unit 130 is positioned below the chamber 110 to apply heat to the substrate. When the lower lamp unit 130 is pulled out from the chamber 110 except for carrying out the process, management such as replacement of the heating lamp 132 is very convenient. As shown in FIG. 3, a transparent window 114 is formed at the bottom of the chamber 110 so that heat emitted from the heating lamp 132 of the lower lamp unit 130 can easily enter the chamber 110. do. Quartz is used as the material of the transparent window 114.

The cracker cell 140 is a portion for supplying selenium gas or sulfur gas into the chamber 110. The cracker cell 140 may stably supply the selenium gas beam or the sulfur gas beam by pyrolysis after evaporating selenium or sulfur. In particular, in the present embodiment, by providing a cracker cell 140 for controlling the discharge of the selenium gas beam or the sulfur gas beam using a valve (not shown), the efficiency of the selenization or sulfiding process may be increased. An example of such a cracker cell 14 is the PV series manufactured by Veeco Instruments.

4 to 6 are views showing an apparatus for manufacturing an I-III-VI ₂ compound semiconductor thin film according to a second embodiment of the present invention.

The selenization device of the present embodiment includes a chamber 210, a lamp unit 220, and a cracker cell 240.

The chamber 210 is a space where a heat treatment operation is performed, and a holder 212 in which a substrate to be subjected to selenization or sulfidation is placed is formed therein. Holder 212 is a structure for supporting the substrate to stand vertically. And the chamber 210 is configured to open the side, the holder 212 is installed so that the supported substrate can face the open side. Thus, the substrate can be supported by the holder 212 through the open side surface.

The lamp unit 220 is a portion in which heat treatment is performed by applying heat to the substrate, and includes a plurality of heating lamps 222 that emit heat. In this embodiment, the heating lamp 222 uses an infrared lamp. The lamp unit 220 is hinged 224 to the open side of the chamber 210 to serve as a door for opening and closing the opening of the chamber 210. When the lamp unit 220 is closed, the chamber 210 and the lamp unit 220 are sealed to each other, and the heating lamp 222 is positioned toward the holder 212.

In addition, since the heating lamp 222 is exposed when the lamp unit 220 is opened, it is very convenient to replace or manage the heating lamp 222.

The cracker cell 240 is a portion for supplying selenium gas or sulfur gas into the chamber 210. The cracker cell 240 may stably supply the selenium gas beam or the sulfur gas beam by thermally decomposing the selenium or the sulfur after evaporation. In this embodiment, the cracker cell 240 is installed to supply the selenium gas beam or the sulfur gas beam toward the substrate from the opposite side of the side opening. Since the cracker cell 240 of the present embodiment controls the discharge of the selenium gas beam or the sulfur gas beam by using a valve (not shown), the selenium beam or the sulfur gas beam can be supplied toward the substrate supported by standing vertically, and the selenium The efficiency of the sulfidation or sulfiding process is also improved.

The apparatus for manufacturing an I-III-VI ₂ compound semiconductor thin film according to the present invention further includes a device for measuring the temperature inside the chamber and a control system for controlling the progress of the process, but such parts may be used without limitation. Detailed descriptions are omitted here.

The I-III-VI ₂ compound semiconductor thin film manufacturing method according to the embodiment of the present invention uses the I-III-VI ₂ compound semiconductor thin film manufacturing apparatus of the I-III-VI ₂ compound semiconductor thin film for solar cells. A method of forming, comprising: mounting a heating lamp suitable for heat treatment conditions, positioning a substrate in a chamber, supplying Se flux or S flux from a cracker cell into the chamber, and operating the heating lamp to heat treat the substrate. It comprises a step.

First, a heating lamp suitable for heat treatment conditions is mounted. Depending on the thickness and composition of the thin film, the conditions of the selenization or sulfiding process are different, and according to the conditions, the step of selecting and mounting a histilamp. Since the manufacturing apparatus of the I-III-VI ₂ compound semiconductor thin film according to the present invention has a structure in which the heating lamp is exposed, it is easy to replace the heating lamp, so that the heating lamp is maximized in the efficiency of the selenization or sulfiding process. You can choose to use it.

Next, the substrate is placed in the chamber. In order to form an I-III-VI ₂ compound semiconductor thin film, a substrate in which Cu-In or Cu-In-Ga is deposited is placed in a holder inside the chamber. In the manufacturing apparatus of the I-III-VI ₂ compound semiconductor thin film according to the present invention, it is very convenient to move the substrate inside by forming a wide opening in the chamber.

And Se flux or S flux from the cracker cell is fed into the chamber. It is a step of supplying Se flux or S flux into the chamber using a cracker cell that pyrolyzes Se gas or S gas to provide Se flux or S flux. In particular, it is possible to stably supply a continuous Se flux or S flux into the chamber by using a cracker cell including a valve that regulates the discharge of the Se flux or S flux.

Finally, the substrate is heat-treated by operating the heating lamp selected previously. A step of manufacturing an I-III-VI ₂ compound semiconductor thin film by reacting Se or S supplied from a cracker cell with Cu-In or Cu-In-Ga deposited on the surface of the substrate.

In the above, the present invention has been shown and described with respect to certain preferred embodiments. However, the present invention is not limited only to the above-described embodiment, and those skilled in the art to which the present invention pertains can make various changes without departing from the technical spirit of the present invention. Therefore, the scope of the present invention should not be limited to the specific embodiments, but should be construed as defined by the appended claims.

1 is a view showing an apparatus for manufacturing an I-III-VI ₂ compound semiconductor thin film according to a first embodiment of the present invention.

FIG. 2 shows a front view of FIG. 1.

3 is a cross-sectional view taken along the line A-A of FIG. 2.

4 is a view showing an apparatus for manufacturing an I-III-VI ₂ compound semiconductor thin film according to a second embodiment of the present invention.

FIG. 5 shows a front view of FIG. 4.

6 is a cross-sectional view taken along the B-B plane of FIG. 5.

Description of the Related Art

110, 210: chamber 112, 212: holder

114: transparent window 120: upper lamp portion

122,132,222: heating lamp 124,224: hinge coupling

130: lower lamp unit 134: guide

140, 240: cracker cell 220: lamp unit

Claims (10)

A chamber in which a holder on which the substrate is placed is formed, and the top of which is open; An upper lamp unit hingedly coupled to the upper chamber and including a heating lamp; And A lower lamp unit coupled to the lower part of the chamber in a sliding manner and including a heating lamp; Including; The heating lamp is composed of a plurality of modules, the module is detachably coupled to the upper lamp portion or the lower lamp portion, respectively, I-III, characterized in that the heating lamp configured in the module can be replaced individually -VI _{2 A} device for producing a compound semiconductor thin film. The method according to claim 1, Apparatus for manufacturing an I-III-VI ₂ compound semiconductor thin film, wherein the heating lamp is an infrared lamp. The method according to claim 1, Apparatus for manufacturing an I-III-VI ₂ compound semiconductor thin film, characterized in that a cracker cell for supplying pyrolyzed selenium gas or sulfur gas into the chamber is coupled to the chamber. delete delete delete delete delete delete delete

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