TW201227984A - Reaction apparatus for forming semiconductor thin film on glass substrate - Google Patents

Abstract

This invention is about a reaction apparatus used for forming semiconductor layer on glass substrate. The said reaction apparatus is used for manufacturing I-III-IV semiconductor thin film solar module. The characteristics of the reaction apparatus are simple structure design, easy to produce and special designed mortise and tenon joint. A buffer space is formed inside the mortise and tenon joint. Through this buffer space in the mortise and tenon joint, control of the vapor quantity of group VI element necessary for formation of I-III-IV semiconductor thin film inside the reaction apparatus can be achieved. This reaction apparatus is used in the sputtering/RTP process for I-III-IV semiconductor thin film solar module production.

Description

201227984 VI. Description of the Invention: [Technical Field] The present invention relates to a reaction vessel for forming a semiconductor thin film on glass, which is a key device required for the production of a dih-νι thin film solar cell. It is also applicable to the sputtering/RTP process in the mass production method of the semiconductor thin film solar cell of the 111. [Prior Art] Thin film solar cells are generally classified into three types: tantalum film, II-VI film, and yttrium-yttrium-VI film. The rare film is represented by amorphous silicon battery as 'II-VI film. The cadmium telluride (CdTe) film is representative of 'the I-III-VI film is represented by copper indium gallium nitride (CuInxGai-xSe2, which is referred to as <1 'CIGS) thin film, and these three thin film batteries have also been There is a US company in which the company is in mass production, in which cadmium telluride thin film batteries are produced.

Fisrt Solar is the most successful, but it is generally believed that CIGS thin film solar cells will be more futuristic than recorded tin thin film solar cells due to the superior photovoltaic properties of ciGS films. At present, substrates used in CIGS thin film solar cells can be roughly classified into rigid substrates (such as glass and stainless steel plates) and flexible substrates (such as stainless steel sheets and polyacrylamide films), and the use of glass substrates is the mainstream in mass production. There are roughly three mainstream processes in production, namely co-evaporation, sputtering/HzSe selenization, and sputtering/RTp selenization. The co-evaporation method uses high vacuum evaporation to simultaneously bond four elements of copper indium gallium code. The vapor bonds are on a high temperature substrate to form a CIGS film. Sputtering/HAe selenization method is to deposit copper indium gallium on the substrate by vacuum sputtering 201227984, and then put the substrate into a high temperature reactor filled with H2Se gas. H2Se gas will decompose into high temperature at high temperature. And hydrogen, produced

The raw selenium reacts with copper indium gallium on the substrate to form a CIGS film. Sputtering/RTP selenization is also performed by first depositing copper indium gallium on the substrate by vacuum sputtering, then depositing selenium on copper indium gallium, and then placing the substrate coated with four elements of copper indium gallium selenide. A Rapid Thermal Process (RTP) heats the substrate to a high temperature in a few minutes to form a CIGS film. The high temperatures mentioned in this section are between 500 ° C and 550 T • if using a glass substrate. Each of the above three methods has advantages and disadvantages, but the process and equipment for forming a CIGS film on a large-area glass must have the following basic characteristics, uniformly heating a large area of glass, precise temperature control, and accurately providing sufficient selenium to Reacts with copper indium gallium.

Compared with other methods, the sputter/RTP selenization method has better performance in terms of heating uniformity, temperature control and selenium control, and it is greatly valued because of the short φ process time. Published by Seimens in 1993 ("Novel Rapid Thermal Processing for CIS Thin-Film Solar Cells", Proc. 23rd IEEE PVSC

Conf., 1993, p. 441), still in the US patent? 6,717,112 discloses a method for converting Siemens research into a mass production process, which mainly involves placing a substrate coated with four elements of copper indium gallium selenide into a reaction vessel, and then transporting the reaction vessel to a different one. The process chamber is formed to form a CIGS film. For example, the reaction vessel is sent to a rapid heating furnace for temperature rise reaction, and then sent to a cooling chamber for cooling, thereby forming a continuous process (in nne 201227984).

Pf_s) 'very suitable for large but the reaction volume H described in this patent is very complicated. The reaction container of the patented towel must have the function of simultaneously introducing other reaction gases, exhaust gas and maintaining the deductive force of the code, so the design The complex exhaust port increases the complexity of the process to avoid the speed-up furnace. In addition, the materials used in the patented reaction vessel include the quartz on the cover, the carbon fiber reinforced composite on the wall of the container, and the graphite on the base. This combination has been added. Difficulties in reaction temperature control. SUMMARY OF THE INVENTION The present invention is a reaction vessel for synthesizing a semiconductor thin film on glass. The reaction vessel can be combined with a Rapid Thermal Process and a rapid heating furnace to cause a sputtering/RTP magnetization process for a CIGS thin film solar cell. Excellent mass production. The reaction container of the present invention comprises an upper cover and a base, and a storage space is formed between the upper cover and the base to place a glass substrate coated with copper indium gallium selenide, and between the upper cover and the glass substrate coated with copper indium gallium selenide Provide appropriate free space to avoid direct contact between the upper cover and the coated surface. During the heating process, the selenium on the glass substrate will be vaporized and filled with free space. Since the fit between the upper cover and the base is not completely in close contact, the selenium in the free space The vapor will escape from the close portion due to the increase of the vapor pressure during the heating process, and diffuse out of the reaction vessel by the close portion during the constant temperature process. Therefore, the present invention provides continuity in the portion where the upper cover and the base fit.卯 structure, this continuity of the 榫卯 structure is characterized by the egg eye larger than the hoe, because the 卯 eye is larger than the hoe, it will form a buffer space in the continuous 榫卯 structure to control the selenization 201227984 reaction in the reaction vessel free The shouting of space (four degrees), the process of scattering will first spread from the freedom of the reaction vessel (4) to the buffer space = then from the buffer (four) to the reaction volume Outside the device, the two-stage diffusion is caused by this buffer space to achieve the purpose of controlling freedom (4). If there is more control over the escape of selenium vapor, more than two consecutive structures can be designed.

The buffer space is designed to control the selenium vapor in the free space of the reaction vessel to achieve the purpose of stabilizing the sputtering/RTP selenization process. Since the deuteration reaction must be carried out at a high temperature, and the high-temperature selenium has a strong attack property, Generally, the magnetization reaction must use materials with high temperature resistance and resistance to code intrusion. Due to the limitation of large-area processing technology of such materials, the upper cover and the base must not be closely matched, and a gap will be generated. At this time, the vapor in the free space is generated. A large amount of these gaps will directly diffuse out of the reaction vessel, which makes the Tibetan plating/RTP confirmation process extremely unstable. After the buffer space is provided, even if the upper cover and the base cannot closely fit together, there is a gap, and the space is located in the free space. The selenium vapor cannot be directly diffused outside the reaction vessel, but must first diffuse into the buffer space and then diffuse from the buffer space to the outside of the reaction vessel. Since the concentration of magnetic vapor in the buffer space is greater than that of the reaction vessel, the freedom can be greatly reduced. The diffusion rate of selenium vapor into the buffer space in the space. Compared with the design of a complex and completely closed selenization reaction vessel, resulting in increased complexity of the production process and operational difficulties, the present invention is completely closed and accepts a limited amount of selenium loss, and achieves control of selenium in a very simple reaction vessel. The purpose of the vapor is to make the sputtering/RTP selenization process more mass-produced. 201227984 [Embodiment] The reaction container described in the present invention is as shown in FIG. 1. FIG. 1 is a structural view of the upper cover 1 of the reaction container and the base 2, and is formed when the upper cover 1 is engaged with the base 2. A central portion of the reaction vessel forms a storage space 8 which is different in size from the glass substrate 9 plated with the layer of copper indium gallium selenide film 4, and has a pre-free space 3 which avoids the upper cover. 1 is in contact with the copper indium gallium selenide film layer 4 on the glass substrate 9. • When the upper cover 1 is engaged with the base 2, since the upper cover 1 has a continuous boring head 51 and the base has a continuous squint 51, a continuity is formed between the compliant surface 6 and the compliant surface 7 when engaged. The structure of the sputum, and because the blink is larger than the hoe, a buffer space 5 is formed in the continuous egg structure. The so-called continuous head 51 and the continuous blink 52 can be illustrated in FIG. 2 and FIG. 3. FIG. 2 shows a top view of the upper cover. The plane 61 and plane 71 of the upper cover 1 Φ are in the base 2 When the engagement surface meets the contact surface, a continuous protrusion head 51 surrounding the upper cover is formed between the plane 61 and the plane 71, and an open space 81 is dug downward in the central portion of the upper cover. The open space 81 is in the future cover 1 and the base. When the 2 fits, the storage space 8 in Fig. 1 will be formed, and the continuous boring head 51 will completely surround the open space 81 dug out. 2 is a front view of the base 2, the plane 62 and the plane 72 of the base 2 are a matching contact surface when engaging with the upper cover 1, and a continuous concave sill around the base is formed between the plane 62 and the plane 72. The eye 52, the continuous blink 52 and the continuous head 51 of the upper cover 1 of Fig. 2, when the upper cover is engaged with the base of 201227984, forms a continuity of the reaction container in Fig. i. In addition, as can be seen from FIG. 2 and FIG. 3, when the upper cover is engaged with the base, the volume of the storage space 8 is completely the same as the volume of the open space 81 excavated by the center of the upper cover, so we can say that the figure i is The storage space 8' of the reaction vessel is completely formed in the upper cover 1. The upper cover 1 and the base 2 shown in Fig. 2 and Fig. 3 are so simple in structure that they are relatively easy to manufacture, and the material selection is the best choice for materials having a high thermal conductivity. For example, graphite can be selected from graphite slabs of appropriate size during production, and the upper cover or the base can be processed by a large-scale precision machining equipment at a time, or can be produced by die casting. In order to more effectively control the escape of magnetic vapor in the free space, more than one continuous steamed bread and continuous blink can be designed on the cover and the base of the reaction vessel for forming more than one structure in the reaction vessel. 'Figure 4 shows a reaction vessel with two ruthenium structures. _ The design of the reaction vessel is not limited to the structure of Fig. 1. The change is that the storage space, the continuous hoe and the continuous mortise are designed on the upper cover or the base. As shown in Fig. 5, the reaction container shown in the upper view of Fig. 5 is very It is obvious that the reaction container in Fig. 1 is inverted, in which case the continuous blink is on the upper cover, the continuous head is on the base, and the volume of the reaction container is completely formed on the base. The middle figure of 圏5 is another design, the continuous blinking is at the base, and the continuous hoe is the same as that of Figure 1 in the upper cover, but the volume of the storage space of the reaction container is completely formed on the base. Only the middle circle of Fig. 5 is turned over, the continuous blink is on the top cover, and the continuity is on the base, 201227984, and the storage space of the reaction container is completely formed on the upper cover. Of course, there is another design as shown in Fig. 6, that is, the partial volume of the storage space of the reaction container is formed on the upper cover, and part of the volume is formed on the base. Alternatively, as shown in Fig. 7, the central portion of the base of the reaction container is slightly convex. It is a platform to place the glass substrate' and the open space excavated from the central part of the upper cover is larger than the required space. Therefore, we can also use the storage space of the reaction container to fully form the upper cover to illustrate the design of Figure 7. . The complete manufacturing procedure for making CIGS thin film solar cells using the sputter/RTP selenization process is as follows: Glass substrate cleaning + cockroach flip electrode (Mo) on the substrate + first laser line "&gt ; CuInGa film on the molybdenum electrode "> key sleeve on the copper indium gallium film ·> RTP selenization process cadmium sulfide (CdS) electroless plating + sputtered zinc oxide buffer layer Two-way mechanical marking, today's sputtering transparent conductive layer (aluminized zinc oxide) + third mechanical cutting + rear module process

The reaction vessel of the present invention is mainly applied to the RTP selenization process, and its application program is as shown in FIG. 8 'Firstly, a glass substrate 9 plated with copper indium gallium selenide and molybdenum electric grade is placed on the bottom plate 2 of the reaction vessel, and then the reaction is carried out. The upper cover 1 of the container is aligned with the bottom plate 101 to be combined with the bottom plate to be combined into a reaction container, and the reaction container containing the glass substrate 9 is sent into a feeding chamber 102, and the air of the feeding chamber is first withdrawn, and the degree of vacuum must be low. At 10_2torr, then an inert gas (nitrogen or argon) is introduced. This operation can replace the air in the reaction vessel with an inert gas, and then transfer the reaction vessel to a rapid heating furnace (RTP 201227984 furnace) 103. The rapid heating is carried out to raise the temperature of the reaction vessel to between 500 Τ and 55 〇 ° C at a temperature increase rate of 5× per second, and then the temperature is maintained for several minutes. The operation of maintaining the temperature after the rapid temperature rise can be achieved by infrared heating. After the process of completing the rapid heating furnace section, the reaction vessel is transferred to the cooling chamber 104 where the reaction vessel is cooled to 1 Torr. The crucible is then sent out to the cooling chamber 104' to finally open the reaction vessel 105 and take out the glass substrate 10 on which the CIGS film has been formed. While the present invention is not limited to the examples, it is intended to cover all modifications and variations of the present invention. 201227984 [Simplified description of the drawings] Fig. 1 is a structural view of a reaction container designed according to the spirit of the present invention. Fig. 2 is a top view of the upper surface of the reaction container disclosed in Fig. 1. Fig. 3 is a reaction container disclosed in Fig. 1. 4 is a front view of a reaction vessel having two crucible structures. FIG. 5 is a view showing the structure of another three reactors designed according to the spirit of the present invention. FIG. 6 shows a structure of a reaction vessel designed in accordance with the spirit of the present invention. Figure 7 is a view showing the structure of a reaction vessel designed in accordance with the spirit of the present invention. Figure 8 is a flow chart of the reaction vessel of the present invention applied to the sputtering/RTP selenization method. [Main component symbol description] 1 : Reaction vessel upper cover 2 : The base of the reaction vessel 3: the free space after the glass substrate is placed in the reaction container storage space 4: the film layer on the glass substrate, including the molybdenum electrode and the copper indium gallium selenide film 5: the buffer formed by the structure of the reaction vessel Zone 6: The mating surface 7 when the upper lid of the reaction vessel is engaged with the base: the mating surface 8 when the upper lid of the reaction vessel is engaged with the base: the storage space of the reaction vessel 9: containing the molybdenum electrode Glass substrate with copper indium gallium selenide film 10: glass substrate 51 containing molybdenum electric grade and CIGS film: continuous boring head 12 201227984 52: continuous blinking 61, 71: fit contact plane 62 of the upper cover, 72: at the base The contact plane 82 is located in the open space 101 of the upper cover lower than the fit contact plane: the action of lowering the upper cover and the base to be combined into a reaction container 102: the feed chamber 103: the rapid heating furnace 104: the cooling chamber 105: the opening reaction Container action

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Claims (1)

201227984 VII. Patent application scope: 1. A reaction container for forming a semiconductor film on glass, comprising an upper cover and a base. When the upper cover and the base are engaged, a storage space is formed at the central portion, and the upper cover and the base are in contact with each other to form a continuous shape. The structure of the reaction container according to the first aspect of the patent application, wherein the volume of the storage space is completely formed in the upper cover. 3. The reaction container according to the first aspect of the patent application, wherein the volume of the space between the objects is completely formed on the base. 4. The reaction container according to claim 1, wherein the empty portion of the storage is formed in the upper cover and the portion is formed in the base. 5. The reaction container according to the first aspect of the patent application, wherein the continuity of the throwing structure is set on the upper cover, and the continuous eye is provided at the bottom. 6. The reaction container according to the first aspect of the patent application, wherein the continuity of the zen egg structure is set on the base, and the continuous eye is set on the upper lid. 7. The reaction vessel according to item 1 of the patent application scope, wherein the continuity of the zen impression structure is greater than the continuity of the koi, and forms a moderate space when it is combined. 8_If the patent application scope The reaction container according to the first aspect, the continuity of the structure, the number of the structures, and the number of the structures are not limited to the above. The reaction container according to the first aspect of the patent application, wherein the upper cover is made of graphite. 10. The reaction container according to the first aspect of the patent application, wherein the bottom cover of the 201227984 material is graphite.