Chamber cleaning method

Abstract

The present invention provides a method for cleaning a chamber for forming a perovskite compound, the chamber cleaning method comprising the steps of: exposing the inside of the chamber to a hydrogen (H)-containing gas plasma; and exposing the inside of the chamber to an oxygen (O)-containing gas plasma, wherein the step of exposing the inside of the chamber to an oxygen (O)-containing gas plasma is performed after the step of exposing the inside of the chamber to a hydrogen (H)-containing gas plasma.

Description

Chamber cleaning method

[0001] The present invention relates to a method for cleaning a chamber.

[0002] A solar cell is a device that converts light energy into electrical energy by utilizing the properties of semiconductors.

[0003] A solar cell has a PN junction structure that joins a P (positive) type semiconductor and an N (negative) type semiconductor, and when sunlight is incident on a solar cell of this structure, holes and electrons are generated within the semiconductor due to the energy of the incident sunlight, and at this time, the holes (+) move toward the P-type semiconductor and the electrons (-) move toward the N-type semiconductor due to the electric field generated at the PN junction, so that a potential is generated, thereby generating electricity.

[0004] In this way, the holes (+) and electrons (-) formed when sunlight is incident on the solar cell move through the transparent conductive layer and electrodes provided in the solar cell, respectively. The electrodes may be provided on each of the upper and lower surfaces of the solar cell substrate, or may be provided on only one of the upper and lower surfaces of the solar cell substrate, and current can move through the holes (+) and electrons (-) that move through each electrode.

[0005] In the past, when manufacturing solar cells using perovskite compounds, after manufacturing the solar cells, the process was stopped, the chamber was disassembled, and the chamber was cleaned using a wet method to clean the chamber in which the solar cells were manufactured. Then, the chamber was reassembled to manufacture the solar cells again. This chamber cleaning method, which was intended to improve the yield of the process, consumed a lot of time for disassembling and reassembling the equipment, which extended the overall process time. Therefore, there was a problem in that the process time was extended and the manufacturing cost increased as a result.

[0006] The present invention has been designed to solve the above-mentioned conventional problems, and the purpose of the present invention is to provide a chamber cleaning method that can prevent excessive time from being required to clean the chamber by cleaning the inside of the chamber in situ without disassembling the chamber.

[0007] In order to achieve the above object, the present invention provides a chamber cleaning method comprising a step of exposing the interior of the chamber to hydrogen (H)-containing gas plasma and a step of exposing the interior of the chamber to oxygen (O)-containing gas plasma, and a step of exposing the interior of the chamber to oxygen (O)-containing gas plasma after the step of exposing the interior of the chamber to hydrogen (H)-containing gas plasma.

[0008] The present invention provides a chamber cleaning method in which the perovskite compound includes a compound of ABX3 (wherein A is composed of a monovalent organic cation of the amine series compound or a monovalent organic cation of the amidine series compound, B is composed of the divalent cation, and X is at least one halogen compound).

[0009] A method for cleaning a chamber for forming a perovskite compound is provided, comprising a step of exposing the interior of the chamber to a hydrogen (H)-containing gas plasma and a step of supplying a gas containing hexafluoroacetylacetone (Hhfac) to the interior of the chamber.

[0010] The present invention provides a chamber cleaning method in which the perovskite compound includes a compound of CABX3 (wherein A is composed of a monovalent organic cation of the amine series compound or a monovalent organic cation of the amidine series compound, B is composed of the divalent cation, C is composed of at least one alkali metal, and X is composed of at least one halogen compound).

[0011] The present invention provides a chamber cleaning method, wherein the step of supplying a gas containing hexafluoroacetylacetone (Hhfac) includes the step of heating the chamber to 100°C or higher.

[0012] The present invention provides a chamber cleaning method, wherein the step of supplying a gas containing hexafluoroacetylacetone (Hhfac) includes a step of exposing the inside of the chamber to a gas plasma containing hexafluoroacetylacetone (Hhfac).

[0013] The present invention provides a chamber cleaning method further comprising a step of exposing the interior of the chamber to an oxygen (O) containing gas plasma.

[0014] The present invention provides a chamber cleaning method comprising a step of providing oxygen (O)-containing gas by plasma treatment after a step of exposing the interior of the chamber to hydrogen (H)-containing gas plasma.

[0015] The present invention provides a chamber cleaning method, wherein the perovskite compound comprises a compound of CBX3 (wherein B is composed of the divalent cation, X is composed of at least one halogen compound, and C is composed of at least one alkali metal).

[0016] The present invention provides a chamber cleaning method, wherein the step of supplying a gas containing hexafluoroacetylacetone (Hhfac) includes the step of heating the chamber to 100°C or higher.

[0017] The present invention provides a chamber cleaning method, wherein the step of supplying a gas containing hexafluoroacetylacetone (Hhfac) includes a step of exposing the inside of the chamber to a gas plasma containing hexafluoroacetylacetone (Hhfac).

[0018] The present invention provides a chamber cleaning method comprising: a step of exposing the interior of the chamber to a hydrogen (H)-containing gas plasma; and a step of exposing the interior of the chamber to an oxygen (O)-containing gas plasma, wherein after the step of exposing the interior of the chamber to the oxygen (O)-containing gas plasma, a step of exposing the interior of the chamber to a hydrogen (H)-containing gas plasma is performed.

[0019] The present invention provides a chamber cleaning method in which the perovskite compound includes a compound of ABX3 (wherein A is composed of a monovalent organic cation of the amine series compound or a monovalent organic cation of the amidine series compound, B is composed of the divalent cation, and X is at least one halogen compound).

[0020] The present invention provides a chamber cleaning method further comprising a step of supplying a gas containing hexafluoroacetylacetone (Hhfac) into the chamber.

[0021] The present invention provides a chamber cleaning method in which the perovskite compound includes a compound of CABX3 (wherein A is composed of a monovalent organic cation of the amine series compound or a monovalent organic cation of the amidine series compound, B is composed of the divalent cation, C is composed of at least one alkali metal, and X is composed of at least one halogen compound).

[0022] According to the present invention as described above, the following effects are achieved.

[0023] According to one embodiment of the present invention, since there is no need to separately disassemble or reassemble the chamber for cleaning, delays in the overall process can be prevented. In other words, by cleaning the chamber in situ without disassembling the chamber separately, the productivity of solar cells can be improved.

[0024] The effects of the present invention are not limited to the effects mentioned above, and other effects not mentioned will be clearly understood by those skilled in the art from the description below.

[0025] Figure 1 is a cross-sectional view of a solar cell according to one embodiment of the present invention.

[0026] FIG. 2a is a block diagram of a chamber cleaning method according to one embodiment of the present invention.

[0027] FIG. 2b is a block diagram of a chamber cleaning method according to another embodiment of the present invention.

[0028] FIG. 3 is a block diagram of a chamber cleaning method according to another embodiment of the present invention.

[0029] Figure 4 is a block diagram of a chamber cleaning method according to another embodiment of the present invention.

[0030] Figure 5 is a block diagram of a chamber cleaning method according to another embodiment of the present invention.

[0031] Figure 6 is a block diagram of a chamber cleaning method according to another embodiment of the present invention.

[0032] FIG. 7a is a block diagram of a chamber cleaning method according to another embodiment of the present invention.

[0033] FIG. 7b is a block diagram of a chamber cleaning method according to another embodiment of the present invention.

[0034] FIG. 8a is a block diagram of a chamber cleaning method according to another embodiment of the present invention.

[0035] FIG. 8b is a block diagram of a chamber cleaning method according to another embodiment of the present invention.

[0036] FIG. 9 is a schematic diagram of a chamber that is a target of a chamber cleaning method according to one embodiment of the present invention.

[0037] It can react with hydrogen (H) and change into a gaseous state. For example, the halogen material can be a material containing bromine (Br) or iodine (I), and when the halogen material reacts with hydrogen (H), hydrogen bromide (HBr) or hydrogen iodide (HI) can be formed. In this case, the hydrogen bromide (HBr) or hydrogen iodide (HI) can exist in a gaseous state under room temperature and pressure conditions.

[0038] Next, in the step (S150) of forming oxygen (O2) or ozone (O3) plasma inside the chamber, the remaining material after forming the perovskite thin film inside the vacuum chamber can be removed. Specifically, by forming a plasma containing oxygen (O) and exposing the inside of the chamber to the oxygen (O) containing gas plasma, at least one of the amine series compound or amidine series compound remaining inside the chamber or on the wall surface of the chamber after forming the perovskite thin film and the hydrocarbon (Hydro Carbon) formed by the reaction of some of the amine series compound or amidine series compound with hydrogen (H) generated after the step (S140) of forming hydrogen (H2) plasma inside the chamber can be removed.

[0039] More specifically, when the oxygen (O2) or ozone (O3) plasma is formed inside the vacuum chamber, the amine series compound or the amidine series compound remaining after the step of forming hydrogen (H2) plasma inside the chamber (S140) may react with the oxygen (O) to form carbon dioxide (Carbon Dioxide; CO2). For example, some of the methyl amine or formamidine remaining inside the vacuum chamber may react with the oxygen (O) by the oxygen (O2) or ozone (O3) plasma to change into carbon dioxide (CO2), ammonia gas (NH3), hydrogen (H2), nitrogen (N2), and moisture (H20).

[0040] Meanwhile, in the step (S140) of forming hydrogen (H2) plasma inside the chamber, the methyl amine or the formamidine (FromAmidine) reacted with hydrogen (H) remains inside the vacuum chamber in the form of hydrocarbon (Hydro Carbon), and the hydrocarbon (Hydro Carbon) remaining inside the vacuum chamber can react with oxygen (O) through the step (S150) of forming oxygen (O2) or ozone (O3) plasma inside the chamber to form carbon dioxide (CO2) and moisture (H2O).

[0041] According to one embodiment of the present invention, after the formation of a solar cell including a perovskite thin film containing ABX3, impurities remaining inside the vacuum chamber are removed in a gaseous state by the hydrogen (H2) plasma and the oxygen (O2) plasma, so that there is no need to separately disassemble or reassemble the chamber to clean it, thereby preventing a delay in the overall process. That is, by cleaning the chamber in situ without separately disassembling the chamber, the productivity of the solar cell can be improved.

[0042] Fig. 2b is a block diagram of a chamber cleaning method according to another embodiment of the present invention. Meanwhile, the embodiment of Fig. 2b is identical to the embodiment of Fig. 2a except for the order of the step (S160) of forming oxygen (O2) or ozone (O3) plasma inside the chamber and the step (S170) of forming hydrogen (H2) plasma inside the chamber. Therefore, the following description will focus on the different configurations.

[0043] As can be seen in FIG. 2b, a chamber cleaning method according to another embodiment of the present invention comprises a step of loading a substrate into a chamber (S110), a step of forming a perovskite thin film containing an ABX3 compound on the substrate (S120), a step of unloading the substrate from the chamber (S130), a step of forming oxygen (O2) or ozone (O3) plasma inside the chamber (S160), and a step of forming hydrogen (H2) plasma inside the chamber (S170).

[0044] According to another embodiment of the present invention, after the formation of a solar cell including a perovskite thin film containing ABX3, impurities remaining inside the vacuum chamber are removed in a gaseous state by the hydrogen (H2) plasma and the oxygen (O2) plasma, so that there is no need to separately disassemble or reassemble the chamber to clean it, thereby preventing a delay in the overall process. That is, by cleaning the chamber in situ without separately disassembling the chamber, the productivity of the solar cell can be improved.

[0045] Figure 3 is a block diagram of a chamber cleaning method according to another embodiment of the present invention.

[0046] As can be seen in FIG. 3, a chamber cleaning method according to an embodiment of the present invention includes a step of loading a substrate into a chamber (S210), a step of forming a perovskite thin film containing a CBX3 compound on the substrate (S220), a step of unloading the substrate from the chamber (S230), a step of forming hydrogen (H2) plasma inside the chamber (S241), and a step of supplying a gas containing hexafluoroacetylacetone (Hhfac) into the chamber (S242). Meanwhile, the step of loading the substrate into the chamber (S210) and the step of unloading the substrate from the chamber (S230) are the same as those of the above-described FIG. 2a, and therefore, a repeated description thereof will be omitted below.

[0047] In the step (S220) of forming a perovskite thin film containing a CBX3 compound on the substrate, a perovskite thin film containing a CBX3 compound can be formed on the substrate provided inside the vacuum chamber.

[0048] Since the above CBX3 compound is the same as that described above in FIG. 1, a repeated description will be omitted.

[0049] According to one embodiment of the present invention, in the CBX3 compound, C may be composed of at least one alkali metal. In this case, C may be, for example, a cesium (Cs) cation. In the CBX3 compound, B may be an organometallic compound containing lead (Pb), and further, X may be I a Br b , in which case a and b are greater than or equal to 0, and a+b=3.

[0050] According to one embodiment of the present invention, the CBX3 compound is, for example, CsPbI3, CsPbBr3 and CsPbBr a I b It can be composed of any one of the compounds.

[0051] By forming in this way, CsPbI3, CsPbBr3 and CsPbBr are formed on the substrate. a I b A perovskite thin film comprising any one of the compounds can be formed.

[0052] In the step (S241) of forming hydrogen (H2) plasma inside the chamber, a substance remaining after forming the perovskite thin film inside the vacuum chamber can be removed. Specifically, by forming a plasma containing hydrogen (H) and exposing the inside of the chamber to the hydrogen (H)-containing gas plasma, at least one of an organometallic compound containing a divalent cation and a halogen substance remaining inside the chamber or on the wall surface of the chamber after forming the perovskite thin film can be removed.

[0053] When the hydrogen (H2) plasma is formed inside the vacuum chamber, the organometallic compound containing the divalent cation remaining inside the chamber can react with the hydrogen (H) and change into a gaseous state. Next, when the hydrogen (H2) plasma is formed inside the vacuum chamber, the halogen material remaining inside the chamber can react with the hydrogen (H) and change into a gaseous state.

[0054] Meanwhile, the appearance of the organometallic compound containing the divalent cation and the halogen substance changing into a gas by the hydrogen (H2) plasma is the same as in Fig. 2a, so a repeated explanation will be omitted.

[0055] Next, in the step (S242) of supplying a gas containing hexafluoroacetylacetone (hereinafter referred to as Hhfac) into the chamber, the remaining material after forming the perovskite thin film inside the vacuum chamber can be removed. Specifically, by supplying a gas containing hexafluoroacetylacetone (Hhfac) into the chamber, at least one alkali metal remaining inside the chamber or on the wall surface of the chamber after forming the perovskite thin film can be removed.

[0056] Specifically, when a gas containing the hexafluoroacetylacetone (Hhfac) is supplied inside the vacuum chamber, at least one alkali metal remaining inside the chamber can be removed in the form of a gas of metal hexafluoroacetylacetonate (Mhfac, where M represents an alkali metal cation) by reacting with the gas containing the hexafluoroacetylacetone (Hhfac). For example, a cesium (Cs) cation remaining inside the vacuum chamber can react with the hexafluoroacetylacetone (Hhfac) and change into the form of cesium hexafluoroacetylacetonate (Cs(Hhfac)). In this case, the cesium hexafluoroacetylacetonate (Cs(Hhfac)) can exist in a gaseous state under room temperature and pressure conditions.

[0057] According to another embodiment of the present invention, in the step (S242) of supplying a gas containing hexafluoroacetylacetone (Hhfac) into the chamber, the inside of the chamber may be heated to a temperature of 100°C or higher after supplying the gas containing hexafluoroacetylacetone (Hhfac). In this case, the reactivity between the gas containing hexafluoroacetylacetone (Hhfac) and the alkali metal substance becomes excellent, so that the alkali metal substance inside the chamber can be removed more easily.

[0058] In addition, according to another embodiment of the present invention, in the step (S242) of supplying a gas containing hexafluoroacetylacetone (Hhfac) into the chamber, a plasma containing hexafluoroacetylacetone (Hhfac) may be formed to expose the inside of the chamber to the gas plasma containing hexafluoroacetylacetone (Hhfac). In this case, the reactivity between the gas containing hexafluoroacetylacetone (Hhfac) and the alkali metal substance becomes excellent, so that the alkali metal substance inside the chamber can be removed more easily.

[0059] Meanwhile, the present invention is not limited thereto, and in the step (S242) of supplying a gas containing hexafluoroacetylacetone (Hhfac) into the chamber, the gas containing hexafluoroacetylacetone (Hhfac) may be supplied into the chamber at a temperature of less than 100°C or without forming plasma.

[0060] According to one embodiment of the present invention, after the formation of a solar cell including a perovskite thin film containing CBX3, impurities remaining inside the vacuum chamber are removed in a gaseous state by the hydrogen (H2) plasma and the hexafluoroacetylacetone (Hhfac), so that there is no need to separately disassemble or reassemble the chamber to clean it, thereby preventing a delay in the overall process. That is, by cleaning the chamber in situ without separately disassembling the chamber, the productivity of the solar cell can be improved.

[0061] Fig. 4 is a block diagram of a chamber cleaning method according to another embodiment of the present invention. Meanwhile, the embodiment of Fig. 4 is identical to the embodiment of Fig. 3 except for the order of the step (S251) of supplying a gas containing hexafluoroacetylacetone (Hhfac) into the chamber and the step (S252) of forming hydrogen (H2) plasma inside the chamber. Therefore, the following description will focus on the different configurations.

[0062] As can be seen in FIG. 4, a chamber cleaning method according to one embodiment of the present invention comprises a step of loading a substrate into a chamber (S210), a step of forming a perovskite thin film containing a CBX3 compound on the substrate (S220), a step of unloading the substrate from the chamber (S230), a step of supplying a gas containing hexafluoroacetylacetone (Hhfac) into the chamber (S251), and a step of forming hydrogen (H2) plasma into the chamber (S252).

[0063] According to another embodiment of the present invention, the step (S251) of supplying a gas containing hexafluoroacetylacetone (Hhfac) into the chamber may be performed prior to the step (S252) of forming hydrogen (H2) plasma into the chamber.

[0064] Therefore, when the gas containing the hexafluoroacetylacetone (Hhfac) is supplied inside the vacuum chamber, at least one alkali metal remaining inside the chamber can be removed in the form of a gas of metal hexafluoroacetylacetonate (Mhfac, where M represents an alkali metal cation) by reacting with the gas containing the hexafluoroacetylacetone (Hhfac). Meanwhile, the appearance of the alkali metal being converted into a gas by the gas containing the hexafluoroacetylacetone (Hhfac) is the same as in Fig. 3, so a repeated description thereof will be omitted.

[0065] Next, a step (S252) of forming hydrogen (H2) plasma inside the chamber may be performed. In this case, the organometallic compound containing the divalent cation remaining inside the chamber may react with the hydrogen (H) and change into a gas by the hydrogen (H2) plasma, and the halogen material remaining inside the chamber may react with the hydrogen (H) and change into a gaseous state. Meanwhile, the appearance of the organometallic compound containing the divalent cation and the halogen material reacting with hydrogen (H) and changing into a gaseous state by the hydrogen (H2) plasma is the same as that described in FIG. 3, so a repeated description thereof will be omitted.

[0066] According to one embodiment of the present invention, after the formation of a solar cell including a perovskite thin film containing CBX3, impurities remaining inside the vacuum chamber are removed in a gaseous state by the hydrogen (H2) plasma and the hexafluoroacetylacetone (Hhfac), so that there is no need to separately disassemble or reassemble the chamber to clean it, thereby preventing a delay in the overall process. That is, by cleaning the chamber in situ without separately disassembling the chamber, the productivity of the solar cell can be improved.

[0067] Figure 5 is a block diagram of a chamber cleaning method according to another embodiment of the present invention.

[0068] As can be seen in FIG. 5, a chamber cleaning method according to an embodiment of the present invention includes a step of loading a substrate into a chamber (S310), a step of forming a perovskite thin film containing a CABX3 compound on the substrate (S320), a step of unloading the substrate from the chamber (S330), a step of forming hydrogen (H2) plasma inside the chamber (S341), a step of forming oxygen (O2) or ozone (O3) plasma inside the chamber (S342), and a step of supplying a gas containing hexafluoroacetylacetone (Hhfac) into the chamber (S343). Meanwhile, the step of loading the substrate into the chamber (S310) and the step of unloading the substrate from the chamber (S330) are the same as those of the above-described FIG. 2a, and therefore, a repeated description thereof will be omitted below.

[0069] In the step (S320) of forming a perovskite thin film containing a CABX3 compound on the substrate, a perovskite thin film containing a CABX3 compound can be formed on the substrate provided inside the vacuum chamber.

[0070] Since the above CABX3 compound is the same as that described above in Figure 1, a repeated description will be omitted.

[0071] According to one embodiment of the present invention, in the CABX3 compound, A may be any one of an amine series compound or an amidine series compound, for example, A may contain form amidine (FA) (Form Amidine; NH2CHNH), and C may be composed of at least one alkali metal. In this case, C may be, for example, a cesium (Cs) cation.

[0072] In addition, among the CBX3 compounds, B may be an organometallic compound containing lead (Pb), and X may be I a Br b, in which case a and b are greater than or equal to 0, and a+b=3.

[0073] According to one embodiment of the present invention, the CABX3 compound is, for example, CsFAPbI3, CsFAPbBr3 and CsFAPbBr a I b It can be composed of any one of the compounds.

[0074] By forming in this way, CsFAPbI3, CsFAPbBr3 and CsFAPbBr are formed on the substrate. a I b A perovskite thin film comprising any one of the compounds can be formed.

[0075] In the step (S341) of forming hydrogen (H2) plasma inside the chamber, a substance remaining after forming the perovskite thin film inside the vacuum chamber can be removed. Specifically, by forming a plasma containing hydrogen (H) and exposing the inside of the chamber to the hydrogen (H)-containing gas plasma, at least one of an amine series compound or an amidine series compound, an organometallic compound containing a divalent cation, and a halogen substance remaining inside the chamber or on the wall surface of the chamber after forming the perovskite thin film can be removed.

[0076] Meanwhile, the method for removing at least one of the amine series compound or amidine series compound, the organometallic compound containing a divalent cation, and the halogen substance by means of hydrogen (H2) plasma is the same as that of the case of FIG. 2a described above, so a repeated description will be omitted.

[0077] According to another embodiment of the present invention, through the step (S341) of forming hydrogen (H2) plasma inside the chamber, some of the amine series compounds or amidine series compounds remaining inside the chamber react with the hydrogen (H) to form hydrocarbons (Hydro Carbon), and other parts of the amine series compounds or amidine series compounds remaining inside the chamber remain inside the chamber, and the organometallic compound containing the divalent cation remaining inside the chamber can react with the hydrogen (H) to change into a gas, and the halogen material remaining inside the chamber can react with the hydrogen (H) to change into a gas.

[0078] In the step (S342) of forming oxygen (O2) or ozone (O3) plasma inside the chamber, a substance remaining after forming the perovskite thin film inside the vacuum chamber can be removed. Specifically, by forming a plasma containing oxygen (O) and exposing the inside of the chamber to the oxygen (O)-containing gas plasma, at least one of an amine-series compound or an amidine-series compound remaining inside the chamber or on the wall surface of the chamber after forming the perovskite thin film, a hydrocarbon (Hydro Carbon) formed by reacting some of the amine-series compound or amidine-series compound with hydrogen (H) generated after the step (S341) of forming hydrogen (H2) plasma inside the chamber, and at least one alkali metal can be removed.

[0079] Meanwhile, the method of forming oxygen (O2) plasma inside the chamber to remove the amine series compound or amidine series compound and the hydrocarbon is the same as in Fig. 2a, so a repeated description will be omitted.

[0080] According to another embodiment of the present invention, by forming a plasma containing oxygen (O) inside the chamber, a metal oxide may be formed by reacting with a portion of at least one alkali metal remaining inside the chamber. For example, the at least one alkali metal may be cesium (Cs), and the cesium (Cs) may react with the oxygen (O) to form cesium oxide (Cs2O). Meanwhile, the remaining cesium (Cs) that has not reacted with the oxygen (O) may remain inside the chamber as is.

[0081] Next, in the step (S343) of supplying a gas containing the hexafluoroacetylacetone (Hhfac) into the chamber, any remaining material after forming the perovskite thin film inside the vacuum chamber can be removed. Meanwhile, the appearance of the alkali metal turning into a gas by the gas containing the hexafluoroacetylacetone (Hhfac) is the same as in Fig. 3, so a repeated explanation will be omitted.

[0082] According to another embodiment of the present invention, the metal oxide formed through the step (S342) of forming oxygen (O2) or ozone (O3) plasma inside the chamber can be removed by reacting with a gas containing hexafluoroacetylacetone (Hhfac). For example, cesium oxide (Cs2O) remaining inside the chamber can react with hexafluoroacetylacetone (Hhfac) to form cesium hexafluoroacetylacetonate (Cs(hfac)). In this case, the cesium hexafluoroacetylacetonate (Cs(hfac)) can exist in a gaseous state.

[0083] According to one embodiment of the present invention, after forming a solar cell including a perovskite thin film containing CABX3, impurities remaining inside the vacuum chamber are removed in a gaseous state by the hydrogen (H2) plasma, the oxygen (O2) plasma, and the hexafluoroacetylacetone (Hhfac), so that there is no need to separately disassemble or reassemble the chamber to clean it, thereby preventing a delay in the overall process. That is, by cleaning the chamber in situ without separately disassembling the chamber, the productivity of the solar cell can be improved.

[0084] Figure 6 is a block diagram of a chamber cleaning method according to another embodiment of the present invention.

[0085] Meanwhile, the embodiment of FIG. 6 is identical to the embodiment of FIG. 5 except for the order of the step (S352) of supplying a gas containing hexafluoroacetylacetone (Hhfac) into the chamber and the step (S353) of forming oxygen (O2) plasma into the chamber, so the following description will focus on the different configuration.

[0086] As can be seen in FIG. 6, a chamber cleaning method according to an embodiment of the present invention comprises a step of loading a substrate into a chamber (S310), a step of forming a perovskite thin film containing a CABX3 compound on the substrate (S320), a step of unloading the substrate from the chamber (S330), a step of forming hydrogen (H2) plasma inside the chamber (S351), a step of supplying a gas containing hexafluoroacetylacetone (Hhfac) inside the chamber (S352), and a step of forming oxygen (O2) or ozone (O3) plasma inside the chamber (S353).

[0087] According to another embodiment of the present invention, the step (S352) of supplying a gas containing hexafluoroacetylacetone (Hhfac) into the chamber may be performed prior to the step (S353) of forming oxygen (O2) plasma into the chamber.

[0088] Therefore, in the step (S352) of supplying a gas containing hexafluoroacetylacetone (Hhfac) into the chamber, at least one alkali metal remaining inside the chamber can react with the gas containing hexafluoroacetylacetone (Hhfac) to be removed in the form of a gas of metal hexafluoroacetylacetonate (Mhfac, where M represents an alkali metal cation). For example, a cesium (Cs) cation remaining inside the vacuum chamber can react with the hexafluoroacetylacetone (Hhfac) to form cesium hexafluoroacetylacetonate (Cs(hfac)). In this case, the cesium hexafluoroacetylacetonate (Cs(hfac)) can exist in a gaseous state.

[0089] Next, a step (S353) of forming oxygen (O2) plasma inside the chamber may be performed. In this case, by the oxygen (O2) plasma, any one of the amine series compound or the amidine series compound remaining inside the chamber and the hydrocarbon (Hydro Carbon) formed from some of the amine series compound or the amidine series compound after the step (S351) of forming hydrogen (H2) plasma inside the chamber can be removed. Meanwhile, the appearance of the amine series compound or the amidine series compound and the hydrocarbon (Hydro Carbon) formed from the amine series compound or the amidine series compound reacting with oxygen (O) and changing into a gaseous state by the oxygen (O2) plasma is the same as that described in FIG. 4, so a repeated description thereof will be omitted.

[0090] According to one embodiment of the present invention, after forming a solar cell including a perovskite thin film containing CABX3, impurities remaining inside the vacuum chamber are removed in a gaseous state by the hydrogen (H2) plasma, the oxygen (O2) plasma, and the hexafluoroacetylacetone (Hhfac), so that there is no need to separately disassemble or reassemble the chamber to clean it, thereby preventing a delay in the overall process. That is, by cleaning the chamber in situ without separately disassembling the chamber, the productivity of the solar cell can be improved.

[0091] FIG. 7a is a block diagram of a chamber cleaning method according to another embodiment of the present invention.

[0092] Meanwhile, the embodiment of FIG. 7a is the same as the embodiment of FIG. 5 except for the order of the step (S361) of supplying a gas containing hexafluoroacetylacetone (Hhfac) into the chamber, the step (S362) of forming hydrogen (H2) plasma into the chamber, and the step (S363) of forming oxygen (O2) plasma into the chamber, so the following description will focus on the different configurations.

[0093] As can be seen in FIG. 7a, a chamber cleaning method according to an embodiment of the present invention comprises a step of loading a substrate into a chamber (S310), a step of forming a perovskite thin film containing a CABX3 compound on the substrate (S320), a step of unloading the substrate from the chamber (S330), a step of supplying a gas containing hexafluoroacetylacetone (Hhfac) into the chamber (S361), a step of forming hydrogen (H2) plasma into the chamber (S362), and a step of forming oxygen (O2) or ozone (O3) plasma into the chamber (S363).

[0094] According to another embodiment of the present invention, the step (S361) of supplying a gas containing hexafluoroacetylacetone (Hhfac) into the chamber may be performed prior to the step (362) of forming hydrogen (H2) plasma into the chamber and the step (S363) of forming oxygen (O2) plasma into the chamber.

[0095] According to one embodiment of the present invention, after forming a solar cell including a perovskite thin film containing CABX3, impurities remaining inside the vacuum chamber are removed in a gaseous state by the hydrogen (H2) plasma, the oxygen (O2) plasma, and the hexafluoroacetylacetone (Hhfac), so that there is no need to separately disassemble or reassemble the chamber to clean it, thereby preventing a delay in the overall process. That is, by cleaning the chamber in situ without separately disassembling the chamber, the productivity of the solar cell can be improved.

[0096] Fig. 7b is a block diagram of a chamber cleaning method according to another embodiment of the present invention. Meanwhile, the embodiment of Fig. 7b is identical to the embodiment of Fig. 7a except for the order of the step (S372) of forming oxygen (O2) or ozone (O3) plasma inside the chamber and the step (S373) of forming hydrogen (H2) plasma inside the chamber. Therefore, the following description will focus on the different configurations.

[0097] As can be seen in FIG. 7b, a chamber cleaning method according to an embodiment of the present invention comprises a step of loading a substrate into a chamber (S310), a step of forming a perovskite thin film containing a CABX3 compound on the substrate (S320), a step of unloading the substrate from the chamber (S330), a step of supplying a gas containing hexafluoroacetylacetone (Hhfac) into the chamber (S371), a step of forming oxygen (O2) or ozone (O3) plasma into the chamber (S372), and a step of forming hydrogen (H2) plasma into the chamber (S373).

[0098] According to one embodiment of the present invention, after forming a solar cell including a perovskite thin film containing CABX3, impurities remaining inside the vacuum chamber are removed in a gaseous state by the hydrogen (H2) plasma, the oxygen (O2) plasma, and the hexafluoroacetylacetone (Hhfac), so that there is no need to separately disassemble or reassemble the chamber to clean it, thereby preventing a delay in the overall process. That is, by cleaning the chamber in situ without separately disassembling the chamber, the productivity of the solar cell can be improved.

[0099] Fig. 8a is a block diagram of a chamber cleaning method according to another embodiment of the present invention. Meanwhile, the embodiment of Fig. 8a is identical to the embodiment of Fig. 7a except for the order of the step (S381) of forming oxygen (O2) or ozone (O3) plasma inside the chamber, the step (S382) of forming hydrogen (H2) plasma inside the chamber, and the step (S383) of supplying a gas containing hexafluoroacetylacetone (Hhfac) inside the chamber. Therefore, the following description will focus on the different configurations.

[0100] As can be seen in FIG. 8a, a chamber cleaning method according to an embodiment of the present invention comprises a step of loading a substrate into a chamber (S310), a step of forming a perovskite thin film containing a CABX3 compound on the substrate (S320), a step of unloading the substrate from the chamber (S330), a step of forming oxygen (O2) or ozone (O3) plasma inside the chamber (S381), a step of forming hydrogen (H2) plasma inside the chamber (S382), and a step of supplying a gas containing hexafluoroacetylacetone (Hhfac) inside the chamber (S383).

[0101] According to one embodiment of the present invention, after forming a solar cell including a perovskite thin film containing CABX3, impurities remaining inside the vacuum chamber are removed in a gaseous state by the hydrogen (H2) plasma, the oxygen (O2) plasma, and the hexafluoroacetylacetone (Hhfac), so that there is no need to separately disassemble or reassemble the chamber to clean it, thereby preventing a delay in the overall process. That is, by cleaning the chamber in situ without separately disassembling the chamber, the productivity of the solar cell can be improved.

[0102] FIG. 8b is a block diagram of a chamber cleaning method according to another embodiment of the present invention.

[0103] Meanwhile, the embodiment of FIG. 8b is identical to the embodiment of FIG. 8a except for the order of the step (S392) of supplying a gas containing hexafluoroacetylacetone (Hhfac) into the chamber and the step (S393) of forming hydrogen (H2) plasma into the chamber, so the following description will focus on the different configurations.

[0104] As can be seen in FIG. 8b, a chamber cleaning method according to an embodiment of the present invention comprises a step of loading a substrate into a chamber (S310), a step of forming a perovskite thin film containing a CABX3 compound on the substrate (S320), a step of unloading the substrate from the chamber (S330), a step of forming oxygen (O2) or ozone (O3) plasma inside the chamber (S391), a step of supplying a gas containing hexafluoroacetylacetone (Hhfac) inside the chamber (S392), and a step of forming hydrogen (H2) plasma inside the chamber (S393).

[0105] According to one embodiment of the present invention, after forming a solar cell including a perovskite thin film containing CABX3, impurities remaining inside the vacuum chamber are removed in a gaseous state by the hydrogen (H2) plasma, the oxygen (O2) plasma, and the hexafluoroacetylacetone (Hhfac), so that there is no need to separately disassemble or reassemble the chamber to clean it, thereby preventing a delay in the overall process. That is, by cleaning the chamber in situ without separately disassembling the chamber, the productivity of the solar cell can be improved.

[0106] FIG. 9 is a schematic diagram of a chamber that is a target of a chamber cleaning method according to one embodiment of the present invention.

[0107] A solar cell deposition device according to one embodiment of the present invention is a device for forming the aforementioned perovskite compound layer on a substrate (W). The substrate (W) may be formed of a semiconductor substrate.

[0108] As can be seen in Fig. 9, a solar cell deposition device according to one embodiment of the present invention comprises a chamber (10), a chamber lid (20), a support (30), a gas injection unit (40), and a gas supply unit (50a, 50b, 50c, 50d).

[0109] The above chamber (10) provides a reaction space for the deposition process.

[0110] An exhaust port (12) for exhausting the reaction space may be provided on one side of the bottom surface of the chamber (10).

[0111] The above chamber lid (20) is installed at the top of the chamber (10) to seal the reaction space.

[0112] The above chamber lid (20) can be connected to a gas supply unit (50a, 50b, 50c, 50d) that supplies gas for the deposition process.

[0113] The above support (30) is installed inside the chamber (10) and supports a substrate (W) loaded from the outside. The support (30) is connected to a lifting unit (32) and can be raised and lowered by the lifting unit (32).

[0114] The gas injection unit (40) may be installed at the lower portion of the chamber lid (20) while facing the support (30). A gas diffusion space (42) may be formed between the gas injection unit (40) and the chamber lid (20), in which gas supplied from a gas supply unit (50a, 50b, 50c, 50d) penetrating the chamber lid (20) is diffused.

[0115] The above gas injection unit (40) can uniformly inject gas supplied from the gas supply unit (50a, 50b, 50c, 50d) to the entire reaction space through a plurality of gas injection ports (44) connected to the gas diffusion space (42).

[0116] The above gas supply units (50a, 50b, 50c, 50d) may include a first gas supply unit (50a) for supplying the alkali metal (C) of the aforementioned FIG. 1, a second gas supply unit (50b) for supplying an amine-based organic compound or an amidine-based organic compound (A), a third gas supply unit (50c) for supplying an organometallic compound (B) containing a divalent cation, and a fourth gas supply unit (50d) for supplying a halogen substance (X). The first to fourth gas supply units (50a) to (50d) may each be formed of individual pipes, and the individual pipes may be combined into one and connected to the chamber lid (20), but this is not necessarily limited thereto, and each individual pipe may not be combined into one and may be connected to the chamber lid (20).

[0117] Although the embodiments of the present invention have been described in more detail with reference to the attached drawings, the present invention is not necessarily limited to these embodiments, and various modifications may be implemented without departing from the technical spirit of the present invention. Therefore, the embodiments disclosed in the present invention are not intended to limit the technical spirit of the present invention, but to explain it, and the scope of the technical spirit of the present invention is not limited by these embodiments. Therefore, it should be understood that the embodiments described above are illustrative in all aspects and not restrictive. The protection scope of the present invention should be interpreted by the claims, and all technical ideas within a scope equivalent thereto should be interpreted as being included in the scope of the rights of the present invention.

Claims

1. A method for cleaning a chamber for forming a perovskite compound, A step of exposing the inside of the chamber to a hydrogen (H) containing gas plasma; and A step of exposing the inside of the chamber to an oxygen (O) containing gas plasma is included, A chamber cleaning method comprising: exposing the interior of the chamber to a hydrogen (H)-containing gas plasma; and then exposing the interior of the chamber to an oxygen (O)-containing gas plasma.

2. In paragraph 1, A chamber cleaning method wherein the perovskite compound comprises a compound of ABX3 (wherein A is composed of a monovalent organic cation of the amine series compound or a monovalent organic cation of the amidine series compound, B is composed of the divalent cation, and X is at least one halogen compound).

3. In a method for cleaning a chamber for forming a perovskite compound, A step of exposing the inside of the chamber to a hydrogen (H) containing gas plasma; and A chamber cleaning method comprising a step of supplying a gas containing hexafluoroacetylacetone (Hhfac) into the chamber.

4. In paragraph 3, A chamber cleaning method wherein the perovskite compound comprises a compound of CABX3 (wherein A is composed of a monovalent organic cation of the amine series compound or a monovalent organic cation of the amidine series compound, B is composed of the divalent cation, C is composed of at least one alkali metal, and X is composed of at least one halogen compound).

5. In paragraph 4, A chamber cleaning method, wherein the step of supplying a gas containing hexafluoroacetylacetone (Hhfac) includes a step of heating the chamber to 100°C or higher.

6. In paragraph 4, A chamber cleaning method, wherein the step of supplying a gas containing hexafluoroacetylacetone (Hhfac) includes a step of exposing the inside of the chamber to a gas plasma containing hexafluoroacetylacetone (Hhfac).

7. In paragraph 4, A chamber cleaning method further comprising a step of exposing the interior of the chamber to an oxygen (O) containing gas plasma.

8. In paragraph 7, A chamber cleaning method comprising: a step of exposing the inside of the chamber to a hydrogen (H)-containing gas plasma; and a step of providing the oxygen (O)-containing gas by plasma treatment.

9. In paragraph 3, A chamber cleaning method wherein the perovskite compound comprises a compound of CBX3 (wherein B is composed of the divalent cation, X is composed of at least one halogen compound, and C is composed of at least one alkali metal).

10. In paragraph 9, A chamber cleaning method, wherein the step of supplying a gas containing hexafluoroacetylacetone (Hhfac) includes a step of heating the chamber to 100°C or higher.

11. In paragraph 9, A chamber cleaning method, wherein the step of supplying a gas containing hexafluoroacetylacetone (Hhfac) includes a step of exposing the inside of the chamber to a gas plasma containing hexafluoroacetylacetone (Hhfac).

12. A method for cleaning a chamber for forming a perovskite compound, A step of exposing the inside of the chamber to a hydrogen (H) containing gas plasma; and A step of exposing the inside of the chamber to an oxygen (O) containing gas plasma is included, A chamber cleaning method comprising: exposing the interior of the chamber to a gas plasma containing hydrogen (H) after the step of exposing the interior of the chamber to a gas plasma containing oxygen (O).

13. In paragraph 12, A chamber cleaning method wherein the perovskite compound comprises a compound of ABX3 (wherein A is composed of a monovalent organic cation of the amine series compound or a monovalent organic cation of the amidine series compound, B is composed of the divalent cation, and X is at least one halogen compound).

14. In paragraph 12, A chamber cleaning method further comprising a step of supplying a gas containing hexafluoroacetylacetone (Hhfac) into the chamber.

15. In paragraph 14, A chamber cleaning method wherein the perovskite compound comprises a compound of CABX3 (wherein A is composed of a monovalent organic cation of the amine series compound or a monovalent organic cation of the amidine series compound, B is composed of the divalent cation, C is composed of at least one alkali metal, and X is composed of at least one halogen compound).

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