KR20240082669A - Perovskite solar cell and Method of manufacturing the same and Apparatus of manufacturing the same - Google Patents

Abstract

The present invention includes forming a first charge transport layer on a substrate; forming a photoelectric conversion layer including a perovskite compound on the first charge transfer layer; and forming a second charge transport layer on the photoelectric conversion layer, wherein forming the second charge transport layer includes forming a fullerene or fullerene derivative layer on the photoelectric conversion layer and the fullerene or A process comprising forming an interface layer on a fullerene derivative layer, wherein the process of forming the fullerene or fullerene derivative layer and the process of forming the interface layer are performed in-situ within the same deposition equipment. A battery manufacturing method is provided.

Description

Perovskite solar cell and method of manufacturing the same and manufacturing equipment {Perovskite solar cell and Method of manufacturing the same and Apparatus of manufacturing the same}

The present invention relates to perovskite solar cells, methods for manufacturing them, and equipment for manufacturing them.

A perovskite solar cell includes a photoelectric conversion layer containing a perovskite compound, an electron transport layer provided on one side of the photoelectric conversion layer, and a hole transport layer provided on the other side of the photoelectric conversion layer.

The electron transport layer includes an organic material layer, and in this case, the organic material layer was laminated using an evaporation method.

In the evaporation method, in a state where the container containing the lamination object is placed on the lower side and the substrate is disposed on the upper side, the container is heated to evaporate the lamination object to form a desired thin film on the lower surface of the substrate disposed on the upper side. This is a layering method.

Therefore, in order to perform the evaporation method, a process of turning over the substrate is required, and after performing the evaporation method, the substrate must be turned over to its original state in order to perform the subsequent process. As such, the conventional method has the disadvantage of requiring a process of flipping the substrate, making the process complicated.

The present invention was designed to solve the above-described conventional problems, and the present invention provides a solar cell manufacturing method and manufacturing equipment capable of layering organic materials by a top-down deposition method without using an evaporation method, and a solar cell manufactured thereby. The purpose is to

In order to achieve the above object, the present invention includes forming a first charge transfer layer on a substrate; forming a photoelectric conversion layer including a perovskite compound on the first charge transfer layer; and forming a second charge transport layer on the photoelectric conversion layer, wherein forming the second charge transport layer includes forming a fullerene or fullerene derivative layer on the photoelectric conversion layer and the fullerene or A process comprising forming an interface layer on a fullerene derivative layer, wherein the process of forming the fullerene or fullerene derivative layer and the process of forming the interface layer are performed in-situ within the same deposition equipment. A battery manufacturing method is provided.

The fullerene or fullerene derivative layer may include C60 or PCBM, and the interface layer may include LiF.

The process of forming the fullerene or fullerene derivative layer may be performed through a top-down CVD process, and the process of forming the interface layer may be performed through a top-down ALD process.

Forming the second charge transfer layer may further include forming a metal oxide layer on the interface layer.

Forming the second charge transfer layer may further include forming a metal nitride layer between the interface layer and the metal oxide layer.

The metal oxide layer may include SnO or ZnO, and the metal nitride layer may include SnN or ZnN.

The process of forming the fullerene or fullerene derivative layer includes supplying a carrier gas through a carrier gas line to supply the source material stored in the source material storage container to a shower head provided at the top of the chamber through the source material transfer line. In this case, the internal temperature of the source material transfer line may be higher than the internal temperature of the source material storage container, and the internal temperature of the shower head may be maintained higher than the internal temperature of the source material transfer line.

The present invention also provides a substrate; a first charge transfer layer provided on the substrate; A photoelectric conversion layer including a perovskite compound provided on the first charge transfer layer; and a second charge transfer layer on the photoelectric conversion layer, wherein the second charge transfer layer includes a fullerene or fullerene derivative layer provided on the photoelectric conversion layer, and an interface provided on the fullerene or fullerene derivative layer. A solar cell comprising a layer and a metal oxide layer provided on the interface layer is provided.

The fullerene or fullerene derivative layer may include C60 or PCBM, the interface layer may include LiF, and the metal oxide layer may include SnO or ZnO.

A metal nitride layer may be additionally provided between the interface layer and the metal oxide layer.

The present invention also provides a chamber; a showerhead provided above the chamber; A susceptor provided below within the chamber; a heating device provided within the showerhead; RF power connected to the showerhead; a source material transfer line connected to the showerhead; a source material storage vessel connected to the source material transfer line; and a carrier gas line connected to the source material storage container, wherein by operation of the heating device, the temperature inside the showerhead is adjusted to the internal temperature of each of the source material transfer line, the source material storage container, and the carrier gas line. Provides deposition equipment maintained at higher temperatures.

The temperature of the source material transfer line may be maintained at a higher temperature than the internal temperature of each of the source material storage vessel and the carrier gas line.

The present invention also provides a transfer device; and a loading/unloading unit, a first deposition equipment, a second deposition equipment, a third deposition equipment, a fourth deposition equipment, and a fifth deposition equipment arranged radially around the transfer device, 1 The deposition equipment is equipped to perform a CVD or ALD process to form a first charge transfer layer, the second deposition equipment is equipped to perform a CVD or ALD process to form a photoelectric conversion layer, and the third deposition equipment is equipped to perform a CVD or ALD process to form a photoelectric conversion layer. It is equipped to perform a CVD or ALD process to deposit a fullerene or fullerene derivative layer and an interface layer in-situ, and the fourth deposition equipment is equipped to perform a CVD or ALD process to form a metal oxide layer. The fifth deposition equipment is equipped to perform a CVD or ALD process for forming a transparent conductive layer, and the third deposition equipment provides solar cell manufacturing equipment consisting of the above-described deposition equipment.

The present invention also provides a crystalline solar cell; A buffer layer provided on the crystalline solar cell; and a perovskite solar cell provided on the buffer layer, wherein the perovskite solar cell provides a tandem solar cell composed of the above-described solar cells.

The present invention also provides a process for forming a crystalline solar cell; A process of forming a buffer layer on the crystalline solar cell; and a step of forming a perovskite solar cell on the buffer layer, wherein the step of forming the perovskite solar cell includes the above-described manufacturing method.

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

According to one embodiment of the present invention, since the first charge transfer layer, the photoelectric conversion layer, the second charge transfer layer, and the transparent conductive layer can be formed using a top-down deposition method, the process of turning over the substrate is not necessary, so The process is simpler compared to .

According to one embodiment of the present invention, the second charge transfer layer includes a fullerene or fullerene derivative layer, an interface layer, and a metal oxide layer, and in this case, the fullerene or fullerene derivative layer and the interface layer are deposited in the same deposition equipment. The process can be simpler because it can be laminated in a continuous (in-situ) process.

According to one embodiment of the present invention, the internal temperature of the source material transfer line is higher than the internal temperature of the source material storage container, and the internal temperature of the shower head can be maintained higher than the internal temperature of the source material transfer line, so that the moving Condensation of gas can be prevented.

According to another embodiment of the present invention, by additionally forming a metal nitride layer between the interface layer and the metal oxide layer, the perovskite compound constituting the photoelectric conversion layer can be prevented from being oxidized when forming the metal oxide layer. there is.

1A to 1E are diagrams showing the manufacturing process of a perovskite solar cell according to an embodiment of the present invention.
Figure 2 shows solar cell manufacturing equipment according to an embodiment of the present invention.
Figure 3 is a solar cell manufacturing system according to an embodiment of the present invention.
4A to 4E are diagrams showing the manufacturing process of a solar cell according to another embodiment of the present invention.

The advantages and features of the present invention and methods for achieving them will become clear by referring to the embodiments described in detail below along with the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below and will be implemented in various different forms. These embodiments only serve to ensure that the disclosure of the present invention is complete and that common knowledge in the technical field to which the present invention pertains is not limited. It is provided to fully inform those who have the scope of the invention, and the present invention is only defined by the scope of the claims.

The shape, size, ratio, angle, number, etc. shown in the drawings for explaining embodiments of the present invention are illustrative, and the present invention is not limited to the details shown. Like reference numerals refer to like elements throughout the specification. Additionally, in describing the present invention, if it is determined that a detailed description of related known technologies may unnecessarily obscure the gist of the present invention, the detailed description will be omitted. When 'includes', 'has', 'consists of', etc. mentioned in this specification are used, other parts may be added unless 'only' is used. In cases where a component is expressed in the singular, the plural is included unless specifically stated otherwise.

When interpreting a component, it is interpreted to include the margin of error even if there is no separate explicit description.

In the case of a description of a positional relationship, for example, if the positional relationship of two parts is described as 'on top', 'on the top', 'on the bottom', 'next to', etc., 'immediately' Alternatively, there may be one or more other parts placed between the two parts, unless 'directly' is used.

In the case of a description of a temporal relationship, for example, if a temporal relationship is described as 'after', 'successfully after', 'after', 'before', etc., 'immediately' or 'directly' Unless used, non-consecutive cases may also be included.

Although first, second, etc. are used to describe various components, these components are not limited by these terms. These terms are merely used to distinguish one component from another. Accordingly, the first component mentioned below may also be the second component within the technical spirit of the present invention.

Each feature of the various embodiments of the present invention can be combined or combined with each other partially or entirely, and various technical interconnections and operations are possible, and each embodiment can be implemented independently of each other or together in a related relationship. It may be possible.

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

1A to 1E are diagrams showing the manufacturing process of a perovskite solar cell according to an embodiment of the present invention.

First, as can be seen in FIG. 1A, a first electrode 20 is formed on the substrate 10, a first charge transfer layer 30 is formed on the first electrode 20, and the first charge A photoelectric conversion layer 40 is formed on the transmission layer 30.

The substrate 10 may be made of a material known in the art, such as glass or plastic.

The first electrode 20 may be made of a conductive oxide such as ITO, but is not necessarily limited thereto. The first electrode 20 may be formed through a deposition process such as CVD (Chemical Vapor Deposition) or ALD (Atomic Layer Deposition).

The first charge transfer layer 30 may be made of a hole transport layer. The hole transport layer is Spiro-MeO-TAD, Spiro-TTB, polyaniline, polypinol, poly-3,4-ethylenedioxythiophene-polystyrenesulfonate (PEDOT-PSS), or poly-[bis(4-phenyl) (2,4,6-trimethylphenyl)amine] (PTAA), Poly (3-hexylthiophene-2,5-diyl) (P3HT), various P-type organic substances known in the art, Ni oxide, Mo oxide or It may include various P-type metal oxides known in the art, such as V oxide, W oxide, Cu oxide, etc., and various other P-type organic or inorganic substances known in the art. The first charge transfer layer 30 may be formed through a deposition process such as CVD (Chemical Vapor Deposition) or ALD (Atomic Layer Deposition).

The photoelectric conversion layer 40 is made of a perovskite compound.

The perovskite compound includes at least one compound selected from amine-based compounds and amidine-based compounds, an organometallic compound containing a divalent cation, and at least one hydrogen halide through CVD (Chemical Vapor Deposition) or ALD (Atomic Layer). It can be obtained through a process of depositing and forming a compound of ABX ₃ by reacting through a (deposition) process.

In ABX ₃ , A may be composed of a monovalent organic cation of the amine-based compound, or may be composed of a monovalent organic cation of the amidine-based compound, and the monovalent organic cation of the amine-based compound and the amidine It may also include a monovalent organic cation of a series compound. The A may have a structure in which the monovalent organic cations of the amine-based compound are included in an x ratio and the monovalent organic cations of the amidine-based compound are included in a y ratio. At this time, x and y are each greater than 0, and x+y=1.

In the ABX ₃ , the B consists of the divalent cation.

In ABX ₃ , X consists of at least one halogen compound.

The amine-based compound may be selected from the group consisting of methylamine, ethylamine, and phenethylamine.

The amidine-based compound may consist of formamidine.

The organometallic compound containing the divalent cation may include a metal selected from the group consisting of Pb, Sn, Ge, Sb, Bi, and Ba.

Specifically, the organometallic compound containing the divalent cation has the following Chemical Formula 1:

Formula 1

(In Formula 1, R ¹ to R ¹² are each independently hydrogen or an alkyl group, and X is selected from the group consisting of Pb, Sn, Ge, Sb, Bi, and Ba)

It may be composed of a compound expressed as .

Alternatively, the organometallic compound containing the divalent cation is Pb(CH ₃ ) ₄ , Pb(C ₂ H ₅ ) ₄ , Pb(SCN) ₂ , (C ₂ H ₅ ) ₃ PbOCH ₂ C(CH ₃ ) ₃ , Pb(C ₁₁ H ₁₉ O ₂ ) ₂ , Pb((CH ₃ ) ₃ C-COCHCO-C(CH ₃ ) ₃ ) ₂ , Pb((C ₆ H ₅ ) ₂ PCH ₂ P(C ₆ H ₅ ) ₂ ) ₂ , Pb(N(CH ₃ ) ₂ C(CH ₃ ) ₂ OH) ₂ , and C ₁₂ H ₂₈ N ₂ O ₂ Pb.

Depending on the type of the organometallic compound containing the divalent cation, the light absorption rate, band gap, carrier mobility, and material stability of the finally obtained perovskite compound can be adjusted.

The hydrogen halide may be selected from the group consisting of HI, HBr, Hf, and HCl. The band gap of the final perovskite compound can be adjusted depending on the type of hydrogen halide.

The amine-based compound, the amidine-based compound, the organometallic compound containing the divalent cation, and the hydrogen halide are made of a material that vaporizes at a temperature in the range of room temperature to 200°C, preferably 50°C to 150°C. It is made of materials that vaporize at a range of temperatures. Accordingly, the process for producing the compound of ABX ₃ can be performed through a chemical vapor deposition (CVD) process or atomic layer deposition (ALD) at a temperature of 200 ℃ or lower, preferably 150 ℃ or lower. This can prevent organic substances in the final ABX ₃ compound from being decomposed during the CVD or ALD process. Meanwhile, it is also possible to apply plasma when performing the CVD or ALD process.

According to another embodiment of the present invention, the perovskite compound is at least one compound selected from amine-based compounds and amidine-based compounds, at least one alkali metal-based compound, an organometallic compound containing a divalent cation, and It can be obtained through a process of reacting hydrogen halide through a CVD (Chemical Vapor Deposition) or ALD (Atomic Layer Deposition) process to deposit and form a compound of CABX ₃ .

In CABX ₃ , A may be composed of a monovalent organic cation of the amine-based compound, may be composed of a monovalent organic cation of the amidine-based compound, or may be composed of a monovalent organic cation of the amine-based compound and the amine It may also include a monovalent organic cation of a Dean-based compound.

In CABX ₃ , C may be made of at least one alkali metal.

The CA has a structure in which the monovalent organic cations of the amine-based compound are contained in an x ratio, the monovalent organic cations of the amidine-based compound are contained in a y ratio, and the monovalent cations of the alkali metal are contained in a z ratio. It can be done. At this time, x, y, and z are each greater than 0, and x+y+z=1.

In CABX ₃ , B consists of the divalent cation, and X consists of at least one halogen compound.

Since the amine-based compound, the amidine-based compound, the organometallic compound containing a divalent cation, and the hydrogen halide are the same as described above, repeated description will be omitted.

The alkali metal-based compound has the following formula 2:

Formula 2

(In Formula 2, R ¹ to R ⁶ are each independently hydrogen or an alkyl group, and Y is an alkali metal)

It may be composed of a compound expressed as .

According to another embodiment of the present invention, the instability of monovalent organic cations, which are vulnerable to moisture, heat, and plasma, can be compensated for by adding at least one alkali metal-based compound to the reactant.

Next, as can be seen in FIG. 1B, a fullerene or fullerene derivative layer 51 is formed on the photoelectric conversion layer 40, and an interface layer is formed on the fullerene or fullerene derivative layer 51. It forms (52).

The fullerene or fullerene derivative layer 51 may include C60 or PCBM (Phenyl-C61-butyric acid methyl ester). The fullerene or fullerene derivative layer 51 may be formed through a deposition process using top-down deposition equipment, such as a CVD process, as shown in FIG. 2, which will be described later.

The interface layer 52 may include LiF. The interface layer 52 may be formed through a deposition process such as ALD (Atomic Layer Deposition), and in this case, plasma may be formed using an RF plasma device.

The fullerene or fullerene derivative layer 51 and the interface layer 52 may be formed in a continuous process (in-situ) within the same deposition equipment, particularly, the same top-down deposition equipment. That is, the fullerene or fullerene derivative layer 51 can be formed in the same top-down deposition equipment, and then the interface layer 52 can be formed through an ALD process.

Next, as can be seen in FIG. 1C, a metal oxide layer 53 is formed on the interface layer 52. Then, a second charge transfer layer 50 consisting of the fullerene or fullerene derivative layer 51, the interface layer 52, and the metal oxide layer 53 can be formed. . The second charge transfer layer 50 may be made of an electron transport layer.

The metal oxide layer 53 may be made of SnO or ZnO, but is not necessarily limited thereto. The metal oxide layer 53 may be formed through a deposition process such as CVD (Chemical Vapor Deposition) or ALD (Atomic Layer Deposition).

Although not shown, a metal nitride layer may be additionally formed below the metal oxide layer 53. The metal nitride layer may include the same metal as the metal oxide layer. For example, the metal nitride layer may be made of SnN or ZnN. By positioning the metal nitride layer below the metal oxide layer 53, the perovskite compound constituting the photoelectric conversion layer 40 can be prevented from being oxidized when forming the metal oxide layer 53. there is.

Next, as can be seen in FIG. 1D, a transparent conductive layer 60 is formed on the second charge transfer layer 50.

The transparent conductive layer 60 is made of a material that has better electrical conductivity than the metal oxide layer 53. For example, the transparent conductive layer 60 may include ITO or IZO, but is not necessarily limited thereto. The transparent conductive layer 60 may be formed through a deposition process such as CVD or ALD.

Next, as can be seen in FIG. 1E, a second electrode 70 is formed on the transparent conductive layer 60.

The second electrode 70 may be made of a metal material such as Ag. The second metal 70 may be patterned into a predetermined shape to allow sunlight to enter the inside of the battery.

According to an embodiment of the present invention as described above, the first charge transfer layer 30, the photoelectric conversion layer 40, the second charge transfer layer 50, and the transparent conductive layer 60. Since it can be formed using a top-down deposition method, there is no need to flip the substrate 10, making the process simpler than before.

According to one embodiment of the present invention, the second charge transfer layer 50 includes a fullerene or fullerene derivative layer 51, an interface layer 52, and a metal oxide layer 53, wherein the Since the fullerene or fullerene derivative layer 51 and the interface layer 52 can be formed in an in-situ process within the same deposition equipment, the process can be further simplified.

Figure 2 is a solar cell manufacturing equipment according to an embodiment of the present invention, in which the above-described fullerene or fullerene derivative layer 51 and the interface layer 52 are formed in a continuous process (in-situ). It is a top-down deposition equipment for forming.

As can be seen in Figure 2, the deposition equipment according to an embodiment of the present invention includes a chamber (1), a susceptor (2), a showerhead (3), a heating device (4), an exhaust unit (5), and an RF power source. (6), including carrier gas lines (7a, 7b), source material transfer lines (8a, 8b), and source material storage containers (9a, 9b).

The susceptor (2) is provided at the lower part of the chamber (1). A substrate 10 is located on the susceptor 2. Although not specifically shown, the above-described first electrode 20, first charge transfer layer 30, and photoelectric conversion layer 40 are formed on the substrate 10.

The showerhead 3 is provided at the upper part of the chamber 1. Accordingly, the source material sprayed through the showerhead 3 may move downward and be deposited on the substrate 10. In this way, the showerhead 3 is disposed above and the substrate 10 is disposed below, so that the gas injected from the showerhead 3 moves downward and is deposited on the substrate 10. , the deposition equipment according to an embodiment of the present invention is a top-down deposition equipment.

Although not specifically shown, the showerhead 3 prevents the first source material supplied from the first source material transfer line 8a from mixing with the second source material supplied from the second source material transfer line 8b. To this end, the movement path of the first source material and the movement path of the second source material may be separated from each other, and the injection port of the first source material and the injection port of the second source material may be formed as a double showerhead separated from each other. there is.

The heating device 4 is provided within the showerhead 3. Accordingly, the temperature inside the showerhead 3 can be maintained within a predetermined temperature range by the heating device 4. Specifically, by the operation of the heating device 4, the temperature inside the showerhead 3 is increased by the carrier gas lines 7a, 7b, the source material transfer lines 8a, 8b, and the source material storage container. (9a, 9b) It can be maintained at a temperature higher than the respective internal temperature, thereby preventing condensation of the injected gas, especially fullerene or fullerene derivative gas. The heating device 4 may be a variety of heaters known in the art.

The exhaust portion 5 may communicate with a wall of the chamber 1, for example a lower wall of the chamber 1. The exhaust unit 5 is connected to a vacuum pump, and the pressure inside the chamber 1 can be maintained in a vacuum state by the operation of the vacuum pump.

The RF power source 6 is connected to the showerhead 3. Therefore, plasma can be generated when the source material is sprayed from the showerhead 3. In particular, the RF power source 6 can generate plasma when forming the interface layer 52 containing LiF described above.

The carrier gas lines 7a, 7b include a first carrier gas line 7a and a second carrier gas line 7b.

The first carrier gas line 7a is connected to a first source material storage container 9a to supply a first carrier gas to the first source material storage container 9a, thereby storing the first source material. Allows the first source material stored in the container 9a to move to the first source material transfer line 8a.

The second carrier gas line 7b is connected to a second source material storage container 9b to supply a second carrier gas to the second source material storage container 9b, thereby storing the second source material. Allows the second source material stored in the container 9b to move to the second source material transfer line 8b.

The first carrier gas and the second carrier gas may be the same or different from each other.

The source mass transfer lines 8a, 8b include a first source mass transfer line 8a and a second source mass transfer line 8b.

The first source material transfer line 8a connects the first source material storage container 9a and the showerhead 3 to transfer the first source material stored in the first source material storage container 9a to the first source material storage container 9a. Delivered to the shower head (3).

The second source material transfer line 8b connects the second source material storage container 9b and the showerhead 3 to transfer the second source material stored in the second source material storage container 9b to the second source material storage container 9b. Delivered to the shower head (3).

The source material storage containers 9a, 9b include a first source material storage container 9a and a second source material storage container 9b. The first source material storage container 9a stores a first source material, and the second source material storage container 9b stores a second source material.

The first source material is a source material for forming the above-described fullerene or fullerene derivative layer 51, and is a fullerene or fullerene derivative, more specifically C60 or PCBM (Phenyl-C61-butyric acid methyl). ester) may be included. The second source material is a source material for forming the above-described interface layer 52. Accordingly, the second source material may include a source material for forming LiF. Although not specifically shown, one source material and one reactant may be required to form the LiF, in which case a separate carrier gas line for supply of the reactant, a reactant transfer line, and reactant storage. Additional containers may be provided.

According to one embodiment of the present invention, the internal temperature of the source material transfer lines (8a, 8b) is higher than the internal temperature of the source material storage containers (9a, 9b), and the internal temperature of the shower head (3) is higher than the internal temperature of the source material storage containers (9a, 9b). The internal temperature of the source material transfer lines 8a, 8b can be maintained, thereby preventing condensation of the moving gas. The internal temperatures of the carrier gas lines (7a, 7b) and the internal temperatures of the source material transfer lines (8a, 8b) may be the same.

According to one embodiment of the present invention, C60 or PCBM is supplied to the showerhead 3 through the first source material transfer line 8a to deposit the above-described fullerene or fullerene derivative on the substrate 10. A source material for forming a (fullerene derivative) layer 51 and then forming LiF through the second source material transfer line 8b to the showerhead 3 in a continuous process, for example, a source material including Li. The fullerene or fullerene derivative is an ALD process that supplies a reactive material including F, for example, for forming LiF to the showerhead 3 through a reactive material transfer line (not shown). The above-described interface layer 52 can be formed on the derivative layer 51.

3 shows solar cell manufacturing equipment according to an embodiment of the present invention, which includes the above-described first charge transfer layer 30, photoelectric conversion layer 40, and fullerene or fullerene derivative layer 51. ), a cluster-type manufacturing equipment for forming the interface layer 52, the metal oxide layer 53, and the transparent conductive layer 60.

As can be seen in FIG. 3, the solar cell manufacturing equipment according to an embodiment of the present invention includes a transfer device 101, a loading/unloading unit 102, a first deposition equipment 103, and a second deposition equipment 104. ), third deposition equipment 105, fourth deposition equipment 106, and fifth deposition equipment 107.

The transfer device 101 is disposed in the center of the cluster, and the loading/unloading unit 102, the first deposition equipment 103, the second deposition equipment 104, the third deposition equipment 105, and the fourth deposition equipment The deposition equipment 106 and the fifth deposition equipment 107 are arranged radially around the transfer device 101.

The first deposition equipment 103 is equipment for forming the above-described first charge transfer layer 30 and is capable of performing a deposition process such as CVD or ALD.

The second deposition equipment 104 is equipment for forming the photoelectric conversion layer 40 described above and is capable of performing a deposition process such as CVD or ALD.

The third deposition equipment 105 is equipment for in-situ depositing the above-described fullerene or fullerene derivative layer 51 and the interface layer 52, and the above-described equipment of FIG. 2 may be applied.

The fourth deposition equipment 106 is equipment for forming the metal oxide layer 53 described above and is capable of performing a deposition process such as CVD or ALD.

The fifth deposition equipment 107 is equipment for forming the transparent conductive layer 60 described above and is capable of performing a deposition process such as CVD or ALD.

4A to 4E are diagrams showing the manufacturing process of a solar cell according to another embodiment of the present invention.

The above-mentioned FIGS. 1A to 1E relate to a method of manufacturing a perovskite solar cell, and FIGS. 4A to 4 relate to a method of manufacturing a tandem solar cell of a perovskite solar cell and a crystalline solar cell.

First, as can be seen in FIG. 4A, a crystalline solar cell 100 is manufactured.

The crystalline solar cell 100 forms an uneven structure by etching one side and the other side of a semiconductor substrate 110 such as a wafer, and dopes a predetermined dopant on one side of the semiconductor substrate 110 to form a first semiconductor layer 120. ) and doping a predetermined dopant on the other side of the semiconductor substrate 110 to form the second semiconductor layer 130.

As one side and the other side of the semiconductor substrate 110 are formed in a concavo-convex structure, the first semiconductor layer 120 and the second semiconductor layer 130 each have a shape corresponding to the concavo-convex structure.

Meanwhile, in the drawing, both one side and the other side of the semiconductor substrate 110 are shown to have a concavo-convex structure, but this is not necessarily limited, and either one of the one side and the other side of the semiconductor substrate 110 has a concavo-convex structure. and the other side may be formed as a flat structure. In some cases, both one side and the other side of the semiconductor substrate 110 may be formed in a flat structure.

The semiconductor substrate 110 may be made of a P-type or N-type wafer, the first semiconductor layer 120 may be doped with a dopant having a different polarity from that of the semiconductor substrate 110, and the second semiconductor layer (130) may be doped with a dopant having the same polarity as the semiconductor substrate 110. For example, the semiconductor substrate 110 may be made of a P-type wafer, the first semiconductor layer 120 may be doped with an N-type dopant, and the second semiconductor layer 130 may be doped with a P-type dopant. It can be made up of a P+ layer.

Next, as can be seen in FIG. 4B, a buffer layer 200 is formed on the upper surface of the crystalline solar cell 100.

The buffer layer 200 is formed on the first semiconductor layer 120. As the first semiconductor layer 120 is formed in a concave-convex structure, the buffer layer 200 is also formed in a concavo-convex structure.

The buffer layer 200 is provided between the crystalline solar cell 100 and the perovskite solar cell formed later, so that the solar cell according to an embodiment of the present invention is a tandem solar cell through a tunnel junction. Create a structure.

The buffer layer 200 is preferably made of a material that allows long-wavelength light passing through the perovskite solar cell to enter the crystalline solar cell 100 without loss. For example, the buffer layer 200 may be made of a transparent conductive oxide, a carbonaceous conductive material, a metallic material, or a conductive polymer, and in some cases, the material may be doped with an n-type or p-type dopant.

Next, as can be seen in FIG. 4C, a first charge transfer layer 30 is formed on the buffer layer 200, and a photoelectric conversion layer 40 is formed on the first charge transfer layer 30.

Since the specific configuration of the first charge transfer layer 30 and the photoelectric conversion layer 40 is the same as described above, repeated description will be omitted.

Next, as can be seen in FIG. 4D, a fullerene or fullerene derivative layer 51, an interface layer 52, and a metal oxide layer 53 are formed on the photoelectric conversion layer 40. A second charge transfer layer 50 is formed.

Since the formation process of the fullerene or fullerene derivative layer 51, the interface layer 52, and the metal oxide layer 53 is the same as described above, repeated description will be omitted. As described above, although not shown, a metal nitride layer may additionally be formed below the metal oxide layer 53.

Next, as can be seen in FIG. 4E, a transparent conductive layer 60 is formed on the second charge transfer layer 50, a second electrode 70 is formed on the transparent conductive layer 60, and the A first electrode 20 is formed on the lower surface of the crystalline solar cell 100.

The formation process of the transparent conductive layer 60 and the second electrode 70 is the same as described above.

The second electrode 70 is formed on the incident surface where sunlight enters, so it is patterned into a predetermined shape, and the first electrode 20 is also patterned into a predetermined shape, so that reflected light from sunlight can be incident into the solar cell. It may be configured to do so, but is not necessarily limited thereto.

Although not specifically shown, a passivation layer may be formed on the second electrode 70. At this time, a portion of the passivation layer is etched to expose the second electrode 70.

Although embodiments of the present invention have been described in more detail with reference to the accompanying drawings, the present invention is not necessarily limited to these embodiments, and various modifications may be made without departing from the technical spirit of the present invention. . Accordingly, the embodiments disclosed in the present invention are not intended to limit the technical idea of the present invention, but are for illustrative purposes, and the scope of the technical idea of the present invention is not limited by these embodiments. Therefore, the embodiments described above should be understood in all respects as illustrative and not restrictive. The scope of protection of the present invention should be interpreted in accordance with the claims, and all technical ideas within the equivalent scope should be interpreted as being included in the scope of rights of the present invention.

1: Chamber 2: Susceptor
3: Showerhead 4: Heating device
5: exhaust 6: RF power
7a, 7b: first and second carrier gas lines
8a, 8b: first and second source mass transfer lines
9a, 9b: first and second source material storage containers
10: substrate 20: first electrode
30: first charge transfer layer 40: photoelectric conversion layer
50: second charge transfer layer 51: fullerene or fullerene derivative layer
52: Interfacial layer 53: Metal oxide layer
60: transparent conductive layer 70: second electrode
100: crystalline solar cell 110: semiconductor substrate
120: first semiconductor layer 130: second semiconductor layer
101: transfer device 102: loading/unloading unit
103-107: first to fifth deposition equipment 200: buffer layer

Claims (15)

forming a first charge transport layer on a substrate;
forming a photoelectric conversion layer including a perovskite compound on the first charge transfer layer; and
Comprising forming a second charge transport layer on the photoelectric conversion layer,
Forming the second charge transport layer includes forming a fullerene or fullerene derivative layer on the photoelectric conversion layer and forming an interface layer on the fullerene or fullerene derivative layer,
A solar cell manufacturing method in which the process of forming the fullerene or fullerene derivative layer and the process of forming the interface layer are performed in-situ within the same deposition equipment. According to paragraph 1,
A method of manufacturing a solar cell, wherein the fullerene or fullerene derivative layer includes C60 or PCBM, and the interface layer includes LiF. According to paragraph 1,
A solar cell manufacturing method wherein the process of forming the fullerene or fullerene derivative layer is a top-down CVD process, and the process of forming the interface layer is a top-down ALD process. According to paragraph 1,
The step of forming the second charge transport layer further includes forming a metal oxide layer on the interface layer. According to paragraph 1,
The step of forming the second charge transport layer further includes forming a metal nitride layer between the interface layer and the metal oxide layer. According to clause 5,
A solar cell manufacturing method wherein the metal oxide layer includes SnO or ZnO, and the metal nitride layer includes SnN or ZnN. According to paragraph 1,
The process of forming the fullerene or fullerene derivative layer includes supplying a carrier gas through a carrier gas line to supply the source material stored in the source material storage container to a shower head provided at the top of the chamber through the source material transfer line. and wherein the internal temperature of the source material transfer line is higher than the internal temperature of the source material storage container, and the internal temperature of the shower head is maintained higher than the internal temperature of the source material transfer line. Board;
a first charge transfer layer provided on the substrate;
A photoelectric conversion layer including a perovskite compound provided on the first charge transfer layer; and
It includes a second charge transfer layer on the photoelectric conversion layer,
The second charge transfer layer includes a fullerene or fullerene derivative layer provided on the photoelectric conversion layer, an interface layer provided on the fullerene or fullerene derivative layer, and a metal oxide layer provided on the interface layer. battery. According to clause 8,
A solar cell wherein the fullerene or fullerene derivative layer includes C60 or PCBM, the interface layer includes LiF, and the metal oxide layer includes SnO or ZnO. According to clause 8,
A solar cell additionally provided with a metal nitride layer between the interface layer and the metal oxide layer. chamber;
a showerhead provided above the chamber;
A susceptor provided below within the chamber;
a heating device provided within the showerhead;
RF power connected to the showerhead;
a source material transfer line connected to the showerhead;
a source material storage vessel connected to the source material transfer line; and
a carrier gas line connected to the source material storage vessel;
Deposition equipment wherein the temperature inside the showerhead is maintained at a higher temperature than the internal temperatures of each of the source material transfer line, the source material storage container, and the carrier gas line by operating the heating device. According to clause 11,
Deposition equipment wherein the temperature of the source material transfer line is maintained at a temperature higher than the internal temperature of each of the source material storage vessel and the carrier gas line. transfer device; and
It includes a loading/unloading unit, a first deposition equipment, a second deposition equipment, a third deposition equipment, a fourth deposition equipment, and a fifth deposition equipment arranged radially around the transfer device,
The first deposition equipment is equipped to perform a CVD or ALD process to form a first charge transfer layer,
The second deposition equipment is equipped to perform a CVD or ALD process for forming a photoelectric conversion layer,
The third deposition equipment is equipped to perform a CVD or ALD process to deposit the fullerene or fullerene derivative layer and the interface layer in-situ,
The fourth deposition equipment is equipped to perform a CVD or ALD process for forming a metal oxide layer,
The fifth deposition equipment is equipped to perform a CVD or ALD process for forming a transparent conductive layer,
The third deposition equipment is solar cell manufacturing equipment consisting of the deposition equipment according to claim 11 or 12 above. crystalline solar cells;
A buffer layer provided on the crystalline solar cell; and
It includes a perovskite solar cell provided on the buffer layer,
The perovskite solar cell is a tandem solar cell consisting of the solar cell according to any one of claims 8 to 11 described above. Process for forming crystalline solar cells;
A process of forming a buffer layer on the crystalline solar cell; and
It includes a process of forming a perovskite solar cell on the buffer layer,
The process of forming the perovskite solar cell is a method of manufacturing a tandem solar cell comprising the manufacturing method according to any one of claims 1 to 7 above.

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