阅读说明：本技术 一种钙钛矿太阳能电池及其制备方法 (Perovskite solar cell and preparation method thereof ) 是由 尹力 赵春 杨莉 刘伊娜 赵策洲 于 2021-08-27 设计创作，主要内容包括：本发明提供了一种钙钛矿太阳能电池及其制备方法,所述钙钛矿太阳能电池中,空穴传输层和顶电极层之间设置有氧化钒钝化层。本发明通过在钙钛矿太阳能电池中的空穴传输层和顶电极层之间设置有氧化钒钝化层,利用氧化钒钝化层,能够起到载流子选择作用提高器件性能,并结合钙钛矿太阳能电池达到一个高效且低成本的目的,此外,本发明通过ALD沉积制备氧化钒钝化层,有效保证钙钛矿太阳能电池不被破坏,从而具有结构简单、制备简易和稳定性高等特点。(The invention provides a perovskite solar cell and a preparation method thereof. In addition, the vanadium oxide passivation layer is prepared through ALD deposition, so that the perovskite solar cell is effectively prevented from being damaged, and the perovskite solar cell has the characteristics of simple structure, easiness in preparation, high stability and the like.)

1. A perovskite solar cell is characterized in that a vanadium oxide passivation layer is arranged between a hole transport layer and a top electrode layer in the perovskite solar cell.

2. The perovskite solar cell according to claim 1, comprising a substrate layer, an electron transport layer, a perovskite layer, a hole transport layer, a vanadium oxide passivation layer and a top electrode layer, which are sequentially stacked;

preferably, the thickness of the vanadium oxide passivation layer is 4-6 nm.

3. The perovskite solar cell of claim 2, wherein the shape of the top electrode layer comprises a rectangular shape and/or a grid line shape;

preferably, the thickness of the top electrode layer is 80-120 nm.

4. The perovskite solar cell according to claim 2 or 3, wherein the hole transport layer is a P-type hole transport layer;

preferably, the thickness of the hole transport layer is 20-50 nm.

5. The perovskite solar cell of any one of claims 2 to 4, wherein the electron transport layer is an N-type electron transport layer;

preferably, the thickness of the electron transport layer is 20-80 nm.

6. The perovskite solar cell according to any one of claims 1 to 5, wherein the material of the perovskite layer comprises a two-dimensional perovskite material, a double perovskite material or a material of general formula ABX₃The perovskite material of (a);

preferably, the general formula is ABX₃In the perovskite material, A is one or the combination of at least two of FA, MA or Cs; b is preferably one or a combination of at least two of Pb, Sn or Ge; c is preferably I, Br or Cl or the combination of at least two of the same;

preferably, the material of the substrate layer comprises ITO and/or FTO.

7. A method of fabricating the perovskite solar cell as defined in any one of claims 1 to 6, wherein the method of fabricating comprises:

and sequentially preparing an electron transport layer, a perovskite layer, a hole transport layer, a vanadium oxide passivation layer and a top electrode layer on the substrate layer to obtain the perovskite solar cell.

8. The method according to claim 7, wherein the vanadium oxide passivation layer is prepared by Atomic Layer Deposition (ALD);

preferably, the specific preparation method of the vanadium oxide passivation layer comprises the following steps: and (4) feeding the vanadium organic precursor solution into an ALD reactor for cyclic deposition.

9. The method of claim 8, wherein the vanadium organic precursor solution comprises a vanadium organic precursor material and a solvent;

preferably, the vanadium organic precursor material comprises vanadium isopropoxide;

preferably, the solvent comprises deionized water.

10. The preparation method according to claim 8 or 9, wherein the temperature of the vanadium organic precursor solution is 45-55 ℃;

preferably, the reaction temperature in the ALD reactor is 75-85 ℃;

preferably, the temperature of the substrate in the ALD reactor is 75-85 ℃;

preferably, the reaction temperature in the ALD reactor is the same as the temperature of the substrate;

preferably, in the cyclic deposition, the thickness of one deposition is 0.6-1.0 angstroms.

Technical Field

The invention belongs to the technical field of solar cells, and particularly relates to a perovskite solar cell and a preparation method thereof.

Background

The perovskite solar cell has the characteristics of low price, simple manufacturing process and the like, has the characteristics of high photoelectric conversion efficiency and adjustable bandwidth, is favorable for being used as an upper cell of a laminated solar cell, and has attracted great attention in recent years.

At present, the conventional positive perovskite solar cell generally has the problem of poor stability under the condition of no packaging, and a molybdenum oxide passivation layer is generally used for improving the stability, but the traditional positive perovskite solar cell is wrinkled under the temperature condition of more than 70 ℃. Therefore, a passivation layer which is resistant to high temperature and does not affect charge transport is required to improve the stability of the device

CN111463349A discloses a method for improving the stability of a perovskite solar cell, wherein the perovskite solar cell comprises an electrode layer, an electron transport layer, a hole transport layer, and a perovskite thin film layer, and a stabilizer is added in the process of preparing the perovskite thin film layer, and the stabilizer is a compound having an F-B structure, wherein F is halogen fluorine, and B is a chemical structure having a strong electron withdrawing effect. The additive is used in the perovskite material to stabilize iodine in the perovskite material and inhibit iodine ion movement, and the perovskite thin film with the active layer doped with the additive and the application of the perovskite thin film in the solar cell are provided, so that the long-term stability of the perovskite thin film solar cell is improved.

CN111092157A discloses a method for preparing a highly efficient and stable perovskite solar cell, which comprises: spin-coating a hole transport layer on a transparent conductive substrate, and annealing at 60-100 ℃; spin coating a perovskite layer on the hole transport layer, and annealing at 80-140 ℃; placing the material spin-coated with the perovskite layer in an air environment with the humidity of 24-39% for standing; spin-coating an electron transport layer on the perovskite layer, and annealing at 80-100 ℃; spin coating the cathode modification layer on the electron transport layer; and (4) evaporating the metal electrode on the cathode modification layer in vacuum. The method of the invention uses the water which is not in the air to process the perovskite film, so that the perovskite film is fully contacted with the air, and the perovskite is decomposed and recrystallized under the action of the water, thereby enlarging perovskite grains, reducing the area of grain boundaries, reducing the defect state density, improving the interface charge transmission and further improving the performance of PSCs devices.

CN109786555A discloses a perovskite solar cell and a preparation method thereof, wherein the solar cell comprises a transparent substrate layer, a transparent anode layer, a hierarchical gradient hole transport layer, a perovskite light absorption layer, an electron transport layer, an electron buffer layer and a metal cathode layer from bottom to top. The layers are mainly prepared by an evaporation process. The solar cell has high open-circuit voltage VOC and photoelectric conversion efficiency PCE, the maximum efficiency can reach 16.8 percent, the open-circuit voltage can reach 1.05V, and the stability is good.

The conventional perovskite solar cell has the problems of complex structure, difficulty in preparation, high cost, poor stability and the like, so that the problem that how to ensure high stability of the perovskite solar cell under the conditions of high efficiency, simple structure, low cost and simplicity in preparation becomes the urgent need to be solved at present.

Disclosure of Invention

Aiming at the defects in the prior art, the invention aims to provide a vanadium oxide passivation layer perovskite solar cell and a preparation method thereof.

In order to achieve the purpose, the invention adopts the following technical scheme:

in a first aspect, the present invention provides a perovskite solar cell in which a vanadium oxide passivation layer is disposed between a hole transport layer and a top electrode layer.

According to the invention, the vanadium oxide passivation layer is arranged between the hole transport layer and the top electrode layer in the perovskite solar cell, the performance of the perovskite solar cell can be improved by utilizing the carrier selection function provided by the vanadium oxide passivation layer, and meanwhile, a compact protective film is provided to improve the water oxygen and thermal stability of the perovskite solar cell under the condition of improving the performance of the perovskite solar cell, so that the perovskite solar cell has the characteristics of high efficiency, simple structure, easiness in preparation, high stability and the like.

As a preferred technical solution of the present invention, the perovskite solar cell includes a substrate layer, an electron transport layer, a perovskite layer, a hole transport layer, a vanadium oxide passivation layer, and a top electrode layer, which are sequentially stacked.

Preferably, the thickness of the vanadium oxide passivation layer is 4-6 nm, such as 4.0nm, 4.2nm, 4.4nm, 4.6nm, 4.8nm, 5.0nm, 5.2nm, 5.4nm, 5.6nm, 5.8nm or 6.0 nm.

According to the invention, the thickness of the vanadium oxide passivation layer is controlled to be 4-6 nm, and if the thickness of the vanadium oxide passivation layer is less than 4nm, holes can be transmitted to the electrode through tunneling action, so that recombination is caused to reduce the service life of carriers; if the thickness of the vanadium oxide passivation layer is greater than 6nm, there is a problem of blocking efficient electron transport to the electrode.

As a preferred embodiment of the present invention, the shape of the top electrode layer includes a rectangle and/or a grid line shape.

It should be noted that the top electrode in the present invention may be a metal electrode or an organic material electrode, and those skilled in the art can reasonably select the top electrode according to design requirements.

Preferably, the thickness of the top electrode layer is 80-120 nm, such as 80nm, 85nm, 90nm, 95nm, 100nm, 105nm, 110nm, 115nm or 120 nm.

In a preferred embodiment of the present invention, the hole transport layer is a P-type hole transport layer.

Preferably, the hole transport layer has a thickness of 20 to 50nm, such as 20nm, 22nm, 24nm, 26nm, 28nm, 30nm, 32nm, 34nm, 36nm, 38nm, 40nm, 42nm, 44nm, 46nm, 48nm, or 50 nm.

As a preferred embodiment of the present invention, the electron transport layer is an N-type electron transport layer.

Preferably, the thickness of the electron transport layer is 20 to 80nm, such as 20nm, 25nm, 30nm, 35nm, 40nm, 45nm, 50nm, 55nm, 60nm, 65nm, 70nm, 75nm or 80 nm.

As a self-service hairIn a preferred embodiment, the perovskite layer is made of a two-dimensional perovskite material, a double perovskite material or a material with a general formula of ABX₃The perovskite material of (a).

Preferably, the general formula is ABX₃In the perovskite material of (a), a is preferably one or a combination of at least two of FA, MA or Cs; b is preferably one or a combination of at least two of Pb, Sn or Ge; c is preferably I, Br or Cl or a combination of at least two of them.

FA represents HC (NH)₂)²⁺MA represents CH₃NH³⁺。

Preferably, the material of the substrate layer comprises ITO and/or FTO.

In a second aspect, the present invention provides a method of fabricating a perovskite solar cell as defined in the first aspect, the method comprising:

and sequentially preparing an electron transport layer, a perovskite layer, a hole transport layer, a vanadium oxide passivation layer and a top electrode layer on the substrate layer to obtain the perovskite solar cell.

As a preferred embodiment of the present invention, the preparation method of the vanadium oxide passivation layer includes atomic layer deposition ALD.

Preferably, the specific preparation method of the vanadium oxide passivation layer comprises the following steps: and (4) feeding the vanadium organic precursor solution into an ALD reactor for cyclic deposition.

As a preferred embodiment of the present invention, the vanadium organic precursor solution comprises a vanadium organic precursor material and a solvent.

Preferably, the vanadium organic precursor material comprises vanadium isopropoxide.

Preferably, the solvent comprises deionized water.

In a preferred embodiment of the present invention, the temperature of the vanadium organic precursor solution is 45 to 55 ℃, for example, 45 ℃, 46 ℃, 47 ℃, 48 ℃, 49 ℃, 50 ℃, 51 ℃, 52 ℃, 53 ℃, 54 ℃ or 55 ℃.

Preferably, the reaction temperature in the ALD reactor is 75-85 ℃, such as 75 ℃, 76 ℃, 77 ℃, 78 ℃, 79 ℃, 80 ℃, 81 ℃, 82 ℃, 83 ℃, 84 ℃ or 85 ℃.

Preferably, the substrate temperature in the ALD reactor is 75-85 deg.C, such as 75 deg.C, 76 deg.C, 77 deg.C, 78 deg.C, 79 deg.C, 80 deg.C, 81 deg.C, 82 deg.C, 83 deg.C, 84 deg.C or 85 deg.C.

Preferably, the reaction temperature in the ALD reactor is the same as the temperature of the substrate.

Preferably, in the cyclic deposition, the thickness of one deposition is 0.6-1.0 angstroms, such as 0.60 angstroms, 0.64 angstroms, 0.68 angstroms, 0.72 angstroms, 0.76 angstroms, 0.80 angstroms, 0.84 angstroms, 0.88 angstroms, 0.92 angstroms, 0.96 angstroms or 1.00 angstroms.

According to the invention, through cyclic deposition, compared with other methods such as spin coating, a vanadium oxide film which is more compact and has fewer defects can be obtained.

Exemplarily, a preparation method of the perovskite solar cell is provided, and the preparation method specifically includes the following steps:

preparing an electron transport layer, a perovskite layer, a hole transport layer, a vanadium oxide passivation layer and a top electrode layer on the substrate layer in sequence, wherein the preparation method of the vanadium oxide passivation layer comprises the following steps: feeding the triisopropoxytrianisum solution with the temperature of 45-55 ℃ into an ALD reactor for cyclic deposition, wherein the reaction temperature in the ALD reactor is 75-85 ℃, the substrate temperature is 75-85 ℃, and the thickness of primary deposition in the cyclic deposition is 0.6-1.0 angstroms.

The recitation of numerical ranges herein includes not only the above-recited numerical values, but also any numerical values between non-recited numerical ranges, and is not intended to be exhaustive or to limit the invention to the precise numerical values encompassed within the range for brevity and clarity.

Compared with the prior art, the invention has the beneficial effects that:

according to the invention, the vanadium oxide passivation layer is arranged between the hole transport layer and the top electrode layer in the perovskite solar cell, the performance of the perovskite solar cell can be improved by utilizing the carrier selection function provided by the vanadium oxide passivation layer, and meanwhile, a compact protective film is provided to improve the water oxygen and thermal stability of the perovskite solar cell under the condition of improving the performance of the perovskite solar cell, so that the perovskite solar cell has the characteristics of high efficiency, simple structure, easiness in preparation, high stability and the like.

Drawings

FIG. 1 is a schematic structural view of a perovskite solar cell provided in one embodiment of the present invention;

FIG. 2 is a graph comparing the stability at 25 deg.C/humidity of 30% for example 1 and comparative example 1;

FIG. 3 is a graph comparing voltage versus current density for example 1 and comparative example 1;

fig. 4 is a schematic explanatory diagram of a carrier selection function provided in the present invention.

Wherein, 1-a substrate layer; 2-an electron transport layer; 3-a perovskite layer; 4-a hole transport layer; 5-vanadium oxide passivation layer; 6-top electrode layer.

Detailed Description

It is to be understood that in the description of the present invention, the terms "center", "longitudinal", "lateral", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc., indicate orientations or positional relationships based on those shown in the drawings, and are used only for convenience in describing the present invention and for simplicity in description, and do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be taken as limiting the present invention.

It should be noted that, in the description of the present invention, unless otherwise explicitly specified or limited, the terms "disposed," "connected" and "connected" are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art through specific situations.

The technical solution of the present invention is further explained by the following embodiments.

In one embodiment, as shown in fig. 1, the present invention provides a perovskite solar cell in which a vanadium oxide passivation layer 5 is disposed between a hole transport layer 4 and a top electrode layer 6.

According to the invention, the vanadium oxide passivation layer 5 is arranged between the hole transport layer 4 and the top electrode layer 6 in the perovskite solar cell, the performance of the perovskite solar cell can be improved by utilizing the carrier selection function provided by the vanadium oxide passivation layer 5, and meanwhile, a compact protective film is provided to improve the water oxygen and thermal stability of the perovskite solar cell under the condition of improving the performance of the perovskite solar cell, so that the perovskite solar cell has the characteristics of high efficiency, simple structure, easiness in preparation, high stability and the like.

Further, the perovskite solar cell comprises a substrate layer 1, an electron transport layer 2, a perovskite layer 3, a hole transport layer 4, a vanadium oxide passivation layer 5 and a top electrode layer 6 which are sequentially stacked. Wherein the thickness of the vanadium oxide passivation layer 5 is 4-6 nm.

Further, the top electrode layer 6 is rectangular and/or grid-line-shaped, and the thickness of the top electrode layer 6 is 80-120 nm. Optionally, the top electrode is a metal electrode or an organic material electrode.

Further, the hole transport layer 4 is a P-type hole transport layer 4, and the thickness of the hole transport layer 4 is 20-50 nm; the electron transport layer 2 is an N-type electron transport layer 2, and the thickness of the electron transport layer 2 is 20-80 nm.

Further, the material of the substrate layer 1 comprises ITO and/or FTO, and the material of the perovskite layer 3 comprises two-dimensional perovskite material, double perovskite material or general formula ABX₃The perovskite material of (a). Further, the general formula is ABX₃In the perovskite material of (a), a is preferably one or a combination of at least two of FA, MA or Cs; b is preferably one or a combination of at least two of Pb, Sn or Ge; c is preferably I, Br or Cl or a combination of at least two of them.

In another embodiment, the present invention provides a method for preparing the above perovskite solar cell, wherein the method specifically comprises the following steps:

preparing an electron transport layer 2, a perovskite layer 3, a hole transport layer 4, a vanadium oxide passivation layer 5 and a top electrode layer 6 on a substrate layer 1 in sequence, wherein the preparation method of the vanadium oxide passivation layer 5 comprises the following steps: feeding the triisopropoxytrianisum solution with the temperature of 45-55 ℃ into an ALD reactor for cyclic deposition, wherein the reaction temperature in the ALD reactor is 75-85 ℃, the substrate temperature is 75-85 ℃, and the thickness of primary deposition in the cyclic deposition is 0.6-1.0 angstroms.

Example 1

This embodiment provides a perovskite solar cell, based on a specific embodiment, wherein the thickness of the vanadium oxide passivation layer 5 is 5nm, the shape of the top electrode layer 6 is rectangular, the thickness of the top electrode layer 6 is 100nm, the top electrode is a metal electrode, the thickness of the hole transport layer 4 is 35nm, the thickness of the electron transport layer 2 is 50nm, the material of the substrate layer 1 is ITO, and the material of the perovskite layer 3 is FAPbI₃。

The embodiment also provides a preparation method of the perovskite solar cell, which specifically comprises the following steps:

preparing an electron transport layer 2, a perovskite layer 3, a hole transport layer 4, a vanadium oxide passivation layer 5 and a top electrode layer 6 on a substrate layer 1 in sequence, wherein the preparation method of the vanadium oxide passivation layer 5 comprises the following steps: and feeding the 50 ℃ vanadium isopropoxide solution into an ALD reactor for cyclic deposition, wherein in the ALD reactor, the reaction temperature is 80 ℃, the substrate temperature is 80 ℃, and in the cyclic deposition, the thickness of one-time deposition is 0.8 angstrom.

Example 2

This example provides a perovskite solar cell, compared with example 1, the difference is that the thickness of the vanadium oxide passivation layer 5 is 4nm, the shape of the top electrode layer 6 is a grid line shape, the thickness of the top electrode layer 6 is 80nm, the top electrode is an organic material electrode, the thickness of the hole transport layer 4 is 20nm, the thickness of the electron transport layer 2 is 20nm, and the material of the base layer 1 is FTO.

The embodiment also provides a preparation method of the perovskite solar cell, which specifically comprises the following steps:

preparing an electron transport layer 2, a perovskite layer 3, a hole transport layer 4, a vanadium oxide passivation layer 5 and a top electrode layer 6 on a substrate layer 1 in sequence, wherein the preparation method of the vanadium oxide passivation layer 5 comprises the following steps: and feeding the triisopropoxytrianisum solution with the temperature of 45 ℃ into an ALD reactor for cyclic deposition, wherein the reaction temperature in the ALD reactor is 85 ℃, the substrate temperature is 85 ℃, and the thickness of primary deposition in the cyclic deposition is 0.6 angstrom.

Example 3

This example provides a perovskite solar cell, compared with example 1, the difference is that the thickness of the vanadium oxide passivation layer 5 is 6nm, the shape of the top electrode layer 6 is rectangular, the thickness of the top electrode layer 6 is 120nm, the top electrode is a metal electrode, the thickness of the hole transport layer 4 is 50nm, the thickness of the electron transport layer 2 is 80nm, and the material of the base layer 1 is ITO and FTO in a mass ratio of 1: 1.

The embodiment also provides a preparation method of the perovskite solar cell, which specifically comprises the following steps:

preparing an electron transport layer 2, a perovskite layer 3, a hole transport layer 4, a vanadium oxide passivation layer 5 and a top electrode layer 6 on a substrate layer 1 in sequence, wherein the preparation method of the vanadium oxide passivation layer 5 comprises the following steps: and (3) feeding the triisopropoxytrianisum solution with the temperature of 55 ℃ into an ALD reactor for cyclic deposition, wherein the reaction temperature in the ALD reactor is 75 ℃, the substrate temperature is 75 ℃, and the thickness of primary deposition in the cyclic deposition is 1.0 angstrom.

Example 4

This example provides a perovskite solar cell, which differs from example 1 in that the vanadium oxide passivation layer 5 has a thickness of 2nm, and the remaining structure and parameters are exactly the same as in example 1.

Example 5

This example provides a perovskite solar cell, which differs from example 1 in that the vanadium oxide passivation layer 5 has a thickness of 8nm, and the remaining structure and parameters are exactly the same as in example 1.

Comparative example 1

This comparative example provides a perovskite solar cell, which is different from example 1 in that the vanadium oxide passivation layer 5 is not provided and the remaining structure and parameters are completely the same as those of example 1.

This comparative example also provides a method of fabricating the perovskite solar cell described above, in which the vanadium oxide passivation layer 5 is not fabricated, as compared to the fabrication method described in example 1, and the remaining structure and operation are completely the same as those of example 1.

Comparative example 2

This comparative example provides a perovskite solar cell, which is different from example 1 in that the vanadium oxide passivation layer 5 is replaced with a molybdenum oxide passivation layer, and the remaining structure and parameters are completely the same as those of example 1.

The perovskite solar cell prepared by the method is subjected to performance test, and the test method specifically comprises the following steps:

performance testing of perovskite Solar cells was performed at 25 ℃ under nitrogen storage conditions using the Keithley 2400 Source Table under AM 1.5G (Newport VeraSol-2LED Class AAA Solar Simulator), where T is₈₀Time represents the time required for the battery to drop to 80% of its original operating efficiency.

The test structure is shown in table 1, and the comparative test results of example 1 and comparative example 1 are shown in fig. 2 and 3.

TABLE 1

	Photoelectric conversion efficiency/%)	T80Time/h
			Example 1	20.26	2700
Example 2	19.83	2600
			Example 3	19.72	2650
Example 4	19.89	2200
			Example 5	19.36	2000
Comparative example 1	19.19	1400
			Comparative example 2	19.97	1200

From the above table, it can be seen that:

(1) compared with the embodiments 4 and 5, the conversion efficiency and the stability of the embodiment 1 are superior to those of the embodiments 4 and 5, and therefore, the method has the advantages that the thickness of the vanadium oxide passivation layer 5 is controlled to be 4-6 nm, and if the thickness of the vanadium oxide passivation layer 5 is smaller than 4nm, holes can be transmitted to an electrode through tunneling action, so that recombination is caused to reduce the service life of carriers; if the thickness of the vanadium oxide passivation layer 5 is greater than 6nm, there is a problem of blocking efficient electron transport to the electrode.

(2) Compared with the comparative examples 1 and 2, the conversion efficiency and stability of the example 1 are superior to those of the comparative examples 1 and 2, and therefore, the vanadium oxide passivation layer 5 is arranged between the hole transport layer 4 and the top electrode layer 6 in the perovskite solar cell, the carrier selection function provided by the vanadium oxide passivation layer 5 is utilized, the performance of the perovskite solar cell can be improved by the aid of a schematic diagram shown in fig. 4, and the water oxygen and thermal stability of the perovskite solar cell are improved by providing a compact protective film under the condition that the performance of the perovskite solar cell is improved, so that the perovskite solar cell has the characteristics of high efficiency, simple structure, simplicity in preparation, high stability and the like. In addition, the vanadium oxide passivation layer 5 is prepared through ALD deposition, the perovskite solar cell is effectively prevented from being damaged, and therefore the perovskite solar cell has the advantages of being simple in structure, easy to prepare, high in stability and the like.

The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.