KR101220304B1 - Up conversion oxide fluorescent composition for solar cell and method of fabrication of high efficiency solar cell using thereof - Google Patents
Up conversion oxide fluorescent composition for solar cell and method of fabrication of high efficiency solar cell using thereof Download PDFInfo
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- KR101220304B1 KR101220304B1 KR1020100062995A KR20100062995A KR101220304B1 KR 101220304 B1 KR101220304 B1 KR 101220304B1 KR 1020100062995 A KR1020100062995 A KR 1020100062995A KR 20100062995 A KR20100062995 A KR 20100062995A KR 101220304 B1 KR101220304 B1 KR 101220304B1
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Abstract
The upconversion oxide phosphor composition for a solar cell according to the present invention and a method of manufacturing a high efficiency solar cell using the same are Er 3+ , Yb 3+ , Tm 3+ , Ho 3+ in a host which is at least one of ZrO 2 , TiO 2, or HfO 2 . Preparing an oxide phosphor composition by doping at least one of Pr 3+ or Eu 3+ ; Preparing a p-type wafer having an upper electrode and a lower electrode formed thereon; A pattern forming step of forming a pattern by etching the lower electrode; Inserting the oxide phosphor composition into an etched pattern of the lower electrode; And a lower electrode completion step of completing the electrode by covering the surface on which the pattern of the lower electrode is formed with a metal paste.
According to the present invention, by applying an upconversion phosphor made of a new material to the back electrode of a thin film solar cell or a silicon solar cell, the light efficiency can be remarkably improved compared to the conventional solar cell, which could not convert light below the bandgap. By using ZrO 2 , TiO 2, or HfO 2 as a host, the phosphor can be made small in nano size, and a pattern can be formed on the electrode, thereby coating nano-sized phosphor particles inside the pattern. There is an advantage that can be easily applied to the desired solar cell device.
Description
The present invention relates to an upconversion oxide phosphor composition for a solar cell and a method for manufacturing a high efficiency solar cell using the same. More specifically, a bandgap is applied by applying an upconversion phosphor composed of a new material to a rear electrode of a thin film solar cell or a silicon solar cell. Compared with the conventional solar cell, which could not convert light below, the light efficiency was remarkably improved, a pattern was formed on the electrode, and nano-sized phosphor particles were coated inside the pattern, thereby improving the applicability. The present invention relates to an oxide phosphor composition and a method of manufacturing a high efficiency solar cell using the same.
Currently, solar cells are the next-generation eco-friendly power generation facilities using solar energy, which is an infinite energy source from the sun, and silicon solar cells are made in bulk form using silicon (Si) with low absorption coefficient to increase the absorption of light to increase NP-type diode junction. The solar cell is formed through the thin film solar cell, and the thin film solar cell forms a solar cell through a thin semiconductor junction having a material having a high absorption coefficient such as CIGS, CdTe or a-Si as an absorption layer. Light that is an energy source of such a solar cell has a spectral distribution as shown in FIGS. 1A and 1B, and light reaching the earth from the sun has a distribution similar to that of black body radiation (5000K). Each different wavelength will have an energy distribution with E phot = hc / λ.
At this time, in order to improve the cell efficiency (photoelectric conversion efficiency) of the solar cell, it is important to make maximum use of sunlight incident on the cell. Existing solar cells are inherently inherent to the efficiency as shown in Figure 2, looking at the specific efficiency degradation factors as follows.
① Transmission or sub-bandgap loss: Loss in which light whose energy is smaller than the bandgap cannot penetrate the absorbing layer and penetrate the cell.
② lattice heat loss (Thermalization loss): The light absorbed by the absorbing layer, the energy of which is greater than the band gap creates an electron-hole pair, and the remaining energy is vibrated the lattice to be converted into thermal energy
③ Recombination loss: A loss in which electron-hole pairs are made but do not contribute to power generation due to recombination in the absorber layer or in another layer.
④ Loss caused by blocking of electrons or holes in the conduction band or valence band
⑤ Loss due to resistance caused by ohmic contact of electrons moving towards the electrode
According to the Shockley-Queisser limit, which theoretically summarizes the ideal maximum efficiency of a solar cell in order to represent the loss of the solar cell described above, it can be summarized as shown in Table 1 below.
According to the analysis, unfortunately, the maximum efficiency of a solar cell to a single cell does not theoretically exceed 33%, and the reality is that the maximum efficiency of a single cell currently produced is 20% or less. In order to reduce these losses and create ultra-high efficiency solar cells, a development approach that can drastically reduce these losses must be preceded.
In particular, transparent loss among photovoltaic efficiency loss is unavoidable loss in the case of semiconductor solar cells. To overcome this loss, module manufacturers are developing high-efficiency solar cells by developing tandem type products. As shown in Table 1, it can be seen that many losses of currently used solar modules are due to transparent losses.
In FIG. 3, in the case of a solar cell having a bandgap of 2.23 eV, a transparent loss corresponding to a transparent loss, that is, a sub bandgap loss is shown. That is, solar light smaller than 2.23 eV is not absorbed by the absorbing layer and transmitted, resulting in a loss of solar cell efficiency.
Tandem solar cells are designed to improve this transparent loss problem, and the basic principle is as follows.
Tandem solar cells attempt to minimize the loss of transparency and the loss of sub bandgap due to the stacking of absorption layers having multiple band gaps in a stacked form. However, as shown in FIG. 4, the structure is complicated as compared with a cell having a single absorbing layer, and there are many problems in technology development due to a lot of room for issue in the process.
The present invention is to solve the above problems, an object of the present invention by applying an up-conversion phosphor composed of a new material to the back electrode of a thin-film solar cell or silicon solar cell, it was not possible to photoconvert light below the bandgap It is an object of the present invention to provide a method for manufacturing a high efficiency solar cell that significantly improves light efficiency compared to a solar cell.
That is, an object of the present invention is to provide a method of manufacturing a high efficiency solar cell that can significantly reduce transparent loss by stacking an upconversion phosphor layer on a rear electrode.
In addition, by using ZrO 2 , TiO 2, or HfO 2 as a host, the phosphor can be made small in nano size, and a pattern can be formed on the electrode to coat nano-sized phosphor particles inside the pattern. It is an object of the present invention to provide a method for manufacturing a high efficiency solar cell, which can be easily applied to a desired solar cell device.
In addition, by using a phosphor that can be manufactured in a small and simple process, it is possible to increase the light efficiency while significantly simplifying the conventional tandem-type structure, manufacturing a high-efficiency solar cell that significantly reduces the production cost due to the simple manufacturing process The purpose is to provide a method.
The present invention is to solve the above problems, the solar cell up-conversion oxide phosphor composition according to the invention, at least one of Er 3+ , Yb 3+ , Tm 3+ , Ho 3+ , Pr 3+ or Eu 3+ And ZrO 2 , TiO 2, or HfO 2 .
The average particle diameter of the upconversion oxide phosphor composition particles for solar cells is characterized in that 10nm to 100nm.
Next, a method of manufacturing a high efficiency solar cell using the upconversion oxide phosphor composition for solar cells according to the present invention for achieving the above object, Er 3+ , in the host of at least one of ZrO 2 , TiO 2 or HfO 2 An oxide phosphor manufacturing step of preparing an oxide phosphor composition by doping at least one of Yb 3+ , Tm 3+ , Ho 3+ , Pr 3+, or Eu 3+ ; Preparing a p-type wafer having an upper electrode and a lower electrode formed thereon; A pattern forming step of forming a pattern by etching the lower electrode; Inserting the oxide phosphor composition into an etched pattern of the lower electrode; And a lower electrode completion step of completing the electrode by covering the surface on which the pattern of the lower electrode is formed with a metal paste.
The preparation step includes an etching step of increasing the surface area by etching the upper surface of the p-type wafer; A P-N junction forming step of forming a P-N junction by doping phosphorus on the p-type wafer; A coating step of depositing an anti-reflective coating on the upper surface of the p-type wafer; An upper electrode forming step of forming an electrode of a metal material on an upper surface of the p-type wafer; And a lower electrode forming step of forming an electrode of a metal material on a lower surface of the p-type wafer.
In addition, in the oxide phosphor manufacturing step, the average particle diameter of the up-conversion oxide phosphor composition particles for the solar cell is characterized in that 10nm to 100nm, the coating step, the silicon nitride (S) on the upper surface of the etched p-type wafer ( Silicon Nitride) is characterized in that the anti-reflective coating is formed by depositing by plasma-enhanced chemical vapor deposition (PECVD).
Further, in the upper electrode forming step and the lower electrode forming step, the metal material is aluminum (Al), platinum (Pt), molybdenum (Mo), copper (Cu), nickel (Ni), iridium (Ir), Ruthenium (Ru), gold (Au), titanium nitride (TiN), tantalum nitride (TaN) or tungsten nitride (WN), characterized in that at least one of the upper electrode forming step and the lower electrode forming step, screen Characterized in that the electrode is formed through a printing method.
The pattern forming step is characterized in that to form a pattern through a photolithography process, the thickness of the oxide phosphor layer formed by the insertion step is characterized in that 1㎛ to 100㎛.
Further, in the lower electrode completion step, the metal paste is aluminum (Al), platinum (Pt), molybdenum (Mo), copper (Cu), nickel (Ni), iridium (Ir), ruthenium (Ru), gold ( Au), titanium nitride (TiN), tantalum nitride (TaN) or tungsten nitride (WN) is characterized in that, at the insertion step, the oxide phosphor composition is characterized in that the screen printing method is inserted.
In the lower electrode completion step, the metal paste may be applied by screen printing.
The solar cell upconversion oxide phosphor composition and a method for manufacturing a high efficiency solar cell using the same are to solve the above problems, by applying an upconversion phosphor composed of a new material to the back electrode of a thin film solar cell or a silicon solar cell, Compared with the conventional solar cell that could not convert light below the bandgap, there is an advantage that can significantly improve the light efficiency.
That is, by laminating an upconversion phosphor layer on the back electrode, there is an advantage that the transparent loss can be significantly reduced.
In addition, by using ZrO 2 , TiO 2, or HfO 2 as a host, the phosphor can be made small in nano size, and a pattern can be formed on the electrode to coat nano-sized phosphor particles inside the pattern. Therefore, there is an advantage that can be easily applied to the desired solar cell device.
In addition, by using a phosphor that can be manufactured in a small size and a simple process, it is possible to increase the light efficiency while significantly simplifying the conventional tandem structure, there is an advantage that the manufacturing process is simple and the production cost can be significantly reduced. .
Figure 1a is a graph showing the distribution of the spectrum according to the light wavelength
1b is a graph showing the spectral distribution of solar air mass 1.5
2 is a schematic diagram simulating the factors that reduce the light conversion efficiency of the conventional solar cell
3 is a schematic diagram illustrating a loss mechanism (bandgap: 2.23 eV) of a conventional solar cell;
Figure 4 is a schematic diagram showing the principle and structure of a conventional tandem solar cell
Figure 5 is a schematic diagram of simulating phosphors by function
6 is a flowchart sequentially showing a method of manufacturing a high efficiency solar cell using the upconversion oxide phosphor composition for solar cells of the present invention.
7 is a schematic diagram illustrating the structure of the solar cell of the present invention excluding the phosphor and a light conversion mechanism according to the structure;
8 is a schematic diagram illustrating the structure and photoconversion mechanism of a solar cell manufactured according to a method of manufacturing a high efficiency solar cell using the upconversion oxide phosphor composition for solar cells of the present invention.
9 is a cross-sectional view schematically showing the structure of a solar cell manufactured according to a method of manufacturing a high efficiency solar cell using the upconversion oxide phosphor composition for solar cells of the present invention.
Hereinafter, a preferred embodiment of the present invention will be described in detail with reference to the accompanying drawings with respect to the solar cell up-conversion oxide phosphor composition and a method of manufacturing a high efficiency solar cell using the same. The present invention may be better understood by the following examples, which are for the purpose of illustrating the present invention and are not intended to limit the scope of protection defined by the appended claims.
First, the upconversion oxide phosphor composition for solar cells includes at least one of Er 3+ , Yb 3+ , Tm 3+ , Ho 3+ , Pr 3+, or Eu 3+ and at least one of ZrO 2 , TiO 2, or HfO 2 . It is done by
Here, at least one of ZrO 2 , TiO 2, or HfO 2 is used as a host, and several experiments have shown that nanoparticles of fluorescent particles can be obtained when such a material is used as a host.
Doping at least one of Er 3+ , Yb 3+ , Tm 3+ , Ho 3+ , Pr 3+, or Eu 3+ with ZrO 2 , TiO 2, or HfO 2 as a host, results in upconversion. This possible nanosized phosphor particles are formed.
Herein, the average particle diameter of the upconversion oxide phosphor composition particles for solar cells is preferably 10 nm to 100 nm, more preferably 30 nm to 80 nm, most preferably 50 nm. If the particle size is less than 10nm, there is a problem that the function as a phosphor, that is, the upconversion performance is degraded, and if the particle size exceeds 100nm, considering that the thickness of the solar cell back electrode is less than 500nm, a pattern is formed on the back electrode. Even if there is a problem that the phosphor can not be inserted into the pattern.
Next, a method of manufacturing a high efficiency solar cell using the upconversion oxide phosphor composition for solar cells according to the present invention will be described with reference to FIG. 6.
Method for manufacturing a high efficiency solar cell using the upconversion oxide phosphor composition for solar cells, oxide phosphor manufacturing step (S10), preparation step (S20), pattern forming step (S30), insertion step (S40) and bottom electrode completion step (S50) )
Here, the oxide phosphor manufacturing step (S10) is at least one of Er 3+ , Yb 3+ , Tm 3+ , Ho 3+ , Pr 3+ or Eu 3+ to a host which is at least one of ZrO 2 , TiO 2 or HfO 2 . Doping to prepare an oxide phosphor composition. The oxide phosphor composition component and its manufacturing method in the oxide phosphor manufacturing step (S10) is as described in the description of the upconversion oxide phosphor composition for solar cells of the present invention.
Next, the preparation step (S20) is a step of preparing a p-type wafer formed with an upper electrode and a lower electrode. This is a process of processing a p-type wafer, forming a P-N junction and an electrode in order to effectively insert the upconversion oxide phosphor composition for a solar cell of the present invention into a lower electrode.
Here, the p-type wafer may be any wafer that functions as a p-type semiconductor, but in order to achieve the optimum effect in the present invention, it is preferable to use CIGS, CdTe, a-Si, or silicon (Si) material, more preferably. It is effective to use silicon (Si).
The preparation step S20 includes an etching step S21, a P-N junction forming step S22, a coating step S23, an upper electrode forming step S24, and a lower electrode forming step S25. These steps are preferably made in order except for the upper electrode forming step (S24) and the lower electrode forming step (S25).
Here, the etching step (S21) is a step of increasing the surface area by etching the upper surface of the p-type wafer. This is a process for improving the light efficiency of the solar cell by significantly increasing the surface area of the wafer, thereby increasing the absorption of sunlight and reducing the reflectance.
Here, the etching method may be used in any manner, but etching is preferably performed by evenly applying an etching solution so that a part of the upper surface of the p-type wafer is etched.
Next, the P-N junction forming step (S22) is a step of forming a P-N junction by doping phosphorus (phosphorus) on the p-type wafer. This is a process of giving a function as a battery by forming a P-N junction.
Herein, any method of doping phosphorus may be used, but it is most preferable to use the optimized implant process in the present invention.
Coating step (S23) is a step of depositing an anti-reflective coating on the upper surface of the p-type wafer. This is a process for increasing efficiency by lowering the reflectivity of the solar cell.
The coating step (S23), it is preferable to form an anti-reflective coating by depositing silicon nitride (Silicon Nitride) on the upper surface of the etched p-type wafer by a plasma-enhanced chemical vapor deposition (PECVD) method. By depositing silicon nitride on the upper surface of the p-type waiter by PECVD, a thin antireflective film is formed, which can significantly lower the reflectivity.
Next, the upper electrode forming step (S24) is a step of forming a metal electrode on the upper surface of the p-type wafer, the lower electrode forming step (S25) is a metal electrode on the lower surface of the p-type wafer Forming. This is a process for forming the upper electrode and the lower electrode.
In the upper electrode forming step (S24) and the lower electrode forming step (S25), the metal material is aluminum (Al), platinum (Pt), molybdenum (Mo), copper (Cu), nickel (Ni), iridium (Ir) ), Ruthenium (Ru), gold (Au), titanium nitride (TiN), tantalum nitride (TaN) or tungsten nitride (WN), and more preferably, aluminum (Al) is effective. to be. This material is the most suitable for the formation of the phosphor layer in the electrode of the present invention, and shows the best performance, using a material that has been proved several times.
In the case of using the metal, the electrode has an advantage of improving the efficiency of the solar cell due to the low series resistance and low coverage area.
In addition, the upper electrode forming step (S24) and the lower electrode forming step (S25) it is preferable to form the electrode through a screen printing method (Screen Printing). This is not only suitable for forming the phosphor layer in the electrode of the present invention, but also effective for forming the electrode in a desired portion of the solar cell in a specific size.
Next, the pattern forming step (S30) is a step of forming a pattern by etching the lower electrode. This is a step of inserting the oxide phosphor prepared by the present invention into the electrode, and etching the electrode to form a pattern.
In the pattern forming step (S30), it is preferable to form a pattern through a photolithography process. Several experiments have shown that a photolithography process is most preferable to effectively etch a space for inserting a phosphor into a metal electrode.
That is, in the pattern forming step S30, a pattern is formed on the screen printed lower electrode by etching using a photolithography process. Here, the shape of the pattern may be any shape as long as a space in which the phosphor can be inserted is secured, but it is most effective to form a checkered pattern.
Inserting step (S40) is a step of inserting the oxide phosphor composition in the etched pattern of the lower electrode. This is a process of forming a phosphor layer by inserting a phosphor into an electrode.
In the insertion step (S40), the oxide phosphor composition prepared by the oxide phosphor manufacturing step (S10) is preferably inserted into the screen printing method. In order to effectively form the phosphor layer in the pattern, the screen print method is more suitable than the other methods.
That is, the phosphor layer is formed in the pattern space formed on the electrode by etching.
The thickness of the oxide phosphor layer thus formed is preferably 1 µm to 100 µm, more preferably 20 µm to 60 µm, most preferably 40 µm. When the thickness of the oxide phosphor layer is less than 1 μm, it is difficult to perform an upconversion function as a phosphor. When the thickness of the oxide phosphor layer exceeds 100 μm, the electrode is excessively thick, making it difficult to manufacture a thin film solar cell, and yield and economical efficiency. There is also a problem of deterioration.
Finally, the lower electrode completion step (S50) is a step of completing the electrode by covering the surface on which the pattern of the lower electrode is formed with a metal paste. This is a process for forming an integrated electrode by covering the etched pattern portion and the phosphor layer with a metal of the same material as the electrode to form the phosphor layer.
In the lower electrode completion step (S50), the metal paste is aluminum (Al), platinum (Pt), molybdenum (Mo), copper (Cu), nickel (Ni), iridium (Ir), ruthenium (Ru), gold At least one of (Au), titanium nitride (TiN), tantalum nitride (TaN) or tungsten nitride (WN) is preferable, and more preferably aluminum (Al) is effective. This is to improve the adhesive strength by making the material of the electrode used for the purpose of covering the preformed lower electrode and the phosphor layer after forming the same.
In addition, in the lower electrode completion step (S50), the metal paste is preferably applied by a screen printing method. This is effective to cover the phosphor layer in the electrode and form the electrode in a desired size by using the same method as the electrode forming method.
Hereinafter, a high efficiency solar cell manufactured using an upconversion oxide phosphor composition for solar cells of the present invention and a conventional solar cell will be compared, and their implementation principles and superiority of the present invention will be described.
First, FIG. 5 is a schematic diagram illustrating a phosphor for each function. The present invention relates to a phosphor performing an up-conversion function and a solar cell having improved efficiency using the same.
In addition, Figure 7 is a schematic diagram of the structure of the solar cell of the present invention except the phosphor and the light conversion mechanism according to it, Figure 8 is a simulation of the structure and the light conversion mechanism according to the solar cell manufactured by the present invention It is a copy diagram.
Referring to FIGS. 7 and 8, it is possible to clearly identify the role of the upconversion phosphor of the present invention and a mechanism for improving efficiency.
Finally, FIG. 9 is a cross-sectional view schematically showing the structure of a solar cell manufactured by the present invention, and includes a
However, the arrangement of the P-
As mentioned above, the structure of this invention was demonstrated in detail with reference to an experimental example. However, the scope of the present invention is not limited to the above experimental examples, and may be embodied in various forms of experimental examples within the scope of the appended claims. Without departing from the gist of the invention as claimed in the claims, it is intended that such modifications can be made by anyone of ordinary skill in the art to be within the scope of the claims.
10: lower electrode
20: upconversion phosphor layer
30: P-type semiconductor
40: N-type semiconductor
50: upper electrode
Claims (13)
Preparing a p-type wafer having an upper electrode and a lower electrode formed thereon;
A pattern forming step of forming a pattern by etching the lower electrode;
Inserting the oxide phosphor composition into an etched pattern of the lower electrode;
A lower electrode completion step of completing the electrode by covering the surface on which the pattern of the lower electrode is formed with a metal paste; a method of manufacturing a high efficiency solar cell using an upconversion oxide phosphor composition for a solar cell
In the preparation step,
an etching step of increasing the surface area by etching the upper surface of the p-type wafer;
A PN junction forming step of forming a PN junction by doping phosphorus on the p-type wafer;
A coating step of depositing an anti-reflective coating on the upper surface of the p-type wafer;
An upper electrode forming step of forming an electrode of a metal material on an upper surface of the p-type wafer;
A lower electrode forming step of forming a metal electrode on the lower surface of the p-type wafer; a method of manufacturing a high efficiency solar cell using an upconversion oxide phosphor composition for a solar cell
In the oxide phosphor manufacturing step, the average particle diameter of the upconversion oxide phosphor composition for the solar cell is a method of manufacturing a high efficiency solar cell using the upconversion oxide phosphor composition for solar cells, characterized in that 10nm to 100nm.
In the coating step, an anti-reflective coating is formed by depositing silicon nitride on a top surface of the etched p-type wafer by plasma-enhanced chemical vapor deposition (PECVD). Manufacturing method of high efficiency solar cell using oxide phosphor composition
In the upper electrode forming step and the lower electrode forming step, the metal material is aluminum (Al), platinum (Pt), molybdenum (Mo), copper (Cu), nickel (Ni), iridium (Ir), ruthenium ( Ru), gold (Au), titanium nitride (TiN), tantalum nitride (TaN) or tungsten nitride (WN) at least one of the manufacturing method of the high efficiency solar cell using a solar cell up-conversion oxide phosphor composition.
The upper electrode forming step and the lower electrode forming step, a method of manufacturing a high efficiency solar cell using the up-conversion oxide phosphor composition for solar cells, characterized in that for forming an electrode through a screen printing method.
The pattern forming step is a method of manufacturing a high efficiency solar cell using the up-conversion oxide phosphor composition for solar cells, characterized in that to form a pattern through a photolithography process.
The thickness of the oxide phosphor layer formed by the insertion step is a manufacturing method of a high efficiency solar cell using the up-conversion oxide phosphor composition for solar cells, characterized in that 1㎛ to 100㎛.
In the insertion step, the oxide phosphor composition is a method of manufacturing a high efficiency solar cell using the up-conversion oxide phosphor composition for solar cells, characterized in that the screen printing method is inserted.
In the lower electrode completion step, the metal paste is aluminum (Al), platinum (Pt), molybdenum (Mo), copper (Cu), nickel (Ni), iridium (Ir), ruthenium (Ru), gold (Au) , Titanium nitride (TiN), tantalum nitride (TaN) or tungsten nitride (WN) at least one of the method of manufacturing a high efficiency solar cell using a solar cell up-conversion oxide phosphor composition
In the lower electrode completion step, the metal paste is a method of manufacturing a high efficiency solar cell using a solar cell up-conversion oxide phosphor composition, characterized in that the coating is applied by a screen printing method.
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| JP2006347826A (en) * | 2005-06-17 | 2006-12-28 | National Institute For Materials Science | Rare-earth element-doped titanium dioxide particle and its manufacturing method |
| JP2008189492A (en) * | 2007-02-02 | 2008-08-21 | Japan Aerospace Exploration Agency | Optical element, titanium-based oxide glass for use in the same, and light emitting method and optical amplification method using titanium-based oxide glass |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104178147A (en) * | 2013-05-22 | 2014-12-03 | 海洋王照明科技股份有限公司 | Praseodymium and holmium co-doped zirconium dioxide up-conversion luminescent material, and preparation method and application thereof |
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