KR102242331B1 - Solar Cell Including a Transparent Electrode Containing a Phosphor and Method for Manufacturing the Same - Google Patents

Abstract

The present invention provides a solar cell including a transparent electrode containing a phosphor capable of improving the efficiency of a solar cell and inducing cost reduction of a solar power generation system, and a method of manufacturing the same. This is a transparent electrode that allows sunlight to be incident at a high transmittance, reduces the contact resistance of the device, and is absorbed by the solar cell by including a nanophosphor that is excited only in ultraviolet rays of 400 nm or less in the transparent electrode and emits light in the visible light band of 400 to 800 nm. By increasing the amount of light that can be absorbed, the photoelectric conversion efficiency of the solar cell can be improved. In addition, compared to the conventional coating of a transparent insulating material containing a nanophosphor, the number of processes can be reduced, thereby reducing material and process costs, thereby inducing cost reduction of the solar power generation system.

Description

Solar Cell Including a Transparent Electrode Containing a Phosphor and Method for Manufacturing the Same}

The present invention relates to a solar cell including a transparent electrode containing a phosphor and a method for manufacturing the same, and more particularly, to a solar cell containing a phosphor that can improve the efficiency of the solar cell and induce cost reduction of the solar power generation system. It relates to a solar cell including a transparent electrode and a method of manufacturing the same.

Recently, demand for new and renewable energy such as solar power generation, wind power generation, geothermal power generation, tidal power generation, etc. is increasing due to environmental pollution, cost problems, risk of nuclear power plants, and burden of social overhead costs due to thermal power generation using fossil fuels.

Among them, solar power generation is one of the most easily available power generation among new and renewable energy, and solar cells for solar power generation have low pollution, infinite resources, and can be used semi-permanently, and are next-generation energy that can solve energy problems. It is in the spotlight as a circle.

A solar cell is a semiconductor device that directly converts light energy into electrical energy using a photovoltaic effect. These solar cells include inorganic solar cells including silicon-based solar cells or thin-film solar cells, dye-sensitized solar cells, and organic solar cells, depending on the material constituting them. cell).

However, for the commercialization of solar cells, improvement of photoelectric conversion efficiency for converting incident sunlight into electrical energy is a very important task, and various studies have been conducted to improve the photoelectric conversion efficiency.

These solar cells hardly absorb ultraviolet rays, which occupy about 5% of sunlight, and as a way to improve solar cell efficiency by absorbing them, technology has been developed to absorb ultraviolet rays and convert them into visible light that can be absorbed. .

Korean Patent Registration 10-1384419

The problem to be solved by the present invention is to include a transparent electrode containing a phosphor that can improve the efficiency of a solar cell by excitation of light in the ultraviolet wavelength band by a phosphor contained in the transparent electrode and then converting it into visible light and absorbing it. To provide a solar cell and a manufacturing method thereof.

In order to solve the above problems, the solar cell of the present invention includes a pn junction semiconductor layer including a p-type semiconductor layer and an n-type semiconductor layer formed on the p-type semiconductor layer, and a transparent electrode layer formed on the n-type semiconductor layer. In addition, the transparent electrode layer includes a nanophosphor for converting a wavelength of incident light.

The nanophosphor may be excited in an ultraviolet ray of 400 nm or less to emit light in a visible ray band of 400 to 800 nm.

The nanophosphor may have a thickness of 100 nm or less.

The nanophosphor is ZnO:Pr, Zn ₂ SiO ₄ :Eu ³ +,Tb, Zn ₂ SiO ₄ :Ce,Li, SrTiO ₃ :Pr,Al, Ca _{1 -x} Sr _x TiO ₃ :Pr(0.3<x< It may be formed of at least any one of 0.7).

In the ZnO:Pr material, the Pr may have a range of 0.9 mol% to 1 mol% based on the total.

In the SrTiO ₃ :Pr,Al material, the Pr may have a range of 0.2 mol% to 0.25 mol% with respect to the total.

The transparent electrode layer may be formed of an n-type doped ZnO:Al material.

In the n-type doped ZnO:Al material, Al may have a range of 1 at% to 2 at%.

In order to solve the above-described problems, the method of manufacturing a solar cell of the present invention includes forming a nanophosphor that is excited in ultraviolet light of 400 nm or less to emit light in a visible light band of 400 to 800 nm, forming a transparent electrode layer to contain the nanophosphor. And forming the transparent electrode layer on a pn junction semiconductor layer including a p-type semiconductor layer and an n-type semiconductor layer formed on the p-type semiconductor layer.

The step of forming the nanophosphor further includes coating a transparent insulating material on the surface of the nanophosphor particle.

The nanophosphor is ZnO:Pr, Zn ₂ SiO ₄ :Eu ³ +,Tb, Zn ₂ SiO ₄ :Ce,Li, SrTiO ₃ :Pr,Al, Ca _{1 -x} Sr _x TiO ₃ :Pr(0.3<x< It may be formed of at least any one of 0.7).

In the SrTiO ₃ :Pr,Al material, the Pr may have a range of 0.2 mol% to 0.25 mol% with respect to the total.

The transparent electrode layer may be formed of an n-type doped ZnO:Al material.

In the n-type doped ZnO:Al material, Al may have a range of 1 at% to 2 at%.

In the step of forming the transparent electrode layer on the p-n junction semiconductor layer, the transparent electrode layer may be formed to have a thickness of 100 nm or less by spin coating on the p-n junction semiconductor layer.

According to the present invention, the photoelectric conversion efficiency of the solar cell can be improved by increasing the amount of light absorption that can be absorbed by the solar cell by including a nanophosphor that is excited only in ultraviolet rays of 400 nm or less in the transparent electrode and emits light in the visible light band of 400 to 800 nm. have.

In addition, compared to the conventional coating of a transparent insulating material containing a nanophosphor, the number of processes can be reduced, thereby reducing material and process costs, thereby inducing cost reduction of the solar power generation system.

Furthermore, the transparent electrode containing the nanophosphor can improve the efficiency of the solar cell by using a transparent electrode having high transmittance and low electrical resistivity.

The technical effects of the present invention are not limited to those mentioned above, and other technical effects that are not mentioned will be clearly understood by those skilled in the art from the following description.

1 is a view showing a solar cell including a transparent electrode containing a nanophosphor of the present invention.
2 is a graph showing the transmittance according to the amount of Al doping for the transparent electrode layer of the present invention.
3 is a graph showing a characteristic result according to the amount of Al doping for the transparent electrode layer of the present invention.
4 to 11 are graphs showing excitation and emission spectra for each nanophosphor of the present invention.
12 is a graph comparing current-voltage characteristics of a solar cell including a transparent electrode containing a nanophosphor of the present invention and a solar cell not containing a nanophosphor.

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

While the present invention allows various modifications and variations, specific embodiments thereof are illustrated and shown in the drawings, and will be described in detail below. However, it is not intended to limit the invention to the particular form disclosed, but rather the invention includes all modifications, equivalents, and substitutions consistent with the spirit of the invention as defined by the claims.

When an element such as a layer, region or substrate is referred to as being “on” another component, it will be understood that it may exist directly on the other element or there may be intermediate elements between them. .

Although terms such as first, second, etc. may be used to describe various elements, components, regions, layers and/or regions, these elements, components, regions, layers and/or regions It will be understood that it should not be limited by these terms.

1 is a view showing a solar cell including a transparent electrode containing a nanophosphor of the present invention.

Referring to FIG. 1, a solar cell including a transparent electrode containing a nanophosphor according to the present invention includes a pn junction semiconductor layer 100 including a p-type semiconductor layer 110 and an n-type semiconductor layer 120, the and a transparent electrode layer 200 positioned on the front surface of the pn junction semiconductor layer 100 (ie, the surface of the n-type semiconductor layer).

The p-n junction semiconductor layer 100 is a layer in which a p-n junction between the p-type semiconductor layer 110 and the n-type semiconductor layer 120 is formed, and serves to generate a current through a photovoltaic effect by receiving light. The p-type semiconductor layer 110 may be, for example, a silicon layer doped with Group III elements such as B, Ga, and In, and the n-type semiconductor layer 120 is, for example, P, As, Sb. It may be a silicon layer doped with Group 5 elements such as. However, it is not limited thereto.

When the semiconductor layer is formed of a silicon layer, the pn junction semiconductor layer 100 is subjected to heat treatment after applying an n-type dopant of a group 5 element to a p-type silicon substrate to diffuse the n-type dopant into the p-type silicon substrate. It can be formed by making it. On the other hand, it may be formed by ion doping using plasma or by laminating a p-type emitter silicon layer on an n-type silicon substrate. However, it is not limited thereto.

A transparent electrode layer 200 may be formed on the p-n junction semiconductor layer 100. In more detail, the transparent electrode layer 200 may be formed on the n-type semiconductor layer 120. Here, the transparent electrode layer 200 may include a nanophosphor 210.

The transparent electrode layer 200 functions as a window that transmits ultraviolet rays, sunlight, and visible light incident from the nanophosphor 210 among sunlight and enters the pn junction semiconductor layer 100 located below it. It can function as an electrode that transfers the current generated from the battery to the outside of the device without large resistance.

Accordingly, the transparent electrode layer 200 is an oxide semiconductor having a high band gap of 3.0 eV or more, and a material having a high transmittance in a visible light band of 400 to 800 nm and a low electrical resistivity may be used.

As an example, the material of the transparent electrode layer 200 is formed of an n-doped oxide semiconductor material, preferably, a small amount of aluminum (Al) is doped into zinc oxide (ZnO) by natural oxygen vacancy. It can be formed of n-ZnO:Al material.

FIG. 2 is a graph showing the transmittance according to the amount of Al doping for the transparent electrode layer of the present invention, and FIG. 3 is a graph showing the characteristic result according to the amount of Al doping for the transparent electrode layer of the present invention.

Here, FIG. 2 shows the transmittances of the transparent electrode layer 200 when the amount of Al doping is 1 at.% and 2 at.% when Al is not doped at the n-ZnO:Al concentration, and FIG. 3 Represents the specific resistance, carrier concentration, and carrier mobility according to each doping amount of Al.

Effective in transmittance, resistivity carrier concentration, and carrier mobility as shown in FIGS. 2 and 3 when the amount of Al doped in the n-ZnO:Al material of the transparent electrode layer 200 is 1 at.% to 2 at.%. It can be seen that, preferably, when the Al doping amount is 2 at.%, it can be confirmed that it is most effective for a transparent electrode for a solar cell.

Subsequently, referring to FIG. 1, the transparent electrode layer 200 may include a nanophosphor 210 capable of wavelength conversion. The nanophosphor 210 may be a down-conversion converting short wavelength ultraviolet (UV) into a long wavelength visible light or up-conversion converting infrared (IR) into visible light. That is, the nanophosphor 210 may absorb light in the ultraviolet or visible wavelength band, or absorb light in the infrared wavelength band, and then emit light in the visible wavelength region to the pn junction semiconductor layer 100. have.

For example, in the case of down-conversion, light in a wavelength band of 400 nm or less may be absorbed and excited to emit light in a wavelength band of 400 nm to 800 nm to the p-n junction semiconductor layer 100. In addition, in the case of up-conversion, light in a wavelength band of 900 nm to 1200 nm may be absorbed and excited to emit light in a wavelength band of 400 nm to 800 nm to the p-n junction semiconductor layer 100.

Therefore, since the pn junction semiconductor layer 100 can absorb more light in the wavelength band of 400 nm to 800 nm, which is the most well absorbed, the photoelectric conversion efficiency of the solar cell is increased by increasing the amount of light absorption that the solar cell can absorb. There is an effect that can improve.

Among these phosphors, in the case of the solar cell of the present invention, the above-described direction conversion phosphor may be applied. That is, a general solar cell hardly absorbs ultraviolet rays, which account for about 5% of sunlight. Therefore, after excitation of ultraviolet rays having a wavelength band of 400 nm or less that cannot be absorbed by using a down-conversion phosphor, the amount of excitons generated at the pn junction is increased by emitting light in the visible light band of 400 nm to 800 nm. By improving the current density flowing through the inside, the efficiency of the solar cell can be improved.

At this time, since the phosphor 210 must be thinner than the thickness of the coating layer on the surface of the solar cell device, it has a nano-level nano phosphor 210 having a particle diameter of 100 nm or less.

In addition, the nanophosphor 210 capable of wavelength conversion may be formed to be contained within the transparent electrode layer 200.

That is, a liquid coating material containing a certain amount of the ultraviolet-excited nanophosphor 210 in a basic liquid coating material as a precursor of the transparent electrode layer 200 is prepared, and the liquid coating material is spin coated, immersed coating, and CBD (chemical bath deposition) coating. The UV-excited nanophosphor 210 may be dispersed and distributed between the transparent electrode materials by coating it to a predetermined thickness and performing heat treatment. The transparent electrode layer 200 may be formed to have high light transmittance and low electrical resistivity.

In addition, the nanophosphor 210 may be coated with a transparent insulating material on the surface of the particle to secure chemical resistance. As an example, the coating thickness may be formed in several to several tens of nm, and the coating method may be coated by performing heat treatment after coating by stirring the nanophosphor 210 in a TEOS solution in the case _{of SiO 2.}

Therefore, compared to the method of separately coating the transparent insulating material containing the phosphor 210, which is a conventional method, the number of processes can be reduced, so that the cost required for the process can be reduced, and overall cost reduction due to improved yield can be induced. There is an advantage to be able to.

The material forming the nanophosphor 210 is a material that is excited in the ultraviolet region having a wavelength band of 400 nm or less and emits light in the visible light wavelength band of 400 nm to 800 nm that can be absorbed by a general solar cell among the wavelength band of 400 nm or more. For example, ZnO:Pr, Zn ₂ SiO ₄ :Eu ^{3 +} ,Tb, Zn ₂ SiO ₄ :Ce,Li, SrTiO ₃ :Pr,Al, Ca _{1 -x} Sr _x TiO ₃ :Pr(0.3 It may be formed of at least any one of materials of <x<0.7).

4 to 11 are graphs showing excitation and emission spectra for each nanophosphor of the present invention.

_{First, FIG. 4 shows the excitation spectrum of the SrTiO 3} :Pr,Al nanophosphor 210 of the nanophosphor 210 according to the present invention. In addition, FIG. 5 is a graph showing the emission spectrum for each Pr content _{in the SrTiO 3 :Pr,Al nanophosphor 210.}

As shown in FIGS. 4 and 5, when the nanophosphor 210 contained in the transparent electrode layer 200 is used as SrTiO ₃ :Pr,Al, it can be seen that it is excited in a wavelength band of 400 nm or less, and among the wavelength bands, a wavelength of 359 nm It can be seen that the largest excitation occurs in. In addition, when the amount of Pr was changed to 0.15%, 0.2%, 0.25%, and 0.3% _{to measure the degree of luminescence of SrTiO 3} :Pr, Al, as in the graph of FIG. 5, the content of Pr was 0.2 mol for the whole. It can be seen that the greatest light emission occurs in the range of% to 0.25 mol%.

6 is Ca ₁ of the nano fluorescent material according to the invention _{- x} Sr _x TiO _3: a graph showing the spectrum and emission spectrum of the nano fluorescent material of this Pr (0.3 <x <0.7) .

As shown in the graph of FIG. 6, it can be seen that when Ca _{1 - x} Sr _x TiO ₃ :Pr (0.3<x<0.7) is used as the nanophosphor 210, it is excited in the wavelength band of 300nm to 400nm, and 600nm to 700nm It can be seen that light emission occurs in the wavelength band of. _{In addition, Ca 0} according to the present invention _{. 65} Sr _{0 . 35} TiO ₃ The nanophosphor 210 of CaTiO ₃ , Ca _{0 . 41} Sr _{0 . 35} Ba _{0 . 24 TiO 3, SiTiO 3, BaTiO} 3 nano fluorescent material 210, and here, as compared to the emission spectrum, Ca _0.65 Sr _0.35 TiO ₃ nano fluorescent material 210 in accordance with the present invention is in the wavelength range of 300nm ~ 400nm It can be seen that the largest excitation occurs compared to other nanophosphor materials, and the highest light emission occurs in a wavelength band of 600 nm to 700 nm.

7 and 8 are graphs showing excitation and emission spectra of each of the nanophosphors _{of Zn 2 SiO 4} :Tb ^{3 +} and Zn ₂ SiO ₄ :Eu ^{3 +} of the nanophosphors according to the present invention.

As shown in FIGS. 7 and 8, it can be seen that excitation is generated in a wavelength band of 400 nm or less in both materials, and light emission is generated in a wavelength band of 400 nm or more.

9 and 10 are Zn ₂ SiO of the nano fluorescent material according to the invention _4: Ce, and Zn ₂ SiO emission spectrum graph of the Li _4: Ce Here, shows a graph of the emission spectrum.

First, as in _{the emission spectrum graph of the Zn 2} SiO ₄ :Ce,Li nanophosphor 210 of FIG. 9, it can be seen that light emission occurs in a wavelength band of 400 nm or more, and Zn ₂ SiO ₄ :Ce nano As shown in the excitation emission spectrum graph of the phosphor 210, it can be seen that excitation is generated in a wavelength band of 400 nm or less, and light emission is generated in a wavelength band of 400 nm or more.

11 is a graph showing the emission spectrum of ZnO:Pr among the nanophosphors according to the present invention.

As in the emission spectrum of FIG. 11, it can be seen that light emission occurs in a wavelength band of 400 nm to 800 nm. In addition, it can be confirmed that high light emission occurs in the range of 0.9 mol% to 1 mol% with respect to the total content of Pr, and preferably, it can be confirmed that the highest light emission occurs at 1 mol% with respect to the total content of Pr. have.

Manufacturing example

Nanophosphor manufacturing

Strontium acetate (Sr(CH ₃ COO) ₂ ), titanium isopropoxide (TTIP), praseodymium acetylacetonate hydrate (Pr(acac) 3· ₂ O), aluminum isopropoxide (AIP) to SrTiO ₃ :0.2 Weigh in the composition ratio of mol.%Pr,1mol.%Al and dissolve in glycol-based solvents (EG, PG, TMG, Et-OH, etc.) to perform hydrothermal synthesis in a temperature range of 200~300℃ in a hydrothermal synthesizer for at least 2 hours. Carry out. Then, the synthesized material is washed with ethanol and dried to synthesize a nanophosphor _{210 of SrTiO 3} :Pr,Al.

Transparent electrode manufacturing

Zinc oxide (ZnO) is a synthetic liquid substance, by dissolving zinc acetate dihydrate (Zn(CH ₃ COO) _2· 2H ₂ O) in isopropanol (i-PrOH) at a ratio and adding a certain amount of ethanolamine (monoethanolamine). It is prepared by stirring to become a transparent sol state. Separately, in order to prepare an aluminum doping solution for aluminum doping, aluminum chloride hexahydrate (AlCl _{3 ·} 6H ₂ O) is dissolved in ethanol to prepare a solution. For aluminum 2 at.% doping, a ZnO:Al precursor liquid material is prepared by adding a certain amount of an aluminum doping solution to a zinc oxide (ZnO) synthetic liquid material and stirring. A predetermined amount of ultraviolet-excited red light-emitting SrTiO ₃ :Pr,Al nanophosphor 210 is added to the prepared liquid material, and a stirred nanophosphor 210-containing transparent electrode coating liquid material is prepared.

Manufacture of nano-phosphor-containing transparent electrode in solar cell

A ZnO:Al transparent electrode layer _{containing SrTiO 3} :Pr,Al nanophosphor 210 manufactured on a GaAs/InGaP double junction structure chip in which a pn junction GaAs layer, an InGaP tunnel junction, and a pn junction InGaP layer are formed on a GaAs substrate (200) After coating the liquid coating material for implementation to a thickness of about 100 nm through spin coating, heat treatment at 400°C for 1 hour in an Ar atmosphere to produce a transparent electrode, and vacuum deposition of Au electrodes to drive solar cells. It is manufactured with.

12 is a graph comparing current-voltage characteristics of a solar cell including a transparent electrode containing a nanophosphor of the present invention and a solar cell not containing a nanophosphor.

Referring to FIG. 12, in the solar cell including the transparent electrode containing the nanophosphor 210 of the present invention, the transparent electrode layer 200 is formed of a ZnO:Al material, but SrTiO ₃ :Pr, Al. The nanophosphor 210 was included, and the transparent electrode layer 200 was formed on a double junction solar cell formed of GaAs/InGaP.

When comparing the solar cell of the present invention prepared as described above with a solar cell not containing the nanophosphor 210, the solar cell containing the nanophosphor 210 according to the present invention as shown in the graph of FIG. It can be seen that the short-circuit current density (Jsc) is increased by about 1.6% compared to the case where the phosphor 210 is not included, and by the increase in the short-circuit current density, the transparent electrode including the nanophosphor 210 of the present invention is included. It can be seen that the luminous efficiency of the solar cell is increased by about 1.2%.

As described above, the solar cell including the transparent electrode containing the nanophosphor 210 according to the present invention and the method of manufacturing the same, as a transparent electrode, allow sunlight to be incident at high transmittance and reduce the contact resistance of the device. In addition, it is possible to improve the photoelectric conversion efficiency of the solar cell by increasing the amount of light absorption that can be absorbed by the solar cell by including the nanophosphor 210 that is excited only in ultraviolet rays of 400 nm or less in the transparent electrode and emits light in the visible light band of 400 to 800 nm. .

In addition, compared to the conventional coating of the transparent insulating material containing the nanophosphor 210, the number of processes can be reduced, thereby reducing material and process costs, thereby inducing cost reduction of the solar power generation system.

On the other hand, the embodiments of the present invention disclosed in the specification and drawings are merely presented specific examples to aid understanding and are not intended to limit the scope of the present invention. In addition to the embodiments disclosed herein, it is apparent to those of ordinary skill in the art that other modified examples based on the technical idea of the present invention may be implemented.

100: pn junction semiconductor layer 110: p-type semiconductor layer
120: n-type semiconductor layer 200: transparent electrode layer
210: nanophosphor

Claims (15)

a pn junction semiconductor layer including a p-type semiconductor layer and an n-type semiconductor layer formed on the p-type semiconductor layer; And
Comprising a transparent electrode layer formed on the n-type semiconductor layer,
The transparent electrode layer includes a nanophosphor for converting a wavelength of incident light,
The transparent electrode layer is formed of an n-type doped ZnO:Al material, and in the n-type doped ZnO:Al material, Al has a range of 1 at% to 2 at%,
The nanophosphor _{is formed of SrTiO 3} :Pr,Al, and in the SrTiO ₃ :Pr,Al material, the Pr has a range of 0.2 mol% to 0.25 mol% with respect to the total solar cell. The method of claim 1,
The nanophosphor is a solar cell that is excited in an ultraviolet ray of 400 nm or less to emit light in a visible light band of 400 to 800 nm. The method of claim 1,
The nanophosphor is a solar cell having a thickness of 100 nm or less. delete delete delete delete delete Forming a nanophosphor that is excited in an ultraviolet ray of 400 nm or less to emit light in a visible ray band of 400 to 800 nm;
Forming a transparent electrode layer to contain the nanophosphor; And
Forming the transparent electrode layer on a pn junction semiconductor layer including a p-type semiconductor layer and an n-type semiconductor layer formed on the p-type semiconductor layer,
The transparent electrode layer is formed of an n-type doped ZnO:Al material, and in the n-type doped ZnO:Al material, Al has a range of 1 at% to 2 at%,
The nanophosphor _{is formed of SrTiO 3} :Pr,Al, wherein in the SrTiO ₃ :Pr,Al material, the Pr has a range of 0.2 mol% to 0.25 mol% with respect to the total of the solar cell manufacturing method. The method of claim 9, wherein forming the nanophosphor,
Solar cell manufacturing method further comprising the step of coating a transparent insulating material on the surface of the nanophosphor particles. delete delete delete delete The method of claim 9, wherein in the step of forming the transparent electrode layer on the pn junction semiconductor layer,
The method of manufacturing a solar cell, wherein the transparent electrode layer is formed to have a thickness of 100 nm or less through spin coating on the pn junction semiconductor layer.

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