KR20110010947A - Organic-inorganic hybrid solar cell - Google Patents

Abstract

PURPOSE: An organic-inorganic hybrid solar cell is provided to simultaneously absorb an infrared ray and a visible ray by forming a p-type semiconductor layer using a p-type chalcogenide system inorganic particle and a p-type conductive polymer material. CONSTITUTION: An organic-inorganic hybrid solar cell comprises a substrate(31), a p-type electrode(32), a n-type electrode, a p-type semiconductor layer, and an n-type semiconductor layer(34). The p-type electrode and the n-type electrode are formed to face the substrate. The p-type semiconductor layer and the n-type semiconductor layer are laminated on a space between the p-type electrode and the n-type electrode. The p-type semiconductor layer is made of a mixture of the p-type chalcogenide compound and the p-type conductive polymer material.

Description

Organic-inorganic hybrid solar cell {ORGANIC-INORGANIC HYBRID SOLAR CELL}

The present invention relates to an organic-inorganic hybrid solar cell, and more particularly, to an organic-inorganic hybrid solar cell in which the P-type semiconductor layer is composed of P-type chalcogenide inorganic particles and P-type conductive polymer material.

In general, not only energy is indispensable for sustainable economic growth, but it must also be clean and continuously available, which does not cause pollution, such as fossil fuels such as coal and oil. In this respect, solar cells (Solar Cells or Photovoltaic Cells) are attracting attention as new energy sources because they use clean and infinite solar light.

Currently, there are solar cells using silicon semiconductors or compound semiconductors, which are inorganic solar cells, and researches on organic solar cells, dye-sensitized solar cells, hybrid solar cells, etc. are being actively conducted.

Currently, commercially available inorganic solar cells using silicon have excellent power conversion efficiency, but are having difficulty in supplying silicon raw materials with high manufacturing cost. Under these circumstances, organic solar cells that do not use silicon materials at all have begun to be studied in earnest, and a low cost process is possible by the printing method, and flexible solar cells can be manufactured regardless of the shape, and are currently attracting much attention. However, no P-type material has been developed that can simultaneously absorb infrared and visible light in organic solar cells. Therefore, there is a limit in improving solar cell efficiency.

The structural diagram of the conventional organic solar cell is shown in FIG.

Referring to FIG. 1, the conventional organic solar cell 10 includes a substrate 11, a P-side electrode 12, an anode planarization layer 13, a P-type semiconductor layer + an N-type semiconductor layer 14, and an N-side electrode. It consists of 15 pieces. The conventional organic solar cell 10 uses indium tin oxide (ITO), which is a transparent electrode having a high work function, as the material of the P-side electrode 12, and Al, Ca, or the like having a low work function, the N-side electrode 15. Used as a substance. The P-type semiconductor layer + N-type semiconductor layer 14 uses a two-layer structure or a composite thin film (mixed (D + A)) structure of a hole acceptor (D) material and an electron acceptor (A) material. Also uses a mixed structure [D / (D + A) / A] in which the latter composite thin film is sandwiched between the hole acceptor and the electron acceptor. In addition, an anode planarization layer 13 or a hole transport layer may be interposed between the ITO electrode, which is the P-side electrode 12, and the P-type semiconductor layer + N-type semiconductor layer 14, as the buffer layer, and the N-side electrode ( An electron transport layer may be sandwiched between 15) and the P-type semiconductor layer + N-type semiconductor layer 14. However, since the organic solar cell 10 does not have a P-type material capable of absorbing infrared and visible light at the same time, as described above, the organic solar cell 10 is configured as various composite films.

On the other hand, chalcogenide-based thin film solar cells exhibit the highest efficiency among solar cells that do not use silicon materials. However, since the chalcogenide-based thin film solar cell has a high manufacturing cost due to the vacuum method using expensive equipment, it is necessary to lower the cost.

2 is a structural diagram of a chalcogenide-based thin film solar cell according to a conventional vacuum method.

Referring to FIG. 2, the conventional chalcogenide thin film solar cell 20 includes a substrate 21, a P-side electrode layer (conductive layer; 22), a P-type semiconductor layer (absorption layer; 23), a buffer layer 24, and N. It has a structure of a type semiconductor layer (transparent window layer) 25 and an N-side electrode (grid electrode) 26. The most important P-type semiconductor layer 23 in the chalcogenide-based thin film solar cell 20 is formed in two ways. As a first method, the process of evaporating and evaporating four metal elements (Cu, In, Ga, Se) has the advantage of easy control of the composition of the four components, but it is recognized that it is not suitable for large-area module manufacturing. . The second method consists of first depositing a precursor by sputtering and heat treatment under a reactive atmosphere. As described above, the P-type semiconductor layer 23 of the chalcogenide-based thin film solar cell 20 has a large influence on the manufacturing cost as well as the performance of the solar cell. This situation is being proposed.

In order to solve these problems, organic-inorganic hybrid solar cells, which are a mixed form of organic and inorganic materials, have recently been proposed. By using an organic-inorganic hybrid solar cell, it is possible to secure high efficiency as well as achieving the light absorption problem of the existing organic solar cell 10 and the low-cost process of the chalcogenide-based thin film solar cell 20.

As discussed above, according to the related art, there is a problem in that the light absorption wavelength region of the conventional P-type semiconductor layer for the organic solar cell 10 is lowered and the efficiency is low, and the P-type semiconductor layer of the chalcogenide-based thin film solar cell 20 ( 23) there is a problem that a high manufacturing cost is formed by using a vacuum method. For commercialization of solar cells, high efficiency and low cost must be achieved. In addition, since the P-type semiconductor material has a narrow light absorption wavelength band, the conventional organic solar cell 10 is limited in light that can be used as mentioned above, and thus there is a limit in improving efficiency.

  On the other hand, in the case of the chalcogenide thin film solar cell 20, the formation of the P-type semiconductor layer 23 by the vacuum process requires a huge initial investment such as sophisticated vacuum equipment, which is not suitable for low-cost solar cells. There is a problem.

Here, the formation of the P-type semiconductor layer 23 by the wet method may contribute to the effect of lowering the manufacturing cost than the method by the vacuum process. However, when the P-type semiconductor nanoparticles are inkized and formed by inkjet printing, there is a problem in that the productivity is low, and the spray coating method has a low film uniformity and a binary oxide and chalcogen phase. There are disadvantages such as impurities such as (chalcogenide phase), presence of reaction by-products such as chlorine or carbon, and the presence of particles of small crystal size.

In addition, in the case of paste coating, it is necessary to prepare a paste using a precursor powder and a polymer binder. In this case, there is a problem in that the properties must be precisely controlled and there is a limit to completely remove the binder polymer after coating.

In addition, in the case of the electrodeposition method using the precursor solution, it is necessary to understand the electrochemical behavior of the element, and to control the components precisely, there is a problem that the system becomes very complicated.

In addition, there is another fatal problem in addition to the above-described problems with respect to the formation of the P-type semiconductor layer by the wet method. That is, the thin film itself formed by each wet coating cannot act as a P-type semiconductor layer, and the P-type semiconductor layer must be subjected to a high temperature heat treatment under an atmosphere of Se (H ₂ Se) or S (H ₂ S), which is a toxic gas. There is a problem that this is completed. The use of such toxic gases and high temperature process has a problem that leads to a decrease in productivity.

Accordingly, an object of the present invention is to provide an organic-inorganic hybrid solar cell in which the P-type semiconductor layer is composed of P-type chalcogenide inorganic particles and P-type conductive polymer materials. .

An organic-inorganic hybrid solar cell according to the present invention comprises a substrate; A P-side electrode and an N-side electrode formed on the substrate so as to face each other; A P-type semiconductor layer and an N-type semiconductor layer stacked between the P-side electrode and the N-side electrode; The P-type semiconductor layer is characterized by consisting of a mixture of a P-type conductive polymer material and a P-type chalcogenide compound.

In addition, the P-type conductive polymer material constituting the P-type semiconductor layer is PEDOT (poly (3,4-ethylenedioxythiophene): PSS (poly (styrenesulfonate)), polyaniline, phthalocyanine, polydiphenyl acetylene, poly (t-butyl) diphenylacetylene, poly (trifluoromethyl) diphenylacetylene, polybis (T-butyldiphenyl) acetylene, poly (trimethylsilyl) diphenylacetylene, poly (carbazole) diphenylacetylene, poly Diacetylene, polyphenylacetylene, polypyridineacetylene, polymethoxyphenylacetylene, polymethylphenylacetylene, poly (t-butyl) phenylacetylene, polynitrophenylacetylene, poly (trifluoromethyl) phenylacetylene, poly (trimethylsilyl) At least one selected from the group consisting of phenylacetylene and derivatives thereof, and the like.

In addition, the P-type chalcogenide compounds constituting the P-type semiconductor layer are CuInS ₂ (CIS), CuGaS ₂ (CGS), CuInSe ₂ (CISe), CuGaSe ₂ (CGSe), CuAlSe ₂ (CASe), CuInTe ₂ At least one of the group consisting of (CITe), CuGaTe ₂ (CGTe), Cu (In, Ga) S ₂ (CIGS), Cu (In, Ga) Se ₂ (CIGSe), Cu ₂ ZnSnS ₄ (CZTS), CdTe, and the like. It is characterized in that the above selection.

In addition, the N-type semiconductor layer is characterized in that at least one selected from the group consisting of fullerene (C60) C60 derivatives, perylene (perylene), perylene derivatives, PTCBI, ZnO, ITO and the like.

In addition, it characterized in that it comprises a buffer layer on the two opposite electrodes.

In addition, any one of the two opposite electrodes is characterized in that formed on glass, plastic, metal foil or ceramic.

As described above, the organic-inorganic hybrid solar cell according to the present invention is composed of a P-type chalcogenide-based inorganic particles and a P-type conductive polymer material, thereby absorbing infrared rays and visible light at the same time. It is advantageous in that it is more stable in terms of charge mobility or increase in contact area between the hole acceptor and the polymer than when only one of the chalcogenide compound semiconductors is used.

Hereinafter, an organic-inorganic hybrid solar cell according to the present invention will be described in detail with reference to the drawings. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear. In addition, terms to be described below are terms defined in consideration of functions in the present invention, and may be changed according to a client or an operator, a user's intention or custom. Therefore, the definition should be based on the contents throughout this specification.

Like numbers refer to like elements throughout the drawings.

3 is a structural diagram of an organic-inorganic hybrid solar cell according to the present invention, Figure 4 is a cross-sectional view of the organic-inorganic hybrid solar cell according to the present invention.

The organic-inorganic hybrid solar cell according to the present invention may be implemented in two forms shown in FIGS. 3 and 4. First, referring to FIG. 3, an organic-inorganic hybrid solar cell 30 according to the present invention may be manufactured. Looking at the method in more detail, it is prepared by the following process, which will be described in detail as follows.

<Formation of substrate / P side electrode and cleaning process>

When the substrate 31 is provided on the light incident surface side of the organic-inorganic hybrid solar cell 30, since the substrate 31 should have light transmittance, it is preferable to be colorless and transparent, but may be somewhat colored. . For example, transparent glass substrates such as soda-lime glass or alkali-free glass, and plastic films arbitrarily produced from polyester, polyamide, epoxy resin, or the like may be used. In addition to ITO, the P-side electrode may be transparent, such as Fluorine-doped Tin Oxide (FTO), Mo, Indium Zinc Oxide (IZO), ZnO-Ga ₂ O ₃ , ZnO-Al ₂ O ₃ , SnO ₂ -Sb ₂ O _3, etc. An electrode can be used.

In forming the P-side electrode 32, sputtering or vacuum deposition may be used. The P-side electrode 32 formed on the substrate is immersed in acetone, alcohol, water, or a mixed solution thereof, followed by ultrasonic cleaning.

<P type Semiconductor layer  Formation>

P-type semiconductor layer 33 of the organic-inorganic hybrid solar cell 30 according to the present invention is composed of a P-type chalcogenide-based inorganic particles and a P-type conductive polymer material, first P-type dissolved in a suitable solvent P-type chalcogenide-based inorganic particles are added to the conductive polymer solution to disperse them properly. The mixed solution of the P-type chalcogenide-based inorganic particles and the P-type conductive polymer solution is coated on the cleaned P-side electrode 33. In this case, a spin coating, a spray coating, a screen printing, a bar coating, a doctor blade method, an inkjet method, and the like may be applied. The film coated in this manner is dried under an appropriate temperature to form a P-type semiconductor thin film. In this case, the P-type semiconductor layer 33 used is PEDOT (poly (3,4-ethylenedioxythiophene): PSS (poly (styrenesulfonate)), polyaniline, polydiphenyl acetylene, poly (t-butyl) diphenylacetylene , Poly (trifluoromethyl) diphenylacetylene, poly (bistrifluoromethyl) acetylene, polybis (T-butyldiphenyl) acetylene, poly (trimethylsilyl) diphenylacetylene, poly (carbazole) diphenylacetylene , Polydiacetylene, polyphenylacetylene, polypyridineacetylene, polymethoxyphenylacetylene, polymethylphenylacetylene, poly (t-butyl) phenylacetylene, polynitrophenylacetylene, poly (trifluoromethyl) phenylacetylene, poly (trimethyl P-type conductive polymer including silyl) phenylacetylene and derivatives thereof and CuInS ₂ (CIS), CuGaS ₂ (CGS), CuInSe ₂ (CISe), CuGaSe ₂ (CGSe), CuAlSe ₂ (CASe), CuInTe ₂ (CITe), CuGaTe ₂ (CGTe), Cu (In, Ga) S ₂ (CIGS), Cu (In, Ga) Se _{2 (CIGSe), Cu 2 ZnSnS 4} (CZTS), Chapter P-type incident, such as CdTe may be mentioned for example a knife Koji arsenide compound.

<N type Semiconductor layer  Formation>

As the electron acceptor of the N-type semiconductor layer 34, fullerene (C60) or [6,6] -phenyl-C61-butyric acid methyl ester (PCBM) designed to dissolve C60 in an organic solvent is used. Perylene, copper, and 3,4,9,10 perylenetetracarboxylic bisbenzimidazole (PTCBI) are used as other single molecules. However, it is not limited to these. As a method that can be applied to the formation of the N-type semiconductor layer 34 may be a vacuum deposition method, spin coating, spray coating, screen printing, inkjet method and the like.

<N side Electrode layer  Formation>

The N-side electrode layer 35 is an electrode for effectively collecting electrons generated in the P-type semiconductor layer 33. It is preferable to use an electrode material composed of a metal, an alloy, an electrically conductive compound having a small work function, and a mixture thereof. As such a material of the N-side electrode layer 35, an alkali metal, sodium-potassium alloy, magnesium-silver mixture, aluminum-lithium alloy, aluminum-lithium fluorine mixture, or the like can be used. These electrode materials can form a film by sputtering or a vacuum vapor deposition method, and the formation method is not specifically limited.

< Sealing process >

Since the organic-inorganic hybrid solar cell 30 may be degraded by moisture and oxygen during operation, it is necessary to block each layer formed from the atmosphere. First, a moisture absorbent capable of absorbing moisture is attached to the center of the protective cap of the glass material, and the sealing material is dispensed on the edge portion. Next, the fabricated device (substrate / P side electrode layer / P type semiconductor layer / N type semiconductor layer / N side electrode layer) is disposed on the dispensed sealing material, and then UV or heat is applied to cure the sealing material. If the sealing material is cured using UV, UV light should not be introduced into the P-type semiconductor layer 33, because the P-type semiconductor layer 33 may be deteriorated by UV. . In addition, the sealing process may use a method of forming a multilayer thin film under vacuum. These sealing processes are already well established in the organic light emitting device industry. In addition, it is possible to seal with EVA (Ethylene Vinyl Acetate) sheet and glass applied to the conventional crystalline silicon solar cell.

As another embodiment of the present invention, an organic-inorganic hybrid solar cell having a structure as shown in FIG. 4 is possible. Referring to FIG. 4, a method of manufacturing the organic-inorganic hybrid solar cell 40 according to the present invention will be described in more detail. It is prepared by the following process, which will be described in detail as follows.

<Formation of substrate / P side electrode and cleaning process>

As the substrate 41, soda-lime silica glass or non-rigid glass and flexible plastics such as copper tape, polyimide, stainless steel sheets, or the like may be used. Formation of the P-side electrode layer 42 is required for such a substrate 41. The P-side electrode layer 42 may be formed of any material having electrical conductivity. However, molybdenum (Mo), a transparent electrode, and other metals having high electrical conductivity and ohmic bonding with chalcogenide-based compounds and excellent stability at high temperatures are possible. Electrodes and the like are mainly used. More preferably, a molybdenum layer having a thickness of about 0.1 to 5 mu m is preferable. Molybdenum of the P-side electrode layer 42 may be formed by DC sputtering or deposition, or alternatively by chemical vapor deposition (CVD), atomic layer deposition (ALD), sol-gel coating, electroplating, or the like. . The P-side electrode 22 formed on the substrate 41 is immersed in acetone, alcohol, water, or a mixed solution thereof, and then ultrasonically cleaned.

<P type Semiconductor layer  Formation>

The P-type semiconductor layer 43 is the same as the formation of the P-type semiconductor layer 33 previously described in connection with FIG. PEDOT (poly (3,4-ethylenedioxythiophene): PSS (poly (styrenesulfonate), polyaniline, phthalocyanine, polydiphenyl acetylene, poly (t-butyl) diphenylacetylene, poly (trifluoromethyl) di Phenylacetylene, Cu-PC (Copper Phthalocyanine) Poly (Bistrifluoromethyl) acetylene, Polybis (T-butyldiphenyl) acetylene, Poly (trimethylsilyl) diphenylacetylene, Poly (carbazole) diphenylacetylene, poly Diacetylene, polyphenylacetylene, polypyridineacetylene, polymethoxyphenylacetylene, polymethylphenylacetylene, poly (t-butyl) phenylacetylene, polynitrophenylacetylene, poly (trifluoromethyl) phenylacetylene, poly (trimethylsilyl) P-type conductive polymers including phenylacetylene and derivatives thereof, CuInS ₂ (CIS), CuGaS ₂ (CGS), CuInSe ₂ (CISe), CuGaSe ₂ (CGSe), CuAlSe ₂ (CASe), CuInTe ₂ ( CITe), CuGaTe ₂ (CGTe), Cu (In, Ga) S ₂ (CIGS), C An incident field chalcogenide compound, which is a P-type inorganic compound such as u (In, Ga) Se ₂ (CIGSe), Cu ₂ ZnSnS ₄ (CZTS), or CdTe, is mixed in a weight ratio. Formation methods may be spin coating, spray coating, screen printing, bar coating, doctor blade method, inkjet method and the like.

<Buffer layer formation>

In forming a pn junction between the P-type semiconductor layer 33 and the N-type semiconductor layer 45, a better bonding is achieved when the buffer layer 44 is introduced. Cadmium sulfide (CdS) may be used as the buffer layer 44, but ZnS, Zn (O, S), ZnSe, (Zn, In) Se, In (OH, S), In, which does not use Cd, which is a heavy metal, may be used. ₂ S ₃ or the like may be used. Typically, CdS used as the buffer layer 44 is preferably deposited to a thickness of 200 to 1000 kPa by chemical bath deposition (CBD).

<N type Semiconductor layer  Formation>

As mentioned above, the N-type semiconductor layer 45 for the pn junction serves to conduct a wide energy band interval of the material of the buffer layer 44 and functions as a transparent electrode on the front surface of the organic-inorganic hybrid solar cell 40. As a result, a zinc oxide layer (ZnO) having high light transmittance and high electrical conductivity may be used. Most of the N-type semiconductor layer 45 is composed of two layers of ZnO, and a portion where the buffer layer 44 contacts is formed of intrinsic ZnO, and n-type ZnO (ZnO: Al) is formed thereon. Is formed. The N-type semiconductor layer 45 may be formed through RF sputtering or a wet process.

<N side electrode ( Grid electrode ) And antireflection film forming process>

The N-side electrode (grid electrode) 46 is mainly composed of two metal contact layers and can be formed by an electron beam method or another method. The first metal contact layer may be formed of Ni having a thickness of about 500 to 1000 kPa, and the second metal contact layer may be formed of Al having a thickness of 1 to 3 μm. MgF ₂ is generally used as the anti-reflection film 47 which reduces the reflection loss of sunlight incident on the organic-inorganic hybrid solar cell 40 and further increases the efficiency. It can be used to form.

Hereinafter, the embodiment of the organic-inorganic hybrid solar cell of the present invention will be embodied by way of examples, but the present invention is not limited to the following examples, which are only presented to aid the understanding of the present invention.

Example 1

As the P-side electrode layer, a transparent ITO having a thickness of 1,500 Pa or less having a sheet resistance of 15 Ω / sq was produced on a glass substrate (hereinafter referred to as an ITO substrate). The ITO substrate is immersed in acetone, semicoclean (manufactured by Fulluchi Scientific, Inc.), and isopropyl alcohol (manufactured by Duksan Chemical Co., Ltd.), followed by ultrasonic cleaning for 15 minutes, and then dried. Next, this ITO substrate is surface-treated for 3 minutes in an atmospheric plasma surface treatment apparatus.

Next, a solution of polyethylene dioxythiophene: polystyrene sulfonate (manufactured by Stalk, PEDOT: PSS) and CITe in a weight ratio of 40:60 was formed as a P-type semiconductor layer on the ITO by spin coating. Dry at 15 ° C for 15 minutes. Next, the substrate was transferred to a glove box in a dry nitrogen atmosphere of 1 ppm or less of oxygen, set in a vacuum deposition apparatus, and a fullerine (C60) was formed thereon by vacuum deposition. Then, lithium fluoride was formed as an N-side electrode as 1 nm. A film having a thickness of 200 nm is formed thereon using a vacuum deposition method. Next, the device having each layer formed is sealed in a glove box of a nitrogen atmosphere to obtain an organic-inorganic hybrid solar cell. The organic-inorganic hybrid solar cell device thus manufactured is heat-treated for 30 minutes on a hot plate set at 150 ° C to measure photoelectric conversion efficiency. The voltage-current density of the solar cell was determined using Keithley 236 Source Measurement and Solar Simulator (300W simulator models 81150 and 81250, Spectra physics Co.) under standard conditions (AM 1.5, 100 mW / cm ² , 25 ° C). Measured in The open circuit voltage (V _oc ) was 0.65 V, the short circuit current (J _sc ) was 8.65 mA / cm ² , and the fill factor (FF) was 63.13%, which is 3.5 Photoelectric conversion efficiency of% was shown.

Example 2

An organic-inorganic hybrid solar cell was manufactured in the same manner except that the components constituting the P-type semiconductor layer were PEDOT: PSS and CIGS in the organic-inorganic hybrid solar cell manufacturing process shown in Example 1. The organic-inorganic hybrid solar cell manufactured as described above was measured to have a Voc value of 0.71, a Jsc value of 8.97, and a FF of 61.38%, and a photoelectric conversion rate of 3.9%.

Example 3

An organic-inorganic hybrid solar cell was manufactured in the same manner except that the components constituting the P-type semiconductor layer were PEDOT: PSS and CdTe in the organic-inorganic hybrid solar cell manufacturing process shown in Example 1. The organic-inorganic hybrid solar cell fabricated in this manner was measured to have a Voc value of 0.71, a Jsc value of 8.83, and a FF of 62.44%, and a photoelectric conversion rate of 3.9%.

Example 4

The organic-inorganic hybrid solar cell was manufactured using polydiphenylacetylene instead of PEDOT: PSS in the organic-inorganic hybrid solar cell manufacturing process shown in Example 1, and all other conditions were the same. The organic-inorganic hybrid solar cell fabricated in this manner was measured to have a Voc value of 0.71, a Jsc value of 9.32, and a FF of 63.26%, and a photoelectric conversion rate of 4.2%.

Example 5

The solar cell was manufactured using polyaniline instead of PEDOT: PSS in the solar cell manufacturing process shown in Example 1, and all other conditions were the same. The organic-inorganic hybrid solar cell fabricated as described above was measured with VOC value of 0.68, Jsc value of 8.87, and FF of 61.76%, and photoelectric conversion rate of 3.7%.

Example 6

An organic-inorganic hybrid solar cell was manufactured in the same manner except that the components constituting the P-type semiconductor layer were polypyridineacetylene and CITe in the organic-inorganic hybrid solar cell manufacturing process shown in Example 1. The organic-inorganic hybrid solar cell fabricated as described above was measured with VOC value of 0.68, Jsc value of 8.87, and FF of 61.76%, and photoelectric conversion rate of 3.7%.

Example 7

In the solar cell fabrication process described in Example 1, the components constituting the N-type semiconductor layer are poly 3-hexyl thiophene (abbreviated as Rieke Metals, P3HT) and [6,6] -Phenyl-C61-butyric acid methyl ester. An organic-inorganic hybrid solar cell was prepared in the same manner except dissolving (manufactured by Nano-C, PCBM) in chlorobenzene at a weight ratio of 1: 0.9 to form the solution by spin coating. The organic-inorganic hybrid solar cell fabricated in this manner was measured to have a Voc value of 0.71, a Jsc value of 8.83, and a FF of 62.44%, and a photoelectric conversion rate of 3.9%.

Example 8

Molybdenum-coated glass substrate (hereinafter referred to as Mo substrate) as the P-side electrode layer was immersed in acetone, semicoclean (manufactured by Fulluchi Science), and isopropyl alcohol (manufactured by Duksan Chemical Co., Ltd.) for 15 minutes After drying, drying was performed. Next, this Mo substrate was surface-treated for 3 minutes in an atmospheric plasma surface treatment apparatus.

Next, CIGS and PEDOT: PSS were mixed at a weight ratio of 80:20 as a P-type semiconductor layer on Mo, and formed by spin coating. Next, CdS was deposited on the buffer layer by chemical bath deposition (CBD). On the N-type semiconductor layer, intrinsic ZnO and n-type ZnO (ZnO: Al) were formed through a deposition process. The photoelectric conversion efficiency of the organic-inorganic hybrid solar cell device thus obtained was measured, and the voltage-current density of the solar cell device was measured using Keithley 236 Source Measurement and Solar Simulator (300W simulator models 81150 and 81250, Spectra physics Co.). It was measured under standard conditions (AM 1.5, 100 mW / cm ² , 25 ° C). The open circuit voltage (V _oc ) was 0.67 V, the short circuit current (J _sc ) was 22.77 mA / cm ² , and FF was 69.43%, indicating a photoelectric conversion efficiency of 10.6%.

Example 9

An organic-inorganic hybrid solar cell was manufactured in the same manner except that CIS and PEDOT: PSS, which are chalcogenide compound semiconductors, were used as P-type semiconductor layers. The organic-inorganic hybrid solar cell fabricated as described above was measured with VOC value of 0.68, Jsc value of 23.15, FF of 70.13%, and photoelectric conversion rate of 11.0%.

Example 10

An organic-inorganic hybrid solar cell was manufactured in the same manner except that CISe and PEDOT: PSS, which are chalcogenide compound semiconductors, were used as P-type semiconductor layers in the manufacturing process of the organic-inorganic hybrid solar cell shown in Example 8. The organic-inorganic hybrid solar cell fabricated as described above had a Voc value of 0.69, a Jsc value of 24.09, an FF of 70.32%, and a photoelectric conversion rate of 11.7%.

Example 11

An organic-inorganic hybrid solar cell was manufactured in the same manner except that the chalcogenide compound semiconductors CZTS and PEDOT: PSS were used as P-type semiconductor layers in the manufacturing process of the organic-inorganic hybrid solar cell shown in Example 8. The organic-inorganic hybrid solar cell fabricated in this manner was measured to have a Voc value of 0.68, a Jsc value of 23.33, an FF of 70.95%, and a photoelectric conversion rate of 11.3%.

Example 12

An organic-inorganic hybrid solar cell was manufactured in the same manner except that CIGSe and PEDOT: PSS, which are chalcogenide compound semiconductors, were used as P-type semiconductor layers. The organic-inorganic hybrid solar cell fabricated in this way was 0.67, Jsc was 23.64, FF was 71.88%, and the photoelectric conversion rate was 11.4%.

Example 13

An organic-inorganic hybrid solar cell was manufactured in the same manner as in Example 8 except that a mixture of polyaniline and a chalcogenide compound semiconductor, CITe, was used as a P-type semiconductor layer. . The organic-inorganic hybrid solar cell fabricated in this manner was measured to have a Voc value of 0.69, a Jsc value of 24.37, and an FF of 71.09%, and a photoelectric conversion rate of 12.0%.

Example 14

An organic-inorganic hybrid solar cell was manufactured in the same manner except that ZnS was used as the buffer layer instead of CdS in the organic-inorganic hybrid solar cell manufacturing process shown in Example 8. The organic-inorganic hybrid solar cell fabricated as described above had a Voc value of 0.67, a Jsc value of 23.27, and an FF of 71.92%, and a photoelectric conversion rate of 11.2%.

As described above, the present invention has been described based on the preferred embodiments, but these embodiments are intended to illustrate the present invention, not to limit the present invention, so that those skilled in the art to which the present invention pertains can perform the above without departing from the technical spirit of the present invention. Various changes, modifications or adjustments to the example will be possible. Therefore, the protection scope of the present invention should be construed as including all changes, modifications or adjustments belonging to the gist of the technical idea of the present invention.

1 is a structural diagram of a conventional organic solar cell

2 is a structural diagram of a chalcogenide-based thin film solar cell according to a conventional vacuum method.

3 is a structural diagram of an organic-inorganic hybrid solar cell according to the present invention.

4 is a structural diagram of an organic-inorganic hybrid solar cell according to the present invention.

Explanation of symbols on main parts of drawing

30, 40: organic-inorganic hybrid solar cell

31, 41: substrate 32, 42: P-side electrode

33, 43: P-type semiconductor layer 34, 45: N-type semiconductor layer

35, 46: N-side electrode 44: buffer layer

47: antireflection film

Claims (6)

A substrate; A P-side electrode and an N-side electrode formed on the substrate so as to face each other; A P-type semiconductor layer and an N-type semiconductor layer stacked between the P-side electrode and the N-side electrode; The P-type semiconductor layer is an organic-inorganic hybrid solar cell, characterized in that made of a mixture of a P-type conductive polymer material and a P-type chalcogenide compound. The P-type conductive polymer material constituting the P-type semiconductor layer is PEDOT (poly (3,4-ethylenedioxythiophene): PSS (poly (styrenesulfonate)), polyaniline, phthalocyanine, polydi. Phenyl acetylene, poly (t-butyl) diphenylacetylene, poly (trifluoromethyl) diphenylacetylene, Cu-PC (Curper Phthalocyanine) poly (bistrifluoromethyl) acetylene, polybis (T-butyldiphenyl) Acetylene, poly (trimethylsilyl) diphenylacetylene, poly (carbazole) diphenylacetylene, polydiacetylene, polyphenylacetylene, polypyridineacetylene, polymethoxyphenylacetylene, polymethylphenylacetylene, poly (t-butyl) phenylacetylene At least one selected from the group consisting of polynitrophenylacetylene, poly (trifluoromethyl) phenylacetylene, poly (trimethylsilyl) phenylacetylene, and derivatives thereof. Inorganic hybrid solar-yu that. The P-type chalcogenide compound constituting the P-type semiconductor layer is CuInS ₂ (CIS), CuGaS ₂ (CGS), CuInSe ₂ (CISe), CuGaSe ₂ (CGSe), CuAlSe ₂ (CASe). ), CuInTe ₂ (CITe), CuGaTe ₂ (CGTe), Cu (In, Ga) S ₂ (CIGS), Cu (In, Ga) Se ₂ (CIGSe), Cu ₂ ZnSnS ₄ (CZTS), CdTe and the like. Organic-inorganic hybrid solar cell, characterized in that at least one selected from the group. The method of claim 1, wherein the N-type semiconductor layer is at least one selected from the group consisting of fullerene (C60) C60 derivatives, perylene, perylene derivatives, PTCBI, ZnO, ITO, etc. Organic-inorganic hybrid solar cell. The organic-inorganic hybrid solar cell of any one of claims 1 to 3, comprising a buffer layer between the two opposing electrodes. 6. The organic-inorganic hybrid solar cell of claim 5, wherein any one of the two opposite electrodes is formed on glass, plastic, metal foil or ceramic.

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