KR20100090898A - Organic photovolatic device with improved conversion efficiency by inserting thin layer of high hole transporting capability and method for fabricating the same - Google Patents

Abstract

PURPOSE: An organic photovoltaic device and a method for manufacturing the same are provided to increase an open voltage and current by minimizing a leakage current with low short-circuit current loss. CONSTITUTION: An electrode protective layer(102) is formed on a transparent substrate in which a transparent electrode is formed. An organic active layer(104) blends an organic semiconductor. A metal anode is deposited on the organic active layer. An organic thin film layer(103) is formed between the electrode protective layer and the organic active layer. The organic thin film layer is a p-type organic semiconductor thin film and is formed using a copolymer with a hole transporting functional group and a photo-crosslinking functional group.

Description

ORGANIC PHOTOVOLATIC DEVICE WITH IMPROVED CONVERSION EFFICIENCY BY INSERTING THIN LAYER OF HIGH HOLE TRANSPORTING CAPABILITY AND METHOD FOR FABRICATING THE SAME}

The present invention relates to an organic photoelectric conversion device and a method for manufacturing the same, and more particularly, to an organic photoelectric conversion device having an excellent hole mobility and an increased energy efficiency using an optical crosslinking thin film forming technology and a method for manufacturing the same. It is about.

Recently, the necessity of clean alternative energy due to high oil prices and environmental pollution is increasingly urgent, and in response to this, countries around the world are putting national emphasis on developing alternative energy sources such as hydrogen / fuel cells, solar cells, and wind power. Accordingly, the demand of solar cells is increasing rapidly, and the rapid expansion of the solar cell industry is causing the over demand of crystalline silicon solar cells, which is the main model, and causing severe supply shortage of silicon materials. Therefore, it is considered that the development of organic thin film solar cell is very important in overcoming the problem of inorganic silicon material, which is already limited in economics and supply and demand.

In 1986, after Tang became known for manufacturing organic thin film solar cells with a photoelectric conversion efficiency of 1% (CW Tang, Appl. Phys. Lett. 48: 183, 1986), Although the research continued, the technology development remained in a stalemate state, and it was not practically used. From the early 2000's, through the dramatic increase in the photoelectric conversion efficiency, it has recently developed to the practical state.

Since organic materials, which are basically p-type semiconductors, have low electron mobility, organic thin film solar cells should be made through the junction of p-type and n-type semiconductors. When the organic thin film solar cell using fullerene having excellent charge mobility was first introduced in 1993, these devices were not attracted much attention due to the very low photoelectric conversion efficiency (NS Sariciftci, et al., Appl. Phys. Lett. 62: 585, 1993; JJM Halls, et al., Appl. Phys. Lett. 68: 3120, 1996). However, through continuous technology development, a device having a photoelectric conversion efficiency of about 2.5% was reported in 2001 by mixing conductive polymer poly (3-hexylthiophene, P3HT] with fullerene (SE Shaheen, et al., Appl. Phys. Lett. 78: 841, 2001), many studies have been conducted to fabricate organic thin film solar cells using the mixture, and in 2003 a device having a photoelectric conversion efficiency of about 3.5% was developed. (F. Padinger, et al., Adv. Funct. Mater. 13: 85, 2003). Then, in 2005, an organic thin film solar cell having a photoelectric conversion efficiency of 5% was developed by changing the mixing ratio of known P3HT and fullerene and increasing the charge mobility using heat treatment (W. Ma, et al., Adv. Funct. Mater. 15: 1617, 2005).

This rapid increase in the photoelectric conversion efficiency is achieved by changing the composition ratio of the composite to make the formation of a bicontinuous phase more smoothly, such as the interpenetrating network, the morphology of the composite through heat treatment and the improved crystallization of P3HT. This is due to the improvement of hole mobility and the improved adhesion between the photoelectric conversion active layer and the metal electrode. Subsequently, organic thin-film solar cells with a photoelectric conversion efficiency (energy conversion efficiency) of about 6% are now produced through continuous improvement of the properties of the composite.

As described above, an organic thin film solar cell using a polymer (an organic thin film solar cell having a polymer laminated structure) currently uses a mixture of P3HT having high hole mobility and fullerene having high electron mobility on an ITO substrate which is a transparent conductive substrate. It is manufactured by the method of apply | coating. This method has the advantage that a device can be manufactured by simple spin coating after mixing two organic semiconductors in a solvent using high processability of the polymer. At this time, in order to obtain high photoelectric conversion efficiency, high current extraction and open voltage are required, and high rectification is required. To do this, first of all, it is necessary to prevent leakage current. That is, the organic polymer photoelectric conversion element (for example, the polymer multilayer organic thin film solar cell) uses a relatively thin organic active layer of about 100 nanometers (due to the characteristics of the polymer semiconductor in which a thick film cannot be used due to low charge mobility). As the thin organic active layer is affected by the roughness of the electrode surface, pin holes are easily formed, which causes a large amount of leakage current and decreases efficiency due to low rectification. Therefore, in order to reduce such leakage current, the use of an organic thin film layer is the most common method. In other words, in order to reduce recombination of electrons formed around the anode (transparent ITO electrode) to the excitons and to prevent the generated excitons from approaching and disappearing from the electrode protective layer, an organic thin film layer, that is, an organic semiconductor charge disappearance prevention thin film layer, is required. .

However, the use of such an organic thin film layer causes an increase in bulk series resistance, thereby reducing current extraction and thus reducing energy efficiency. In other words, the use of a thin film layer that does not use an appropriate material and device fabrication technique usually results in a decrease in efficiency due to a loss of short-circuit current due to an increase in volume series resistance, rather than a gain obtained while reducing leakage current. In addition, since the organic thin film layer is dissolved in the solvent of the organic active layer, there is a problem in that it cannot be applied to a general organic polymer photoelectric conversion device (polymer laminated organic thin film solar cell) in which the organic active layer should be stacked on the thin film layer.

An object of the present invention is to increase the open voltage and rectification by minimizing the leakage current while reducing the loss of short-circuit current by using the organic semiconductor thin film formation technology of the excellent hole mobility and optical cross-linking method of organic semiconductor having excellent energy efficiency The present invention provides a photoelectric conversion device and a method of manufacturing the same.

According to one aspect of the present invention, an organic photoelectric conversion device having a superior energy efficiency by increasing the open voltage and rectification is disclosed and a method of manufacturing the same. This organic photoelectric conversion element includes an electrode protective layer formed on a transparent substrate on which a transparent electrode is formed; An organic active layer blended with an organic semiconductor; A metal anode deposited on the organic active layer; And an organic thin film layer formed between the electrode protective layer and the organic active layer and having high hole mobility and photocrosslinking. In one embodiment, the organic thin film layer is a p- type organic semiconductor thin film, an organic semiconductor charge disappearance prevention thin film layer formed using a copolymer polymer comprising a hole transporting functional group and a photocrosslinking functional group, the organic semiconductor charge disappearance prevention thin film layer is It does not dissolve in the solvent of the organic active layer, and can prevent a leakage current. In addition, a method of manufacturing an organic photoelectric conversion device includes forming an electrode protective layer on a transparent substrate on which a transparent electrode is formed; Forming a copolymer polymer thin film and then photocrosslinking to form an organic semiconductor charge disappearance prevention thin film layer; Blending the organic semiconductors to form an organic active layer; And depositing a metal anode on the organic active layer.

According to the present invention, a p-type organic semiconductor thin film capable of photocrosslinking is inserted between an electrode protective layer and an organic active layer, thereby minimizing leakage current, thereby increasing open voltage and rectification and having good hole mobility. Because of this, since the storage of the movement of holes extracted by the ITO transparent electrode is minimized, it does not cause a large increase in volume resistance, thereby minimizing the reduction of short-circuit current, thereby manufacturing a device having increased photoelectric conversion efficiency.

In addition, the p-type copolymer polymer used in the present invention includes a functional group capable of photocrosslinking. When photocrosslinking is performed using ultraviolet rays after forming a thin film, a thin film insoluble in an organic solvent is formed to spin-coated the organic active layer directly. Since the laminated structure can be formed, the device fabrication process does not require a special process such as high temperature and vacuum, and thus can be usefully used in the fabrication and development of next generation large area flat panel organic devices.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the following description, well-known functions or constructions will not be described in detail if they obscure the subject matter of the present invention.

1 is a cross-sectional view of an organic photoelectric conversion element according to an exemplary embodiment of the present invention and shows a cross section of a p-n junction type polymer photoelectric conversion element.

As shown in the figure, the organic photoelectric conversion element according to the present invention, an electrode protective layer (for example, poly-3,4-ethylenediox) formed on a transparent substrate on which a transparent electrode 101 such as indium tin oxide (ITO) is formed A Citiopen (PEDOT) electrode protective layer) 102, an organic active layer 104 blended with an organic semiconductor, a metal anode (eg, a metal anode such as aluminum) 105 deposited on the organic active layer 104, and And an organic thin film layer 103 formed between the electrode protective layer 102 and the organic active layer 104.

The organic thin film layer 103 is formed using a 'crosslinking thin film forming technology'. 'Photocrosslinking thin film formation technology' is a method of forming an organic polymer semiconductor material having a similar solubility in an organic solvent in a stacked structure. In the present invention, the organic thin film layer 103 having a high selective charge mobility of holes is formed. Inserted between the electrode protective layer 102 and the organic active layer 104, the thickness of the thin film layer 103 is adjusted to minimize the increase in the bulk series resistance while minimizing the increase in open voltage and leakage current. Increase the rectification through.

The organic thin film layer 103 is a p-type organic semiconductor thin film layer having high hole mobility (selective charge mobility of holes) and capable of photocrosslinking, and is referred to in the present invention as a 'base-based conductive charge preventing thin film layer'.

The organic semiconductor charge disappearance prevention thin film layer 103 has a thickness such that it does not cause a large increase in volume series resistance. In one embodiment, the organic semiconductor charge disappearance prevention thin film layer 103 includes a carbazole functional group having good hole mobility and a copolymer polymer (eg, polyvinyl carbazole has oxytans) including a photocrosslinkable functional group. Copolymerized synthetic polymer) to form a thin film having a thickness of about 10 nanometers. Since the organic semiconductor charge disappearance prevention thin film layer 103 is a p-type organic semiconductor thin film which minimizes leakage current and increases open voltage and rectification, and also has good hole mobility, the organic semiconductor charge disappearance thin film layer 103 Minimized resistance does not cause a large increase in volumetric series resistance, minimizing the reduction of short-circuit currents (ie, increasing open-circuit voltage and rectification without a significant reduction in short-circuit current), enabling the fabrication of devices with increased photoelectric conversion efficiency. In addition, since the organic semiconductor charge disappearance prevention thin film layer 103 includes a functional group capable of photocrosslinking, when the photocrosslinking is performed using ultraviolet rays after forming the thin film, a thin film that does not dissolve in an organic solvent can be formed, and thus the organic active layer 104 Can be directly spin-coated to form a laminated structure.

Hereinafter, a method of fabricating an organic photoelectric conversion device having increased open voltage and rectification on a transparent electrode will be described.

First, the electrode protective layer 102 is formed on the transparent substrate on which the transparent electrode 101 is formed. Further, on the electrode protective layer 102, a copolymer polymer semiconductor thin film, which is a p-type organic semiconductor thin film, is formed and then photocrosslinked to form the organic semiconductor charge disappearance prevention thin film layer 103. In addition, the organic semiconductor is blended on the organic semiconductor charge disappearance prevention thin film layer 103 to form an organic active layer 104. In addition, a metal electrode 105 is deposited on the organic active layer (oil-based conductor composite film) 104.

In one embodiment, the transparent substrate may be selected from the group consisting of glass, quartz, transparent plastic, polyethylene terephthalate (PET), polyethersulfone, and the like.

In one embodiment, the transparent electrode 101 is selected from the group consisting of indium tin oxide (ITO), polyethylene dioxythiophene (PEDOT), polyaniline, polypyrrole, and the like. Can be.

In one embodiment, the electrode protective layer 102 may be selected from the group consisting of polyethylene dioxythiophene (PEDOT), polyaniline or polypyrrole.

In one embodiment, the metal electrode 105 may be selected from the group consisting of aluminum, magnesium, lithium, calcium, copper, silver, gold, platinum and alloys thereof.

In particular, in an embodiment, the organic semiconductor charge disappearance prevention thin film layer 103 inserted between the electrode protective layer 102 and the organic active layer 104 is capable of photocrosslinking with a carbazole group, which is a hole transporting functional group. Poly {9- (4-vinyl-benzyl) -9H-carbazole-co-3-methyl-3- (4-vinyl-benzyloxymethyl) -oxetane}, a copolymer polymer containing an oxetane group as a functional group, was used. Produce using The structure of this copolymer is shown in FIG. The copolymer may be photocrosslinked using only ultraviolet rays, and crosslinking may be easier and faster by adding a well known initiator, a, a'-azobisisobutyronitrile (AIBN). The use of the organic semiconductor charge disappearance prevention thin film layer 103 including the functional group capable of photocrosslinking is very useful in an organic thin film device having a polymer laminate structure using organic solvents having similar conditions. That is, as described above, in order to increase the open-circuit voltage and reduce the leakage current to increase the rectification, a charge dissipation prevention thin film layer having semiconductor characteristics is essential, but in the case of an organic thin film device having a polymer laminated structure, such a thin film layer is generally organic. Since it is soluble in the solvent of the active layer, its use is limited. However, in the present invention, the organic semiconductor charge disappearance prevention thin film layer 103 does not dissolve in the solvent of the organic active layer 104 to be stacked next to serve as a semiconductor to prevent leakage current.

Here, the hole transporting functional group of the organic semiconductor charge disappearance prevention thin film layer 103 may be selected from the group consisting of organic substances having excellent hole mobility and derivatives thereof such as carbazole, triphenylamine and the like, and the photocrosslinking functional group may be oxytane. It may be selected from the group consisting of organic materials capable of photocrosslinking such as double bonds or triple bonds or photocrosslinking using an initiator and derivatives thereof.

The polymer exhibits improved internal quantum efficiency due to increased charge mobility due to external low applied voltage, excellent processability, device fabrication by coating or printing technology at room temperature, and easy fabrication of large area devices. It is gaining the spotlight as a next-generation photoelectric conversion device because it has various advantages such as flexibility, low cost of device fabrication, and control of band gap through molecular design. Using the polymer blend as described above has the advantage that a large area of the device can be easily manufactured by spin coating a sample of a solution to form a dual continuous interpenetrating network polymer composite film of a thin film. Thus, when the p-n junction type dual continuous interpenetrating network type polymer composite film is formed, the separation ability of excitons generated by light absorption into electron-holes is increased due to the increase of the p-n junction interface. In addition, the dual-continuous interpenetrating network structure is characterized in that p-type and n-type polymers are connected to each of the required electrodes, thereby facilitating movement of generated electrons or holes to the electrodes, thereby increasing photoelectric efficiency and recombining with excitons. It can prevent. In addition, it is possible to prevent charges from accumulating in the device by smooth transportation through the secured charge transfer path, thereby extending the life of the device by preventing the load from being loaded inside the device.

By using the 'crosslinking thin film formation technology' of the present invention, it is possible to manufacture an organic photoelectric conversion device that continuously shows excellent photoelectric conversion efficiency. According to the present invention, since all systems are capable of processing with solution at room temperature and do not include a particularly complicated process, the high temperature process required in the dye-sensitized organic-inorganic hybrid nanoparticle system, which is drawing attention recently, is not required. In addition, flexible ultra-thin photoelectric materials having high quantum efficiency can be developed and used as solar cells or optical sensors.

3 is poly {9- (4-vinyl-benzyl) -9H-carbazole-co-3-methyl-3 which is a copolymer polymer including a carbazole group as a hole transporting functional group and an oxytan group as a photocrosslinkable functional group Ultraviolet spectrum analysis results before and after photocrosslinking of-(4-vinyl-benzyloxymethyl) -oxetane} are shown. 330 nm and 345 nm are well known as characteristic absorption peaks of the carbazole group.

FIG. 4 shows images of atomic force microscopy (AFM) before and after optical crosslinking of the organic semiconductor charge disappearance prevention thin film layer capable of optical crosslinking.

FIG. 5 illustrates current-voltage characteristics of a general organic polymer photoelectric conversion device (polymer stacked organic thin film solar cell) that does not include an organic semiconductor charge disappearance prevention thin film layer, and FIG. 6 illustrates an organic semiconductor charge according to an embodiment of the present invention. The current-voltage characteristics of the organic photoelectric conversion element including the anti-quenching thin film layer are shown.

Hereinafter, the present invention will be described in more detail with reference to specific examples.

First, the optical crosslinking characteristics of the organic semiconductor charge disappearance prevention thin film layer 103 will be described.

The light-crosslinkable organic semiconductor charge dissipation prevention thin film layer 103 is a poly {9 copolymer, which is a copolymer of a carbazole group, a functional group (hole transporting functional group) having excellent hole transporting ability, and an oxytan group, a photocrosslinkable functional group (photocrosslinking functional group). -(4-vinyl-benzyl) -9H-carbazole-co-3-methyl-3- (4-vinyl-bennzyloxymethyl) -oxetane} and the ratio of the hole transporting functional group and the photocrosslinking functional group in the copolymerized polymer. Is 2: 1. The molecular weight of the copolymer was analyzed by Gel Permeation Chromatography (GPC), and the number-average molecular weight and the weight-average molecular weight were 8500 and 16,000 g, respectively. / mol. In addition, the glass transition temperature of the copolymer using a differential scanning calorimeter was 115 degrees. The glass transition temperature is a major parameter that determines which temperature should be irradiated with heat treatment at a temperature in order to photocrosslink the formed organic semiconductor charge disappearance prevention thin film layer 103. This photocrosslinked thin film is completely insoluble in common organic solvents (eg, toluene, chloroform, tetrahydrofuran (THF)).

The organic thin film is irradiated with ultraviolet rays (UV) at 254 nm having an intensity of 40 mW / cm ² for 10 seconds to form photocrosslinks. As shown in FIG. 3, after washing the organic thin film with tetrahydrofuran (THF), which is a typical organic solvent before and after photocrosslinking using infrared spectroscopy, size changes of 330 nm and 345 nm, which are typical absorption peaks of a carbazole functional group, were observed. It was confirmed that the peak size of the carbazole functional group of the thin film washed with an organic solvent did not change, it was confirmed that the photocrosslinking is well made. FIG. 4 shows an image of an atomic force microscope before (a) and after (b) optical crosslinking of the organic semiconductor charge disappearance prevention thin film layer 103. The organic semiconductor charges are washed with an organic solvent after photocrosslinking (b). The surface roughness of the anti-decaying thin film layer 103 is slightly increased, which is a function of washing the organic solvent and the ultraviolet absorbance of the carbazole functional group does not change, so that the organic semiconductor charge disappearance preventing thin film layer 103 is completely cross-linked to the organic solvent. It was confirmed that it did not melt in. In addition, it was confirmed that the thickness of the thin film did not change even in the thickness measurement before (a) and after (b) optical crosslinking using a surface profiler.

Now, the manufacturing process of the organic photoelectric conversion device will be described.

1 × 1 inch ITO glass washed with chloroform, isopropyl alcohol and acetone was subjected to O ₂ plasma treatment for 15 minutes, followed by PEDOT (poly 3,4-ethylenedioxythiophene) (Dow Chemical) as an electrode protective layer. Spin coating and drying in a 110 ℃ vacuum oven. As described above, the organic semiconductor charge disappearance prevention thin film layer 103 is formed and then photocrosslinked to prevent the organic semiconductor charge disappearance prevention thin film layer 103 from being dissolved in the solvent of the organic active layer 104 to be stacked next. The organic active layer is a blend solution in which poly (3-hexylthiophene) and fullerene derivatives (PCBM: [6,6] -phenyl C61-butyric acid methyl ester) are dissolved in chlorobenzene, an organic solvent. The organic active layer 104 was stacked on the organic semiconductor charge dissipation prevention thin film layer 103 and then LiF and aluminum were vacuum deposited on the metal electrode 105 to complete the device. 5 and 6, a general organic polymer photoelectric conversion element (polymer stacked organic thin film solar cell) without the organic semiconductor charge disappearance prevention thin film layer 103 and an organic photoelectric conversion element including the organic semiconductor charge disappearance prevention thin film layer 103 are formed. The current-voltage characteristics are compared and shown. The two devices have the same condition except that the organic semiconductor charge disappearance prevention thin film layer 103 is included. The characteristics of the two devices are shown in Table 1 below.

Comparative element (organic polymer photoelectric conversion element) Organic photoelectric conversion element including charge extinction prevention thin film layer Short circuit current (mA / cm ² ) 9.943 9.143 Open voltage (V) 0.400 0.532 fill factor 0.506 0.555 Conversion efficiency (%) 2.015 2.699

As shown in Table 1, the short-circuit current is lower than the comparable device (organic polymer photoelectric conversion device) in the organic photoelectric conversion device of the present invention including the organic semiconductor charge disappearance prevention thin film layer 103, but the open circuit voltage and rectification The fill factor is shown to be superior to the organic photoelectric conversion device of the present invention including the organic semiconductor charge disappearance prevention thin film layer (103). As a result, the overall conversion efficiency is found to increase by 34% in the organic photoelectric conversion device of the present invention including the organic semiconductor charge disappearance prevention thin film layer (103). That is, in the organic solar cell using the thin film of the organic active layer 104 in order to obtain the highest efficiency due to the low charge mobility of the organic material, the organic semiconductor charge disappearance prevention thin film layer 103 to the electrode protective layer 102 and the organic active layer 104 By inserting between), the leakage current is reduced and the rectification is increased to increase the conversion efficiency through the increase of open voltage and fill factor.

For reference, the efficiency of the solar cell is calculated from the current-voltage curve. Power Conversion Efficiency (PCE) is defined by Equation 1 below.

Where V _OC is the open voltage of the solar cell, I _SC is the short-circuit current, FF is the fill factor, and P _in is the intensity of incident light. In the fill factor, V _P and I _P are the values at the point showing the maximum power during solar current-voltage measurement, respectively. It can be understood that I _SC is determined by the following specific factors.

I _SC ∝ ε _ext = ε _A * ε _int = ε _A * ε _ED * ε _CT * ε _CC

Where ε _ext is external quantum efficiency, ε _int is internal quantum efficiency, ε _A is photon absorption efficieny, ε _ED is exciton diffusion efficiency, ε _CT is charge trnsfer efficiency, and ε _CC is charge collection efficiency. ε _A depends on the light absorption capacity of the semiconductor material itself and the device, ε _ED and ε _CT represent the lifetime and charge transport of the excition, and ε _CC represents the efficiency of charge collection at the electrode.

Although the present invention has been described in connection with some embodiments thereof, it should be understood that various changes and modifications may be made therein without departing from the spirit and scope of the invention as understood by those skilled in the art. something to do. It is also contemplated that such variations and modifications are within the scope of the claims appended hereto.

1 is a cross-sectional view of an organic photoelectric conversion device according to an exemplary embodiment of the present invention.

Figure 2 is a structural formula of the copolymer forming the organic semiconductor charge disappearance prevention thin film layer of Figure 1;

3 is a graph showing the results of ultraviolet spectrum analysis before and after photocrosslinking of the copolymer according to the embodiment of the present invention.

FIG. 4 is a view showing atomic microscope images before and after photocrosslinking of an organic semiconductor charge disappearance prevention thin film layer capable of photocrosslinking according to an exemplary embodiment of the present invention. FIG.

5 is a graph showing current-voltage characteristics of a general organic polymer photoelectric conversion device (polymer stacked organic thin film solar cell) that does not include an organic semiconductor charge disappearance prevention thin film layer.

6 is a graph showing current-voltage characteristics of an organic photoelectric conversion device including an organic semiconductor charge disappearance prevention thin film layer according to an embodiment of the present invention.

* Explanation of symbols for the main parts of the drawings

101: transparent electrode 102: electrode protective layer

103: organic thin film layer 104: organic active layer

105: metal anode

Claims (17)

As an organic photoelectric conversion element, An electrode protective layer formed on the transparent substrate on which the transparent electrode is formed; An organic active layer blended with an organic semiconductor; A metal anode deposited on the organic active layer; And And an organic thin film layer formed between the electrode protective layer and the organic active layer and having high hole mobility and capable of photocrosslinking. The method of claim 1, The organic thin film layer is a p-type organic semiconductor thin film, an organic semiconductor charge disappearance prevention thin film layer formed using a copolymer polymer comprising a hole transporting functional group and a photocrosslinking functional group, The organic semiconductor charge disappearance prevention thin film layer is insoluble in the solvent of the organic active layer can prevent the leakage current, the organic photoelectric conversion element. The method of claim 2, The copolymer is poly {9- (4-vinyl-benzyl) -9H-carbazole-co-3-methyl-3-, which is a copolymer of a carbazole group having excellent hole transporting ability and an oxytan group which is a photocrosslinkable functional group. The organic photoelectric conversion element produced using (4-vinyl- benzyloxymethyl) -oxetane}. The method of claim 2, The copolymer polymer is an organic photoelectric conversion device capable of directly spin coating the organic active layer by forming a thin film insoluble in an organic solvent by crosslinking with only ultraviolet rays or by adding an initiator. The method of claim 2, The hole transport functional group is selected from the group consisting of organic substances having excellent hole mobility and derivatives thereof such as carbazole and triphenylamine, The photocrosslinking functional group is selected from the group consisting of organic materials capable of photocrosslinking such as oxytane, double bonds or triple bonds or photocrosslinking using an initiator and derivatives thereof. 6. The method according to any one of claims 1 to 5, The transparent substrate is an organic photoelectric conversion device, selected from the group consisting of glass, quartz, polyethylene terephthalate (PET) or polyethersulfone. 6. The method according to any one of claims 1 to 5, The transparent electrode is selected from the group consisting of indium tin oxide (ITO), polyethylene dioxythiophene (PEDOT), polyaniline (polyaniline) or polypyrrole (organic photoelectric conversion device). 6. The method according to any one of claims 1 to 5, The electrode protective layer is selected from the group consisting of polyethylene dioxythiophene (PEDOT), polyaniline (polyaniline) or polypyrrole (organic photoelectric conversion device). 6. The method according to any one of claims 1 to 5, The metal electrode is selected from the group consisting of aluminum, magnesium, lithium, calcium, copper, silver, gold, platinum and alloys thereof. As a manufacturing method of an organic photoelectric conversion element, Forming an electrode protective layer on the transparent substrate on which the transparent electrode is formed; Forming a copolymer polymer thin film and then photocrosslinking to form an organic semiconductor charge disappearance prevention thin film layer; Blending the organic semiconductors to form an organic active layer; And Depositing a metal anode on the organic active layer Organic photoelectric conversion device manufacturing method comprising a. The method of claim 10, The organic semiconductor charge disappearance prevention thin film layer is a p-type organic semiconductor thin film, which is formed by using a copolymer polymer including a hole transporting functional group and a photocrosslinking functional group, which is insoluble in a solvent of the organic active layer and prevents leakage current. Photoelectric conversion device manufacturing method. The method of claim 11, The copolymer polymer can be spin-coated directly with the organic active layer by forming a thin film insoluble in the organic solvent by crosslinking only with ultraviolet light or by adding an initiator. The method of claim 11, The hole transport functional group is selected from the group consisting of organic substances having excellent hole mobility and derivatives thereof such as carbazole and triphenylamine, The photocrosslinking functional group is selected from the group consisting of organic materials capable of photocrosslinking such as oxytane, double bonds or triple bonds or photocrosslinking using an initiator and derivatives thereof. The method of claim 11, The copolymer is poly {9- (4-vinyl-benzyl) -9H-carbazole-co-3-methyl-3-, which is a copolymer of a carbazole group having excellent hole transporting ability and an oxytan group which is a photocrosslinkable functional group. The manufacturing method of the organic photoelectric conversion element manufactured using (4-vinyl benzyloxymethyl) -oxetane}. The method according to any one of claims 10 to 14, The transparent substrate is selected from the group consisting of glass, quartz, polyethylene terephthalate (PET) or polyethersulfone, The transparent electrode is selected from the group consisting of indium tin oxide (ITO), polyethylenedioxythiophene (PEDOT), polyaniline or polypyrrole, The electrode protective layer is selected from the group consisting of polyethylene dioxythiophene (PEDOT), polyaniline (polyaniline) or polypyrrole, The metal electrode is selected from the group consisting of aluminum, magnesium, lithium, calcium, copper, silver, gold, platinum and alloys thereof. The solar cell using the element manufactured by the organic photoelectric conversion element manufacturing method of any one of Claims 10-14. The optical sensor using the element manufactured by the organic photoelectric conversion element manufacturing method of any one of Claims 10-14.

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