KR100670857B1 - Conducting polymer nano structure photovoltaic device prepared by electrochemical polymerization method using block copolymer nano template and method for fabricating the same - Google Patents

Abstract

A conducting polymer nano structure photovoltaic device and a method for manufacturing the same are provided to reduce the loss of an absorbed light by obtaining a high density P type polymer nano structure using a block copolymer nano template. A nano template with nano porosities is formed on a transparent substrate by using a block copolymer. A P type polymer nano structure is formed on the nano template. The nano template is removed from the resultant structure by using an organic solvent. An N type organic material is coated on the P type polymer nano structure. A metal electrode layer is deposited on the N type organic material.

Description

Conductive polymer nanostructure photoelectric conversion device manufactured using a block copolymer nanotemplate and a method for manufacturing the same

1 is a cross-sectional view of an organic photoelectric device formed of a polymer nanostructure of p-n junction type.

Figure 2 is a schematic diagram showing a method of growing a p-type conductive polymer nanostructure using a nano template to make a polymer p-n type organic photoelectric device.

3 is an ideal nanostructure assuming that the average life time of the exciton of the organic polymer is 10 nm.

Figure 4 is a FE-SEM image photograph of the formed polypyrrole nano structure.

5a to 5c is a cross-sectional FE-SEM image photograph of the polypyrrole nano structure formed by reacting for 10, 20, 40 minutes.

Figure 6 is a graph showing the change in the amount of current with the change in the electrochemical reaction time ((a) in the absence of polystyrene film and (b) in the presence of 100 nm thick polystyrene).

7 is a graph showing the degree of filling of a template with a chronoamperogram.

8 is a graph showing the current-voltage characteristics of the fabricated nanostructured organic photoelectric conversion device.

Figure 9 is a cross-sectional FE-SEM image photograph of the fabricated nano-template.

<Explanation of symbols for the main parts of the drawings>

101: glass substrate

102: ITO electrode

103: PEDOT electrode protective layer

104: p-type polymer nanostructure layer

105: n-type organic compound layer

106: metal anode

The present invention relates to fabrication of an organic polymer photoelectric conversion device using a polymer nano template. Specifically, the present invention forms a nano-template having a high pore density on the transparent electrode using a block copolymer, and then grow the p-type polymer in the nano-pores, then remove the nano-template and the p-type organic film The present invention relates to a technology capable of making a device exhibiting excellent photoelectric conversion effect by coating on a type polymer.

Nano-template technology has been developed and used. In 1986, Martin and his colleagues reported a method of growing conductive polymer fibers using a commercially available, particle track-etched polycarbonate membrane [RM Penner, CR Martin, J. Electrochem. Soc., 133, 2206 (1986)]. Since then, nanotemplate technology has been used frequently to grow nanoscale polymers and metal fibers. Nano-templated nano templates include electron particle etched polycarbonate films and anodized aluminum oxide films. As another technique for preparing a polymer nano template, an external electric field is applied to an asymmetric block copolymer to form nano pores arranged in the form of a hexagonal body [T. Thurn-Albrecht, J. Schotter, GA Kaestle, N. Emley, T. Shibauchi, L. Krusin-Elbaum, K. Guarini, CT Black, MT Tuominen, TP Russell, Science, 290, 2126 (2000) A method of forming organic compound nano domains that can be easily removed in the nanopores of a block copolymer by blending a small amount of organic compounds in a copolymer [A. Sidorenko, I. Tokarev, S. Minko, M. Stamm, J. Am. Chem . Soc ., 125, 12211 (2000)] and a method of fabricating nano-templates by making pin-shaped molds on SiO ₂ using reactive ion etching technology and dipping them on polymer membranes such as polymethylmethacrylate [SY Chou, PR Krauss, PJ Renstrom, Appl . Phys. Lett ., 67, 3114 (1995); SY Chou, PR Krauss, W. Zhang, L. Guo, L. Zhuang, J. Vac . Technol . B , 15, 2897 (1997).

Commercially available commercial polymer nanotemplates have a relatively low pore density. The pore density ranges from 10 ⁵ to 10 ⁹ / cm ² and the cigar-like shape of nano-sized pores is randomly distributed throughout the membrane. Although attempts have been made to form photoelectric conversion devices using commercial nanotemplates, this method has a much lower pore density than the block copolymer polymer nanotemplates used in the present invention. In addition, the conventional technology is a template used to grow a p-type polymer by forming an electrode by depositing an electrode material such as gold on one side of a commercial nano-plate having nano pores or an anodized aluminum oxide film when forming a photoelectric conversion device Although the method is used to sputter the transparent electrode again, the present technology first forms a block copolymer film capable of forming a nanostructure on the transparent electrode ITO, and then forms nanopores using phase separation of the polymer and then uses the same. Since the fabrication of the photoelectric conversion device is easy, the device is easy to fabricate, and conventional techniques are using a completely different method from causing an undesired reaction in the photoelectric conversion layer using harsh conditions.

Therefore, an object of the present invention is to solve the problems of the prior art, a photoelectric conversion device that can achieve excellent photoelectric conversion efficiency using a device manufacturing technology and a polymer material superior to the conventional photoelectric conversion device manufacturing technology using nano-templates To provide.

In the present invention, by forming a nano-template having a high pore density on the transparent electrode using a block copolymer, the p-type polymer is grown in nano-pores, the nano-template is removed and the n-type organic film is coated on the p-type polymer The photoelectric conversion element is manufactured. This technology nanostructured p-type polymer with high density on the transparent electrode to ensure the high specific surface area, which is the basic condition for showing excellent photoelectric conversion effect, as well as the transfer path of generated charges, and also has an ideal nanostructure. All of the photoelectric conversion layers become effective separation regions, thereby reducing the amount of absorbed light, thereby making it possible to fabricate an organic photoelectric conversion device having high efficiency.

In addition, an object of the present invention to develop a flexible ultra-thin photoelectric material having a high photoelectric conversion efficiency with such a structure, the photoelectric device using them can be used as a solar cell or an optical sensor.

More specifically, the present invention comprises the steps of forming a nano template having nano pores on the transparent electrode using a block copolymer, forming a p-type polymer nanostructure on the formed nano-template, nano-template using an organic solvent It provides a method of manufacturing a photoelectric conversion device comprising the step of removing, coating the n-type organic material on the p-type polymer nanostructure and depositing a metal electrode layer on the n-type organic material.

In the above method, the p-type polymer is selected from the group consisting of polypyrrole and derivatives thereof, polyaniline and derivatives thereof, or polythiophene and derivatives thereof.

n-type organic compounds include polyquinoline and its derivatives, poly (para-phenylenevinylene) and its derivatives, polythiophene and its derivatives, poly (para-phenylene) and its derivatives, polyflorene and its derivatives, Polyacetylene and derivatives thereof, tetratracynoquinodimethane, fullerene, 1,4,5,8-naphthalene tetracarboxylic dianhydride and derivatives thereof, 1,4,5,8-naphthalene Tetracarboxylic acid diimide and its derivatives, 11,11,12,12-tetracyanonaphtho-2,6-quinomimethane and its derivatives, 3,4,9,10-perylenetetracarboxylic acid dianhydra Id and 3,4,9,10-perylenetetracarboxylic acid diimide and its derivatives, derivatives of metallophthalocyanine, sexithiophene and its derivatives, and pentacene. have.

The transparent substrate is polyethylene (terephthalate) or polyethersulfone (PET) which is glass, quartz, or transparent plastic, and the transparent electrode is indium tin oxide (ITO). Polyethylenedioxythiophene (PEDOT), polyaniline or polypyrrole can be used.

The metal electrode is selected from the group consisting of aluminum, magnesium, lithium, calcium, copper, silver, gold, platinum, and alloys thereof, and the block copolymer may be a polystyrene-b-polymethylmethacrylate block copolymer. have.

In addition, the present invention is a photoelectric conversion comprising a transparent electrode, a p-type polymer nanostructure formed thereon, an n-type organic material coated on the p-type polymer nanostructure, a metal electrode layer deposited on the n-type organic material As an element, there is provided a photoelectric conversion element exhibiting an excellent photoelectric conversion effect, which is produced by the method of the present invention.

Other objects and features of the present invention will appear more clearly in the configuration and claims of the invention to be described later.

The present invention provides a novel method of making a nano-structured polymer photoelectric conversion device having a structure that can be excellent in photoelectric conversion efficiency. 1 is a cross-sectional view of such a p-n junction nanostructure polymer photoelectric conversion device. 101 is a transparent substrate such as glass, 102 is a transparent electrode such as ITO, 103 is an electrode protective layer such as poly-3,4-ethylenedioxythiophene (PEDOT), 104 is a p-type polymer semiconductor, 105 is an n-type organic material Semiconductor 106 represents a metal anode, such as aluminum.

The present invention provides a method of fabricating a p-type polymer nanostructure by first forming a template having a high pore density on the transparent electrode using a block copolymer to produce a p-type polymer nanostructure and coating an n-type organic material to produce a photoelectric conversion device. . This method is applied to the existing method of fabricating a photoelectric conversion device by forming a p-type polymer by coating an electrode on a template prepared by using a conventional nano-template method, and then coating the n-type polymer and then sputtering the transparent electrode ITO. Compared to the breakthrough method.

Recently, the development of technology using organic materials in optoelectronic devices has been steadily made. This is because the polymer has an increased mobility of charges due to the external small applied voltage, which increases the internal quantum efficiency and excellent processability. It is possible to manufacture devices by coating or printing technology at room temperature. This is because photoelectric devices using polymers are in the spotlight as next generation photoelectric devices because they have various advantages such as low cost and the ability to adjust band gap through molecular design.

In order to optimize an optoelectronic device using organic materials, it is necessary to first understand photoelectric phenomenon occurring in an organic system. The basic principle of charge generation in organic photoelectric devices is that photons entering organic photovoltaic devices excite organic materials (excite excitons), and excitons are excited by the potential difference generated at the pn junction interface. ) And separated into charges (electrons and holes), the generated charges move to their respective electrodes to generate current.

In this principle, in order to increase photoelectric efficiency, light absorbance must be good first. In other words, the more light is absorbed to produce more excitons, the easier it is to generate charge. Second, the charge separation at the p-n interface (ie electron-hole separation) must be large. The difference between HOMO and LUMO between p-type and n-type semiconductors must be large to overcome the exciton binding energy, and thus the excitons can be separated into electrons and holes. Excitons should be formed in nearby photoactive regions. If the generated electrons and holes do not move again, they recombine with excitons, and thus, recombination of electrons and holes should be prevented through smooth transport of generated charges. Third, the uniform transport of electrons and holes must prevent any single charge from accumulating in the device. In particular, most polymers have a much lower charge mobility compared to inorganic materials, so a smooth migration path must be ensured, and electrons or holes must have similar mobility so that one type of charge does not accumulate in the device. If the charge is well transferred to the electrode, holes or electrons do not accumulate in the device, so that a large load is not applied to the inside of the device, thereby extending the life of the device. In general, organic / inorganic or low molecular / polymer heterojunctions have different transport mechanisms and show different mobility, so p and n materials are preferably the same type of material having similar charge mobility. In addition, it is desirable to form an ohmic contact between the device material and the metal electrode material so that the charge is transferred to the electrode with low resistance.

Among the above-mentioned conditions, the method of increasing the specific surface area of the photoelectric conversion active region by controlling the morphology of the interface is known to be physically controllable and has a direct and excellent effect on increasing the photoelectric efficiency. When the p-n junction-type polymer nanostructure is formed as described above, the resolution of the exciton generated by light absorption due to the increase of the p-n junction interface is increased to the electron-hole. The increase in the junction surface increases the photoelectric efficiency by increasing the probability that the generated excitons are formed in an effective charge separation active area that is broken into electrons and holes. Also, since the distance that can be moved in the lifetime of the generated excitons is usually about 10 nm, about 10 nm from the interface contact surface is regarded as an effective separation region capable of generating electrons and holes. By forming the p-type polymer nanostructures by such effective separation regions, it is possible to design all regions in the device as separation active regions. The increase in photoelectric conversion efficiency is expected to be very large. In addition, in the organic photoelectric conversion device manufactured by the method according to the present invention, the charges generated in each organic semiconductor polymer have a passage toward the electrode to which they should move. That is, in the case of a typical organic blend photoelectric conversion device, a continuous phase commonly found in a domain and a device consisting of a domain, the charge generated in the domain passes through a continuous phase which is not favorable for charge transfer to move to an appropriate electrode along the spontaneous charge flow direction. The burden to go is caused to reduce the photoelectric conversion efficiency, but the device formed with nano structure is expected to increase the photoelectric conversion efficiency because the passage toward the electrode to move them is secured. The p- and n-type polymers are connected to each of the required electrodes, so that the generated electrons or holes are easily moved to the electrodes, which not only increases the photoelectric efficiency but also prevents recombination into excitons. It is also possible to prevent charges from accumulating in the device through transportation, thereby preventing the load from being loaded inside the device, thereby increasing the life of the device.

Photoelectric conversion device fabrication method using the electrochemical polymerization method of the electroconductive polymer using the nano-template used in the present invention can easily form such a polymer nanostructure. 2 shows a method of making a polymer nanostructure using a nano template in the present invention. First, a nano template having nano pores is formed on the transparent electrode using a block copolymer, and then nano pores are formed using a phase separation phenomenon of a polymer. Thereafter, p-type polymer nanostructures are formed using an electrochemical method. Electrochemically formed nanostructures are insoluble in organic solvents, thereby removing nanotemplates. Thereafter, the n-type organic material is spin-coated and a metal electrode layer is deposited to fabricate a photoelectric conversion device.

Figure 3 shows the ideal nanostructure assuming that the average life time of the exciton of the organic polymer is 10 nm. Having such a structure is expected to have a superior specific surface area when using commercially available nano-templates, and all the photoelectric conversion layers become effective separation regions and thus exhibit excellent photoelectric conversion efficiency.

4 and 5 show SEM images of polymer nanostructures made using one embodiment of such a nanotemplate method. In this case, the electrochemical reaction time required to form a p-type polymer was obtained by fixing the molar ratio of pyrrole monomer and dopant to 10: 1 and applying a voltage of 0.64 V using a template having a nanopore size of 20 nm. Fixed in minutes. In the electropolymerization method using a nano template, when the size of the nano pores is 40 nm or less, wetting of monomers and dopants into the narrow nano pores is difficult, so that the filling time of the nano pores through electropolymerization is increased.

Figure 5 shows a cross-sectional scanning electron image of the polymer nanostructure made by the nano-template method, it can be seen that the height of the p-type polymer nanostructure can be adjusted by controlling the electrochemical reaction time of the pyrrole monomer as shown in the image ( 5a is 10 minutes, FIG. 5b is 20 minutes, and FIG. 5c is 40 minutes).

Unlike commercial polymer nanotemplates on the market, templates made of block copolymer membranes utilize phase separation of polymers, so that a regular hexagonal structure is present uniformly within the template, with about 10 ¹¹ pieces / cm ² . Has a pore density of. In addition, since the polymer film having such regularly vertically aligned nano pores cannot be manufactured to a few microns (μm) in thickness, the electrochemical polymerization method using such a thin film requires precise control of the external applied voltage. Electropolymerization using such polymer thin films requires control of the minimum oxidation potential of the monomers used, as well as the selection of electrolytes, dopants and suitable solvents.

6 shows the conditions for finding such a microconditioning method by the amount of current generated during the electropolymerization of the found pyrrole. Polystyrene, a component of the block copolymer used as a nano-template, must be made to the same thickness as the nano-template to find an appropriate monomer minimum oxidation potential point where the monomer oxidizes in the nanopores but the monomer cannot oxidize on the template. The amount of current generated during the electropolymerization of pyrrole in (b) with and without (100) with a 100 nm thick polystyrene film. The reaction was carried out under the same reaction conditions, but in case of (a), the current flow due to the electrochemical reaction of pyrrole appeared large over time, but in case of (b) with a polystyrene film having a thickness of 100 nm, the electrochemical reaction of pyrrole This does not happen.

In order to form nanostructures of appropriate height, not only the proper potential difference described above but also the proper polymerization time is essential. By applying the appropriate potential difference between the electrodes, the pyrrole monomer begins to grow in the nanopores formed in the nanotemplate. At this time, if the polymerization time is not sufficient, the size of the nanostructure is too small, and if the polymerization time is too long, the polypyrrole growing in the formed nanopores fills the pores and forms a polypyrrole film on the template. .

In order to form a nanostructure having a desired height, it is important to first determine the required polymerization time by measuring the degree of filling in the pores according to the polymerization time through an electron micrograph of the cut surface of the template. Potentiiostats are used to record changes in current with time of electropolymerization, and current change-nano structure correlations are identified through electron micrographs of the cutting planes for each situation. In this case, as shown in FIG. 7, the potential difference and the electropolymerization time must be well controlled to form a nanostructure having a desired size.

8 is a graph illustrating current-voltage characteristics of the nanostructured polymer organic photoelectric device thus formed. The current-voltage characteristics of a device made of polythiophene nanostructure and n-type organic material or polymer are shown. As can be seen in Figure 8, the polymer nanostructure photoelectric conversion device exhibits an excellent photoelectric effect. This polymer nanostructure heterojunction has a high quantum efficiency since the effective separation region, which is the basis for the quantum efficiency of the photoelectric effect, is increased than that of the conventional simple stacked p-n junction photoelectric device. In addition, the p and n-type polymers are connected to each required electrode to facilitate the transfer of generated charges, thereby preventing recombination of the generated charges, and the charges are smoothly transported through the secured movement path, thereby accumulating charges in the device. It can be prevented to increase the lifetime of the device.

As a material for forming a p-type polymer that can be used as a material in the present invention, all monomers capable of electrochemistry such as pyrrole and its derivatives, thiophene and its derivatives, aniline and its derivatives can be used. In addition, all systems are capable of processing with solutions at room temperature and do not involve particularly complex processes, eliminating the high temperature processes required by the dye-sensitized organic-inorganic hybrid nanoparticle systems of recent interest. With this structure, flexible ultra-thin photoelectric materials having high quantum efficiency can be developed and used as solar cells or optical sensors.

Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are only for illustrating the present invention in more detail, it will be apparent to those of ordinary skill in the art that the scope of the present invention is not limited by these examples in accordance with the gist of the present invention. .

Example 1 Preparation of Nano Template

Fabrication of nano-templates was performed by PEDOT (poly3,4-ethylene) purchased from Dow Chemical after 15 minutes of O ₂ plasma treatment of 1 × 1 inch ITO glass washed with chloroform and isopropyl alcohol acetone. Deoxythiophene) was spin coated with an electrode protective layer and dried in a 120 ^° C. vacuum oven. Hydroxy terminated random copolymer of styrene and methyl methacrylate (PS-) to form nano-sized domains of PMMA vertically aligned on a substrate on the electrode protective layer spin-coated) and then heat-treated in a 170 ^° C vacuum oven for 3 days. The weight fraction of styrene of this PS-r-PMMA is 0.58, the weight average molecular weight of the copolymer is 11,000 g / mol, and the polydispersity is 1.13. After washing with toluene, it was confirmed that about 6 nm thick PS-r-PMMA was fixed on the surface. On top of this a toluene solvent mixture of asymmetric polystyrene-b-polymethylmethacrylate block copolymer (PS-b-PMMA) and polymethylmethacrylate homopolymer (PMMA homopolymer) to be used as a template was spin coated. The weight average molecular weight of the asymmetric polystyrene-polymethyl methacrylate block copolymer used at this time is 66,000 g / mol, polydispersity 1.19, the weight fraction of polystyrene in the copolymer is 0.70, Atom Transfer Radical Polymerization ) Was synthesized. In addition, the PMMA homopolymer used herein had a weight average molecular weight of 31,800 g / mol and a polydispersity of 1.08.

The template film thus formed was heat-treated at 150 ^° C. for 2 days and then quenched to room temperature. The thickness of the template film was adjusted to 30 to 300 nm by adjusting the concentration of the solution and the speed of spin coating as needed. PMMA was removed using acetic acid to form nano pores in this template film. 9 shows a scanning electron image taken at an inclined angle of the nano-template thus produced.

Example 2 Formation of Nanostructure (I)

Polypyrrole nanostructures were prepared by electrochemically polymerizing pyrrole. The electrolyte used was prepared by mixing 0.01 M of vacuum distilled pyrrole monomer and 0.001 M of lithium perchlorate (LiClO ₄ ) used as a dopant with propylene carbonate. At this time, nano pores were formed, and the templated ITO glass was used as a working electrode and platinum (Pt) as a counter electrode, and the potential difference between the two electrodes was 0.64 V. As described above, Ag / AgCl electrodes are used as reference electrodes to control minute potential differences between the electrodes. The potentiometer controlled by ADInsutment's PowerLab / 4SP was used to record the current change over time of the polymerization. By applying an appropriate potential difference between the electrodes, pyrrole monomers were grown from PEDOT coated ITO glass exposed to the electrolytic solution by nanopores formed in the nanoplatelets. At this time, the potential difference and the electropolymerization time must be well controlled as shown in FIG. 6 to form a nanostructure of a desired size. If the polymerization time is not enough, the size of the nanostructure becomes too small and if the polymerization time is too long, the polypyrrole growing in the formed nanopores fills the pores and forms a polypyrrole film on the template. .

As shown in Fig. 7, it is important to first determine the required polymerization time by measuring the correlation between the degree of filling in the pores according to the polymerization time through an electron micrograph of the cut surface of the template. The nanostructure thus formed was obtained by removing the template using an organic solvent such as toluene. In addition, it was washed several times with the used electrolytic solvent (that is, propylene carbonate) to dissolve unnecessary electrolyte and then washed several times with organic solvent and dried in a vacuum oven.

Example 3 Formation of Nanostructures (II)

Polythiophene nanostructures can be fabricated using two methods to form thiophene by electrochemical polymerization. The first method is to prepare an electrochemical synthesis solution by mixing 0.57 g of ethylenedioxythiophene and 0.0424 g of lithium perchlorate (LiClO ₄ ) in propylene carbonate to make an electrochemical synthesis solution. The potential difference between the phosphorus platinum electrodes was adjusted to 0.99 V and allowed to react for 30 minutes. In the second method, 0.14 g of dodecylbenzenesulfuric acid is added to 200 ml of distilled water and completely dissolved to form micelles. Then, 0.16 g of ethylenedioxythiophene is added, and the amount of distilled water is increased to 1 liter. Stir for time.

The electric potential difference between the prepared electrochemical synthesis solution electrode ITO glass and the counter electrode platinum electrode was adjusted to 0.90 V and reacted for 25 minutes. An Ag / AgCl electrode was used as a reference electrode to control the minute potential difference between the electrodes. Nanostructures were formed by the same electrochemical method as that shown in Example 2. The nanostructure thus formed was removed using an organic solvent such as toluene, washed several times with the electrolytic solvent used (ie, propylene carbonate or distilled water), and then washed several times with an organic solvent and dried in a vacuum oven.

Example 4 Fabrication and Measurement of Photoelectric Conversion Device

The optoelectronic device is a 150 nm thick aluminum or lithium-aluminum alloy as an electrode for electron collection after spin coating n-type organic material or vacuum-evaporating n-type organic material on the p-type conductive polymer nanostructures formed in Examples 2 and 3. (Lithium-Aluminium alloy) was used by vacuum deposition. Current-voltage (I-V) characteristics of the optoelectronic devices were measured using a Keithley 2400 source-measure unit. At this time, 300W Xe lamp was used as a light source, and neutral density filter was used as necessary in an environment of light that mimics the wavelength of irradiation of sunlight by using Oriel's AM 1.5 Air Mass Filter. To adjust the light intensity. Oleel's ARC 150 monochromator was used to select wavelengths. Dimming intensity was measured using a calibrated broadband optical power meter (Spectra Physics model 404).

Polymeric photovoltaic devices manufactured as described above showed very high values of VOC [open circuit potential] of 0.6 V and isc [short circuit current] of 87 μm.

Having described the specific part of the present invention in detail, it is obvious to those skilled in the art that such a specific description is only a preferred embodiment, thereby not limiting the scope of the present invention. something to do. Thus, the substantial scope of the present invention will be defined by the appended claims and their equivalents.

As described above in detail, according to the present invention, the nano-structured p-type conductive polymer is formed on the transparent electrode at a high density to generate a charge transfer path having a high specific surface area, which is a basic condition for showing an excellent photoelectric conversion effect. The secured photoelectric conversion element can be manufactured. In addition, in the conductive polymer nanostructure composite film prepared in consideration of the exciton lifetime of the organic polymer, all the photoelectric conversion layers become effective separation regions, thereby reducing the amount of light absorbed. In addition, according to the present invention, unlike the conventional laminated technology or interpenetrating network [IPN (interpenetrating network) polymer composite film structure, it is possible to manufacture the optimum device to obtain the maximum photoelectric efficiency, and the device fabrication process is performed at high temperature, It does not require a special process such as vacuum, so it can be widely used in the development of next generation large area flat panel organic device manufacturing.

Claims (11)

Forming a nano template having nano pores using a block copolymer on a transparent electrode formed on a transparent substrate, Forming a p-type polymer nanostructure on the formed nanotemplate, Removing the nanotemplate using an organic solvent, coating the n-type organic material on the p-type polymer nanostructure and Method of manufacturing a photoelectric conversion device comprising the step of depositing a metal electrode layer on the n-type organic material. The method of claim 1, wherein the p-type polymer is selected from the group consisting of polypyrrole and derivatives thereof, polyaniline and derivatives thereof, or polythiophene and derivatives thereof. The n-type organic material according to claim 1, wherein the n-type organic material is polyquinoline and its derivatives, poly (para-phenylenevinylene) and its derivatives, polythiophene and its derivatives, poly (para-phenylene) and its derivatives, polyple Lauren and its derivatives, polyacetylene and its derivatives, tetracyanoquinodimethane, fullerene, 1,4,5,8-naphthalene tetracarboxylic dianhydride and its derivatives, 1,4, 5,8-naphthalene tetracarboxylic acid diimide and its derivatives, 11,11,12,12-tetracyanonaphtho-2,6-quinodimethane and its derivatives, 3,4,9,10-perylenetetra Carboxylic dianhydride and 3,4,9,10-perylenetetracarboxylic acid diimide and its derivatives, derivatives of metallophthalocyanine, sexithiophene and its derivatives and pentacene Selected from the group. 2. The indium tin oxide (ITO) according to claim 1, wherein the transparent substrate is polyethylene terephthalate (PET) or polyethersulfone (PET) which is glass, quartz or transparent plastic. Polyethylenedioxythiophene (PEDOT), polyaniline or polypyrrole. The method of claim 1 wherein the metal electrode is selected from the group consisting of aluminum, magnesium, lithium, calcium, copper, silver, gold, platinum and alloys thereof. The method of claim 1, wherein the block copolymer is a polystyrene-b-polymethylmethacrylate block copolymer. A transparent substrate, a transparent electrode formed on the transparent substrate, a p-type polymer nanostructure formed thereon, an n-type organic material coated on the p-type polymer nanostructure, and a metal electrode layer deposited on the n-type organic material A photoelectric conversion element comprising, manufactured by the method of claim 1, wherein the photoelectric conversion element exhibiting excellent photoelectric conversion effect. 8. The photoelectric conversion element according to claim 7, wherein the p-type polymer is selected from the group consisting of polypyrrole and derivatives thereof, polyaniline and derivatives thereof, or polythiophene and derivatives thereof. 8. The organic compound of claim 7, wherein the n-type organic material is polyquinoline and its derivatives, poly (para-phenylenevinylene) and its derivatives, polythiophene and its derivatives, poly (para-phenylene) and its derivatives, polyple Lauren and its derivatives, polyacetylene and its derivatives, tetracyanoquinodimethane, fullerene, 1,4,5,8-naphthalene tetracarboxylic dianhydride and its derivatives, 1,4, 5,8-naphthalene tetracarboxylic acid diimide and its derivatives, 11,11,12,12-tetracyanonaphtho-2,6-quinodimethane and its derivatives, 3,4,9,10-perylenetetra Carboxylic acid dianhydride and 3,4,9,10-perylenetetracarboxylic acid diimide and its derivatives, derivatives of metallophthalocyanine, sexithiophene and its derivatives, and pentacene The photoelectric conversion element is selected from the group. 8. The indium tin oxide (ITO) according to claim 7, wherein the transparent substrate is polyethylene terephthalate (PET) or polyethersulfone (PET) which is glass, quartz or transparent plastic. A photoelectric conversion element which is polyethylenedioxythiophene (PEDOT), polyaniline or polypyrrole. The photoelectric conversion element according to claim 7, wherein the metal electrode is selected from the group consisting of aluminum, magnesium, lithium, calcium, copper, silver, gold, platinum, and alloys thereof.

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