KR100924366B1 - Organic-inorganic hybrid solar cell and method for preparing the same - Google Patents

Abstract

An organic-inorganic hybrid solar cell is provided.

An organic-inorganic hybrid solar cell according to the present invention includes a work electrode having a work function smaller than that of CdTe; CdTe composite nanotubes arranged vertically on the working electrode and filled with a conductive polymer therein; An electropolymerization conductive polymer layer in which the CdTe composite nanotubes are impregnated therein; And a metal electrode provided on the conductive polymer layer and having a work function larger than that of the electropolymerizable polymer. The organic-inorganic hybrid solar cell according to the present invention has a high absorption rate in the visible light wavelength range, and There is almost no defect between the transporter and the conductive polymer, and because the contact area between the electron transporter and the conductive polymer is very wide, the light conversion efficiency is very excellent.

Description

Organic-inorganic hybrid solar cell and method for preparing the same}

1 is a cross-sectional view of a conventional organic solar cell.

Figure 2 is a schematic diagram of the organic-inorganic hybrid solar cell according to the present invention and a diagram showing the relationship between the energy band of the conductive polymer and the CdTe nanotubes.

3 is a schematic diagram of a CVDP apparatus used in the present invention.

Figure 4 is a SEM photograph of the CdTe composite nanotubes prepared in Example 1.

5 is a TEM photograph of the CdTe composite nanotubes prepared in Example 1. FIG.

6 is an X-ray diffraction spectrum of CdTe nanotubes prepared in Example 1- (2).

7 is an absorption spectrum of CdTe composite nanotubes prepared in Example 1- (3).

8 is a view showing the results of measuring photoluminescence of the solar cells manufactured by Example 1 and Comparative Example 1 and simply PPV.

9 shows voltage-current density curves for the solar cells manufactured by Examples 1 and 2 and Comparative Example 1. FIG.

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

1 ... transparent electrode 2 ... aluminum electrode

3.electron acceptor 4 ... hole acceptor

10 ... gold electrode 11 ... CdTe nanotubes

12 ... conductive polymer nanotubes 13 ... conductive polymer layer

21 ... Quartz tube 23 ... Boat

24 ... Tube 25 ... Mantle

26. Porous material 27. Vacuum pump

28.Massflow Controller

The present invention relates to an organic-inorganic hybrid solar cell, and more particularly, to a hybrid solar cell having improved efficiency using a semiconductor nanotube and a conductive polymer, and a method of manufacturing the same.

Representative prior arts related to organic solar cells are US Pat. No. 5,331,183. 1 is a cross-sectional view of a conventional organic solar cell. As shown in the drawing, a conventional organic solar cell includes a substrate and a transparent electrode (anode) 1 such as a tindoped indium oxide (ITO) thin film formed thereon. A bulk heterojunction structure in which an electron acceptor 3 and a hole acceptor 4 are mixed between the aluminum electrodes (cathodes) 2 is provided. As the hole acceptor 4, a conjugated polymer having conductivity such as PPV (poly-para-phenylene vinylene) is used, and as the electron acceptor 3, fullerene (60) is used. The conjugated polymer and fullerene are mixed between two electrodes. The conjugated polymer absorbs light to generate electron-hole pairs, and electrons and holes are collected at the anode and the cathode through the fullerene and conjugated polymer, respectively. Has However, the fullerene used as the electron acceptor in the above technology is a structure in which 60 carbon atoms are bonded in the shape of a soccer ball, and is an ideal electron acceptor that accepts the separated electrons well, but is not a suitable material for transferring electrons to the electrode. Therefore, there is a problem that the efficiency of the organic polymer solar cell is low because the electrons received by the electron acceptor are not sufficiently delivered to the cathode.

On the other hand, Alivisatos et al. Published a study on organic-inorganic hybrid solar cells using CdSe nanorods and poly (3-hexylthiophene) (Science 295 (2002) 2425), but the band gap of CdSe is about 2.3 eV. Not only do not absorb the light in the visible region well, because the CdSe is not oriented perpendicular to the cathode, the carrier path is long, the light conversion efficiency is low, in particular the CdSe nanorods and poly (3-hexyl tea) There is a problem that the bonding surface area of the offen) is not sufficient.

In addition, Korean Patent Laid-Open Publication No. 2005-87247 discloses an organic solar cell including a carbon nanotube arranged vertically on a cathode, a photoelectric conversion layer interposed between a cathode and an anode and in which a hole acceptor and an electron acceptor are mixed. In addition, since the carbon nanotubes themselves hardly absorb light, the light conversion efficiency decreases, and the photoelectric conversion layer including the conductive polymer and the fullerene is applied to the carbon nanotubes by spin coating or the like, including the conductive polymer. The high viscosity of the composition for forming a photoelectric conversion layer is not uniformly applied to the gaps of the carbon nanotubes, which may cause defects. As a result, the contact between the carbon nanotubes and the photoelectric conversion layer is not sufficient, resulting in high light conversion efficiency. There was a problem less than expected.

Accordingly, the first technical problem to be achieved by the present invention is high optical absorption because the wavelength of visible region wavelength is high, there is almost no defect between the electron transporter and the conductive polymer, and the contact area between the electron transporter and the conductive polymer is very wide. It is to provide an organic-inorganic hybrid solar cell with excellent conversion efficiency.

The second technical problem to be achieved by the present invention is to provide a method of manufacturing the organic-inorganic hybrid solar cell.

The present invention to achieve the first technical problem,

a working electrode having a work function smaller than that of n-type CdTe;

CdTe composite nanotubes arranged vertically on the working electrode and filled with a conductive polymer therein;

An electropolymerization conductive polymer layer in which the CdTe composite nanotubes are impregnated therein; And

It is provided on the conductive polymer layer, and provides an organic-inorganic hybrid solar cell comprising a metal electrode having a work function larger than the electropolymerizable conductive polymer.

The present invention to achieve the second technical problem,

(a) depositing a working electrode layer on one surface of the nano-membrane porous membrane;

(b) forming CdTe nanotubes in the pores of the membrane;

(c) forming conductive polymer nanotubes or nanowires through chemical vapor deposition polymerization in the nanotubes;

(d) forming a conductive polymer layer on the CdTe composite nanotube by electrical polymerization; And

(e) it provides a method of manufacturing an organic-inorganic hybrid solar cell comprising the step of forming a metal electrode on the conductive polymer layer.

Hereinafter, the present invention will be described in more detail.

The organic-inorganic hybrid solar cell according to the present invention directly grows CdTe nanotubes vertically on a metal electrode in order to minimize the absorption of sunlight in the visible region and the movement path of electrons generated by the organic light, and the inside of the CdTe nanotubes. By depositing a conductive polymer, the area of contact interface between the electron acceptor and the hole acceptor is greatly increased, and the conductive polymer layer deposited around the CdTe nanotube is formed by electrical polymerization, thereby forming an interface between the CdTe composite nanotube and the conductive polymer. The efficiency is greatly improved by making almost no defects.

The material that can be employed as the working electrode used in the present invention is not particularly limited as long as it is commonly used in the art as a metal having a smaller work function than n-type CdTe. For example, titanium may be used. The titanium may also reduce stress with vertically deposited CdTe, and may have ohmic contact because the work function is smaller than that of n-type CdTe. This is because the transport of electrons is smooth. Therefore, any metal having similar properties to titanium can be used without particular limitation. On the other hand, the metal electrode is not particularly limited as long as the work function is a metal larger than the electropolymerizable conductive polymer, for example, gold (Au) may be used.

CdTe used in the present invention is an inorganic material suitable for use in solar cells because its bandgap energy is 1.45 eV and its absorption coefficient for visible light is 10 ⁴ cm ⁻¹ . According to Hall effect measurement, the specific resistance of the CdTe nanotubes is 2 X 10 ⁶ Ω cm and the electron density is 1.3 X 10 ¹⁰ cm ^-3 . On the other hand, when the chalcogenide is insufficient in the chalcogenide compound has the characteristics of the n-type semiconductor, the concentration of Cd as a result of measuring the energy dispersive spectrum (EDS) for the CdTe nanotube according to the present invention Since it was 54%, it can be seen that the CdTe nanotubes used in the solar cell according to the present invention are n-type semiconductors.

In the organic-inorganic hybrid solar cell according to the present invention, the CdTe nanotubes serve as electron acceptors, and the conductive polymers inside and outside of the CdTe nanotubes serve as hole acceptors. Exciton formed is rapidly decomposed at the interface between the CdTe and the conductive polymer, and contributes to the transfer of electrons without recombination, thereby increasing the efficiency of the battery. In addition, since the CdTe nanotubes have a nanotube or a nanowire made of a conductive polymer, the interface between the electron acceptor and the hole acceptor is further increased, and the efficiency is further increased.

The average spacing of the CdTe composite nanotubes and other adjacent CdTe composite nanotubes is preferably 50 nm or less, more preferably 20 nm or less. The reason is that the dispersion distance of excitons generated by light is about 10 nm, and the smaller the distance between the CdTe composite nanotubes, the faster the excitons can be decomposed.

Meanwhile, the conductive polymer layer serving as a photoelectric conversion layer while surrounding the outer surface of the CdTe composite nanotube is generally deposited in bulk units by spin coating, and the viscosity of the polymer solution forming the conductive polymer layer is not sufficiently low. Therefore, after the actual process is completed, there is a high possibility that pores are formed at the interface between the CdTe composite nanotube and the conductive polymer, and this may act as a defect. When such pores exist, the excitons formed by light are difficult to decompose immediately The efficiency of the battery is reduced because it prevents the transfer of electrons to the CdTe nanotubes. However, in the present invention, rather than spin-coating the bulk conductive polymer, the present invention is characterized in that vapor deposition can be carried out so that the voids or defects are almost eliminated by polymerizing the monomers by electrical polymerization. Thus, the generated excitons can be quickly decomposed to contribute to the transfer of electrons.

The characteristics of the interface between the CdTe composite nanotube and the conductive polymer surrounding the CdTe composite nanotube can be measured indirectly by using an EBIC (Electron beam induced current) analysis method, and the built-in- You can see that the potential has been generated, and the size of the built-in-potential generated is approximately 1 eV.

Figure 2 shows the schematic diagram of the organic-inorganic hybrid solar cell according to the present invention and the relationship between the energy band and the conductive polymer and CdTe nanotubes. As can be seen in FIG. 2, the CdTe nanotubes serve as electron transfer channels and the conductive polymers act as hole transfer channels.

The conductive polymer inside the CdTe nanotube is not particularly limited as long as it is a conductive polymer that can be formed inside the CdTe nanotube by CVDP, and may be, for example, PPV or PTV (Polythienylenevinylene, hereinafter referred to as PTV). CVDP is a deposition method that allows gaseous units to form polymer films on a given surface through chemical reactions.

In addition, the conductive polymer inside the CdTe nanotube may be the same or different from the conductive polymer used in the conductive polymer layer, it is preferable to use a conductive polymer having a different absorption wavelength for solar light in terms of efficiency of the solar cell. . For example, when the conductive polymer inside the CdTe nanotube is PPV, the absorption spectrum of the PPV is in the wavelength range of about 370 to 520 nm. Therefore, it is preferable to use a conductive polymer having a longer absorption band in the conductive polymer layer. It is preferable to improve absorption efficiency of visible light. The conductive polymer used in the conductive polymer layer is not particularly limited as long as it can be formed by electrical polymerization, for example, PPV, PDMTT (Poly (3,6-dimethoxy-thieno [3,2-b] thiophene) Or P3HT (Poly (3-hexylthiophene). The absorption wavelength band of the conductive polymer used in the conductive polymer layer is preferably 350 to 650 nm.

Method for producing an organic-inorganic hybrid solar cell according to the present invention comprises the steps of (a) depositing a working electrode layer on one surface of the nano-porous porous membrane; (b) forming CdTe nanotubes in the pores of the membrane; (c) forming conductive polymer nanotubes or nanowires through chemical vapor deposition polymerization in the nanotubes; (d) forming a conductive polymer layer on the CdTe composite nanotube by electrical polymerization; And (e) forming a metal electrode on the conductive polymer layer.

In the step (a), the porous membrane is not particularly limited as long as it is commonly used in the art, and may be, for example, an anodized aluminum oxide (AAO) membrane. Such anodized aluminum membrane may be prepared by an aluminum anodizing method applying a current of 100 mA / cm ² under a 25 ° C., 0.2 M phosphoric acid electrolyte.

Next, after vacuum depositing titanium as a working electrode on the anodized aluminum oxide membrane thus prepared, CdTe nanotubes were subjected to cathodic deposition on 1M CdSO ₄ and 5 × 10 ⁻⁴ M TeO ₂ aqueous solution. It is formed inside the voids.

3 shows a schematic diagram of a CVDP apparatus used in the present invention. The pressure in the quartz tube 21 can be controlled by using a vacuum pump 27, and the argon gas is flown at a constant speed using a mass flow controller (manufactured by MKS instrument: 28) on the left side of the vaporization region. The temperature is adjusted to 50 to 100 ° C. The mass flow controller is provided with a reader for controlling the mass flow controller. The temperature of the pyrolysis zone can be adjusted using an external temperature controller (manufactured by Sanup, SDM-9000: 29). In the present invention, the tube furnace 24 is heated before performing the CVDP, and after vaporizing the unit in the vaporization region, the vaporized unit is moved to the pyrolysis region by argon gas flowing at a constant rate. The unit moved to the pyrolysis zone is converted into a highly reactive intermediate in the tube furnace 24.

Next, as soon as the intermediate reaches the porous substrate provided in the deposition region through the tube passage 24, polymerization occurs with a precursor polymer, and the nanotubes are formed according to the pore size of the porous substrate 26. The diameter of is determined. The precursor polymer thus produced is dehydrogenated when the heat treatment is performed for a predetermined time using the mantle 25 to form a conductive polymer.

In Formula 1, PPV is formed by using α, α' - dichloroxylene as a monomer according to the present invention, and in Formula 2, PTV is formed by using 2,5-bis (chloromethyl) thiophene as a monomer. The process of formation is shown.

In formulas (1) and (2), (1) is α, α' - dichloroxylene, (4) is 2,5-bis (chloromethyl) thiophene, (2) and (5) are intermediates, (3) and (6) is a precursor polymer.

In the present invention, by using the CVDP, CdTe composite nanotubes are prepared by forming conductive-conjugated polymer nanotubes or nanowires inside the CdTe nanotubes and heat-treating them at a temperature of 100 to 350 ° C. Finally, the porous substrate should be removed. In the case of an AAO membrane, it can be dissolved in a sodium hydroxide solution.

The heat treatment temperature for the dehydrochlorination may be 100 ~ 350 ℃, the heat treatment temperature depends on the type of precursor polymer. For example, about 250 ° C. for PPV precursor polymers and about 150 ° C. for PTV precursor polymers, the heat treatment time is not particularly limited, but it takes about 5 to 6 hours at the above temperature, and the heat treatment temperature is lowered. The longer the required heat treatment time becomes. When the temperature is less than 100 ° C dehydrochlorination does not occur well, if it exceeds 350 ° C there is a risk that the polymer itself is decomposed.

Subsequently, the step of forming the conductive polymer layer by electrical polymerization on the CdTe composite nanotube proceeds as follows. For example, when polymerizing PPV, p-xylyenebis (triphenyl phosphonium bromide) or α, α`-dichloro-p-xylene (α, α`- dibromo-α, α`-dichloro-p-xylen) can be used to form a PPV conductive polymer layer by electrical polymerization, and when PDMTT is polymerized, 3,6-dimethoxy-thieno [3,2- b] thiophene can be used to form a conductive polymer layer by electrical polymerization, in addition to this, any monomer capable of electrical polymerization commonly known in the art can be used without particular limitation.

After forming the conductive polymer layer, it is necessary to anneal, in order to suppress the formation of carbonyl defects. The carbonyl defect is preferably suppressed because it degrades conductivity by reducing the conjugation length. Finally, the organic-inorganic hybrid solar cell according to the present invention can be manufactured by depositing a gold electrode using a shadow mask on the conductive polymer layer.

Hereinafter, the present invention will be described in more detail with reference to preferred examples, but the present invention is not limited thereto.

Example 1

1- (1) AAO Membrane  Produce

An AAO membrane was prepared by anodizing aluminum at 100 ° C./cm ² under a 0.2 M phosphoric acid electrolyte at 25 ° C., and the pore diameter of the AAO membrane was 200 nm, the length was 30 μm, and the density was 5 × 10. ⁸ cm ^-2 and the mean gap spacing was about 40 nm.

1- (2) CdTe  Preparation of Nanotubes

After vacuum depositing titanium on one surface of the AAO membrane to form a working electrode having a size of 1 cm x 1 cm, and adjusting the pH to 2 to 3 using concentrated hydrochloric acid in 1M CdSO ₄ and 5x10 ^-4 M TeO ₂ aqueous solution. , CdTe nanotubes were formed inside the pores of the anodized aluminum membrane by using a cathode deposition method applying a voltage of −0.7 V to the titanium electrode for about 1 minute.

1- (3) CdTe  Manufacture of Composite Nanotubes

In order to deposit conductive polymer nanotubes or wires inside the CdTe nanotubes, a CVDP device as shown in FIG. 3 was prepared. The pressure in the quartz tube was adjusted to 0.8torr and the temperature of the vaporization zone was set to 80 ° C while flowing argon gas at a rate of 8 SCCM using a mass flow controller (manufactured by MKS instrument: 28). As a unit, 40 mg of α, α' - dichloroxylene was used, the temperature of the pyrolysis zone was set to 650 ° C., and the temperature of the deposition zone was set to room temperature. The reaction time was 1 hour. After the deposition of the precursor polymer on the porous membrane, dehydrochlorination was performed by heat treatment for 1 hour in an argon atmosphere at 750 ° C. to prepare PPV nanotubes. Finally, the membrane was dissolved in an aqueous 1 M NaOH solution at 25 ° C. for 1 hour to finally prepare a CdTe composite nanotube and a conductive polymer composite vertically arranged on the electrode. The SEM picture of the CdTe composite nanotubes prepared above is shown in FIG. 4, and FIG. 5 illustrates an enlarged TEM image of one layer of the composite nanotubes in order to observe the bilayer structure of the CdTe composite nanotubes in detail. Referring to FIG. 5, it can be seen that PPV nanotubes are formed inside the CdTe nanotubes.

1- (4) organic weapons hybrid  Manufacture of solar cell

0.05 g p-xylenebis (triphenyl phosphonium bromide) (p-xylyenebis (triphenyl phosphonium bromide)) was dissolved in 50 ml of acetonitrile, and the impregnated titanium working electrode and the Pt relative electrode were prepared and the voltage of 5.5V Was applied for about 2 hours to form a PPV conductive polymer layer having a thickness of about 30 μm on the working electrode by electrical polymerization. Next, an organic-inorganic hybrid solar cell was manufactured by vacuum depositing a gold electrode having a diameter of about 1 mm using a shadow mask on the PPV conductive polymer layer.

Example 2

2- (1) AAO Membrane  Produce

An AAO membrane was prepared by anodizing aluminum at 100 ° C./cm ² under a 0.2 M phosphoric acid electrolyte at 25 ° C., and the pore diameter of the AAO membrane was 200 nm, the length was 30 μm, and the density was 5 × 10. ⁸ cm ^-2 and the mean gap spacing was about 40 nm.

2- (2) CdTe  Preparation of Nanotubes

After vacuum depositing titanium on one surface of the AAO membrane to form a working electrode having a size of 1 cm x 1 cm, and adjusting the pH to 2 to 3 using concentrated hydrochloric acid in 1M CdSO ₄ and 5x10 ^-4 M TeO ₂ aqueous solution. , CdTe nanotubes were formed inside the pores of the anodized aluminum membrane by using a cathode deposition method applying a voltage of −0.7 V to the titanium electrode for about 1 minute.

2- (3) CdTe  Manufacture of Composite Nanotubes

In order to deposit conductive polymer nanotubes or wires inside the CdTe nanotubes, a CVDP device as shown in FIG. 3 was prepared. The pressure in the quartz tube was adjusted to 0.8torr and the temperature of the vaporization zone was set to 80 ° C while flowing argon gas at a rate of 8 SCCM using a mass flow controller (manufactured by MKS instrument: 28). As a unit, 40 mg of α, α' - dichloroxylene was used, the temperature of the pyrolysis zone was set to 650 ° C., and the temperature of the deposition zone was set to room temperature. The reaction time was 1 hour. After the deposition of the precursor polymer on the porous membrane, dehydrochlorination was performed by heat treatment for 1 hour in an argon atmosphere at 750 ° C. to prepare PPV nanotubes. Finally, the membrane was dissolved in an aqueous 1 M NaOH solution at 25 ° C. for 1 hour to finally prepare a CdTe composite nanotube and a conductive polymer composite vertically arranged on the electrode.

2- (4) organic weapons hybrid  Manufacture of solar cell

10 mM 3,6-dimethoxy-thieno [3,2-b] thiophene in 0.1M Bu ₄ NPF ₆ / CH ₂ After dissolving in Cl ₂ solution, impregnating the titanium working electrode prepared above and the Pt relative electrode and applying a voltage of −0.3 V for about 2 hours to electrically polymerize a PDMTT conductive polymer layer having a thickness of about 30 μm on the working electrode. Formed by. Next, an organic-inorganic hybrid solar cell was manufactured by vacuum depositing a gold electrode having a diameter of about 1 mm using a shadow mask on the PDMTT conductive polymer layer.

Comparative Example 1

Except for forming the MEH-PPV layer by vertically forming CdTe nanorods on the titanium electrode instead of CdTe composite nanotubes, then spin-coating a solution of bulk MEH-PPV dissolved in chloroform as a conductive polymer layer. An organic-inorganic hybrid solar cell was manufactured in the same manner as in Example 1.

Test Example 1

X-ray diffraction  Test

X-ray diffraction test was performed on the CdTe nanotubes prepared in Example 1- (2) and the results are shown in FIG. 6. Referring to FIG. 6, it can be seen that the nanotubes formed in the solar cell according to the present invention consist of CdTe because they coincide with the peak of CdTe corresponding to JCPDS number: 15-0770.

Test Example 2

Measurement of Absorption Spectrum

The absorption spectrum of the CdTe composite nanotubes prepared in Example 1- (3) was measured using a UV-visible spectrophotometer (842, manufactured by Hewlett-Packard), and the results are shown in FIG. 7. Referring to FIG. 7, the absorption peak of about 370 to 520 nm corresponds to the absorption peak of PPV, and the absorption peak of the CdTe tube is formed between about 650 to 950 nm, and thus the region of the absorption spectrum is considerably wider. It can be seen that the light absorption region of the solar cell is widely distributed over the visible light region.

Test Example 3

PL  Measure

The organic-inorganic composite film and pure PPV prepared before forming the gold electrode according to Example 1 and Comparative Example 1 were excited using a 488 nm argon ion laser (1 mW), and then photoluminescence was measured. The results are shown in FIG. In this case, the life time of each of the pure PPVs was about 13 ns, whereas the life time of the organic-inorganic composite film prepared in Comparative Example 1 was about 250 ps. In the case of the prepared organic-inorganic composite film, the life time was about 210 ps. Therefore, in the case of the organic-inorganic composite film prepared according to the present invention, the conductive polymer is present inside the CdTe nanotubes, and because the interface property of the CdTe composite nanotubes and the conductive polymer layer outside is very excellent, It can be seen that the formed excitons decompose more quickly than in the case of Comparative Example 1.

Test Example 4

Short circuit current density, V _OC  And measurement of power conversion efficiency

After connecting the positive electrodes of the solar cells manufactured in Examples 1, 2 and Comparative Example 1 to KEITHLY equipment (current-voltage, voltage-current measuring equipment), in a test box After irradiating light under standard condition of air mass 1.5 using halogen lamp, measure the current value while gradually increasing the voltage from 0 to 1V (about 0.01V / sec), and measure the short-circuit current density, V _OC and power conversion efficiency. The values are shown in FIG. 9 and Table 1 below.

Short circuit current density (mA / cm ² ) V _OC Power conversion efficiency Example 1 3.48 0.725 V 1.35% Example 2 3.75 0.726 V 1.21% Comparative Example 1 3.12 0.714 V 1.06%

Referring to FIG. 9 and the following table, in the case of Comparative Example 1, the short-circuit current density was 3.12 mA / cm ² , and the power conversion efficiency was 1.06%. In Example 2, the short-circuit current density was 3.75 mA. / cm ² , the power conversion efficiency is 1.21%, and in the case of Example 1 it can be seen that the efficiency of the solar cell according to the invention is very excellent because it shows a larger value than that.

As described above, the organic-inorganic hybrid solar cell according to the present invention has a high absorption rate in the visible wavelength range, almost no void space between the electron transporter and the conductive polymer, and the contact area between the electron transporter and the conductive polymer is high. Since it is very wide, there is an advantage that the light conversion efficiency is very excellent.

Claims (13)

a working electrode having a work function smaller than that of n-type CdTe; CdTe composite nanotubes arranged vertically on the working electrode and filled with a conductive polymer therein; An electropolymerization conductive polymer layer in which the CdTe composite nanotubes are impregnated therein; And The organic-inorganic hybrid solar cell provided on the electropolymerization conductive polymer layer, the work function comprising a metal electrode larger than the electropolymerization conductive polymer. The organic-inorganic hybrid solar cell of claim 1, wherein the working electrode is made of titanium, and the metal electrode is made of gold. The organic-inorganic hybrid solar cell of claim 1, wherein the conductive polymer inside the CdTe composite nanotube is different from the conductive polymer used in the electropolymerized conductive polymer layer. The organic-inorganic hybrid solar cell of claim 1, wherein the conductive polymer inside the CdTe composite nanotube is PPV or PTV, and the conductive polymer forming the electropolymerized conductive polymer layer is PPV, PDMTT, or P3HT. The organic-inorganic hybrid solar cell of claim 1, wherein the conductive polymer used in the electropolymerized conductive polymer layer has an absorption wavelength of 350 to 650 nm. The organic-inorganic hybrid solar cell of claim 1, wherein the conductive polymer inside the CdTe composite nanotube is PPV and the conductive polymer forming the electropolymerized conductive polymer layer is PDMTT. The organic-inorganic hybrid solar cell of claim 1, wherein an average distance between the CdTe composite nanotube and another adjacent CdTe composite nanotube is 50 nm or less. (a) depositing a working electrode layer on one surface of the nano-membrane porous membrane; (b) forming CdTe nanotubes in the pores of the membrane; (c) forming conductive polymer nanotubes or nanowires through chemical vapor deposition polymerization inside the CdTe nanotubes; (d) forming a conductive polymer layer on the CdTe nanotubes by electrical polymerization; And (e) a method of manufacturing an organic-inorganic hybrid solar cell comprising forming a metal electrode on the conductive polymer layer. The method of claim 8, wherein the forming of the CdTe nanotubes of (b) is performed on an aqueous solution of CdSO ₄ and TeO ₂ . The method of claim 8, wherein the chemical vapor deposition polymerization step (c) comprises the steps of placing the membrane in the deposition region in the quartz tube and vaporizing a unit in which chlorine is substituted in the vaporization region in the quartz tube; Moving the vaporized unit into a pyrolysis zone by a carrier gas and then pyrolyzing to form an intermediate; Moving the generated intermediate to a deposition region by a carrier gas, and then forming a precursor polymer while passing through the porous substrate; And forming a conductive polymer nanotube or a nanowire by dehydrochlorination through heat treatment. The method of claim 10, wherein the unit in which chlorine is substituted is α, α′ - dichloroxylene or 2,5-bis (chloromethyl) thiophene. The method of claim 10, wherein the heat treatment temperature for the dehydrochlorination is 100 ~ 350 ℃ manufacturing method of an organic-inorganic hybrid solar cell. The method of claim 8, wherein the monomer (d) during the electrical polymerization is characterized in that p-xylenebis (triphenyl phosphonium bromide) or 3,6-dimethoxy-thieno [3,2-b] thiophene Organic-inorganic hybrid solar cell manufacturing method.

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