TW201024335A - Structure of hole-collecting layer made of sulfonated polyaniline derivative and electron-collecting layer made of titanium dioxide and manufacture method therefor - Google Patents

Abstract

A structure of a hole-collecting layer made of sulfonated polyaniline derivative and an electron-collecting layer made of titanium dioxide and a manufacture method therefor are provided. The structure includes a conductive substrate, the electron-collecting layer, an active layer, and the hole-collecting layer. The conductive substrate is formed with a conductive layer on which the electron-collecting layer, the active layer and the hole-collecting layer are stacked in turn. The hole-collecting layer is a conductive polymer layer made of sulfonated polyaniline derivative selected from sulfonated poly(diphenylamine), sulfonated poly(triphenylamine), or copolymer thereof. The electron-collecting layer is titanium dioxide formed by titanium(IV) isoprooxide as a precursor of titanium dioxide.

Description

201024335 VI. Description of the Invention: [Technical Field] The present invention relates to a structure of an organic optoelectronic semiconductor device and a method of fabricating the same, and more particularly to a polyacid anilide derivative as a hole collecting layer and/or The structure of the electron collecting layer and the manufacturing method thereof are used. [Prior Art] In recent years, development of various sources of regenerative performance (e.g., solar cells, fuel cells, wind power generation) has been increasingly emphasized because of the large consumption of fossil fuels. For example, an organic polymer solar cell (organic p〇lymer sdar cell) is a regenerative energy source that is inexpensive and easy to manufacture. The light absorbing layer material commonly used in such solar cell systems is poly(3-hexylthiophene). (poly(3-hexylthiohene), hereinafter abbreviated as P3HT) and carbon sixty derivative ((6,6)-stupyl carbon hexadecanoate methyl ester, (6,6> phenyl C6i butyde add methyl ester' A conjugated polymer blending system referred to as PCBM) has recently been used to maximize the formation of a heterogeneous interfacial structure between two molecules. If the current international standard is used, the light conversion efficiency is about 4%. Recently, some infrared light active layer materials have been developed and synthesized, and the highest light conversion efficiency is claimed to be 5.5%. Due to the continuous research and development of relevant researchers, 'the practicality of organic polymer solar cells is gradually improved. Even have the opportunity to replace inorganic solar cells. In the heterojunction structure of traditional organic polymer solar cells, the electrons and holes in solar cells must be both yin and yang. Conduction, one of the holes on the hole-collecting layer (HCL) side will use the 201024335 high-work function metal material, and an electron-collecting layer (hereinafter referred to as The electrode on the side of the ECL) needs to be a metal material with a low work function. However, the metal with a low work function is often susceptible to attack by water vapor and oxygen in the air, and is converted into a non-conductive metal oxide, which naturally affects the solar energy. Battery performance and stability. In order to improve the above problems, an organic polymer solar cell with a reverse structure is proposed. This inverted structure can avoid the use of a metal with a low work function and select a stable metal as a Electrode on the side of the electron collecting layer. However, in the inverted structure, the electrode on the side of the electron collecting layer usually uses indium tin oxide dT. According to the principle of semiconductor physics, the PCBM energy level difference between the IT glass and the active layer is too large, which causes obstacles in electron transfer, and the separation of the internal electrons in the battery is unbalanced, which may cause a space charge effect inside the device. , which in turn affects its light conversion efficiency. Therefore, the researchers have continuously developed and improved the highly stable electron-collecting layer (ECL). (4) Many of the materials in the towel are related to the oxidationist (4) fines oxide ' TiOJ and zinc oxide (zinc 〇xide, Zn〇). A metal oxide which can be used to modify the work function of ITO glass and has good electron conduction characteristics and high stability. However, in the case of titanium oxide, its water solubility is very low and it can only be suspended in water. In the process, the suspension of titanium oxide is usually coated on the surface of the ITO glass, and then the water is evaporated in a sintered manner to leave a film of oxide, but the titanium oxide film produced by such a process is too large. The surface has a rough degree and its flatness is too low. Furthermore, recent studies have also used carbon tetrazolium (III) ium C3rb〇nate 'Cs2C〇3) as an electron-collecting layer' and oxidized anadium oxide 'V2〇5' as a hole collecting layer (HCL). Light to 201024335 - Solar cells with improved efficiency, but barium carbonate is a highly water-absorbing salt, perhaps not a good stability material. In addition, in the part of the hole collection layer (HCL), some studies have pointed out that metals such as gold or silver can be used directly. However, due to the often dipole effect between the organic active layer and the metal, there is often the problem of an energy barrier where there is an interface. In order to overcome the above problems, there have also been related studies using a metal-like conductive polymer as a hole collecting layer, such as poly(vinyldioxythiophene): poly(styrenesulfonic acid) • (P〇1y(3, 4-e%lenedioxythiophene): poly(styrene sulfonate), hereinafter referred to as PEDOT: PSS), which can be used to improve the problems of the organic layer and the metal. For example, please refer to FIG. 1 , which discloses a structure of a conventional organic polymer solar cell including a conductive substrate n , a hole collecting layer 12 , an active layer 13 and an electron collecting layer 14 . The conductive substrate n is a transparent glass having an indium tin oxide layer ln, the hole collecting layer 12 is a hybrid system of ❹ PEDOT * PSS, and the active layer 13 is a conjugated molecular hybrid system of P3HT : PCBM And the electron collecting layer 14 is a metal layer of calcium and aluminum. However, the hole collecting layer 12 is a low-water-soluble substance (ie, pED〇T:pSS mixing system), which can only be suspended in water and is insoluble in other organic solvents, so that the spin-coated film process is difficult to perform. . Furthermore, since the active layer 13 of the solar cell is often a hydrophobic material (ie, a p3HT: pcBM mixing system), when the active layer 13 is formed by a spin coating process, the polarity difference is too large to be easily formed. A polymer matrix problem is formed on the hole collecting layer 12. Therefore, it is necessary to provide a structure of an organic optoelectronic semiconductor device and its manufacture 6 201024335 method to solve the problem of material characteristics of an electron collecting layer (ECL) and a hole collecting layer (HCL) existing in the prior art. SUMMARY OF THE INVENTION The main object of the present invention is to provide a structure in which a sulfonated polyaniline derivative is used as a hole collecting layer, which is a sulfonated poly(diphenylamine), hereinafter referred to as SPDPA. Or other similar polyacidified polyaniline derivatives as a hole collection layer, which has better solubility in water or polar organic solvents, which can improve the dipole moment between the organic layer and the metal interface on the wet process. The problem that the energy barrier is not matched is beneficial to improve the efficiency of hole transmission. A secondary object of the present invention is to provide a method for fabricating a structure in which titanium dioxide is used as an electron collecting layer by first coating a titanium isopropoxide (Ti(OC3H7)4) sol, followed by hydrolysis and heating to form A titanium dioxide film having high flatness and high porosity serves as an electron collecting layer, thereby facilitating electron transfer efficiency and improving element stability. Another object of the present invention is to provide a structure or a manufacturing method using a sulfonated polyaniline derivative as a hole collecting layer and titanium dioxide as an electron collecting layer, which uses a polyaniline derivative as a hole collecting layer. And a titanium dioxide film formed by hydrolysis of titanium isopropoxide as an electron collecting layer, which has better environmental stability and can protect the active layer from moisture or oxygen, thereby facilitating improvement of light conversion efficiency. In order to achieve the above object, the present invention provides a structure in which a sulfonated polyaniline derivative is used as a hole collecting layer, comprising a conductive substrate, an electron 201024335 - a collecting layer, an active layer and a hole collecting layer, wherein The conductive substrate has a conductive layer, and the electron collecting layer, the active layer and the hole collecting layer are sequentially stacked on the conductive layer of the conductive substrate, and the hole collecting layer comprises at least a conductive polymer sulfonated polyaniline derivative. It is selected from the group consisting of sulfonated polydiphenylamine, sulfonated polytriphenylamine or a copolymer thereof. In another aspect, the present invention provides a method of fabricating a structure in which titanium dioxide is used as an electron collecting layer, which comprises a conductive substrate, an electron collecting layer, an active layer, and a hole collecting layer. The collecting layer, the active layer and the hole collecting layer are sequentially stacked on one conductive layer of the conductive substrate, and the method for manufacturing the electron collecting layer comprises the steps of: providing a sol of titanium isopropoxide; A titanium sol is coated on the conductive substrate to be hydrolyzed into a titania gel; and the titanium dioxide gel on the conductive substrate is heated at a high temperature to form a titanium oxide film as the electron collecting layer. In another aspect, the present invention provides a structure in which a polyaniline derivative is used as a hole collecting layer and titanium dioxide is used as an electron collecting layer, which comprises a conductive substrate, an electron collecting layer, an active layer, and The hole (four) layer 'where the conductive substrate has a conductive layer, the electron collecting layer, the active layer and the electric (4) are sequentially stacked on the conductive sound of the conductive substrate, the hole collecting layer containing at least the conductive polymer顾化聚笨^ derivative, and the electron (four) layer is a oxidized zirconia film formed of titanium isopropoxide. The scented scented material is selected from the group consisting of polyamine, sulfonated polytriphenylamine or a copolymer thereof. . In the present invention, the implementation of the f substrate is self-transparent 201024335 substrate * the conductive layer is a tin oxide layer. In one embodiment of the invention, the surface of the electron collecting layer is further formed with a polymer modifying layer interposed between the electron collecting layer and the active layer. In one embodiment of the invention, the polymeric modification layer is selected from the group consisting of amine propane trimethoxy decane (APTMS), N-trimethoxydecyl ethylene diamine (EDAPTMS) or chloropropyl tridecyl decane. (CPTMS). In one embodiment of the invention, the active layer is selected from the group consisting of poly(3-hexylthiohene), P3HT, and a carbon sixty derivative ((6,6)-phenyl carbon). A composite polymer blending system (ie, P3HT: PCBM) of hexammonium butyrate, (6,6)-phenyl C61 butyric acid methyl ester (PCBM). In one embodiment of the invention, the structure further includes a metal electrode layer stacked on an outer surface of one of the hole collecting layers. In an embodiment of the invention, the metal electrode layer is selected from the group consisting of a gold layer, a silver layer, or a combination thereof. In one embodiment of the invention, the structure is an inverted type organic optoelectronic semiconductor device, wherein the electron collecting layer, the active layer, and the hole collecting layer are sequentially stacked on the conductive layer on the lower surface of one of the conductive substrates. In an embodiment of the invention, the structure is selected from the group consisting of a polymer photovoltaic cell, a polymer thin film transistor (OTFT), or a polymer light-emitting diode (polymer light-emitting diode). , PLED). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention and other objects of the present invention will be apparent from the following detailed description.

Referring to FIG. 2, the structure of the present invention is characterized in that the acidified polyaniline derivative is used as a silk layer and the titanium dioxide is used as an electronic structure. The main structure comprises: - a conductive substrate 2 - an electron collecting layer 22 An active layer, a hole collecting layer 24, and a metal electrode layer 25, wherein the lower surface of the conductive substrate 021 has a conductive layer 21, the electron collecting layer 22, an active layer, and a hole collecting layer 24 The metal electrode layer 25 is sequentially stacked on the conductive layer 211 on the lower surface of the conductive substrate 21. In the present invention, the conductive layer 2 ι is preferably selected from the group consisting of an indium tin oxide (ITO) layer; the hole collecting layer μ contains at least a conductive polymerized acidified polyphenylene bismuth, and a hybrid polydiphenylamine (suiwed P) 〇_Phenylamine), hereinafter referred to as SPDPA), sulfonated poly(triphenylamine ' hereinafter referred to as SPTPA) or a copolymer thereof; and the electron collecting layer 22 is made of titanium isopropoxide (Ti(〇) C3H7) 4) A titanium dioxide film formed. The above structure and its manufacturing method will be further described in detail below with reference to the accompanying drawings. Referring to Figure 2, the preferred embodiment of the present invention uses a polyacidified polyaniline derivative as a hole collecting layer and a structure in which titanium dioxide is used as an electron collecting layer to use sulfonated polydiphenylamine (SPDPA). For the hole collecting layer 24, for example, the sulfonated polydiphenylamine is preferably prepared by the following methods: First, the following agents are prepared: diphenyiamine (referred to as DPA, 201024335 * 融融-company) 'It is used as a monomer; ammonium peroxydisulfate (abbreviated as aps, made by the company), which is used as an oxidizing agent; sulfiiric acid (H2S04, manufactured by Riedel-deHagn Co., Ltd.) As a solvent and a dopant (4); acetone (acetatene, manufactured by Riedel-deHaSn), which is used as a solvent and a cleaning agent; ammonia (ammonia 'Fluka), which is used as a a dopant; ethanol (ethan〇1, manufactured by Riedel-deHa & i), which is used as a solvent for reducing agents and products; and fuming sulfuric acid (fUming sulfUnic acid, manufactured by Riedel-deHagn Co., Ltd.) Polymer sulfonic acid Pharmacy. Furthermore, in another embodiment, if sulfonated diphenylamine (SPTPA) is used as the hole collecting layer 24, it is necessary to replace diphenylamine (DPA) with triphenylamine (TPA). The following synthetic steps. In still another embodiment, if a copolymer of sulfonated polydiphenylamine (SPDPA) and sulfonated polytriphenylamine (SPTPA) is used as the hole collecting layer 24, it is necessary to simultaneously prepare a proper mixing ratio of diphenylamine ( DPA) and triphenylamine (TPA) were used to carry out the following synthetic steps. Followed by 'poly(diphenylamine, hereinafter referred to as PDPA) synthesis. DPA3.4 g (g), 0.04 mole (mole) into a 1 ml (ml) round bottom clip The mixture was continuously stirred and stirred in a reactor, and 3 ml of a 2 mol concentration (M) aqueous sulfuric acid solution and 200 ml of acetone were added as a solvent for polymer polymerization. This reaction was carried out at 5 ° C. Then, 30 ml of a 2 M aqueous sulfuric acid solution containing an oxidizing agent APS (4.5 g, 0.04 mole) was slowly added dropwise. When the polymerization started, the color of the solution was changed from transparent and colorless to green, and the total reaction time was 16 hours. When the reaction is terminated, green precipitates are precipitated, and the precipitate is collected by suction filtration. The precipitate is washed with deionized water in a large amount until it passes through the water. The liquid at the bottom of the unit is not colored. The root ion is a polydiphenylamine (PDPA) of the dopant and requires a neutralization of 1 equivalent of (9) aqueous ammonia solution to dope the sulfate ion, and the dedoping time takes at least 24 hours. Thereafter, the excess aqueous ammonia solution is washed by means of suction filtration and using a large amount of deionized water to form a PDPA in a neutral state. Next, the neutral PDPA is dissolved in ethanol and stirred for at least 12 hours to reduce PDPA, after which the PDPA is washed with a large amount of ethanol and then centrifuged.

The PDPA was collected by washing and purifying the ions and the low molecular weight polymer after several times of cleaning. It was dried in a vacuum oven for 24 hours, at which time an off-white PDPA was obtained. Next, the synthesis of polyacidified polyaniline (SPDPA) is carried out: 0.5 g of PDPA after purification s is placed in 80 ml of fuming sulfuric acid to carry out acidification sulfonation. At this time, the reactor temperature needs to be controlled in the environment of the cavity. The situation of avoiding ^ should be too fast. The overall time of this sulfonation step is about 〖hours, after the reaction is completed, it is put into the original pre-cooled C, so that the precipitated impurities are precipitated, and then the centrifugation is carried out. Wei #, its complex _ a large number of _ wash strips and centrifugal filtration, in order to remove excess sulfuric acid and fresh washed. Finally, the solvent is removed, you can get the job, and then make (four) filter insoluble ^ The substance and the main miscellaneous secretary can get the end product spDpA. Further, ^ Dissolve SPDPA in ethanol to form the film to form the tear.

The collection layer 24' has a weight percent concentration of 1% <> The chemical structure of the SpDpA synthesis is as shown in the following equation: J 12 201024335

❹ Please take the county photo 2, this is a good implementation of the acidified polyaniline derivative as electricity, riding the layer and the structure of the use of titanium dioxide as an electron collection layer using ♦ glue · gel method (sd_gel pr_s) and Xiang Isopropoxy oxime (Ti(OC3H7)4) is used as a precursor (tetra)_〇r) to form a dioxide film as the electron collection layer 22, wherein the method for producing the electron collection layer a comprises the following Providing a fine oxy-transformation; the miscellaneous propane filament is coated on the conductive substrate 21 to be hydrolyzed and converted into a titania gel; and the titanium oxide gel on the conductive soil plate 21 is heated at a high temperature. The titanium oxide film is formed as the electron collecting layer 22. 13 201024335 First of all, when providing the solution of isopropoxy oxime, take an appropriate amount of isopropyl alcohol (IPA), and further add isopropoxyl:isopropanol = 1:1.5 Titanium is 〇pr〇〇xide, which is 11 (0 (3⁄43⁄4) 4 'Aldrich, purity 99.999 %), and stirred until homogeneous. This solution is a sol of titanium isopropoxide. The present invention does not limit the ratio of use of the above-mentioned agents, which may be changed according to actual requirements or process conditions. Next, before coating the sol of titanium isopropoxide on the conductive substrate 21, the present invention is preferably in advance. The conductive layer 2n for cleaning the conductive substrate 21 is washed one by one with a detergent, deionized water, acetone, and isopropyl alcohol, and washed with ultrasonic vibration, and then the conductive layer 211 of the conductive substrate 21 is made to utilize ultraviolet ozone. The method of (UVQ) clears the surface of the machine (4). After cleaning, the present invention preferably coats the sol of titanium isopropoxide on the conductive substrate 21 by means of spin coating or the like. The first stage of rotation on the conductive layer 211 The number of revolutions is 1000 rpm for 5 seconds, and the second stage is 4 seconds. The film thickness is 80 nm (nm); in order to make the film thickness thinner, the operating conditions can also be set to 5 rpm. 6 sec. After that, the titanium isopropoxide sol is further thinned on the conductive substrate 21 and allowed to hydrolyze for at least i hours to convert it into titanium dioxide (Ti〇2) or other titanium oxide type (Ti〇(10) gel. Finally, the titanium dioxide gel film on the conductive substrate 21 is subjected to local temperature heating of 4 Torr for sintering for 1 hour (or -I sintering Μ minute) to form = titanium oxide as the electron (4) 22 phase. Compared with the conventional process, only the suspension of titanium dioxide is coated on the surface of the IT glass and then the titanium oxide film is formed by sintering. The present invention is hydrolyzed by the first coating of titanium dioxide precursor (isopropoxy 14 201024335 titanium). And the titanium dioxide film having high alkalinity and high porosity of the base is used as the electron collecting layer 22. As shown in Fig. 2, the preferred embodiment of the present invention is a polyacidified polyaniline. The derivative acts as a hole collecting layer and uses titanium dioxide as an electron collection The U method of the layer is made of an organic polymer solar cell as an example. The layered structure of the organic polymer solar cell of the present invention includes the conductive substrate 21, the electron collecting layer 22, the active layer 23, and the hole. In the present embodiment, the layered structure is: ITO glass m〇2/P3HT: PCBM/sPDPA/Au+Ag, wherein the conductive substrate 21 is a transparent substrate. It may be selected from glass or a flexible plastic plate or the like, wherein the flexible plastic plate may be selected from a polyimide plate or an acrylic plate or the like, but is not limited thereto. The conductive layer 211 of the conductive substrate 21 is preferably an indium tin oxide (IT〇) layer, which is used as an electrode on the electron collecting layer 22 side. The surface of the indium tin oxide layer of the bismuth glass is preferably cleaned before the formation of the titanium oxide film. The cleaning process and the coating process can be referred to the above paragraph regarding the manufacturing method of the electron collecting layer 22. This will not be repeated here. The thickness of the dioxide film is about 80 nanometers (nm). Furthermore, in another embodiment, the surface of the niobium monoxide film may additionally form a polymer modification layer (not shown, for example, selected from the group consisting of amine propane-based tridecyloxydecane APTMS, N-trimethoxylate). Ethylenediamine EDATMS or chloropropyltrimethoxydecane CPTMS, collectively referred to as a SAM polymer modification layer, is interposed between the titanium dioxide film and the subsequently formed active layer 23 to enhance the Interface bonding strength and electron transfer efficiency. In one embodiment of the present invention, an ITO glass having a titanium oxide film can be immersed in a prepared SAM solution. The SAM solution can be selected from 3 15 201024335 different functional groups of trimethoxysilane. ), respectively, 3-amniopropiyltrimethoxysilane (APTMS), N-[3-(Trimethoxysilyl)propyl]ethylenediamine (EDAPTMS) or aerobic 3-chloropropryltrimethoxysilane (CPTMS) 'The condition is lwt%' The solvent selected is toluene (t〇iuene), soaked and vortexed for 2 minutes in a sonic wave, and then taken out and then purely 曱The benzene solvent acts as a cleaning action to remove unbonded molecules. The mechanism is as follows:

2=Si—OMe Ί- 2Η2〇^·2=Si—OH+2MeOH = Si—OH+HO—Si=—^ = Si—〇—Si= +H2O When the present invention is an amine propane-based tridecyloxy fluorene When the (APTMS) or N-trimethoxydecyl ethylenediamine (EDAPTMS) is used as an example, the processes of bonding to the titanium dioxide thin film of the IT glass are as shown in the following reaction formula:

After forming a oxidized film (and a polymer modified layer) on the surface of the indium tin oxide layer of the bismuth glass, 'the hexanol porphin is mixed at a weight ratio of 1:1. 16 201024335 • (P〇ly(3) -hexylthiohene), P3HT) and (6,6)-phenyl C61 butyric acid methyl ester (PCBM) are dissolved in (1,2-dichlorobenzene, manufactured by Aldrich). Its weight percent concentration is 2% (for P3HT). Next, a mixture of the common polymer blending system (ie, P3HT. PCBM) is applied onto the surface of the titanium dioxide film by a spin coating method (rotation speed of 6 〇〇 jpjQ for 60 seconds), and according to the solvent. The principle of solvent annealing is to place the structure in a closed chamber (such as a petri dish) with a saturated vapor pressure to slow down the P3HT: solvent evaporation in the PCBM thinner, causing the P3HT: PCBM to be arranged in order. On the surface of the titanium dioxide film, the final thickness of the P3HT:PCBM film is about 200 nm (mn) until the solvent is completely evaporated. Next, the sulfonated polydiphenylamine (SPDPA) (or the sulfonated polytriphenylamine or a copolymer of the two) was spin-coated (rotation speed 5000 rpm for 60 seconds) to a thickness of about 1 〇 nm. Finally, it was placed in a hot steamer to form a gold layer (Au) having a thickness of about 4 Å and a silver layer (Ag) having a thickness of about 100 nm, respectively, as electrodes on the side of the hole collecting layer 24. After the Φ layer structure is completed, the reverse structure is the structure of the inverted type organic polymer solar cell, and the effective area of the element is 〇.〇8 square centimeters (cm; 2). Referring to FIG. 2 again, in the preferred embodiment of the present invention, the polyacidified polyaniline derivative is used as the hole collecting layer and the titanium dioxide is used as the electron collecting layer. Since the solar cell is composed of hundreds of nanometer PN junctions, it is obviously important to control the energy level position of each layer of film. Because the indium tin oxide layer of IT0 glass belongs to the high work function metal oxide, it is not conducive to electron transfer when it is used on the reverse type organic optoelectronic semiconductor device, so it must be etched and modified. 17 201024335 layer 'The surface roughness of the indium tin oxide layer of the ITO glass is also too large, which tends to cause the formation of tip discharge. In order to change the above-mentioned ride, the electron collecting layer 22 of the present invention uses the above-described titanium dioxide touch, and the measurement of the energy level position of the oxidized film is very important. Referring to FIG. 3, an ultraviolet photoelectron spectrum (ultraviolet Ph〇toelectron spectroscoPy, ups) of the titanium oxide film on the tantalum oxide layer of the ιτ〇 glass of the preferred embodiment of the present invention is disclosed. The energy level of the conduction band and the valence band of the two φ titanium oxide film. From the 3rd electronic spectrum, the position of the work function of the titanium dioxide film can be seen. For the Ν·type semiconductor, the work function position is very close to the conductive band, and the cut-off (Cu_ region can define the conductive band). The position is about 3. 9 electron volts (eV). Please refer to the 4th _, which reveals the thin TiO2 spectrum of the titanium dioxide on the indium tin oxide layer of the 佳τ〇 glass. -vis spectmm), which is used to measure the energy gap fine surface of the dioxide film. From the absorption spectrum of Fig. 4, the energy gap of the titanium dioxide film can be measured to be about 3·2 eV. The position of the biddable electric tape can be converted to the position of 71..., so the position of the band can be judged as anatase. (anatase) type of titanium dioxide. In addition, for the surface roughness of the indium tin oxide layer of the IT0 glass, after modifying the indium tin oxide layer by the oxidized film, the surface roughness of the dioxide film is additionally subjected to an atomic force microscope (at 〇rnicforcemicrosc). The surface height measurement of 〇py, the surface height measurement results are shown in the upper right corner of Figure 4. It can be seen from the figure that the root mean square roughness (4) of the indium oxide layer of the original ITO glass is 2.66 nm. The root mean square roughness (rms) after modification with the titanium dioxide film is 18 201024335 0.97 nm, so it can be confirmed that the titanium dioxide film is indeed flatter than the indium tin oxide layer of the original ITO glass. Furthermore, the analysis of the structure of the titanium dioxide film itself is also very important. We can calculate the conversion of isopropoxy iridium (Ti(OC3H7)4) to cerium oxide by spectrogram obtained by X-ray photoelectron (XPS). The structure of (Ti〇2) 'O(is) for the bonding energy position of Ti-0_Ti is 53〇.4eV and the bonding energy position of Ti-0-Χ (where X=C, H) is 531.9eV, The ratio of conversion to Ti-〇_Ti is 83.4%. Therefore, the analysis results of the titanium dioxide film are considered to be effective for modifying the ITO glass and serving as the electron collecting layer 22 of the organic polymer solar cell. Please refer to FIG. 5, which discloses a conventional organic polymer solar cell (ITO glass/PEDOT: PSS/P3HT: PCBM/Ca+Al, as shown in the figure i, the curve is represented by □) and the organic matter of the present invention. Molecular solar cell (ιτο玻璃/Ti02/P3HT: PCBM/SPDPA/Au+Ag, as shown in Figure 2, the curve shows the voltage/current density of ▲ for the curve without 'Ti〇2') The Φ map, together with Figures 3 and 4, further defines the energy level positions of the various layer structures of the present invention. As shown in Fig. 5, the component characteristics (□) of the conventional organic 1% molecular solar cell are as follows: open circuit voltage (Voc) is 〇.6〇v, and short circuit current density (Jsc) is 9.43. mA/cm2, power conversion efficiency (PCE) was 3.74%, and fill factor factor, FF) was 0.66. Furthermore, when the (reverse type) organic polymer solar cell of the present invention is not modified with a titanium dioxide film, the layered structure thereof is IT 〇 glass / Ρ3 ΗΤ: PCBM/SPDPA/Au+Ag ', and its element characteristics (♦) are as follows · v〇c (10) V, Jsc = 0.74 mA/cm2, PCE = 0.02%, and FF = 0.25. In contrast, 19 201024335 found that the performance of this component is ideal, the main reason for the discovery is that the difference between the energy barrier between the glass and the active layer p3HT: pcBM is 4.7eV, the lowest unoccupied orbital energy level of PCBM ( LUMO) ...4.3eV) 'causes electrons to appear obstruction during transmission; the second is HQ glass indium 钖 oxygen (10) layer _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The p_N junction can be known from this component (4) = _ too small. On the other hand, the present invention can be observed that the characteristics of the battery (4) are greatly improved by the structure (10) of the oxidized film (10), the glass melon & DM, PCBM/Sm>A/Au+Ag, and the · V〇c = 0.58 V, Jsc = 10.46 mA/cm2, PCE = 3.91%,

And FF = 0.64 'where the value of this Voc is the difference between the highest occupied orbital energy level (HOMO) of p3HT and the lowest unoccupied orbital energy level (LUM〇) of PCBM, which is almost equal to the two electrodes (indium tin oxide layer and gold /Vot layer) and active layer: PCBM) when the ohmic contact is formed (ie, without any energy barrier) will show the Voc characteristics 'thus, therefore, the selected titanium dioxide fine and acidified polydiphenylamine (SPDPA) and other materials used in the present invention It is good at the leg position. On the ride, the larger Jsc value can be judged that the titanium dioxide film has good electron conduction characteristics, while the other side of the sulfonated polydiphenylamine film has good hole conduction characteristics. In addition, the sulfonated polydiphenylamine film may have an optical spacer, which may cause the sunlight to have a gain intensity in the active layer, so that it can be found that the se is larger and the electronic hole of the component is separated. The situation is better 'there is no space charge in the component, thus ensuring component efficiency. Please refer to FIG. 6 , which discloses a density/current 20 201024335 ' density chart of four embodiments of the present invention, in which a sulfonated polyaniline derivative is used as a hole collecting layer and titanium dioxide is used as an electron collecting layer. Refer to Fig. 2 for the organic optoelectronic semiconductor device constructed by the structure. In Fig. 6, the layered structure of the organic optoelectronic semiconductor device of the first embodiment of the present invention is: ITO glass / Ti02 / P3HT : PCBM / SPDPA / Au + Ag (the curve is indicated by ▲); the second embodiment of the present invention The layered structure of the example is: ITO glass / Ti02 / P3HT: PCBM / Au + Ag (the curve is represented by Δ); the layered structure of the organic optoelectronic semiconductor component of the third embodiment of the present invention is: ITO glass / TKVP3HT : PCBM /SPDPA/Ag (the curve is indicated by #); and the layered structure of the organic optoelectronic semiconductor device of the fourth embodiment of the present invention is: ITO glass / Ti02 / P3HT : PCBM / Ag (the curve is represented by 〇). In the first and second embodiments in which Au+Ag is vapor-deposited, the first embodiment further coats the sulfonated polydiphenylamine (SPDPA) on the active layer 23 (P3HT: PCBM), and the device characteristics can be Voc=0.22 V is raised to 0.58 V. In the third and fourth embodiments in which Ag is deposited, the third embodiment further coats the active layer 23 with a sulfonated polydiphenylamine (SPDPA), which can be improved from Voc=0.12 V 到 to 〇·56 V, this Voc value implies that the energy level difference between the work function of SPDPA and the highest occupied orbital level (HOMO) of P3HT is an ohmic contact relationship. Therefore, the light conversion efficiency of the element of the first embodiment is actually 3.91%, and the light conversion efficiency of the third embodiment is 3.44%. Since the difference in work function between SPDPA and Ag is still too large, there are still some micro-energy barriers between the two, so there is no match between SPDPA and Au+Ag. Referring again to Fig. 6, in the second embodiment, the result of the Voc value when p3HT:PCBM is in contact with Au+Ag is not as expected. The HOMO of P3HT is 4.9eV, and the work function of Au is 5.0eV. In theory, it should be Euro 21 201024335. The contact is actually 'Sch〇ttky contact'. The reason is that A dipole energy barrier is created at the interface between the two. Similarly, in the Ag system of the fourth embodiment, a similar phenomenon was observed when P3HT:PCBM was in contact with Ag. On the other hand, in the first embodiment, when P3ht:PCBM/SPDPA is in contact with Au, since SPDPA itself is a highly doped conductive polymer substance, its characteristics will exhibit similar metal properties, so the interface between SPDPA and Au That is, it is not easy to generate energy barriers, and SPDPA and P3HT: PCBM are due to the disordered arrangement of the polymer, so there is no dipole moment in a specific direction, that is, it can neutralize all dipoles at the interface. The energy barrier is such that when the Au is vapor-deposited on the SPDPA in the first embodiment, stable work function characteristics are produced. This result does let us know that the modification of SPDPA can effectively overcome the energy barrier problem between the original organic layer and the metal (such as the structure of the second and fourth embodiments), and also shows that the battery has better performance. Therefore, a sulfonated polyaniline derivative such as sulfonated polydiphenylamine SPDPA, sulfonated polytriphenylamine SPTPA or a copolymer thereof is very suitable as the hole collecting layer 24. Refer to Figures 7, 8, 9 and 10 for the disclosure of conventional organic polymer solar cells (IT0 glass/PEDOT: PSS/P3HT: PCBM/Ca+Al, as shown in Figure 1 □ indicates) and the open circuit voltage (v〇c) and short-circuit current of the organic polymer solar cell of the present invention (IT0 glass/TKVP3HT: PCBM/SPDPA/Au+Ag, as shown in Fig. 2, whose curve is indicated by ▲) Statistical graph of (Jsc), light conversion efficiency (PCE) and fill factor (FF). As shown in Fig. 7, after 400 hours, the Voc of the present invention is changed from 0 6v to 〇57V, and the % value thereof hardly changes, indicating that the selected titanium dioxide film and spDpA film are very stable materials in the air, so the IT0 glass Steel tin oxide layer (or 22 201024335

Both the Au+Ag metal electrode layer and the active layer maintain good ohmic contact. As shown in Fig. 8, after 400 hours, the present invention; fsc slightly degraded from the original 10.26 mA/cm2 to 9.34 mA/cm2. As shown in Fig. 9, after 400 hours, the PCE of the present invention was changed from 3.81% to 2 82%. As shown in Fig. 1, after 400 hours, the FF of the present invention is changed from 0 62 to 〇·55, which affects the maximum change in the efficiency of the component of the organic polymer solar cell, possibly because it is not packaged. The moisture in the air and the oxygen easily invade the active layer' cause the organic matter of the active layer to deteriorate, affecting the separation and transmission of the electron hole, so the element stability is slightly degraded. In contrast, the light conversion efficiency (peg) of traditional organic polymer solar cells was initially comparable to the present invention, but after 4 hours of exposure to air, the PCE turned sharply. The main cause of the decline is the oxidation of the metal layer (Ca) and the active layer is relatively more susceptible to environmental attack. It can be seen from the above test results that the present invention selects an electron collection layer 2 (i.e., titanium dioxide) and a production system 24 (i.e., SPDPA) having a relatively high environmental stability, and the towel is made of a oxidized film as the smear layer 22 (4). Considering the ohmic contact between the Wei electron collecting layer 22 and the active layer 23, which facilitates the transfer of electrons, the SPDPA is used as the scale hole to transfer the layer between the organic material of the Qishan line layer and the metal layer. A dipole energy problem that may exist in essence. Therefore, the component structure provided by the invention does not affect the change of the male cast effect of the component, and is beneficial for suppressing the diffusion of moisture or oxygen to the active layer, and is indeed advantageous for ensuring the transmission efficiency and improving the component prisonerness. The method of manufacturing the step extension element = must be further. The method for producing the polyaniline/butylate of the (four) 24 and the electron collecting layer 22 (titanium dioxide) provided by the present invention can be applied to the manufacture of 23 201024335 * Various organic optoelectronic semiconductors The device can be applied to an organic thin film transistor (OTFT) or a polymer having a similar actuation principle, in addition to the polymer photovoltaic cell enumerated in the above embodiments. An organic optoelectronic semiconductor component such as a light-emitting diode 〇) 〇iymer diode 'PLED). While the present invention has been described in its preferred embodiments, it is not intended to limit the invention, and it is intended that the invention may be modified and modified without departing from the spirit and scope of the invention. The scope of the invention is defined by the scope of the appended claims. [Circular Simple Description] Figure 1: Schematic diagram of the structure of a conventional organic polymer solar cell. Fig. 2 is a schematic view showing the structure of a sulfonated polyaniline derivative as a hole collecting layer and titanium dioxide as an electron collecting layer in a preferred embodiment of the present invention. _ Figure 3: Ultraviolet photoelectron spectroscopy of a titanium dioxide film according to a preferred embodiment of the present invention. Fig. 4 is a view showing the ultraviolet absorption spectrum of the titanium dioxide film of the preferred embodiment of the present invention, and the surface roughness measurement of the titanium dioxide film measured by atomic force microscopy. Fig. 5 is a graph showing the voltage/current density of a conventional organic polymer solar cell (shown by □ in the curve) and the organic polymer solar cell of the present invention (the curve is represented by ▲ 'the curve without Ti〇2 is indicated by ♦), And a schematic diagram of the energy level of the various layers of the present invention. 24 201024335 Fig. 6 is a graph of the electric/current density of four embodiments of the present invention (the curves are shown in the figures, Δ, 吁, and 分别, respectively). Figures 7, 8, 9 and 10 · Open circuit voltage (Voc) and short-circuit current (Jsc) of an organic polymer solar cell (shown by □) and the organic polymer solar cell of the present invention (shown by ▲) , graph of light conversion efficiency (PCE) and fill factor pF). [Main component symbol description] 11 conductive substrate 12 hole collecting layer 14 electron collecting layer 211 conductive layer 111 marriage tin oxide layer 13 active layer 21 conductive substrate 22 electron collecting layer 23 active layer 24 hole collecting layer 25 metal electrode layer

25

Claims (1)

201024335 • VII. Patent application scope: 1. A structure called acidified polyphenylene bribe as a hole-receiving structure, comprising: a conductive substrate having a conductive layer; - an electron collecting layer formed on the conductive On the conductive layer of the substrate; an active layer formed on the electron collecting layer; and a hole collecting layer formed on the active layer, and the hole collecting layer is at least ❹ & A benzoic organism selected from the group consisting of hybrid polydiphenylamine, sulfonated polytriphenylamine or a copolymer thereof. 2. If you apply for a special fiber! The structure of the Jewish broth is used as the structure of the hole collecting layer, wherein a polymer modified layer is formed on the electron collecting layer, which is interposed between the electron collecting layer and the active layer, and the polymer modifying layer It is selected from the group consisting of amide trimethoxy Wei, N_trimethoxyweig ethylenediamine or chloropropyltrimethoxy oxalate. ❿ 3. For example, t-fiber (4) 丨 技 杂 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 , , , , , , , , , , , , , , , , , , , , , , , , Sixty-butyric acid A_ a total of her polymer mixing system. 4. The structure of the polyacidified polyaniline derivative as a hole collecting layer as described in the scope of the patent application, wherein the structure further comprises a metal electrode layer stacked on the hole collecting layer. The electrode layer is selected from the group consisting of a gold layer, a silver layer or a combination thereof. 5. 5. As claimed in the patent scope! The polyaniline derivative described in the section is a 26-layer layer of 26 201024335. The structure of the structure is an inverted structure, and the electron collection, the enthalpy and the electrically conductive layer are sequentially stacked on the conductive layer on the lower surface of the f-substrate. 6. ^Shen (4)^ Item_Technology is used as the structure of the hole collecting layer, wherein the structure is selected from an organic polymer solar battery, an organic thin germanium transistor or a polymer light emitting diode. 7. A method for manufacturing a structure in which titanium oxide is used as an electron collecting layer, wherein the structure comprises a conductive substrate, an electron collecting layer, an active layer, and a hole collecting layer, the layer 'the electron collecting layer, and an active layer The layer and the hole collecting layer are sequentially stacked on the conductive layer of the conductive second plate, and the manufacturing method of the electron collecting layer comprises the step of providing a sol of isopropoxy oxime; The pulse is converted into an oxidized gel; and the remaining dioxin is heated at a high temperature to form a titanium dioxide film as the electron collecting layer. 8. If the application of the dioxin sew as the structure of the electron collecting layer is described in the application, the polymer layer is formed on the anger electronically transferred layer, which is interposed between the electron collecting layer and the active layer. Between the polymer modification layer is selected from the group consisting of amine propyl trimethoxy zeoxime, N. trimethoxy weiyl ethylene diamine or chloropropyl trimethoxy ketone. 9. For example, the manufacturing method of the structure of the seventh item such as titanium dioxide for the scale collection layer 27 201024335, wherein the main _ is the postal sequel) and the base carbon meter - the yoke _ listening polymer Mixing system. 10. If the application of the titanium dioxide as the structure of the lepton collection layer is as follows, the structure is purely containing a surface layer, which is stacked on the electro-contact layer, and the metal electrode layer is selected. From gold, silver or a combination thereof. 11. The method for manufacturing a structure of an electron collecting layer 2 using titanium dioxide as described in claim 7, wherein the structure is a reverse structure, and the electron collecting layer, the active layer and the hole collecting layer are sequentially stacked. On the conductive layer on the lower surface of one of the conductive substrates. 12. The method for producing a structure using titanium dioxide as an electron collecting layer as described in claim 7, wherein the anger structure is selected from the group consisting of an organic polymer solar cell, an organic thin film transistor, or a polymer light emitting diode. 13. A structure in which an acidified polyphenylene bribe is used as a hole collecting layer and a dioxide is used as an electron collecting layer, comprising: a conductive substrate having a conductive layer; and an electron collecting layer formed thereon On the conductive layer of the conductive substrate, the electron collecting layer is a dioxide film formed by using titanium isopropoxide; an active layer formed on the electron collecting layer; and a hole collecting layer formed on the active layer On the layer, and the electric current layer is at least: a hetero-polymerized polyacidified polyphenylene bile, which is selected from the group consisting of polydiamine, shunt polytriamine or a copolymer thereof. 28 201024335 , 14. For example, _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ It is interposed between the electron collecting layer and the active layer, and the polymer modifying layer is selected from the group consisting of aminopropyltrimethoxywei, ruthenium triyloxyethylenediamine or chloropropyltrimethoxy aspartame. 15. If the application is as specified in Item 13, the porphyrin lining organism is used as the hole collecting layer and the structure of the electronic (four) layer of titanium dioxide material, wherein the main moving layer is poly(3-hexyl hydrazine).吩) face 6) - phenyl carbon hexadecanoate vinegar vinegar a total of two-molecular mixing system. 16. The structure of the acidified polyaniline derivative as the hole collecting layer and the titanium dioxide as the electron transfer layer as described in the scope of claim 帛I3, wherein the structure further comprises a metal electrode layer stacked thereon On the hole collecting layer, the metal electrode layer is selected from the group consisting of a gold layer, a silver layer, or a combination thereof. Lu 17. The structure of the polyacidified polyaniline derivative as a hole collecting layer and the use of titanium dioxide as an electron collecting layer as described in claim 13 of the patent scope, wherein the structure-reverse type Lin' electron collecting layer The main ride and the hole collecting layer are sequentially stacked on the conductive layer on the lower surface of one of the conductive substrates. Μ The structure of the sulfonated polyaniline derivative as the hole collecting layer and the titanium dioxide as the electron collecting layer as described in claim 13 wherein the structure is selected from the group consisting of organic polymer solar cells and organic thin films. A transistor or a polymer light-emitting diode. 29