TWI453312B - Preparation the polymer fiber for solar cells and light emitting device by directly electrospinning technique - Google Patents

Description

Organic fiber for solar panel and photoexcited light element

The invention relates to an organic fiber for a solar panel and a photoexcited light element and a preparation material thereof, in particular to an organic conjugated polymer fiber which is directly electrospun by electrospinning without adding other components and preparation. material.

According to the "Liangyang Fibers and Materials" of the Republic of China Invention Patent Publication No. 200833888, it is pointed out that the luminescent fiber materials are mostly brittle materials, so that the problem of fiber rupture often occurs when electrospinning is used. Therefore, the invention patent provides a luminescent fiber material suitable for being prepared by an electrospinning process comprising blending a conjugated luminescent polymer and a transparent non-conjugated polymer. The core/shell bilayer structure fiber is prepared, and the transparent non-conjugated polymer is dissolved by a solvent to form a luminescent nanofiber.

In addition, the "light-emitting fiber material" of the Republic of China Patent Publication No. 200833889 indicates that the luminescent fiber material is mostly a brittle material, so that the problem of fiber rupture often occurs when electrospinning is used. Therefore, the invention patent provides a luminescent fiber material, and the invention provides a luminescent fiber material which is prepared by an electrospinning process, which comprises a conjugated luminescent polymer and a hydrophilic group. Molecular material is used to prepare a core/shell bilayer structure fiber, and a polymer material having a hydrophilic group is dissolved by a solvent. It is a luminous nanofiber.

However, the above process is complicated (it is necessary to first mix the conjugated luminescent polymer with other polymer materials and subsequently process the solvent to dissolve the non-conjugated polymer material) and the structure of the conjugated polymer fiber prepared therefrom. Difficult to control and complex process and high process cost are its main disadvantages.

Accordingly, the present invention provides a material which can directly spin various organic conjugated polymer fibers by electrospinning to obtain high light absorption efficiency and high light conversion efficiency.

Further, the present invention relates to an organic solar cell fiber, particularly a nano-sized organic polymer fiber, and is an organic solar panel prepared by an electrospinning process. Conjugated polymer fiber and its preparation material.

Organic polymer fiber for organic solar panel is one of the currently attracting optoelectronic or optical conversion materials, which can be applied to various industries, such as organic solar panels for personal use, organic solar panels for industrial use, and organic solar panels for home decoration. Organic solar panels for outdoor use, organic solar panels for 3C products, etc.

In addition, the present invention relates to a conjugated polymer light emitting fiber, particularly a nanofiber, and is a conjugated polymer photoexcited fiber prepared by an electrospinning process and Its material.

The conjugated polymer photoexcited fiber is one of the most attractive materials for photoelectric displays or photoexcited components, and can be applied to various industries, such as personal display panels, industrial light-emitting components, lighting components for home decoration, and outdoor use. (Inner) A light-emitting element, an organic light-emitting element for a 3C product, or the like. The conjugated polymer fiber prepared by the present invention is directly produced by an electrospinning technique without adding other materials.

Further, the above organic conjugated polymer includes poly-3-alkylthiophenes and derivatives thereof, polyfluorenes (PFO) and derivatives thereof, polyphenylene vinylene (PPV) and One of its derivatives, conjugated polymers such as poly-p-phenylene and its derivatives.

Further, the conjugated polymer comprises a conjugated polymer blending material selected from the group consisting of poly-3-alkylthiophenes and derivatives thereof and polyfluorenes (PFO) and derivatives thereof. Conjugated polymer blending materials, poly-3-alkylthiophenes and derivatives thereof, and conjugated polymer blending materials of polyphenylene vinylene (PPV) and its derivatives, Conjugated polymeric blends of poly-3-alkylthiophenes and their derivatives with poly-p-phenylene and its derivatives, polyfluorenes (PFO) and poly Conjugated polymer blended material of polyphenylene vinylene (PPV) and its derivatives or conjugated polymer of polyfluorenes (PFO) and poly-p-phenylene and its derivatives One of the materials, and mixed with each other The weight ratio of the conjugated polymer is between 1 and 99 to 99 to 1.

Further, the conjugated polymer comprises a conjugated polymer copolymer material selected from the group consisting of polyfluorenes (PFO) and derivatives thereof and poly(fluorine-co-thiophene). Conjugated polymer copolymer, poly(fluorine-co-phenylene vinylene) conjugated polymer copolymer, poly(thiophene-co-styrene) (poly(thiophene-) One of co-phenylene vinylene) and its derivatives conjugated polymer copolymer.

The organic conjugated polymer fiber proposed by the invention is directly prepared by an electrospinning process, and does not need to add other materials to help the filamentity. The diameter of the organic conjugated polymer fiber is from 10 nm to 100 μm. .

The preparation material of the organic conjugated polymer fiber of the invention comprises a conjugated polymer and a solvent, the solvent is a single solvent or a cosolvent, and the single solvent is selected from the group consisting of methyl chloride, dichloromethane, chloroform, toluene or xylene. In one of them, the co-solvent is selected from at least two solvents including methylene chloride, dichloromethane, chloroform, toluene or xylene.

The invention at least includes the following advantages:

1. The invention provides a preparation material capable of directly preparing an organic conjugated polymer fiber by electrospinning, without adding other materials and without post-processing, so that direct electrospinning technology is economical and excellent for preparing organic conjugated polymer fiber. Preparation method.

2. The conjugated polymer organic photoexcited optical fiber provided by the invention has a continuous non-breaking and strong light absorption and photoexcitation ability than a general film, so that the light energy conversion efficiency of the organic photoexcited optical element is improved.

3. The conjugated polymer fiber provided by the invention has a continuous non-breaking property and a light absorption capability is stronger than that of a general film, and the photoexcitation light behavior is small, so that the light energy conversion efficiency of the organic solar panel is improved.

4. The invention adopts the direct blending of the conjugated polymer and the solvent, and is combined with the electrospinning technology as the organic fiber for the organic solar panel, so that the continuous fiber with smooth surface or uneven surface can be prepared, and the obtained organic fiber can be prepared. The diameter can be adjusted from micron to nanometer. Therefore, the light scattering behavior between the organic fibers is used to increase the wavelength range of the absorption spectrum of the organic fibers, and since the molecular chain internality of the organic fibers is significantly increased, the transmission rate of the electron hole particles inside the organic fiber material is significantly increased, so It has high light absorption efficiency and high light conversion efficiency.

In order to make the above features and advantages of the present invention more comprehensible, the present embodiments are described in detail with reference to the accompanying drawings.

The first figure is a schematic view of a nano organic polymer fiber for an organic solar panel according to an embodiment of the present invention, and the nano organic polymer fiber for the organic solar panel prepared is a continuous nanofiber. And the nano organic fiber for the organic solar panel of the present embodiment is directly electrospun from a conjugated polymer.

The second figure is a nano organic organic light excitation light according to an embodiment of the present invention. A schematic diagram of a polymer fiber, wherein the nano-organic fiber for the organic solar panel prepared is a continuous nanofiber, and the nano-organic fiber for organic photoexcitation light of the embodiment is also a conjugated polymer. Made directly by electrospinning.

In the above embodiments, the conjugated polymer is, for example, selected from the group consisting of poly-3-alkylthiophenes and derivatives thereof, polyfluorenes (PFO) and derivatives thereof, and polystyrene ( One of conjugated polymers such as polyphenylene vinylene, PPV) and its derivatives, poly-p-phenylene and its derivatives.

In the above embodiments, the conjugated polymer comprises a conjugated polymer blending material: poly-3-alkylthiophenes and derivatives thereof, and polyfluorenes (PFO) and derivatives thereof. Conjugated polymer blending materials, poly-3-alkylthiophenes and derivatives thereof and polyphenylene vinylene (PPV) and its derivatives conjugated polymer blending materials or poly Conjugated polymeric blends of poly-3-alkylthiophenes and their derivatives with poly-p-phenylene and its derivatives, polyfluorenes (PFO) and polyphenylene Conjugated polymer blending materials of polyphenylene vinylene (PPV) and its derivatives, or conjugated polymer blending of polyfluorenes (PFO) and poly-p-phenylene and its derivatives The weight ratio of the material and the conjugated polymer blended with each other is between 1 and 99 to 99 to 1.

In the above embodiments, the conjugated polymer includes conjugated polymer copolymerization thereof The material is selected from the group consisting of polyfluorenes (PFO) and derivatives thereof and poly(fluorine-co-thiophene) conjugated polymer copolymer materials, poly(茀-co-benzene) Poly(fluorine-co-phenylene vinylene) conjugated polymer copolymer, poly(thiophene-co-phenylene vinylene) and its derivatives conjugated polymer One of the copolymer materials.

In addition, the solvent for using the nano organic polymer fiber material for the organic solar panel of the present embodiment includes a single solvent or a cosolvent, wherein the single solvent includes chloromethane and dichloromethane. ), toluene, chloroform or xylene, the cosolvent may be a cosolvent selected from the group consisting of at least two solvents including methyl chloride, dichloromethane, toluene, chloroform and xylene. . Wherein, when the above cosolvent is composed of toluene and xylene, the volume ratio of toluene to xylene is from 99/1 to 1/99.

First, the conjugated polymer material is dissolved in a suitable solvent (such as toluene) and injected into a syringe. Thereafter, the conjugated polymer material is electrostatically injected from the end of the nozzle to form a liquid column, and the charged liquid column passes through the liquid column. During the stretching and whipping of electrostatic force, the fiber diameter is gradually refined, and the solvent in the conjugated polymer solution is continuously volatilized, and the diameter of the conjugated polymer fiber is greatly reduced from several hundred micrometers to several tens Nano, then an organic solar panel with a diameter between about 10 nm and 100 μm can be obtained on a grounded collector plate. Use organic fiber materials.

The optical characteristics of the nanofiber for organic solar panel of the present invention will be described in detail below using an experimental example.

Example: using poly(3-hexylthiophene-2,5-diyl)(P3HT) conjugated polymer material or poly(9,9-dioctylfluorene-2,7-diyl) (PFO) conjugated polymer material Chloroform is a solvent, and the concentration of the conjugated polymer material is from 4.0 to 40.0% by weight. The experimental conditions are that the distance from the end of the nozzle to the collecting plate is about 10 to 50 cm, the high voltage is 5 to 35 KeV, and the flow rate of the conjugated polymer is about 0.5 to 10 ml/h. An organic polymer fiber for an organic solar panel of P3HT is prepared by an electrospinning technique; or an organic polymer fiber for photoexcitation of PFO is prepared by an electrospinning technique.

The third picture is an optical microscope photograph of the P3HT nano-organic polymer fiber for the prepared organic solar panel, and the magnification is 400 times: (a) is a bright field (OM) P3HT nanofiber observation photograph, and (b) is Photograph of P3HT nanofibers observed under orthogonal polarized light (POM), (c) photoexcitation behavior of P3HT nanofibers under excitation of 320 nm excitation source; P3HT nanofibers found in Fig. (b) under polarized light The nanofiber material with crystallographic properties is proved by the figure (c) that the P3HT nanofiber view does not produce photoexcitation light behavior under ultraviolet light, which proves that the light absorption efficiency is obviously improved.

The fourth picture is an optical micrograph of the PFO nano-organic polymer fiber prepared by the organic photoexcitation light, and the magnification is 400 times: (a) is a bright field (OM) PFO nanofiber observation photograph, (b) is Under orthogonal polarization (POM) Observing the photo of PFO nanofibers, (c) is the photoexcitation behavior of PFO nanofibers under the excitation of 320nm excitation light source; it is found in Fig. (b) that PFO nanofibers have optical properties with high directional crystals under polarized light. The nanofiber material, as shown in Figure (c), proves that the PFO nanofibers emit ultraviolet light under the ultraviolet light and produce a very beautiful blue light luminescence behavior, which proves that the luminescence behavior has a blue shift phenomenon.

The fifth picture shows the UV light absorption and PL light excitation spectrum of the P3HT nano-polymer fiber, P3HT solution and P3HT gel drop-cast film for the prepared organic solar panel: (a) is the UV light absorption spectrum, ( b) is the spectral spectrum of PL light excitation; it is proved in Figure (a) that the light absorption efficiency of P3HT nano-polymer fiber is significantly higher than that of P3HT solution and P3HT gel film, and P3HT nanofiber is proved in PL in Figure (b) The luminescence behavior in the spectrum of the photoexcitation light is significantly lower than that of the P3HT solution and the P3HT gel film, indicating that it does not excite the absorbed light energy and significantly improves the light conversion efficiency.

The sixth picture shows the UV light absorption and PL light excitation spectrum of PFO nano-polymer fiber, PFO solution and PFO gel drop-cast film for photoexcitation light prepared: (a) is a UV light absorption spectrum, ( b) is the spectral spectrum of PL light excitation; it is proved in Figure (a) that the absorption wavelength of PFO nano-polymer fiber is significantly higher than that of PFO solution and PFO gel film, which means higher light absorption efficiency, as shown in Figure (b) It is proved that the luminescence behavior of PFO nanofibers in the PL photoexcitation spectrum is significantly higher than that of PFO solution and PFO film, and it means blue light shift, which means that PFO nanofibers also have excellent photoexcitation efficiency and significantly improve light conversion efficiency. .

The seventh picture is an electron micrograph of the P3HT nano-polymer fiber for the prepared organic solar panel: (a) the magnification is 500 times, and (b) is The magnification is 5,000 times.

The eighth graph is an electron micrograph of the prepared PFO nano-polymer fiber for organic light-exciting light: (a) the magnification is 500 times, and (b) the magnification is 5,000 times.

The ninth drawing is an electron micrograph of the P3HT nano-polymer fiber for the prepared organic solar panel: (a) the magnification is 1,000 times; and (b) the magnification is 10,000 times.

The tenth photograph is an electron micrograph of a P3HT nanofiber for an organic solar panel having a diameter of about 200 nm, and the magnification is 20,000 times.

In summary, the present invention is characterized in that various organic solar panels and organic optical fiber materials for organic photoexcitation are directly prepared by electrospinning, and the prepared organic fiber materials have a diameter of 10 nm to 100 μm.

The organic photoexcited optical fiber material prepared by the invention has a larger light absorption range than a general spin coating film, and the photoexcitation light intensity of the prepared organic photoexcited light nanofiber is higher than that of a general spin coating film. High, so the light absorption efficiency and photoexcitation efficiency can be significantly increased. Conjugated polymer photoexcited nano-organic fiber is one of the most attractive materials for photoelectric displays or photoexcited components, and can be applied to various industries such as personal display panels, industrial light-emitting components, and home lighting. Element, outdoor (inner) light-emitting element, 3C product organic light-emitting element, etc. The conjugated polymer prepared by the present invention is directly produced by an electrospinning technique without adding other materials.

In addition, the organic fiber material for the organic solar panel prepared by the invention has a larger light absorption range than the general spin coating film, and the prepared nano-organic fiber material for the organic solar panel has a small photoexcitation light behavior, so Significantly increase light absorption efficiency and light conversion efficiency. The conjugated polymer of the present invention is used as a nano-organic fiber material for an organic solar panel, and can be applied to various industries, such as a personal organic solar panel, an industrial organic solar panel, an organic solar panel for home decoration, and an outdoor solar panel for outdoor use. 3C products use organic solar panels.

However, the above description is only the present embodiment of the present invention, and the scope of the present invention is not limited thereto, and the simple equivalent changes and modifications according to the scope of the invention and the description of the invention are covered by the present invention. Within the scope.

The first figure is a schematic view of a P3HT nanofiber material for an organic solar panel according to an embodiment of the present invention, and the magnification is 400 times.

The second drawing is a schematic view of a PFO nanofiber material for organic light-exciting light according to an embodiment of the present invention, and the magnification is 400 times.

The third figure is an optical micrograph of the prepared P3HT nanofiber for the organic solar panel, and the magnification is 400 times.

The fourth figure is an optical micrograph of the prepared PFO nanofiber for organic light excitation light, and the magnification is 400 times.

The fifth picture shows the UV light absorption and PL light excitation of P3HT nanofiber, P3HT solution and P3HT gel drop casting film for organic solar panel prepared. Spectrum.

The sixth figure shows the UV light absorption and PL light excitation spectrum of the PFO nanofiber, PFO solution, and PFO gel drop cast film for the organic light excitation light prepared.

The seventh photograph is an electron micrograph of the prepared P3HT nanofiber for an organic solar panel: (a) the magnification is 500 times; and (b) the magnification is 5,000 times.

The eighth graph is an electron micrograph of the prepared PFO nanofiber for organic photoexcitation light: (a) the magnification is 500 times; and (b) the magnification is 5,000 times.

The ninth drawing is an electron micrograph of the prepared P3HT nanofiber for an organic solar panel: (a) is a magnification of 1,000 times; and (b) is a magnification of 10,000 times.

The tenth photograph is an electron micrograph of the prepared P3HT nanofiber for an organic solar panel having a diameter of about 200 nm, and the magnification is 20,000 times.

Claims (7)

An organic fiber for a solar panel and a photoexcitable element is directly spun by an electrospinning technique, and the organic fiber is composed only of a conjugated polymer selected from the group consisting of poly 3 -poly-3-alkylthiophenes and their derivatives, polyfluorenes (PFO) and their derivatives, polyphenylene vinylene (PPV) and its derivatives or poly-p One of -phenylene) and a derivative thereof, or is selected from the group consisting of poly-3-alkylthiophenes and derivatives thereof and polyfluorenes (PFO) and derivatives thereof. Mixed material, poly-3-alkylthiophenes and derivatives thereof, conjugated polymer blending materials of polyphenylene vinylene (PPV) and its derivatives, poly-3-alkyl Conjugated polymeric blends of poly-3-alkylthiophenes and their derivatives with poly-p-phenylene and its derivatives, polyfluorenes (PFO) and polyphenylene (polyphenylene) Conjugated polymer blended material or polyfluorene (polyvinylene, PPV) and its derivatives One of conjugated polymer blend materials of fluorenes, PFO) and poly-p-phenylene and its derivatives. The organic fiber for a solar panel and a photo-exciting element according to claim 1, wherein the conjugated polymer blended material has a weight ratio of conjugated polymer to 1 to 99 to 99 Between 1 and 1. Solar panel and photoexcitation as described in claim 1 An organic fiber for an optical element, wherein the conjugated polymer comprises a conjugated polymer copolymer material selected from the group consisting of polyfluorenes (PFO) and derivatives thereof and poly(fluorine) (poly(fluorine) -co-thiophene)) conjugated polymer copolymer, poly(fluorine-co-phenylene vinylene) conjugated polymer copolymer, poly(thiophene-co-styrene) (poly(thiophene-co-phenylene vinylene)) and its derivatives are one of conjugated polymer copolymer materials. The organic fiber for a solar panel and a photo-exciting element according to any one of claims 1 to 3, wherein the organic fiber has a diameter of between 10 nm and 100 μm. The organic fiber for a solar panel and a photo-exciting element according to any one of claims 1 to 3, wherein the conjugated polymer is dissolved in a solvent during the preparation process, and the weight percentage is The system is between 4% and 40%, and the aforementioned solvent is a single solvent or a co-solvent. The organic fiber for a solar panel and a photoexcited element according to claim 5, wherein the single solvent is one selected from the group consisting of monochloromethane, dichloromethane, toluene, chloroform or xylene. The organic fiber for a solar panel and a photoexcited element according to claim 5, wherein the cosolvent is selected from the group consisting of methyl chloride, dichloromethane, toluene, chloroform or xylene. A cosolvent formed.