KR101689587B1 - Process for Preparing Silicon Ink, and Solar Cell using Thereof - Google Patents
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Abstract
The present invention relates to a method for producing a polysilane ink by synthesizing a Si precursor by a liquid phase method and then adding single-walled carbon nanotubes (SWNT) or graphene nanoribbons (GNR). More specifically, a Si precursor is synthesized through a three-step synthesis process, and single-walled carbon nanotubes or graphene nanoribbons are dispersed in the synthesized solution. Polysilanes are formed by photopolymerization using the dispersion, The method comprising: The present invention also provides a method of manufacturing a solar cell by forming a thin film by ink jet or spin coating method using the ink thus prepared.
Description
The present invention relates to a process for producing a polysilane ink using a photocuring reaction by preparing cyclopentasilane and adding a single-walled carbon nanotube (SWNT) and a graphene nanoribbon (GNR) Battery. Conventionally, a solar cell was manufactured by a wafer or a vacuum deposition method in the case of a solar cell, but this method has a disadvantage that it is expensive and takes a long time. Therefore, the present invention solves this problem and provides a low-cost, high-efficiency ultra-low-cost solar cell as a printing method.
In the case of silicon solar cells, it is a type of green energy that is used in real life to convert solar energy into electrical energy. The use of solar cells has been applied to various fields such as construction of general power plants, home power generation, and portable batteries.
In the case of conventional silicon solar cells, solar cells were fabricated by wafer and vacuum deposition. Silicon is divided into intrinsic semiconductors, p-type semiconductors and n-type semiconductors by doping, and silicon solar cells are fabricated by deposition on p-type wafers. In this case, the process time is very long, and there is a disadvantage that a high cost is consumed for manufacturing a solar cell.
DISCLOSURE OF THE INVENTION The present invention has been made to solve the above problems, and it is an object of the present invention to provide a method of synthesizing a silicon precursor using a wet method and adding single wall carbon nanotubes (SWNT) and graphene nanoribbons (GNR) to the synthesized precursor, To a method for producing a polysilicon ink. Also, the present invention relates to a method for preparing a thin film solar cell by preparing p-type and n-type silicon inks by doping Group 3 and Group 5 in a synthesis step using a precursor.
The present invention relates to a method for producing a polysilicon ink, which comprises adding a single-walled carbon nanotube (SWNT) and a graphene nanoribbons (GNR) to provide a composite silicone ink and manufacturing solar cells using the produced ink, And can be used as materials for next-generation solar cells and printing electrons to replace crystalline Si or vacuum-deposited amorphous thin film Si.
A method for producing a silicon ink for a solar cell according to the present invention comprises the steps of: a) reacting dichlorodiphenylsilane of
(Formula 1)
(2)
(Formula 3)
(Formula 4)
Characteristically, in step a), PBr 3 is added in an amount of 10 to 90% by weight of dichlorodiphenylsilane to prepare an n-type silicon ink.
Characteristically, in step a), BBr 3 is further added in an amount of 10 to 90% by weight of dichlorodiphenylsilane to prepare p-type silicon ink.
In the production process according to the present invention, the dispersion in step d) is preferably an ultrasonic dispersion.
The method for manufacturing a solar cell according to the present invention is characterized in that a silicon ink for a solar cell manufactured by the above-described manufacturing method is manufactured by forming an Si layer of thin film on an electrode by inkjet, gravure, offset or flexo method.
The manufacturing process of the solar cell using the carbon nanotube (SWNT) and the graphene nanoribbon (GNR) composite polysilicon ink made by the present invention simplifies the process compared with the conventional deposition method, It is possible. In addition, by using simple silicon ink, it is possible to overcome the light efficiency characteristics, which were changed by cracks and surface roughness during printing or coating, by using carbon nanotubes (SWNT) and graphene nanoribbons (GNR) It can contribute to development.
1 shows the FT-IR spectrum of the cyclopentasilane prepared according to Example 1
2 shows the NMR spectra of the cyclopentasilane prepared according to Example 1
3 is a graph showing the efficiency of a solar cell manufactured according to Example 5
The manufacturing method of the present invention will be described in detail with reference to the accompanying drawings. The following drawings are provided by way of example so that those skilled in the art can fully understand the spirit of the present invention. Therefore, the present invention is not limited to the following drawings, but may be embodied in other forms, and the following drawings may be exaggerated in order to clarify the spirit of the present invention. Also, throughout the specification, like reference numerals designate like elements.
Hereinafter, the technical and scientific terms used herein will be understood by those skilled in the art without departing from the scope of the present invention. Descriptions of known functions and configurations that may be unnecessarily blurred are omitted.
The present invention relates to a process for producing a silicon ink by preparing a silicon precursor by a liquid phase synthesis method and dispersing carbon nanotubes (SWNT) and graphene nanoribbons (GNR) in a solution, followed by photocuring reaction, To provide a thin film solar cell.
A method for producing a silicon ink for a solar cell according to the present invention is characterized by the following steps.
a) reacting dichlorodiphenylsilane of
b) reacting decaphenyl-substituted cyclopentasilane of formula (3) with aluminum chloride and reacting in a hydrogen chloride gas or hydrogen bromide gas atmosphere to prepare chlorinated or brominated cyclopentasilane of formula (4);
c) reduction reaction with chlorinated or brominated cyclopentasilane of formula (4) and lithium aluminum hydride to produce cyclopentasilane of formula (1); And
d) adding single-walled carbon nanotubes or graphene nanoribbons to the cyclopentasilane of Formula 1, and dispersing and then photo-curing the polysilane inks.
(Formula 1)
(2)
(Formula 3)
(Formula 4)
Specifically, the cyclopentasilane compound employed in the silicone ink according to the present invention is prepared through the steps described in the following Reaction Scheme 1.
(Scheme 1)
Specifically, 1 to 20 parts by weight, preferably 1 to 10 parts by weight of lithium and 30 to 100 parts by weight, preferably 40 to 80 parts by weight of dichlorodiphenylsilane are dissolved in tetrahydrofuran ( THF), and the mixture is stirred in an argon atmosphere for 5 to 24 hours, preferably 10 to 20 hours to prepare decaphenyl-substituted cyclopentasilane.
In the second step reaction, 3 to 20 parts by weight, preferably 5 to 15 parts by weight, of aluminum chloride is added to the prepared decaphenyl-substituted cyclopentasilane, and the mixture is reacted in a hydrogen chloride gas (HCl) or hydrogen bromide gas (HBr) atmosphere for 5 to 24 hours , Preferably 10 to 20 hours, to prepare a chlorinated or brominated cyclopentasilane.
In the three-step reaction, 1 to 10 parts by weight, preferably 1 to 5 parts by weight, of lithium aluminum hydride is added and reacted for 5 to 20 hours, preferably 8 to 15 hours to synthesize cyclopentasilane do.
After 1 to 0.1 wt% of carbon nanotubes (SWNT) or graphene nanoribbons (GNR) are dispersed by ultrasonication in the thus synthesized cyclopentasilane and then irradiated with ultraviolet rays, polysilane is obtained by photo-curing reaction. And can be applied to printing by making ink.
An n-type or p-type silicon ink is prepared by reacting 10 to 90% by weight of PBr 3 , based on the weight of dichlorodiphenylsilane, in a one-step reaction as shown in the following
(Scheme 2)
(Scheme 3)
(Example 1) Production of silicone ink
3 g of lithium and 60 g of dichlorodiphenylsilane were dissolved in 200 g of tetrahydrofuran and stirred in an argon atmosphere for 10 hours to obtain 40 g of decaphenyl-substituted cyclopentasilane. After 15 g of aluminum chloride was added to the obtained decaphenyl-substituted cyclopentasilane, 12 g of chlorinated cyclopentasilane was obtained by reacting with hydrogen chloride gas (HCl) for 15 hours. Then, 2 g of lithium aluminum hydride was added to the chlorinated cyclopentasilane And the mixture was reacted for 10 hours to obtain 5 g of cyclopentasilane.
Synthesis of Si precursor was confirmed using FT-IR and NMR as shown in Figs. 1 and 2 using the prepared ink.
(Example 2) Production of p-type or n-type silicon ink
A p-type or n-type Si ink was prepared in the same manner as in Example 1 except that 0.5 g of BBr 3 or 0.5 g of PBr 3 was further added to lithium and dichlorodiphenylsilane.
(Example 3)
A semiconductor ink was prepared by adding 0.2 wt% of SWNT (single wall carbon nanotubes) to the ink prepared in Example 1 above. The prepared ink was irradiated with 100 mW UV for 10 seconds to prepare a semiconductor ink. The prepared ink was spin-coated with ink containing SWNT on a p-Si wafer to form a film, and then the film was heat-treated at 500 ° C for 30 minutes to prepare a thin film. As the top electrode, silver ink was used to form the upper electrode and the efficiency was measured.
(Example 4)
The efficiency was measured after forming a thin film according to Example 3 and all the processes except that 0.2 wt% of graphene nanoribbons (GRN) was added to the ink prepared in Example 1 to prepare a semiconductor ink.
(Example 5)
A thin film was formed in the same manner as in Example 3, except that 0.2 wt% of SWNT (single wall carbon nanotube) was added to the p-type ink prepared in Example 2 to produce a p-type semiconductor ink. Respectively.
(Example 6)
A thin film was formed in the same manner as in Example 3 except that 0.2 wt% of graphene nanoribbons (GRN) was added to the n-type ink prepared in Example 2 to prepare an n-type semiconductor ink, Respectively.
(Example 7)
The n-type semiconductor ink prepared in Example 6 was spin-coated on a p-Si wafer to form an n-Si film, and then the thin film was prepared by heat treatment at 500 ° C for 30 minutes. The upper electrode was formed using silver ink as the upper electrode. Then, the efficiency was measured using a solar simulator, and the measured efficiency was as shown in FIG.
(Example 8)
The p-type semiconductor ink prepared in Example 5 was spin-coated on a transparent electrode (ITO electrode) to produce a p-Si thin film. The prepared thin film was heat-treated at 500 ° C. for 30 minutes, and then the intrinsic Si (i-Si) thin film was formed on the heat-treated p-Si thin film by spin coating the ink prepared in Example 3, The prepared intrinsic thin film was heat-treated at 500 ° C for 30 minutes, and then the n-type semiconductor ink prepared in Example 6 was spin-coated thereon to form an n-Si thin film. The formed thin film was subjected to heat treatment at 500 DEG C for 30 minutes. Then, an upper electrode was formed using silver ink. Then, the efficiency was measured using a solar simulator.
(Example 9)
The p-type semiconductor ink prepared in Example 5 was spin-coated on the transparent electrode (ITO electrode), and the ink prepared in Example 3 was subjected to inkjet printing, and again the n-type semiconductor ink prepared in Example 6 was inkjet printed A silicon solar cell was prepared in the same manner as in Example 8. [ Then, the efficiency was measured using a solar simulator.
(Example 10)
A silicon solar cell was prepared in the same manner as in Example 8 except that the n-Si, i-Si and p-Si thin films were all manufactured by a printing method using an ink jet. Then, the efficiency was measured using a solar simulator.
While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, Those skilled in the art will recognize that many modifications and variations are possible in light of the above teachings.
Accordingly, the spirit of the present invention should not be construed as being limited to the embodiments described, and all of the equivalents or equivalents of the claims, as well as the following claims, belong to the scope of the present invention .
Claims (5)
b) reacting decaphenyl-substituted cyclopentasilane of formula (3) with aluminum chloride and reacting in a hydrogen chloride gas or hydrogen bromide gas atmosphere to prepare chlorinated or brominated cyclopentasilane of formula (4);
c) reduction reaction with chlorinated or brominated cyclopentasilane of formula (4) and lithium aluminum hydride to produce cyclopentasilane of formula (1);
d) adding a single-walled carbon nanotube or graphene nanoribbons to the cyclopentasilane of Formula 1, dispersing and then curing to produce a polysilane ink;
Wherein the method further comprises the steps of:
(Formula 1)
(2)
(Formula 3)
(Formula 4)
wherein in step (a), 10 to 90% by weight of dichlorodiphenylsilane is further added to PBr 3 to produce an n-type silicon ink.
wherein in step (a), BBr 3 is further added in an amount of 10 to 90% by weight of dichlorodiphenylsilane to produce a p-type silicon ink.
wherein the dispersion in step d) is an ultrasonic dispersion.
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| KR1020100049504A KR101689587B1 (en) | 2010-05-27 | 2010-05-27 | Process for Preparing Silicon Ink, and Solar Cell using Thereof |
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| KR1020100049504A KR101689587B1 (en) | 2010-05-27 | 2010-05-27 | Process for Preparing Silicon Ink, and Solar Cell using Thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7173180B2 (en) | 2001-08-14 | 2007-02-06 | Jsr Corporation | Silane composition, silicon film forming method and solar cell production method |
| JP2010018696A (en) | 2008-07-10 | 2010-01-28 | Toray Ind Inc | Carbon nanotube dispersing solution, organic semiconductor composite solution, organic semiconductor thin film and organic field-effect transistor |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7173180B2 (en) | 2001-08-14 | 2007-02-06 | Jsr Corporation | Silane composition, silicon film forming method and solar cell production method |
| JP2010018696A (en) | 2008-07-10 | 2010-01-28 | Toray Ind Inc | Carbon nanotube dispersing solution, organic semiconductor composite solution, organic semiconductor thin film and organic field-effect transistor |
Non-Patent Citations (1)
| Title |
|---|
| Y. F. Zhang 외 6명. Photovoltaic enhancement of Si solar cells by assembled carbon nanotubes, nano-micro letters, Vol. 2, 22-25, 2010.03.20 |
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