WO2011074888A2 - Electrode paste composition for rear surface of solar cell - Google Patents

Abstract

The present invention relates to an electrode paste composition for the rear surfaces of solar cells, and comprises (a) a conductive powder of spherical or planar particles with an average particle size (D50) of 0.3 to 1.5 ㎛; (b) Bi₂O₃-SiO₂-Al₂O₃-B₂O₃-Sr O glass frit; and (c) an organic vehicle.

Description

Silver paste composition for solar cell back electrode

The present invention relates to a silver paste composition for a solar cell back electrode.

The present invention relates to the Korean Patent Application No. 10-2009-0125885 filed with the Korean Patent Office on December 17, 2009 and the Korean Patent Application No. 10-2010-0128828 filed to the Korean Patent Office on December 16, 2010. Claiming benefit, the entire contents of which are incorporated herein by reference.

The manufacturing method of a silicon crystalline solar cell is as follows.

First, an n-type impurity layer such as phosphorus (P) is formed on one surface of the P-type silicon substrate. At this time, the P-type silicon substrate is preferably 180 to 220㎛ thickness. The n-type impurity layer preferably has a thickness of 0.2 to 0.6 µm.

Subsequently, an antireflection film is formed on the n-type impurity layer to reduce reflection loss of sunlight. SiNx layer may be used as the anti-reflection film.

Subsequently, a front electrode is formed on the antireflection film. A back electrode is formed on the P-type silicon on which the n-type impurity layer is not formed. In this case, the electrode may be formed by applying an electroconductive paste by screen printing or the like, and drying it, followed by a two-step firing process of low temperature (about 600 ° C.) and high temperature (800-950 ° C.). In general, the conductive paste diffuses into the P-type silicon substrate during the firing process, thereby forming the conductive metal particle-Si alloy layer. And, by such spreading, a BSF (B ack S urface F ield) to prevent recombination of electrons generated by the solar cell and improve the collection efficiency of generated carriers (Carrier) are formed. Here, the efficiency of the solar cell depends on the thickness and uniformity of the BSF layer, but the thinner the thickness, the lower the efficiency of the solar cell, the higher the efficiency.

On the other hand, research and development for the solar cell back electrode is in progress. Representative examples include the following patents.

Republic of Korea Patent Publication No. 10-2006-0108550 relates to a thick film conductive composition comprising metal particles, glass particles, organic vehicle having a size of 3 to 15㎛. Since the registered patent has a large size of the metal particles, the voids between the metal particles increase after firing, thereby increasing the resistance of the solar cell, thereby reducing efficiency.

In addition, Korean Patent Laid-Open Publication No. 10-2006-0108552 relates to an electrically conductive thick film composition comprising an electrically conductive metal particle, a Pb-free glass frit, and an organic medium. However, the registered patent has a problem in that thermal stability such as crystallization occurs in the glass frit in the thermal process, and solder properties are not excellent.

In order to solve such a problem, the development of a new paste composition for solar cell back electrode is urgently needed.

An object of the present invention is to provide a silver paste composition for a solar cell back electrode that can improve the efficiency of the solar cell by reducing the resistance of the back electrode.

In addition, the present invention is to provide a silver paste composition for a solar cell back electrode that can improve the soldering characteristics when manufacturing a solar cell module.

The present invention (a) spherical or plate-like conductive silver powder having an average particle diameter (D50) of 0.3 to 1.5㎛; (b) Bi ₂ O ₃ -SiO ₂ -Al ₂ O ₃ -B ₂ O ₃ -SrO-based glass frit; And (c) provides a silver paste composition for a solar cell back electrode comprising an organic vehicle.

The silver paste composition for solar cell back electrode of the present invention lowers the resistance of the back electrode, minimizes the impurity content, improves soldering properties, and improves the efficiency of the solar cell and the module.

Hereinafter, the present invention will be described in detail.

The silver paste composition for solar cell back electrode of this invention contains (a) electroconductive silver powder, (b) glass frit, and (c) organic vehicle.

For solar cell back contact according to the present invention is (a) electrically conductive silver powder has a spherical or plate-shaped having an average particle diameter (D ₅₀₎ is 0.3 to 1.5㎛ contained in the paste composition. In addition, the (a) conductive silver powder preferably has a maximum particle size (D _MAX ) of 4.5 μm and a minimum particle size (D _MIN ) of 0.1 μm. If the average particle diameter (D ₅₀ ) and the minimum particle size (D _MIN ) are less than the above-mentioned ranges, the specific surface area of the silver powder is widened, so that the paste viscosity is high. Due to the increased viscosity, the printability is poor and limited to increasing the content of silver powder. When the average particle diameter (D ₅₀ ) and the maximum particle diameter (D _MAX ) exceed the above-mentioned ranges, the density of silver particles in the paste decreases, and a large amount of voids in the wiring are generated after the firing process, thereby increasing the resistance of the wiring.

The (a) conductive silver powder is preferably included in 65 to 75% by weight based on the total weight of the composition. When included below the above-mentioned range, the printed silver wiring layer becomes thinner after firing, so that the back wiring resistance increases, and the soldering characteristics may decrease. If the above range is exceeded, the printing thickness becomes too thick, which may result in warpage of the silicon wafer.

For solar cell back contact according to the present invention (b) a glass frit is a type _{Bi 2 O 3 -SiO 2 -Al 2} O 3 -B 2 O 3 -SrO contained in the paste composition. The glass frit (b) is melted to impart adhesion between the silver wiring layer and the silicon wafer layer.

SrO included in the glass frit serves to control the transition temperature of the glass frit to alkaline earth metal. At this time, since SrO has a large size of the ion radius, problems of lowering thermal stability such as crystallization are suppressed. And SrO improves a solder characteristic. As a side effect, the efficiency of the solar cell is increased.

(B) The glass frit is preferably included in an amount of 0.01 to 10% by weight, more preferably 0.5 to 7% by weight, and even more preferably 1 to 5% by weight, based on the total weight of the composition. . When included below the above-mentioned range, the adhesion force with the P-type silicon substrate, which is a substrate of the solar cell after the firing process, may be degraded. If it is included beyond the above range, the resistance may be increased and the efficiency of the solar cell may be reduced.

The composition ratio of the glass frit (b) is not particularly limited, but 20 to 30 mol% of Bi ₂ O ₃ , 25 to 35 mol% of SiO ₂ , 5 to 15 mol% of Al ₂ O ₃ , 20 to 40 mol% of B ₂ O _3, and SrO It is preferred to have a composition of 1 to 10 mol%. The physical properties of the glass depend on a suitable ratio of the Si, B component, which is a mesh forming agent, and the Bi, Al component, which is a network intermediate oxide, and the Sr component, which is an alkali metal component. Therefore, it is preferable to use a frit having a composition within the above numerical limits.

Moreover, it is preferable that the softening point (Tg) of the glass frit used by this invention is 400-500 degreeC. If it is less than the above-described range, while the thermal expansion coefficient of the glass frit is relatively large, the phenomenon that the wafer is bent after the firing process during the solar cell manufacturing process may be increased. When it exceeds the above-mentioned range, the glass frit may not be sufficiently melted during the firing process, and thus adhesion may be degraded.

(C) The organic vehicle included in the silver paste composition for solar cell back electrode of the present invention is preferably included in 20 to 34.9% by weight based on the total weight of the composition. When included in less than the above-described range, the viscosity may be too high and printability may be degraded. When it exceeds the above-mentioned range, powder content may fall and it may be difficult to ensure the thickness of a sufficient silver wiring layer.

The organic vehicle (c) is prepared by dissolving a polymer resin in an organic solvent, and may further include a thixotropic agent, a humectant, an additive, and the like, as necessary.

The polymer resin is preferably contained in an amount of 1 to 25% by weight, more preferably 5 to 25% by weight based on the total weight of the organic vehicle (c). When included in less than the above range, the printability and dispersion stability of the silver paste prepared with the composition of the present invention may be lowered. If the above range is exceeded, the paste may not be printed.

Examples of the polymer resin include polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, ethyl cellulose, rosin, phenol resin or acrylic resin.

The solvent is a solvent having a breaking point in the range of about 150 to 300 ℃ to prevent the drying of the paste during the printing process and to control the fluidity. The solvent is preferably included in the remaining amount so that the total weight of the organic vehicle (c) is 100% by weight.

Although the solvent is not particularly limited, the glycol ether series is tripropylene glycol methyl ether, dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, propylene glycol phenyl ether, diethylene glycol Ethyl ether, diethylene glycol n-butyl ether, diethylene glycol hexyl ether, ethylene glycol hexyl ether, triethylene glycol methyl ether, triethylene glycol ethyl ether, triethylene glycol n-butyl ether, ethylene glycol phenyl ether, terpinol, Texanol® (brand name) or ethylene glycol etc. are mentioned.

The thixotropic agent and the wetting agent are preferably included in an amount of 5 wt% or less based on the total weight of the organic vehicle (c). The thixotropic agent and the wetting agent are not particularly limited as long as they are generally used in this field. However, as the thixotropic agent THIXATROL @ ST of Elementis, the wetting agent may be used Silwet L-77, Silwet L-7500, Silwet L-7280, etc. of Momentive.

The additive is preferably included in an amount of 1 to 10% by weight, and more preferably in an amount of 1 to 5% by weight based on the total weight of the (c) organic vehicle. The additives include those generally used in this field such as dispersants. Commercially available surfactants can be used as the dispersant, and these can be used alone or in combination of two or more thereof. Examples of the surfactant include an ether type such as alkyl polyoxyethylene ether, alkylaryl polyoxyethylene ether, polyoxyethylene polyoxypropylene copolymer as nonionic surfactant; Ester ether types such as polyoxyethylene ether of glycerin ester, polyoxyethylene ether of sorbitan ester, and polyoxyethylene ether of sorbitol ester; Ester type such as polyethylene glycol fatty acid ester, glycerin ester, sorbitan ester, propylene glycol ester, sugar ester, alkyl polyglucoside; Nitrogen-containing types such as fatty acid alkanolamides, polyoxyethylene fatty acid amides, polyoxyethylene alkylamines, amine oxides; Examples of the polymeric surfactant include polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, polyacrylic acid-maleic acid copolymer, poly 12-hydroxystearic acid, and the like.

In addition, products commercially available as the surfactant include hypermer KD (manufactured by Uniqema), AKM 0531 (manufactured by Nippon Yuji Co., Ltd.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), and polyflow (POLYFLOW) Esha Chemical Co., Ltd., EFTOP (Tochem Products Co., Ltd.), Asahi guard, Suflon (above, Asahi Glass Co., Ltd.), SOLSPERSE (Geneneka Co., Ltd.) Manufacture), EFKA (made by EFKA Chemicals Co., Ltd.), PB 821 (made by Ajinomoto Co., Ltd.), BYK-184, BYK-185, BYK-2160, Anti-Terra U (made by BYK Corporation), etc. are mentioned.

The silver paste composition for a solar cell back electrode of the present invention lowers the resistance of the back electrode, minimizes the impurity content, and improves soldering properties to improve the efficiency of the solar cell and the module.

Hereinafter, the present invention will be described in more detail with reference to Examples, Preparation Examples and Test Examples. However, the scope of the present invention is not limited by the following examples, preparation examples and test examples.

Examples 1 to 3, Comparative Examples 1 to 4: Preparation of silver paste composition for solar cell back electrode

The components described in Table 1 below were mixed to the amounts described in Table 1 below. Thereafter, the mixture was stirred at 1,000 rpm for 3 minutes using a mixer that simultaneously rotates and rotates to prepare a silver paste composition for solar cell rear electrodes.

In addition, the composition of glass frit, Tg (transition point), a thermal expansion coefficient, and Tdsp (softening point) are described in Table 2.

Table 1

	Silver powder		Aluminum powder		Glass frit		Organic vehicle
	Average particle size (D 50 )	weight%	Average particle size (D 50 )	weight%	Frit1	Frit2	C-1	C-2	total
					weight%	weight%	weight%	weight%	weight%
Example 1	0.5 μm	70	-	-	4.5	-	21	4.5	25.5
Example 2	1.0 μm	70	-	-	4.5	-	21	4.5	25.5
Example 3	1.5 μm	70	-	-	4.5	-	21	4.5	25.5
Comparative Example 1	3 μm	70	-	-	4.5	-	21	4.5	25.5
Comparative Example 2	0.1 μm	70	-	-	4.5	-	21	4.5	25.5
Comparative Example 3	1.0 μm	67.5	4.5 ㎛	2.5	4.5	-	21	4.5	25.5
Comparative Example 4	1.0 μm	70	-	-	-	4.5	21	4.5	25.5

c-1: diethylene glycol monobutyl ether

c-2: ethyl cellulose

TABLE 2

	Bi 2 O 3 (mol%)	SiO 2 (mol%)	Al 2 O 3 (mol%)	B 2 O 3 (mol%)	SrO (mol%)	Tg (℃)	Thermal expansion coefficient (10 -7 / ℃)	Tdsp (℃)
Frit1	26	32	6.5	30.0	5.5	453	77	507
Frit2	28.5	34	6.5	31.0	0	462	77	515

Preparation Example 1 to Preparation Example 3, Comparative Preparation Example 1 to Comparative Preparation Example 4 Preparation of Solar Cell

A surface texturing process was performed on a single crystal wafer having a size of 156 × 156 mm and a thickness of 200 μm to form a pyramid height of about 4 to 6 μm. Thereafter, SiN _x was coated on the N-side of the wafer. Subsequently, a bus bar was printed and dried on the back surface of the wafer using the silver paste composition for solar cell back electrodes of Examples 1 to 3 and Comparative Examples 1 to 4. Thereafter, Dongwoo Fine Chem's aluminum electrode paste (trade name: AMP-BL122C) was applied and dried using a screen printing plate, and a finger line was printed and dried on the front SiNx side using silver paste. It was. The silicon wafer passed through the above process was fired in an infrared continuous firing furnace so that the temperature of the firing region was 800 to 950 ° C. to manufacture a solar cell. Here, the firing process may be performed by simultaneous firing of the front and rear surfaces while passing the silicon wafer into the belt furnace. At this time, the belt furnace includes a burn-out section at about 600 ° C. and a firing section at about 860 ° C., after burning off the organic material in the paste, the front and rear surfaces of silver or silver Melt aluminum to form an electrode.

On the other hand, according to the silver paste composition for solar cell back electrode of Examples 1 to 3 and Comparative Examples 1 to 4 used to form the bus bar, Preparation Examples 1 to 3, Comparative Preparation Examples 1 to Comparative Preparation Example 4 named the solar cell.

Test Example: Evaluation of Characteristics of Solar Cell

<Evaluation of Solar Cell Efficiency>

It was evaluated using SCM-1000, a FitTech solar cell performance evaluation apparatus, and the results are shown in Table 3 below.

<Warping evaluation>

The warpage was evaluated and the results are shown in Table 3 below. The measure of curvature is:

Good: less than 1 mm, NG: greater than 1 mm

<Evaluation of Battery Soldering Characteristics>

The soldering characteristics of the solar cells were evaluated using ribbons of 96.5Sn / 3.5Ag coated copper and ribbons of 62Sn / 36Pb / 2Ag. The soldering temperature for Pb-containing (62Sn / 36Pb / 2Ag) soldering was 230 ° C., the soldering temperature for Pb-free (96.5Sn / 3.5Ag) soldering was 320 ° C., and the soldering time was 5-7 seconds. The flux used was MF200.

And soldering characteristic is evaluated by adhesive strength. Adhesive strength was obtained by pulling the ribbon at an angle of 90 ° to the surface of the cell. Adhesive strength of less than 200 g is low and values in the range of 200 g to 300 g are appropriate; A value of 300 to 400 g or more was evaluated as good as the adhesive strength, the results are shown in Table 3.

TABLE 3

		Preparation Example 1	Preparation Example 2	Preparation Example 3	Comparative Production Example 1	Comparative Production Example 2	Comparative Production Example 3	Comparative Production Example 4
Solar cell efficiency (%)		17.5	17.6	17.5	17.3	17.1	17.1	17.4
Warpage		Good	Good	Good	Good	NG	Good	Good
Soldering Characteristics (g)	62Sn / 36Pb / 2Ag	564	523	635	453	374	321	380
	96.5Sn / 3.5Ag	379	321	346	286	223	199	293

Referring to Table 3, the manufacturing examples according to the present invention is 0.2 ~ 0.5% difference in efficiency than the comparative manufacturing example, it can be seen that the efficiency is excellent, the soldering characteristics are also excellent.

Claims (6)

1. (a) a conductive silver powder having an average particle diameter (D ₅₀ ) of 0.3 to 1.5 µm and having a spherical or plate shape;

   (b) Bi ₂ O ₃ -SiO ₂ -Al ₂ O ₃ -B ₂ O ₃ -SrO-based glass frit; And

   (c) A silver paste composition for solar cell back electrode, comprising an organic vehicle.
2. The method according to claim 1,

   Regarding the total weight of the composition,

   65 to 75% by weight of the (a) conductive silver powder;

   0.1 to 10% by weight of the (b) Bi ₂ O ₃ -SiO ₂ -Al ₂ O ₃ -B ₂ O ₃ -SrO-based glass frit; And

   The silver paste composition for a solar cell back electrode comprising (c) 20 to 34.9% by weight of the organic vehicle.
3. The method according to claim 1,

   The (a) conductive silver powder has a maximum particle size (D _MAX ) of 4.5 μm and a minimum particle size (D _MIN ) of 0.1 μm, wherein the silver paste composition for a solar cell back electrode.
4. The method according to claim 1,

   The composition ratio of the (b) Bi ₂ O ₃ -SiO ₂ -Al ₂ O ₃ -B ₂ O ₃ -SrO-based glass frit is Bi ₂ O ₃ 20-30 mol%, SiO ₂ 25-35 mol%, Al ₂ O ₃ 5 To 15 mol%, B ₂ O ₃ 20 to 40 mol%, and SrO 1 to 10 mol%, the silver paste composition for a solar cell back electrode.
5. The method according to claim 1,

   (C) the organic vehicle,

   The silver paste composition for a solar cell rear electrode, characterized in that (c) based on the total weight of the organic vehicle, 1 to 25% by weight of the polymer resin and the remaining amount of the solvent.
6. The method according to claim 1,

   The silver paste composition for solar cell back electrodes characterized by not containing aluminum powder.