KR20160128098A - Composition forforming electrode, electrode manufactured using the same and solar cell - Google Patents
Composition forforming electrode, electrode manufactured using the same and solar cell Download PDFInfo
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- KR20160128098A KR20160128098A KR1020150059901A KR20150059901A KR20160128098A KR 20160128098 A KR20160128098 A KR 20160128098A KR 1020150059901 A KR1020150059901 A KR 1020150059901A KR 20150059901 A KR20150059901 A KR 20150059901A KR 20160128098 A KR20160128098 A KR 20160128098A
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- 239000001257 hydrogen Substances 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
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- 125000002373 5 membered heterocyclic group Chemical group 0.000 claims description 5
- 125000004070 6 membered heterocyclic group Chemical group 0.000 claims description 5
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- 125000002636 imidazolinyl group Chemical group 0.000 claims description 3
- 125000002883 imidazolyl group Chemical group 0.000 claims description 3
- 125000000842 isoxazolyl group Chemical group 0.000 claims description 3
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- 125000002270 phosphoric acid ester group Chemical group 0.000 claims description 3
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- 125000002755 pyrazolinyl group Chemical group 0.000 claims description 3
- 125000003226 pyrazolyl group Chemical group 0.000 claims description 3
- 125000001422 pyrrolinyl group Chemical group 0.000 claims description 3
- 239000003381 stabilizer Substances 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 239000012756 surface treatment agent Substances 0.000 claims description 3
- 125000003831 tetrazolyl group Chemical group 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 125000001425 triazolyl group Chemical group 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000013530 defoamer Substances 0.000 claims description 2
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- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 2
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- 239000000326 ultraviolet stabilizing agent Substances 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims 2
- 239000011734 sodium Substances 0.000 claims 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
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- 239000011574 phosphorus Substances 0.000 claims 1
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- JGRPZAGOYKNIAC-UHFFFAOYSA-N ethyl n-propan-2-ylcarbamate Chemical compound CCOC(=O)NC(C)C JGRPZAGOYKNIAC-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000000592 heterocycloalkyl group Chemical group 0.000 description 1
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- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
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- 125000005647 linker group Chemical group 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
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- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
Description
A composition for forming electrodes, an electrode made therefrom, and a solar cell.
Solar cells generate electrical energy by using photoelectric effect of pn junction that converts photon of sunlight into electricity. The solar cell is formed with a front electrode and a rear electrode on a semiconductor wafer or substrate upper and lower surfaces, respectively, where a pn junction is formed. The photovoltaic effect of the pn junction is induced in the solar cell by the sunlight incident on the semiconductor wafer, and the electrons generated from the pn junction provide a current flowing to the outside through the electrode.
The electrode of such a solar cell can be formed in a predetermined pattern on the surface of the wafer by applying, patterning and firing the composition for electrode formation.
In order to improve the conversion efficiency of the solar cell, the contact resistance (Rc) and the series resistance (Rs) can be minimized by improving the contact with the wafer, or the line width of the screen mask line is formed to increase the short-circuit current I sc . However, a method of reducing the line width of the electrode pattern using a screen mask may cause an increase in the series resistance Rs and may deteriorate the continuous printability of the fine pattern.
The composition for electrode formation uses an organic vehicle to impart viscosity and rheological properties suitable for printing, and the organic vehicle may typically include an organic binder, a solvent, and the like.
Development of an organic binder capable of improving the printing property of the composition for electrode formation has been desired.
One embodiment provides a composition for forming an electrode capable of forming a fine pattern with high resolution and having excellent printing characteristics.
Another embodiment provides an electrode made of the electrode forming composition.
Another embodiment provides a solar cell comprising the electrode.
According to an embodiment, there is provided a composition for forming an electrode comprising a conductive powder, a glass frit, an organic binder and a solvent, wherein the organic binder includes a structural unit represented by the following formula (1).
[Chemical Formula 1]
In Formula 1,
R 1 , R 2 and R 3 are each independently hydrogen, a substituted or unsubstituted straight or branched chain C1 to C15 alkyl group, a substituted or unsubstituted straight or branched chain C2 to C15 alkenyl group, a substituted or unsubstituted A substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 heterocycloalkyl group, a substituted or unsubstituted C3 to C20 aryl group, a substituted or unsubstituted C3 to C20 heteroaryl group, And at least one of R 1 , R 2, and R 3 is a substituent represented by the following formula (2).
(2)
In Formula 2,
R a and R b are each independently hydrogen or a straight or branched chain C1 to C10 alkyl group,
n is an integer of 0 to 10,
X is a substituted or unsubstituted straight or branched chain C1 to C18 alkyl group, a hydroxy group (-OH), a halogen, a carboxyl group (-COOH), an ester group (COOR, wherein R is a linear or branched C1 to C6 alkyl group ), phosphate groups (phosphoric acid, -OP (= O ) (OH) 2), a phosphoric acid ester group (-OP (= O) (oR ) 2) ( wherein R is a straight or branched chain C1 to C6 alkyl group Im) , A substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, and a substituted or unsubstituted N, O, S, and combinations thereof. 5-or 6-membered heterocyclic,
* Represents a position connected to the oxygen (O) of OR 1 , OR 2 and OR 3 in formula (1).
In the above formula (2), at least one substituted or unsubstituted methylene group (- (C (R a ) (R b ))) not adjacent to the amide group may be replaced by -O-, -S-, -C -, -S (= O) -, -S (= O) 2- , -C (= O) -O-, -OC Hydrogen or a C1 to C6 alkyl group), and combinations thereof.
The 5-membered or 6-membered heterocyclic group containing at least one hetero atom selected from the above substituted or unsubstituted N, O, S and combinations thereof may be an imidazolyl group, an imidazolinyl group A pyrazolyl group, a pyrazolinyl group, a pyrrolinyl group, a triazolyl group, a tetrazolyl group, a furfuryl group, And may be selected from an isoxazolyl group.
The weight average molecular weight (Mw) of the compound represented by Formula 1 may be 5,000 g / mol to 200,000 g / mol.
In the compound represented by the general formula (1), one or two substituents represented by the general formula (2) may exist per cellulose structural unit.
Wherein the composition for electrode formation comprises 60 to 95% by weight of a conductive powder; 0.5 to 20% by weight of glass frit; 1 to 20% by weight of an organic binder, and a residual amount of a solvent.
The glass frit may be at least one selected from the group consisting of Pb, Tell, Bi, Li, P, Ge, (Si), Zn (Zn), W, Mg, Cs, Sr, Mo, Ti, (V), Ba, Ni, Cu, Na, K, As, Cob, Zr, Mn and Aluminum (Al), and the like.
The solvent may be selected from the group consisting of methyl cellosolve, ethyl cellosolve, butyl cellosolve, aliphatic alcohol,? -Terpineol,? -Terpineol, At least one selected from dihydro-terpineol, ethylene glycol, ethylene glycol mono butyl ether, butyl cellosolve acetate and texanol, . ≪ / RTI >
The glass frit may have an average particle diameter (D50) of 0.1 占 퐉 to 10 占 퐉.
The composition for electrode formation may further include at least one additive selected from a surface treatment agent, a dispersant, a thixotropic agent, a viscosity stabilizer, a defoamer, a pigment, a UV stabilizer, an antioxidant and a coupling agent.
Another embodiment provides an electrode made of the electrode forming composition.
Another embodiment provides a solar cell comprising the electrode.
The composition for electrode formation can form a fine pattern with high resolution and has excellent printing properties.
1 is a schematic view briefly showing a structure of a solar cell according to one embodiment.
Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings, which will be readily apparent to those skilled in the art to which the present invention pertains. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
In the drawings, the thickness is enlarged to clearly represent the layers and regions. Like parts are designated with like reference numerals throughout the specification. It will be understood that when an element such as a layer, film, region, plate, or the like is referred to as being "on" another portion, it includes not only the element directly over another element, Conversely, when a part is "directly over" another part, it means that there is no other part in the middle.
Unless otherwise specified herein, "substituted" means that at least one hydrogen atom is replaced by a halogen atom (F, Cl, Br, I), a hydroxy group, a C1 to C20 alkoxy group, a nitro group, a cyano group, A thiol group, an ester group, an ether group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a C 1 -C 6 alkyl group, a C 1 -C 6 alkoxy group, A C2 to C20 alkynyl group, a C6 to C30 aryl group, a C3 to C20 cycloalkyl group, a C3 to C20 cycloalkenyl group, a C3 to C20 cycloalkynyl group, a C2 to C20 alkynyl group, Means a substituted with a substituent of a heterocycloalkyl group of 1 to 20 carbon atoms, a C2 to C20 heterocycloalkenyl group, a C2 to C20 heterocycloalkynyl group, a C3 to C30 heteroaryl group, or a combination thereof.
Also, unless otherwise specified herein, "hetero" means that at least one heteroatom of N, O, S and P is included in the ring group.
The composition for electrode formation according to one embodiment includes conductive powder; Glass frit; Organic binders; And a solvent. Hereinafter, the present invention will be described in detail.
The electrode forming composition according to one embodiment may use a metal powder as the conductive powder. The metal powder may be at least one selected from the group consisting of Ag, Au, Pd, Pt, Ru, Rh, Os, Ir, (Ti), niobium (Nb), tantalum (Ta), aluminum (Al), copper (Cu), nickel (Ni), molybdenum (Mo), vanadium (V), zinc (Zn) May include one or more metal powders selected from Y, Co, Zr, Fe, W, Sn, Cr and Mn, , But is not limited thereto.
The conductive powder may be a powder having a particle size of nano size or micro size, for example, a conductive powder having a size of several tens to several hundreds of nanometers, a conductive powder of several to several tens of micrometers, Conductive powder may be mixed and used.
The conductive powder may have a spherical shape, a plate shape, or an amorphous shape. The average particle diameter (D50) of the conductive powder is preferably 0.1 占 퐉 to 10 占 퐉, and more preferably 0.5 占 퐉 to 5 占 퐉. The average particle diameter was measured using a 1064LD model manufactured by CILAS after dispersing the conductive powder in isopropyl alcohol (IPA) at room temperature (24 ° C to 25 ° C) for 3 minutes using ultrasonic waves. Within this range, the contact resistance and line resistance can be lowered.
The conductive powder may be contained in an amount of 60 to 95% by weight, preferably 70 to 90% by weight based on 100% by weight of the total amount of the electrode forming composition. In the above range, And it is possible to prevent the paste from becoming difficult due to the relative reduction in the amount of the organic vehicle. The glass frit is produced by etching the antireflection film during the firing process of the electrode forming composition to melt the conductive powder particles to produce metal crystal grains of conductive powder in the emitter region so that the resistance can be lowered, The adhesion between the conductive powder and the wafer is improved, and softening at the time of sintering induces an effect of lowering the firing temperature.
Increasing the area of the solar cell in order to increase the efficiency of the solar cell may increase the contact resistance of the solar cell. Therefore, the damage to the pn junction should be minimized while the series resistance should be minimized. In addition, it is preferable to use a glass frit which can sufficiently secure thermal stability even at a wide firing temperature because the range of variation in firing temperature becomes large as wafers of various sheet resistances increase.
The glass frit may be typically at least one of a flexible glass frit and a lead-free glass frit used in an electrode-forming composition.
The glass frit may be at least one selected from the group consisting of Pb, Tell, Bi, Li, P, Ge, (Si), Zn (Zn), W, Mg, Cs, Sr, Mo, Ti, (V), Ba, Ni, Cu, Na, K, As, Cob, Zr, Mn and Aluminum (Al), and the like.
The glass frit may be derived from an oxide of the metallic element described above using conventional methods. For example, a mixture prepared by mixing the oxides of the metal elements in a specific composition may be melted, quenched, and then ground again. The mixing process may be performed using a ball mill or a planetary mill. The melting process may be performed at a temperature of 700 ° C to 1300 ° C, and the crystallization process may be performed at room temperature (24 ° C to 25 ° C). The pulverizing process may be performed using a disk mill, But the present invention is not limited thereto.
The glass frit may have an average particle diameter (D50) of 0.1 탆 to 10 탆, and may be contained in an amount of 0.5 to 20% by weight based on 100% by weight of the total amount of the electrode forming composition. Within the above range, the adhesion strength of the electrode can be improved within a range that does not impair the electrical characteristics of the electrode.
The shape of the glass frit may be spherical or non-shape. In one embodiment, two types of glass frit having different transition temperatures may be used. For example, a first glass frit having a transition temperature of 200 ° C or higher and 350 ° C or lower and a second glass frit having a transition temperature of 350 ° C or higher and 550 ° C or lower may be mixed at a weight ratio of 1: 0.2 to 1: 1.
The organic binder may be represented by the following general formula (1).
[Chemical Formula 1]
In Formula 1,
R 1 , R 2 and R 3 are each independently hydrogen, a substituted or unsubstituted straight or branched chain C1 to C15 alkyl group, a substituted or unsubstituted straight or branched chain C2 to C15 alkenyl group, a substituted or unsubstituted A substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 heterocycloalkyl group, a substituted or unsubstituted C3 to C20 aryl group, a substituted or unsubstituted C3 to C20 heteroaryl group, And at least one of R 1 , R 2, and R 3 is a substituent represented by the following formula (2).
(2)
In Formula 2,
R a and R b are each independently hydrogen or a straight or branched chain C1 to C10 alkyl group, specifically a straight or branched chain C1 to C6 alkyl group,
n is an integer of 0 to 10,
X is a substituted or unsubstituted straight or branched chain C1 to C18 alkyl group, a hydroxy group (-OH), a halogen (-F, -Cl, -Br or -I), a carboxyl group (-COOH) (= O (OH) 2 ), phosphoric acid ester group (-OP (= O) (OR) 2 ) (wherein R is a straight or branched alkyl group having 1 to 6 carbon atoms) R is a straight chain or branched chain C1 to C6 alkyl group), a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, and substituted or unsubstituted N, O, S, Membered heterocyclic group containing at least one heteroatom selected from a combination of < RTI ID = 0.0 >
* Represents a position connected to the oxygen (O) of OR 1 , OR 2 and OR 3 in formula (1).
The substituted or unsubstituted straight or branched chain C1 to C15 alkyl group may be, for example, a straight or branched chain C1 to C15 hydroxyalkyl group substituted with at least one hydroxy group.
The substituted or unsubstituted straight-chain or branched-chain C1 to C15 alkyl group may have a substituent such as a methyl group, an ethyl group, an n-propyl group, a sec-butyl group, an isopropyl group, , Isobutyl group and the like.
In the above formula (2), at least one substituted or unsubstituted methylene group (- (C (R a ) (R b ))) not adjacent to the amide group may be replaced by -O-, -S-, -C -, -S (= O) -, -S (= O) 2- , -C (= O) -O-, -OC Hydrogen or a C1 to C6 alkyl group), and combinations thereof. When two or more of the connectors are replaced, the connectors to be replaced do not exist adjacent to each other.
At least one substituted or unsubstituted methylene group of the substituted or unsubstituted straight or branched C1 to C15 alkyl group may be replaced by -O-, -S-, -C (= O) -, -S (= O) (= O) 2 -, -C (= O) -O-, -OC (= O) -, -C (= O) NR- wherein R is hydrogen or a C1 to C6 alkyl group, Lt; / RTI > may be replaced with a connector selected from a combination of < RTI ID = When two or more of the connectors are replaced, the connectors to be replaced do not exist adjacent to each other. In the above formula (2), when n is 0, the substituted linking group is not present continuously with the amide group of formula (2).
The 5-membered or 6-membered heterocyclic group containing at least one hetero atom selected from the above substituted or unsubstituted N, O, S and combinations thereof may be an imidazolyl group, an imidazolinyl group A pyrazolyl group, a pyrazolinyl group, a pyrrolinyl group, a triazolyl group, a tetrazolyl group, a furfuryl group, And may be selected from an isoxazolyl group.
The compound represented by Formula 1 may be prepared by reacting a cellulose or cellulose derivative with an isocyanate compound represented by Formula 2a below.
(2a)
In the above formula (2a)
R a and R b , n and X are the same as in the formula (2).
A hydroxy group or an alkoxy group of a cellulose or a cellulose derivative may react with an isocyanate group of an isocyanate compound of the above formula (2a) to form a urethane bond (-O-C (= O) -N (H) -).
The organic binder includes at least one urethane bond in the main chain of the cellulose, thereby improving the printing property of the electrode forming composition and improving the dispersibility and storage stability. In addition, the organic binder may form an entanglement structure between constituent components of the electrode forming composition, for example, an organic binder having a cellulose main chain or conductive powder particles so as to be in intimate contact with each other. The wettability of the substrate can be improved and the affinity between the composition for electrode formation and the substrate can be improved. Thus, when the composition for electrode formation is printed on a substrate, it is possible to prevent the width of the electrode pattern from increasing due to the bleeding of the composition for electrode formation, and the width of the electrode can be kept constant, Sectional width of the electrode pattern) can be realized.
The organic binder includes a urethane bond to induce electrostatic bonding with the surface charge of the conductive powder to maximize the dispersibility of the conductive powder, thereby improving the storage stability. As a result, The resistivity characteristic can be obtained.
In addition, the organic binder increases the hydrogen bonding force in the organic binder, thereby reducing the phenomenon of widening the width of the paste by crushing the paste due to the heat generated during firing, thereby enabling to realize a fine pattern of high aspect ratio, chain effect, shear thinning is possible and high-resolution electrode patterns can be realized.
In addition, the organic binder improves the compatibility of the additive to be described later with the organic binder, thereby improving the printing property of the electrode-forming composition.
The weight average molecular weight (Mw) of the compound represented by Formula 1 may be 5,000 to 200,000 g / mol. The dispersibility and printing characteristics of the composition for electrode formation can be improved in the above range.
In the compound represented by the general formula (1), one or two substituents represented by the general formula (2) may exist per cellulose structural unit. When the substituent represented by Formula 2 is present, the dispersion stability of the composition for forming an electrode can be improved and a fine electrode pattern having a high aspect ratio can be obtained.
The substituent represented by the general formula (2) may exist at the 3-position of the cellulose structural unit.
The organic binder may be contained in an amount of 0.1 to 20% by weight, preferably 0.2 to 15% by weight based on 100% by weight of the total amount of the electrode forming composition. It is possible to obtain an appropriate viscosity of the electrode forming composition within the above range and to prevent the adhesion strength with the substrate from being lowered and the decomposition of the organic binder during firing is not smoothly carried out and the resistance is increased and the electrodes are cracked, Can be prevented.
The solvent may be selected from the group consisting of methyl cellosolve, ethyl cellosolve, butylcellosolve, aliphatic alcohol,? -Terpineol, dihydro-terpineol, ethylene glycol, ethylene glycol mono butyl ether, butyl cellosolveacetate, texanol, texanol) may be used alone or in combination of two or more.
The solvent may be contained in an amount remaining in the composition for forming an electrode, specifically, 1 to 30% by weight based on 100% by weight of the total amount of the electrode forming composition. Within this range, sufficient adhesive strength and excellent printability can be ensured.
In addition to the above-described components, the composition for electrode formation may further include conventional additives as needed in order to improve flow characteristics, process characteristics, and stability. The additive may be used alone or as a mixture of two or more thereof, such as a surface treatment agent, a dispersant, a thixotropic agent, a viscosity stabilizer, a defoaming agent, a pigment, an ultraviolet stabilizer, an antioxidant and a coupling agent.
The additive may be contained in an amount of 0.1 to 5% by weight based on 100% by weight of the total amount of the composition for electrode formation, but the content may be changed if necessary. The content of the additive may be selected in consideration of the printing property, dispersibility, and storage stability of the electrode-forming composition.
According to another embodiment, there is provided an electrode formed from the electrode forming composition.
According to another embodiment, there is provided a solar cell including the electrode.
A solar cell according to an embodiment will be described with reference to FIG. 1 is a schematic view briefly showing a structure of a solar cell according to one embodiment.
1, a composition for electrode formation is printed on a
In addition, a preparation step for the front electrode can be performed by printing a composition for electrode formation on the entire surface of the wafer and then drying it. Thereafter, the front electrode and the rear electrode can be formed by performing a sintering process by sintering at 400 to 980 ° C, preferably 700 to 980 ° C for about 30 seconds to 210 seconds.
Hereinafter, the present invention will be described in more detail by way of examples, but these examples are for illustrative purposes only and should not be construed as limiting the present invention.
Synthetic example One
The flask was charged with 300 ml of 1,4-dioxane and ethylcellulose (STD-45, 1 eq, replacement ratio: 50%) in a 1 L round-bottomed flask and slowly heated to 80 ° C. Triethylamine (3 eq. After maintaining the temperature, cyclohexyl isocyanate (1 eq.) Was added and reacted at 50 ° C for 4 hours. The reaction mixture was re-dissolved in deionized water (DW) and filtered. The precipitate was washed three times with deionized water. The resulting product was vacuum dried to obtain the final product, cellulose cyclohexyl urethane (CCHU).
Synthetic example 2
A cellulose isopropyl urethane (CIU) was obtained in the same manner as in Synthesis Example 1, except that isopropyl isocyanate (1 eq.) Was used instead of cyclohexyl isocyanate (1 eq.).
Synthetic example 3
A cellulose furfuryl urethane (CFU) was obtained in the same manner as in Synthesis Example 1 except that per furyl isocyanate (1 eq.) Was used in place of cyclohexyl isocyanate (1 eq.).
Synthetic example 4
A cellulose hexyl urethane (CHU) was obtained in the same manner as in Synthesis Example 1 except that hexyl isocyanate (1 eq.) Was used instead of cyclohexyl isocyanate (1 eq.).
Example One
3% by weight of cellulose cyclohexylurethane (CCHU) prepared from Synthesis Example 1 as an organic binder was sufficiently dissolved in 4% by weight of butyl carbitol as a solvent at 60 占 폚, and spherical silver having an average particle diameter of 2 占 퐉 2% by weight of a flexible glass powder (Flexible Glass, particle size: CI-124, manufactured by Dowa Hightech CO. LTD., 5-11F) having an average particle diameter of 1 탆 and a transition point of 341 캜, 2 wt% of dispersant BYK-chemie and 2 wt% of Thixatrol ST (ElementisCo.) As a thixotropic agent were mixed and dispersed by a three roll kneader to prepare a composition for forming a solar cell electrode.
Example 2 to 4
Except that each of the cellulose urethanes prepared in Synthesis Examples 2 to 4 was used in place of cellulose cyclohexyl urethane as an organic binder and the composition was prepared in the following Table 1, The composition was prepared.
Comparative Example One
A composition for forming a solar cell electrode was prepared in the same manner as in Example 1, except that ethylcellulose (STD4) was used instead of cellulose cyclohexylurethane as an organic binder and the composition of the following Table 1 was used .
(wt%)
(CCHU)
(CIU)
(CFU)
(CHU)
(STD45)
Property evaluation
(1) Storage stability
The storage stability (percentage,%) of the compositions for electrode formation prepared according to Examples 1 to 4 and Comparative Example 1 was evaluated by the rate of change in viscosity before and after storage according to the following formula 1. The results are shown in Table 2 Respectively.
[Equation 1]
In the above equation (1)
F 0 is a viscosity value measured at room temperature (24 ° C) after storing the composition for electrode formation at 25 ° C and 50 ± 5% relative humidity for 1 day and F 1 is a viscosity value measured at 25 ° C and 50 ± 5% relative It is a viscosity value measured at room temperature (25 ° C) after storage for 30 days in a humidity condition.
The viscosity values were obtained by using a Brookfield viscometer (HBDV-2 + pro) with a SC4-14 spindle and an SC4-6RP chamber, applying a preshear at 25 ° C for 30 seconds at 10 rpm and measuring the viscosity.
(2) Evaluation of fine pattern
The electrode forming composition prepared according to Examples 1 to 4 and Comparative Example 1 was screen-printed on the entire surface of a polyP type silicon wafer having a surface resistance of 90? Using a screen mask (SUS325 type) bar) was printed and dried using an infrared drying furnace. Thereafter, a composition for forming an electrode containing aluminum was printed on the rear surface of the wafer by back printing and then dried by the same method. The cells thus formed were fired at 400 to 950 DEG C for 30 seconds to 50 seconds using a belt-type firing furnace to form a pattern. The line width and the thickness of the electrode lines in each process step, that is, the line width (L1), the line width after drying (L2), the line width after firing (L3) and the thickness after firing (D1) were measured using a VK equipment (KEYENCE VK9710) . The results are shown in Table 2 below. The change with time (? (L2-L1)) of the line width and the aspect ratio after firing were calculated and are shown together in Table 2.
One
2
3
4
One
It can be seen from Table 2 that the composition for electrode formation according to Examples 1 to 4 using the compound represented by Chemical Formula 1 as an organic binder has excellent storage stability and little change with time over the line width as compared with Comparative Example 1 using ethylcellulose, It can be seen that the fine line width can be realized because the aspect ratio is excellent.
It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
101: p layer (or n layer) 102: n layer (or p layer)
210: rear electrode 230: front electrode
Claims (12)
Wherein the organic binder is a compound containing a structural unit represented by the following formula (1):
[Chemical Formula 1]
In Formula 1,
R 1 , R 2 and R 3 are each independently hydrogen, a substituted or unsubstituted straight or branched chain C1 to C15 alkyl group, a substituted or unsubstituted straight or branched chain C2 to C15 alkenyl group, a substituted or unsubstituted A substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 heterocycloalkyl group, a substituted or unsubstituted C3 to C20 aryl group, a substituted or unsubstituted C3 to C20 heteroaryl group, , At least one of R 1 , R 2 and R 3 is a substituent represented by the following formula (2)
(2)
In Formula 2,
R a and R b are each independently hydrogen or a straight or branched chain C1 to C10 alkyl group,
n is an integer of 0 to 10,
X is a substituted or unsubstituted straight or branched chain C1 to C18 alkyl group, a hydroxy group (-OH), a halogen, a carboxyl group (-COOH), an ester group (COOR, wherein R is a linear or branched C1 to C6 alkyl group ), phosphate groups (phosphoric acid, -OP (= O ) (OH) 2), a phosphoric acid ester group (-OP (= O) (oR ) 2) ( wherein R is a straight or branched chain C1 to C6 alkyl group Im) , A substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, and a substituted or unsubstituted N, O, S, and combinations thereof. 5-or 6-membered heterocyclic,
* Represents a position connected to the oxygen (O) of OR 1 , OR 2 and OR 3 in formula (1).
In the above formula 1, at least one substituted or unsubstituted methylene group (- (C (R a ) (R b )) - or - (C (R c ) (R d ))) -O-, -S-, -C (= O ) -, -S (= O) -, -S (= O) 2 -, -C (= O) -O-, -OC (= O) - , -C (= O) NR- wherein R is hydrogen or a C1 to C6 alkyl group, and combinations thereof.
The 5-membered or 6-membered heterocyclic group containing at least one hetero atom selected from the above substituted or unsubstituted N, O, S and combinations thereof may be an imidazolyl group, an imidazolinyl group A pyrazolyl group, a pyrazolinyl group, a pyrrolinyl group, a triazolyl group, a tetrazolyl group, a furfuryl group, And is selected from an isoxazolyl group.
Wherein the compound represented by Formula 1 has a weight average molecular weight (Mw) of 5,000 to 200,000 g / mol.
In the compound represented by Formula 1, one or two substituents represented by Formula 2 are present in the cellulose structural unit.
60 to 95% by weight of the conductive powder;
0.5 to 20% by weight of the glass frit;
0.1 to 20% by weight of the organic binder; And
And the remaining amount of the solvent.
The glass frit is made of lead (Pb), tellurium (Te), bismuth (Li), phosphorus (P)
(Ga), Ce, Fe, Si, Zn, W, Mg, Cs, Sr, The metal layer may include at least one selected from the group consisting of molybdenum (Mo), titanium (Ti), tin (Sn), indium (In), vanadium (V), barium (Ba), nickel (Ni), copper (Cu), sodium (Na) At least one metal element selected from the group consisting of arsenic (As), cobalt (Co), zirconium (Zr), manganese (Mn) and aluminum (Al).
The solvent may be selected from the group consisting of methyl cellosolve, ethyl cellosolve, butyl cellosolve, aliphatic alcohol,? -Terpineol,? -Terpineol, At least one selected from the group consisting of dihydro-terpineol, ethylene glycol, ethylene glycol monobutyl ether, butyl cellosolve acetate and texanol, By weight based on the total weight of the composition.
Wherein the glass frit has an average particle diameter (D50) of 0.1 占 퐉 to 10 占 퐉.
Wherein the composition for electrode formation further comprises at least one additive selected from the group consisting of a surface treatment agent, a dispersant, a thixotropic agent, a viscosity stabilizer, a defoamer, a pigment, an ultraviolet stabilizer, an antioxidant and a coupling agent.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20180105910A (en) * | 2017-03-16 | 2018-10-01 | 삼성에스디아이 주식회사 | Composition for forming electrode, electrode manufactured using the same and solar cell |
| CN109872832A (en) * | 2017-12-05 | 2019-06-11 | 三星Sdi株式会社 | It is used to form the constituent of electrode of solar battery and the electrode using its preparation |
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| JP4497395B2 (en) | 2001-08-06 | 2010-07-07 | 富士フイルム株式会社 | Method for producing photoelectric conversion element and photoelectric conversion element |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180105910A (en) * | 2017-03-16 | 2018-10-01 | 삼성에스디아이 주식회사 | Composition for forming electrode, electrode manufactured using the same and solar cell |
| CN108630337A (en) * | 2017-03-16 | 2018-10-09 | 三星Sdi株式会社 | It is used to form the composition of electrode, using the electrode and solar cell of its manufacture |
| US10734536B2 (en) | 2017-03-16 | 2020-08-04 | Samsung Sdi Co., Ltd. | Composition for forming electrode, electrode manufactured using the same and solar cell |
| CN109872832A (en) * | 2017-12-05 | 2019-06-11 | 三星Sdi株式会社 | It is used to form the constituent of electrode of solar battery and the electrode using its preparation |
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