CN111316381A - Composition for forming electrode, electrode prepared from same, and solar cell - Google Patents

Composition for forming electrode, electrode prepared from same, and solar cell Download PDF

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Publication number
CN111316381A
CN111316381A CN201880071089.7A CN201880071089A CN111316381A CN 111316381 A CN111316381 A CN 111316381A CN 201880071089 A CN201880071089 A CN 201880071089A CN 111316381 A CN111316381 A CN 111316381A
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composition
electrode
solar cell
chemical formula
peroxide
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CN111316381B (en
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河京珍
文成日
朴相熙
李汉松
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Shanghai Jiangju New Material Co.,Ltd.
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Samsung SDI Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/08—Frit compositions, i.e. in a powdered or comminuted form containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/10—Frit compositions, i.e. in a powdered or comminuted form containing lead
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/10—Esters of organic acids, i.e. acylates
    • C08L1/12—Cellulose acetate
    • 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
    • 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
    • H01L31/04—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
    • H01L31/06—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 characterised by at least one potential-jump barrier or surface barrier
    • H01L31/068—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 characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction 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
    • H01L31/04—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
    • H01L31/06—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 characterised by at least one potential-jump barrier or surface barrier
    • H01L31/068—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 characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells
    • H01L31/0682—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 characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells back-junction, i.e. rearside emitter, solar cells, e.g. interdigitated base-emitter regions back-junction cells
    • 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
    • Y02E10/547—Monocrystalline silicon PV cells

Abstract

The invention provides a composition for forming a solar cell electrode, a solar cell electrode manufactured by using the composition for forming the solar cell electrode, and a solar cell comprising the electrode. A composition for forming a solar cell electrode includes a conductive powder, a glass frit, an organic binder including a cellulose-based polymer represented by a specific chemical formula, a thermal polymerization initiator, and a solvent.

Description

Composition for forming electrode, electrode prepared from same, and solar cell
Technical Field
The present invention relates to a composition for forming an electrode, an electrode manufactured using the same, and a solar cell.
Background
Solar cells generate electrical energy using the photovoltaic effect (photovoltaic effect) of a pn junction that converts photons of sunlight into electricity. In a solar cell, a front electrode and a rear electrode are formed on a front surface and a rear surface of a semiconductor substrate (semiconductor wafer) having a pn junction, respectively. The photovoltaic effect of the pn junction is induced by sunlight entering the semiconductor substrate, and electrons generated by the photovoltaic effect of the pn junction supply an electric current to the outside via the front electrode and the rear electrode.
The front and rear electrodes of the solar cell may be formed on the surface of the substrate in a predetermined pattern by forming a composition for the electrodes and patterning and firing the composition.
It is known that the conversion efficiency of solar cells is improved byHigh: improve the contact property (contact resistance) of the electrode and the substrate, thereby making the contact resistance (R)c) And series resistance (R)s) Minimization; or the pattern line width of the screen mask having the organic material is adjusted to be smaller, thereby forming a fine line and increasing a short circuit current (I)sc). However, reducing the pattern line width of the halftone mask may result in a series resistance (R)s) And continuous printability of a fine pattern is increased and deteriorated.
The electrode composition includes an organic vehicle to impart viscosity (viscocity) and rheological (rheological) properties suitable for printing, and the organic vehicle generally includes an organic binder and a solvent.
In order to increase dispersibility and storage stability, the amount of the organic binder used may be increased or a polymer having a high molecular weight may be used.
When the amount of the organic binder used increases, the resistance also increases during the formation of the electrode; and when an organic binder having a high molecular weight is used, there are problems of tailing phenomena (tailing phenomenon) and printing defects due to an increase in viscosity even at a high shear rate (high shear rate).
Therefore, attempts have been made to improve printing characteristics by modifying organic binders or adding novel additives to the composition.
Disclosure of Invention
Technical problem
Embodiments of the present invention provide an electrode composition for forming a solar cell, which includes a modified organic binder and a thermal polymerization initiator and thus has excellent printing characteristics and low viscosity.
Another embodiment of the present invention provides an electrode manufactured using the composition for forming an electrode.
Yet another embodiment of the present invention provides a solar cell including the electrode.
Technical scheme
According to an embodiment, a composition for forming an electrode of a solar cell includes a conductive powder, a glass frit, an organic binder including a cellulose-based polymer represented by chemical formula 1, a thermal polymerization initiator, and a solvent.
[ chemical formula 1]
Figure BDA0002474917240000021
In chemical formula 1, R1To R8Independently a hydrogen atom or a compound represented by chemical formula 2 or 3, wherein R1To R8At least one of which is represented by chemical formula 3,
and n is an integer ranging from 1 to 10000,
[ chemical formula 2]
Figure BDA0002474917240000022
In the chemical formula 2, the first and second organic solvents,
R9is a substituted or unsubstituted C1 to C20 alkyl (alkyl group),
[ chemical formula 3]
Figure BDA0002474917240000031
In the chemical formula 3, the first and second,
R10is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,
L1to L3Independently a single bond, a substituted or unsubstituted C6 to C20 arylene group, -C (═ O) -, -C (═ O) O-, or-OC (═ O) -,
L4is a substituted or unsubstituted C1 to C20 alkylene group, and
m is an integer of 0 or 1.
L1Can be-C (═ O) -, L2May be a substituted or unsubstituted C6 to C20 arylene group, and L3May be ═ C (═ O) O —.
L2May be a substituted or unsubstituted phenylene (phenylene) groupne group)。
L2May be represented by chemical formula 4.
[ chemical formula 4]
Figure BDA0002474917240000032
The thermal polymerization initiator may initiate a thermal polymerization reaction at a temperature of 100 ℃ to 200 ℃.
The thermal polymerization initiator may be a peroxide-based compound.
The peroxide-based compound may include t-butyl peroxide (tetra-butyl peroxide), dilauryl peroxide (dilauroyl peroxide), dibenzoyl peroxide (dibenzoyl peroxide), tert-butyl peroxyneodecanoate (tert-butyl peroxycarbonate), tert-amyl peroxypivalate (tert-amyl peroxypivalate), di (2-ethylhexyl) peroxydicarbonate (di (2-ethylhexyl) peroxydicarbonate), di (3-methoxy) butyl peroxydicarbonate (di (3-methoxy) butyl peroxydicarbonate), 3-hydroxy-1,1-dimethylbutyl peroxyneodecanoate (3-hydroxy-1,1-dimethylbutyl peroxyneodecanoate), di (3,5,5-trimethyl hexanoyl) peroxide (3,5,5-trimethyl peroxyhexanoyl) peroxide (3-hydroxy-1,1-dimethyl peroxyneodecanoate (3-hydroxy-1, 5-trimethyl-5, 5-trimethyl peroxyhexanoyl) peroxide (3,5,5-trimethyl peroxyneodecanoate), Tertiary amyl peroxy-2-ethylhexanoate (tert-amyl peroxy-2-ethylhexanoate), tertiary butyl peroxy-2-ethylhexanoate (tert-butyl peroxy-2-ethylhexanoate), tertiary butyl isopropyl monoperoxycarbonate (tert-butyl isoperoxycarbonate), tertiary butyl peroxy-2-ethylhexyl carbonate (tert-butyl-2-ethylhexylcarbonate), dibenzoyl peroxide (dibenzoyl peroxide), tertiary butyl 2-ethylhexyl monoperoxycarbonate (tert-amyl 2-ethylhexyl monoperoxycarbonate), tertiary butyl peroxide (tert-butyl hydroperoxide), tetrabutyl peroxide (tetrabutyl-butyl peroxide), tetrabutyl peroxide (tetrabutyl isopropyl benzoate), tributyl isopropyl benzoate (tributyl-butyl benzoate), tert-butyl peroxybenzoate (tributyl-isopropyl benzoate), and mixtures thereof, 1,1,3,3-tetramethylbutyl peroxyneodecanoate (1,1,3, 3-tetramethylbutylperoxidocarbonate), dicumyl peroxide (dicumyl peroxide), didecanyl peroxide (dicaprylyl peroxide), or a combination thereof.
The organic binder may have a weight average molecular weight (Mw) of 5,000 grams/mole (g/mol) to 200,000 grams/mole.
The solvent may include at least one selected from the group consisting of methyl cellosolve (methyl cellosolve), ethyl cellosolve (ethyl cellosolve), butyl cellosolve (butyl cellosolve), fatty alcohol (aliphatic alcohol), α -terpineol (α -terpineol), β -terpineol (β -terpineol), dihydro-terpineol (dihydro-terpineol), ethylene glycol (ethylene glycol), ethylene glycol monobutyl ether (ethylene glycol monobutylether), butyl cellosolve acetate (butyl cellosolve) and 2,2,4-trimethyl-1,3-pentanediol isobutyrate (2,2,4-trimethyl-1,3-pentanediol isobutyrate) (Texanol).
The conductive powder may be silver powder.
The composition for forming an electrode of a solar cell may include 60 weight percent (wt%) to 95 wt% of the conductive powder; 0.5 to 20 weight percent of the glass frit; 0.1 to 20 weight percent of the organic binder; 0.1 to 10 weight percent of the thermal polymerization initiator; and 1 to 30 weight percent of the solvent.
The glass frit may include at least one metal element selected from the group consisting of: lead (Pb), tellurium (Te), bismuth (Bi), lithium (Li), phosphorus (P), germanium (Ge), gallium (Ga), cerium (Ce), iron (Fe), silicon (Si), zinc (Zn), tungsten (W), magnesium (Mg), cesium (Cs), strontium (Sr), molybdenum (Mo), titanium (Ti), tin (Sn), indium (In), vanadium (V), barium (Ba), nickel (Ni), copper (Cu), sodium (Na), potassium (K), arsenic (As), cobalt (Co), zirconium (Zr), manganese (Mn), and aluminum (Al).
The composition for forming an electrode of a solar cell may further include at least one selected from the group consisting of: surface treatment agents, dispersants, thixotropic agents (thixotropic agents), viscosity stabilizers (viscostability stabilizers), plasticizers, defoamers, pigments, Ultraviolet (UV) stabilizers, antioxidants, and coupling agents.
Another embodiment provides an electrode manufactured using the composition for forming an electrode of a solar cell.
Another embodiment provides a solar cell including the electrode.
The solar cell may have a Passive Emitter and Rear Cell (PERC) structure.
Effects of the invention
By modifying a conventional cellulose organic binder with a carbon-carbon double bond-introduced cellulose organic binder, a composition for forming an electrode of a solar cell has a small line width spread characteristic (small-spread characteristics) after printing and thus has an excellent short-circuit current (I)sc) A characteristic wherein a thermal polymerization initiator is added as an additive to the composition.
Drawings
Fig. 1 is a schematic diagram illustrating a structure of a solar cell according to an embodiment.
Fig. 2 is a schematic diagram illustrating a solar cell having a Passive Emitter and Rear Cell (PERC) structure according to another embodiment.
Detailed Description
The present disclosure now will be described more fully hereinafter with reference to the accompanying drawings, in which exemplary embodiments of the invention are shown. Those skilled in the art will recognize that the described embodiments can be modified in various different ways, all without departing from the spirit or scope of the present invention.
In the drawings, the thickness of various layers, films, sheets, regions, etc. may be exaggerated for clarity. Like reference numerals refer to like elements throughout the specification. It will be understood that when an element (e.g., a layer, film, region, or substrate) is referred to as being "on" another element, it can be directly on the other element or intervening elements may also be present. In contrast, when an element is referred to as being "directly on" another element, there are no intervening elements present.
In the present specification, when a specific definition is not otherwise provided, "substituted" means that at least one hydrogen is replaced with a substituent selected from: halogen (halogen) (F, Cl, Br or I), hydroxyl (hydroxy group), C1 to C20 alkoxy (alkoxy group), nitro (nitro group), cyano (cyano group), amine (amino group), imine (imino group), azide (azido group), amidine (amidino group), hydrazine (hydrazino group), hydrazono (hydrazono group), carbonyl (carbonyl group), carbamoyl (carbomyl group), thiol (thiol group), ester (ester group), ether (ether group), carboxyl (carboxalyl group I) or a salt thereof, sulfonic acid (sulfo acid group) or a salt thereof, phosphoric acid (phosphoric acid group) or a salt thereof, C24 to C24 alkyl group (C) or a salt thereof, cycloalkyl (C637 to C824684) or a salt thereof, cycloalkenyl (C6346 to C6346) or a salt thereof, cycloalkenyl (C27 to C27 alkyl group), cycloalkenyl (C7 to C7 group) or a salt thereof, cycloalkenyl (C6346 to C6346) or a salt thereof, cycloalkyl group (cycloalkynyl group), cycloalkenyl group (C6342 to C20) or a salt thereof, and a salt thereof, A C2 to C20 heterocycloalkyl (heterocyclylalkyl), C2 to C20 heterocycloalkenyl (heterocyclylalkyl), C2 to C20 heterocycloalkynyl (heterocycloalkynyl group), C3 to C30 heteroaryl (heterocycloaryl group), or a combination thereof.
In the present specification, when a specific definition is not otherwise provided, the term "hetero" may refer to a substituent substituted with at least one C of N, O, S and P, and not a cyclic substituent.
In the present specification, "+" indicates a position where the same or different atom or chemical formula is attached, when a specific definition is not otherwise provided.
A composition for forming an electrode according to an embodiment includes a conductive powder, a glass frit, an organic binder including a cellulose-based polymer represented by chemical formula 1, a thermal polymerization initiator, and a solvent.
[ chemical formula 1]
Figure BDA0002474917240000061
In the chemical formula 1, the first and second,
R1to R8Independently a hydrogen atom or a compound represented by chemical formula 2 or 3, wherein R1To R8At least one of which is represented by chemical formula 3,
and n is an integer ranging from 1 to 10000,
[ chemical formula 2]
Figure BDA0002474917240000071
In the chemical formula 2, the first and second organic solvents,
R9is a substituted or unsubstituted C1 to C20 alkyl group,
[ chemical formula 3]
Figure BDA0002474917240000072
In the chemical formula 3, the first and second,
R10is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,
L1to L3Independently a single bond, substituted or unsubstituted C6 to C20 arylene, -C (═ O) -, -C (═ O) O-or-OC (═ O) -, L4Is a substituted or unsubstituted C1 to C20 alkylene group,
and m is an integer of 0 or 1.
Hereinafter, each component of the composition for forming the electrode of the solar cell is described in detail.
The composition for forming the electrode of the solar cell may use metal powder as the conductive powder. The metal powder may include at least one metal selected from the group consisting of: silver (Ag), gold (Au), palladium (Pd), platinum (Pt), ruthenium (Ru), rhodium (Rh), osmium (Os), iridium (Ir), rhenium (Re), titanium (Ti), niobium (Nb), tantalum (Ta), aluminum (Al), copper (Cu), nickel (Ni), molybdenum (Mo), vanadium (V), zinc (Zn), magnesium (Mg), yttrium (Y), cobalt (Co), zirconium (Zr), iron (Fe), tungsten (W), tin (Sn), chromium (Cr), and manganese (Mn), but are not limited thereto. For example, the conductive powder may be silver (Ag) powder.
The particle size (particle size) of the conductive powder may be nano-sized or micro-sized. For example, the conductive powder may have a particle size of tens of nanometers to hundreds of nanometers or single digit micrometers to tens of micrometers. In other embodiments, the conductive powder may be two silver powders or a mixture of two or more silver powders having different particle sizes.
The conductive powder may have a spherical (spherical shape), sheet-shaped (sheet-sheet), or amorphous (amophorus shape) particle shape. The conductive powder may have an average particle size (D50) of 0.1 to 10 microns; for example, 0.5 to 5 microns. The average particle diameter may be measured by ultrasonic treatment using, for example, a model 1064D (cilasco, Ltd.) apparatus after dispersing the conductive powder in isopropyl alcohol (IPA) at room temperature (20 to 25 ℃) for 3 minutes. Within these ranges, the composition can provide low contact resistance (low contact resistance) and low line resistance (low line resistance).
The conductive powder may be present in an amount of 60 to 95 weight percent, based on the total amount (100 weight percent) of the composition for forming the electrode of the solar cell; for example, 70 to 90 weight percent. Within these ranges, the conversion efficiency can be prevented from being deteriorated due to the increase in resistance, and also the difficulty in forming paste due to the relative decrease in organic vehicle can be prevented.
Glass frit (glass frit) can be used to enhance adhesion between conductive powder and wafer or substrate, and to form silver grains in an emitter region (emitter region) by etching (etc.) an anti-reflection layer (anti-reflection layer) and melting the conductive powder, to reduce contact resistance during a firing (or sintering) process of a composition for forming an electrode of a solar cell. In addition, during the firing process, the glass frit may be softened and the firing temperature may be lowered.
When the area of the solar cell is increased in order to improve the efficiency of the solar cell, there is a possibility that the contact resistance of the solar cell may be increased. Therefore, it is desirable to minimize the influence on a pn junction (pn junction) while minimizing the series resistance. In addition, as the use of various wafers with different sheet resistances increases, the firing temperature may vary over a wide range. It is desirable to ensure that the glass frit has sufficient thermal stability to withstand a wide range of firing temperatures.
The glass frit may be one or more of a lead glass frit (lead glass frit) and a non-lead glass frit (non-lead glass frit) which are commonly used in a composition for forming an electrode of a solar cell.
The glass frit may include at least one metal element selected from the group consisting of: lead (Pb), tellurium (Te), bismuth (Bi), lithium (Li), phosphorus (P), germanium (Ge), gallium (Ga), cerium (Ce), iron (Fe), silicon (Si), zinc (Zn), tungsten (W), magnesium (Mg), cesium (Cs), strontium (Sr), molybdenum (Mo), titanium (Ti), tin (Sn), indium (In), vanadium (V), barium (Ba), nickel (Ni), copper (Cu), sodium (Na), potassium (K), arsenic (As), cobalt (Co), zirconium (Zr), manganese (Mn), and aluminum (Al).
The glass frit may be prepared from the oxide of the metallic element by any suitable method. For example, the metal oxide can be obtained by: oxides of metal elements are mixed in a predetermined ratio, the resultant mixture is melted, the resultant is quenched, and then the quenched product is pulverized. 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 to 1300 ℃, and the quenching process may be performed at room temperature (20 to 25 ℃). The pulverizing process can be performed using a disk mill (disk mill) or a planetary mill, but is not limited thereto.
The glass frit may have an average particle diameter (D50) of 0.1 to 10 micrometers, and the glass frit may be present in an amount of 0.5 to 20 weight percent based on the total amount (100 weight percent) of the composition for forming an electrode of a solar cell. Within these ranges, the frit can ensure excellent adhesive strength of the solar cell electrode while not deteriorating electrical characteristics of the electrode.
The frit may have a spherical or amorphous shape. In embodiments, two different types of frits having different transition temperatures may be used. For example, a first frit having a transition temperature in the range of greater than or equal to 200 ℃ to less than or equal to 350 ℃ may be mixed with a second frit having a transition temperature in the range of greater than 350 ℃ to less than or equal to 550 ℃.
The organic binder in the (paste) composition for forming an electrode of a solar cell may include a cellulose-based polymer including a structural unit represented by chemical formula 1.
[ chemical formula 1]
Figure BDA0002474917240000091
In the chemical formula 1, the first and second,
R1to R8Independently a hydrogen atom or a compound represented by chemical formula 2 or 3, wherein R1To R8At least one of which is represented by chemical formula 3,
and n is an integer ranging from 1 to 10000,
[ chemical formula 2]
Figure BDA0002474917240000092
In the chemical formula 2, the first and second organic solvents,
R9is a substituted or unsubstituted C1 to C20 alkyl group.
[ chemical formula 3]
Figure BDA0002474917240000093
In the chemical formula 3, the first and second,
R10is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,
L1to L3Independently a single bond, substituted or unsubstituted C6 to C20 arylene, -C (═ O) -, -C (═ O) O-or-OC (═ O) -, L4Is a substituted or unsubstituted C1 to C20 alkylene group,
and m is an integer of 0 or 1.
Generally, as for the organic binder, a cellulose-based binder having a large thickening effect is mainly applied, and in particular, ethyl cellulose (ethyl cellulose) is widely used in the same industry. However, it is common to simply add a commercially available ethyl cellulose binder resin (e.g., Elcel (Ethocel) STD series, Dow chemical Company (DOW chemical Company)) without changing its specific chemical structure (in terms of viscosity/concentration/individual substance/mixture, etc.)) To use an organic binder. Conventional cellulosic-based binders are designed to have a high viscosity of greater than or equal to 400,000 centipoise (cps) to maintain high aspect ratios. The designed cellulose-based binder has small spreading characteristics and thus excellent short circuit current (I) during the printing processsc) Efficiency. However, such conventional cellulose-based binders (ethyl cellulose binder resins, etc.) may not be structurally cured, and thus cause problems of enlarging and widening line widths during a drying process and a firing process after a printing process. Such a problem runs counter to the recent trend of requiring fine line widths to improve the light efficiency of solar panels, and thus may become an increasingly large problem.
In addition, various additives (thickeners, plasticizers, dispersants, etc.) may be used in order to improve printing properties, dispersion, storage stability, etc., but various additives have disadvantages of increasing residue, etc., after firing, and may cause a side effect of increasing resistance during formation of an electrode of a solar cell. In addition, when an acrylic-based binder is used, it is known that there is a drawback of tailing during a screen printing process.
The organic binder according to one embodiment is modified to have a photocurable structure by introducing carbon-carbon double bonds into Cellulose Acetate Phthalate (CAP) and simultaneously becomes to have a low viscosity on the structure, and thus may minimize a line width expansion phenomenon and prevent a short circuit current (I)sc) The efficiency is deteriorated.
For example, L1Can be-C (═ O) -, L2May be a substituted or unsubstituted C6 to C20 arylene group, and L3May be ═ C (═ O) O —.
For example, L2May be a substituted or unsubstituted phenylene group.
For example, L2May be represented by chemical formula 4.
[ chemical formula 4]
Figure BDA0002474917240000111
Specifically, the organic binder (modified organic binder) including the polymer including the structural unit represented by chemical formula 1 may have a weight average molecular weight (Mw) of 5,000 g/mole to 200,000 g/mole.
When the molecular weight of the organic binder is decreased within this range, the amount of the organic binder used in the composition for forming an electrode of a solar cell may be increased, and thus the flow behavior and thixotropy may be improved, and thus the printing properties of the composition for forming an electrode of a solar cell may be improved. Therefore, the composition for forming an electrode comprising the organic binder may be suitably used to form an electrode in a solar cell having a Passive Emitter and Rear Cell (PERC) structure.
A passive emitter and back cell (PERC) structured solar cell will be described later.
The composition for forming an electrode of a solar cell may include 60 to 95 weight percent of the conductive powder, based on the total amount of the composition for forming an electrode of a solar cell; 0.5 to 20 weight percent of the glass frit; 0.1 to 20 weight percent of the organic binder; 0.1 to 10 weight percent of the thermal polymerization initiator; and 1 to 30 weight percent of the solvent. Within these ranges, the composition for forming an electrode of a solar cell may obtain an appropriate viscosity, and thus prevent adhesion deterioration with a substrate, and additionally prevent an increase in resistance due to unstable decomposition (unsmooth decomposition) of an organic binder during a firing process and generation of cracks, openings, pinholes, etc. of the electrode.
The solvent has a boiling point greater than or equal to 100 ℃ and may include one or more of methyl cellosolve, ethyl cellosolve, butyl cellosolve, fatty alcohols, α -terpineol, β -terpineol, dihydro-terpineol, ethylene glycol monobutyl ether, butyl cellosolve acetate, and 2,2,4-trimethyl-1,3-pentanediol isobutyrate (Teflon).
The thermal polymerization initiator may be a compound that initiates a thermal polymerization reaction at a temperature of 100 ℃ to 200 ℃. For example, the thermal polymerization initiator may preferably be a peroxide-based compound used in polymerization.
Specific examples of the peroxide-based compound may include tertiary butyl peroxide, tetrabutyl peroxide, dilauryl peroxide, dibenzoyl peroxide, tertiary butyl peroxyneodecanoate, tertiary amyl peroxypivalate, bis (2-ethylhexyl) peroxydicarbonate, bis (3-methoxy) butyl peroxydicarbonate, 3-hydroxy-1,1-dimethylbutyl peroxyneodecanoate, bis (3,5,5-trimethylhexanoyl) peroxide, tertiary amyl peroxy-2-ethylhexanoate, tertiary butyl isopropyl monoperoxycarbonate, tertiary butyl peroxy-2-ethylhexyl carbonate, dibenzoyl peroxide, tertiary amyl (2-ethylhexyl) monoperoxycarbonate, But are not limited to, tertiary butyl peroxide, tetrabutyl peroxide, tertiary butyl peroxyisopropyl carbonate, tertiary butyl peroxybenzoate, 1,3, 3-tetramethylbutylperoxyneodecanoate, diisopropylphenyl peroxide, didecanoyl peroxide, or combinations thereof.
In addition to the constituent elements, the composition for forming an electrode of a solar cell may further include typical additives as necessary to enhance flow properties, handling properties, and stability. Additives may include surface treatment agents, dispersants, thixotropic agents, viscosity stabilizers, plasticizers, antifoaming agents, pigments, Ultraviolet (UV) stabilizers, antioxidants, coupling agents, and the like. These additives may be used alone or as a mixture thereof.
The additive may be included in an amount of 0.1 to 5 weight percent based on the total amount (100 weight percent) of the composition for forming an electrode of a solar cell, and the amount of the additive used may be changed as needed. The amount of the additive to be used may be selected in consideration of printing characteristics, dispersion, and storage stability of the composition for forming an electrode of a solar cell.
Another embodiment provides an electrode formed of the composition for forming an electrode of a solar cell.
In addition, another embodiment provides a solar cell including the electrode.
Referring to fig. 1, a solar cell is shown, according to an embodiment. Fig. 1 is a schematic diagram illustrating a structure of a solar cell according to an embodiment.
Referring to fig. 1, a solar cell (100) according to an embodiment includes a front electrode (120) and a rear electrode (130) formed in the following manner. The composition for forming an electrode is formed by printing the composition for forming an electrode on a substrate (110) including a p layer (or an n layer) (111) and an n layer (or a p layer) (113) as an emitter and firing the composition.
For example, the previous preparation step of the rear electrode may be performed by printing the electrode composition on the rear surface of the wafer and drying at 200 to 400 ℃ for 10 to 60 seconds. In addition, the previous preparation step of the front electrode may be performed by printing the electrode composition on the front surface of the wafer and drying it. The front electrode (120) and the back electrode (130) may then be fired at 400 ℃ to 1,000 ℃ (and particularly 600 ℃ to 950 ℃) for 30 seconds to 240 seconds.
Fig. 2 is a schematic diagram illustrating a solar cell having a Passive Emitter and Rear Cell (PERC) structure according to another embodiment.
Referring to fig. 2, in the solar cell (200) according to the embodiment, the front electrode (220) and the rear electrode (240) may be manufactured in the following manner. A post-passivation layer (230) and a hole (232) penetrating the post-passivation layer (230) are formed on a substrate (210) as an emitter including a p layer (or an n layer) (211) and an n layer (or a p layer) (213), and then a composition for forming an electrode is printed and fired. The back passivation layer (230) may be formed of a dielectric material capable of providing electrical contact between the substrate (210) and the back electrode (240). Such dielectric material may be aluminum oxide, silicon nitride or mixtures thereof. The rear passivation layer (230) may reflect light entering the substrate (210) and thus reduce light absorbed in the rear electrode (240), and as a result increase the amount of current generated thereby.
For example, the composition for forming the electrode may be print-coated on the post-passivation layer (230) of the substrate and dried at a temperature of 200 to 400 ℃ for 10 to 60 seconds as a preliminary step of manufacturing the post-electrode. In addition, a composition for forming an electrode is printed on the front surface of the substrate and dried as a preliminary step for manufacturing a front electrode. Subsequently, the coated substrate may be fired at 400 to 900 ℃ (e.g., 600 to 900 ℃) for 30 to 240 seconds to manufacture the front electrode (220) and the back electrode (240).
Mode for the invention
Hereinafter, the present disclosure is described in more detail with reference to examples. However, these examples are exemplary, and the present disclosure is not limited thereto.
Synthesis of organic binders
< Synthesis example >
After cellulose acetate propionate (CAP-482-0.5, Eastman Chemical Company) was dissolved in butyl carbitol acetate (butyl carbitol acetate) to have a solid content of 10 weight percent, 1 weight percent of 2-isocyanate ethyl methacrylate (MOI, Showa Denko K.K.)) was added to the above cellulose acetate propionate solution. Subsequently, the above mixture was reacted at 40 ℃ in the presence of 100ppm dibutyltin dilaurate (DBTDL) catalyst and by Fourier transform infrared spectroscopy (FT-IR) (2270 cm)-1) After disappearance of the isocyanate group (inactivation) was confirmed, the reaction was further carried out for 12 hours to modify cellulose acetate propionate, thereby obtaining an organic binder (viscosity: 3500cps, 10 rpm).
Preparation of composition for forming electrode
< example 1>
0.5 weight percent of the organic binder of the synthesis example was sufficiently dissolved in 7.5 weight percent of Texanol (eastman chemical company) at 60 ℃, and then 88.5 weight percent of spherical silver powder (AG-5-11F, homo and high tech limited (Dowa Hightech Co. ltd.)) having an average particle diameter of 2.0 μm, 3 weight percent of Bi-Te based lead-free glass frit powder (ABT-1, Asahi glass Co.) (Asahi glass Co.) having an average particle diameter of 1.0 μm, 0.2 weight percent of thermal polymerization initiator (TBPB, n.o.f company (japan)), 0.1 weight percent of dispersant (BYK-102, bick chemical company (BYK-Chemie)) and 0.2 weight percent of thixotropic agent (west krolol (thixatl) ST, hai Co.) (hexanol Co) were added thereto, and then three roll mill was used to mix them, to prepare a composition for forming an electrode of a solar cell.
< comparative example 1>
A composition for forming an electrode of a solar cell was prepared according to the same method as example 1, except that ethyl cellulose (Mw ═ 40,000 g/mol, dow chemical company) was used instead of the organic binder of the synthesis example.
< comparative example 2>
A composition for forming an electrode of a solar cell was prepared in the same manner as in example 1, except that cellulose acetate propionate (CAP-482-0.5, Mw 90,000 g/mol, eastman chemical) was used instead of the organic binder of the synthesis example.
< comparative example 3>
A composition for forming an electrode of a solar cell was prepared in the same manner as in example 1, except that 0.2 weight percent of a dispersant (BYK-102, pycnochem chemical) and 0.3 weight percent of a thixotropic agent (cektrol ST, hainshans) were used instead of the thermal polymerization initiator.
Manufacture of a battery
The electrode-forming compositions of example 1 and comparative examples 1 to 3 were each screen-printed on the front surface of a p-type polysilicon wafer (REC, Singapole) of PERC using a screen mask to print an electrode pattern (finger), and dried using an infrared drying oven. Subsequently, a composition containing aluminum for forming an electrode (RX-8252X-2, such as Ruxing) was printed on the rear surface thereof, dried in a ribbon type oven at 200 to 400 ℃ for 30 seconds and then baked in the ribbon type oven at 400 to 800 ℃ for 40 seconds to manufacture a cell of a solar cell.
Evaluation of
The number of line openings was counted using an Electroluminescence (EL) tester (MV Tech Inc.) to check whether the front electrodes of example 1 and comparative examples 1 to 3 were disconnected. The wire width and thickness of the electrode wire were measured using a VK device (VK9710, Keyence Corp.). And, efficiency was measured using a solar cell efficiency measuring apparatus (CT-801, Pasan Measurement Systems). The results are shown in tables 1 and 2.
(Screen mask: SUS360 type; emulsion thickness: 15 μm; finger: line width: 28 μm; number: 108)
[ Table 1]
Example 1 Comparative example 1 Comparative example 2 Comparative example 3
Line width after firing (μm) 50 60 65 60
Thickness after firing (μm) 16 15 15 15.5
Aspect ratio (thickness/line width) 0.32 0.25 0.23 0.26
Printability (number of broken lines) 1 14 6 7
Efficiency (%) 19.8 19.3 19.4 19.5
Referring to table 1, compared to each electrode (comparative examples 1 to 3) fabricated using a composition comprising a cellulose-based polymer having a structural unit represented by chemical formula 1 for forming an electrode of a solar cell and a thermal polymerization initiator, the electrode (example 1) fabricated using the composition comprising the cellulose-based polymer-containing organic binder having the structural unit represented by chemical formula 1 for forming an electrode of a solar cell and the thermal polymerization initiator achieved a fine line width and exhibited a high aspect ratio, excellent printing properties, and a low generation rate of disconnections. In addition, the battery including the electrode fabricated using the composition for forming an electrode of a solar cell according to example 1 showed an excellent improved efficiency, compared to the batteries including the respective electrodes fabricated using the compositions for forming an electrode of a solar cell according to comparative examples 1 to 3, respectively.
Simple modifications or alterations of the present disclosure may be effected by those skilled in the art, and such modifications or alterations are considered to be included within the scope of the present disclosure.
[ description of symbols ]
100. 200: solar cell 120, 220: front electrode
130. 230: rear electrodes 111, 211: p layer (n layer)
113. 213: n-layer (p-layer) 110, 210: substrate
230: rear passivation layer 232: hole(s)

Claims (14)

1. A composition for forming an electrode of a solar cell, comprising:
conductive powder;
a glass frit;
an organic binder comprising a cellulose-based polymer represented by chemical formula 1;
a thermal polymerization initiator; and
a solvent, a water-soluble organic solvent,
[ chemical formula 1]
Figure FDA0002474917230000011
Wherein in the chemical formula 1, the metal oxide,
R1to R8Independently a hydrogen atom or represented by chemical formula 2 or chemical formula 3, and R1To R8Is represented by chemical formula 3, and
n is an integer ranging from 1 to 10000,
[ chemical formula 2]
Figure FDA0002474917230000012
Wherein in the chemical formula 2, the metal oxide,
R9is a substituted or unsubstituted C1 to C20 alkyl group,
[ chemical formula 3]
Figure FDA0002474917230000013
Wherein in the chemical formula 3, the,
R10being hydrogen atoms or substitutedOr unsubstituted C1 to C20 alkyl,
L1to L3Independently a single bond, a substituted or unsubstituted C6 to C20 arylene group, -C (═ O) -, -C (═ O) O-or-OC (═ O) -,
L4is a substituted or unsubstituted C1 to C20 alkylene group, and
m is an integer of 0 or 1.
2. The composition of claim 1, wherein L1is-C (═ O) -, L2Is a substituted or unsubstituted C6 to C20 arylene group, and L3is-C (═ O) O-.
3. The composition of claim 2, wherein L2Is a substituted or unsubstituted phenylene group.
4. The composition of claim 1, wherein
The thermal polymerization initiator initiates a thermal polymerization reaction at a temperature of 100 ℃ to 200 ℃.
5. The composition of claim 1, wherein
The thermal polymerization initiator includes tertiary butyl peroxide, tetrabutyl peroxide, dilauryl peroxide, dibenzoyl peroxide, tertiary butyl peroxyneodecanoate, tertiary amyl peroxypivalate, bis (2-ethylhexyl) peroxydicarbonate, bis (3-methoxy) butyl peroxydicarbonate, 3-hydroxy-1,1-dimethylbutyl peroxyneodecanoate, bis (3,5,5-trimethylhexanoyl) peroxide, tertiary amyl peroxy-2-ethylhexanoate, tertiary butyl isopropyl monoperoxycarbonate, tertiary butyl peroxy-2-ethylhexyl carbonate, dibenzoyl peroxide, tertiary amyl (2-ethylhexyl) monoperoxycarbonate, tertiary butyl peroxy-2-ethylhexyl carbonate, tertiary butyl peroxyl-2-ethyl hexanoate, tertiary butyl isopropyl monoperoxycarbonate, tertiary butyl peroxyl-2-ethyl hexanoate, dibenzoyl peroxide, tertiary pentyl (2-ethylhexyl) monoperoxycarbonate, tertiary butyl peroxyl carbonate, tertiary butyl peroxyl, tertiary, Tertiary butyl peroxide, tetrabutyl peroxide, tertiary butyl peroxy isopropyl carbonate, tertiary butyl peroxybenzoate, 1,3,3-tetramethylbutyl peroxyneodecanoate, dicumyl peroxide, didecanyl peroxide, or combinations thereof.
6. The composition of claim 1, wherein the organic binder has a weight average molecular weight of 5,000 to 200,000 g/mole.
7. The composition of claim 1, wherein the solvent comprises at least one selected from the group consisting of methyl cellosolve, ethyl cellosolve, butyl cellosolve, fatty alcohol, α -terpineol, β -terpineol, dihydro-terpineol, ethylene glycol monobutyl ether, butyl cellosolve acetate, and 2,2,4-trimethyl-1,3-pentanediol isobutyrate.
8. The composition as set forth in claim 1, wherein the conductive powder is silver powder.
9. The composition as set forth in claim 1, wherein the conductive powder is used in an amount ranging from 60 to 95 wt%, the glass frit is used in an amount ranging from 0.5 to 20 wt%, the organic binder is used in an amount ranging from 0.1 to 20 wt%, the thermal polymerization initiator is used in an amount ranging from 0.1 to 10 wt%, and the solvent is used in an amount ranging from 1 to 30 wt%, based on the total amount of the composition for forming an electrode of a solar cell.
10. The composition of claim 1, wherein the glass frit comprises at least one metallic element selected from the group consisting of: lead (Pb), tellurium (Te), bismuth (Bi), lithium (Li), phosphorus (P), germanium (Ge), gallium (Ga), cerium (Ce), iron (Fe), silicon (Si), zinc (Zn), tungsten (W), magnesium (Mg), cesium (Cs), strontium (Sr), molybdenum (Mo), titanium (Ti), tin (Sn), indium (In), vanadium (V), barium (Ba), nickel (Ni), copper (Cu), sodium (Na), potassium (K), arsenic (As), cobalt (Co), zirconium (Zr), manganese (Mn), and aluminum (Al).
11. The composition of claim 1, further comprising at least one of: surface treating agent, dispersant, thixotropic agent, viscosity stabilizer, plasticizer, defoamer, pigment, ultraviolet stabilizer, antioxidant and coupling agent.
12. A solar cell electrode manufactured using the composition for forming an electrode of a solar cell according to any one of claims 1 to 11.
13. A solar cell comprising the electrode of claim 12.
14. The solar cell of claim 13, wherein the solar cell has a passive emitter and a back cell structure.
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