WO2016084915A1 - Composition conductrice - Google Patents

Composition conductrice Download PDF

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Publication number
WO2016084915A1
WO2016084915A1 PCT/JP2015/083278 JP2015083278W WO2016084915A1 WO 2016084915 A1 WO2016084915 A1 WO 2016084915A1 JP 2015083278 W JP2015083278 W JP 2015083278W WO 2016084915 A1 WO2016084915 A1 WO 2016084915A1
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WIPO (PCT)
Prior art keywords
mol
electrode
less
conductive composition
glass frit
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PCT/JP2015/083278
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English (en)
Japanese (ja)
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航介 角田
正生 山岸
高啓 杉山
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株式会社ノリタケカンパニーリミテド
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Application filed by 株式会社ノリタケカンパニーリミテド filed Critical 株式会社ノリタケカンパニーリミテド
Priority to CN201580064430.2A priority Critical patent/CN107004457A/zh
Publication of WO2016084915A1 publication Critical patent/WO2016084915A1/fr

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    • 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
    • C03C8/18—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing free metals
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
    • H01L21/288—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition
    • 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

Definitions

  • the present invention relates to a conductive composition. More particularly, the present invention relates to a conductive composition that can be used to form a solar cell electrode.
  • This application claims priority based on Japanese Patent Application No. 2014-240215 filed on Nov. 27, 2014, the entire contents of which are incorporated herein by reference.
  • a phosphorus-containing solution is first applied to the entire light-receiving surface of a silicon substrate to construct an n-Si layer (hereinafter also referred to as an n + layer) on the substrate surface.
  • An antireflection film is formed.
  • a conductive composition for forming an electrode is supplied in a desired electrode pattern on the antireflection film and fired.
  • the conductive composition for forming an electrode typically includes a conductive powder, a glass frit, and an organic vehicle. During firing, the glass frit contained in the conductive composition reacts with the antireflection film, and the constituent components of the antireflection film are taken into the glass.
  • Patent Documents 1 to 9 are known as conventional techniques related to such a conductive composition for forming an electrode of a solar cell.
  • the surface recombination rate can be lowered by thinning the n + layer of the silicon substrate.
  • a substrate having a thin n + layer Lightly Doped Emitter; LDE
  • sheet resistance is increased, and ohmic contact with the light-receiving surface electrode by fire-through is realized in the thin n + layer. It was difficult. Further, if the erosion of the silicon substrate by the light receiving surface electrode is suppressed, there is a problem that sufficient adhesion between the electrode and the substrate cannot be obtained.
  • the present invention has been made in view of such circumstances, and its main purpose is to provide a conductive composition that can form an electrode having good fire-through properties and good adhesion and bonding properties with a substrate. Is to provide.
  • Another object of the present invention is to provide a solar cell element with improved functions or performance realized by the use of the conductive composition.
  • the present invention provides a conductive composition for forming a solar cell electrode.
  • the conductive composition includes a conductive powder, glass frit, and an organic vehicle.
  • the glass frit has the following basic components: PbO 1 mol% or more and 20 mol% or less; TeO 2 35 mol% or more and 90 mol% or less; Bi 2 O 3 0.1 mol% or more and 10 mol% or less.
  • a conductive composition that can form an electrode that has good fire-through properties and good adhesion and bonding properties to the substrate.
  • the basic component contains the ZnO, the MgO, and the WO 3 in a ratio of 5 mol% to 40 mol% in total.
  • the basic component includes all of the ZnO, the MgO, and the WO 3 . With this configuration, the characteristics of the formed electrode can be further enhanced.
  • the metal species constituting the conductive powder is any one selected from the group consisting of silver, copper, gold, palladium, platinum, tin, aluminum, and nickel. It is characterized by containing one or more elements. Such a configuration provides a conductive composition capable of forming an electrode with higher conversion efficiency.
  • the technology disclosed herein provides a solar cell element.
  • This solar cell element is characterized in that a light-receiving surface electrode formed by using any one of the conductive compositions described above is provided on a light-receiving surface of a substrate.
  • the solar cell element can be formed with a light-receiving surface electrode having good adhesion and bonding properties to the substrate.
  • a solar cell element including an electrode having thermoelectric conversion performance represented by a fill factor and good bonding strength is realized.
  • an antireflection film is provided in a region where the light receiving surface electrode is not formed on the light receiving surface of the substrate.
  • FIG. 1 is a cross-sectional view schematically showing an example of the structure of a solar cell.
  • FIG. 2 is a plan view schematically showing a pattern of electrodes formed on the light receiving surface of the solar cell.
  • FIG. 3 is a diagram for explaining how to measure the bonding strength of the electrodes.
  • the conductive composition disclosed herein is typically a conductive composition for forming a solar cell electrode by firing.
  • the conductive composition is essentially the same as the conventional conductive composition of this type.
  • the conductive powder, the glass frit, and the organic vehicle component for dispersing these components (described later, A mixture of an organic binder and a dispersant).
  • this glass frit is characterized by the total amount of the following basic components being 95 mol% or more of the whole glass frit in the composition when converted into an oxide.
  • this glass frit contains four components of PbO, TeO 2 , Bi 2 O 3 and Li 2 O as essential constituent components.
  • these components are contained in amounts of Bi 2 O 3 and Li 2 O so that the proportion of TeO 2 is large and the proportion of PbO is small in the range where the softening point of the glass frit is 250 ° C. or more and 600 ° C. or less.
  • three components of ZnO, MgO and WO 3 are included.
  • the glass frit does not prevent other components from being contained, but the content of such components is limited to 5 mol% or less. That is, the glass frit disclosed here can be understood as being essentially composed of the above seven basic components.
  • TeO 2 functions as a network former and is an indispensable component for realizing good ohmic contact in the glass frit contained in the conductive composition for forming a solar cell electrode.
  • the conductive powder contains silver (Ag)
  • the amount of Ag solid solution in the glass phase is increased in order to achieve good contact at the interface between the electrode being fired and the silicon substrate of the solar cell. It is hoped that Here, the presence of Te in the glass phase can greatly increase the amount of Ag solid solution.
  • Ag dissolved in the glass phase can be precipitated as Ag fine particles.
  • TeO 2 is present in the glass phase, so that the precipitation of Ag is moderate with respect to the change in the firing temperature, and the control range (margin) of the firing temperature can be widened.
  • TeO 2 is preferably a larger amount.
  • TeO 2 is preferably the main component (maximum component) of this glass frit.
  • the content of TeO 2 is preferably 40 mol% or more, more preferably 45 mol% or more, and further preferably 50 mol% or more.
  • the content of TeO 2 is limited to 90 mol% or less.
  • PbO is a preferable component in that it functions as a network former in the glass frit disclosed herein, exhibits good fire-through characteristics, and can improve the electrical characteristics of the formed electrode.
  • PbO is blended at a ratio of 1 mol% or more and 20 mol% or less in order to compensate for the erosion property of the silicon substrate which is reduced as a result of containing a large amount of TeO 2 .
  • PbO is preferably 2 mol% or more, and more preferably 3 mol% or more.
  • PbO is also a component for which it is preferable to reduce the content as much as possible from the viewpoint of environmental load in recent years.
  • the content of PbO is preferably 15 mol% or less, more preferably 13 mol% or less, still more preferably 10 mol% or less, and particularly preferably 8 mol% or less, for example, 5 mol% % Or less.
  • Bi 2 O 3 is a component included for the purpose of exhibiting good fire-through characteristics together with the PbO, although it does not form glass in a binary system with TeO 2 .
  • Bi 2 O 3 is also preferable in that it has an effect of suppressing an increase in viscosity of the glass frit when the glass frit is melted by firing. If the content of Bi 2 O 3 is less than 0.1 mol%, it may be difficult to develop sufficient fire-through characteristics, which is not preferable. Therefore, the content of Bi 2 O 3 is preferably 0.1 mol% or more, more preferably 0.5 mol% or more, and particularly preferably 1 mol% or more.
  • Bi 2 O 3 is not preferable if the content exceeds 10 mol% because the silicon substrate tends to be excessively eroded and the electrical characteristics can be adversely affected.
  • the content of Bi 2 O 3 is preferably 8 mol% or less, more preferably 7 mol% or less, and particularly preferably 5 mol% or less.
  • Li 2 O is a component that can serve as a dopant for the n + layer of the silicon substrate.
  • the conductive composition can have a donor compensation function for the n + layer.
  • action of the fall of an electrical property which is seen by other alkali components is not seen, but since a softening point can be lowered
  • the conductive composition disclosed herein may be particularly suitable for use in electrode formation for solar cells employing a shallow emitter structure that has a low donor element concentration and is likely to have a high sheet resistance.
  • the content of Li 2 O is preferably 0.5 mol% or more, more preferably 1 mol% or more, and particularly preferably 5 mol% or more.
  • the content of Li 2 O exceeds 30 mol%, the content of TeO 2 becomes relatively low, which is not preferable.
  • the content of Li 2 O is preferably 28 mol% or less, more preferably 25 mol% or less, and particularly preferably 22 mol% or less.
  • ZnO is not an essential component, but can be preferably included because it has an effect of improving the electrical characteristics of the formed electrode. For example, the open circuit voltage and the short circuit current can be improved. It also has the effect of increasing the stability of the glass to widen the vitrification range and making it difficult to crystallize the glass frit after firing. When the content of ZnO exceeds 30 mol%, the content of TeO 2 is relatively low, which may cause a decrease in electrical characteristics.
  • MgO is not an essential component, but it improves the solubility of glass to suppress the occurrence of bubble defects, lowers the softening point of glass, increases the stability of glass, widens the vitrification range, and fires Since it has the effect of making it difficult to crystallize the subsequent glass frit, it can be preferably contained.
  • the content of ZnO exceeds 20 mol%, the content of TeO 2 becomes relatively low, which is not preferable because the electrical characteristics may be deteriorated.
  • WO 3 is not an essential component, but functions as a network former in Te-based glass, and has the effect of stably expanding the vitrification range and stabilizing Te in the glass phase. Therefore, it can be preferably included. Moreover, in the formulation with a small amount of PbO, WO 3 may be a preferable component from the viewpoint that the effect of enhancing the adhesiveness can be expressed. If the content of WO 3 exceeds 30 mol%, the content of TeO 2 becomes relatively low, which may cause a decrease in electrical characteristics.
  • the three basic components ZnO, MgO and WO 3 are not necessarily limited to this, but in order to avoid a relatively low TeO 2 content, a total of 40 mol % Or less (preferably 36 mol% or less). Further, these three components are preferably added in a total amount of 5 mol% or more (preferably 7 mol% or more, for example, 10 mol% or more) in order to improve the stability of the glass phase.
  • the glass frit can contain other various glass components and additive components as long as the characteristics are not impaired.
  • One element selected from the group consisting of a single element or a combination of two or more elements may be included. However, inclusion of unnecessary elements can impair the electrical characteristics of the formed electrode.
  • the components other than the above seven basic components are 5 mol% or less in total, preferably 4 mol% or less, more preferably 3 mol% or less, particularly preferably 2 mol% or less, for example, 1 mol%. It can be as follows. Or it is good also as 0 mol% substantially except the component mixed unavoidable. In other words, the above seven basic components may be substantially 100 mol%.
  • Such a glass frit is a component that can function as an inorganic binder in addition to the function of exhibiting the fire characteristic as described above in the conductive composition. It also has a function of enhancing the bonding between the conductive particles constituting the conductive powder and between the conductive particles and the substrate (object on which the electrode is formed).
  • Such a glass frit is preferably adjusted to a size equal to or smaller than that of the conductive powder described below.
  • the average particle size is preferably 3 ⁇ m or less, more preferably 2 ⁇ m or less, and more preferably about 0.1 ⁇ m or more and 2 ⁇ m or less.
  • the softening point of the glass constituting the glass frit is not particularly limited, but is preferably about 250 to 600 ° C. (for example, 300 to 400 ° C.).
  • the glass frit specifically exemplified in the following examples has a softening point adjusted within a range of 300 ° C. or more and 600 ° C. or less.
  • the conductive composition containing glass frit having such a softening point is used, for example, when forming a light-receiving surface electrode of a solar cell element, it exhibits good fire-through characteristics and forms a high-performance electrode. Preferred to contribute.
  • the conductive powder forming the main component of the solid content of the conductive composition disclosed herein powders made of various conductive materials having desired conductivity and other physical properties according to the application can be used.
  • the material constituting the conductive powder include, for example, gold (Au), silver (Ag), copper (Cu), palladium (Pd), platinum (Pt), tin (Sn), ruthenium (Ru), Powders made of metals such as rhodium (Rh), iridium (Ir), osmium (Os), nickel (Ni) and aluminum (Al), and alloys thereof can be considered.
  • simple metals such as gold, silver, platinum, palladium and alloys thereof (Ag—Pd alloy, Pt—Pd alloy, etc.), nickel, copper, tin, aluminum,
  • materials made of these alloys and the like are particularly preferable as materials constituting the conductive powder.
  • a powder made of silver and its alloy hereinafter sometimes simply referred to as “Ag powder”.
  • Ag powder the conductive composition of the present invention will be described using an example in which Ag powder is used as the conductive powder.
  • the particle size of the Ag powder and other conductive powders is not particularly limited, and those having various particle sizes according to the application can be used. Typically, those having an average particle diameter of 5 ⁇ m or less based on the laser / scattering diffraction method are suitable, and those having an average particle diameter of 3 ⁇ m or less (typically 1 to 3 ⁇ m, for example 1 to 2 ⁇ m) are preferably used. It is done.
  • the shape of the particles constituting the conductive powder is not particularly limited. Typically, a spherical shape, a flake shape (flake shape), a conical shape, a rod shape, or the like can be preferably used. Spherical or scaly particles are preferably used for reasons such as easy formation of a fine light-receiving surface electrode with good filling properties.
  • the conductive powder to be used those having a sharp (narrow) particle size distribution are preferable.
  • a conductive powder having a sharp particle size distribution that does not substantially contain particles having a particle diameter of 10 ⁇ m or more is preferably used.
  • the ratio (D10 / D90) of the particle size (D10) when the cumulative volume is 10% and the particle size (D90) when the cumulative volume is 90% in the particle size distribution based on the laser scattering diffraction method can be adopted.
  • the value of D10 / D90 is 1, and conversely, the value of D10 / D90 approaches 0 as the particle size distribution becomes wider.
  • a conductive composition using a conductive powder having such an average particle size and particle shape has a good filling property of the conductive powder and can form a dense electrode. This is advantageous in forming a fine electrode pattern with high shape accuracy.
  • the conductive powder such as Ag powder is not particularly limited by the manufacturing method thereof.
  • conductive powder typically Ag powder
  • a known wet reduction method, gas phase reaction method, gas reduction method or the like can be classified and used as necessary.
  • classification can be performed using, for example, a classification device using a centrifugal separation method.
  • the vehicle for dispersing the above conductive powder and glass frit various types conventionally used in this type of conductive composition can be used without particular limitation depending on the desired purpose.
  • the vehicle can be composed of organic binders and organic solvents of various compositions.
  • organic vehicle component all of the organic binder may be dissolved in an organic solvent, or only a part thereof may be dissolved or dispersed (may be a so-called emulsion type organic vehicle).
  • organic binder examples include cellulose polymers such as ethyl cellulose and hydroxyethyl cellulose, acrylic resins such as polybutyl methacrylate, polymethyl methacrylate, and polyethyl methacrylate, epoxy resins, phenol resins, alkyd resins, polyvinyl alcohol, and polyvinyl butyral.
  • An organic binder based on is preferably used.
  • a cellulosic polymer for example, ethyl cellulose
  • a viscosity characteristic capable of performing particularly good screen printing can be realized.
  • a preferable solvent constituting the organic vehicle is an organic solvent having a boiling point of about 200 ° C. or higher (typically about 200 to 260 ° C.).
  • An organic solvent having a boiling point of about 230 ° C. or higher (typically about 230 to 260 ° C.) is more preferably used.
  • organic solvents include ester solvents such as butyl cellosolve acetate and butyl carbitol acetate (BCA: diethylene glycol monobutyl ether acetate), ether solvents such as butyl carbitol (BC: diethylene glycol monobutyl ether), ethylene glycol and diethylene glycol.
  • An organic solvent such as a derivative, toluene, xylene, mineral spirit, terpineol, mentanol, or texanol can be preferably used.
  • Particularly preferred solvent components include butyl carbitol (BC), butyl carbitol acetate (BCA), 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate and the like.
  • the blending ratio of each constituent component contained in the conductive composition may vary depending on the electrode formation method, typically the printing method, etc., but generally conforms to the conductive composition of the composition conventionally employed. It can be set as a mixture ratio.
  • the ratio of each component can be determined using the following formulation as a guide. That is, the content of the conductive powder in the conductive composition is approximately 70% by mass or more (typically 70% by mass to 95% by mass) when the entire conductive composition is 100% by mass. More preferably, it is preferably about 80 to 90% by mass, for example about 85% by mass. Increasing the content of the conductive powder is preferable from the viewpoint that a precise electrode pattern can be formed with good shape accuracy. On the other hand, when the content ratio is too high, the handleability of the conductive composition, suitability for various printability, and the like may be deteriorated.
  • the ratio of the glass frit to the conductive powder is typically 0.1 parts by mass or more when the conductive powder is 100 parts by mass in order to obtain good fire-through characteristics and adhesion to the substrate. It is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more. Excessive addition is not preferable in order to increase the resistance of the electrode to be formed, and can be typically 12 parts by mass or less, preferably 10 parts by mass or less, and 8 parts by mass or less. Is more preferable.
  • the organic binder is preferably contained at a ratio of about 15% by mass or less, typically about 1% by mass to 10% by mass when the mass of the conductive powder is 100% by mass. . Particularly preferred is a ratio of 2% by mass to 6% by mass with respect to 100% by mass of the conductive powder.
  • this organic binder may contain the organic binder component which is melt
  • the organic binder component dissolved in the organic solvent and the organic binder component not dissolved are included, the ratio thereof is not particularly limited, but for example, the organic binder component dissolved in the organic solvent is 40 to 10).
  • the content ratio of the organic vehicle as a whole is variable in accordance with the properties (typically, viscosity, concentration, etc.) required for the conductive composition.
  • properties typically, viscosity, concentration, etc.
  • the total amount of the conductive composition is 100% by mass, for example, an amount of 5% by mass to 30% by mass is appropriate, and preferably 5% by mass to 20% by mass. An amount of 15% by mass (particularly 7% by mass to 12% by mass) is more preferable.
  • the conductive composition disclosed herein can contain various inorganic additives and / or organic additives other than those described above without departing from the object of the present invention.
  • the inorganic additive include metal oxide powders other than those described above (for example, NiO, ZnO 2 , Al 2 O 3, etc.) and other various fillers.
  • additives such as surfactant, an antifoamer, antioxidant, a dispersing agent, a viscosity modifier, are mentioned, for example.
  • the above conductive composition is suitable as a printing composition (sometimes referred to as paste, slurry or ink) applied to screen printing, gravure printing, offset printing, ink jet printing, and the like.
  • a printing composition sometimes referred to as paste, slurry or ink
  • it can be particularly preferably used when such a general-purpose printing means is employed in forming an electrode pattern that requires thinning and a high aspect ratio. Therefore, a description will be given of the solar cell element disclosed herein, showing an example in which a comb-shaped electrode pattern including a fine finger electrode is formed on the light receiving surface by screen printing, taking a crystalline silicon type solar cell element as an example.
  • the solar cell element may be the same as the conventional solar cell except for the configuration of the light-receiving surface electrode that characterizes the present invention. The detailed description is omitted.
  • FIG. 1 and FIG. 2 schematically show an example of a solar cell element (cell) 10 that can be suitably manufactured by implementing the present invention, and is made of single crystal, polycrystalline, or amorphous silicon (Si).
  • This is a so-called silicon-type solar cell element 10 that uses the wafer as the semiconductor substrate 11.
  • a cell 10 shown in FIG. 1 is a general single-sided light receiving solar cell element 10.
  • this type of solar cell element 10 includes an n-Si layer 16 formed by forming a pn junction on the light-receiving surface side of a p-Si layer (p-type crystalline silicon) 18 of a silicon substrate (Si wafer) 11.
  • an antireflection film 14 made of titanium oxide or silicon nitride formed by CVD or the like, and light receiving surface electrodes 12 and 13 made of a conductive composition mainly containing Ag powder or the like. .
  • the back side of the p-Si layer 18 As with the light-receiving surface electrode 12, the back side outside formed by a predetermined conductive composition (typically a conductive paste whose conductive powder is Ag powder).
  • a connection electrode 22 and a back surface aluminum electrode 20 having a so-called back surface field (BSF) effect are provided.
  • the aluminum electrode 20 is formed on substantially the entire back surface by printing and baking a conductive composition mainly composed of aluminum powder.
  • an Al—Si alloy layer (not shown) is formed, and aluminum diffuses into the p-Si layer 18 to form a p + layer 24.
  • the p + layer 24 that is, the BSF layer, the photogenerated carriers are prevented from recombining in the vicinity of the back electrode, and for example, an improvement in short circuit current and open circuit voltage (Voc) is realized.
  • the bus bar electrode 12 is a connection electrode for collecting carriers collected by the finger electrode 13. The portion where the light receiving surface electrodes 12 and 13 are formed forms a non-light receiving portion (light shielding portion) on the light receiving surface 11A of the solar cell element.
  • the bus bar electrode 12 and the finger electrode 13 are made as fine lines as possible to reduce the corresponding non-light receiving portion (light shielding portion).
  • the light receiving area per unit cell area is enlarged. This can extremely simply improve the output per unit area of the solar cell element 10.
  • the height of the thinned electrode is high and uniform, but for example, when a sagging or a dent occurs in a part of the electrode, the sagging or the dent causes an increase in resistance, thereby collecting current. Loss will occur. Moreover, if even a part of the thinned electrode is broken, it is impossible to collect the generated current through the broken part (current collection loss occurs as a current flowing through the high-resistance substrate). Current will be collected). Therefore, the formation of the light-receiving surface electrode of the solar cell element requires a conductive composition having excellent electrical stability and excellent shape stability by printing.
  • Such a solar cell element 10 is generally manufactured through the following process. That is, an appropriate silicon wafer is prepared, and the p-Si layer 18 and the n-Si layer 16 are formed by doping a predetermined impurity by a general technique such as a thermal diffusion method or ion plantation. A substrate (semiconductor substrate) 11 is produced. Next, an antireflection film 14 made of silicon nitride or the like is formed by a technique such as plasma CVD. Thereafter, on the back surface 11B side of the silicon substrate 11, first, a predetermined pattern is screen-printed using a predetermined conductive composition (typically a conductive composition in which the conductive powder is Ag powder) and dried.
  • a predetermined conductive composition typically a conductive composition in which the conductive powder is Ag powder
  • a back side conductor coated material that becomes the back side external connection electrode 22 (see FIG. 1) after firing is formed.
  • a conductive composition containing aluminum powder as a conductor component is applied (supplied) by a screen printing method or the like on the entire back surface, and dried to form an aluminum film.
  • the conductive composition of the present invention is typically printed (supplied) on the antireflection film 14 formed on the surface side of the silicon substrate 11 with a wiring pattern as shown in FIG. 2 based on a screen printing method.
  • the line width to be printed is not particularly limited, but by adopting the conductive composition of the present invention, the line width is about 70 ⁇ m or less (preferably in the range of about 50 ⁇ m to 60 ⁇ m, more preferably in the range of about 40 ⁇ m to 50 ⁇ m. ) Of the electrode pattern including the finger electrodes of () is formed.
  • the substrate is dried in an appropriate temperature range (typically about 100 ° C. to 200 ° C., for example, about 120 ° C. to 150 ° C.). The contents of a suitable screen printing method will be described later.
  • the silicon substrate 11 on which the paste application (dried film-like application) is formed on both sides is subjected to an appropriate baking temperature (for example, using a baking furnace such as a near-infrared high-speed baking furnace) in an air atmosphere. Baked at 700 to 900 ° C.).
  • a fired aluminum electrode 20 is formed together with the light-receiving surface electrodes (typically Ag electrodes) 12 and 13 and the backside external connection electrode (typically Ag electrode) 22, and at the same time, Al (not shown)
  • a -Si alloy layer is formed and aluminum is diffused into the p-Si layer 18 to form the p + layer (BSF layer) 24 described above, and the solar cell element 10 is manufactured.
  • firing for forming the light receiving surface electrodes typically Ag electrodes 12 and 13 on the light receiving surface 11A side, the aluminum electrode 20 on the back surface 11B side, and external connection
  • the firing for forming the electrode 22 may be performed separately.
  • Glass frit having the composition of Examples 1 to 50 shown in Table 1 below was prepared by the following procedure. First, lead Pb 3 O 4 as the Pb source, TeO 2 as the Te source, Bi 2 O 3 as the Bi source, lithium carbonate Li 2 CO 3 as the Li source, and ZnO as the Zn source. MgO was used as the Mg source, WO 3 was used as the W source, SiO 2 was used as the Si source, MoO 3 was used as the Mo source, and sodium carbonate Na 2 CO 3 was used as the Na source. These raw materials were blended in a stoichiometric composition so as to obtain the desired glass composition, charged into a crucible, melted by heating at 900 to 1100 ° C., and rapidly cooled to obtain a glass composition.
  • the glass composition was pulverized using a planetary mill and classified as necessary to obtain a glass frit having an average particle size in the range of 0.3 to 3 ⁇ m.
  • the average particle diameter of the glass frit is a sphere equivalent diameter calculated based on the specific surface area measured based on the air permeation method and the true density of the glass frit.
  • total of basic components seven oxide components that are basic components of the glass frit disclosed herein; PbO, TeO 2 , Bi 2 O 3 , Li 2 O, ZnO, The total ratio of MgO and WO 3 ; is shown.
  • the conductive powder an approximately spherical silver (Ag) powder having an average particle diameter of 2 ⁇ m was used.
  • the organic vehicle ethyl cellulose (EC) dissolved in terpineol was used. Texanol was used as the solvent.
  • the silver powder: glass frit: organic vehicle: solvent ratio is weighed so that the mass ratio is 89: 2: 6: 3, mixed using a stirrer or the like, and then dispersed with, for example, a three roll mill.
  • the conductive compositions of Examples 1 to 50 were prepared by performing. In this example, the conductive compositions of Examples 1 to 50 were adjusted so as to have a viscosity of 180 to 200 Pa ⁇ s (20 rpm, 25 ° C.) in order to make printing properties described later substantially equivalent.
  • n-Si layer (n + layer) having a thickness of about 0.5 ⁇ m on the light receiving surface of the silicon substrate.
  • PECVD plasma CVD
  • the back side electrode pattern was formed on the back side of the silicon substrate by screen printing using a predetermined silver electrode forming paste and drying.
  • This back surface side electrode pattern becomes a back surface side external connection electrode by baking of a post process.
  • an aluminum electrode forming paste was screen-printed on the entire back surface side and dried to form an aluminum film.
  • the conductive compositions of Examples 1 to 50 prepared above were screen-printed on the antireflection film and dried at 120 ° C. to form an electrode pattern for the light-receiving surface electrode (silver electrode).
  • a screen mesh (manufactured by SUS400, wire diameter 18 ⁇ m, emulsion thickness 15 ⁇ m) was used for printing plate making, and the printing conditions were set so that the width of the grid lines was 45 ⁇ m.
  • the substrate on which the electrode pattern was printed in this manner was baked at a baking temperature of 700 to 800 ° C. in an air atmosphere using a near-infrared high-speed baking furnace, thereby producing solar cells for evaluation of Examples 1 to 50.
  • the adhesive strength of the silver electrode in the solar cells of Examples 1 to 50 produced as described above was evaluated.
  • the adhesion strength (peel strength) of the silver electrode was evaluated using a peel tester 300 as shown in FIG. Specifically, the glass substrate 41 is fixed on the fixing jig 40 of the peeling tester 300 via the fixing screw 43 and the locking plate 44, and the evaluation is performed on the glass substrate 41 via the epoxy adhesive 42.
  • the solar cell 10 was placed with the light-receiving surface side up and the back surface side down, and was fixed.
  • the tab wire 35 was soldered via the solder layer 30 on the silver electrode 12 positioned on the upper surface side of the solar cell for evaluation fixed on the glass substrate 41 in this way.
  • the peeling tester 300 is tilted so that the bottom surface of the fixing jig 40 has an angle of 180 °, and the extension portion 35e formed in advance on the tab wire 35 is pulled vertically upward (see arrow 45).
  • the adhesion strength of the wire 35 / solder layer 30 / silver electrode 12 was measured.
  • ⁇ when the measurement result of the adhesive strength is 3 N / mm or more, ⁇ when the measurement result is 2 N / mm or more and less than 3 N / mm, and ⁇ when it is less than 2 N / mm. Filled in.
  • Each of the conductive compositions of Examples 1 to 50 in the present embodiment includes a glass frit containing TeO 2 as a main glass constituent.
  • Examples 14 to 23 show cases where the content of TeO 2 is changed greatly.
  • the amount of TeO 2 is in the range of 35 to 90 mol%, the Ag component is taken in (solid solution) from the silver powder to the glass phase at the time of firing and precipitated as Ag fine particles at the time of cooling.
  • the amount of TeO 2 was less than 35 mol% as in Example 14 and Example 15, it was confirmed that these effects were not sufficiently exhibited and the output characteristics and adhesive strength were not sufficiently obtained.
  • the amount of TeO 2 exceeded 90 mol% as in Example 23, it was found that the fire-through characteristics were not sufficiently obtained and the ohmic contact was hindered.
  • Examples 1 to 13 show cases where the content of PbO is greatly changed.
  • PbO is a component that can be contained in a large amount exceeding 20 mol% in relation to other components.
  • the amount of PbO is set within a range of about 1 to 20 mol%. It was confirmed that sufficient output characteristics and adhesive strength were obtained even when the PbO amount was 1 mol%.
  • Examples 1 and 2 particularly as can be seen from the comparison between Example 2 and Example 3
  • the amount of PbO is less than 1 mol%, the effect of improving the output by PbO cannot be sufficiently obtained. Therefore, it was confirmed that sufficient output characteristics could not be obtained.
  • Example 12 and Example 13 in this system, when the PbO amount exceeds 20 mol%, the output characteristics are sufficient, but it is difficult to obtain sufficient adhesion to the substrate. It was.
  • Examples 24 to 30 show cases where the content of Bi 2 O 3 is greatly changed.
  • the amount of Bi 2 O 3 is in the range of 0.1 to 10 mol%.
  • the softening temperature of the glass frit is not sufficiently lowered, and the output characteristics are rapidly deteriorated. It was.
  • the amount of Bi 2 O 3 exceeds 10 mol%, it is difficult to obtain sufficient electrical characteristics.
  • Examples 31 to 35 show cases in which the content of Li 2 O is greatly changed.
  • the amount of Li 2 O is in the range of 0.1 to 30 mol%.
  • Example 31 when the amount of Li 2 O is not included, the effect of Li 2 O as a dopant and the effect of reducing the softening point cannot be obtained, and the output characteristics are rapidly deteriorated.
  • Example 35 it was confirmed that when the amount of Li 2 O exceeded 30 mol%, it was difficult to obtain sufficient output characteristics and adhesive strength.
  • Examples 36 to 39 show cases where the content of ZnO is changed. In the technique disclosed herein, as shown in Example 39, it was confirmed that when the amount of ZnO exceeds 30 mol%, it is difficult to sufficiently obtain output characteristics and adhesive strength.
  • Examples 40 to 43 show cases where the content of MnO is changed. In the technique disclosed herein, as shown in Example 43, it was confirmed that when the MgO amount exceeds 20 mol%, it is difficult to sufficiently obtain output characteristics and adhesive strength.
  • Examples 44 to 47 show cases where the content of WO 3 is changed. In the technique disclosed herein, as shown in Example 47, it was confirmed that when the amount of WO 3 exceeds 20 mol%, it is difficult to obtain sufficient output characteristics.
  • Examples 48 to 50 show cases where components other than the above basic components (in this embodiment, SiO 2 , MoO 3 , Na 2 O) are included.
  • components other than the above basic components in this embodiment, SiO 2 , MoO 3 , Na 2 O
  • the total amount is small (for example, a range of 5 mol% or less)
  • it is contained without impairing output characteristics and adhesive strength. It was shown that it can be done.
  • this invention was demonstrated by suitable embodiment, such description is not a limitation matter and of course various modifications are possible.

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Abstract

L'invention concerne une composition conductrice qui présente de bonnes propriétés de cuisson par diffusion et qui est capable de former une électrode qui présente une bonne adhésion et de se lier à un substrat. La présente invention concerne une composition conductrice destinée à former une électrode pour cellules solaires. Cette composition conductrice contient une poudre conductrice, de la fritte de verre et un véhicule. La fritte de verre présente une telle composition en termes d'oxydes, dans laquelle le total des composants de base suivants, de 1 % molaire à 20 % molaires (inclus) de PbO, de 35 % molaires à 90 % molaires (inclus) de TeO2, de 0,1 % molaire à 10 % molaires (inclus) de Bi2O3, de 0,1 % molaire à 30 % molaires (inclus) de Li2O, de 0 % molaire à 30 % molaires (inclus) de ZnO, de 0 % molaire à 20 % molaires (inclus) de Mg, et de 0 % molaire à 30 % molaires (inclus) de WO3, est de 95 % molaires ou plus de la totalité de la fritte de verre.
PCT/JP2015/083278 2014-11-27 2015-11-26 Composition conductrice WO2016084915A1 (fr)

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TWI745562B (zh) * 2017-04-18 2021-11-11 美商太陽帕斯特有限責任公司 導電糊料組成物及用其製成的半導體裝置
JP6917028B2 (ja) * 2017-09-14 2021-08-11 Ｄｏｗａエレクトロニクス株式会社 銀被覆鉛テルルガラス粉およびその製造方法、ならびに導電性ペースト
KR20190045758A (ko) * 2017-10-24 2019-05-03 삼성에스디아이 주식회사 태양전지 전극 형성용 조성물 및 이로부터 제조된 전극
CN108321224A (zh) * 2017-10-30 2018-07-24 无锡帝科电子材料科技有限公司 用于制备太阳能电池电极的多元纳米材料、包括其的糊剂组合物及太阳能电池电极和电池
KR102060425B1 (ko) * 2017-10-31 2020-02-11 엘에스니꼬동제련 주식회사 태양전지 전극용 도전성 페이스트 및 이에 포함되는 유리 프릿, 그리고 태양 전지
WO2019183934A1 (fr) * 2018-03-30 2019-10-03 深圳市首骋新材料科技有限公司 Pâte conductrice côté avant de cellule solaire en silicium cristallin, son procédé de préparation et cellule solaire
CN110603605A (zh) * 2018-03-30 2019-12-20 深圳市首骋新材料科技有限公司 晶硅太阳能电池正面导电浆料及其制备方法和太阳能电池
WO2020262109A1 (fr) * 2019-06-26 2020-12-30 日本電気硝子株式会社 Composition de verre et matériau d'étanchéité
JP7385169B2 (ja) * 2019-06-26 2023-11-22 日本電気硝子株式会社 ガラス組成物及び封着材料

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