JP5522900B2 - Electrode forming conductive composition and the method of forming the solar cell - Google Patents

Electrode forming conductive composition and the method of forming the solar cell Download PDF

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JP5522900B2
JP5522900B2 JP2008040913A JP2008040913A JP5522900B2 JP 5522900 B2 JP5522900 B2 JP 5522900B2 JP 2008040913 A JP2008040913 A JP 2008040913A JP 2008040913 A JP2008040913 A JP 2008040913A JP 5522900 B2 JP5522900 B2 JP 5522900B2
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conductive composition
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JP2009200276A (en
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克也 谷津
隆昭 平井
敦史 室田
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東京応化工業株式会社
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    • YGENERAL 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
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Description

本発明は、電極形成用導電性組成物及び太陽電池の形成方法に関する。 The present invention, electrode formation conductive composition and to a method of forming a solar cell.

太陽電池用電極は、p型シリコン基板の受光面側にリン(P)等のn型不純物原子を高温で熱的に拡散させることよりn型拡散層を形成し、その後導電性組成物を、n型拡散層を含む基板の上にスクリーン印刷等により塗布し焼成することにより、形成される。 Solar cell electrode, an n-type diffusion layer than be thermally diffusing an n-type impurity atoms such as phosphorus (P) on the light receiving surface of the p-type silicon substrate at an elevated temperature, followed conductive composition, by applying calcined by screen printing or the like on a substrate including the n-type diffusion layer is formed. このような導電性組成物には、銀粉末等の導電性金属粉末、ガラス粉末(ガラスフリット)並びに種々の添加剤及び有機溶媒等が含まれている。 Such conductive composition, a conductive metal powder of silver powder and the like, includes a glass powder (glass frit) and various additives and organic solvents. ここで、ガラスフリットは焼成時に溶解し、電極と基板とを接着する役割を有するが、電極と基板との間の抵抗を低く抑えつつ、接着強度を高めることが求められている。 Here, the glass frit dissolves during firing, has a role of bonding the electrode and the substrate, while suppressing the resistance between the electrode and the substrate, it is required to increase the adhesive strength. このような課題を解決する試みとして、例えば特許文献1には、銀粉末、カドミウムを含有しないガラス粉末、並びに0.1〜10.0重量%のFe 、FeO、MnO及びCu Oの群から選択される少なくとも1種の金属酸化物の粒子を含み、全ての粉末が有機媒質中に分散される、銀導体組成物が開示されている。 In an attempt to solve such a problem, for example, Patent Document 1, silver powder, glass powder containing no cadmium, and 0.1 to 10.0 wt% of Fe 2 O 3, FeO, MnO and Cu 2 O comprises particles of at least one metal oxide selected from the group of all the powder is dispersed in an organic medium, silver conductor composition is disclosed.
特表2005−504409号公報 JP-T 2005-504409 JP

しかしながら、従来の技術では、添加できる金属酸化物が制限されているだけでなく、形成した電極と基板との間の抵抗の抑制効果に限界があった。 However, in the prior art, not only the metal oxide which may be added is limited, there is a limit to the effect of suppressing the resistance between the formed electrode and the substrate. さらに、本発明者によれば、用いたガラスフリットの成分によっては電極−基板間の抵抗が抑制されないことも見出された。 Furthermore, according to the inventors, by components of the glass frit using electrodes - resistance between the substrates was also found that not suppressed.

したがって、本発明は、汎用性が高く、すなわち、用いるガラスフリットと金属化合物との選択肢が広く、電極と基板間の抵抗をより低く抑えることが可能な電極形成用導電性組成物を提供することを目的とする。 Accordingly, the present invention is versatile, i.e., to provide a wide choice of glass frit and the metal compound, the electrodes and the resistance can be suppressed to lower the electrode formation conductive composition between the substrates to be used With the goal.

本発明者らは、ガラスフリットにIII族元素の酸化物及び/又はV族元素の酸化物が含まれる場合には、金属化合物としてFe 、FeO、MnO及びCu Oに限定することなく種々 の金属窒化物を添加しても、形成した電極と基板との間の抵抗を低く抑えられることを見出し、本発明を完成するに至った。 The present inventors have found that if it contains oxides of oxides and / or group V element of the Group III element gas Rasufuritto is to limit as metal compounds Fe 2 O 3, FeO, the MnO and Cu 2 O be added without various metallic nitrides, it found a low suppress this resistance between the formed electrode and the substrate, thereby completing the present invention.

具体的には、本発明は以下のものを提供する。 Specifically, the present invention provides the following.

本発明は、第一の態様として、(a)導電性粉末、(b)ガラスフリット及び (c )金属窒化物を含み、前記(b)成分がIII族元素の酸化物及び/又はV族元素の酸化物を含む、電極形成用導電性組成物を提供する。 The present invention provides, as a first aspect, (a) conductive powder, (b) comprises a glass frit and (c) Metal nitrides, wherein (b) an oxide of component III group element and / or group V containing an oxide of an element, it provides an electrode-forming conductive composition.

さらに、本発明は第の態様として、上記の電極形成用導電性組成物をシリコン基板上に塗布、乾燥及び焼成する工程を含む太陽電池の製造方法を提供する。 Furthermore, the present invention as the second embodiment, applying the electrode-forming conductive composition on a silicon substrate, to provide a method of manufacturing a solar cell comprising a step of drying and firing.

本発明によれば、III族元素の酸化物及び/又はV族元素の酸化物を含むガラスフリットを用いることにより金属化合物としてFe 、FeO、MnO及びCu Oに限定することなく種々 の金属窒化物を添加しても、形成した電極と基板との間の抵抗を低く抑えることができる According to the present invention, by using a glass frit containing an oxide of oxides and / or Group V element Group III element, without limitation as a metal compound Fe 2 O 3, FeO, the MnO and Cu 2 O be added various metals nitride, it is possible to suppress the resistance between the formed electrode and the substrate low.

以下、本発明の実施形態について詳説するが、本発明は以下の実施形態になんら限定されるものではない。 Hereinafter be described in detail embodiments of the present invention, the present invention is not intended to be limited to the following embodiments. なお、以下の説明では、本発明に係る電極形成用導電性組成物を「導電性組成物」と称することがある。 In the following description, the electrode formation conductive composition according to the present invention may be referred to as "electrically conductive composition".

(第一の態様) (First aspect)
本発明は、第一の態様として、(a)導電性粉末、(b)ガラスフリット及び (c )金属窒化物を含み、前記(b)成分がIII族元素の酸化物及び/又はV族元素の酸化物を含む、電極形成用導電性組成物を提供する。 The present invention provides, as a first aspect, (a) conductive powder, (b) comprises a glass frit and (c) Metal nitrides, wherein (b) an oxide of component III group element and / or group V containing an oxide of an element, it provides an electrode-forming conductive composition. この電極形成用導電性組成物における各成分(a)〜(c)は次のとおりである。 Each component in the electrode formation conductive composition (a) ~ (c) are as follows.

((a)導電性粉末) ((A) conductive powder)
(a)導電性粉末(以下、(a)成分ともいう。)として、従来公知のいかなる導電性粉末を使用することができる。 (A) conductive powder (hereinafter, (a) component and referred to.) Can be used as a conventionally known any conductive powder. 例えば、銀粉末や、酸化銀、炭酸銀、酢酸銀等の焼成によって銀単体が析出するような粉末、銅、ニッケル等が挙げられる。 For example, silver powder or silver oxide, silver carbonate, powders such as silver alone is precipitated by firing, such as silver acetate, copper and nickel. これらは単独又は2種以上混合して使用することができるが、銀粉末が好ましい。 These may be used alone or in combination, silver powder is preferred. このような(a)成分として、初めから粉末状のものを使用しても、例えばフレーク状のものを公知の手段によって粉末にすることにより調製してもよい。 Such component (a), also be used as from the beginning powdered, may be prepared by a powder by, for example, flaky known means what. ここで、粉末の粒径は、粒径が大きいほど焼結速度は遅くなることから所望の焼結速度と電極を形成する工程において与える影響とを考慮して任意に設定することができる。 Here, the powder particle size can be arbitrarily set in consideration of the influence in the process of forming the desired sintering rate and electrode since the slower sintering rate as the particle diameter is large. 本発明において粒径は、10μm以下が好ましく、1μm以下がさらに好ましい。 Particle size in the present invention is preferably 10μm or less, more preferably 1μm or less. (a)成分の純度は、電極として通常要求される条件を満たせばいかなる純度でもよいが、例えば銀粉末の場合、純度90%以上が好ましく、95%以上がさらに好ましい。 (A) component purity can be a normal requested any purity satisfies conditions are as electrodes, but for example, in the case of silver powder, 90% pure by weight, more preferably 95% or more. 導電性組成物中の(a)成分の量は、全固形分に対し40質量%以上が好ましく、60質量%以上がさらに好ましい。 The amount of component (a) in the conductive composition is preferably at least 40 wt% based on the total solid content, more preferably at least 60 wt%.

((b)ガラスフリット) ((B) glass frit)
(b)ガラスフリット(以下、(b)成分ともいう。)は、上記の導電性粉末の焼結する際に金属が基板に強く接着するための成分であって、従来公知のガラスフリットを使用することができる。 (B) glass frit (hereinafter, also referred to as component (b).) Is a component of the metal during sintering of the conductive powder adheres strongly to the substrate, using a conventional glass frit can do. (b)成分の例として、ケイ酸、ホウケイ酸等の変性ケイ酸、アルミノケイ酸等が挙げられる。 Examples of component (b), silicic acid, modified silicic acid, such as borosilicate, etc. aluminosilicate acid. (b)成分は、B 、SiO 、Al 、CdO、CaO、BaO、ZnO、Na O、Li O、PbO、TiO 、Bi 及びZrO等の酸化物を1種以上含んでもよいが、環境に与える影響を考慮すると、鉛やカドミウム等の重金属を含まない方が好ましい。 (B) component, B 2 O 3, SiO 2 , Al 2 O 3, CdO, CaO, BaO, ZnO, Na 2 O, Li 2 O, PbO, TiO 2, Bi 2 O 3 and oxides such as ZrO the may contain one or more, but considering the impact on the environment, it is preferable that does not contain heavy metals such as lead and cadmium. (b)成分は、1000℃以下の軟化点を有することが好ましく、800℃以下の軟化点を有することがさらに好ましい。 Component (b) preferably has a softening point below 1000 ° C., further preferably has a softening point below 800 ° C.. また、導電性組成物における(b)成分は、(a)成分に対して0.1質量%〜10質量%含まれることが好ましい。 Further, (b) component in the conductive composition is preferably contained 0.1 wt% to 10 wt% relative to component (a).

さらに、第一の態様に係る(b)成分は、III族元素の酸化物及び/又はV族元素の酸化物を含む。 Further, (b) component according to the first embodiment includes an oxide of an oxide and / or group V element of the Group III elements. このIII族元素の酸化物及び/又はV族元素の酸化物を含むことにより、電極を形成する工程においてシリコン基板内にp型又はn型拡散層を形成することができ、形成した電極と基板との抵抗を抑制することができる。 By including the oxide of the oxide and / or group V elements of the III group element, it is possible to form a p-type or n-type diffusion layer in the silicon substrate in the step of forming the electrode, forming the electrode and the substrate it is possible to suppress the resistance of the. 例えばp型拡散層を形成しようとすればIII族元素の酸化物から、n型拡散層を形成しようとすればV族元素の酸化物から選択することができる。 For example, if an attempt is made to form a p-type diffusion layer of an oxide of Group III element may be selected from oxides of Group V element if an attempt is made to form an n-type diffusion layer. また、所望の拡散層の性質に応じて、III族元素の酸化物とV族元素の酸化物とから任意に組み合わせて用いてもよい。 Also, depending on the nature of the desired diffusion layer, it may be used in any combination from the oxides of the oxide and the Group V element of the Group III elements. このような、III族元素及びV族元素の酸化物には、例えば、B 、Al 、Bi 、P 等が挙げられ、(b)成分には、拡散層をp型にするかn型にするか所望に応じて、これらのうち1種類以上が含まれる。 Such, the oxide of a Group III element and a group V element, for example, B 2 O 3, Al 2 O 3, Bi 2 O 3, P 2 O 5 and the like, the component (b), the diffusion layer as desired or on whether n-type to p-type, include one or more of these. 中でも、B 、Al 、Bi が軟化点を低くすることができる点、接着性を向上させることができる点及び電極形成時の抵抗を抑制できる点で好ましい。 Among them, B 2 O 3, Al 2 O 3, Bi 2 O 3 is that it can lower the softening point, preferably in that the resistance at the time point and the electrode formation can be improved adhesion can be suppressed. このようなIII族元素の酸化物及び/又はV族元素の酸化物は、(b)成分に対して、5質量%以上含まれることが好ましく、10質量%以上含まれることがさらに好ましい。 Such oxides and / or oxides of Group V elements of the III group element, relative to component (b) preferably contained more than 5% by weight, still more preferably contained more than 10 wt%.

((c)金属窒化物) ((C) metal nitride)
(c)金属窒化物(以下、(c)成分ともいう。)は、(b)成分中のIII族元素及び/又はV族元素をシリコン基板内に拡散させる。 (C) a metal nitride (hereinafter, also referred to as component (c).) Diffuses the III group element and / or Group V element in the component (b) in the silicon substrate. このような(c)成分として、いかなる金属窒化物を挙げることができる And such a component (c), may be mentioned have kana Rukin nitrides. c)成分としては、I族元素、II族元素、III族元素及びIV族元素の窒化物が好ましく、例えば、銅、銀、金、亜鉛、カドミウム、水銀、スカンジウム、イットリウム、ランタノイド、アクチノイド、ホウ素、アルミニウム、ガリウム、インジウム、タリウム、珪素、ゲルマニウム、スズ及び鉛の窒化物が挙げられる。 The component (c), I group element, II group elements, the nitride products of group III element and a Group IV element preferably, for example, copper, silver, gold, zinc, cadmium, mercury, scandium, yttrium, lanthanides, actinides, boron, aluminum, gallium, indium, thallium, silicon, germanium, and a nitride compound of tin and lead. 中でもCuO、Y 、La 、ZnO、AlN、Si が好ましい。 Of these CuO, Y 2 O 3, La 2 O 3, ZnO, AlN, Si 3 N 4 are preferred. (c)成分は、(a)成分と(b)成分との合計質量に対して0.1質量%〜10質量%含まれることが好ましい。 (C) component, is preferably contained 0.1 wt% to 10 wt% based on the total weight of the component (a) and component (b).

(その他の成分) (Other Components)
本発明に係る導電性組成物は、前述の各成分を混合し、電極を形成する諸工程における最適な特性を得るために有機バインダーをさらに含んでよい。 Electrically conductive composition of the present invention, by mixing the components described above may further include an organic binder in order to obtain optimum properties in various forming an electrode. かかる特性には、例えば、固形分の安定的な分散性及び濡れ性、スクリーン印刷における導電性組成物の粘度及びチクソトロピー、良好な揮発性、焼成時に形成された電極に影響を与えるような残渣等を発生しない焼成性が挙げられる。 Such characteristics include, for example, stable dispersibility and wettability of the solids, the viscosity of the electrically conductive composition in the screen printing and thixotropic, good volatility, residue and the like that affect the electrode formed at the time of firing sintering property which does not generate the like. このような有機バインダーは、従来公知のいかなるものでもよいが、例えばポリマー溶液が好ましい。 Such organic binders are conventionally known may be any, but for example, a polymer solution is preferred. ポリマーの例として、エチルセルロース、エチルヒドロキシエチルセルロース、エチルセルロースとフェノール樹脂との混合物、低級アルコールのポリメタクリレート等が挙げられる。 Examples of polymers, ethyl cellulose, ethyl hydroxyethyl cellulose, mixtures of ethyl cellulose and phenolic resins, polymethacrylates and the like lower alcohol. ポリマーを溶かす溶媒の例として、テトラヒドロフラン、フラン、テトラヒドロピラン、ピラン、ジオキサン、1,3−ジオキソラン、トリオキサンなどの環状エーテル系化合物;N,N−ジメチルホルムアミド、N,N−ジメチルアセトアミドなどのジアルキルケトアミド系化合物;ジメチルスルホキシド、ジエチルスルホキシドなどのジアルキルスルホキシド系化合物;アセトン、メチルエチルケトン、ジエチルケトンなどのケトン系化合物;エタノール、2−プロパノール、1−ブタノール、ターピネオールなどのアルコール系化合物;ジクロロエチレン、ジクロロエタン、ジクロロベンゼンなどの塩素化炭化水素系化合、2,2,4−トリメチル−1,3−ペンタンジオールモノアセテート、2,2,4−トリメチル−1,3−ペン Examples of solvents that dissolve the polymer, tetrahydrofuran, furan, tetrahydropyran, pyran, dioxane, 1,3-dioxolane, cyclic ether compounds such as trioxane; N, N- dimethylformamide, N, dialkyl keto such as N- dimethylacetamide amide compounds; dimethyl sulfoxide, dialkyl sulfoxide compounds such as diethyl sulfoxide; acetone, methyl ethyl ketone, ketone compounds such as diethyl ketone; ethanol, 2-propanol, 1-butanol, alcohol compounds such as terpineol; dichloroethylene, dichloroethane, chlorinated hydrocarbon compounds such as chlorobenzene, 2,2,4-trimethyl-1,3-pentanediol mono-acetate, 2,2,4-trimethyl-1,3-pen ンジオールモノプロピオレート、2,2,4−トリメチル−1,3−ペンタンジオールモノブチレート、2,2,4−トリメチル−1,3−ペンタンジオールモノイソブチレート、2,2,4−トリエチル−1,3−ペンタンジオールモノアセテートなどの多価アルコールのエステル系化合物;α−テルピネン、ミルセン、アロオシメン、リモネン、ジペンテン、α−ピネン、β−ピネン、ターピネオール、カルボン、オシメン、フェランドレンなどのテルペン系化合物及びこれらの混合物が挙げられる。 Emissions diol mono propiolate, 2,2,4-trimethyl-1,3-pentanediol mono-butyrate, 2,2,4-trimethyl-1,3-pentanediol mono-isobutyrate, 2,2,4 ester compounds of polyhydric alcohols, such as triethyl-1,3-pentanediol monoacetate; alpha-terpinene, myrcene, alloocimene, limonene, dipentene, alpha-pinene, beta-pinene, terpineol, carvone, ocimene, such as phellandrene terpene compounds and mixtures thereof. 有機バインダーは、(a)〜(c')成分等の固形成分に対し任意の割合で混合することができるが、この固形成分に対し5質量%以下の範囲で混合することが好ましい。 The organic binder is based on the solid components, such as (a) ~ (c ') component can be mixed in any proportion, is preferably mixed in a range of 5 mass% or less relative to the solid components.

(太陽電池の形成方法) (A method of forming a solar cell)
本発明は、第の態様として、上記の電極形成用導電性組成物をシリコン基板上に塗布、乾燥及び焼成する工程を含む太陽電池の製造方法を提供する。 The present invention provides, as a second aspect, applying the electrode-forming conductive composition on a silicon substrate, to provide a method of manufacturing a solar cell comprising a step of drying and firing. この形成方法は、( a)〜(c)成分を含む導電性組成物を調製し、シリコン基板上に塗布、乾燥及び焼成する工程を含む。 This forming method comprises (a) ~ (c) a component papermaking regulating the including conductive composition, coated on a silicon substrate, drying and baking to process. 各工程について以下に説明する。 Each step will be described below.

(導電性組成物の調製) (Preparation of conductive composition)
導電性組成物の調製は次による。 Preparation of conductive composition shall be as follows. すなわち、( a)〜(c)成分と有機バインダー成分とをロールミル等従来公知の混合機を用いて、塗布工程に適した物性を有するペースト状になるように混合する。 That is, with a roll mill such as a conventional known mixer and (a) ~ (c) forming minute organic binder component are mixed so that the paste having physical properties suitable for the application process.

(導電性組成物の塗布及び乾燥) (Coating and drying of the conductive composition)
このようにして調製した導電性組成物をシリコン基板上に塗布し、乾燥する。 Thus a conductive composition prepared was applied to a silicon substrate, and dried. ここで、塗布方法としては、スクリーン印刷等太陽電池の製造において用いられる従来公知の方法によることができる。 Here, the coating method may be performed by a conventionally known method used in the production of screen printing such as solar cells. 次に、任意のパターン形状を印刷する。 Then, to print a desired pattern shape. パターンの形状は、任意の形状でよいが、例えば、平行線状、格子状であることが好ましく、ここで塗布された導電性ペーストは、次の焼成工程によって表面電極を形成する。 Shape of the pattern may be any shape, for example, parallel lines, is preferably a lattice pattern, wherein the applied conductive paste, to form a surface electrode by the following firing step. 導電性組成物の塗布後、電気乾燥機等従来公知の乾燥機を用いて乾燥する。 After application of the conductive composition is dried with an electric dryer or the like conventionally known dryer.

(焼成及び太陽電池の形成) (Firing and formation of the solar cell)
次に、電気炉等を用いて焼成する。 Then, they fired in an electric furnace or the like. 焼成は不活性ガス雰囲気下でも大気雰囲気下でもよい。 Firing may be an air atmosphere or an inert gas atmosphere. 焼成温度は、500℃〜800℃が好ましい。 The baking temperature is preferably 500 ° C. to 800 ° C.. かかる焼成工程により、電極を形成すると同時にIII族元素の酸化物及び/又はV族元素の酸化物がシリコン基板内に拡散し、添加した元素に応じてp型又はn型拡散層を形成する。 Such baking step, oxides of oxides and / or Group V element at the same time the group III element when forming the electrode is diffused into the silicon substrate to form a p-type or n-type diffusion layer in accordance with the added elements. この後電極に導線を取り付ける等常法により、太陽電池を形成する。 The equal conventional method of attaching the leads to the following electrode, forming a solar cell.

本発明について、以下の実施例により詳説する。 The present invention will be illustrated by the following examples. しかしながら、この実施例は本発明について例示するものであり、本発明の範囲を限定されるものではない。 However, this embodiment is intended to illustrate the invention and are not intended to be limiting the scope of the present invention.

参考例1) (Reference Example 1)
(1)バインダー溶液(エチルセルロース(10重量%濃度)ターピネオール溶液)の調製 フラスコに90質量部のターピネオールと10質量部のエチルセルロース(日進化成社製7CPS)を投入し、80℃で3時間撹拌した。 (1) Binder solution (ethyl cellulose (10 wt% concentration) terpineol solution) 90 parts by mass of terpineol and 10 parts by weight of ethyl cellulose to prepare flask (Nisshin Kasei Co., Ltd. 7 cps) was charged and stirred for 3 hours at 80 ° C. . この溶液をエチルセルロース(10質量%濃度)ターピネオール溶液とした。 The solution was ethyl cellulose (10 wt% concentration) terpineol solution.
(2)電極形成用導電性組成物の調製 0.3μm粒径のAg紛及びガラスフリットの総量に対して、0.50質量部のCuO(添加剤1)及び1.50質量部のチタンブラック12S(添加剤2)(三菱マテリアル社製)をメノウ鉢に入れすり潰した。 (2) relative to the total amount of Ag powder and a glass frit preparation 0.3μm particle size of the electrode formation conductive composition, 0.50 parts by weight of CuO (Additive 1) and 1.50 parts by weight of titanium black 12S (manufactured by Mitsubishi Materials Corporation) (additive 2) were ground into an agate bowl. さらに、87.48質量部の0.3μm粒径のAg紛、2.19質量部%のB −Bi −SiO 系ガラスフリット(旭硝子社製ASF−1100B)、上記(1)で調製した8.75質量部のエチルセルロース(10質量%濃度)ターピネオール溶液及び1.58質量部のターピネオールをメノウ鉢に加えて十分に混合した後、3本ロールを用いて分散し、ペースト状の導電性組成物とした。 Furthermore, Ag powder of 0.3μm grain size of 87.48 parts by weight, 2.19 parts by weight% of B 2 O 3 -Bi 2 O 3 -SiO 2 based glass frit (manufactured by Asahi Glass Company, ASF-1100B), the ( after mixing thoroughly terpineol ethyl cellulose (10 wt% concentration) terpineol solution of 8.75 parts by weight was prepared and 1.58 parts by mass in addition to the agate mortar in 1), and dispersed using a three roll paste It was Jo of the electrically conductive composition.
(3)太陽電池用電極の形成 上記導電性組成物をP−Type 6インチシリコン基板及びN−Type 6インチシリコン基板にスクリーン印刷機(MT2030型、ムラカミテクノ社製)を用いてそれぞれ印刷した。 (3) solar cell formed of an electrode the conductive composition P-Type 6 inch silicon substrate and N-Type 6 inch silicon substrate in a screen printing machine (MT2030 type, Murakami Techno Co., Ltd.) were respectively printed with. 印刷条件は、印圧が4.2kgf/cm 、スキージ速度が3.52cm/sec、スキージ硬度;70°であった。 Printing conditions, printing pressure is 4.2kgf / cm 2, squeegee speed 3.52cm / sec, squeegee hardness; was 70 °. 印刷後、乾燥機にて100℃で10分間乾燥し、大気雰囲気下で電気炉にてP−Type 6インチシリコン基板は500℃で30分、N−Type 6インチシリコン基板は700℃で30分それぞれ焼成した。 After printing, then dried for 10 minutes at 100 ° C. in a dryer for 30 minutes at P-Type 6 inch silicon substrate 500 ° C. in an electric furnace under air atmosphere, 30 minutes N-Type 6 inch silicon substrate 700 ° C. He was fired, respectively.

(実施例1 ,2 、参考例2〜 13 (Example 1, 2, Reference Example 2-13)
添加剤の種類及び添加量を表1に記載のとおりとした他は、参考例1と同様の手順により太陽電池用電極を形成した。 Except that were as is shown in Table 1 the type and amount of additives, to form an electrode for a solar cell by the same procedure as in Reference Example 1.

(比較例1) (Comparative Example 1)
87.48質量部の0.3μm粒径のAg紛、2.19質量部のB −Bi −SiO 系ガラスフリット(旭硝子社製ASF−1100B)、上記(1)で調製した8.75質量部のエチルセルロース(10質量%濃度)ターピネオール溶液及び1.58質量部のターピネオールをメノウ鉢に加えて十分に混合した後、3本ロールを用いて分散し、ペースト状の導電性組成物とした後、 参考例1と同様の手順により太陽電池用電極を形成した。 87.48 parts by weight of 0.3μm grain size of Ag powder, 2.19 parts by weight of B 2 O 3 -Bi 2 O 3 -SiO 2 based glass frit (manufactured by Asahi Glass Company, ASF-1100B), in the above (1) after mixing thoroughly terpineol prepared 8.75 parts by weight of ethyl cellulose (10 wt% concentration) terpineol solution and 1.58 parts by mass in addition to the agate mortar and dispersed using a three roll pasty conductive after the gender composition, to form an electrode for a solar cell by the same procedure as in reference example 1.
(比較例2〜3) (Comparative Example 2-3)
添加剤の種類及び添加量を表1に記載のとおりとした他は、 参考例1と同様の手順により太陽電池用電極を形成した。 Except that were as is shown in Table 1 the type and amount of additives, to form an electrode for a solar cell by the same procedure as in Reference Example 1.

(評価) (Evaluation)
このようにして形成した太陽電池用電極の電極間の抵抗値をテスター(アナログマルチテスター EM7000 、三和電気計器社製)を用いて測定した。 Thus the resistance between the electrodes of the formed solar cell electrode tester (analog Multitester EM7000, Sanwa Electric Instrument Co., Ltd.) was used. 結果は表1の通りである。 The results are shown in Table 1.

金属酸化物及び/又は金属窒化物を添加した導電性組成物を用いた場合の電極間抵抗値は、このような金属酸化物及び/又は金属窒化物を添加しなかった比較例1の値と比較したところ、いずれも低く抑えられた(実施例1 ,2 、参考例1〜 13 )。 The inter-electrode resistance value in the case of using a metal oxide and / or metal nitride conductive composition added with the value of Comparative Example 1 was not added such metal oxides and / or metal nitride were compared, both were kept low (example 1, 2, reference example 1 to 13). また、更に低次酸化物又は低次窒化物を添加した例では電極間抵抗値が減少した(参考例1 〜3対参考例 、参考例対参考例 )。 Also, the interelectrode resistance value is decreased by further example of adding a low-order oxide or low-order nitride (Ref Reference Example 1-3 vs. Example 7, Example 4 vs. Example 9). したがって、本願記載の電極形成用導電性組成物は、抵抗の小さい太陽電池用電極を形成できることがわかった。 Therefore, electrode formation conductive composition described in the present, it has been found capable of forming a small solar cell electrode resistance.
一方、比較例2〜3の結果から明らかな通り、Mn酸化物、及び低次酸化物のCu Oを添加した場合には、本発明のもとめる効果が得られないことがわかった。 On the other hand, as is clear from the results of Comparative Example 2 to 3, Mn oxides, and in the case of adding Cu 2 O of low order oxides have been found to seek the effect of the present invention can not be obtained.

Claims (4)

  1. p型又はn型のシリコン基板上に塗布、乾燥及び焼成して電極を形成するために用いられる電極形成用導電性組成物であって、 p-type or applied to n-type silicon substrate, an electrode formation conductive composition used to form the dried and calcined to electrodes,
    (a)導電性粉末、(b)ガラスフリット及び(c)金属窒化物を含み、前記(b)成分が 及びBi を含み、前記(c)成分がAlN及びSi から選ばれる少なくとも1種である、電極形成用導電性組成物。 (A) conductive powder, (b) comprises a glass frit and (c) a metal nitride, wherein component (b) comprises B 2 O 3 and Bi 2 O 3, wherein the component (c) is AlN and Si 3 it is at least one selected from N 4, electrode formation conductive composition.
  2. 前記(c)成分が前記(a)成分と(b)成分との合計質量に対して0.1質量%〜10質量%含まれる、請求項1に記載の電極形成用導電性組成物。 Wherein component (c) is contained in an amount of 0.1 wt% to 10 wt% based on the total weight of the component (a) and component (b), the electrode formation conductive composition of claim 1.
  3. 更に有機バインダーを含む、請求項1又は2に記載の電極形成用導電性組成物。 Further comprising an organic binder, according to claim 1 or electrode formation conductive composition according to 2.
  4. 請求項1〜3のいずれか1項に記載の電極形成用導電性組成物をp型又はn型のシリコン基板上に塗布、乾燥及び焼成する工程を含む太陽電池の製造方法。 Applying an electrode forming a conductive composition according to any one of claims 1 to 3 p-type or n-type silicon substrate, method of manufacturing a solar cell comprising a step of drying and firing.
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TWI488222B (en) * 2010-04-23 2015-06-11 Hitachi Chemical Co Ltd Composition for forming p-type diffusion layer, method for forming p-type diffusion layer, and method for producing photovoltaic cell element
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JP5693265B2 (en) * 2010-07-07 2015-04-01 ナミックス株式会社 Solar cell and electrode-forming conductive paste
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US20150099352A1 (en) * 2011-07-19 2015-04-09 Hitachi Chemical Company, Ltd. COMPOSITION FOR FORMING n-TYPE DIFFUSION LAYER, METHOD OF PRODUCING n-TYPE DIFFUSION LAYER, AND METHOD OF PRODUCING PHOTOVOLTAIC CELL ELEMENT
WO2013015284A1 (en) * 2011-07-25 2013-01-31 日立化成工業株式会社 Semiconductor substrate, manufacturing method therefor, solar-cell element, and solar cell
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JP2015179866A (en) * 2015-05-25 2015-10-08 日立化成株式会社 P-type diffusion layer formation composition, and solar cell and method for manufacturing the same
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JP2016021589A (en) * 2015-09-14 2016-02-04 日立化成株式会社 P-type diffusion layer forming composition, method for manufacturing p-type diffusion layer, and method for manufacturing solar cell element

Family Cites Families (3)

* Cited by examiner, † Cited by third party
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JPH0558646B2 (en) * 1987-09-19 1993-08-27 Taiyo Yuden Kk
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