TW201530791A - Composition for forming n-type diffusion layer, method for producing n-type diffusion layer and method for producing photovoltaic cell - Google Patents

Composition for forming n-type diffusion layer, method for producing n-type diffusion layer and method for producing photovoltaic cell Download PDF

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TW201530791A
TW201530791A TW104113908A TW104113908A TW201530791A TW 201530791 A TW201530791 A TW 201530791A TW 104113908 A TW104113908 A TW 104113908A TW 104113908 A TW104113908 A TW 104113908A TW 201530791 A TW201530791 A TW 201530791A
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diffusion layer
type diffusion
forming composition
glass
ether
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Yoichi Machii
Masato Yoshida
Takeshi Nojiri
Kaoru Okaniwa
Mitsunori Iwamuro
Shuichiro Adachi
Tetsuya Sato
Keiko Kizawa
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Hitachi Chemical Co Ltd
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    • 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/22—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities
    • H01L21/2225—Diffusion sources
    • H—ELECTRICITY
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    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/22—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities
    • H01L21/225—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities using diffusion into or out of a solid from or into a solid phase, e.g. a doped oxide layer
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
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    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/22—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities
    • H01L21/225—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities using diffusion into or out of a solid from or into a solid phase, e.g. a doped oxide layer
    • H01L21/2251—Diffusion into or out of group IV semiconductors
    • H01L21/2254—Diffusion into or out of group IV semiconductors from or through or into an applied layer, e.g. photoresist, nitrides
    • H01L21/2255—Diffusion into or out of group IV semiconductors from or through or into an applied layer, e.g. photoresist, nitrides the applied layer comprising oxides only, e.g. P2O5, PSG, H3BO3, doped oxides
    • H—ELECTRICITY
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    • 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
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    • 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
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    • 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
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic System
    • 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
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    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/547—Monocrystalline silicon PV 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
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    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

A composition for forming an n-type diffusion layer; the composition including: a dispersion medium and a glass powder. The glass powder contains P2O5 and at least one selected from the group consisting of ZrO2, Al2O3, TiO2, ZnO, MgO, CaO, SrO and BaO.

Description

n型擴散層形成組成物、n型擴散層的製造方法及太 陽電池單元的製造方法 Method for producing n-type diffusion layer forming composition, n-type diffusion layer, and Positive battery unit manufacturing method

本發明是有關於一種n型擴散層形成組成物、n型擴散層的製造方法及太陽電池單元的製造方法，更詳細而言，本發明是有關於一種可於作為半導體基板的矽基板的特定的部分形成n型擴散層的技術。 The present invention relates to an n-type diffusion layer forming composition, a method of manufacturing an n-type diffusion layer, and a method of manufacturing a solar cell. More specifically, the present invention relates to a specific substrate which can be used as a semiconductor substrate. The part forms a technique of an n-type diffusion layer.

對先前的矽太陽電池單元的製造步驟進行說明。 The manufacturing steps of the prior 矽 solar cell unit will be described.

首先，為了促進光學侷限效應來謀求高效率化，準備形成有紋理構造的p型矽基板，繼而於***(POCl3)、氮氣及氧氣的混合氣體環境下以800℃~900℃進行幾十分鐘的處理，而同樣地形成n型擴散層。於該先前的方法中，因使用混合氣體進行磷的擴散，故不僅於表面形成n型擴散層，而且於側面、背面亦形成n型擴散層。因此，需要用以去除側面的n型擴散層的側蝕步驟。另外，背面的n型擴散層必需轉換成p+型擴散層。因此，於 背面的n型擴散層上賦予含有作為第13族元素的鋁的鋁膏後，進行熱處理，藉由鋁的擴散而自n型擴散層轉換成p+型擴散層，同時獲得歐姆接觸。 First, in order to promote the optical confinement effect and to achieve high efficiency, a p-type germanium substrate having a textured structure is prepared, and then subjected to a mixed gas atmosphere of phosphorus oxychloride (POCl 3 ), nitrogen, and oxygen at 800 ° C to 900 ° C. The treatment of several tens of minutes is performed similarly to form an n-type diffusion layer. In this prior method, since phosphorus is diffused by using a mixed gas, an n-type diffusion layer is formed not only on the surface but also on the side surface and the back surface. Therefore, a side etching step for removing the side n-type diffusion layer is required. In addition, the n-type diffusion layer on the back side must be converted into a p + -type diffusion layer. Therefore, after the aluminum paste containing aluminum as the Group 13 element is applied to the n-type diffusion layer on the back surface, heat treatment is performed, and the n-type diffusion layer is converted into the p + -type diffusion layer by diffusion of aluminum, and ohmic contact is obtained at the same time. .

另一方面，於半導體的製造領域中，提出有藉由塗佈含有五氧化二磷(P2O5)或磷酸二氫銨(NH4H2PO4)等磷酸鹽的溶液來形成n型擴散層的方法(例如，參照日本專利特開2002-75894號公報)。但是，因於該方法中使用溶液，故與使用上述混合氣體的氣相反應法相同，磷的擴散亦到達側面及背面，不僅於表面形成n型擴散層，而且於側面、背面亦形成n型擴散層。 On the other hand, in the field of semiconductor manufacturing, it has been proposed to form an n-type by applying a solution containing a phosphate such as phosphorus pentoxide (P 2 O 5 ) or ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ). A method of diffusing a layer (for example, refer to Japanese Laid-Open Patent Publication No. 2002-75894). However, since the solution is used in the method, the diffusion of phosphorus reaches the side surface and the back surface in the same manner as the gas phase reaction method using the mixed gas described above, and not only an n-type diffusion layer is formed on the surface but also an n-type is formed on the side surface and the back surface. Diffusion layer.

如上所述，當形成n型擴散層時，於使用***的氣相反應中，不僅於原本需要n型擴散層的一面(通常為受光面、表面)形成n型擴散層，而且於另一面(非受光面、背面)或側面亦形成n型擴散層。另外，於塗佈含有磷酸鹽的溶液並進行熱擴散的方法中，與氣相反應法相同，在表面以外亦形成n型擴散層。因此，元件具有pn接合構造，故必需於側面進行蝕刻，於背面將n型擴散層轉換成p型擴散層。通常，於背面塗佈作為第13族元素的鋁的膏，並進行煅燒，從而將n型擴散層轉換成p型擴散層。 As described above, when the n-type diffusion layer is formed, in the gas phase reaction using phosphorus oxychloride, an n-type diffusion layer is formed not only on the side (usually the light-receiving surface or the surface) where the n-type diffusion layer is originally required, but also An n-type diffusion layer is also formed on the other side (non-light-receiving surface, back surface) or side surface. Further, in the method of applying a solution containing a phosphate and performing thermal diffusion, an n-type diffusion layer is formed on the surface other than the gas phase reaction method. Therefore, since the element has a pn junction structure, it is necessary to perform etching on the side surface and convert the n-type diffusion layer into a p-type diffusion layer on the back surface. Usually, a paste of aluminum as a Group 13 element is coated on the back surface and calcined to convert the n-type diffusion layer into a p-type diffusion layer.

本發明是鑒於以上的先前的問題點而完成的發明，其課題在於提供一種於使用結晶矽基板的太陽電池單元的製造步驟 中，可不形成不需要的n型擴散層而於特定的部分形成n型擴散層的n型擴散層形成組成物、n型擴散層形成組成物的製造方法、n型擴散層的製造方法及太陽電池單元的製造方法。 The present invention has been made in view of the above problems, and an object of the invention is to provide a manufacturing step of a solar cell using a crystalline germanium substrate. An n-type diffusion layer forming composition for forming an n-type diffusion layer in a specific portion without forming an unnecessary n-type diffusion layer, a method for producing an n-type diffusion layer forming composition, a method for producing an n-type diffusion layer, and a sun A method of manufacturing a battery unit.

解決上述課題的方法如下所述。 The method for solving the above problems is as follows.

<1>一種n型擴散層形成組成物，包括：分散媒；以及玻璃粉末，所述玻璃粉末含有選自ZrO2、Al2O3、TiO2、ZnO、MgO、CaO、SrO及BaO中的至少1種及P2O5。 <1> An n-type diffusion layer forming composition comprising: a dispersing medium; and a glass powder containing a material selected from the group consisting of ZrO 2 , Al 2 O 3 , TiO 2 , ZnO, MgO, CaO, SrO, and BaO At least one species and P 2 O 5 .

<2>如上述<1>所述之n型擴散層形成組成物，其中上述玻璃粉末含有30質量%~90質量%的P2O5。 <2> The n-type diffusion layer forming composition according to the above <1>, wherein the glass powder contains 30% by mass to 90% by mass of P 2 O 5 .

<3>如上述<1>或<2>所述之n型擴散層形成組成物，其中上述玻璃粉末的體積平均粒徑為100μm以下。 <3> The n-type diffusion layer forming composition according to the above <1>, wherein the glass powder has a volume average particle diameter of 100 μm or less.

<4>一種n型擴散層的製造方法，包括：塗佈如上述<1>~<3>中任一項所述之n型擴散層形成組成物的步驟；以及實施熱擴散處理的步驟。 <4> A method for producing an n-type diffusion layer, comprising: a step of applying the n-type diffusion layer forming composition according to any one of the above <1> to <3>; and a step of performing a thermal diffusion treatment.

<5>一種太陽電池單元的製造方法，包括：於半導體基板上塗佈如上述<1>~<3>中任一項所述之n型擴散層形成組成物的步驟；以及實施熱擴散處理來形成n型擴散層的步驟。 (5) A method of producing a solar cell according to any one of the above <1> to <3>, wherein the step of forming the composition of the n-type diffusion layer according to any one of the above <1> to <3>; and performing thermal diffusion treatment The step of forming an n-type diffusion layer.

根據本發明，可提供一種於使用結晶矽基板的太陽電池單元的製造步驟中，可不形成不需要的n型擴散層而於特定的部分形成n型擴散層的n型擴散層形成組成物。另外，可提供一種使用該n型擴散層形成組成物的n型擴散層的製造方法、及太陽 電池單元的製造方法。 According to the present invention, it is possible to provide an n-type diffusion layer forming composition in which an n-type diffusion layer is formed in a specific portion without forming an unnecessary n-type diffusion layer in a manufacturing step of a solar cell using a crystalline germanium substrate. In addition, a method for producing an n-type diffusion layer using the n-type diffusion layer to form a composition, and a solar A method of manufacturing a battery unit.

10‧‧‧p型半導體基板 10‧‧‧p type semiconductor substrate

11‧‧‧n型擴散層形成組成物層 11‧‧‧n type diffusion layer forming composition layer

12‧‧‧n型擴散層 12‧‧‧n type diffusion layer

13‧‧‧組成物 13‧‧‧Composition

14‧‧‧高濃度電場層 14‧‧‧High concentration electric field layer

16‧‧‧抗反射膜 16‧‧‧Anti-reflective film

18‧‧‧表面電極 18‧‧‧ surface electrode

20‧‧‧背面電極 20‧‧‧Back electrode

30‧‧‧匯流條電極 30‧‧‧Bus Bar Electrode

32‧‧‧指狀電極 32‧‧‧ finger electrode

圖1(1)~圖1(6)是概念性地表示本發明的太陽電池單元的製造步驟的一例的剖面圖。 1(1) to 1(6) are cross-sectional views conceptually showing an example of a manufacturing procedure of a solar battery cell of the present invention.

圖2A是自表面所觀察到的太陽電池單元的俯視圖。 2A is a top plan view of a solar cell unit as viewed from the surface.

圖2B是將圖2A的一部分放大表示的立體圖。 Fig. 2B is a perspective view showing a part of Fig. 2A in an enlarged manner.

首先，對本發明的n型擴散層形成組成物進行說明，其次對使用n型擴散層形成組成物的n型擴散層及太陽電池單元的製造方法進行說明。 First, the n-type diffusion layer forming composition of the present invention will be described. Next, an n-type diffusion layer using a n-type diffusion layer forming composition and a method for producing a solar cell will be described.

再者，於本說明書中，「步驟」這一用語不僅是指獨立的步驟，當無法與其他步驟明確地加以區分時，只要達成該步驟的預期的作用，則亦包含於本用語中。 Furthermore, in the present specification, the term "step" means not only an independent step, but also cannot be clearly distinguished from other steps, and is included in the term as long as the intended effect of the step is achieved.

另外，於本說明書中，使用「~」所示的數值範圍表示分別包括其前後所記載的數值作為最小值及最大值的範圍。 Further, in the present specification, the numerical range indicated by "~" indicates a range including the numerical values described before and after the minimum value and the maximum value.

進而，組成物中的各成分的量在組成物中存在多個相當於各成分的物質的情況下，只要事先無特別說明，則表示組成物中所存在的該多個物質的合計量。 Further, when the amount of each component in the composition is such that a plurality of substances corresponding to the respective components are present in the composition, unless otherwise specified, the total amount of the plurality of substances present in the composition is indicated.

[n型擴散層形成組成物] [n-type diffusion layer forming composition]

本發明的n型擴散層形成組成物含有玻璃粉末與分散媒，進而考慮塗佈性等，亦可視需要而含有其他添加劑。另外，上述玻璃粉末含有作為磷成分的P2O5來作為含施體元素的物質，且含有選自ZrO2、Al2O3、TiO2、ZnO、MgO、CaO及BaO中的至少1種來作為玻璃成分物質。 The n-type diffusion layer forming composition of the present invention contains a glass powder and a dispersion medium, and further contains other additives as needed in consideration of coatability and the like. Further, the glass powder contains P 2 O 5 as a phosphorus component as a substance containing a donor element, and contains at least one selected from the group consisting of ZrO 2 , Al 2 O 3 , TiO 2 , ZnO, MgO, CaO, and BaO. Come as a glass component.

此處，所謂n型擴散層形成組成物，是指含有施體元素，且可藉由塗佈於矽基板上後使該施體元素熱擴散來形成n型擴散層的材料，本發明中使用P(磷)作為施體元素。而且，藉由使用本發明的n型擴散層形成組成物，僅於所期望的部位形成n型擴散層，而不於背面或側面形成不需要的n型擴散層。 Here, the n-type diffusion layer forming composition refers to a material containing a donor element and which can be thermally diffused by applying the donor element to the germanium substrate to form an n-type diffusion layer. In the present invention, P is used. (Phosphorus) as a donor element. Further, by using the n-type diffusion layer of the present invention to form a composition, an n-type diffusion layer is formed only at a desired portion, and an unnecessary n-type diffusion layer is not formed on the back surface or the side surface.

因此，若應用本發明的n型擴散層形成組成物，則不需要先前廣泛採用的氣相反應法中所必需的側蝕步驟，從而使步驟簡單化。另外，亦不需要於背面將n型擴散層轉換成p+型擴散層的步驟。因此，背面的p+型擴散層的形成方法，或者背面電極的材質、形狀及厚度並無限制，所應用的製造方法或材質、形狀的選擇項擴大。另外，由背面電極的厚度所引起的矽基板內的內應力的產生得到抑制，矽基板的翹曲亦得到抑制，詳細情況將後述。 Therefore, if the n-type diffusion layer of the present invention is used to form a composition, the side etching step necessary in the gas phase reaction method which has been widely used previously is not required, so that the steps are simplified. In addition, there is no need to convert the n-type diffusion layer to the p + -type diffusion layer on the back side. Therefore, the method of forming the p + -type diffusion layer on the back surface or the material, shape, and thickness of the back surface electrode is not limited, and the selection method of the applied manufacturing method, material, and shape is expanded. In addition, generation of internal stress in the crucible substrate due to the thickness of the back surface electrode is suppressed, and warpage of the crucible substrate is also suppressed, and details will be described later.

再者，藉由煅燒而使本發明的n型擴散層形成組成物中所含有的玻璃粉末熔融，從而於n型擴散層上形成玻璃層。但是，於先前的氣相反應法或塗佈含有磷酸鹽的溶液的方法中，亦於n型擴散層上形成玻璃層，因此本發明中所生成的玻璃層可與先前的方法同樣地藉由蝕刻來去除。因此，即便與先前的方法相比， 本發明的n型擴散層形成組成物亦不產生不需要的產物，亦不增加步驟。 Further, the glass powder contained in the n-type diffusion layer forming composition of the present invention is melted by calcination to form a glass layer on the n-type diffusion layer. However, in the prior gas phase reaction method or the method of coating a solution containing a phosphate, a glass layer is also formed on the n-type diffusion layer, so that the glass layer produced in the present invention can be similarly used in the prior art. Etching to remove. Therefore, even compared to the previous method, The n-type diffusion layer forming composition of the present invention also does not produce an undesired product, nor does it add steps.

另外，玻璃粉末與含有磷酸鹽的溶液不同，即便於煅燒過程中，施體元素的揮發亦得到抑制，因此防止n型擴散層因含有施體元素的揮發氣體的產生而不僅形成於表面，亦形成至背面或側面的情況。其原因可認為如下：由於施體成分與玻璃粉末中的元素結合、或者被導入至玻璃中，因此難以揮發。 Further, unlike the phosphate-containing solution, the glass powder is suppressed from volatilization during the calcination process, thereby preventing the n-type diffusion layer from being formed not only on the surface but also on the surface due to the generation of the volatile gas containing the donor element. Formed to the back or side. The reason for this is considered to be that it is difficult to volatilize because the donor component is combined with an element in the glass powder or introduced into the glass.

進而，於本發明的n型擴散層形成組成物中，如上所述，使用P2O5作為含施體元素的物質，且使用選自ZrO2、Al2O3、TiO2、ZnO、MgO、CaO、SrO及BaO中的至少1種作為玻璃成分物質。藉此，與上述不使用玻璃成分物質的情況相比，形成n型擴散層時的位置選擇性提昇。 Further, in the n-type diffusion layer forming composition of the present invention, as described above, P 2 O 5 is used as a substance containing a donor element, and a material selected from ZrO 2 , Al 2 O 3 , TiO 2 , ZnO, MgO is used. At least one of CaO, SrO, and BaO is used as a glass component. Thereby, the positional selectivity in forming the n-type diffusion layer is improved as compared with the case where the glass component is not used.

具體而言，可認為：因氧化磷對於水的溶解度大，故若n型擴散層形成組成物中所含有的玻璃粉末吸濕，則氧化磷與水進行反應而生成磷酸。而且，若使用含有磷酸的n型擴散層形成組成物來形成n型擴散層，則存在如下的情況：磷酸因加熱而蒸發，所蒸發的磷酸附著於基板的背面等未塗佈n型擴散層形成組成物的部位，而形成不需要的n型擴散層。 Specifically, it is considered that phosphorus oxide has a large solubility in water. Therefore, when the glass powder contained in the n-type diffusion layer forming composition absorbs moisture, phosphorus oxide reacts with water to form phosphoric acid. Further, when an n-type diffusion layer is formed by using an n-type diffusion layer containing phosphoric acid to form a composition, there is a case where phosphoric acid is evaporated by heating, and the evaporated phosphoric acid adheres to an uncoated n-type diffusion layer such as a back surface of the substrate. A portion of the composition is formed to form an unnecessary n-type diffusion layer.

可認為：藉由使用選自ZrO2、Al2O3、TiO2、ZnO、MgO、CaO、SrO及BaO中的至少1種作為玻璃成分物質，n型擴散層形成組成物的耐水性會提昇，因此由玻璃粉末的吸濕所引起的不需要的n型擴散層的形成會得到抑制。 It is considered that by using at least one selected from the group consisting of ZrO 2 , Al 2 O 3 , TiO 2 , ZnO, MgO, CaO, SrO, and BaO as the glass component substance, the water resistance of the n-type diffusion layer forming composition is improved. Therefore, formation of an unnecessary n-type diffusion layer caused by moisture absorption of the glass powder is suppressed.

即，上述本發明的n型擴散層形成組成物為上述構成，因此即便於例如在高溫高濕環境下保存後形成n型擴散層，因耐水性高，故亦根據特定的部分而選擇性地形成n型擴散層。 In other words, since the n-type diffusion layer forming composition of the present invention has the above-described configuration, even if the n-type diffusion layer is formed after storage in a high-temperature and high-humidity environment, for example, since the water resistance is high, it is selectively selected according to a specific portion. An n-type diffusion layer is formed.

以下，有時將ZrO2、Al2O3、TiO2、ZnO、MgO、CaO、SrO及BaO總稱為「耐水性提昇玻璃成分物質」。 Hereinafter, ZrO 2 , Al 2 O 3 , TiO 2 , ZnO, MgO, CaO, SrO, and BaO may be collectively referred to as “water resistance-enhancing glass component substance”.

<玻璃粉末> <Glass Powder>

對本發明的玻璃粉末進行詳細說明。 The glass powder of the present invention will be described in detail.

如上所述，本發明的玻璃粉末含有作為磷成分的P2O5來作為含施體元素的物質，且含有上述耐水性提昇玻璃成分物質的至少1種來作為玻璃成分物質。 As described above, the glass powder of the present invention contains P 2 O 5 as a phosphorus component as a material containing a donor element, and contains at least one of the above-described water-resistant lifting glass component materials as a glass component.

作為含施體元素的物質的P2O5中所含有的P(磷)是可藉由摻雜於矽基板中而形成n型擴散層的元素(施體元素)的一種，且為施體元素之中就安全性、玻璃化的容易性等的觀點而言較佳的元素。 P (phosphorus) contained in P 2 O 5 as a substance containing a donor element is one of elements (donor elements) which can be formed by doping into a ruthenium substrate to form an n-type diffusion layer, and is a donor body Among the elements, an element which is preferable from the viewpoints of safety, easiness of vitrification, and the like.

作為玻璃成分物質，使用上述耐水性提昇玻璃成分物質的至少1種。亦可使用2種以上的耐水性提昇玻璃成分物質。 As the glass component, at least one of the above-described water resistance-improving glass component materials is used. It is also possible to use two or more kinds of water resistance-improving glass component substances.

另外，除耐水性提昇玻璃成分物質以外，亦可併用耐水性提昇玻璃成分物質以外的玻璃成分物質(以下，有時稱為「其他玻璃成分物質」)。藉由併用耐水性提昇玻璃成分物質與其他玻璃成分物質，可控制耐水性、熔融溫度、軟化點、玻璃轉移點、化學耐久性等。 In addition to the water resistance-enhancing glass component, a glass component other than the glass component (hereinafter sometimes referred to as "other glass component") may be used in combination with water resistance. Water resistance, melting temperature, softening point, glass transition point, chemical durability, and the like can be controlled by using a water-repellent glass component and other glass component materials together.

作為其他玻璃成分物質，例如可列舉：SiO2、K2O、Na2O、 Li2O、BeO、PbO、CdO、SnO、MoO3、La2O3、Nb2O5、Ta2O5、Y2O3、GeO2、TeO2及Lu2O3等。 Examples of other glass component substances include SiO 2 , K 2 O, Na 2 O, Li 2 O, BeO, PbO, CdO, SnO, MoO 3 , La 2 O 3 , Nb 2 O 5 , and Ta 2 O 5 . , Y 2 O 3 , GeO 2 , TeO 2 and Lu 2 O 3 , and the like.

上述其他玻璃成分物質之中，就耐水性的觀點而言，更佳為SiO2、Y2O3、Nb2O5及La2O3。 Among the other glass component materials, SiO 2 , Y 2 O 3 , Nb 2 O 5 and La 2 O 3 are more preferable from the viewpoint of water resistance.

另一方面，關於上述其他玻璃成分物質之中，有可能引起耐水性下降的Na2O、K2O及Li2O，就耐水性的觀點而言，較佳為玻璃粉末整體的5質量%以下，更佳為不含Na2O、K2O及Li2O。 On the other hand, among the other glass component materials, Na 2 O, K 2 O, and Li 2 O, which may cause a decrease in water resistance, are preferably 5 mass% of the entire glass powder from the viewpoint of water resistance. Hereinafter, it is more preferable that Na 2 O, K 2 O, and Li 2 O are not contained.

上述玻璃粉末中，P2O5的含有比率較佳為30質量%~90質量%，更佳為35質量%~85質量%。 The content ratio of P 2 O 5 in the glass powder is preferably 30% by mass to 90% by mass, and more preferably 35% by mass to 85% by mass.

作為玻璃粉末的具體例，例如可列舉：P2O5-ZrO2系玻璃、P2O5-Al2O3系玻璃、P2O5-TiO2系玻璃、P2O5-ZnO系玻璃、P2O5-MgO系玻璃、P2O5-CaO系玻璃、P2O5-BaO系玻璃、P2O3-SrO系玻璃。 Specific examples of the glass powder include P 2 O 5 -ZrO 2 -based glass, P 2 O 5 -Al 2 O 3 -based glass, P 2 O 5 -TiO 2 -based glass, and P 2 O 5 -ZnO-based system. Glass, P 2 O 5 -MgO-based glass, P 2 O 5 -CaO-based glass, P 2 O 5 -BaO-based glass, or P 2 O 3 -SrO-based glass.

於上述中例示了包含2種成分的複合玻璃，但視需要亦可為P2O5-Al2O3-ZnO、P2O5-CaO-SiO2等3種成分以上的複合玻璃。 In the above, a composite glass containing two components is exemplified, but a composite glass of three or more components such as P 2 O 5 —Al 2 O 3 —ZnO and P 2 O 5 —CaO—SiO 2 may be used as necessary.

玻璃粉末中的玻璃成分物質(即，耐水性提昇玻璃成分物質及其他玻璃成分物質)的含有比率較理想的是考慮耐水性、熔融溫度、軟化點、玻璃轉移點、化學耐久性而適宜設定，通常較佳為0.1質量%以上、95質量%以下，更佳為0.5質量%以上、90質量%以下。 The content ratio of the glass component (that is, the water-resistant glass component and the other glass component) in the glass powder is preferably set in consideration of water resistance, melting temperature, softening point, glass transition point, and chemical durability. It is usually preferably 0.1% by mass or more and 95% by mass or less, more preferably 0.5% by mass or more and 90% by mass or less.

另外，玻璃粉末中的耐水性提昇玻璃成分物質的含有比率就耐水性的觀點而言，較佳為1質量%以上、50質量%以下，更佳為 5質量%以上、40質量%以下，進而更佳為5質量%以上、30質量%以下。 In addition, the content ratio of the water resistance-improving glass component in the glass powder is preferably 1% by mass or more and 50% by mass or less, more preferably from the viewpoint of water resistance. 5 mass% or more and 40 mass% or less, and more preferably 5 mass% or more and 30 mass% or less.

進而，耐水性提昇玻璃成分物質的含量就耐水性的觀點而言，較佳為含施體元素的物質的含量的0.05倍以上、2倍以下，更佳為0.1倍以上、1倍以下。 Furthermore, the content of the water-resistant glass component is preferably 0.05 times or more and 2 times or less, more preferably 0.1 times or more and 1 or less times the content of the substance containing the donor element from the viewpoint of water resistance.

具體而言，例如於P2O5-CaO系玻璃的情況下，CaO的含有比率較佳為1質量%以上、50質量%以下，更佳為5質量%以上、30質量%以下。 Specifically, for example, in the case of P 2 O 5 —CaO-based glass, the content ratio of CaO is preferably 1% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 30% by mass or less.

玻璃粉末的軟化點就擴散處理時的擴散性、滴液的觀點而言，較佳為200℃~1000℃，更佳為300℃~900℃。 The softening point of the glass powder is preferably from 200 ° C to 1000 ° C, more preferably from 300 ° C to 900 ° C, from the viewpoint of diffusibility at the time of diffusion treatment and dripping.

玻璃粉末的體積平均粒徑較理想的是100μm以下。當使用具有100μm以下的粒徑的玻璃粉末時，容易獲得平滑的塗膜。進而，玻璃粉末的粒徑更理想的是50μm以下。更佳為10μm以下。玻璃粉末的體積平均粒徑的下限值並無特別限定，但若鑒於塗佈的分散性、或玻璃粉末的製造成本，則較佳為0.01μm以上，更佳為0.1μm以上，進而更佳為0.5μm以上。 The volume average particle diameter of the glass powder is desirably 100 μm or less. When a glass powder having a particle diameter of 100 μm or less is used, a smooth coating film is easily obtained. Further, the particle diameter of the glass powder is more preferably 50 μm or less. More preferably, it is 10 μm or less. The lower limit of the volume average particle diameter of the glass powder is not particularly limited, and is preferably 0.01 μm or more, more preferably 0.1 μm or more, and further preferably in view of the dispersibility of the coating or the production cost of the glass powder. It is 0.5 μm or more.

此處，上述玻璃粉末的頻度分布是例如使用粒度分布測定裝置(Beckmancoulter股份有限公司製造，型號：LS13320)作為測定裝置，對使玻璃粉末分散於溶劑(例如水)中而成的分散液進行測定而獲得。 Here, the frequency distribution of the glass powder is, for example, a particle size distribution measuring apparatus (manufactured by Beckman Coulter Co., Ltd., model: LS13320) as a measuring device, and the dispersion liquid obtained by dispersing the glass powder in a solvent (for example, water) is measured. And get.

作為玻璃粉末的形狀，可列舉大致球狀、扁平狀、塊狀、板狀、及鱗片狀等，就製成n型擴散層形成組成物時的對於基板 的塗佈性或均勻擴散性的觀點而言，較理想的是大致球狀、扁平狀或板狀。 Examples of the shape of the glass powder include a substantially spherical shape, a flat shape, a block shape, a plate shape, and a scale shape, and the substrate is formed by forming an n-type diffusion layer. From the viewpoint of coatability or uniform diffusibility, it is preferably substantially spherical, flat or plate-like.

玻璃粉末是藉由以下的程序來製作。 The glass powder was produced by the following procedure.

首先，稱量原料(例如上述含施體元素的物質與玻璃成分物質)，然後填充至坩堝中。坩堝的材質可列舉鉑、鉑-銠、銥、氧化鋁、石英、碳等，可考慮熔融溫度、環境、與熔融物質的反應性等而適宜選擇。 First, a raw material (for example, the above-mentioned substance containing a donor element and a glass component substance) is weighed and then filled into a crucible. Examples of the material of the crucible include platinum, platinum-rhodium, iridium, aluminum oxide, quartz, carbon, and the like, and are appropriately selected in consideration of the melting temperature, the environment, and the reactivity with the molten material.

其次，藉由電爐以對應於玻璃組成的溫度進行加熱而製成熔液。此時，較理想的是以使熔液變得均勻的方式進行攪拌。 Next, a molten metal is prepared by heating in an electric furnace at a temperature corresponding to the composition of the glass. At this time, it is preferable to stir so that the melt becomes uniform.

繼而，使已變得均勻的熔液流出至氧化鋯基板或碳基板等上而將熔液玻璃化。 Then, the melt which has become uniform flows out onto a zirconia substrate, a carbon substrate or the like to vitrify the melt.

最後，粉碎玻璃而形成粉末狀。粉碎可應用噴射磨機、珠磨機、球磨機等公知的方法。 Finally, the glass is pulverized to form a powder. A known method such as a jet mill, a bead mill, or a ball mill can be applied to the pulverization.

n型擴散層形成組成物中的玻璃粉末的含有比率是考慮塗佈性、施體元素的擴散性等而決定。通常，n型擴散層形成組成物中的玻璃粉末的含有比率較佳為0.1質量%以上、95質量%以下，更佳為1質量%以上、90質量%以下，進而更佳為5質量%以上、80質量%以下。 The content ratio of the glass powder in the n-type diffusion layer forming composition is determined in consideration of coatability, diffusibility of the donor element, and the like. In general, the content ratio of the glass powder in the n-type diffusion layer forming composition is preferably 0.1% by mass or more and 95% by mass or less, more preferably 1% by mass or more, 90% by mass or less, and still more preferably 5% by mass or more. 80% by mass or less.

<分散媒> <Dispersion media>

其次，對分散媒進行說明。 Next, the dispersing medium will be described.

所謂分散媒，是指於組成物中使上述玻璃粉末分散的介質。具體而言，採用黏合劑或溶劑等作為分散媒。 The dispersion medium refers to a medium in which the glass powder is dispersed in the composition. Specifically, a binder, a solvent, or the like is used as a dispersion medium.

作為黏合劑，例如可適宜選擇：(甲基)丙烯酸二甲基胺基乙酯聚合物、聚乙烯醇、聚丙烯醯胺類、聚乙烯醯胺類、聚乙烯吡咯啶酮、聚(甲基)丙烯酸類、聚環氧乙烷類、聚磺酸、丙烯醯胺烷基磺酸、纖維素醚類、纖維素衍生物、羧甲基纖維素、羥乙基纖維素、乙基纖維素、明膠、澱粉及澱粉衍生物、海藻酸鈉類、三仙膠、瓜爾膠及瓜爾膠衍生物、硬葡聚糖及硬葡聚糖衍生物、黃蓍膠及黃蓍膠衍生物、糊精及糊精衍生物、丙烯酸樹脂、丙烯酸酯樹脂、丁二烯樹脂、苯乙烯樹脂及該些的共聚物，以及二氧化矽等。該些可單獨使用1種、或將2種以上組合使用。 As the binder, for example, dimethylaminoethyl (meth)acrylate polymer, polyvinyl alcohol, polypropylene decylamine, polyvinyl decylamine, polyvinylpyrrolidone, poly(methyl) can be suitably selected. Acrylic, polyethylene oxide, polysulfonic acid, acrylamide alkylsulfonic acid, cellulose ethers, cellulose derivatives, carboxymethyl cellulose, hydroxyethyl cellulose, ethyl cellulose, Gelatin, starch and starch derivatives, sodium alginate, sanmon gum, guar gum and guar gum derivatives, scleroglucan and scleroglucan derivatives, tragacanth and tragacanth derivatives, paste Fine and dextrin derivatives, acrylic resins, acrylate resins, butadiene resins, styrene resins and copolymers thereof, and cerium oxide and the like. These may be used alone or in combination of two or more.

黏合劑的分子量並無特別限制，較理想的是鑒於作為組成物的所期望的黏度而適宜調整。 The molecular weight of the binder is not particularly limited, and is preferably adjusted in view of the desired viscosity as a composition.

作為溶劑，例如可列舉：丙酮、甲基乙基酮、甲基-正丙基酮、甲基-異丙基酮、甲基-正丁基酮、甲基-異丁基酮、甲基-正戊基酮、甲基-正己基酮、二乙基酮、二丙基酮、二-異丁基酮、三甲基壬酮、環己酮、環戊酮、甲基環己酮、2,4-戊二酮、丙酮基丙酮等酮系溶劑；二***、甲基乙基醚、甲基-正丙醚、二-異丙醚、四氫呋喃、甲基四氫呋喃、二噁烷、二甲基二噁烷、乙二醇二甲醚、乙二醇二***、乙二醇二-正丙醚、乙二醇二丁醚、二乙二醇二甲醚、二乙二醇二***、二乙二醇甲基乙基醚、二乙二醇甲基-正丙醚、二乙二醇甲基-正丁醚、二乙二醇二-正丙醚、二乙二醇二-正丁醚、二乙二醇甲基-正己醚、三乙二醇二甲醚、三乙二醇二***、三乙二醇甲基乙基醚、三乙二醇甲基-正丁醚、三乙二醇二- 正丁醚、三乙二醇甲基-正己醚、四乙二醇二甲醚、四乙二醇二***、四二乙二醇甲基乙基醚、四乙二醇甲基-正丁醚、二乙二醇二-正丁醚、四乙二醇甲基-正己醚、四乙二醇二-正丁醚、丙二醇二甲醚、丙二醇二***、丙二醇二-正丙醚、丙二醇二丁醚、二丙二醇二甲醚、二丙二醇二***、二丙二醇甲基乙基醚、二丙二醇甲基-正丁醚、二丙二醇二-正丙醚、二丙二醇二-正丁醚、二丙二醇甲基-正己醚、三丙二醇二甲醚、三丙二醇二***、三丙二醇甲基乙基醚、三丙二醇甲基-正丁醚、三丙二醇二-正丁醚、三丙二醇甲基-正己醚、四丙二醇二甲醚、四丙二醇二***、四二丙二醇甲基乙基醚、四丙二醇甲基-正丁醚、二丙二醇二-正丁醚、四丙二醇甲基-正己醚、四丙二醇二-正丁醚等醚系溶劑；乙酸甲酯、乙酸乙酯、乙酸正丙酯、乙酸異丙酯、乙酸正丁酯、乙酸異丁酯、乙酸第二丁酯、乙酸正戊酯、乙酸第二戊酯、乙酸3-甲氧基丁酯、乙酸甲酯戊酯、乙酸2-乙基丁酯、乙酸2-乙基己酯、乙酸2-(2-丁氧基乙氧基)乙酯、乙酸苄酯、乙酸環己酯、乙酸甲基環己酯、乙酸壬酯、乙醯乙酸甲酯、乙醯乙酸乙酯、乙酸二乙二醇甲醚、乙酸二乙二醇單***、乙酸二丙二醇甲醚、乙酸二丙二醇***、乙二醇二乙酸酯、甲氧基三乙二醇乙酸酯、丙酸乙酯、丙酸正丁酯、丙酸異戊酯、草酸二乙酯、草酸二-正丁酯、乳酸甲酯、乳酸乙酯、乳酸正丁酯、乳酸正戊酯、乙二醇甲醚丙酸酯、乙二醇***丙酸酯、乙二醇甲醚乙酸酯、乙二醇***乙酸酯、丙二醇甲醚乙酸酯、丙二醇***乙酸酯、丙二醇丙醚乙酸酯、γ-丁內酯、γ-戊內酯等酯 系溶劑；乙腈、N-甲基吡咯烷酮、N-乙基吡咯烷酮、N-丙基吡咯烷酮、N-丁基吡咯烷酮、N-己基吡咯烷酮、N-環己基吡咯烷酮、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、二甲基亞碸等非質子性極性溶劑；甲醇、乙醇、正丙醇、異丙醇、正丁醇、異丁醇、第二丁醇、第三丁醇、正戊醇、異戊醇、2-甲基丁醇、第二戊醇、第三戊醇、3-甲氧基丁醇、正己醇、2-甲基戊醇、第二己醇、2-乙基丁醇、第二庚醇、正辛醇、2-乙基己醇、第二辛醇、正壬醇、正癸醇、第二-十一醇、三甲基壬醇、第二-十四基醇、第二-十七醇、苯酚、環己醇、甲基環己醇、苄醇、乙二醇、1,2-丙二醇、1,3-丁二醇、二乙二醇、二丙二醇、三乙二醇、三丙二醇等醇系溶劑；乙二醇單甲醚、乙二醇單***、乙二醇單苯醚、二乙二醇單甲醚、二乙二醇單***、二乙二醇單-正丁醚、二乙二醇單-正己醚、乙氧基三甘醇、四乙二醇單-正丁醚、丙二醇單甲醚、二丙二醇單甲醚、二丙二醇單***、三丙二醇單甲醚等二醇單醚系溶劑；α-萜品烯、α-萜品醇、月桂油烯、別羅勒烯、檸檬烯、雙戊烯、α-蒎烯、β-蒎烯、松脂醇、香旱芹酮、羅勒烯、水芹烯等萜烯系溶劑；水。該些可單獨使用1種、或將2種以上組合使用。 Examples of the solvent include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-isopropyl ketone, methyl-n-butyl ketone, methyl-isobutyl ketone, and methyl group. N-pentyl ketone, methyl-n-hexyl ketone, diethyl ketone, dipropyl ketone, di-isobutyl ketone, trimethyl fluorenone, cyclohexanone, cyclopentanone, methylcyclohexanone, 2 a ketone solvent such as 4-pentanedione or acetonylacetone; diethyl ether, methyl ethyl ether, methyl-n-propyl ether, di-isopropyl ether, tetrahydrofuran, methyltetrahydrofuran, dioxane, dimethyl Dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol di-n-propyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethyl Glycol methyl ethyl ether, diethylene glycol methyl-n-propyl ether, diethylene glycol methyl-n-butyl ether, diethylene glycol di-n-propyl ether, diethylene glycol di-n-butyl ether, Diethylene glycol methyl-n-hexyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol methyl ethyl ether, triethylene glycol methyl-n-butyl ether, triethylene glycol two- N-butyl ether, triethylene glycol methyl-n-hexyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol methyl ethyl ether, tetraethylene glycol methyl-n-butyl ether , diethylene glycol di-n-butyl ether, tetraethylene glycol methyl-n-hexyl ether, tetraethylene glycol di-n-butyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol di-n-propyl ether, propylene glycol dibutyl Ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol methyl ethyl ether, dipropylene glycol methyl-n-butyl ether, dipropylene glycol di-n-propyl ether, dipropylene glycol di-n-butyl ether, dipropylene glycol methyl - n-Hexyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol methyl ethyl ether, tripropylene glycol methyl-n-butyl ether, tripropylene glycol di-n-butyl ether, tripropylene glycol methyl-n-hexyl ether, tetrapropylene glycol Dimethyl ether, tetrapropylene glycol diethyl ether, tetrapropylene glycol methyl ethyl ether, tetrapropylene glycol methyl-n-butyl ether, dipropylene glycol di-n-butyl ether, tetrapropylene glycol methyl-n-hexyl ether, tetrapropylene glycol di-n-butyl ether Ether ether solvent; methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, acetic acid Butyl ester, second butyl acetate, n-amyl acetate, second amyl acetate, 3-methoxybutyl acetate, amyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate , 2-(2-butoxyethoxy)ethyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, decyl acetate, methyl acetate, ethyl acetate, acetic acid Diethylene glycol methyl ether, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, dipropylene glycol ethyl acetate, ethylene glycol diacetate, methoxy triethylene glycol acetate, ethyl propionate, N-butyl propionate, isoamyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, ethylene glycol methyl ether propionate , ethylene glycol ethyl ether propionate, ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol diethyl ether acetate, propylene glycol propyl ether acetate, γ-butane Ester, γ-valerolactone and other esters Solvent; acetonitrile, N-methylpyrrolidone, N-ethylpyrrolidone, N-propylpyrrolidone, N-butylpyrrolidone, N-hexylpyrrolidone, N-cyclohexylpyrrolidone, N,N-dimethylformamide , aprotic polar solvents such as N,N-dimethylacetamide, dimethylhydrazine; methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, second butanol, Tributanol, n-pentanol, isoamyl alcohol, 2-methylbutanol, second pentanol, third pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, second Alcohol, 2-ethylbutanol, second heptanol, n-octanol, 2-ethylhexanol, second octanol, n-nonanol, n-nonanol, second-undecanol, trimethylnonanol , second-tetradecyl alcohol, second heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, benzyl alcohol, ethylene glycol, 1,2-propanediol, 1,3-butanediol, two Alcohol solvent such as ethylene glycol, dipropylene glycol, triethylene glycol or tripropylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol Alcohol monoethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-hexyl ether, a glycol monoether solvent such as ethoxylated triethylene glycol, tetraethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether or tripropylene glycol monomethyl ether; Terpene such as olefin, α-terpineol, lauryl olefin, allo-ocimene, limonene, dipentene, α-pinene, β-pinene, rosinol, fragrant celery, basilene, and celery Solvent; water. These may be used alone or in combination of two or more.

n型擴散層形成組成物中的分散媒的含有比率是考慮塗佈性、施體濃度(P(磷)濃度)而決定。 The content ratio of the dispersion medium in the n-type diffusion layer forming composition is determined in consideration of coatability and donor concentration (P (phosphorus) concentration).

考慮到塗佈性，n型擴散層形成組成物的黏度較佳為10mPa．S以上、1000000mPa．S以下，更佳為50mPa．S以上、500000mPa．S以下。 Considering the coating property, the viscosity of the n-type diffusion layer forming composition is preferably 10 mPa. Above S, 1000000mPa. Below S, more preferably 50mPa. S or above, 500000mPa. S below.

[n型擴散層及太陽電池單元的製造方法] [Method for manufacturing n-type diffusion layer and solar cell unit]

其次，一面參照圖1(1)~圖1(6)一面對本發明的n型擴散層及太陽電池單元的製造方法進行說明。圖1(1)~圖1(6)是概念性地表示本發明的太陽電池單元的製造步驟的一例的示意剖面圖。於以下的圖式中，對相同的構成要素標註同一符號。 Next, a method of manufacturing the n-type diffusion layer and the solar cell of the present invention will be described with reference to Figs. 1(1) to 1(6). 1(1) to 1(6) are schematic cross-sectional views conceptually showing an example of a manufacturing procedure of a solar battery cell of the present invention. In the following drawings, the same components are denoted by the same reference numerals.

圖1(1)中，對作為p型半導體基板10的結晶矽賦予鹼性溶液來去除損壞層，並藉由蝕刻而獲得紋理構造。 In Fig. 1 (1), an alkaline solution is applied to the crystal ruthenium as the p-type semiconductor substrate 10 to remove the damaged layer, and a texture structure is obtained by etching.

詳細而言，利用20質量%苛性鈉去除自鑄錠進行切片時所產生的矽表面的損壞層。繼而，利用1質量%苛性鈉與10質量%異丙醇的混合液進行蝕刻，而形成紋理構造(圖中省略紋理構造的記載)。太陽電池單元藉由在受光面(表面)側形成紋理構造，而可促進光學侷限效應，謀求高效率化。 Specifically, the damaged layer of the crucible surface generated when slicing from the ingot was removed using 20% by mass of caustic soda. Then, etching was carried out by using a mixed solution of 1% by mass of caustic soda and 10% by mass of isopropyl alcohol to form a texture structure (the description of the texture structure is omitted in the drawing). By forming a texture structure on the light-receiving surface (surface) side, the solar cell unit can promote optical confinement effects and achieve high efficiency.

圖1(2)中，將上述n型擴散層形成組成物塗佈於p型半導體基板10的表面即成為受光面的面上，形成n型擴散層形成組成物層11。本發明中，塗佈方法並無限制，例如有印刷法、旋轉法、毛刷塗佈、噴霧法、刮刀法、輥塗機法、噴墨法等。 In the above-described (1), the n-type diffusion layer forming composition is applied onto the surface of the p-type semiconductor substrate 10, that is, the surface on which the light-receiving surface is formed, and the n-type diffusion layer forming composition layer 11 is formed. In the present invention, the coating method is not limited, and examples thereof include a printing method, a spinning method, a brush coating method, a spray method, a doctor blade method, a roll coater method, and an inkjet method.

上述n型擴散層形成組成物的塗佈量並無特別限制，例如可設為10g/m2~250g/m2，較佳為20g/m2~150g/m2。 The coating amount of the n-type diffusion layer forming composition is not particularly limited, and may be, for example, 10 g/m 2 to 250 g/m 2 , and preferably 20 g/m 2 to 150 g/m 2 .

再者，根據n型擴散層形成組成物的組成，有時需要用以於塗佈後，使組成物中所含有的溶劑揮發的乾燥步驟。於該情況下，於80℃~300℃左右的溫度下，當使用加熱板時乾燥1分鐘~10分鐘，當使用乾燥機等時乾燥10分鐘~30分鐘左右。該乾 燥條件依存於n型擴散層形成組成物的溶劑組成，於本發明中並不特別限定於上述條件。 Further, depending on the composition of the n-type diffusion layer forming composition, a drying step for volatilizing the solvent contained in the composition after coating may be required. In this case, it is dried for 1 minute to 10 minutes when using a hot plate at a temperature of about 80 ° C to 300 ° C, and dried for about 10 minutes to 30 minutes when using a dryer or the like. The stem The drying condition depends on the solvent composition of the n-type diffusion layer forming composition, and is not particularly limited to the above conditions in the present invention.

另外，當使用本發明的製造方法時，背面的p+型擴散層(高濃度電場層)14的製造方法並不限定於藉由鋁來將所形成的n型擴散層轉換成p型擴散層的方法，亦可採用先前公知的任何方法，可擴大製造方法的選擇項。因此，例如可賦予含有B(硼)等第13族的元素的組成物13來形成高濃度電場層14。 Further, when the manufacturing method of the present invention is used, the method of manufacturing the p + -type diffusion layer (high-concentration electric field layer) 14 on the back surface is not limited to conversion of the formed n-type diffusion layer into a p-type diffusion layer by aluminum. The method can also be extended by any method previously known to expand the selection of the manufacturing method. Therefore, for example, the composition 13 containing an element of Group 13 such as B (boron) can be imparted to form the high-concentration electric field layer 14.

繼而，於600℃~1200℃下對形成有上述n型擴散層形成組成物層11的半導體基板10進行熱擴散處理。藉由該熱擴散處理，如圖1(3)所示，施體元素朝半導體基板中擴散，而形成n型擴散層12。熱擴散處理可應用公知的連續爐、分批式爐等。另外，熱擴散處理時的爐內環境亦可適宜調整成空氣、氧氣、氮氣等。 Then, the semiconductor substrate 10 on which the above-described n-type diffusion layer forming composition layer 11 is formed is subjected to thermal diffusion treatment at 600 ° C to 1200 ° C. By this thermal diffusion treatment, as shown in FIG. 1 (3), the donor element is diffused into the semiconductor substrate to form the n-type diffusion layer 12. As the heat diffusion treatment, a known continuous furnace, a batch furnace, or the like can be applied. In addition, the furnace environment during the thermal diffusion treatment may be appropriately adjusted to air, oxygen, nitrogen, or the like.

熱擴散處理時間可對應於n型擴散層形成組成物中所含有的施體元素的含有率等而適宜選擇。例如，可設為1分鐘~60分鐘，更佳為2分鐘~30分鐘。 The thermal diffusion treatment time can be appropriately selected in accordance with the content ratio of the donor element contained in the n-type diffusion layer forming composition. For example, it can be set to 1 minute to 60 minutes, more preferably 2 minutes to 30 minutes.

因於所形成的n型擴散層12的表面形成有磷酸玻璃等玻璃層(未圖示)，故藉由蝕刻來去除該磷酸玻璃。蝕刻可應用浸漬於氫氟酸等酸中的方法、浸漬於苛性鈉等鹼中的方法等公知的方法。 Since a glass layer (not shown) such as phosphoric acid glass is formed on the surface of the formed n-type diffusion layer 12, the phosphoric acid glass is removed by etching. The etching can be carried out by a known method such as a method of immersing in an acid such as hydrofluoric acid or a method of immersing in an alkali such as caustic soda.

於圖1(2)及圖1(3)所示的使用本發明的n型擴散層形成組成物11來形成n型擴散層12的本發明的n型擴散層的形 成方法中，僅於所期望的部位形成n型擴散層12，而不於背面或側面形成不需要的n型擴散層。 The shape of the n-type diffusion layer of the present invention in which the n-type diffusion layer 12 is formed using the n-type diffusion layer of the present invention to form the n-type diffusion layer 12 as shown in Figs. 1 (2) and 1 (3) In the method, the n-type diffusion layer 12 is formed only at a desired portion, and an unnecessary n-type diffusion layer is formed on the back side or the side surface.

因此，於先前廣泛採用的藉由氣相反應法來形成n型擴散層的方法中，為了去除形成於側面的不需要的n型擴散層需要側蝕步驟，但根據本發明的製造方法，則不需要側蝕步驟，從而使步驟簡單化。 Therefore, in the previously widely used method of forming an n-type diffusion layer by a gas phase reaction method, a side etching step is required in order to remove an unnecessary n-type diffusion layer formed on the side, but according to the manufacturing method of the present invention, The side etching step is not required, thereby simplifying the steps.

另外，於先前的製造方法中，必需將形成於背面的不需要的n型擴散層轉換成p型擴散層，作為其轉換方法，採用如下的方法：於背面的n型擴散層上塗佈作為第13族元素的鋁的膏，並進行煅燒，使鋁擴散至n型擴散層而將n型擴散層轉換成p型擴散層。於該方法中，為了充分地將n型擴散層轉換成p型擴散層，進而形成p+層的高濃度電場層，而需要某種程度以上的鋁量，因此必需將鋁層形成得厚。但是，鋁的熱膨脹係數與用作基板的矽的熱膨脹係數相差大，因此於煅燒及冷卻的過程中，在矽基板中產生較大的內應力，而成為矽基板的翹曲的原因。 Further, in the prior manufacturing method, it is necessary to convert an unnecessary n-type diffusion layer formed on the back surface into a p-type diffusion layer, and as a conversion method, the following method is employed: coating on the n-type diffusion layer on the back surface A paste of aluminum of a Group 13 element is calcined to diffuse aluminum to the n-type diffusion layer to convert the n-type diffusion layer into a p-type diffusion layer. In this method, in order to sufficiently convert the n-type diffusion layer into a p-type diffusion layer and further form a high-concentration electric field layer of the p + layer, a certain amount of aluminum is required. Therefore, it is necessary to form the aluminum layer to be thick. However, since the coefficient of thermal expansion of aluminum differs greatly from the coefficient of thermal expansion of the crucible used as the substrate, a large internal stress is generated in the crucible substrate during the calcination and cooling, which causes the warpage of the crucible substrate.

存在該內應力對結晶的晶界造成損傷、電力損失變大的課題。另外，翹曲於模組步驟中的太陽電池單元的搬送、或者與被稱為TAB線的導線的連接過程中，容易使單元破損。近年來，由於切片加工技術的提高，因此結晶矽基板的厚度逐漸薄型化，而存在單元更加容易破裂的傾向。 This internal stress causes a problem that the grain boundary of the crystal is damaged and the power loss is increased. In addition, it is easy to break the cell during warpage of the solar cell unit in the module step or connection with a wire called a TAB wire. In recent years, as the slicing technology has been improved, the thickness of the crystallized tantalum substrate has been gradually reduced, and there has been a tendency that the unit is more likely to be broken.

但是，根據本發明的製造方法，不於背面形成不需要的n型擴散層，因此無需進行自n型擴散層朝p型擴散層的轉換，而 不必使鋁層變厚。其結果，可抑制矽基板內的內應力的產生或翹曲。作為結果，可抑制電力損失的增大、或單元的破損。 However, according to the manufacturing method of the present invention, an unnecessary n-type diffusion layer is not formed on the back surface, so that conversion from the n-type diffusion layer to the p-type diffusion layer is not required, and It is not necessary to thicken the aluminum layer. As a result, generation or warpage of internal stress in the ruthenium substrate can be suppressed. As a result, an increase in power loss or breakage of the unit can be suppressed.

另外，當使用本發明的製造方法時，背面的p+型擴散層(高濃度電場層)14的製造方法並不限定於藉由鋁來將所形成的n型擴散層轉換成p型擴散層的方法，亦可採用先前公知的任何方法，可擴大製造方法的選擇項。 Further, when the manufacturing method of the present invention is used, the method of manufacturing the p + -type diffusion layer (high-concentration electric field layer) 14 on the back surface is not limited to conversion of the formed n-type diffusion layer into a p-type diffusion layer by aluminum. The method can also be extended by any method previously known to expand the selection of the manufacturing method.

另外，如後述般，用於背面的表面電極20的材料並不限定於第13族的鋁，例如可應用Ag(銀)或Cu(銅)等，背面的表面電極20的厚度亦可比先前的厚度更薄地形成。 Further, as will be described later, the material of the surface electrode 20 for the back surface is not limited to aluminum of Group 13, for example, Ag (silver) or Cu (copper) may be applied, and the thickness of the surface electrode 20 on the back surface may be larger than that of the prior art. The thickness is formed thinner.

圖1(4)中，於n型擴散層12上形成抗反射膜16。抗反射膜16是應用公知的技術而形成。例如，當抗反射膜16為氮化矽膜時，藉由將SiH4與NH3的混合氣體作為原料的電漿化學氣相沈積(Chemical Vapor Deposition，CVD)法來形成。此時，氫於結晶中擴散，不參與矽原子的鍵結的軌道，即懸鍵與氫鍵結，而使缺陷鈍化(氫鈍化)。 In FIG. 1 (4), an anti-reflection film 16 is formed on the n-type diffusion layer 12. The anti-reflection film 16 is formed using a well-known technique. For example, when the anti-reflection film 16 is a tantalum nitride film, it is formed by a plasma chemical vapor deposition (CVD) method using a mixed gas of SiH 4 and NH 3 as a raw material. At this time, hydrogen diffuses in the crystal, does not participate in the orbital of the bonding of the ruthenium atom, that is, the dangling bonds are hydrogen-bonded, and the defects are passivated (hydrogen passivation).

更具體而言，於上述混合氣體流量比NH3/SiH4為0.05~1.0，反應室的壓力為0.1Torr~2Torr(13.3Pa~266.6Pa)，成膜時的溫度為300℃~550℃，用於電漿的放電的頻率為100kHz以上的條件下形成。 More specifically, the mixed gas flow rate ratio NH 3 /SiH 4 is 0.05 to 1.0, the pressure in the reaction chamber is 0.1 Torr to 2 Torr (13.3 Pa to 266.6 Pa), and the temperature at the time of film formation is 300 to 550 ° C. It is formed under the condition that the frequency of discharge of the plasma is 100 kHz or more.

圖1(5)中，藉由網版印刷法將表面電極用金屬膏印刷塗佈於表面(受光面)的抗反射膜16上，並使其乾燥，從而形成表面電極18。表面電極用金屬膏將(1)金屬粒子與(2)玻璃粒 子作為必需成分，且視需要包含(3)樹脂黏合劑、(4)其他添加劑等。 In Fig. 1 (5), the surface electrode is printed on the anti-reflection film 16 of the surface (light-receiving surface) with a metal paste by a screen printing method, and dried to form the surface electrode 18. Surface electrode with metal paste to (1) metal particles and (2) glass particles The subcomponent is an essential component, and if necessary, (3) a resin binder, (4) other additives, and the like.

繼而，於上述背面的高濃度電場層14上亦形成背面電極20。如上所述，本發明中背面電極20的材質或形成方法並無特別限定。例如，可塗佈包含鋁、銀或銅等金屬的背面電極用膏，並使其乾燥而形成背面電極20。此時，為了模組步驟中的單元間的連接，亦可於背面的一部分上設置銀電極形成用銀膏。 Then, the back surface electrode 20 is also formed on the high-concentration electric field layer 14 on the back surface. As described above, the material or formation method of the back surface electrode 20 in the present invention is not particularly limited. For example, a paste for a back surface electrode containing a metal such as aluminum, silver or copper may be applied and dried to form the back surface electrode 20. At this time, in order to connect the cells in the module step, a silver paste for silver electrode formation may be provided on a part of the back surface.

圖1(6)中，對電極進行煅燒，製成太陽電池單元。若於600℃~900℃的範圍內煅燒幾秒~幾分鐘，則於表面側，作為絕緣膜的抗反射膜16因電極用金屬膏中所含有的玻璃粒子而熔融，進而矽基板10表面的一部分亦熔融，膏中的金屬粒子(例如銀粒子)與矽基板10形成接觸部並凝固。藉此，所形成的表面電極18與矽基板10被導通。將此稱為燒透(fire through)。 In Fig. 1 (6), the electrode is calcined to form a solar cell unit. When calcined in the range of 600 ° C to 900 ° C for a few seconds to several minutes, the antireflection film 16 as an insulating film is melted on the surface side by the glass particles contained in the metal paste for the electrode, and further the surface of the substrate 10 is melted. A part is also melted, and metal particles (for example, silver particles) in the paste form a contact portion with the tantalum substrate 10 and solidify. Thereby, the formed surface electrode 18 and the germanium substrate 10 are electrically connected. This is called fire through.

對表面電極18的形狀進行說明。表面電極18包含匯流條電極30、及與該匯流條電極30交叉的指狀電極32。圖2A是自表面觀察太陽電池單元的俯視圖，上述太陽電池單元是將表面電極18設為包含匯流條電極30、及與該匯流條電極30交叉的指狀電極32的構成，圖2B是將圖2A的一部分放大表示的立體圖。 The shape of the surface electrode 18 will be described. The surface electrode 18 includes a bus bar electrode 30 and a finger electrode 32 that intersects the bus bar electrode 30. 2A is a plan view of the solar battery cell viewed from the surface, wherein the solar cell unit has a configuration in which the surface electrode 18 includes a bus bar electrode 30 and a finger electrode 32 that intersects the bus bar electrode 30, and FIG. 2B is a view. A perspective view of a part of 2A is enlarged.

此種表面電極18可藉由例如上述金屬膏的網版印刷、或者電極材料的鍍敷、高真空中的利用電子束加熱的電極材料的蒸鍍等方法而形成。眾所周知，包含匯流條電極30與指狀電極32的表面電極18通常用作受光面側的電極，可應用受光面側的匯流 條電極及指狀電極的公知的形成方法。 Such a surface electrode 18 can be formed by, for example, screen printing of the above-described metal paste, plating of an electrode material, vapor deposition of an electrode material by electron beam heating in a high vacuum, or the like. It is known that the surface electrode 18 including the bus bar electrode 30 and the finger electrode 32 is generally used as an electrode on the light-receiving surface side, and the converging side on the light-receiving surface side can be applied. A well-known method of forming a strip electrode and a finger electrode.

於上述中，對在表面形成n型擴散層，在背面形成p+型擴散層，進而在各個層上設置有表面電極及背面電極的太陽電池單元進行了說明，但若使用本發明的n型擴散層形成組成物，則亦可製作背接觸型的太陽電池單元。 In the above description, a solar cell in which an n-type diffusion layer is formed on the surface, a p + -type diffusion layer is formed on the back surface, and a surface electrode and a back electrode are provided on each layer has been described. However, the n-type of the present invention is used. When the diffusion layer forms a composition, a back contact type solar cell can be fabricated.

背接觸型的太陽電池單元是將電極全部設置於背面而增大受光面的面積的太陽電池單元。即，於背接觸型的太陽電池單元中，必需於背面形成n型擴散部位及p+型擴散部位兩者來形成pn接合構造。本發明的n型擴散層形成組成物可僅於特定的部位形成n型擴散部位，因此可較佳地應用於背接觸型的太陽電池單元的製造。另外，本發明的n型擴散層形成組成物亦可應用於例如僅於電極正下方形成高濃度n型擴散層(n++層)的選擇性射極。 The back contact type solar cell unit is a solar cell unit in which all of the electrodes are provided on the back surface to increase the area of the light receiving surface. In other words, in the back contact type solar cell, it is necessary to form both the n-type diffusion portion and the p + -type diffusion portion on the back surface to form a pn junction structure. Since the n-type diffusion layer forming composition of the present invention can form an n-type diffusion site only at a specific portion, it can be preferably applied to the manufacture of a back contact type solar cell. Further, the n-type diffusion layer forming composition of the present invention can also be applied to, for example, a selective emitter which forms a high-concentration n-type diffusion layer (n ++ layer) directly under the electrode.

再者，藉由參照而將日本申請案2011-032430中所揭示的全部內容引用於本說明書中。 Further, the entire contents disclosed in Japanese Patent Application No. 2011-032430 are incorporated herein by reference.

本說明書中所記載的所有文獻、專利申請案、及技術規格是以與具體地且個別地記載藉由參照而引用各個文獻、專利申請案、及技術規格時相同的程度，藉由參照而引用於本說明書中。 All of the documents, patent applications, and technical specifications described in the specification are the same as those which are specifically and individually described by reference to the respective documents, patent applications, and technical specifications, and are cited by reference. In this manual.

[實例] [Example]

以下，更具體地說明本發明的實例，但本發明並不受該些實例限制。再者，只要事先無特別記述，則化學品全部使用了試劑。另外，只要事先無說明，則「%」表示「質量%」。 Hereinafter, examples of the invention will be more specifically described, but the invention is not limited by the examples. Further, as long as there is no special description in advance, the reagents are all used in the chemicals. In addition, "%" means "% by mass" as long as there is no explanation in advance.

[實例1] [Example 1]

將P2O5-CaO系玻璃(P2O5：80%、CaO：20%)粉末(體積平均粒徑為3μm)裝入至已開封的容器中，於溫度50℃、濕度70%的環境下放置24小時。 P 2 O 5 -CaO-based glass (P 2 O 5 : 80%, CaO: 20%) powder (volume average particle diameter of 3 μm) was placed in an opened container at a temperature of 50 ° C and a humidity of 70%. Leave it in the environment for 24 hours.

其次，將該玻璃粉末10g、乙基纖維素5g、及乙酸2-(2-丁氧基乙氧基)乙酯85g混合並膏化，製備n型擴散層形成組成物。 Next, 10 g of the glass powder, 5 g of ethyl cellulose, and 85 g of 2-(2-butoxyethoxy)ethyl acetate were mixed and paste-formed to prepare an n-type diffusion layer forming composition.

藉由網版印刷將n型擴散層形成組成物以塗佈量成為15g/m2~20g/m2的方式塗佈於p型矽基板表面，並於150℃的加熱板上乾燥5分鐘。繼而，利用設定成1000℃的電爐進行10分鐘熱擴散處理，其後，為了去除玻璃層而將基板於氫氟酸中浸漬5分鐘，然後進行流水清洗。其後進行乾燥。 The n-type diffusion layer forming composition was applied onto the surface of the p-type ruthenium substrate by screen printing so as to have a coating amount of 15 g/m 2 to 20 g/m 2 , and dried on a hot plate at 150 ° C for 5 minutes. Then, the thermal diffusion treatment was performed for 10 minutes in an electric furnace set at 1000 ° C, and thereafter, the substrate was immersed in hydrofluoric acid for 5 minutes in order to remove the glass layer, and then washed with running water. It is then dried.

塗佈有n型擴散層形成組成物之側的表面的片電阻為15Ω/□，P(磷)擴散而形成n型擴散層。背面的片電阻為測定上限(1000000Ω/□)以上而無法測定，n型擴散層並未形成。 The sheet resistance of the surface coated with the side of the n-type diffusion layer forming composition was 15 Ω/□, and P (phosphorus) was diffused to form an n-type diffusion layer. The sheet resistance on the back surface was not measured by the upper limit of measurement (1,000,000 Ω/□), and the n-type diffusion layer was not formed.

再者，上述表面的片電阻的值是於156cm×156cm的區域中等間隔地進行5點×5點測定，並表示其平均的值(以下的實例及比較例中亦相同)。 In addition, the value of the sheet resistance of the above surface was measured at 5 dots × 5 points at intervals of 156 cm × 156 cm, and the average value was shown (the same applies to the following examples and comparative examples).

[實例2] [Example 2]

作為玻璃粉末，使用P2O5-ZnO系玻璃(P2O5：70%、ZnO：30%)粉末(體積平均粒徑為3μm)，除此以外，以與實例1相同的方式形成n型擴散層。 In the same manner as in Example 1, except that P 2 O 5 —ZnO-based glass (P 2 O 5 : 70%, ZnO: 30%) powder (volume average particle diameter: 3 μm) was used as the glass powder. Type diffusion layer.

塗佈有n型擴散層形成組成物之側的表面的片電阻為20Ω/□，P(磷)擴散而形成n型擴散層。 The sheet resistance of the surface coated with the side of the n-type diffusion layer forming composition was 20 Ω/□, and P (phosphorus) was diffused to form an n-type diffusion layer.

背面的片電阻為測定上限(1000000Ω/□)以上而無法測定，n型擴散層並未形成。 The sheet resistance on the back surface was not measured by the upper limit of measurement (1,000,000 Ω/□), and the n-type diffusion layer was not formed.

[實例3] [Example 3]

作為玻璃粉末，使用P2O5-SiO2-CaO系玻璃(P2O5：50%、SiO2：40%、CaO：10%)粉末(體積平均粒徑為1μm)，除此以外，以與實例1相同的方式形成n型擴散層。 P 2 O 5 —SiO 2 —CaO-based glass (P 2 O 5 : 50%, SiO 2 : 40%, CaO: 10%) powder (volume average particle diameter: 1 μm) was used as the glass powder, and An n-type diffusion layer was formed in the same manner as in Example 1.

塗佈有n型擴散層形成組成物之側的表面的片電阻為17Ω/□，P(磷)擴散而形成n型擴散層。 The sheet resistance of the surface coated with the side of the n-type diffusion layer forming composition was 17 Ω/□, and P (phosphorus) was diffused to form an n-type diffusion layer.

背面的片電阻為測定上限(1000000Ω/□)以上而無法測定，n型擴散層並未形成。 The sheet resistance on the back surface was not measured by the upper limit of measurement (1,000,000 Ω/□), and the n-type diffusion layer was not formed.

[實例4] [Example 4]

作為玻璃粉末，使用P2O5-Al2O3-ZnO系玻璃(P2O5：65%、Al2O3：5%、ZnO：30%)粉末(體積平均粒徑為5μm)，除此以外，以與實例1相同的方式形成n型擴散層。 As the glass powder, a powder of P 2 O 5 —Al 2 O 3 —ZnO-based glass (P 2 O 5 : 65%, Al 2 O 3 : 5%, ZnO: 30%) (volume average particle diameter: 5 μm) was used. Except for this, an n-type diffusion layer was formed in the same manner as in Example 1.

塗佈有n型擴散層形成組成物之側的表面的片電阻為17Ω/□，P(磷)擴散而形成n型擴散層。 The sheet resistance of the surface coated with the side of the n-type diffusion layer forming composition was 17 Ω/□, and P (phosphorus) was diffused to form an n-type diffusion layer.

背面的片電阻為測定上限(1000000Ω/□)以上而無法測定，n型擴散層並未形成。 The sheet resistance on the back surface was not measured by the upper limit of measurement (1,000,000 Ω/□), and the n-type diffusion layer was not formed.

[實例5] [Example 5]

作為玻璃粉末，使用P2O5-ZnO-TiO2系玻璃(P2O5：60%、ZnO：35%、TiO2：5%)粉末(體積平均粒徑為3μm)，除此以外，以與實例1相同的方式形成n型擴散層。 P 2 O 5 —ZnO—TiO 2 -based glass (P 2 O 5 : 60%, ZnO: 35%, TiO 2 : 5%) powder (volume average particle diameter: 3 μm) was used as the glass powder, and An n-type diffusion layer was formed in the same manner as in Example 1.

塗佈有n型擴散層形成組成物之側的表面的片電阻為21Ω/□，P(磷)擴散而形成n型擴散層。 The sheet resistance of the surface coated with the side of the n-type diffusion layer forming composition was 21 Ω/□, and P (phosphorus) was diffused to form an n-type diffusion layer.

背面的片電阻為測定上限(1000000Ω/□)以上而無法測定，n型擴散層並未形成。 The sheet resistance on the back surface was not measured by the upper limit of measurement (1,000,000 Ω/□), and the n-type diffusion layer was not formed.

[實例6] [Example 6]

作為玻璃粉末，使用P2O5-ZnO-ZrO2系玻璃(P2O5：63%、ZnO：35%、ZrO2：2%)粉末(體積平均粒徑為2μm)，除此以外，以與實例1相同的方式形成n型擴散層。 P 2 O 5 —ZnO—ZrO 2 -based glass (P 2 O 5 : 63%, ZnO: 35%, ZrO 2 : 2%) powder (volume average particle diameter: 2 μm) was used as the glass powder, and An n-type diffusion layer was formed in the same manner as in Example 1.

塗佈有n型擴散層形成組成物之側的表面的片電阻為21Ω/□，P(磷)擴散而形成n型擴散層。 The sheet resistance of the surface coated with the side of the n-type diffusion layer forming composition was 21 Ω/□, and P (phosphorus) was diffused to form an n-type diffusion layer.

背面的片電阻為測定上限(1000000Ω/□)以上而無法測定，n型擴散層並未形成。 The sheet resistance on the back surface was not measured by the upper limit of measurement (1,000,000 Ω/□), and the n-type diffusion layer was not formed.

[實例7] [Example 7]

作為玻璃粉末，使用P2O5-ZnO-Mgo系玻璃(P2O5：60%、ZnO：30%、MgO：10%)粉末(體積平均粒徑為4μm)，除此以外，以與實例1相同的方式形成n型擴散層。 P 2 O 5 —ZnO-Mgo-based glass (P 2 O 5 : 60%, ZnO: 30%, MgO: 10%) powder (volume average particle diameter: 4 μm) was used as the glass powder, and Example 1 formed an n-type diffusion layer in the same manner.

塗佈有n型擴散層形成組成物之側的表面的片電阻為25Ω/□，P(磷)擴散而形成n型擴散層。 The sheet resistance of the surface coated with the side of the n-type diffusion layer forming composition was 25 Ω/□, and P (phosphorus) was diffused to form an n-type diffusion layer.

背面的片電阻為測定上限(1000000Ω/□)以上而無法測定，n型擴散層並未形成。 The sheet resistance on the back surface was not measured by the upper limit of measurement (1,000,000 Ω/□), and the n-type diffusion layer was not formed.

[實例8] [Example 8]

作為玻璃粉末，使用P2O5-BaO-CaO系玻璃(P2O5：60%、BaO： 20%、CaO：20%)粉末(體積平均粒徑為3μm)，除此以外，以與實例1相同的方式形成n型擴散層。 As the glass powder, P 2 O 5 —BaO—CaO-based glass (P 2 O 5 : 60%, BaO: 20%, CaO: 20%) powder (volume average particle diameter: 3 μm) was used, and Example 1 formed an n-type diffusion layer in the same manner.

塗佈有n型擴散層形成組成物之側的表面的片電阻為17Ω/□，P(磷)擴散而形成n型擴散層。 The sheet resistance of the surface coated with the side of the n-type diffusion layer forming composition was 17 Ω/□, and P (phosphorus) was diffused to form an n-type diffusion layer.

背面的片電阻為測定上限(1000000Ω/□)以上而無法測定，n型擴散層並未形成。 The sheet resistance on the back surface was not measured by the upper limit of measurement (1,000,000 Ω/□), and the n-type diffusion layer was not formed.

[實例9] [Example 9]

作為玻璃粉末，使用P2O5-SiO2-SrO系玻璃(P2O5：45%、SiO2：35%、SrO：20%)粉末(體積平均粒徑為1μm)，除此以外，以與實例1相同的方式形成n型擴散層。 P 2 O 5 —SiO 2 —SrO-based glass (P 2 O 5 : 45%, SiO 2 : 35%, SrO: 20%) powder (volume average particle diameter: 1 μm) was used as the glass powder. An n-type diffusion layer was formed in the same manner as in Example 1.

塗佈有n型擴散層形成組成物之側的表面的片電阻為21Ω/□，P(磷)擴散而形成n型擴散層。 The sheet resistance of the surface coated with the side of the n-type diffusion layer forming composition was 21 Ω/□, and P (phosphorus) was diffused to form an n-type diffusion layer.

背面的片電阻為測定上限(1000000Ω/□)以上而無法測定，n型擴散層並未形成。 The sheet resistance on the back surface was not measured by the upper limit of measurement (1,000,000 Ω/□), and the n-type diffusion layer was not formed.

[比較例1] [Comparative Example 1]

將磷酸二氫銨(NH4H2PO4)粉末20g與乙基纖維素3g、乙酸2-(2-丁氧基乙氧基)乙酯7g混合並膏化，製備n型擴散層組成物。 20 g of ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ) powder was mixed with 3 g of ethyl cellulose and 7 g of 2-(2-butoxyethoxy)ethyl acetate, and paste-formed to prepare an n-type diffusion layer composition. .

其次，藉由網版印刷將所製備的膏塗佈於p型矽基板表面，並於150℃的加熱板上乾燥5分鐘。繼而，利用設定成1000℃的電爐進行10分鐘熱擴散處理，其後，為了去除玻璃層而將基板於氫氟酸中浸漬5分鐘，然後進行流水清洗、乾燥。 Next, the prepared paste was applied to the surface of the p-type ruthenium substrate by screen printing, and dried on a hot plate at 150 ° C for 5 minutes. Then, heat diffusion treatment was performed for 10 minutes in an electric furnace set to 1000 ° C, and thereafter, the substrate was immersed in hydrofluoric acid for 5 minutes in order to remove the glass layer, and then washed with water and dried.

塗佈有n型擴散層形成組成物之側的表面的片電阻為14Ω/□，P(磷)擴散而形成n型擴散層。但是，背面的片電阻為50Ω/□，於背面亦形成有n型擴散層。 The sheet resistance of the surface coated with the side of the n-type diffusion layer forming composition was 14 Ω/□, and P (phosphorus) was diffused to form an n-type diffusion layer. However, the sheet resistance of the back surface was 50 Ω/□, and an n-type diffusion layer was formed on the back surface.

[比較例2] [Comparative Example 2]

將磷酸二氫銨(NH4H2PO4)粉末1g與純水7g、聚乙烯醇0.7g、異丙醇1.5g混合來製備溶液，然後製備n型擴散層組成物。 A solution of 1 g of ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ) powder was mixed with 7 g of pure water, 0.7 g of polyvinyl alcohol, and 1.5 g of isopropyl alcohol to prepare a solution, and then an n-type diffusion layer composition was prepared.

其次，利用旋轉塗佈機(2000rpm，30sec)將所製備的溶液塗佈於p型矽基板表面，並於150℃的加熱板上乾燥5分鐘。繼而，利用設定成1000℃的電爐進行10分鐘熱擴散處理，其後，為了去除玻璃層而將基板於氫氟酸中浸漬5分鐘，然後進行流水清洗、乾燥。 Next, the prepared solution was applied onto the surface of a p-type ruthenium substrate by a spin coater (2000 rpm, 30 sec), and dried on a hot plate at 150 ° C for 5 minutes. Then, heat diffusion treatment was performed for 10 minutes in an electric furnace set to 1000 ° C, and thereafter, the substrate was immersed in hydrofluoric acid for 5 minutes in order to remove the glass layer, and then washed with water and dried.

塗佈有n型擴散層形成組成物之側的表面的片電阻為10Ω/□，P(磷)擴散而形成n型擴散層。但是，背面的片電阻為100Ω/□，於背面亦形成有n型擴散層。 The sheet resistance of the surface coated with the side of the n-type diffusion layer forming composition was 10 Ω/□, and P (phosphorus) was diffused to form an n-type diffusion layer. However, the sheet resistance of the back surface was 100 Ω/□, and an n-type diffusion layer was formed on the back surface.

[比較例3] [Comparative Example 3]

作為玻璃粉末，使用P2O5-SiO2系玻璃(P2O5：40%、SiO2：60%)粉末(體積平均粒徑為1μm)，除此以外，以與實例1相同的方式形成n型擴散層。 In the same manner as in Example 1, except that P 2 O 5 —SiO 2 -based glass (P 2 O 5 : 40%, SiO 2 : 60%) powder (volume average particle diameter: 1 μm) was used as the glass powder. An n-type diffusion layer is formed.

塗佈有n型擴散層形成組成物之側的表面的片電阻為27Ω/□，P(磷)擴散而形成n型擴散層。 The sheet resistance of the surface coated with the side of the n-type diffusion layer forming composition was 27 Ω/□, and P (phosphorus) was diffused to form an n-type diffusion layer.

背面的片電阻為750Ω/□，於背面亦形成有n型擴散層。 The sheet resistance on the back side is 750 Ω/□, and an n-type diffusion layer is also formed on the back surface.

根據以上的結果可知，若使用實例中所調製的n型擴散 層形成組成物，則可於背面不形成n型擴散層而僅於表面形成n型擴散層，與比較例相比，形成n型擴散層的位置選擇性更高。 According to the above results, if the n-type diffusion modulated in the example is used When the layer is formed into a composition, an n-type diffusion layer can be formed only on the back surface, and an n-type diffusion layer can be formed only on the surface, and the positional selectivity of the n-type diffusion layer is higher than that of the comparative example.

10‧‧‧p型半導體基板 10‧‧‧p type semiconductor substrate

12‧‧‧n型擴散層 12‧‧‧n type diffusion layer

14‧‧‧高濃度電場層 14‧‧‧High concentration electric field layer

16‧‧‧抗反射膜 16‧‧‧Anti-reflective film

18‧‧‧表面電極 18‧‧‧ surface electrode

20‧‧‧背面電極 20‧‧‧Back electrode

Claims (5)

一種n型擴散層形成組成物，包括：分散媒；以及玻璃粉末，含有選自ZrO2、Al2O3、TiO2、ZnO、MgO、CaO、SrO及BaO中的至少1種及P2O5。 An n-type diffusion layer forming composition comprising: a dispersing medium; and a glass powder containing at least one selected from the group consisting of ZrO 2 , Al 2 O 3 , TiO 2 , ZnO, MgO, CaO, SrO, and BaO, and P 2 O 5 . 如申請專利範圍第1項所述之n型擴散層形成組成物，其中上述玻璃粉末含有30質量%~90質量%的P2O5。 The n-type diffusion layer forming composition according to claim 1, wherein the glass powder contains 30% by mass to 90% by mass of P 2 O 5 . 如申請專利範圍第1項所述之n型擴散層形成組成物，其中上述玻璃粉末的體積平均粒徑為100μm以下。 The n-type diffusion layer forming composition according to claim 1, wherein the glass powder has a volume average particle diameter of 100 μm or less. 一種n型擴散層的製造方法，包括：塗佈如申請專利範圍第1項至第3項中任一項所述之n型擴散層形成組成物的步驟；以及實施熱擴散處理的步驟。 A method of producing an n-type diffusion layer, comprising: a step of coating an n-type diffusion layer forming composition according to any one of claims 1 to 3; and a step of performing a thermal diffusion treatment. 一種太陽電池單元的製造方法，包括：於半導體基板上塗佈如申請專利範圍第1項至第3項中任一項所述之n型擴散層形成組成物的步驟；以及實施熱擴散處理來形成n型擴散層的步驟。 A method of manufacturing a solar cell unit, comprising: coating a semiconductor substrate with an n-type diffusion layer forming composition according to any one of claims 1 to 3; and performing thermal diffusion treatment The step of forming an n-type diffusion layer.
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