TW201335070A - Composition for forming barrier layer, barrier layer, method of producing substrate for photovoltaic cell and method of producing photovoltaic cell element - Google Patents

Composition for forming barrier layer, barrier layer, method of producing substrate for photovoltaic cell and method of producing photovoltaic cell element Download PDF

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TW201335070A
TW201335070A TW102100934A TW102100934A TW201335070A TW 201335070 A TW201335070 A TW 201335070A TW 102100934 A TW102100934 A TW 102100934A TW 102100934 A TW102100934 A TW 102100934A TW 201335070 A TW201335070 A TW 201335070A
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barrier layer
forming
composition
metal
group
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Akihiro Orita
Masato Yoshida
Takeshi Nojiri
Yasushi Kurata
Mitsunori Iwamuro
Shigeru Nobe
Yuuhei Okada
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Hitachi Chemical Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • 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
    • H01L21/225—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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Abstract

A composition for forming a barrier layer includes a metal compound containing an alkali earth metal or an alkali metal; a dispersion medium; and at least one specific compound selected from the group consisting of a metal alkoxide, a silicon alkoxide, a silicate oligomer and silicone oil.

Description

阻擋層形成用組成物、阻擋層、太陽電池用基板的製造方法以及太陽電池元件的製造方法 Barrier layer forming composition, barrier layer, method for producing solar cell substrate, and method for manufacturing solar cell element

本發明是有關於一種阻擋層形成用組成物、阻擋層、太陽電池用基板的製造方法以及太陽電池元件的製造方法。 The present invention relates to a barrier layer-forming composition, a barrier layer, a method for producing a solar cell substrate, and a method for producing a solar cell element.

對現有的矽太陽電池元件的製造步驟進行說明。 The manufacturing steps of the conventional tantalum solar cell element will be described.

首先，為了促進光侷限效應(light trapping effect)來實現高效率化，而準備在受光面(表面)形成有紋理結構的p型矽基板，繼而，在磷醯氯(phosphorus oxychloride)(POCl3)、氮及氧的混合氣體環境中於800℃~900℃下進行數十分鐘的處理，在p型矽基板的表面同樣地形成n型擴散層。繼而，於受光面塗佈銀(Ag)等電極膏，且於背面側塗佈鋁(Al)等電極膏後，進行焙燒，藉此獲得太陽電池元件。 First, in order to promote the light trapping effect to achieve high efficiency, a p-type germanium substrate having a textured structure on the light receiving surface (surface) is prepared, and then, phosphorous oxychloride (POCl 3 ) is prepared. In a mixed gas atmosphere of nitrogen and oxygen, the treatment is performed at 800 ° C to 900 ° C for several tens of minutes, and an n-type diffusion layer is formed similarly on the surface of the p-type germanium substrate. Then, an electrode paste such as silver (Ag) is applied to the light-receiving surface, and an electrode paste such as aluminum (Al) is applied to the back surface side, followed by baking to obtain a solar cell element.

然而，由於太陽光並不入射到受光面側的電極的正下 方，故而該部分並不發電。因此開發出一種背面電極型太陽電池，該背面電極型太陽電池在受光面並無電極，於背面具有n+型擴散層以及p+型擴散層，且於各自的擴散層上具有n電極以及p電極(例如參照日本專利特開2011-507246號公報)。 However, since sunlight does not enter directly below the electrode on the light-receiving surface side, this portion does not generate electricity. Therefore, a back electrode type solar cell has been developed which has no electrode on the light receiving surface, an n + -type diffusion layer and a p + -type diffusion layer on the back surface, and has n electrodes and p on the respective diffusion layers. The electrode (for example, see Japanese Patent Laid-Open Publication No. 2011-507246).

對形成上述背面電極型太陽電池的方法進行說明。於n型矽基板的受光面及背面的整個面形成阻擋層(barrier layer)。此處，阻擋層具有抑制摻雜劑擴散至矽基板內的功能。接著，將矽基板的背面的阻擋層的一部分去除而形成開口部。然後，若使p型摻雜劑自阻擋層的開口部擴散至矽基板的背面，則僅在與開口部對應的區域形成p+型擴散層。接著，將矽基板的背面的阻擋層全部去除後，再次於矽基板的背面的整個面形成阻擋層。然後，將與形成有上述p+型擴散層的區域不同的區域的阻擋層的一部分去除而形成開口部，使n型摻雜劑自該開口部擴散至矽基板的背面，從而形成n+型擴散層。繼而，將矽基板的背面的阻擋層全部去除，藉此於背面形成p+型擴散層及n+型擴散層。進而，藉由形成紋理結構、抗反射膜、鈍化膜(passivation film)、電極等而製成背面電極型太陽電池。 A method of forming the above-described back electrode type solar cell will be described. A barrier layer is formed on the entire surface of the light receiving surface and the back surface of the n-type germanium substrate. Here, the barrier layer has a function of suppressing diffusion of dopant into the germanium substrate. Next, a part of the barrier layer on the back surface of the ruthenium substrate is removed to form an opening. Then, when the p-type dopant is diffused from the opening of the barrier layer to the back surface of the germanium substrate, the p + -type diffusion layer is formed only in the region corresponding to the opening. Next, after all the barrier layers on the back surface of the ruthenium substrate were removed, a barrier layer was formed on the entire surface of the back surface of the ruthenium substrate again. Then, a part of the barrier layer in a region different from the region in which the p + -type diffusion layer is formed is removed to form an opening, and the n-type dopant is diffused from the opening to the back surface of the germanium substrate, thereby forming an n + type Diffusion layer. Then, the barrier layer on the back surface of the ruthenium substrate is entirely removed, whereby a p + -type diffusion layer and an n + -type diffusion layer are formed on the back surface. Further, a back electrode type solar cell is formed by forming a texture structure, an antireflection film, a passivation film, an electrode, or the like.

提出有利用藉由熱氧化法而生成於矽基板表面的氧化膜作為上述阻擋層的方法(例如參照日本專利特開2002-329880號公報)。另一方面，亦提出有使用包含SiO2前驅物的遮蔽膏(masking paste)的阻擋層的形成方法(例如參照日本專利特開 2007-49079號公報)。 A method of using an oxide film formed on the surface of a tantalum substrate by a thermal oxidation method as the above-mentioned barrier layer has been proposed (for example, refer to Japanese Laid-Open Patent Publication No. 2002-329880). On the other hand, a method of forming a barrier layer using a masking paste containing a SiO 2 precursor has also been proposed (for example, refer to Japanese Laid-Open Patent Publication No. 2007-49079).

但是，上述日本專利特開2002-329880號公報中記載的藉由熱氧化法而於矽基板表面生成氧化膜的方法中，由於生產量長，故而存在製造成本提高的問題。 However, in the method of forming an oxide film on the surface of a tantalum substrate by a thermal oxidation method described in the above-mentioned Japanese Patent Publication No. 2002-329880, since the production amount is long, there is a problem that the manufacturing cost is increased.

另外，日本專利特開2007-49079號公報中記載的使用含有SiO2前驅物的遮蔽膏的方法中，由於該方法為物理性防止施體元素或者受體元素擴散的方法，而且包含SiO2的阻擋層由於難以形成緻密的膜而容易形成針孔，因此難以充分防止摻雜劑向基板的擴散。 In the method of using a masking paste containing a SiO 2 precursor described in Japanese Laid-Open Patent Publication No. 2007-49079, the method is a method for physically preventing diffusion of a donor element or an acceptor element, and includes SiO 2 . Since the barrier layer is difficult to form a dense film, pinholes are easily formed, and thus it is difficult to sufficiently prevent diffusion of the dopant to the substrate.

因此，本發明是鑒於以上的現有問題而形成，課題為提供一種能夠充分防止施體元素或者受體元素向半導體基板的擴散、抑制半導體基板的表面粗糙的阻擋層形成用組成物；使用該阻擋層形成組成物而形成的阻擋層；使用該阻擋層形成組成物的太陽電池用基板的製造方法以及太陽電池元件的製造方法。 Therefore, the present invention has been made in view of the above conventional problems, and it is an object of the invention to provide a barrier layer-forming composition capable of sufficiently preventing diffusion of a donor element or an acceptor element onto a semiconductor substrate and suppressing surface roughness of the semiconductor substrate; A barrier layer formed by forming a composition of a layer; a method for producing a substrate for a solar cell using the barrier layer to form a composition; and a method for producing a solar cell element.

用來解決上述課題的具體方法如下所述。 The specific method for solving the above problems is as follows.

<1>一種阻擋層形成用組成物，包含：含有鹼土金屬或鹼金屬的金屬化合物；分散介質(dispersion medium)；以及選自由金屬烷氧化物、矽烷氧化物、矽酸酯低聚物(silicate oligomer)以及矽酮油所組成組群中的1種以上特定化合物。 <1> A barrier layer-forming composition comprising: a metal compound containing an alkaline earth metal or an alkali metal; a dispersion medium; and a metal alkoxide, a decane oxide, a silicate oligomer (silicate) Isomorphic) and one or more specific compounds in the group consisting of oxime oil.

<2>如上述<1>所述的阻擋層形成用組成物，其中上 述特定化合物包含選自由矽烷氧化物、矽酸甲酯低聚物及矽酸乙酯低聚物所組成組群中的1種以上。 <2> The composition for forming a barrier layer according to the above <1>, wherein The specific compound contains one or more selected from the group consisting of a decane oxide, a methyl phthalate oligomer, and an ethyl citrate oligomer.

<3>如上述<1>或<2>所述的阻擋層形成用組成物，其中上述特定化合物包含矽烷氧化物，並且上述矽烷氧化物包含選自由四甲氧基矽烷及四乙氧基矽烷所組成組群中的1種以上。 The composition for forming a barrier layer according to the above <1>, wherein the specific compound contains a decane oxide, and the decane oxide is selected from the group consisting of tetramethoxy decane and tetraethoxy decane. One or more of the constituent groups.

<4>如上述<1>至<3>中任一項所述的阻擋層形成用組成物，其中不揮發成分中的上述特定化合物的含有率為0.5質量%以上、50質量%以下。 The composition for forming a barrier layer according to any one of the above aspects, wherein the content of the specific compound in the nonvolatile component is 0.5% by mass or more and 50% by mass or less.

<5>如上述<1>至<4>中任一項所述的阻擋層形成用組成物，其中上述含有鹼土金屬或鹼金屬的金屬化合物包含選自由鎂、鈣、鈉、鉀、鋰、銣、銫、鈹、鍶、鋇及鐳所組成組群中的1種以上作為金屬元素。 The barrier layer-forming composition according to any one of the above-mentioned, wherein the alkaline earth metal or alkali metal-containing metal compound is selected from the group consisting of magnesium, calcium, sodium, potassium, lithium, One or more of the group consisting of 铷, 铯, 铍, 锶, 钡, and radium is used as a metal element.

<6>如上述<1>至<5>中任一項所述的阻擋層形成用組成物，其中上述含有鹼土金屬或鹼金屬的金屬化合物包含選自由氧化鎂、氧化鈣、氧化鉀、碳酸鎂、碳酸鈣、硫酸鎂、硫酸鈣、硝酸鈣、氫氧化鎂及氫氧化鈣所組成組群中的1種以上。 The composition for forming a barrier layer according to any one of the above aspects, wherein the metal compound containing an alkaline earth metal or an alkali metal is selected from the group consisting of magnesium oxide, calcium oxide, potassium oxide, and carbonic acid. One or more of the group consisting of magnesium, calcium carbonate, magnesium sulfate, calcium sulfate, calcium nitrate, magnesium hydroxide, and calcium hydroxide.

<7>如上述<1>至<6>中任一項所述的阻擋層形成用組成物，其中上述含有鹼土金屬或鹼金屬的金屬化合物是在常溫下為固體的粒子，且上述粒子的體積平均粒徑為30 μm以下。 The composition for forming a barrier layer according to any one of the above-mentioned, wherein the metal compound containing an alkaline earth metal or an alkali metal is a solid which is solid at normal temperature, and the particles are The volume average particle diameter is 30 μm or less.

<8>如上述<1>至<7>中任一項所述的阻擋層形成 用組成物，其中更包含有機黏合劑。 <8> The barrier layer formation according to any one of the above <1> to <7> The composition further comprises an organic binder.

<9>如上述<8>所述的阻擋層形成用組成物，其中上述有機黏合劑包含選自由丙烯酸樹脂、丁醛樹脂及纖維素樹脂所組成組群中的1種以上。 The composition for forming a barrier layer according to the above-mentioned <8>, wherein the organic binder contains one or more selected from the group consisting of an acrylic resin, a butyral resin, and a cellulose resin.

<10>如上述<1>至<9>中任一項所述的阻擋層形成用組成物，其中上述分散介質包含選自由水、醇系溶劑、醚系溶劑、二醇單醚系溶劑及萜(terpene)系溶劑所組成組群中的1種以上。 The composition for forming a barrier layer according to any one of the above aspects, wherein the dispersion medium is selected from the group consisting of water, an alcohol solvent, an ether solvent, a glycol monoether solvent, and The terpene is one or more selected from the group consisting of solvents.

<11>如上述<1>至<10>中任一項所述的阻擋層形成用組成物，其中不揮發成分中的上述含有鹼土金屬或鹼金屬的金屬化合物的含有率為0.5質量%以上、且小於100質量%。 The composition for forming a barrier layer according to any one of the above-mentioned, wherein the content of the alkaline earth metal or alkali metal-containing metal compound in the nonvolatile component is 0.5% by mass or more. And less than 100% by mass.

<12>如上述<1>至<11>中任一項所述的阻擋層形成用組成物，其中25℃下的黏度為0.5 Pa．s以上、400 Pa．s以下。 The composition for forming a barrier layer according to any one of the above-mentioned <1>, wherein the viscosity at 25 ° C is 0.5 Pa. s above, 400 Pa. s below.

<13>如上述<1>至<12>中任一項所述的阻擋層形成用組成物，其中不揮發成分中的上述含有鹼土金屬或鹼金屬的金屬化合物的含有率為10質量%以上、55質量%以下。 The composition for forming a barrier layer according to any one of the above-mentioned items, wherein the content of the alkaline earth metal or alkali metal-containing metal compound in the nonvolatile component is 10% by mass or more. , 55 mass% or less.

<14>如上述<1>至<13>中任一項所述的阻擋層形成用組成物，其中25℃下的黏度為40 Pa．s以上、200 Pa．s以下。 The composition for forming a barrier layer according to any one of the above-mentioned <1>, wherein the viscosity at 25 ° C is 40 Pa. s above, 200 Pa. s below.

<15>如上述<1>至<14>中任一項所述的阻擋層形成用組成物，其中上述含有鹼土金屬或鹼金屬的金屬化合物包含選自由氧化鈣及碳酸鈣所組成組群中的1種以上。 The composition for forming a barrier layer according to any one of the above aspects, wherein the alkaline earth metal or alkali metal-containing metal compound is selected from the group consisting of calcium oxide and calcium carbonate. One or more.

<16>如上述<1>至<15>中任一項所述的阻擋層形成用組成物，其中更含有觸變劑(thixotropic agent)。 The composition for forming a barrier layer according to any one of the above aspects, which further comprises a thixotropic agent.

<17>如上述<1>至<16>中任一項所述的阻擋層形成用組成物，其用於形成阻擋層，該阻擋層用來在半導體基板上部分性地形成擴散層。 The barrier layer-forming composition according to any one of the above-mentioned <1> to <16> which is used for forming a barrier layer for partially forming a diffusion layer on a semiconductor substrate.

<18>一種阻擋層，其為如上述<1>至<17>中任一項所述的阻擋層形成用組成物的乾燥體。 <18> A dry layer of the barrier layer-forming composition according to any one of the above-mentioned <1> to <17>.

<19>一種太陽電池用基板的製造方法，包括：將如上述<1>至<17>中任一項所述的阻擋層形成用組成物施用至半導體基板上而形成圖案狀的阻擋層的步驟；以及於上述半導體基板上的未形成上述阻擋層的部分，使施體元素或者受體元素擴散，在上述半導體基板內部分性地形成擴散層的步驟。 <19> A method for producing a substrate for a solar cell, comprising: applying the barrier layer-forming composition according to any one of the above-mentioned items <1> to <17> to a semiconductor substrate to form a patterned barrier layer And a step of partially forming a diffusion layer in the semiconductor substrate by diffusing a donor element or an acceptor element on a portion of the semiconductor substrate where the barrier layer is not formed.

<20>如上述<19>所述的太陽電池用基板的製造方法，其中上述施用阻擋層形成用組成物的方法為印刷法或者噴墨法。 The method for producing a substrate for a solar cell according to the above <19>, wherein the method of applying the composition for forming a barrier layer is a printing method or an inkjet method.

<21>一種太陽電池元件的製造方法，包括在利用如上述<19>或<20>所述的製造方法而獲得的太陽電池用基板的擴散層上形成電極的步驟。 <21> A method of producing a solar cell element, comprising the step of forming an electrode on a diffusion layer of a substrate for a solar cell obtained by the production method according to the above <19> or <20>.

依據本發明，可提供一種能夠充分防止施體元素或者受 體元素向半導體基板的擴散，抑制半導體基板的表面粗糙的阻擋層形成用組成物；使用該阻擋層形成用組成物而形成的阻擋層；使用該阻擋層形成用組成物的太陽電池用基板的製造方法以及太陽電池元件的製造方法。 According to the present invention, it is possible to provide a method capable of sufficiently preventing donor elements or being subjected to a barrier layer-forming composition that diffuses a bulk element to a semiconductor substrate, suppresses surface roughness of the semiconductor substrate, a barrier layer formed using the barrier layer-forming composition, and a solar cell substrate using the barrier layer-forming composition Manufacturing method and method of manufacturing solar cell element.

10‧‧‧基板 10‧‧‧Substrate

11‧‧‧阻擋層形成用組成物 11‧‧‧Block formation composition

12、13‧‧‧塗佈用擴散材料 12, 13‧‧‧Developing diffusion materials

14‧‧‧n+型擴散層 14‧‧‧n + type diffusion layer

15‧‧‧p+型擴散層 15‧‧‧p + diffusion layer

12'、13'‧‧‧塗佈用擴散材料的焙燒物 12', 13'‧‧‧Roasting materials for coating diffusion materials

16‧‧‧抗反射膜 16‧‧‧Anti-reflective film

17‧‧‧鈍化膜 17‧‧‧ Passivation film

18、19‧‧‧電極 18, 19‧‧‧ electrodes

圖1是概念性表示本發明的太陽電池用基板以及太陽電池元件的製造步驟的一例的剖面圖。 FIG. 1 is a cross-sectional view conceptually showing an example of a manufacturing procedure of a solar cell substrate and a solar cell element of the present invention.

首先，對本發明的阻擋層形成用組成物進行說明，接著對使用阻擋層形成用組成物的太陽電池用基板的製造方法以及太陽電池元件的製造方法進行說明。 First, the composition for forming a barrier layer of the present invention will be described. Next, a method for producing a substrate for a solar cell using a composition for forming a barrier layer and a method for producing a solar cell element will be described.

此外，本說明書中所謂「步驟」的用語，不僅包含獨立的步驟，即便是無法與其他步驟明確區分的情況，只要達成該步驟的目的，則亦包含於本用語中。另外，本說明書中「~」是指包含其前後所記載的數值來分別作為最小值及最大值的範圍者。進而本說明書中，在組成物中存在多種符合各成分的物質的情況下，只要無特別說明，則組成物中的各成分的量是指組成物中所存在的該多種物質的合計量。 In addition, the term "step" in the present specification includes not only an independent step but also a case where it cannot be clearly distinguished from other steps, and is included in the term as long as the purpose of the step is achieved. In the present specification, "~" means a range including the numerical values described before and after the respective values as the minimum value and the maximum value. Further, in the present specification, when a plurality of substances satisfying the respective components are present in the composition, the amount of each component in the composition means the total amount of the plurality of substances present in the composition unless otherwise specified.

另外，有時將施體元素或者受體元素稱為摻雜劑。 In addition, the donor element or the acceptor element is sometimes referred to as a dopant.

此外，當將半導體基板視作為平面圖來觀察時，本發明中的阻擋層不僅包含形成於整個面的情況，亦包含形成於一部分 上的情況。 Further, when the semiconductor substrate is viewed as a plan view, the barrier layer in the present invention includes not only the case where it is formed on the entire surface but also the portion formed in part. On the situation.

<阻擋層形成用組成物> <Composition for forming a barrier layer>

本發明的阻擋層形成用組成物包含：含有鹼土金屬或鹼金屬的金屬化合物(以下亦稱為「特定鹼化合物」)；分散介質；以及選自由金屬烷氧化物、矽烷氧化物、矽酸酯低聚物以及矽酮油所組成組群中的1種以上特定化合物。本發明的阻擋層形成用組成物阻礙作為摻雜劑的施體元素或者受體元素向半導體基板的擴散。因此，藉由在半導體基板中的不希望擴散施體元素或者受體元素的區域，使用本發明的阻擋層形成用組成物來形成阻擋層，能夠充分防止施體元素及受體元素於上述區域中的擴散。因此，能夠於半導體基板內選擇性地形成摻雜區域。關於其原因，可如下般考慮。 The barrier layer-forming composition of the present invention comprises: a metal compound containing an alkaline earth metal or an alkali metal (hereinafter also referred to as "specific alkali compound"); a dispersion medium; and a metal alkoxide, a decane oxide, a phthalate ester. One or more specific compounds in the group consisting of oligomers and fluorenone oils. The barrier layer-forming composition of the present invention inhibits diffusion of a donor element or an acceptor element as a dopant to a semiconductor substrate. Therefore, by forming the barrier layer by using the barrier layer-forming composition of the present invention in a region of the semiconductor substrate where the donor element or the acceptor element is not desired to be diffused, it is possible to sufficiently prevent the donor element and the acceptor element from being in the above region. The spread in the middle. Therefore, a doped region can be selectively formed in the semiconductor substrate. Regarding the reason, it can be considered as follows.

若使特定鹼化合物包含於阻擋層形成用組成物中，將該阻擋層形成用組成物塗佈至半導體基板上，然後施用含有摻雜劑的摻雜化合物，則在特定鹼化合物與摻雜化合物之間產生反應。由於該反應的反應性高於摻雜化合物與半導體基板的反應，故而被認為阻礙施體元素或者受體元素向半導體基板擴散。 When a specific alkali compound is contained in a composition for forming a barrier layer, the composition for forming a barrier layer is applied onto a semiconductor substrate, and then a dopant compound containing a dopant is applied, and a specific alkali compound and a dopant compound are used. A reaction occurs between them. Since the reactivity of the reaction is higher than the reaction between the dopant compound and the semiconductor substrate, it is considered that the diffusion of the donor element or the acceptor element to the semiconductor substrate is inhibited.

此外，通常，含有施體元素或者受體元素的摻雜化合物是使用氧化磷、氧化硼、磷醯氯等，該些化合物均為酸性化合物(或者與水反應而表現出酸性的化合物)。因此，特定鹼化合物特佳為鹼性化合物。在鹼性化合物的特定鹼化合物與摻雜化合物之 間進行酸鹼反應，該酸鹼反應的反應性高，因此更有效果地阻礙施體元素或者受體元素向半導體基板擴散。 Further, in general, a doping compound containing a donor element or an acceptor element is phosphorus oxide, boron oxide, phosphonium chloride or the like, and these compounds are all acidic compounds (or compounds which react with water to exhibit acidity). Therefore, a specific base compound is particularly preferably a basic compound. Specific base compound and doping compound in basic compound The acid-base reaction is carried out, and the reactivity of the acid-base reaction is high, so that the donor element or the acceptor element is more effectively inhibited from diffusing into the semiconductor substrate.

上述特定鹼化合物較佳為在500℃以上的高溫下亦為熱 性穩定的金屬化合物。鹼性的金屬化合物較佳為含有鹼土金屬或鹼金屬的金屬化合物。 The specific alkali compound is preferably hot at a high temperature of 500 ° C or higher. A stable metal compound. The basic metal compound is preferably a metal compound containing an alkaline earth metal or an alkali metal.

含有鹼土金屬或鹼金屬的金屬化合物當熔入半導體基 板中時，在半導體基板中不作為載子的再結合中心來發揮作用，因此能夠抑制使太陽電池用基板的轉變效率下降這一不良情況。 a metal compound containing an alkaline earth metal or an alkali metal when melted into a semiconductor base In the case of the plate, the semiconductor substrate does not function as a recombination center of the carrier. Therefore, it is possible to suppress the problem that the conversion efficiency of the solar cell substrate is lowered.

另外，本發明的阻擋層形成用組成物包含選自由金屬烷 氧化物、矽烷氧化物、矽酸酯低聚物以及矽酮油所組成組群中的1種以上特定化合物。藉由使用包含特定化合物的阻擋層形成用組成物，可於阻擋層的形成步驟中，抑制由特定鹼化合物引起的半導體基板的侵蝕，且抑制半導體基板的表面粗糙的產生。藉由抑制半導體基板的表面粗糙的產生，能夠抑制對作為半導體基板的矽基板的損傷，且能夠抑制使用該半導體基板的太陽電池元件的發電特性的下降。 Further, the barrier layer-forming composition of the present invention contains a metal alkane selected from the group consisting of One or more specific compounds in the group consisting of an oxide, a decane oxide, a phthalate oligomer, and an oxime oil. By using the composition for forming a barrier layer containing a specific compound, it is possible to suppress the erosion of the semiconductor substrate caused by the specific alkali compound in the step of forming the barrier layer, and suppress the generation of surface roughness of the semiconductor substrate. By suppressing the occurrence of surface roughness of the semiconductor substrate, it is possible to suppress damage to the tantalum substrate as the semiconductor substrate, and it is possible to suppress a decrease in power generation characteristics of the solar cell element using the semiconductor substrate.

(含有鹼土金屬或鹼金屬的金屬化合物) (metal compound containing alkaline earth metal or alkali metal)

本發明的阻擋層形成用組成物包括含有鹼土金屬或鹼金屬的金屬化合物。藉由使用包括含有鹼土金屬或鹼金屬的金屬化合物的阻擋層形成用組成物，能夠阻礙施體元素或者受體元素向半導體基板擴散。 The barrier layer-forming composition of the present invention includes a metal compound containing an alkaline earth metal or an alkali metal. By using a composition for forming a barrier layer comprising a metal compound containing an alkaline earth metal or an alkali metal, it is possible to prevent the donor element or the acceptor element from diffusing into the semiconductor substrate.

含有鹼土金屬或鹼金屬的金屬化合物在常溫(約20℃) 下可為液體，亦可為固體。為了在高溫下亦保持充分的阻擋層性能，必需在高溫下亦具有化學穩定性，就該觀點而言，較佳為在熱擴散的高溫(例如500℃以上)下為固體。此處，例如含有鹼土金屬或鹼金屬的金屬化合物，可列舉：含有鹼土金屬或鹼金屬的金屬氧化物、以及含有鹼土金屬或鹼金屬的金屬鹽。 a metal compound containing an alkaline earth metal or an alkali metal at normal temperature (about 20 ° C) The bottom can be a liquid or a solid. In order to maintain sufficient barrier properties at a high temperature, it is necessary to have chemical stability at a high temperature. From this point of view, it is preferably a solid at a high temperature (for example, 500 ° C or higher) at which heat is diffused. Here, examples of the metal compound containing an alkaline earth metal or an alkali metal include a metal oxide containing an alkaline earth metal or an alkali metal, and a metal salt containing an alkaline earth metal or an alkali metal.

含有鹼土金屬或鹼金屬的金屬化合物並無特別限制，較 佳為在使施體元素或者受體元素進行熱擴散的700℃以上的高溫下變化為鹼性化合物的材料。進而就表現出強鹼性的觀點而言，金屬化合物較佳為含有選自由鎂、鈣、鈉、鉀、鋰、銣、銫、鈹、鍶、鋇及鐳所組成組群中的1種以上作為金屬元素，更佳為含有選自鎂、鈣、鋇、鉀、鈉所組成組群中的1種以上，尤佳為含有選自由鎂、鈣及鉀所組成組群中的1種以上，就低毒性、獲取的容易度的觀點而言，特佳為含有選自由鎂及鈣所組成組群中的1種以上。而且，就化學穩定性的觀點而言，較佳為選自由金屬氧化物、金屬碳酸鹽、金屬硝酸鹽、金屬硫酸鹽及金屬氫氧化物所組成組群中的1種以上，更佳為選自由金屬氧化物、金屬碳酸鹽及金屬氫氧化物所組成組群中的1種以上，上述金屬氧化物、金屬碳酸鹽、金屬硝酸鹽、金屬硫酸鹽及金屬氫氧化物含有選自由該些金屬元素所組成組群中的1種以上。 The metal compound containing an alkaline earth metal or an alkali metal is not particularly limited, It is preferably a material which changes to a basic compound at a high temperature of 700 ° C or higher at which the donor element or the acceptor element is thermally diffused. Further, from the viewpoint of exhibiting strong alkalinity, the metal compound preferably contains one or more selected from the group consisting of magnesium, calcium, sodium, potassium, lithium, cesium, rubidium, cesium, cesium, strontium, and radium. The metal element is preferably one or more selected from the group consisting of magnesium, calcium, barium, potassium, and sodium, and more preferably one or more selected from the group consisting of magnesium, calcium, and potassium. From the viewpoint of low toxicity and ease of availability, it is particularly preferable to contain one or more selected from the group consisting of magnesium and calcium. Further, from the viewpoint of chemical stability, it is preferably one or more selected from the group consisting of metal oxides, metal carbonates, metal nitrates, metal sulfates, and metal hydroxides, and more preferably selected. One or more of the group consisting of a free metal oxide, a metal carbonate, and a metal hydroxide, wherein the metal oxide, the metal carbonate, the metal nitrate, the metal sulfate, and the metal hydroxide are selected from the metals selected from the group consisting of One or more of the groups formed by the elements.

尤佳為使用：氧化鈉、氧化鉀、氧化鋰、氧化鈣、氧化 鎂、氧化銣、氧化銫、氧化鈹、氧化鍶、氧化鋇、氧化鐳等金屬氧化物及它們的複合氧化物；氫氧化鈉、氫氧化鉀、氫氧化鋰、氫氧化鈣、氫氧化鎂、氫氧化銣、氫氧化銫、氫氧化鈹、氫氧化鍶、氫氧化鋇、氫氧化鐳等金屬氫氧化物；碳酸鈉、碳酸鉀、碳酸鋰、碳酸鈣、碳酸鎂、碳酸銣、碳酸銫、碳酸鈹、碳酸鍶、碳酸鋇、碳酸鐳等金屬碳酸鹽；硝酸鈉、硝酸鉀、硝酸鋰、硝酸鈣、硝酸鎂、硝酸銣、硝酸銫、硝酸鈹、硝酸鍶、硝酸鋇、硝酸鐳等金屬硝酸鹽；硫酸鈉、硫酸鉀、硫酸鋰、硫酸鈣、硫酸鎂、硫酸銣、硫酸銫、硫酸鈹、硫酸鍶、硫酸鋇、硫酸鐳等金屬硫酸鹽；乙二酸鈣、乙二酸鎂、乙二酸鋇、乙二酸鉀、乙二酸鈉、乙二酸鋰等乙二酸鹽；氯化鉀、氯化鋰、氯化鈉、氯化鎂、氯化鈣、氯化鋇、氯化鍶、氯化銫、氯化銣等氯化物等。 Especially good for use: sodium oxide, potassium oxide, lithium oxide, calcium oxide, oxidation Metal oxides such as magnesium, cerium oxide, cerium oxide, cerium oxide, cerium oxide, cerium oxide, and radium oxide, and composite oxides thereof; sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide, a metal hydroxide such as barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide or radium hydroxide; sodium carbonate, potassium carbonate, lithium carbonate, calcium carbonate, magnesium carbonate, barium carbonate, barium carbonate, Metal carbonates such as barium carbonate, barium carbonate, barium carbonate, and radium carbonate; metals such as sodium nitrate, potassium nitrate, lithium nitrate, calcium nitrate, magnesium nitrate, barium nitrate, barium nitrate, barium nitrate, barium nitrate, barium nitrate, and radium nitrate Nitrate; sodium sulfate, potassium sulfate, lithium sulfate, calcium sulfate, magnesium sulfate, barium sulfate, barium sulfate, barium sulfate, barium sulfate, barium sulfate, radium sulfate, etc.; metal oxalate, magnesium oxalate, Oxalate such as oxalate, potassium oxalate, sodium oxalate or lithium oxalate; potassium chloride, lithium chloride, sodium chloride, magnesium chloride, calcium chloride, barium chloride, barium chloride , chloride such as barium chloride or barium chloride.

更佳為使用選自由上述金屬氧化物及它們的複合氧化物、金屬氫氧化物、以及金屬碳酸鹽所組成組群中的1種以上。 More preferably, one or more selected from the group consisting of the above metal oxides and composite oxides thereof, metal hydroxides, and metal carbonates are used.

該些化合物中，就低毒性及獲取的容易度的觀點而言，較佳為使用選自碳酸鈉、氧化鈉、碳酸鉀、氧化鉀、碳酸鈣、氫氧化鈣、氧化鈣、碳酸鎂、氫氧化鎂、硫酸鎂、硫酸鈣、硝酸鈣、及氧化鎂中的1種以上，更佳為使用選自由氧化鎂、氧化鈣、碳酸鎂、碳酸鈣、硫酸鎂、硫酸鈣、硝酸鈣、氧化鉀、氫氧化鎂、硬脂酸鈣、及氫氧化鈣所組成組群中的1種以上，尤佳為使用選自碳酸鈣、氧化鈣、氧化鉀、氫氧化鈣、碳酸鎂及氧化鎂中的1 種以上，特佳為使用選自碳酸鈣、氧化鈣中的1種以上。 Among these compounds, from the viewpoints of low toxicity and ease of availability, it is preferred to use a salt selected from the group consisting of sodium carbonate, sodium oxide, potassium carbonate, potassium oxide, calcium carbonate, calcium hydroxide, calcium oxide, magnesium carbonate, and hydrogen. One or more selected from the group consisting of magnesium oxide, magnesium sulfate, calcium sulfate, calcium nitrate, and magnesium oxide, and more preferably selected from the group consisting of magnesium oxide, calcium oxide, magnesium carbonate, calcium carbonate, magnesium sulfate, calcium sulfate, calcium nitrate, and potassium oxide. One or more of the group consisting of magnesium hydroxide, calcium stearate, and calcium hydroxide, and particularly preferably selected from the group consisting of calcium carbonate, calcium oxide, potassium oxide, calcium hydroxide, magnesium carbonate, and magnesium oxide. 1 In particular, it is particularly preferable to use one or more selected from the group consisting of calcium carbonate and calcium oxide.

含有鹼土金屬或鹼金屬的金屬化合物、或者將該金屬化 合物在800℃以上於空氣中或者惰性環境中進行熱處理而成的化合物的鹼強度較佳為12.2以上，更佳為17.2以上，尤佳為26.5以上。所謂800℃以上，是指實際上可作為使施體元素或受體元素擴散的溫度而採用的溫度，反映出實際的使用環境。在含有鹼土金屬或鹼金屬的金屬化合物的表面積或粒徑相等的情況下，鹼強度越大，使用該金屬化合物而形成的阻擋層的阻擋能力，即阻礙施體元素或受體元素擴散的能力越提高。 a metal compound containing an alkaline earth metal or an alkali metal, or metallizing the metal compound The alkali strength of the compound which is heat-treated at 800 ° C or higher in air or in an inert atmosphere is preferably 12.2 or more, more preferably 17.2 or more, and still more preferably 26.5 or more. The term "800 ° C or higher" refers to a temperature which can be practically used as a temperature at which a donor element or an acceptor element is diffused, and reflects an actual use environment. In the case where the surface area or particle diameter of the metal compound containing an alkaline earth metal or an alkali metal is equal, the greater the alkali strength, the barrier property of the barrier layer formed using the metal compound, that is, the ability to inhibit the diffusion of the donor element or the acceptor element. The more you improve.

此處所謂的鹼強度，是指使用哈密特(Hammett)指示劑而得的酸度函數H-，可根據吸附指示劑時的顏色變化來測定。具體而言，使用2,4,6-三硝基苯胺作為指示劑而由黃色變化為紅橙色的情況下的H-為12.2以上，使用2,4-二硝基苯胺作為指示劑而由黃色變化為紫色的情況下的H-為15.0以上，使用4-氯-2-硝基苯胺作為指示劑而由黃色變化為橙色的情況下的H-為18.4以上，使用4-氯苯胺作為指示劑而由黃色變化為粉紅色的情況下的H-為26.5以上。 The term "base strength" as used herein refers to an acidity function H - obtained by using a Hammett indicator, which can be measured according to the change in color when the indicator is adsorbed. Specifically, 2,4,6-nitroaniline as the indicator changes from yellow to red-orange lower case H - 12.2 above, using 2,4-dinitroaniline as an indicator and the yellow H is changed in the case where purple - 15.0 above, using 4-chloro-2-nitroaniline as the indicator changes from yellow to orange in the case where H - is 18.4 or more, using 4-chloroaniline as an indicator H pink while the case is changed from yellow - 26.5 or more.

含有鹼土金屬或鹼金屬的金屬化合物的表面可經氧化矽、氧化鋯、氧化鋅、氧化鈦、氧化鋁等金屬氧化物進行表面處理。藉由實施表面處理，存在能夠抑制含有鹼土金屬或鹼金屬的金屬化合物與矽基板的反應性，且能夠抑制施用了該金屬化合物 的半導體基板的表面粗糙的傾向。 The surface of the metal compound containing an alkaline earth metal or an alkali metal may be surface-treated with a metal oxide such as cerium oxide, zirconium oxide, zinc oxide, titanium oxide or aluminum oxide. By performing the surface treatment, there is a possibility that the reactivity of the metal compound containing an alkaline earth metal or an alkali metal with the ruthenium substrate can be suppressed, and the application of the metal compound can be suppressed. The surface of the semiconductor substrate has a tendency to be rough.

利用金屬氧化物的表面處理量並無特別限制，相對於含 有鹼土金屬或鹼金屬的金屬化合物，金屬化合物的表面中的金屬氧化物的量較佳為0.01質量%以上、30質量%以下，更佳為0.5質量%以上、20質量%以下，尤佳為1質量%以上、15質量%以下。 The amount of surface treatment using metal oxide is not particularly limited, as opposed to The metal compound having an alkaline earth metal or an alkali metal, the amount of the metal oxide in the surface of the metal compound is preferably 0.01% by mass or more and 30% by mass or less, more preferably 0.5% by mass or more and 20% by mass or less, and particularly preferably 1% by mass or more and 15% by mass or less.

於含有鹼土金屬或鹼金屬的金屬化合物在常溫(25℃) 下為固體的情況且呈現出粒子形狀的情況下，該粒子的粒徑較佳為30 μm以下，更佳為0.01 μm~30 μm，尤佳為0.02 μm~10 μm，特佳為0.03 μm~5 μm。 For metal compounds containing alkaline earth metals or alkali metals at room temperature (25 ° C) In the case where the lower portion is a solid and exhibits a particle shape, the particle diameter of the particles is preferably 30 μm or less, more preferably 0.01 μm to 30 μm, particularly preferably 0.02 μm to 10 μm, and particularly preferably 0.03 μm. 5 μm.

若粒徑為30 μm以下，則容易使施體元素或者受體元素 於半導體基板的所需區域均勻擴散(摻雜)。另外，若粒徑為0.01 μm以上，則容易使含有鹼土金屬或鹼金屬的金屬化合物分散於阻擋層形成用組成物中。另外，含有鹼土金屬或鹼金屬的金屬化合物亦可溶解於分散介質中。 If the particle size is 30 μm or less, it is easy to make a donor element or an acceptor element. Uniform diffusion (doping) in a desired region of the semiconductor substrate. In addition, when the particle diameter is 0.01 μm or more, the metal compound containing an alkaline earth metal or an alkali metal is easily dispersed in the composition for forming a barrier layer. Further, the metal compound containing an alkaline earth metal or an alkali metal may also be dissolved in the dispersion medium.

此外，粒徑表示體積平均粒徑，可利用雷射散射繞射法 粒度分布測定裝置等來測定。檢測出對粒子照射的雷射光的散射光強度與角度的關係，基於米氏散射理論(Mie scattering theory)來算出體積平均粒徑。對測定時的分散介質並無特別限制，但較佳為使用並不溶解作為測定對象的粒子的分散介質。 In addition, the particle size represents the volume average particle size, and the laser scattering diffraction method can be utilized. It is measured by a particle size distribution measuring apparatus or the like. The relationship between the intensity of the scattered light of the laser light irradiated to the particles and the angle was detected, and the volume average particle diameter was calculated based on the Mie scattering theory. The dispersion medium at the time of measurement is not particularly limited, but a dispersion medium which does not dissolve the particles to be measured is preferably used.

獲得粒徑為30 μm以下的特定鹼化合物的粒子的方法並 無特別限制，例如可進行粉碎處理而獲得。粉碎方法可採用乾式 粉碎法及濕式粉碎法。乾式粉碎法可採用噴磨機(jet mill)、振磨機(vibration mill)、球磨機(ball mill)等。濕式粉碎法可使用珠磨機(beads mill)、球磨機等。 A method of obtaining particles of a specific alkali compound having a particle diameter of 30 μm or less and It is not particularly limited and can be obtained, for example, by pulverization treatment. The pulverization method can be dry Crushing method and wet pulverization method. The dry pulverization method may employ a jet mill, a vibration mill, a ball mill, or the like. As the wet pulverization method, a beads mill, a ball mill or the like can be used.

若粉碎處理時由粉碎裝置引起的雜質混入於阻擋層形 成用組成物中，則存在導致半導體基板內的載子的壽命下降的顧慮，因此粉碎容器、珠粒、球珠等的材質較佳為選擇對半導體基板的影響少的材質。粉碎時適宜使用的容器等的材質可列舉氧化鋁、部分穩定化氧化鋯等。另外，獲得粒徑為30 μm以下的特定鹼化合物的粒子的方法除了粉碎方法以外，可使用氣相氧化法、水解法等。 If the impurities caused by the pulverizing device during the pulverization process are mixed into the barrier layer In the composition for use, there is a concern that the life of the carrier in the semiconductor substrate is lowered. Therefore, the material of the pulverization container, the beads, the beads, or the like is preferably a material having a small influence on the semiconductor substrate. Examples of the material of the container or the like which is suitably used for pulverization include alumina, partially stabilized zirconia, and the like. Further, a method of obtaining particles of a specific alkali compound having a particle diameter of 30 μm or less may be a gas phase oxidation method, a hydrolysis method, or the like, in addition to the pulverization method.

另外，特定鹼化合物的粒子可為以包括含有鹼土金屬或 鹼金屬的金屬化合物以外的化合物的粒子(例如氧化矽粒子)作為載體，且於該載體的表面包覆或者分散承載有含有鹼土金屬或鹼金屬的金屬化合物的材料。該形態下，可擴大含有鹼土金屬或鹼金屬的金屬化合物的有效表面積，存在阻礙施體元素或者受體元素向半導體基板的擴散的特性提高的可能性。 In addition, the particles of the specific alkali compound may be included to include an alkaline earth metal or A particle of a compound other than the metal compound of an alkali metal (for example, cerium oxide particles) is used as a carrier, and a material carrying a metal compound containing an alkaline earth metal or an alkali metal is coated or dispersed on the surface of the carrier. In this form, the effective surface area of the metal compound containing an alkaline earth metal or an alkali metal can be enlarged, and there is a possibility that the property of inhibiting diffusion of the donor element or the acceptor element into the semiconductor substrate is increased.

上述載體較佳為顯示10 m2/g以上的布厄特(Brunauer-Emmett-Teller，BET)比表面積的材料，可例示SiO2、活性碳、碳纖維、氧化鋅等無機材料的粒子。 The carrier preferably has a Brunauer-Emmett-Teller (BET) specific surface area of 10 m 2 /g or more, and examples thereof include particles of an inorganic material such as SiO 2 , activated carbon, carbon fibers, or zinc oxide.

特定鹼化合物的粒子的形狀並無特別限制，可為大致球狀、扁平狀、鱗片狀、塊狀、橢球狀、板狀、海膽狀、多孔質球 狀及棒狀中的任一種。上述粒子的形狀可利用電子顯微鏡等來確認。 The shape of the particles of the specific alkali compound is not particularly limited, and may be a substantially spherical shape, a flat shape, a scale shape, a block shape, an ellipsoid shape, a plate shape, a sea urchin shape, or a porous ball. Any of a shape and a stick shape. The shape of the above particles can be confirmed by an electron microscope or the like.

阻擋層形成用組成物中的含有鹼土金屬或鹼金屬的金 屬化合物的含量是考慮到塗佈性、施體元素或者受體元素的擴散性等來決定。通常，阻擋層形成用組成物中的含有鹼土金屬或鹼金屬的金屬化合物的含有率較佳為0.1質量%以上、95質量%以下，更佳為0.1質量%以上、80質量%以下，尤佳為0.1質量%以上、70質量%以下，特佳為2質量%以上、60質量%以下，極佳為10質量%以上、55質量%以下。若含有鹼土金屬或鹼金屬的金屬化合物的含有率為0.1質量%以上，則可充分阻礙施體元素或者受體元素向半導體基板中的擴散。若含有鹼土金屬或鹼金屬的金屬化合物的含有率為95質量%以下，則阻擋層形成用組成物中的含有鹼土金屬或鹼金屬的金屬化合物的分散性變得良好，對基板的塗佈性提高。 Gold containing an alkaline earth metal or an alkali metal in the composition for forming a barrier layer The content of the genus compound is determined in consideration of coatability, diffusibility of a donor element or an acceptor element, and the like. In general, the content of the alkaline earth metal or alkali metal-containing metal compound in the barrier layer-forming composition is preferably 0.1% by mass or more and 95% by mass or less, more preferably 0.1% by mass or more and 80% by mass or less. It is 0.1% by mass or more and 70% by mass or less, particularly preferably 2% by mass or more and 60% by mass or less, and most preferably 10% by mass or more and 55% by mass or less. When the content of the metal compound containing an alkaline earth metal or an alkali metal is 0.1% by mass or more, diffusion of the donor element or the acceptor element into the semiconductor substrate can be sufficiently inhibited. When the content of the metal compound containing an alkaline earth metal or an alkali metal is 95% by mass or less, the dispersibility of the metal compound containing an alkaline earth metal or an alkali metal in the composition for forming a barrier layer is good, and the coating property to the substrate is good. improve.

另外，阻擋層形成用組成物的所有不揮發成分中的含有 鹼土金屬及鹼金屬的金屬化合物的含有率較佳為0.5質量%以上且小於100質量%，更佳為5質量%以上、70質量%以下，尤佳為10質量%以上、55質量%以下。藉由為上述範圍內，存在獲得充分的阻擋層控制效果的傾向。 In addition, the content of all non-volatile components of the barrier layer-forming composition The content of the metal compound of the alkaline earth metal and the alkali metal is preferably 0.5% by mass or more and less than 100% by mass, more preferably 5% by mass or more and 70% by mass or less, and particularly preferably 10% by mass or more and 55% by mass or less. Within the above range, there is a tendency to obtain a sufficient barrier layer control effect.

此處，所謂不揮發成分，是指在600℃以上、1500℃以 下進行熱處理時不揮發的成分。此外，不揮發成分可利用熱重量 分析儀(thermogravimetry，TG)來求出，不揮發成分中的含有鹼土金屬及鹼金屬的金屬化合物的總含有率可利用感應耦合電漿(inductively coupled plasma，ICP)發射光譜分析(emission spectrochemical analysis)/質量分析法(inductively coupled plasma-mass spectrometry method，ICP-MS法)、原子吸光法來求出。 Here, the term "non-volatile component" means at 600 ° C or higher and 1500 ° C. A component that does not volatilize when heat treated. In addition, non-volatile components can utilize thermal weight An analyzer (thermogravimetry, TG) is used to determine the total content of the alkaline earth metal and alkali metal-containing metal compound in the non-volatile component by inductively coupled plasma (ICP) emission spectrochemical analysis. / Inductively coupled plasma-mass spectrometry method, ICP-MS method, atomic absorption method.

(特定化合物) (specific compound)

本發明的阻擋層形成用組成物包含選自由金屬烷氧化 物、矽烷氧化物、矽酸酯低聚物以及矽酮油所組成組群中的1種以上特定化合物。藉由包含特定化合物，可抑制阻擋層的形成步驟中的半導體基板的侵蝕，且可抑制半導體基板的表面粗糙的產生。 The barrier layer forming composition of the present invention comprises an oxidation selected from a metal alkane One or more specific compounds in the group consisting of a substance, a decane oxide, a phthalate oligomer, and an oxime oil. By including a specific compound, erosion of the semiconductor substrate in the step of forming the barrier layer can be suppressed, and generation of surface roughness of the semiconductor substrate can be suppressed.

半導體基板的表面粗糙可根據自半導體基板的表面隨 機選取的各部分的算術平均粗糙度(Ra)、最大高度(Ry)、十點平均粗糙度(Rz)、凹凸的平均間隔(Sm)、局部頂端的平均間隔(S)的算術平均值或者負荷長度率(tp)的算術平均值來評價。具體而言，可依據JISB0633：2001/ISO 4288：1996進行測定來評價，其中較佳為以算術平均粗糙度(Ra)進行評價。 The surface roughness of the semiconductor substrate can be based on the surface of the semiconductor substrate The arithmetic mean roughness (Ra), the maximum height (Ry), the ten-point average roughness (Rz), the average interval of the bumps (Sm), the arithmetic mean of the average interval (S) of the local tip, or The arithmetic mean of the load length ratio (tp) was evaluated. Specifically, it can be evaluated in accordance with JIS B0633:2001/ISO 4288:1996, and it is preferable to evaluate it by arithmetic mean roughness (Ra).

所獲得的半導體基板的算術平均粗糙度(Ra)較佳為 0.1 μm以下，更佳為0.05 μm以下，尤佳為0.01 μm以下。若Ra為0.1 μm以下，則存在使用該半導體基板的太陽電池的特性難以下降的傾向。 The arithmetic mean roughness (Ra) of the obtained semiconductor substrate is preferably 0.1 μm or less, more preferably 0.05 μm or less, and particularly preferably 0.01 μm or less. When Ra is 0.1 μm or less, the characteristics of the solar cell using the semiconductor substrate tend to be less likely to decrease.

阻擋層形成用組成物的所有不揮發成分中的上述特定 化合物的含有率較佳為0.5質量%以上、50質量%以下，更佳為1質量%以上、25質量%以下，尤佳為5質量%以上、20質量%以下。 The above specific one of all nonvolatile components of the barrier layer forming composition The content of the compound is preferably 0.5% by mass or more and 50% by mass or less, more preferably 1% by mass or more and 25% by mass or less, and particularly preferably 5% by mass or more and 20% by mass or less.

[金屬烷氧化物] [Metal alkoxide]

金屬烷氧化物為特定金屬原子與醇進行反應而得的化合物，較佳為下述通式(1)所表示的化合物。 The metal alkoxide is a compound obtained by reacting a specific metal atom with an alcohol, and is preferably a compound represented by the following formula (1).

M(OR1)a (1)式(1)中，M表示選自Li、Na、K、Mg、Ca、Sr、Ba、La、Ti、B、Zr、Hf、V、Nb、Ta、Cr、Mo、W、Mn、Fe、Co、Ni、Cu、Zn、Pb及Bi中的金屬，a為與金屬M的價數對應的1~7的正數，R1為去除醇的OH基的殘基。 M(OR 1 ) a (1) In the formula (1), M represents a selected from the group consisting of Li, Na, K, Mg, Ca, Sr, Ba, La, Ti, B, Zr, Hf, V, Nb, Ta, Cr. a metal in Mo, W, Mn, Fe, Co, Ni, Cu, Zn, Pb, and Bi, a is a positive number of 1 to 7 corresponding to the valence of the metal M, and R 1 is a residue of the OH group from which the alcohol is removed. base.

形成上述金屬烷氧化物的醇例如可列舉下述式(2)所示的醇作為較佳例。 An example of the alcohol in which the metal alkoxide is formed is an alcohol represented by the following formula (2).

R1OH (2)式(2)中，R1表示碳原子數1~6的飽和或不飽和的烴基、或者經碳原子數1~6的烷氧基取代的總碳原子數2~20的飽和或不飽和的烴基。 R 1 OH (2) In the formula (2), R 1 represents a saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms or a total of 2 to 20 carbon atoms substituted by an alkoxy group having 1 to 6 carbon atoms; a saturated or unsaturated hydrocarbon group.

上述通式(2)中，R1所表示的碳原子數1~6的飽和或不飽和的烴基可為直鏈、分支鏈狀及環狀中的任一種。另外，較佳為飽和的烴基。 In the above formula (2), the saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms represented by R 1 may be any of a straight chain, a branched chain, and a cyclic group. Further, a saturated hydrocarbon group is preferred.

上述通式(2)中，在R1為碳原子數1~6的飽和或不 飽和的烴基的情況下，式(2)所表示的醇例如可列舉：甲醇、乙醇、1-丙醇、2-丙醇、丁醇、戊醇、環己醇等。 In the above formula (2), when R 1 is a saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, the alcohol represented by the formula (2) may, for example, be methanol, ethanol or 1-propanol. 2-propanol, butanol, pentanol, cyclohexanol, and the like.

另外，上述通式(2)中，在R1所表示的經碳原子數1~6的烷氧基取代的總碳原子數2~20的飽和或不飽和的烴基的情況下，可為直鏈、分支鏈狀及環狀中的任一種烴基。另外，較佳為飽和的烴基。進而，烷氧基的取代數較佳為1~5，更佳為1~4，尤佳為1~3。 Further, in the above formula (2), in the case of a saturated or unsaturated hydrocarbon group having 2 to 20 total carbon atoms substituted by an alkoxy group having 1 to 6 carbon atoms represented by R 1 , it may be straight Any of a chain, a branched chain, and a cyclic hydrocarbon group. Further, a saturated hydrocarbon group is preferred. Further, the number of substitution of the alkoxy group is preferably from 1 to 5, more preferably from 1 to 4, still more preferably from 1 to 3.

上述通式(2)中，在R1為經碳原子數1~6的烷氧基取代的烴基的情況下，式(2)所表示的醇例如可列舉：甲氧基甲醇、甲氧基乙醇、乙氧基甲醇、乙氧基乙醇、甲氧基丙醇、乙氧基丙醇、丙氧基丙醇等。 In the above formula (2), when R 1 is a hydrocarbon group substituted with an alkoxy group having 1 to 6 carbon atoms, the alcohol represented by the formula (2) may, for example, be methoxymethanol or methoxy group. Ethanol, ethoxymethanol, ethoxyethanol, methoxypropanol, ethoxypropanol, propoxypropanol, and the like.

[矽烷氧化物] [decane oxide]

矽烷氧化物較佳為下述式(3)所表示的化合物。 The decane oxide is preferably a compound represented by the following formula (3).

(R2)nSi(OR3)4-n (3)式(3)中，R2表示甲基、苯基、乙烯基、環氧基、苯乙烯基、甲基丙烯醯基(methacryl)、丙烯醯基(acryl)、胺基、脲基、巰基、硫化物基或者異氰酸酯基，R3表示甲基、乙基或者丙基，n表示0~3。 (R 2 ) n Si(OR 3 ) 4-n (3) In the formula (3), R 2 represents a methyl group, a phenyl group, a vinyl group, an epoxy group, a styryl group, or a methacryl group. , acryl, amine, ureido, sulfhydryl, sulfide or isocyanate, R 3 represents methyl, ethyl or propyl, and n represents 0 to 3.

式(3)中，R2較佳為甲基或者苯基，R3較佳為甲基或者乙基。n較佳為0~2，更佳為0或者1，尤佳為0。 In the formula (3), R 2 is preferably a methyl group or a phenyl group, and R 3 is preferably a methyl group or an ethyl group. n is preferably 0 to 2, more preferably 0 or 1, and particularly preferably 0.

具體而言，矽烷氧化物較佳為使用選自由四乙氧基矽 烷、四甲氧基矽烷、甲基三甲氧基矽烷及甲基三乙氧基矽烷所組成組群中的1種以上，更佳為使用選自由四乙氧基矽烷及四甲氧基矽烷所組成組群中的1種以上。四乙氧基矽烷及四甲氧基矽烷富有反應性，因此容易在半導體基板與特定鹼化合物的界面形成氧化矽層，容易抑制半導體基板的表面粗糙。 Specifically, the decane oxide is preferably selected from the group consisting of tetraethoxy ruthenium. One or more selected from the group consisting of an alkane, a tetramethoxy decane, a methyltrimethoxy decane, and a methyltriethoxy decane, more preferably selected from the group consisting of tetraethoxy decane and tetramethoxy decane. One or more of the group is formed. Since tetraethoxy decane and tetramethoxy decane are highly reactive, it is easy to form a ruthenium oxide layer at the interface between a semiconductor substrate and a specific alkali compound, and it is easy to suppress surface roughness of a semiconductor substrate.

若將金屬烷氧化物與矽烷氧化物進行比較，則就抑制半導體基板的表面粗糙的觀點而言，較佳為矽烷氧化物。 When the metal alkoxide is compared with the decane oxide, a decane oxide is preferable from the viewpoint of suppressing surface roughness of the semiconductor substrate.

[矽酸酯低聚物、矽酮油] [phthalate oligomer, anthrone oil]

另外，矽烷氧化物可以一部分聚合的矽酸酯低聚物或者矽酮油的狀態使用。即，可在矽烷氧化物進行了水解及聚縮合的狀態下使用。 Further, the decane oxide may be used in the form of a partially polymerized phthalate oligomer or an oxime oil. That is, it can be used in a state where the decane oxide is hydrolyzed and polycondensed.

為了使水解進行，可視需要添加水、觸媒等。觸媒可例示：鹽酸、硝酸、硫酸、硼酸、磷酸、氫氟酸等無機酸；以及甲酸、乙酸、丙酸、丁酸、油酸、亞麻油酸(linoleic acid)、水楊酸、苯甲酸、鄰苯二甲酸、乙二酸、乳酸、丁二酸等有機酸。另外，亦可添加氨、胺等鹼作為觸媒。含有鹼土金屬或鹼金屬的金屬化合物可兼具作為觸媒的功能。 In order to carry out the hydrolysis, water, a catalyst, or the like may be added as needed. The catalyst can be exemplified by inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, boric acid, phosphoric acid, hydrofluoric acid; and formic acid, acetic acid, propionic acid, butyric acid, oleic acid, linoleic acid, salicylic acid, and benzoic acid. Organic acids such as phthalic acid, oxalic acid, lactic acid and succinic acid. Further, a base such as ammonia or an amine may be added as a catalyst. A metal compound containing an alkaline earth metal or an alkali metal can function as a catalyst.

此處所謂的矽酸酯低聚物，較佳為將矽烷氧化物進行水解以及聚縮合而得的SinOn-1(OR)2(n+1)所表示的化合物[R表示甲基、乙基或者丙基，n表示3~10的整數]。矽酸酯低聚物可溶解或者分散於甲醇、乙醇、丙醇、丁醇等醇系溶劑中。 The phthalate oligomer referred to herein is preferably a compound represented by Si n O n-1 (OR) 2 (n+1) obtained by hydrolyzing and polycondensing a decane oxide [R represents a methyl group. , ethyl or propyl, n represents an integer from 3 to 10]. The phthalate oligomer can be dissolved or dispersed in an alcohol solvent such as methanol, ethanol, propanol or butanol.

如上所述的矽酸酯低聚物或者矽酮油可列舉：多摩化學 工業股份有限公司製造的矽酸酯(矽酸酯40、矽酸酯45、M矽酸酯51等)、Colcoat股份有限公司製造的矽酸酯(矽酸甲酯51、矽酸甲酯53A、矽酸乙酯40、矽酸乙酯48)、EMS-485之類的矽酸酯低聚物，聚二甲基矽氧烷等甲基矽酮油、甲基苯基矽酮油、甲基氫化矽酮油、改質矽酮油等矽酮油類。 The phthalate oligomer or oxime oil as described above can be exemplified by Tama Chemical Citrate (manate 40, phthalate 45, M phthalate 51, etc.) manufactured by Industrial Co., Ltd., phthalate ester manufactured by Colcoat Co., Ltd. (methyl decanoate 51, methyl decanoate 53A, Ethyl decanoate 40, ethyl decanoate 48), phthalate oligomer such as EMS-485, methyl fluorenone oil such as polydimethyl siloxane, methyl phenyl fluorenone oil, methyl Anthrone oil such as hydrogenated ketone oil or modified ketone oil.

該些特定化合物中，包含選自由矽烷氧化物、矽酸甲酯 低聚物及矽酸乙酯低聚物所組成組群中的1種以上，由於存在不會使阻擋性能下降，可抑制表面粗糙的傾向，故而較佳。 Among the specific compounds, selected from the group consisting of decane oxides and methyl decanoates One or more of the group consisting of the oligomer and the ethyl decanoate oligomer is preferred because it does not lower the barrier properties and suppresses surface roughness.

(分散介質) (dispersion medium)

本發明的阻擋層形成用組成物含有分散介質。所謂分散 介質，是指於組成物中使上述含有鹼土金屬或鹼金屬的金屬化合物分散或者溶解的介質。 The composition for forming a barrier layer of the present invention contains a dispersion medium. Dispersion The medium refers to a medium in which the above-mentioned alkaline earth metal or alkali metal-containing metal compound is dispersed or dissolved in the composition.

上述溶劑例如可列舉：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-正丙基醚、二異丙基醚、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、二乙二醇單丁醚、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-正丙基醚、二乙二醇甲基-正丁基醚、二乙二醇二-正丙醚、二乙二醇二-正丁醚、二乙二醇甲基-正己基醚、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-正丁基醚、三乙二醇二-正丁醚、三乙二醇甲基-正己基醚、四乙二醇二甲醚、四乙二醇二***、四乙二醇甲基-乙基醚、四乙二醇甲基-正丁基醚、二乙二醇二-正丁醚、四乙二醇甲基-正己基醚、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-正丁基醚、二丙二醇二-正丙醚、二丙二醇二-正丁醚、二丙二醇甲基-正己基醚、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-正丁基醚、三丙二醇二-正丁醚、三丙二醇甲基-正己基醚、四丙二醇二甲醚、四丙二醇二***、四丙二醇甲基-乙基醚、四丙二醇甲基-正丁基醚、四丙二醇二-正丁醚、四丙二醇甲基-正己基醚、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、乙酸甲基戊酯、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、二乙二醇甲醚乙酸酯、二乙二醇單***乙酸酯、二乙二醇單正丁醚乙酸酯、二丙二醇甲醚乙酸酯、二丙二醇 ***乙酸酯、二乙酸二醇酯、乙酸甲氧基三甘醇、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(acetonitrile)、N-甲基吡咯啶酮(N-methyl pyrrolidinone)、N-乙基吡咯啶酮、N-丙基吡咯啶酮、N-丁基吡咯啶酮、N-己基吡咯啶酮、N-環己基吡咯啶酮、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、第二-十四醇、第二-十七醇、苯酚、環己醇、甲基環己醇、苯甲醇、異莰基環己醇、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***(賽珞蘇)、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、乙氧基三乙二醇、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-松油烯(α-terpinene)、α-松脂醇(α-terpineol)、月桂 烯(myrcene)、別羅勒烯(alloocimene)、檸檬烯(limonene)、雙戊烯、α-蒎烯(α-pinene)、β-蒎烯、松油醇、香旱芹酮、羅勒烯(ocimene)、水芹烯(phellandrene)等萜(terpene)系溶劑，異莰基苯酚、1-異丙基-4-甲基-雙環[2.2.2]辛-5-烯-2,3-二甲酸酐、以及對薄荷烯基苯酚(p-menthenyl phenol)。該些溶劑可單獨使用1種，或者將2種以上組合使用。 Examples of the solvent include acetone, methyl ethyl ketone, and methyl-n-propyl acrylate. Ketone, methyl isopropyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, methyl-n-pentyl ketone, methyl-n-hexyl ketone, diethyl ketone, dipropyl ketone, Ketone solvents such as diisobutyl ketone, trimethyl fluorenone, cyclohexanone, cyclopentanone, methylcyclohexanone, 2,4-pentanedione, acetone acetone; diethyl ether, methyl ethyl ether , methyl-n-propyl ether, diisopropyl 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 monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene 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 - 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-positive 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, three Propylene glycol methyl-positive Ether, tetrapropylene glycol dimethyl ether, tetrapropylene glycol diethyl ether, tetrapropylene glycol methyl-ethyl ether, tetrapropylene glycol methyl-n-butyl ether, tetrapropylene glycol di-n-butyl ether, tetrapropylene glycol methyl-n-hexyl ether, four An ether solvent such as propylene glycol di-n-butyl ether; methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, dibutyl acetate, n-amyl acetate, Dipentyl acetate, 3-methoxybutyl acetate, methyl amyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, 2-(2-butoxyethoxy) acetate Ethyl ester, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, decyl acetate, methyl acetate, ethyl acetate, diethylene glycol methyl ether acetate, diethylene glycol Ethyl acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol methyl ether acetate, dipropylene glycol Ethyl acetate, diacetate, methoxytriethylene acetate, ethyl propionate, n-butyl propionate, isoamyl propionate, diethyl oxalate, di-n-butyl oxalate, lactate Ester, 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, An ester solvent such as propylene glycol methyl ether acetate, propylene glycol diethyl ether acetate, propylene glycol propyl ether acetate, γ-butyrolactone or γ-valerolactone; acetonitrile, N-methylpyrrolidone (N -methyl pyrrolidinone), N-ethylpyrrolidone, N-propylpyrrolidone, N-butylpyrrolidone, N-hexylpyrrolidone, N-cyclohexylpyrrolidone, N,N-dimethyl Aprotic polar solvent such as carbamide, N,N-dimethylacetamide, dimethyl hydrazine; methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, second Butanol, tert-butanol, n-pentanol, isoamyl alcohol, 2-methylbutanol, second pentanol, third pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol , second hexanol, 2-ethylbutanol, second heptanol , n-octanol, 2-ethylhexanol, second octanol, n-nonanol, n-nonanol, second-undecanol, trimethylnonanol, second-tetradecanol, second-seventeenth Alcohol, phenol, cyclohexanol, methylcyclohexanol, benzyl alcohol, isodecylcyclohexanol, ethylene glycol, 1,2-propanediol, 1,3-butanediol, diethylene glycol, dipropylene glycol, Alcohol solvent such as triethylene glycol or tripropylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether (cellulose), ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol single Ether, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxy triethylene glycol, tetraethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, a glycol monoether solvent such as dipropylene glycol monoethyl ether or tripropylene glycol monomethyl ether; α-terpinene, α-terpineol, and laurel Myrcene, allophymene, limonene, dipentene, α-pinene, β-pinene, terpineol, celery, ocimene , terpene solvent such as phellandrene, isodecyl phenol, 1-isopropyl-4-methyl-bicyclo[2.2.2] oct-5-ene-2,3-dicarboxylic anhydride And p-menthenyl phenol. These solvents may be used alone or in combination of two or more.

該些溶劑中，就對半導體基板的塗佈性的觀點而言，分 散介質較佳為水、醇系溶劑、二醇單醚系溶劑、或者萜系溶劑，更佳為水、醇、賽珞蘇、α-松脂醇、二乙二醇單-正丁醚、或者二乙二醇單-正丁醚乙酸酯，進而佳為水、醇、α-松脂醇或者賽珞蘇。 Among these solvents, from the viewpoint of the coatability of the semiconductor substrate, The dispersing medium is preferably water, an alcohol solvent, a glycol monoether solvent, or an oxime solvent, more preferably water, alcohol, celecoxime, α-rosinol, diethylene glycol mono-n-butyl ether, or Diethylene glycol mono-n-butyl ether acetate, and thus preferably water, alcohol, alpha-rosinol or celecoxime.

阻擋層形成用組成物中的分散介質的含有率是考慮到 塗佈性、及摻雜劑濃度來決定，例如阻擋層形成用組成物中，分散介質的含有率較佳為5質量%以上、99質量%以下，更佳為20質量%以上、95質量%以下，尤佳為40質量%以上、90質量%以下。 The content ratio of the dispersion medium in the barrier layer forming composition is considered The coating property and the dopant concentration are determined. For example, the content of the dispersion medium in the barrier layer-forming composition is preferably 5% by mass or more and 99% by mass or less, more preferably 20% by mass or more and 95% by mass. In the following, it is particularly preferably 40% by mass or more and 90% by mass or less.

(有機黏合劑) (organic binder)

本發明的阻擋層形成用組成物較佳為包含有機黏合 劑。藉由包含有機黏合劑，容易在高溫下使含有鹼土金屬或鹼金屬的金屬化合物彼此黏結，並且使含有鹼土金屬或鹼金屬的金屬化合物與半導體基板黏結。 The barrier layer-forming composition of the present invention preferably contains an organic binder Agent. By including an organic binder, it is easy to bond the alkaline earth metal or alkali metal-containing metal compound to each other at a high temperature, and to bond the alkaline earth metal or alkali metal-containing metal compound to the semiconductor substrate.

有機黏合劑例如可適當選擇：聚乙烯醇；聚丙烯醯胺樹 脂；聚乙烯醯胺樹脂；聚乙烯吡咯啶酮樹脂；聚環氧乙烷樹脂；聚碸樹脂；丙烯醯胺烷基碸樹脂；纖維素醚、羧甲基纖維素、羥乙基纖維素、乙基纖維素等纖維素衍生物；明膠、明膠衍生物；澱粉、澱粉衍生物；褐藻酸鈉類；三仙膠(xanthan)；瓜爾膠(guar gum)、瓜爾膠衍生物；硬葡聚糖(scleroglucan)、硬葡聚糖衍生物；黃芪膠(tragacanth)、黃芪膠衍生物；糊精(dextrin)、糊精衍生物；(甲基)丙烯酸樹脂；(甲基)丙烯酸烷基酯樹脂、(甲基)丙烯酸二甲基胺基乙酯樹脂等(甲基)丙烯酸酯樹脂；丁二烯樹脂；苯乙烯樹脂；丁醛樹脂；以及它們的共聚物。 The organic binder can be suitably selected, for example, as a polyvinyl alcohol; a polyacrylamide tree Grease; polyvinylamine resin; polyvinylpyrrolidone resin; polyethylene oxide resin; polyfluorene resin; acrylamide alkyl hydrazine resin; cellulose ether, carboxymethyl cellulose, hydroxyethyl cellulose, Cellulose derivatives such as ethyl cellulose; gelatin, gelatin derivatives; starch, starch derivatives; sodium alginate; xanthan; guar gum, guar gum derivatives; Scleroglucan, scleroglucan derivative; tragacanth, xanthine derivative; dextrin, dextrin derivative; (meth)acrylic resin; alkyl (meth)acrylate (meth) acrylate resin such as resin, dimethylaminoethyl (meth) acrylate resin; butadiene resin; styrene resin; butyraldehyde resin; and copolymers thereof.

該些有機黏合劑中，就分解性、以及防止絲網印刷時的 液體流掛(sagging)的觀點而言，較佳為包含丙烯酸樹脂、丁醛樹脂或者纖維素衍生物。該些有機黏合劑可單獨使用1種，或者將2種以上組合使用。 Among these organic binders, they are decomposable and prevent screen printing. From the viewpoint of liquid sagging, it is preferred to contain an acrylic resin, a butyral resin or a cellulose derivative. These organic binders may be used alone or in combination of two or more.

有機黏合劑的分子量並無特別限制，理想的是根據作為 組成物的所需黏度來適當調整。此外，阻擋層形成用組成物中，包含有機黏合劑時的含有率較佳為0.5質量%以上、30質量%以下，更佳為3質量%以上、25質量%以下，尤佳為3質量%以上、20質量%以下。 The molecular weight of the organic binder is not particularly limited, and it is desirable to The desired viscosity of the composition is adjusted as appropriate. Further, the content of the barrier layer-forming composition when the organic binder is contained is preferably 0.5% by mass or more and 30% by mass or less, more preferably 3% by mass or more, 25% by mass or less, and particularly preferably 3% by mass. The above is 20% by mass or less.

另外，含有鹼土金屬及鹼金屬的金屬化合物的總含量與 有機黏合劑的總含量的質量比率(鹼土金屬及鹼金屬的金屬化合物)/(有機黏合劑)較佳為99.9/0.1~0.1/99.9，更佳為99/1~ 20/80。 In addition, the total content of metal compounds containing alkaline earth metals and alkali metals is The mass ratio of the total content of the organic binder (metal compound of an alkaline earth metal and an alkali metal) / (organic binder) is preferably 99.9/0.1 to 0.1/99.9, more preferably 99/1~ 20/80.

此外，亦可使用溶解有機黏合劑的分散介質作為上述分 散介質以及有機黏合劑。 In addition, a dispersion medium in which an organic binder is dissolved may also be used as the above-mentioned fraction. Bulk media and organic binders.

此外，阻擋層形成用組成物亦可將作為溶劑而例示的異 莰基環己醇與有機黏合劑一起使用或者作為替代有機黏合劑的材料來使用。異莰基環己醇可作為「Terusolve MTPH」(日本萜化學公司製造，商品名)而從商業途徑獲取。異莰基環己醇的沸點高至308℃~318℃，並且當從阻擋層上去除時，不需要如有機黏合劑般藉由焙燒進行脫脂處理，可藉由進行加熱使其氣化而使其消失。 Further, the composition for forming a barrier layer may also be exemplified as a solvent. Nonylcyclohexanol is used with organic binders or as a substitute for organic binders. Isodecylcyclohexanol is commercially available as "Terusolve MTPH" (manufactured by Nippon Chemical Co., Ltd., trade name). The isodecylcyclohexanol has a boiling point as high as 308 ° C to 318 ° C, and when removed from the barrier layer, does not need to be degreased by baking as an organic binder, and can be vaporized by heating. It disappears.

在阻擋層形成用組成物含有異莰基環己醇的情況下，阻 擋層形成用組成物的總質量中，異莰基環己醇的含有率較佳為0.5質量%~85質量%，更佳為1質量%~80質量%，尤佳為2質量%~80質量%。 In the case where the barrier layer-forming composition contains isodecylcyclohexanol, the resistance In the total mass of the composition for forming a barrier layer, the content of isodecylcyclohexanol is preferably 0.5% by mass to 85% by mass, more preferably 1% by mass to 80% by mass, and particularly preferably 2% by mass to 80% by mass. quality%.

(其他成分) (other ingredients)

阻擋層形成用組成物除了包含：含有鹼土金屬或鹼金屬 的金屬化合物，分散介質，以及選自由金屬烷氧化物、矽烷氧化物、矽酸酯低聚物以及矽酮油所組成組群中的1種以上特定化合物以外，視需要，亦可包含增稠劑、濕潤劑、界面活性劑、無機粉末、觸變劑等各種添加劑作為其他成分。 The barrier layer forming composition includes, in addition to: an alkaline earth metal or an alkali metal a metal compound, a dispersion medium, and one or more specific compounds selected from the group consisting of metal alkoxides, decane oxides, phthalate oligomers, and oxime oils, and may also contain thickening if necessary Various additives such as a humectant, a wetting agent, a surfactant, an inorganic powder, and a thixotropic agent are used as other components.

上述界面活性劑可列舉非離子系界面活性劑、陽離子系 界面活性劑、陰離子系界面活性劑等。其中，就向半導體元件中帶入的重金屬等雜質少的方面而言，較佳為非離子系界面活性劑或者陽離子系界面活性劑。進而例示矽系界面活性劑、氟系界面活性劑及烴系界面活性劑作為非離子系界面活性劑，就在擴散等的加熱時快速焙燒的方面而言，較佳為烴系界面活性劑。 Examples of the surfactant include a nonionic surfactant and a cationic system. Surfactant, anionic surfactant, and the like. Among them, a nonionic surfactant or a cationic surfactant is preferred in that the amount of impurities such as heavy metals introduced into the semiconductor element is small. Further, a quinone-based surfactant, a fluorine-based surfactant, and a hydrocarbon-based surfactant are exemplified as the nonionic surfactant, and a hydrocarbon-based surfactant is preferred in terms of rapid calcination during heating such as diffusion.

烴系界面活性劑可例示：環氧乙烷-環氧丙烷的嵌段共 聚物、乙炔二醇(acetylene glycol)化合物等，就更減少半導體元件的電阻值的不均的方面而言，更佳為乙炔二醇化合物。 The hydrocarbon-based surfactant can be exemplified by a block of ethylene oxide-propylene oxide. The polymer, the acetylene glycol compound or the like is more preferably an acetylene glycol compound from the viewpoint of further reducing the unevenness of the resistance value of the semiconductor element.

無機粉末可例示：氧化矽、氮化矽、碳化矽等的粉末。 The inorganic powder may, for example, be a powder of cerium oxide, cerium nitride, cerium carbide or the like.

阻擋層形成用組成物可含有觸變劑。藉此能夠容易控制觸變性，能夠構成具有適合於絲網印刷的黏度的絲網印刷用的阻擋層形成用組成物、具有適合於噴墨印刷的黏度的噴墨用的阻擋層形成用組成物。進而，藉由控制觸變性，能夠抑制印刷時阻擋層形成用組成物自印刷圖案中滲出或流掛。 The composition for forming a barrier layer may contain a thixotropic agent. By this, it is possible to easily control thixotropy, and it is possible to constitute a barrier layer-forming composition for screen printing having a viscosity suitable for screen printing, and a barrier layer-forming composition for inkjet having a viscosity suitable for inkjet printing. . Further, by controlling the thixotropy, it is possible to suppress the formation of the barrier layer forming composition from the printed pattern during printing.

觸變劑可例示：聚醚化合物、脂肪酸醯胺、有機填料、無機填料、氫化蓖麻油、脲胺基甲酸酯醯胺、生物膠(biogum)、瓜爾膠、刺槐豆膠(Locust bean gum)、鹿角菜膠(carrageenan)、果膠(pectin)、瓊脂(agar)、β-葡聚糖(β-glucan)、羅望子膠(tamarind seed gum)、車前子膠(psyllium seed gum)、聚乙烯基吡咯啶酮、矽酮系增稠凝膠化劑以及油系凝膠化劑(商品名：GEL ALL(新日本理化製造))。 The thixotropic agent can be exemplified by a polyether compound, a fatty acid decylamine, an organic filler, an inorganic filler, hydrogenated castor oil, urea amide amide, biogum, guar gum, locust bean gum (Locust bean gum). ), carrageenan, pectin, agar, β-glucan, tamarind seed gum, psyllium seed gum, Polyvinylpyrrolidone, anthrone-based thickening gelling agent, and oil-based gelling agent (trade name: GEL ALL (manufactured by Shin-Nippon Chemical Co., Ltd.)).

上述有機黏合劑可兼具觸變劑的作用，此種材料可列舉乙基纖維素。 The above organic binder may function as a thixotropic agent, and such a material may be exemplified by ethyl cellulose.

就本發明的阻擋層形成用組成物不會污染半導體基板，即抑制半導體基板中的載子的再結合的觀點而言，鐵、鎢、金、鎳、鉻、錳等的含有率在阻擋層形成用組成物中較佳為10質量%以下，更佳為5質量%以下，尤佳為1質量%以下。 The content of iron, tungsten, gold, nickel, chromium, manganese, or the like is in the barrier layer from the viewpoint that the composition for forming a barrier layer of the present invention does not contaminate the semiconductor substrate, that is, suppresses recombination of carriers in the semiconductor substrate. The composition for formation is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 1% by mass or less.

阻擋層形成用組成物的黏度並無特別限制。具體而言，較佳為在25℃下利用E型黏度計且以旋轉速度0.5 rpm~5 rpm進行測定而得的黏度為0.5 Pa．s~400 Pa．s，更佳為40 Pa．s~200 Pa．s。若阻擋層形成用組成物的黏度為0.5 Pa．s以上，則當塗佈於半導體基板上時難以產生液體流掛，另外，若阻擋層形成用組成物的黏度為400 Pa．s以下，則可形成細的塗佈圖案。 The viscosity of the composition for forming a barrier layer is not particularly limited. Specifically, it is preferred to use a E-type viscometer at 25 ° C and measure at a rotational speed of 0.5 rpm to 5 rpm to obtain a viscosity of 0.5 Pa. s~400 Pa. s, more preferably 40 Pa. s~200 Pa. s. If the composition for forming the barrier layer has a viscosity of 0.5 Pa. Above s, it is difficult to cause liquid sag when applied to a semiconductor substrate, and the viscosity of the barrier layer-forming composition is 400 Pa. Below s, a fine coating pattern can be formed.

本發明的阻擋層形成用組成物可藉由使用摻合機、混合機、研缽、或者轉子(rotor)，將含有鹼土金屬或鹼金屬的金屬化合物，分散介質，選自由金屬烷氧化物、矽烷氧化物、矽酸酯低聚物以及矽酮油所組成組群中的1種以上特定化合物，與視需要添加的成分進行混合而獲得。另外，混合時，可視需要進行加熱。此時的加熱溫度例如可設為30℃~100℃。 The barrier layer-forming composition of the present invention may be a metal compound containing an alkaline earth metal or an alkali metal, a dispersion medium selected from a metal alkoxide, by using a blender, a mixer, a mortar, or a rotor. One or more specific compounds in the group consisting of a decane oxide, a phthalate oligomer, and an oxime oil are obtained by mixing with a component to be added as needed. In addition, heating may be performed as needed. The heating temperature at this time can be, for example, 30 ° C to 100 ° C.

<太陽電池用基板以及太陽電池元件的製造方法> <Solar cell substrate and method for manufacturing solar cell element>

本發明的太陽電池用基板的製造方法包括：將上述阻擋層形成用組成物施用至半導體基板上而形成圖案狀阻擋層的步 驟；以及在上述半導體基板上的未形成上述阻擋層的部分，使施體元素或者受體元素擴散，在上述半導體基板內部分性地形成擴散層的步驟。 The method for producing a substrate for a solar cell of the present invention comprises the step of applying the composition for forming a barrier layer to a semiconductor substrate to form a patterned barrier layer. And a step of partially forming a diffusion layer in the semiconductor substrate by diffusing a donor element or an acceptor element on a portion of the semiconductor substrate where the barrier layer is not formed.

另外，本發明的太陽電池元件的製造方法包括在利用上述製造方法而獲得的太陽電池用基板的擴散層上形成電極的步驟。 Moreover, the method for producing a solar cell element of the present invention includes the step of forming an electrode on a diffusion layer of a substrate for a solar cell obtained by the above-described production method.

此處，對於使用本發明阻擋層形成用組成物的太陽電池用基板以及太陽電池元件的製造方法，參照圖1來進行說明。圖1是概念性表示本發明的太陽電池用基板以及太陽電池元件的製造步驟的一例的示意剖面圖。 Here, a solar cell substrate and a method for producing a solar cell element using the composition for forming a barrier layer of the present invention will be described with reference to FIG. 1 . FIG. 1 is a schematic cross-sectional view showing an example of a manufacturing procedure of a solar cell substrate and a solar cell element according to the present invention.

此外，圖1中對背面電極型的太陽電池用基板以及太陽電池元件進行說明，但本發明的阻擋層形成用組成物亦可適用於任一形式的太陽電池用基板以及太陽電池元件。 In addition, although the back electrode type solar cell substrate and the solar cell element are described in FIG. 1, the barrier layer forming composition of the present invention can be applied to any type of solar cell substrate and solar cell element.

背面電極型以外的其他形式可例示選擇性射極型以及雙面受光型。選擇性射極型的太陽電池用基板中，於受光面側的電極正下方形成有摻雜劑濃度高於其他區域的擴散層。為了形成該高濃度的擴散層的區域，可使用本發明的阻擋層形成用組成物。另外，雙面受光型的太陽電池元件中，於雙面形成有指狀棒(finger bar)以及匯流排(bus bar)作為電極，且於半導體基板的其中一面形成n+型擴散層，於另一面形成p+型擴散層。為了位置選擇性地形成該n+型擴散層以及p+型擴散層，可使用本發明的 阻擋層形成用組成物。 Other forms other than the back electrode type can be exemplified by a selective emitter type and a double-sided light receiving type. In the substrate for a solar cell of the selective emitter type, a diffusion layer having a higher dopant concentration than other regions is formed directly under the electrode on the light-receiving surface side. In order to form a region of the high concentration diffusion layer, the composition for forming a barrier layer of the present invention can be used. Further, in the double-sided light-receiving type solar cell element, a finger bar and a bus bar are formed as electrodes on both sides, and an n + -type diffusion layer is formed on one side of the semiconductor substrate, and the other is A p + -type diffusion layer is formed on one side. In order to selectively form the n + -type diffusion layer and the p + -type diffusion layer in position, the barrier layer-forming composition of the present invention can be used.

圖1中的(1)中，於作為n型半導體基板10的矽基板上施用鹼溶液(alkaline solution)而去除損壞層，藉由蝕刻而獲得紋理結構。 In (1) of FIG. 1, an alkali solution is applied to a ruthenium substrate as the n-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%的苛性鈉來去除自鑄錠上切片時產生的矽基板表面的損壞層。繼而，利用1質量%苛性鈉與10質量%異丙醇的混合液來蝕刻矽基板，於n型半導體基板10上形成紋理結構(圖中省略紋理結構的記載)。太陽電池元件藉由在n型半導體基板10的受光面(表面)側形成紋理結構，而促進光侷限效應，實現高效率化。 Specifically, 20% by mass of caustic soda was used to remove the damaged layer on the surface of the crucible substrate generated when slicing on the ingot. Then, the tantalum substrate is etched by a mixed solution of 1% by mass of caustic soda and 10% by mass of isopropyl alcohol to form a texture structure on the n-type semiconductor substrate 10 (the description of the texture structure is omitted in the drawing). The solar cell element forms a texture structure on the light-receiving surface (surface) side of the n-type semiconductor substrate 10, thereby promoting the optical confinement effect and achieving high efficiency.

圖1中的(2)中，於n型半導體基板10的表面(即受光面)以及與該受光面相反的面(即背面)施用本發明的阻擋層形成用組成物11。本發明中，施用方法並無特別限制，可列舉印刷法、旋轉法、刷塗、噴射法、刮刀法、輥塗法、噴墨法等，較佳為使用印刷法或者噴墨法。 In (2) of FIG. 1, the barrier layer-forming composition 11 of the present invention is applied to the surface (i.e., the light-receiving surface) of the n-type semiconductor substrate 10 and the surface opposite to the light-receiving surface (i.e., the back surface). In the present invention, the application method is not particularly limited, and examples thereof include a printing method, a spinning method, a brushing method, a spraying method, a doctor blade method, a roll coating method, and an inkjet method. Preferably, a printing method or an inkjet method is used.

上述阻擋層形成用組成物的施用量並無特別限制，較佳為設為0.01 g/m2以上、100 g/m2以下，更佳為0.1 g/m2以上、20 g/m2以下。對上述阻擋層形成用組成物的塗佈厚度並無特別限制，較佳為0.1 μm以上、50 μm以下，更佳為1 μm以上、30 μm以下。 The application amount of the barrier layer-forming composition is not particularly limited, but is preferably 0.01 g/m 2 or more and 100 g/m 2 or less, more preferably 0.1 g/m 2 or more and 20 g/m 2 or less. . The coating thickness of the barrier layer-forming composition is not particularly limited, but is preferably 0.1 μm or more and 50 μm or less, and more preferably 1 μm or more and 30 μm or less.

另外，根據阻擋層形成用組成物的組成，有時在施用後，需要用於使組成物中所含的分散介質揮發的乾燥步驟。該情 況下，在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。該乾燥條件依存於阻擋層形成用組成物的分散介質的含量，本發明中對上述條件並無特別限定。該情況下，阻擋層可作為使阻擋層形成用組成物乾燥而成的乾燥體而獲得。 Further, depending on the composition of the composition for forming a barrier layer, a drying step for volatilizing the dispersion medium contained in the composition may be required after the application. The situation In the case of using a hot plate at a temperature of about 80 ° C to 300 ° C, it is dried for 1 minute to 10 minutes, and dried for 10 minutes to 30 minutes when using a dryer or the like. The drying conditions depend on the content of the dispersion medium of the barrier layer-forming composition, and the above conditions are not particularly limited in the present invention. In this case, the barrier layer can be obtained as a dried body obtained by drying a composition for forming a barrier layer.

此外，在印刷法、噴墨法等情況下，圖案狀的阻擋層可 藉由將阻擋層形成用組成物11施用成圖案狀而獲得。另一方面，在旋轉法、刷塗、噴射法、刮刀法、輥塗法等情況下，圖案狀的阻擋層可藉由將阻擋層形成用組成物11塗佈於整個面後，進行蝕刻等來部分性地去除，從而獲得圖案狀的阻擋層。 In addition, in the case of printing, inkjet, etc., the patterned barrier layer can It is obtained by applying the barrier layer forming composition 11 into a pattern. On the other hand, in the case of a spin method, a brushing method, a spray method, a doctor blade method, a roll coating method, or the like, the pattern-shaped barrier layer can be applied to the entire surface by applying the barrier layer-forming composition 11 to etching, etc. Partially removed to obtain a patterned barrier layer.

繼而，圖1中的(3)中，塗佈用於形成n+型擴散層以 及p+型擴散層的塗佈用擴散材料12、塗佈用擴散材料13。繼而，圖1中的(4)中，進行熱擴散，於n型半導體基板10上形成n+型擴散層14、p+型擴散層15。藉由用以熱擴散的熱處理，塗佈用擴散材料12、塗佈用擴散材料13成為塗佈用擴散材料的焙燒物12'、塗佈用擴散材料的焙燒物13'，並且通常形成玻璃層。用以熱擴散的熱處理溫度並無特別限制，較佳為在750℃~1050℃的溫度、1分鐘~300分鐘的條件下進行熱處理。 Then, in (3) of FIG. 1, a coating diffusion material 12 and a coating diffusion material 13 for forming an n + -type diffusion layer and a p + -type diffusion layer are applied. Then, in (4) of FIG. 1, thermal diffusion is performed to form the n + -type diffusion layer 14 and the p + -type diffusion layer 15 on the n-type semiconductor substrate 10. The coating diffusion material 12, the coating diffusion material 13 becomes the calcined product 12' of the coating diffusion material, the calcined product 13' of the coating diffusion material, and usually forms a glass layer by heat treatment for thermal diffusion. . The heat treatment temperature for thermal diffusion is not particularly limited, and it is preferably heat-treated at a temperature of 750 ° C to 1050 ° C for 1 minute to 300 minutes.

此處，雖圖示了同時形成n+型擴散層14與p+型擴散層 15的方法，但亦可各別地擴散。即，亦可首先塗佈用於形成p+型擴散層15的塗佈用擴散材料13，使其熱擴散，去除塗佈用擴散材 料的焙燒物13'，然後塗佈用於形成n+型擴散層14的塗佈用擴散材料12，使其熱擴散，去除塗佈用擴散材料的焙燒物12'。 Here, although the method of simultaneously forming the n + -type diffusion layer 14 and the p + -type diffusion layer 15 is shown, it may spread separately. In other words, the coating diffusion material 13 for forming the p + -type diffusion layer 15 may be first coated, thermally diffused, the calcined product 13' of the coating diffusion material may be removed, and then coated for formation of n + type. The diffusion material 12 for application of the diffusion layer 14 is thermally diffused to remove the baked product 12' of the diffusion material for coating.

另外，此處雖已對使用塗佈用擴散材料12、塗佈用擴散 材料13的情況進行說明，但亦可同樣地應用於使用POCl3氣體或BBr3氣體的方法。該情況下，首先在n型半導體基板10中將形成p+型擴散層15的預定區域作為開口部，於作為該開口部的區域以外，利用阻擋層形成用組成物來形成阻擋層。然後，在與該開口部對應的n型半導體基板10上形成p+型擴散層15，然後去除阻擋層。繼而，將形成n+型擴散層14的預定區域作為開口部，在作為該開口部的區域以外，利用阻擋層形成用組成物來形成阻擋層。然後，在與該開口部對應的n型半導體基板10上形成n+型擴散層14。 In addition, although the case where the coating diffusion material 12 and the coating diffusion material 13 are used has been described here, the method of using POCl 3 gas or BBr 3 gas can also be applied similarly. In this case, first, a predetermined region in which the p + -type diffusion layer 15 is formed is used as an opening portion in the n-type semiconductor substrate 10, and a barrier layer is formed by using a barrier layer-forming composition other than the region as the opening portion. Then, a p + -type diffusion layer 15 is formed on the n-type semiconductor substrate 10 corresponding to the opening portion, and then the barrier layer is removed. Then, a predetermined region in which the n + -type diffusion layer 14 is formed is used as an opening portion, and a barrier layer is formed using a composition for forming a barrier layer in addition to the region as the opening portion. Then, an n + -type diffusion layer 14 is formed on the n-type semiconductor substrate 10 corresponding to the opening.

繼而，圖1中的(5)中將阻擋層形成用組成物11、以 及塗佈用擴散材料的焙燒物12'、塗佈用擴散材料的焙燒物13'去除，獲得太陽電池用基板。上述去除方法可列舉浸漬於包含酸的水溶液中等方法，較佳為根據阻擋層形成用組成物11、以及用於形成n+型擴散層14及p+型擴散層15的塗佈用擴散材料的焙燒物12'、塗佈用擴散材料的焙燒物13'的組成來決定。具體而言，較佳為包括以下步驟：利用包含氫氟酸的水溶液，對藉由熱擴散處理而生成於半導體基板上的玻璃層進行蝕刻。更具體而言，可列舉如下方法：利用鹽酸(例如10質量%的HCl水溶液)來去除含有 鹼土金屬或鹼金屬的金屬化合物，然後進行水洗，進而利用氫氟酸水溶液(例如2.5質量%的HF水溶液)對塗佈用擴散材料的焙燒物12'、塗佈用擴散材料的焙燒物13'進行蝕刻後，進行水洗。 Then, in (5) of FIG. 1, the barrier layer-forming composition 11 and the calcined product 12' of the coating diffusion material and the calcined product 13' of the coating diffusion material are removed to obtain a solar cell substrate. The above-mentioned removal method may be immersed in an aqueous solution containing an acid, and is preferably a composition for forming a barrier layer 11 and a diffusion material for coating for forming the n + -type diffusion layer 14 and the p + -type diffusion layer 15 . The composition of the calcined product 12' and the calcined product 13' of the diffusion material for coating is determined. Specifically, it is preferable to include a step of etching a glass layer formed on the semiconductor substrate by thermal diffusion treatment using an aqueous solution containing hydrofluoric acid. More specifically, a method of removing a metal compound containing an alkaline earth metal or an alkali metal by using hydrochloric acid (for example, 10% by mass aqueous HCl solution), followed by washing with water, and further using an aqueous solution of hydrofluoric acid (for example, 2.5% by mass of HF) In the aqueous solution, the calcined product 12' of the diffusion material for coating and the calcined product 13' of the diffusion material for coating are etched, and then washed with water.

繼而，圖1中的(6)中，於作為受光面的表面施用抗 反射膜16，且於背面施用鈍化膜17。抗反射膜16與鈍化膜17的組成可相同，亦可不同。抗反射膜16例如可列舉氮化矽膜，鈍化膜17例如可列舉氧化矽膜。對抗反射膜及鈍化膜的膜厚並無特別限制，較佳為設為10 nm~300 nm，更佳為設為30 nm~150 nm。 Then, in (6) of Fig. 1, the application is applied to the surface as the light receiving surface. The film 16 is reflected and the passivation film 17 is applied on the back side. The composition of the anti-reflection film 16 and the passivation film 17 may be the same or different. The anti-reflection film 16 is, for example, a tantalum nitride film, and the passivation film 17 is, for example, a hafnium oxide film. The film thickness of the antireflection film and the passivation film is not particularly limited, but is preferably 10 nm to 300 nm, more preferably 30 nm to 150 nm.

繼而，圖1中的(7)中，於鈍化膜17上，使形成電極 的部位開口。對開口的方法並無特別限制，例如可藉由利用噴墨法等於欲開口的部位塗佈蝕刻液(例如包含氫氟酸、氟化銨或者磷酸的溶液)，進行熱處理而開口。 Then, in (7) of FIG. 1, on the passivation film 17, an electrode is formed The opening of the part. The method of the opening is not particularly limited. For example, an etching solution (for example, a solution containing hydrofluoric acid, ammonium fluoride or phosphoric acid) may be applied by a portion corresponding to the opening to be opened by an inkjet method, and heat-treated to be opened.

繼而，圖1中的(8)中，於n+型擴散層14、以及p+型 擴散層15上分別形成n電極18以及p電極19。本發明中，n電極18以及p電極19的材質或形成方法並無特別限定。例如，可塗佈包含鋁、銀或銅的金屬的電極形成用膏，使其乾燥，形成n電極18以及p電極19。繼而，將n電極18以及p電極19進行焙燒，製成太陽電池元件。 Then, in (8) of FIG. 1, the n-electrode 18 and the p-electrode 19 are formed on the n + -type diffusion layer 14 and the p + -type diffusion layer 15, respectively. In the present invention, the material or formation method of the n electrode 18 and the p electrode 19 is not particularly limited. For example, an electrode forming paste containing a metal of aluminum, silver or copper may be applied and dried to form an n electrode 18 and a p electrode 19. Then, the n electrode 18 and the p electrode 19 are baked to form a solar cell element.

此外，若使用包含玻璃粉(glass frit)者作為上述電極 形成用膏，則可省略圖1中的(7)所示的開口的步驟。若將包含玻璃粉的電極形成用膏塗佈於鈍化膜17上，在600℃~900℃的範 圍焙燒數秒~數分鐘，則玻璃粉使背面側的鈍化膜17熔融，膏中的金屬粒子(例如銀粒子)與矽基板10形成接觸部而凝固。藉此，所形成的表面電極18、表面電極19與矽基板10導通。將其稱為燒穿(fire through)。 In addition, if a glass frit is used as the above electrode The paste for forming can omit the step of the opening shown in (7) of Fig. 1 . When a paste for electrode formation containing glass frit is applied to the passivation film 17, the range is from 600 ° C to 900 ° C. After baking for several seconds to several minutes, the glass frit melts the passivation film 17 on the back side, and metal particles (for example, silver particles) in the paste form a contact portion with the tantalum substrate 10 to be solidified. Thereby, the formed surface electrode 18 and surface electrode 19 are electrically connected to the ruthenium substrate 10. This is called fire through.

<太陽電池> <solar battery>

太陽電池包含上述太陽電池元件的1種以上，於太陽電 池元件的電極上配置配線材料而構成。太陽電池亦可進而視需要，經由配線材料而連結多個太陽電池元件，進而以密封材料進行密封。 The solar cell includes one or more of the above solar cell elements, and is in solar power. A wiring material is disposed on the electrode of the cell element. The solar cell may further connect a plurality of solar cell elements via a wiring material as needed, and further seal with a sealing material.

上述配線材料及密封材料並無特別限制，可自業界通常 使用的材料中適當選擇。 The above wiring materials and sealing materials are not particularly limited and can be commonly used in the industry. Appropriate choice of materials used.

此外，日本申請案2012-002633的揭示是藉由參照而將 其整體併入至本說明書中。 In addition, the disclosure of Japanese application No. 2012-002633 is by reference. It is incorporated in this specification as a whole.

本說明書中記載的所有文獻、專利申請案、以及技術規 格是與具體且分別記載各文獻、專利申請案、以及技術規格藉由參照而結合的情況同樣地，藉由參照而併入至本說明書中。 All documents, patent applications, and technical specifications described in this manual The same applies to the detailed description of the respective documents, patent applications, and technical specifications, which are incorporated by reference.

[實施例] [Examples]

以下，對本發明的實施例進一步進行具體說明，但本發 明並不限制於該些實施例。此外，只要無特別記述，則化學品全部使用試劑。另外，只要無特別說明，則「%」是指「質量%」。 Hereinafter, embodiments of the present invention will be further specifically described, but the present invention It is not limited to these embodiments. Further, as long as there is no special description, the reagents are all used in the chemicals. In addition, "%" means "% by mass" unless otherwise specified.

另外，實施例中的含有鹼土金屬或鹼金屬的金屬化合物 的體積平均粒徑是利用雷射繞射散射法粒度分布測定裝置(貝克曼庫爾特(Beckman Coulter)製造的LS 13 320)，在分散狀態下測定粒徑。 In addition, the alkaline earth metal or alkali metal-containing metal compound in the examples The volume average particle diameter is measured by a laser diffraction scattering particle size distribution measuring apparatus (LS 13 320 manufactured by Beckman Coulter), and the particle diameter is measured in a dispersed state.

<實施例1> <Example 1>

(阻擋層形成用組成物1的製備) (Preparation of composition 1 for barrier layer formation)

將氧化鈣(宇部材料製造的「CSQ」，體積平均粒徑為15.0 μm，非晶形(amorphous)粒子)10 g(18質量%)、四乙氧基矽烷(多摩化學工業製造的「正矽酸乙酯」)10 g、純水1.25 g、以及丁基卡必醇(和光純藥工業製造)8.75 g加入至氧化鋯製罐中。進而，於氧化鋯製罐中加入3 mm的珠粒50 g，使用行星式球磨機(ball mill)(弗里茨(Fritsch)公司製造的「pulverisette」)，以600 rpm進行30分鐘分散處理，獲得分散液。 Calcium oxide ("CSQ" made of Ube material, volume average particle diameter of 15.0 μm, amorphous particles) 10 g (18 mass%), tetraethoxy decane ("Nanoic acid" manufactured by Tama Chemical Industry Co., Ltd. 10 g of ethyl ester"), 1.25 g of pure water, and 8.75 g of butyl carbitol (manufactured by Wako Pure Chemical Industries, Ltd.) were added to a zirconia can. Further, 50 g of 3 mm beads were placed in a zirconia can, and a ball mill ("Pulverisette" manufactured by Fritsch) was used for dispersion treatment at 600 rpm for 30 minutes. Dispersions.

繼而，使用自轉公轉混合機(新基(Thinky)製造的「AR-100」)，將該分散液15 g與溶解有15質量%的乙基纖維素(陶氏化學(Dow Chemical)製造，STD200)的松脂醇(萜化學製造的「Terpineol-LW」)10 g進行混合，製備阻擋層形成用組成物1。 Then, 15 g of the dispersion was dissolved in 15% by mass of ethyl cellulose (manufactured by Dow Chemical, STD 200) using a rotation revolution mixer ("AR-100" manufactured by Shinky). 10 g of rosin ("Terpineol-LW" manufactured by Seiko Chemical Co., Ltd.) was mixed to prepare a composition 1 for forming a barrier layer.

該阻擋層形成用組成物1在25℃、5 rpm下的黏度為45 Pa．s。黏度是使用E型黏度計(東京計器製造)，將阻擋層形成用組成物的取樣量設為0.5 ml進行測定。 The barrier layer-forming composition 1 had a viscosity of 45 Pa at 25 ° C and 5 rpm. s. The viscosity was measured using an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd.), and the sample amount of the barrier layer-forming composition was set to 0.5 ml.

(磷擴散液的製備) (Preparation of phosphorus diffusion liquid)

製備磷酸二氫銨(和光純藥工業製造)的20質量%水溶 液，將上清液(supernatant liquid)的飽和磷酸二氫銨水溶液用作磷擴散液。 Preparation of 20% by mass of water-soluble ammonium dihydrogen phosphate (manufactured by Wako Pure Chemical Industries, Ltd.) As a solution, a saturated aqueous solution of ammonium dihydrogen phosphate in a supernatant liquid was used as a phosphorus diffusion liquid.

(熱擴散及蝕刻步驟) (thermal diffusion and etching steps)

於經紋理化(texture)處理的n型矽基板(以下亦稱為「n型矽基板」)表面上，藉由絲網印刷(MT-320T，中晶科技(Microtek)製造)來塗佈阻擋層形成用組成物1，於150℃的加熱板上乾燥5分鐘後，以500℃的加熱板乾燥1分鐘。將其作為帶有阻擋層的基板。 On the surface of an n-type ruthenium substrate (hereinafter also referred to as "n-type ruthenium substrate") which is textured, it is coated by screen printing (MT-320T, manufactured by Microtek). The layer forming composition 1 was dried on a hot plate at 150 ° C for 5 minutes, and then dried on a hot plate at 500 ° C for 1 minute. This was used as a substrate with a barrier layer.

繼而，準備另一塊矽基板，以500 rpm來旋轉塗佈(三笠(Mikasa)公司製造，MS-A100)磷擴散液，在200℃下乾燥。將其作為對向擴散用基板。 Then, another tantalum substrate was prepared, and spin-coated (Mikasa Co., Ltd., MS-A100) phosphorus diffusion liquid was spin-coated at 500 rpm, and dried at 200 °C. This was used as a substrate for counter diffusion.

在使帶有阻擋層的基板與對向擴散用基板以距離1 mm而對向的狀態下，於950℃下加熱10分鐘，使磷在帶有阻擋層的基板中擴散。然後，將帶有阻擋層的基板在10質量%HCl水溶液中浸漬5分鐘，然後水洗，進而於2.5質量%HF水溶液中浸漬5分鐘。將其水洗、乾燥後，進行下述評價。 The substrate with the barrier layer and the counter diffusion substrate were heated at 950 ° C for 10 minutes in a state of being opposed to each other by a distance of 1 mm to diffuse phosphorus in the substrate having the barrier layer. Then, the substrate with the barrier layer was immersed in a 10 mass% aqueous HCl solution for 5 minutes, then washed with water, and further immersed in a 2.5 mass% HF aqueous solution for 5 minutes. After washing with water and drying, the following evaluation was carried out.

(薄片電阻的測定) (Measurement of sheet resistance)

塗佈有阻擋層形成用組成物1的部分的基板的薄片電阻是使用三菱化學(股)製造的Loresta-EP MCP-T360型低電阻率計，利用四探針法來測定。塗佈有阻擋層形成用組成物1的部分的薄片電阻為240 Ω/□。未塗佈的部分的薄片電阻為40 Ω/□。 The sheet resistance of the substrate coated with the portion of the barrier layer-forming composition 1 was measured by a four-probe method using a Loresta-EP MCP-T360 type low resistivity meter manufactured by Mitsubishi Chemical Corporation. The sheet resistance of the portion to which the barrier layer-forming composition 1 was applied was 240 Ω/□. The sheet resistance of the uncoated portion was 40 Ω/□.

此外，作為參照試樣，將切片後的n型矽基板在2.5質量%HF水溶液中浸漬5分鐘，對將其水洗、乾燥後的薄片電阻進行測定，結果為240 Ω/□。 In addition, as a reference sample, the sliced n-type ruthenium substrate was immersed in a 2.5% by mass HF aqueous solution for 5 minutes, and the sheet resistance obtained by washing and drying the sheet was measured and found to be 240 Ω/□.

(表面粗糙度的測定) (Measurement of surface roughness)

使用表面粗糙度測定裝置(三豐股份有限公司製造，Surftest「SJ-2100」來測定塗佈有阻擋層的部分的表面粗糙度。平均表面粗糙度Ra為0.01 μm以下。此處，表面粗糙度是對紋理結構的棱錐形狀的一面進行測定。 The surface roughness of the portion coated with the barrier layer was measured using a surface roughness measuring device (manufactured by San Fung Co., Ltd., Surftest "SJ-2100". The average surface roughness Ra was 0.01 μm or less. Here, the surface roughness It is measured on one side of the pyramid shape of the texture structure.

<實施例2~實施例11、比較例1、比較例2> <Example 2 to Example 11, Comparative Example 1, Comparative Example 2>

製備表1及表2所示組成的阻擋層形成組成物，以與實施例1相同的方式進行評價。將結果示於表1及表2中。此外，表1及表2中所示的材料如下所述。此外，表中「-」表示未添加。 The barrier layer forming compositions of the compositions shown in Tables 1 and 2 were prepared and evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2. Further, the materials shown in Tables 1 and 2 are as follows. In addition, "-" in the table means not added.

碳酸鈣：宇部材料製造 Calcium carbonate: Ube material manufacturing

碳酸鎂：和光純藥工業製造，體積平均粒徑為8.9 μm Magnesium carbonate: manufactured by Wako Pure Chemical Industries, with a volume average particle size of 8.9 μm

氧化鎂：達保化學工業(Tateho Chemical Industries)製造，體積平均粒徑為2.4 μm Magnesium oxide: manufactured by Tateho Chemical Industries, with a volume average particle size of 2.4 μm

矽酸酯40：多摩化學工業製造 Phthalate 40: manufactured by Tama Chemical Industry

異丙醇鈦：和光純藥工業製造 Titanium isopropoxide: manufactured by Wako Pure Chemical Industries

乙醯基丙酮：和光純藥工業製造 Acetylacetone: manufactured by Wako Pure Chemical Industries

異丙醇鋯：和光純藥工業製造 Zirconium isopropoxide: manufactured by Wako Pure Chemical Industries

聚乙二醇：日油製造，數量平均分子量為20000 Polyethylene glycol: manufactured by Nippon Oil, with a mean molecular weight of 20,000

MR-2G：總研化學公司製造，實心(密實)白色樹脂粒子，平均粒徑為1.0 μm MR-2G: Solid (compact) white resin particles manufactured by the Institute of Chemical Research, with an average particle size of 1.0 μm

矽酮油：信越化學工業製造，二甲基矽酮油，KF-96 Anthrone oil: manufactured by Shin-Etsu Chemical Industry, dimethyl ketone oil, KF-96

根據以上可知，藉由使用包括含有鹼土金屬或鹼金屬的金屬化合物，分散介質，以及選自由金屬烷氧化物、矽烷氧化物、矽酸酯低聚物以及矽酮油所組成組群中的1種以上特定化合物的阻擋層形成用組成物，能夠充分防止摻雜劑向半導體基板的擴 散，另外，能夠抑制形成有阻擋層的部位的半導體基板表面的粗糙的產生。 According to the above, by using a metal compound including an alkaline earth metal or an alkali metal, a dispersion medium, and a group selected from the group consisting of a metal alkoxide, a decane oxide, a phthalate oligomer, and an oxime oil The composition for forming a barrier layer of the above specific compound can sufficiently prevent the diffusion of the dopant to the semiconductor substrate Further, it is possible to suppress the occurrence of roughness of the surface of the semiconductor substrate in the portion where the barrier layer is formed.

10‧‧‧基板 10‧‧‧Substrate

11‧‧‧阻擋層形成用組成物 11‧‧‧Block formation composition

12、13‧‧‧塗佈用擴散材料 12, 13‧‧‧Developing diffusion materials

12'、13'‧‧‧塗佈用擴散材料的焙燒物 12', 13'‧‧‧Roasting materials for coating diffusion materials

14‧‧‧n+型擴散層 14‧‧‧n + type diffusion layer

15‧‧‧p+型擴散層 15‧‧‧p + diffusion layer

16‧‧‧抗反射膜 16‧‧‧Anti-reflective film

17‧‧‧鈍化膜 17‧‧‧ Passivation film

18、19‧‧‧電極 18, 19‧‧‧ electrodes

Claims (21)

一種阻擋層形成用組成物，包含：含有鹼土金屬或鹼金屬的金屬化合物；分散介質；以及選自由金屬烷氧化物、矽烷氧化物、矽酸酯低聚物以及矽酮油所組成組群中的1種以上特定化合物。 A barrier layer-forming composition comprising: a metal compound containing an alkaline earth metal or an alkali metal; a dispersion medium; and a group selected from the group consisting of a metal alkoxide, a decane oxide, a phthalate oligomer, and an anthrone oil One or more specific compounds. 如申請專利範圍第1項所述的阻擋層形成用組成物，其中上述特定化合物包含選自由矽烷氧化物、矽酸甲酯低聚物及矽酸乙酯低聚物所組成組群中的1種以上。 The composition for forming a barrier layer according to claim 1, wherein the specific compound comprises one selected from the group consisting of a decane oxide, a methyl phthalate oligomer, and an ethyl citrate oligomer. More than one species. 如申請專利範圍第1項或第2項所述的阻擋層形成用組成物，其中上述特定化合物包含矽烷氧化物，且上述矽烷氧化物包含選自由四甲氧基矽烷及四乙氧基矽烷所組成組群中的1種以上。 The composition for forming a barrier layer according to claim 1 or 2, wherein the specific compound contains a decane oxide, and the decane oxide is selected from the group consisting of tetramethoxy decane and tetraethoxy decane. One or more of the group is formed. 如申請專利範圍第1項至第3項中任一項所述的阻擋層形成用組成物，其中不揮發成分中的上述特定化合物的含有率為0.5質量%以上、50質量%以下。 The composition for forming a barrier layer according to any one of the first to third aspects, wherein the content of the specific compound in the nonvolatile component is 0.5% by mass or more and 50% by mass or less. 如申請專利範圍第1項至第4項中任一項所述的阻擋層形成用組成物，其中上述含有鹼土金屬或鹼金屬的金屬化合物包含選自由鎂、鈣、鈉、鉀、鋰、銣、銫、鈹、鍶、鋇及鐳所組成組群中的1種以上作為金屬元素。 The barrier layer-forming composition according to any one of claims 1 to 4, wherein the alkaline earth metal or alkali metal-containing metal compound is selected from the group consisting of magnesium, calcium, sodium, potassium, lithium, and cesium. One or more of the groups consisting of 铯, 铍, 铍, 锶, 钡, and radium are used as the metal element. 如申請專利範圍第1項至第5項中任一項所述的阻擋層形成用組成物，其中上述含有鹼土金屬或鹼金屬的金屬化合物包含選自由氧化鎂、氧化鈣、氧化鉀、碳酸鎂、碳酸鈣、硫酸鎂、硫 酸鈣、硝酸鈣、硬脂酸鈣、氫氧化鎂及氫氧化鈣所組成組群中的1種以上。 The barrier layer-forming composition according to any one of claims 1 to 5, wherein the alkaline earth metal or alkali metal-containing metal compound is selected from the group consisting of magnesium oxide, calcium oxide, potassium oxide, and magnesium carbonate. , calcium carbonate, magnesium sulfate, sulfur One or more of the group consisting of calcium acid, calcium nitrate, calcium stearate, magnesium hydroxide, and calcium hydroxide. 如申請專利範圍第1項至第6項中任一項所述的阻擋層形成用組成物，其中上述含有鹼土金屬或鹼金屬的金屬化合物是在常溫下為固體的粒子，且上述粒子的體積平均粒徑為30 μm以下。 The barrier layer-forming composition according to any one of the preceding claims, wherein the alkaline earth metal or alkali metal-containing metal compound is a solid at a normal temperature, and the volume of the particles is The average particle size is 30 μm or less. 如申請專利範圍第1項至第7項中任一項所述的阻擋層形成用組成物，其中更包含有機黏合劑。 The composition for forming a barrier layer according to any one of claims 1 to 7, further comprising an organic binder. 如申請專利範圍第8項所述的阻擋層形成用組成物，其中上述有機黏合劑包含選自由丙烯酸樹脂、丁醛樹脂及纖維素樹脂所組成組群中的1種以上。 The composition for forming a barrier layer according to the invention of claim 8, wherein the organic binder comprises one or more selected from the group consisting of an acrylic resin, a butyral resin, and a cellulose resin. 如申請專利範圍第1項至第9項中任一項所述的阻擋層形成用組成物，其中上述分散介質包含選自由水、醇系溶劑、醚系溶劑、二醇單醚系溶劑及萜系溶劑所組成組群中的1種以上。 The composition for forming a barrier layer according to any one of the preceding claims, wherein the dispersion medium comprises a solvent selected from the group consisting of water, an alcohol solvent, an ether solvent, a glycol monoether solvent, and a hydrazine. One or more of the groups consisting of the solvent. 如申請專利範圍第1項至第10項中任一項所述的阻擋層形成用組成物，其中不揮發成分中的上述含有鹼土金屬或鹼金屬的金屬化合物的含有率為0.5質量%以上、且小於100質量%。 The composition for forming a barrier layer according to any one of the first to tenth aspect, wherein the content of the alkaline earth metal or alkali metal-containing metal compound in the nonvolatile component is 0.5% by mass or more. And less than 100% by mass. 如申請專利範圍第1項至第11項中任一項所述的阻擋層形成用組成物，其中25℃下的黏度為0.5 Pa．s以上、400 Pa．s以下。 The composition for forming a barrier layer according to any one of claims 1 to 11, wherein the viscosity at 25 ° C is 0.5 Pa. s above, 400 Pa. s below. 如申請專利範圍第1項至第12項中任一項所述的阻擋層形成用組成物，其中不揮發成分中的上述含有鹼土金屬或鹼金屬的金屬化合物的含有率為10質量%以上、55質量%以下。 The composition for forming a barrier layer according to any one of the items 1 to 12, wherein the content of the alkaline earth metal or alkali metal-containing metal compound in the nonvolatile component is 10% by mass or more. 55 mass% or less. 如申請專利範圍第1項至第13項中任一項所述的阻擋層形成用組成物，其中25℃下的黏度為40 Pa．s以上、200 Pa．s以下。 The composition for forming a barrier layer according to any one of claims 1 to 13, wherein the viscosity at 25 ° C is 40 Pa. s above, 200 Pa. s below. 如申請專利範圍第1項至第14項中任一項所述的阻擋層形成用組成物，其中上述含有鹼土金屬或鹼金屬的金屬化合物包含選自由氧化鈣及碳酸鈣所組成組群中的1種以上。 The barrier layer-forming composition according to any one of claims 1 to 14, wherein the alkaline earth metal or alkali metal-containing metal compound is selected from the group consisting of calcium oxide and calcium carbonate. More than one type. 如申請專利範圍第1項至第15項中任一項所述的阻擋層形成用組成物，其中更含有觸變劑。 The composition for forming a barrier layer according to any one of claims 1 to 15, further comprising a thixotropic agent. 如申請專利範圍第1項至第16項中任一項所述的阻擋層形成用組成物，其用於形成阻擋層，上述阻擋層用來在半導體基板上部分性地形成擴散層。 The barrier layer-forming composition according to any one of claims 1 to 16, which is used for forming a barrier layer for partially forming a diffusion layer on a semiconductor substrate. 一種阻擋層，其為如申請專利範圍第1項至第17項中任一項所述的阻擋層形成用組成物的乾燥體。 A barrier layer which is a dried body of the barrier layer-forming composition according to any one of claims 1 to 17. 一種太陽電池用基板的製造方法，包括：將如申請專利範圍第1項至第17項中任一項所述的阻擋層形成用組成物施用至半導體基板上而形成圖案狀阻擋層的步驟；以及在上述半導體基板上的未形成上述阻擋層的部分，使施體元素或者受體元素擴散，在上述半導體基板內部分性地形成擴散層的步驟。 A method for producing a substrate for a solar cell, comprising: a step of applying a composition for forming a barrier layer according to any one of claims 1 to 17 to a semiconductor substrate to form a patterned barrier layer; And a step of partially forming a diffusion layer in the semiconductor substrate by diffusing a donor element or an acceptor element on a portion of the semiconductor substrate where the barrier layer is not formed. 如申請專利範圍第19項所述的太陽電池用基板的製造方法，其中施用上述阻擋層形成用組成物的方法為印刷法或者噴墨 法。 The method for producing a substrate for a solar cell according to claim 19, wherein the method of applying the composition for forming a barrier layer is a printing method or an inkjet method. law. 一種太陽電池元件的製造方法，包括在利用如申請專利範圍第19項或第20項所述的製造方法而獲得的太陽電池用基板的上述擴散層上形成電極的步驟。 A method for producing a solar cell element, comprising the step of forming an electrode on the diffusion layer of a substrate for a solar cell obtained by the production method according to claim 19 or 20.
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