TWI556289B - Composition for forming p-type diffusion layer, method for forming p-type diffusion layer, and method for producing photovoltaic cell element - Google Patents
Composition for forming p-type diffusion layer, method for forming p-type diffusion layer, and method for producing photovoltaic cell element Download PDFInfo
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- TWI556289B TWI556289B TW103135128A TW103135128A TWI556289B TW I556289 B TWI556289 B TW I556289B TW 103135128 A TW103135128 A TW 103135128A TW 103135128 A TW103135128 A TW 103135128A TW I556289 B TWI556289 B TW I556289B
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- Prior art keywords
- diffusion layer
- type diffusion
- forming
- composition
- glass powder
- Prior art date
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- H—ELECTRICITY
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- H01L21/22—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities
- H01L21/2225—Diffusion sources
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/22—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
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- Y02E10/547—Monocrystalline silicon PV cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Description
本發明是有關於一種太陽電池元件的形成p型擴散層的組成物、p型擴散層的製造方法及太陽電池元件的製造方法,更詳細而言,本發明是有關於一種可減少作為半導體基板的矽基板的內應力、抑制結晶粒界(crystal grain boundary)的損壞、抑制結晶缺陷(crystal defects)的增長及抑制翹曲的p型擴散層形成技術。 The present invention relates to a composition for forming a p-type diffusion layer of a solar cell element, a method for producing a p-type diffusion layer, and a method for manufacturing a solar cell element. More specifically, the present invention relates to a semiconductor substrate which can be reduced as a semiconductor substrate. The internal stress of the ruthenium substrate, the damage of the crystal grain boundary, the growth of crystal defects, and the p-type diffusion layer formation technique for suppressing warpage.
對先前的矽太陽電池元件的製造步驟進行說明。 The manufacturing steps of the prior 矽 solar cell element will be described.
首先,為了促進光學侷限效應(confinement effect)來謀求高效率化,準備形成有紋理(texture)構造的p型矽基板,繼而於氧氯化磷(POCl3)、氮氣、氧氣的混合氣體環境下以800℃~900℃進行幾十分鐘的處理,從而於基板上同樣地形成n型擴散層。於該先前的方法中,因使用混合氣體進行磷的擴散,故不僅於表面形成n型擴散層,而且於側面、背面亦形成n型擴散層。由於 這些原因,需要側蝕刻(side etching)來進行用於去移除側面的n型擴散層。另外,需將背面的n型擴散層轉換成p+型擴散層,因此於背面印刷鋁膏,然後對其進行煅燒(燒結),以使n型擴散層轉變p+型層並同時獲得歐姆接觸。 First, in order to promote the optical confinement effect to achieve high efficiency, a p-type germanium substrate having a texture structure is prepared, and then in a mixed gas atmosphere of phosphorus oxychloride (POCl 3 ), nitrogen, and oxygen. The treatment was performed at 800 ° C to 900 ° C for several tens of minutes to form an n-type diffusion layer on the substrate in the same manner. In this prior method, since phosphorus is diffused by using a mixed gas, an n-type diffusion layer is formed not only on the surface but also on the side surface and the back surface. For these reasons, side etching is required to perform an n-type diffusion layer for removing the side. In addition, the n-type diffusion layer on the back side needs to be converted into a p + -type diffusion layer, so that the aluminum paste is printed on the back side and then calcined (sintered) so that the n-type diffusion layer is transformed into the p + type layer while obtaining ohmic contact. .
但是,由鋁膏所形成的鋁層的導電率低,為了降低薄片電阻(sheet resistance),通常形成於整個背面的鋁層於煅燒後必需具有10μm~20μm左右的厚度。進而,若如上述般形成較厚的鋁層,則由於矽的熱膨脹係數與鋁的熱膨脹係數相差較大,因此這種差別導致於煅燒及冷卻的過程中在矽基板中產生較大的內應力,而促進了結晶粒界的損壞、結晶缺陷的增長及翹曲的原因。 However, the aluminum layer formed of the aluminum paste has a low electrical conductivity, and in order to reduce the sheet resistance, the aluminum layer usually formed on the entire back surface must have a thickness of about 10 μm to 20 μm after firing. Further, if a thick aluminum layer is formed as described above, since the coefficient of thermal expansion of the crucible differs greatly from the coefficient of thermal expansion of aluminum, this difference causes a large internal stress in the crucible substrate during calcination and cooling. It promotes the damage of crystal grain boundaries, the growth of crystal defects, and the cause of warpage.
為了解決該問題,存在減少膏組成物的塗佈量,使背面電極層變薄的方法。但是,若減少膏組成物的塗佈量,則自p型矽半導體基板的表面擴散至內部的鋁的量變得不充分。其結果,無法達成所期望的背面電場(Back Surface Field,BSF)效果(生成載子(carrier)的收集效率(collection efficiency)因p+型層的存在而提高的效果),因此產生太陽電池的特性下降的問題。 In order to solve this problem, there is a method of reducing the amount of coating of the paste composition and making the back electrode layer thin. However, when the coating amount of the paste composition is reduced, the amount of aluminum diffused from the surface of the p-type germanium semiconductor substrate to the inside becomes insufficient. As a result, the desired back surface field (BSF) effect (the effect of increasing the collection efficiency of the carrier due to the presence of the p + type layer) cannot be achieved, and thus the solar cell is generated. The problem of declining characteristics.
因此,例如於日本專利特開2003-223813號公報中提出有一種膏組成物,其包含鋁粉末,有機媒劑(organic vehicle),以及熱膨脹係數小於鋁且熔融溫度、軟化溫度及分解溫度中的任一者高於鋁的熔點的無機化合物粉末。 For example, a paste composition comprising aluminum powder, an organic vehicle, and a thermal expansion coefficient smaller than aluminum and having a melting temperature, a softening temperature, and a decomposition temperature is proposed in Japanese Patent Laid-Open Publication No. 2003-223813. An inorganic compound powder which is higher than the melting point of aluminum.
但是,當使用日本專利特開2003-223813號公報中所記載 的膏組成物時,亦存在無法充分地抑制翹曲的情況。 However, it is described in Japanese Patent Laid-Open Publication No. 2003-223813. In the case of the paste composition, there is also a case where warpage cannot be sufficiently suppressed.
本發明是鑒於以上的先前的問題點而完成的發明,其課題在於提供一種於使用矽基板的太陽電池元件的製造步驟中,可抑制矽基板中的內應力、基板的翹曲的產生,並形成p型擴散層,且可製作表面電阻值低的太陽電池元件的形成p型擴散層的組成物、p型擴散層的製造方法及太陽電池元件的製造方法。 The present invention has been made in view of the above problems, and an object of the invention is to provide a method for manufacturing a solar cell element using a tantalum substrate, thereby suppressing occurrence of internal stress in the tantalum substrate and warpage of the substrate. A p-type diffusion layer is formed, and a composition for forming a p-type diffusion layer of a solar cell element having a low surface resistance value, a method for producing a p-type diffusion layer, and a method for producing a solar cell element can be produced.
解決上述課題的方法如下。 The method for solving the above problems is as follows.
<1>一種形成p型擴散層的組成物,其包括含有受體元素(acceptor element)的玻璃粉末、及分散介質,上述玻璃粉末包括含有受體元素的物質、及玻璃成分物質,上述玻璃粉末中的上述含有受體元素的物質的含有比率為1質量%以上至90質量%以下。 <1> A composition for forming a p-type diffusion layer, comprising: a glass powder containing an acceptor element, and a dispersion medium, wherein the glass powder includes a substance containing an acceptor element, and a glass component substance, the glass powder The content ratio of the above-mentioned receptor element-containing substance is from 1% by mass to 90% by mass.
<2>如上述<1>所述之形成p型擴散層的組成物,其中上述受體元素是選自B(硼)、Al(鋁)及Ga(鎵)中的至少一種。 <2> The composition for forming a p-type diffusion layer according to the above <1>, wherein the acceptor element is at least one selected from the group consisting of B (boron), Al (aluminum), and Ga (gallium).
<3>如上述<1>或<2>所述之形成p型擴散層的組成物,其中含有上述受體元素的玻璃粉末包括:選自B2O3、Al2O3及Ga2O3中的至少一種含有受體元素的物質;以及選自SiO2、K2O、Na2O、Li2O、BaO、SrO、CaO、MgO、BeO、ZnO、PbO、CdO、Tl2O、SnO、ZrO2及MoO3中的至少一種玻璃成分物質。 <3> The composition for forming a p-type diffusion layer according to the above <1> or <2>, wherein the glass powder containing the above-mentioned acceptor element comprises: selected from the group consisting of B 2 O 3 , Al 2 O 3 and Ga 2 O At least one of 3 containing an acceptor element; and selected from the group consisting of SiO 2 , K 2 O, Na 2 O, Li 2 O, BaO, SrO, CaO, MgO, BeO, ZnO, PbO, CdO, Tl 2 O, At least one glass component substance of SnO, ZrO 2 and MoO 3 .
<4>一種p型擴散層的製造方法,其包括:塗佈如上述<1>~<3>中任一項所述之形成p型擴散層的組成物的步 驟、以及實施熱擴散處理的步驟。 <4> A method for producing a p-type diffusion layer, comprising: a step of forming a composition for forming a p-type diffusion layer according to any one of <1> to <3> above And the step of performing thermal diffusion treatment.
<5>一種太陽電池元件的製造方法,其包括:於半導體基板上塗佈如上述<1>~<3>中任一項所述之形成p型擴散層的組成物的步驟、實施熱擴散處理來形成p型擴散層的步驟、以及於所形成的上述p型擴散層上形成電極的步驟。 <5> A method for producing a solar cell element, comprising the step of applying a composition for forming a p-type diffusion layer according to any one of the above <1> to <3> on a semiconductor substrate, and performing thermal diffusion a step of forming a p-type diffusion layer and a step of forming an electrode on the formed p-type diffusion layer.
根據本發明,於使用矽基板的太陽電池元件的製造步驟中,可抑制矽基板中的內應力、基板的翹曲,並形成p型擴散層。另外,藉由設定成本發明的含有受體元素的物質的含有比率的範圍,表面電阻值下降,可提高作為太陽電池元件的性能。 According to the present invention, in the manufacturing step of the solar cell element using the tantalum substrate, the internal stress in the tantalum substrate and the warpage of the substrate can be suppressed, and the p-type diffusion layer can be formed. Further, by setting the range of the content ratio of the substance containing the acceptor element of the invention, the surface resistance value is lowered, and the performance as a solar cell element can be improved.
為讓本發明之上述和其他目的、特徵和優點能更明顯易懂,下文特舉較佳實施例,並配合所附圖式,作詳細說明如下。 The above and other objects, features and advantages of the present invention will become more <RTIgt;
首先,對本發明的形成p型擴散層的組成物進行說明,其次對使用形成p型擴散層的組成物的p型擴散層及太陽電池元件的製造方法進行說明。 First, the composition for forming a p-type diffusion layer of the present invention will be described. Next, a method for producing a p-type diffusion layer and a solar cell element using a composition for forming a p-type diffusion layer will be described.
再者,於本說明書中,「步驟(process)」這一用語不僅是指獨立的步驟,亦包含在無法與其他步驟明確地加以區分的情況下,若該步驟能達成所預期的作用,則亦包含於本用語中。另外, 於本說明書中,「~」表示分別包括其前後所記載的數值作為最小值及最大值的範圍。進而,於本說明書中,當論及組成物中的各成分的量時,在組成物中存在多個相當於各成分的物質的情況下,只要事先無特別說明,則表示組成物中所存在的該多個物質的合計量。 Furthermore, in the present specification, the term "process" means not only an independent step but also a case where it cannot be clearly distinguished from other steps, and if the step can achieve the intended effect, then Also included in this term. In addition, In the present specification, "~" means a range including the numerical values described before and after the minimum value and the maximum value, respectively. Further, in the present specification, when the amount of each component in the composition is referred to, when a plurality of substances corresponding to the respective components are present in the composition, unless otherwise specified, the presence of the composition is indicated. The total amount of the plurality of substances.
本發明的形成p型擴散層的組成物包括至少含有受體元素的玻璃粉末(以下,有時僅稱為「玻璃粉末」)、以及分散介質,進而考慮塗佈性等,亦可視需要含有其他添加劑。 The composition for forming a p-type diffusion layer of the present invention includes a glass powder containing at least an acceptor element (hereinafter sometimes referred to simply as "glass powder"), and a dispersion medium, and may further contain other properties as needed. additive.
此處,所謂形成p型擴散層的組成物,是指含有受體元素,且可藉由例如塗佈於矽基板上後進行熱擴散處理(煅燒/燒結)而使該受體元素熱擴散來形成p型擴散層的材料。藉由使用本發明的形成p型擴散層的組成物,可分離p+型擴散層的形成步驟與歐姆接觸的形成步驟,從而拓展了對用於形成歐姆接觸的電極材料的選擇項,並且還拓展了對電極構造的選擇項。例如,若將銀等低電阻材料用於電極,則能夠以較薄的膜厚達成低電阻。另外,電極亦無需形成於整個面上,亦可如梳型等形狀般部分地形成梳型電極。藉由如以上般形成薄膜或梳型形狀等部分形狀,可一面抑制矽基板中的內應力、基板的翹曲的產生,一面形成p型擴散層。 Here, the composition forming the p-type diffusion layer means that the acceptor element is contained, and the acceptor element can be thermally diffused by, for example, being applied to a tantalum substrate and then subjected to thermal diffusion treatment (calcination/sintering). A material that forms a p-type diffusion layer. By using the composition for forming a p-type diffusion layer of the present invention, the formation step of the p + -type diffusion layer and the step of forming the ohmic contact can be separated, thereby expanding the selection of the electrode material for forming the ohmic contact, and also Expanded options for electrode construction. For example, when a low-resistance material such as silver is used for the electrode, a low resistance can be achieved with a thin film thickness. Further, the electrode does not need to be formed on the entire surface, and the comb-shaped electrode may be partially formed in a shape such as a comb shape. By forming a partial shape such as a film or a comb shape as described above, it is possible to form a p-type diffusion layer while suppressing internal stress in the ruthenium substrate and occurrence of warpage of the substrate.
因此,若應用本發明的形成p型擴散層的組成物,則抑制先前廣泛採用的方法中所產生於基板中的內應力及基板的翹曲的產生,前述之先前廣泛採用的方法為:印刷鋁膏,然後對其進 行煅燒,與使n型擴散層變成p+型擴散層的同時獲得歐姆接觸的方法。 Therefore, when the composition for forming a p-type diffusion layer of the present invention is applied, the generation of internal stress generated in the substrate and the warpage of the substrate in the previously widely used method are suppressed, and the previously widely used method is: printing The aluminum paste is then calcined, and a method of obtaining an ohmic contact while making the n-type diffusion layer into a p + -type diffusion layer.
進而,玻璃粉末中的受體成分於煅燒中亦難以揮發(sublimation),因此抑制p型擴散層因揮發氣體的產生而形成至所期望的區域以外的情況。其原因可認為例如受體成分與玻璃粉末中的元素結合、或者被導入至玻璃中,因此難以揮發。 Further, since the acceptor component in the glass powder is hardly sublimated during calcination, it is suppressed that the p-type diffusion layer is formed outside the desired region due to the generation of the volatilized gas. The reason for this is considered to be that, for example, the acceptor component is bonded to an element in the glass powder or introduced into the glass, so that it is difficult to volatilize.
進而,本發明的形成p型擴散層的組成物中所包含的玻璃粉末中的含有受體元素的物質的含有比率為1質量%以上至90質量%以下。藉此,表面電阻值下降,作為太陽電池元件的性能可提高。含有受體元素的物質的詳細情況將後述。 Furthermore, the content ratio of the receptor element-containing substance in the glass powder contained in the composition for forming a p-type diffusion layer of the present invention is 1% by mass or more and 90% by mass or less. Thereby, the surface resistance value is lowered, and the performance as a solar cell element can be improved. The details of the substance containing the acceptor element will be described later.
對本發明的含有受體元素的玻璃粉末進行詳細說明。所謂受體元素,是指藉由摻雜於矽基板中而可形成p型擴散層的元素。受體元素可使用第13族的元素,例如可列舉:B(硼)、Al(鋁)及Ga(鎵)等。 The glass powder containing the acceptor element of the present invention will be described in detail. The term "receptor element" means an element which can form a p-type diffusion layer by being doped into a germanium substrate. As the acceptor element, a group 13 element can be used, and examples thereof include B (boron), Al (aluminum), and Ga (gallium).
作為用於將受體元素導入至玻璃粉末中的含有受體元素的物質,可列舉B2O3、Al2O3、及Ga2O3,較佳為使用選自B2O3、Al2O3及Ga2O3中的至少一種。 Examples of the acceptor element-containing substance for introducing an acceptor element into the glass powder include B 2 O 3 , Al 2 O 3 , and Ga 2 O 3 , preferably selected from B 2 O 3 , Al. At least one of 2 O 3 and Ga 2 O 3 .
另外,含有受體元素的玻璃粉末可視需要調整成分比率,藉此控制熔融溫度、軟化溫度、玻璃轉移溫度、化學耐久性等。較佳為進而包含以下所述的玻璃成分物質。 Further, the glass powder containing the acceptor element may be adjusted in composition ratio as needed, thereby controlling the melting temperature, the softening temperature, the glass transition temperature, the chemical durability, and the like. It is preferable to further contain the glass component substance described below.
作為玻璃構成成分,可列舉:SiO2、K2O、Na2O、Li2O、BaO、SrO、CaO、MgO、BeO、ZnO、PbO、CdO、Tl2O、V2O5、SnO、 ZrO2、MoO3、La2O3、Nb2O5、Ta2O5、Y2O3、TiO2、GeO2、TeO2及Lu2O3等,較佳為使用選自SiO2、K2O、Na2O、Li2O、BaO、SrO、CaO、MgO、BeO、ZnO、PbO、CdO、Tl2O、SnO、ZrO2、及MoO3中的至少一種。 Examples of the glass constituent component include SiO 2 , K 2 O, Na 2 O, Li 2 O, BaO, SrO, CaO, MgO, BeO, ZnO, PbO, CdO, Tl 2 O, V 2 O 5 , and SnO. ZrO 2 , MoO 3 , La 2 O 3 , Nb 2 O 5 , Ta 2 O 5 , Y 2 O 3 , TiO 2 , GeO 2 , TeO 2 , Lu 2 O 3 , etc., preferably selected from SiO 2 , At least one of K 2 O, Na 2 O, Li 2 O, BaO, SrO, CaO, MgO, BeO, ZnO, PbO, CdO, Tl 2 O, SnO, ZrO 2 , and MoO 3 .
作為含有受體元素的玻璃粉末的具體例,可列舉包括上述含有受體元素的物質與上述玻璃成分物質兩者的體系,可列舉:B2O3-SiO2體系(以含有受體元素的物質-玻璃成分物質的順序記載,以下相同)、B2O3-ZnO體系、B2O3-PbO體系、B2O3單獨體系等包含B2O3作為含有受體元素的物質的體系,Al2O3-SiO2體系等包含Al2O3作為含有受體元素的物質的體系,Ga2O3-SiO2體系等包含Ga2O3作為含有受體元素的物質的體系等的玻璃粉末。 Specific examples of the glass powder containing the acceptor element include a system including both the above-described acceptor element-containing substance and the above-described glass component substance, and examples thereof include a B 2 O 3 —SiO 2 system (containing an acceptor element). The system-glass component substance is described in the following order, the B 2 O 3 -ZnO system, the B 2 O 3 -PbO system, the B 2 O 3 individual system, and the like, including B 2 O 3 as a substance containing an acceptor element. , Al 2 O 3 -SiO 2 system contains Al 2 O 3 and the like as a material system containing the receptor element, Ga 2 O 3 -SiO 2 system, and comprises Ga 2 O 3 as the acceptor element-containing material systems like Glass powder.
另外,亦可為如Al2O3-B2O3體系、Ga2O3-B2O3體系等般,包含兩種以上的含有受體元素的物質的玻璃粉末。 Further, it may be a glass powder containing two or more kinds of substances containing an acceptor element, such as an Al 2 O 3 -B 2 O 3 system or a Ga 2 O 3 -B 2 O 3 system.
於上述中例示了包含一種成分的玻璃或包含兩種成分的複合玻璃,但亦可為如B2O3-SiO2-Na2O體系等般,包含三種成分以上的物質的玻璃粉末。 In the above, a glass containing one component or a composite glass containing two components is exemplified, but a glass powder containing three or more components such as a B 2 O 3 —SiO 2 —Na 2 O system may be used.
另外,玻璃粉末可視需要調整成分比率,藉此控制熔融溫度、軟化溫度、玻璃轉移溫度、化學耐久性等。 Further, the glass powder may be adjusted in composition ratio as needed, thereby controlling the melting temperature, the softening temperature, the glass transition temperature, the chemical durability, and the like.
考慮到受體元素於矽基板中的摻雜濃度,玻璃粉末的熔融溫度、軟化溫度、玻璃轉移溫度、化學耐久性,玻璃粉末中的含有受體元素的物質的含有比率為1質量%以上至90質量%以下。 In consideration of the doping concentration of the acceptor element in the ruthenium substrate, the melting temperature, the softening temperature, the glass transition temperature, and the chemical durability of the glass powder, the content ratio of the substance containing the acceptor element in the glass powder is 1% by mass or more. 90% by mass or less.
當玻璃粉末中的含有受體元素的物質的含有比率未滿1 質量%時,受體元素於矽基板中的摻雜濃度過低,p型擴散層未充分地形成。另外,當含有受體元素的物質的含有比率大於90質量%時,含有受體元素的物質於熱擴散處理中揮發,因此存在受體元素的擴散亦到達側面及背面,不僅於表面形成p型擴散層,而且於所期望的部位以外的側面、背面亦形成p型擴散層的可能性。 When the content ratio of the substance containing the acceptor element in the glass powder is less than 1 In the mass%, the doping concentration of the acceptor element in the tantalum substrate is too low, and the p-type diffusion layer is not sufficiently formed. In addition, when the content ratio of the substance containing the acceptor element is more than 90% by mass, the substance containing the acceptor element is volatilized in the thermal diffusion treatment, so that the diffusion of the acceptor element also reaches the side surface and the back surface, and not only the surface is formed into a p-type. The diffusion layer may have a p-type diffusion layer formed on the side surface and the back surface other than the desired portion.
進而,玻璃粉末中的含有受體元素的物質的含有比率較佳為2質量%以上至80質量%以下,更佳為10質量%以上至70質量%以下。 Furthermore, the content ratio of the substance containing an acceptor element in the glass powder is preferably 2% by mass or more and 80% by mass or less, and more preferably 10% by mass or more and 70% by mass or less.
尤其,若考慮如下兩個方面,則玻璃粉末中的含有受體元素的物質的含有比率更佳為30質量%以上、70質量%以下,上述兩個方面是指即便一面斟酌充分地形成p型擴散層的受體元素的量,一面於形成p型擴散層的組成物中添加一定量以上的受體元素,具有所形成的p型擴散層的表面的薄片電阻亦不會下降至超過一定值;以及必需抑制含有受體元素的物質的揮發的影響。 In particular, when the following two aspects are considered, the content ratio of the substance containing the acceptor element in the glass powder is more preferably 30% by mass or more and 70% by mass or less, and the above two aspects mean that the p-type is sufficiently formed even if one side is considered. The amount of the acceptor element of the diffusion layer is such that a certain amount or more of the acceptor element is added to the composition forming the p-type diffusion layer, and the sheet resistance of the surface of the formed p-type diffusion layer does not fall below a certain value. And the necessity to inhibit the volatilization of substances containing acceptor elements.
另外,玻璃粉末中的玻璃成分物質的含有比率較理想的是考慮熔融溫度、軟化溫度、玻璃轉移溫度、化學耐久性而適宜設定,一般而言,較佳為10質量%以上至99質量%以下,更佳為20質量%以上至98質量%以下,進而更佳為30質量%以上至90質量%以下。 In addition, the content ratio of the glass component in the glass powder is preferably set in consideration of the melting temperature, the softening temperature, the glass transition temperature, and the chemical durability, and is generally preferably 10% by mass or more and 99% by mass or less. It is more preferably 20% by mass or more and 98% by mass or less, and still more preferably 30% by mass or more and 90% by mass or less.
具體而言,當為B2O3-SiO2體系玻璃時,B2O3的含有比率較佳為1質量%以上至90質量%以下,更佳為2質量%以上至80質量%以下。 Specifically, when it is a B 2 O 3 -SiO 2 system glass, the content ratio of B 2 O 3 is preferably from 1% by mass to 90% by mass, more preferably from 2% by mass to 80% by mass.
玻璃粉末的軟化溫度就擴散處理時的擴散性、滴液(dripping)的觀點而言,較佳為200℃~1000℃,更佳為300℃~900℃。 The softening temperature of the glass powder is preferably from 200 ° C to 1000 ° C, more preferably from 300 ° C to 900 ° C from the viewpoint of diffusibility at the time of diffusion treatment and dripping.
再者,玻璃粉末的軟化溫度可藉由公知的示差熱分析裝置(Differential Thermal Analyzer,DTA),根據其吸熱波峰而容易地測定。 Further, the softening temperature of the glass powder can be easily measured based on the endothermic peak by a well-known differential thermal analyzer (DTA).
作為玻璃粉末的形狀,可列舉:大致球狀、扁平狀、塊狀、板狀、及鱗片狀等,就製成形成n型擴散層的組成物時的對於基板的塗佈性或均勻擴散性的觀點而言,較理想的是大致球狀、扁平狀、或板狀。玻璃粉末的粒徑並無特別限制,較理想的是100μm以下。當使用具有100μm以下的粒徑的玻璃粉末時,易於獲得更平滑的塗膜。進而,玻璃粉末的粒徑更理想的是50μm以下。進而,玻璃粉末的粒徑更理想的是10μm以下。再者,下限並無特別限制,但較佳為0.01μm以上。 The shape of the glass powder includes a substantially spherical shape, a flat shape, a block shape, a plate shape, a scale shape, and the like, and the coating property or uniform diffusion property to the substrate when the composition for forming the n-type diffusion layer is formed. From the viewpoint, it is preferable to be substantially spherical, flat, or plate-shaped. The particle diameter of the glass powder is not particularly limited, and is preferably 100 μm or less. When a glass powder having a particle diameter of 100 μm or less is used, a smoother coating film is easily obtained. Further, the particle diameter of the glass powder is more preferably 50 μm or less. Further, the particle diameter of the glass powder is more preferably 10 μm or less. Further, the lower limit is not particularly limited, but is preferably 0.01 μm or more.
此處,玻璃的粒徑表示平均粒徑,可藉由雷射散射繞射法(laser scattering diffraction method)粒度分布(particle size distribution)測定裝置等來測定。 Here, the particle diameter of the glass means an average particle diameter, and can be measured by a laser scattering diffraction method particle size distribution measuring apparatus or the like.
含有受體元素的玻璃粉末是藉由以下的程序來製作。 The glass powder containing the acceptor element was produced by the following procedure.
首先,稱量原料並將其填充至坩堝中。坩堝的材質可列舉鉑、鉑-銠、銥、氧化鋁、石英、碳等,可考慮熔融溫度、環境、與熔融物質的反應性等而適宜選擇。 First, the raw material is weighed and filled into the crucible. Examples of the material of the crucible include platinum, platinum-rhodium, iridium, aluminum oxide, quartz, carbon, and the like, and are appropriately selected in consideration of the melting temperature, the environment, and the reactivity with the molten material.
其次,藉由電爐以對應於玻璃組成的溫度進行加熱而製成熔 液。此時,較理想的是以使熔液變得均勻的方式進行攪拌。 Secondly, it is made into a melting by heating in an electric furnace at a temperature corresponding to the composition of the glass. liquid. At this time, it is preferable to stir so that the melt becomes uniform.
繼而,使所獲得的熔液流出至石墨板、鉑板、鉑-銠合金板、氧化鋯板等上而將熔液玻璃化。 Then, the obtained melt flows out onto a graphite plate, a platinum plate, a platinum-ruthenium alloy plate, a zirconia plate or the like to vitrify the melt.
最後,粉碎玻璃而形成粉末狀。粉碎可應用噴射磨機、珠磨機、球磨機等公知的方法。 Finally, the glass is pulverized to form a powder. A known method such as a jet mill, a bead mill, or a ball mill can be applied to the pulverization.
形成p型擴散層的組成物中的含有受體元素的玻璃粉末的含有比率是考慮塗佈性、受體元素的擴散性等而決定。一般而言,形成p型擴散層的組成物中的玻璃粉末的含有比率較佳為0.1質量%以上至95質量%以下,更佳為1質量%以上至90質量%以下,進而更佳為1.5質量%以上至85質量%以下,特佳為2質量%以上至80質量%以下。 The content ratio of the glass powder containing the acceptor element in the composition forming the p-type diffusion layer is determined in consideration of coatability, diffusibility of the acceptor element, and the like. In general, the content ratio of the glass powder in the composition forming the p-type diffusion layer is preferably 0.1% by mass or more and 95% by mass or less, more preferably 1% by mass or more and 90% by mass or less, and still more preferably 1.5% by mass or less. The mass% or more is 85% by mass or less, and particularly preferably 2% by mass or more and 80% by mass or less.
其次,對分散介質進行說明。 Next, the dispersion medium will be described.
所謂分散介質,是指於組成物中使上述玻璃粉末分散的介質。具體而言,採用黏合劑或溶劑等作為分散介質。 The dispersion medium refers to a medium in which the glass powder is dispersed in the composition. Specifically, a binder, a solvent, or the like is used as a dispersion medium.
作為黏合劑,例如可適宜選擇聚乙烯醇、聚丙烯醯胺類、聚乙烯醯胺類、聚乙烯吡咯啶酮、聚環氧乙烷類、聚磺酸、丙烯醯胺烷基磺酸、纖維素醚類、纖維素衍生物、羧甲基纖維素、羥乙基纖維素、乙基纖維素、明膠、澱粉及澱粉衍生物、海藻酸鈉類(sodium alginate)、三仙膠(xanthan)、瓜爾膠及瓜爾膠衍生物、硬葡聚糖及硬葡聚糖衍生物、黃蓍膠及黃蓍膠衍生物、糊精及糊精衍生物、(甲基)丙烯酸樹脂、(甲基)丙烯酸酯樹脂(例如(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)、丁二 烯樹脂、苯乙烯樹脂、或該些的共聚物,除此以外,亦可適宜選擇矽氧烷樹脂。該些可單獨使用一種、或者組合兩種以上來使用。 As the binder, for example, polyvinyl alcohol, polypropylene decylamine, polyvinyl decylamine, polyvinylpyrrolidone, polyethylene oxide, polysulfonic acid, acrylamide sulfonic acid, fiber can be suitably selected. Ethers, cellulose derivatives, carboxymethyl cellulose, hydroxyethyl cellulose, ethyl cellulose, gelatin, starch and starch derivatives, sodium alginate, xanthan, Guar gum and guar gum derivatives, scleroglucan and scleroglucan derivatives, tragacanth and xanthan gum derivatives, dextrin and dextrin derivatives, (meth)acrylic resin, (methyl Acrylate resin (for example, alkyl (meth)acrylate resin, dimethylaminoethyl (meth)acrylate resin, etc.) In addition to the olefin resin, the styrene resin, or the copolymers thereof, a decane resin may be appropriately selected. These may be used alone or in combination of two or more.
黏合劑的分子量並無特別限制,較理想的是鑒於作為組成物的所期望的黏度而適宜調整。 The molecular weight of the binder is not particularly limited, and is preferably adjusted in view of the desired viscosity as a composition.
作為溶劑,例如可列舉:丙酮、甲基乙基酮、甲基-正丙基酮、甲基-異丙基酮、甲基-正丁基酮、甲基-異丁基酮、甲基-正戊基酮、甲基-正己基酮、二乙基酮、二丙基酮、二-異丁基酮、三甲基壬酮、環己酮、環戊酮、甲基環己酮、2,4-戊二酮、丙酮基丙酮等酮系溶劑;二乙醚、甲基乙基醚、甲基-正丙醚、二-異丙醚、四氫呋喃、甲基四氫呋喃、二噁烷、二甲基二噁烷、乙二醇二甲醚、乙二醇二乙醚、乙二醇二-正丙醚、乙二醇二丁醚、二乙二醇二甲醚、二乙二醇二乙醚、二乙二醇甲基乙基醚、二乙二醇甲基-正丙醚、二乙二醇甲基-正丁醚、二乙二醇二-正丙醚、二乙二醇二-正丁醚、二乙二醇甲基-正己醚、三乙二醇二甲醚、三乙二醇二乙醚、三乙二醇甲基乙基醚、三乙二醇甲基-正丁醚、三乙二醇二-正丁醚、三乙二醇甲基-正己醚、四乙二醇二甲醚、四乙二醇二乙醚、四-二乙二醇甲基乙基醚、四乙二醇甲基-正丁醚、二乙二醇二-正丁醚、四乙二醇甲基-正己醚、四乙二醇二-正丁醚、丙二醇二甲醚、丙二醇二乙醚、丙二醇二-正丙醚、丙二醇二丁醚、二丙二醇二甲醚、二丙二醇二乙醚、二丙二醇甲基乙基醚、二丙二醇甲基-正丁醚、二丙二醇二-正丙醚、二丙二醇二-正丁醚、二丙二醇甲基-正己醚、三丙二醇二甲醚、三丙二醇二乙醚、三丙二醇甲基 乙基醚、三丙二醇甲基-正丁醚、三丙二醇二-正丁醚、三丙二醇甲基-正己醚、四丙二醇二甲醚、四丙二醇二乙醚、四-二丙二醇甲基乙基醚、四丙二醇甲基-正丁醚、二丙二醇二-正丁醚、四丙二醇甲基-正己醚、四丙二醇二-正丁醚等醚系溶劑;乙酸甲酯、乙酸乙酯、乙酸正丙酯、乙酸異丙酯、乙酸正丁酯、乙酸異丁酯、乙酸第二丁酯、乙酸正戊酯、乙酸第二戊酯、乙酸3-甲氧基丁酯、乙酸甲基戊酯、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、乙酸二乙二醇甲醚、乙酸二乙二醇單乙醚、乙酸二乙二醇-正丁醚、乙酸二丙二醇甲醚、乙酸二丙二醇乙醚、乙二醇二乙酸酯、乙氧基三甘醇乙酸酯、丙酸乙酯、丙酸正丁酯、丙酸異戊酯、草酸二乙酯、草酸二-正丁酯、乳酸甲酯、乳酸乙酯、乳酸正丁酯、乳酸正戊酯、乙二醇甲醚丙酸酯、乙二醇乙醚丙酸酯、乙二醇甲醚乙酸酯、乙二醇乙醚乙酸酯、二乙二醇甲醚乙酸酯、二乙二醇乙醚乙酸酯、二乙二醇-正丁醚乙酸酯、丙二醇甲醚乙酸酯、丙二醇乙醚乙酸酯、丙二醇丙基醚乙酸酯、二丙二醇甲醚乙酸酯、二丙二醇乙醚乙酸酯、γ-丁內酯、γ-戊內酯等酯系溶劑;乙腈、N-甲基吡咯酮、N-乙基吡咯酮、N-丙基吡咯酮、N-丁基吡咯酮、N-己基吡咯酮、N-環己基吡咯酮、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、苄醇、乙二醇、1,2-丙二醇、1,3-丁二醇、二乙二醇、二丙二醇、三乙二醇、三丙二醇等醇系溶劑;乙二醇甲醚、乙二醇乙醚、乙二醇單苯醚、二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇單-正丁醚、二乙二醇單-正己醚、乙氧基三甘醇、四乙二醇單-正丁醚、丙二醇單甲醚、二丙二醇單甲醚、二丙二醇單乙醚、三丙二醇單甲醚等二醇單醚系溶劑;α-萜品烯、α-萜品醇、月桂油烯、別羅勒烯(allo-ocimene)、檸檬烯、雙戊烯、α-蒎烯、β-蒎烯、松脂醇(terpineol)、香旱芹酮、羅勒烯、水芹烯等萜烯系溶劑;水。該些可單獨使用一種、或者組合兩種以上來使用。 Examples of the solvent include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-isopropyl ketone, methyl-n-butyl ketone, methyl-isobutyl ketone, and methyl group. N-pentyl ketone, methyl-n-hexyl ketone, diethyl ketone, dipropyl ketone, di-isobutyl ketone, trimethyl fluorenone, cyclohexanone, cyclopentanone, methylcyclohexanone, 2 a ketone solvent such as 4-pentanedione or acetonylacetone; diethyl ether, methyl ethyl ether, methyl-n-propyl ether, di-isopropyl ether, tetrahydrofuran, methyltetrahydrofuran, dioxane, dimethyl Dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol di-n-propyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethyl Glycol methyl ethyl ether, diethylene glycol methyl-n-propyl ether, diethylene glycol methyl-n-butyl ether, diethylene glycol di-n-propyl ether, diethylene glycol di-n-butyl ether, Diethylene glycol methyl-n-hexyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol methyl ethyl ether, triethylene glycol methyl-n-butyl ether, triethylene glycol Di-n-butyl ether, triethylene glycol methyl-n-hexyl ether, tetraethylene glycol dimethyl ether, tetraethylene Alcohol diethyl ether, tetra-diethylene glycol methyl ethyl ether, tetraethylene glycol methyl-n-butyl ether, diethylene glycol di-n-butyl ether, tetraethylene glycol methyl-n-hexyl ether, tetraethylene Alcohol 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 Base-n-butyl ether, dipropylene glycol di-n-propyl ether, dipropylene glycol di-n-butyl ether, dipropylene glycol methyl-n-hexyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol methyl Ethyl ether, tripropylene glycol methyl-n-butyl ether, tripropylene glycol di-n-butyl ether, tripropylene glycol methyl-n-hexyl ether, tetrapropylene glycol dimethyl ether, tetrapropylene glycol diethyl ether, tetra-dipropylene glycol methyl ethyl ether, An ether solvent such as tetrapropylene glycol methyl-n-butyl ether, dipropylene glycol di-n-butyl ether, tetrapropylene glycol methyl-n-hexyl ether or tetrapropylene glycol di-n-butyl ether; methyl acetate, ethyl acetate, n-propyl acetate, Isopropyl acetate, n-butyl acetate, isobutyl acetate, second butyl acetate, n-amyl acetate, second amyl acetate, 3-methoxybutyl acetate, methyl amyl acetate, acetic acid 2- Ethyl butyl acrylate, 2-ethylhexyl acetate, 2-(2-butoxyethoxy)ethyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, decyl acetate, B Methyl acetate, ethyl acetate, diethylene glycol methyl ether, diethylene glycol monoethyl acetate, diethylene glycol-n-butyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, ethylene Alcohol diacetate, ethoxy triethylene glycol acetate, ethyl propionate, n-butyl propionate, isoamyl propionate, diethyl oxalate, oxalic acid di- N-butyl ester, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, ethylene glycol methyl ether propionate, ethylene glycol ether propionate, ethylene glycol methyl ether acetate, ethylene Alcohol ether acetate, diethylene glycol methyl ether acetate, diethylene glycol diethyl ether acetate, diethylene glycol-n-butyl ether acetate, propylene glycol methyl ether acetate, propylene glycol diethyl ether acetate, An ester solvent such as propylene glycol propyl ether acetate, dipropylene glycol methyl ether acetate, dipropylene glycol diethyl ether acetate, γ-butyrolactone or γ-valerolactone; acetonitrile, N-methylpyrrolidone, N- Ethylpyrrolidone, N-propylpyrrolidone, N-butylpyrrolidone, N-hexylpyrrolidone, N-cyclohexylpyrrolidone, N,N-dimethylformamide, N,N-dimethyl An aprotic polar solvent such as acetamide or 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, Dioctanol, n-nonanol, n-nonanol, second-undecanol, trimethylnonanol, second-tetradecanol, second heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol , an alcohol solvent such as benzyl alcohol, ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol or tripropylene glycol; ethylene glycol methyl ether, ethylene glycol Alcohol ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxy triethylene glycol , glycol monoether ether such as tetraethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether; α-terpinene, α-product Alcohol, lauryl olefin, allo-ocimene, limonene, dipentene, α-pinene, β-pinene, terpineol, erysone, basilene, parsyl, etc. Alkene solvent; water. These may be used alone or in combination of two or more.
當製成形成n型擴散層的組成物時,就對於基板的塗佈性的觀點而言,較佳為α-萜品醇、二乙二醇單-正丁醚、乙酸2-(2-丁氧基乙氧基)乙酯。 When the composition for forming the n-type diffusion layer is formed, from the viewpoint of coatability of the substrate, α-terpineol, diethylene glycol mono-n-butyl ether, and acetic acid 2-(2- are preferable. Butoxyethoxy)ethyl ester.
形成p型擴散層的組成物中的分散介質的含有比率是考慮塗佈性、受體濃度而決定。 The content ratio of the dispersion medium in the composition forming the p-type diffusion layer is determined in consideration of coatability and receptor concentration.
考慮到塗佈性,形成p型擴散層的組成物的黏度較佳為10mPa.S以上至1000000mPa.S以下,更佳為50mPa.S以上至500000mPa.S以下。 Considering the coating property, the viscosity of the composition forming the p-type diffusion layer is preferably 10 mPa. S above to 1000000mPa. Below S, more preferably 50mPa. S above to 500000mPa. S below.
其次,對本發明的p型擴散層及太陽電池元件的製造方 法進行說明。 Next, the manufacturer of the p-type diffusion layer and the solar cell element of the present invention The law is explained.
首先,對作為p型半導體基板的矽基板賦予鹼性溶液來去除損壞層,並藉由蝕刻獲得紋理構造。 First, an alkaline solution is applied to a tantalum substrate as a p-type semiconductor substrate to remove the damaged layer, and a texture structure is obtained by etching.
詳細而言,利用20質量%苛性鈉去除自鑄錠進行切片時所產生的矽表面的損壞層。繼而,利用1質量%苛性鈉與10質量%異丙醇的混合液進行蝕刻,形成紋理構造。太陽電池元件藉由在受光面(表面)側形成紋理構造,而可促進光學侷限效應,謀求高效率化。 Specifically, the damaged layer of the crucible surface generated when slicing from the ingot was removed using 20% by mass of caustic soda. Then, etching was carried out by using a mixed solution of 1% by mass of caustic soda and 10% by mass of isopropyl alcohol to form a texture structure. By forming a texture structure on the light-receiving surface (surface) side, the solar cell element can promote an optical confinement effect and achieve high efficiency.
其次,於氧氯化磷(POCl3)、氮氣、氧氣的混合氣體環境下以800℃~900℃進行幾十分鐘的處理,從而同樣地形成n型擴散層。此時,於使用氧氯化磷環境的方法中,磷的擴散亦到達側面及背面,n型擴散層不僅形成於表面,而且亦形成於側面、背面。因此,為了去除側面的n型擴散層而實施側蝕。 Next, the treatment is performed at 800 ° C to 900 ° C for several tens of minutes in a mixed gas atmosphere of phosphorus oxychloride (POCl 3 ), nitrogen, and oxygen to form an n-type diffusion layer in the same manner. At this time, in the method using the phosphorus oxychloride environment, the diffusion of phosphorus also reaches the side surface and the back surface, and the n-type diffusion layer is formed not only on the surface but also on the side surface and the back surface. Therefore, side etching is performed in order to remove the n-type diffusion layer on the side.
然後,於p型半導體基板的背面,即並非受光面的面的n型擴散層上塗佈上述形成p型擴散層的組成物。於本發明中,塗佈方法並無限制,例如有印刷法、旋塗法、毛刷塗佈、噴霧法、刮刀法、輥塗機法、噴墨法等。 Then, the composition for forming the p-type diffusion layer is applied onto the back surface of the p-type semiconductor substrate, that is, the n-type diffusion layer which is not the surface of the light-receiving surface. In the present invention, the coating method is not limited, and examples thereof include a printing method, a spin coating method, a brush coating method, a spray method, a doctor blade method, a roll coater method, an inkjet method, and the like.
上述形成p型擴散層的組成物的塗佈量並無特別限制。例如,作為玻璃粉末量,可設定為0.01g/m2~100g/m2,較佳為0.1g/m2~10g/m2。 The coating amount of the composition forming the p-type diffusion layer is not particularly limited. For example, the amount of the glass powder can be set to 0.01 g/m 2 to 100 g/m 2 , preferably 0.1 g/m 2 to 10 g/m 2 .
再者,根據形成p型擴散層的組成物的組成,亦可設置用以於塗佈後,使組成物中所含有的溶劑揮發的乾燥步驟。於該 情況下,於80℃~300℃左右的溫度下,當使用加熱板時乾燥1分鐘~10分鐘,當使用乾燥機等時乾燥10分鐘~30分鐘左右。該乾燥條件依存於形成n型擴散層的組成物的溶劑組成,於本發明中並不特別限定於上述條件。 Further, depending on the composition of the composition forming the p-type diffusion layer, a drying step for volatilizing the solvent contained in the composition after coating may be provided. In this In the case, at a temperature of about 80 ° C to 300 ° C, it is dried for 1 minute to 10 minutes when using a hot plate, and dried for about 10 minutes to 30 minutes when using a dryer or the like. The drying conditions depend on the solvent composition of the composition forming the n-type diffusion layer, and are not particularly limited to the above conditions in the present invention.
於600℃~1200℃下對塗佈了上述形成p型擴散層的組成物的半導體基板進行熱擴散處理。藉由該熱擴散處理,受體元素向半導體基板中擴散,而形成p+型擴散層。熱擴散處理可應用公知的連續爐、分批式爐等。另外,熱擴散處理時的爐內環境亦可適宜調整成空氣、氧氣、氮氣等。 The semiconductor substrate coated with the composition for forming the p-type diffusion layer described above is subjected to thermal diffusion treatment at 600 ° C to 1200 ° C. By this thermal diffusion treatment, the acceptor element diffuses into the semiconductor substrate to form a p + -type diffusion layer. As the heat diffusion treatment, a known continuous furnace, a batch furnace, or the like can be applied. In addition, the furnace environment during the thermal diffusion treatment may be appropriately adjusted to air, oxygen, nitrogen, or the like.
熱擴散處理時間可對應於形成p型擴散層的組成物中所含有的受體元素的含有率等而適宜選擇。例如,可設定為1分鐘~60分鐘,更佳為2分鐘~30分鐘。 The thermal diffusion treatment time can be appropriately selected in accordance with the content ratio of the acceptor element contained in the composition forming the p-type diffusion layer. For example, it can be set to 1 minute to 60 minutes, more preferably 2 minutes to 30 minutes.
由於在所形成的p+型擴散層的表面形成有玻璃層,故藉由蝕刻而去除該玻璃層。蝕刻可應用浸漬於氫氟酸等酸中的方法、浸漬於苛性鈉等鹼中的方法等公知的方法。 Since a glass layer is formed on the surface of the formed p + -type diffusion layer, the glass layer is removed by etching. The etching can be carried out by a known method such as a method of immersing in an acid such as hydrofluoric acid or a method of immersing in an alkali such as caustic soda.
另外,於先前的製造方法中,於背面印刷鋁膏,然後對其進行煅燒,使n型擴散層轉變成p+型擴散層的同時獲得歐姆接觸。但是,由鋁膏所形成的鋁層的導電率低,為了降低薄片電阻,通常形成於整個背面的鋁層於煅燒後必需具有10μm~20μm左右的厚度。進而,若如上述般形成較厚的鋁層,則由於矽的熱膨脹係數與鋁的熱膨脹係數相差較大,因此於煅燒及冷卻的過程中,在矽基板中產生較大的內應力,而成為翹曲的原因。 Further, in the prior manufacturing method, the aluminum paste was printed on the back side and then calcined to convert the n-type diffusion layer into a p + -type diffusion layer while obtaining an ohmic contact. However, the aluminum layer formed of the aluminum paste has a low electrical conductivity, and in order to reduce the sheet resistance, the aluminum layer usually formed on the entire back surface must have a thickness of about 10 μm to 20 μm after firing. Further, if a thick aluminum layer is formed as described above, since the coefficient of thermal expansion of the crucible differs greatly from the coefficient of thermal expansion of aluminum, a large internal stress is generated in the crucible substrate during the calcination and cooling, and becomes The reason for warping.
存在該內應力對結晶的結晶粒界造成損傷、電力損失變大的課題。另外,翹曲於模組製程中的太陽電池元件的搬送、或者與被稱為分支線路(tab wire)的銅線的連接過程中,容易使太陽電池元件破損。近年來,由於切片加工技術的提高,因此矽基板的厚度正被薄型化,而存在太陽電池元件更加容易破裂的傾向。 This internal stress causes a problem that the crystal grain boundary of the crystal is damaged and the power loss is increased. Further, in the process of transferring the solar cell element in the module process or the connection with a copper wire called a tab wire, the solar cell element is easily broken. In recent years, as the slicing technology has been improved, the thickness of the tantalum substrate is being thinned, and the solar cell element tends to be more easily broken.
但是,根據本發明的製造方法,於藉由上述本發明的形成p型擴散層的組成物將n型擴散層轉換成p+型擴散層後,在該p+型擴散層上另外設置電極。因此,用於背面的電極的材料並不限定於鋁,例如可應用Ag(銀)或Cu(銅)等,背面的電極的厚度亦可比先前的厚度更薄地形成,並且另外無需形成於整個面上。因此,可減少於煅燒及冷卻的過程中所產生的矽基板中的內應力及翹曲。 However, according to the manufacturing method of the present invention, after the n-type diffusion layer is converted into the p + -type diffusion layer by the composition for forming a p-type diffusion layer of the present invention described above, an electrode is additionally provided on the p + -type diffusion layer. Therefore, the material of the electrode for the back surface is not limited to aluminum, and for example, Ag (silver) or Cu (copper) or the like can be applied, and the thickness of the electrode on the back surface can be formed thinner than the previous thickness, and it is not necessary to form the entire surface. on. Therefore, internal stress and warpage in the tantalum substrate generated during the calcination and cooling can be reduced.
於上述所形成的n型擴散層上形成抗反射膜。抗反射膜是應用公知的技術而形成。例如,當抗反射膜為氮化矽膜時,藉由將SiH4與NH3的混合氣體作為原料的電漿化學氣相沈積(Chemical Vapor Deposition,CVD)法來形成。此時,氫於結晶中擴散,不參與矽原子之鍵結的軌道,即懸鍵(dangling bond)與氫鍵結,而使缺陷鈍化(氫鈍化)。 An anti-reflection film is formed on the n-type diffusion layer formed as described above. The antireflection film is formed using a well-known technique. For example, when the antireflection film is a tantalum nitride film, it is formed by a plasma chemical vapor deposition (CVD) method using a mixed gas of SiH 4 and NH 3 as a raw material. At this time, hydrogen diffuses in the crystal, does not participate in the orbital of the bond of the helium atom, that is, the dangling bond and the hydrogen bond, and passivate the defect (hydrogen passivation).
更具體而言,於上述混合氣體流量比NH3/SiH4為0.05~1.0,反應室的壓力為0.1Torr~2Torr,成膜時的溫度為300℃~550℃,使電漿放電的頻率為100kHz以上的條件下形成。 More specifically, the mixed gas flow rate ratio NH 3 /SiH 4 is 0.05 to 1.0, the reaction chamber pressure is 0.1 Torr to 2 Torr, and the film formation temperature is 300 ° C to 550 ° C, so that the frequency of the plasma discharge is Formed under conditions of 100 kHz or more.
於表面(受光面)的抗反射膜上,藉由網版印刷法印刷 塗佈表面電極用金屬膏並使其乾燥,而形成表面電極。表面電極用金屬膏是將金屬粒子與玻璃粒子作為必需成分,且視需要包含樹脂黏合劑、其他添加劑等。 Printing on the anti-reflection film on the surface (light-receiving surface) by screen printing A surface electrode is coated with a metal paste and dried to form a surface electrode. The metal paste for surface electrodes contains metal particles and glass particles as essential components, and if necessary, a resin binder, other additives, and the like are contained.
繼而,於上述背面的p+型擴散層上亦形成背面電極。如上所述,本發明中背面電極的材質或形成方法並無特別限定。例如,可塗佈包含鋁、銀或銅等金屬的背面電極用膏,並使其乾燥而形成背面電極。此時,為了模組製程中的太陽電池元件間的連接,亦可於背面的一部分上設置形成銀電極的銀膏。 Then, a back surface electrode is also formed on the p + -type diffusion layer on the back surface. As described above, the material or formation method of the back surface electrode in the present invention is not particularly limited. For example, a paste for a back surface electrode containing a metal such as aluminum, silver or copper may be applied and dried to form a back electrode. At this time, in order to connect the solar cell elements in the module process, a silver paste forming a silver electrode may be provided on a part of the back surface.
對上述電極進行煅燒,製成太陽電池元件。若於600℃~900℃的範圍內煅燒幾秒~幾分鐘,則於表面側,作為絕緣膜的抗反射膜因電極用金屬膏中所含有的玻璃粒子而熔融,進而矽表面的一部分亦熔融,膏中的金屬粒子(例如銀粒子)與矽基板形成接觸部並凝固。藉此,所形成的表面電極與矽基板被導通。將此稱為燒透(fire through)。 The above electrode was calcined to prepare a solar cell element. When calcined in the range of 600 ° C to 900 ° C for several seconds to several minutes, the antireflection film as an insulating film is melted on the surface side by the glass particles contained in the metal paste for the electrode, and a part of the surface of the crucible is also melted. The metal particles (for example, silver particles) in the paste form a contact portion with the tantalum substrate and solidify. Thereby, the formed surface electrode and the germanium substrate are electrically connected. This is called fire through.
對表面電極的形狀進行說明。表面電極是由匯流條電極、以及與該匯流條電極交叉的指狀電極構成。 The shape of the surface electrode will be described. The surface electrode is composed of a bus bar electrode and a finger electrode that intersects the bus bar electrode.
此種表面電極可藉由例如上述金屬膏的網版印刷、或者電極材料的鍍敷、高真空中的利用電子束加熱的電極材料的蒸鍍等方法而形成。眾所周知,包含匯流條電極與指狀電極的表面電極一般是用作受光面側的電極,可應用受光面側的匯流條電極及指狀電極的公知的形成方法。 Such a surface electrode can be formed by, for example, screen printing of the above-described metal paste, plating of an electrode material, vapor deposition of an electrode material by electron beam heating in a high vacuum, or the like. It is known that a surface electrode including a bus bar electrode and a finger electrode is generally used as an electrode on the light-receiving surface side, and a known method of forming a bus bar electrode and a finger electrode on the light-receiving surface side can be applied.
再者,於上述的p型擴散層及太陽電池元件的製造方法 中,為了於作為p型半導體基板的矽基板上形成n型擴散層,而使用氧氯化磷(POCl3)、氮氣及氧氣的混合氣體,但亦可使用形成n型擴散層的組成物來形成n型層。於形成n型擴散層的組成物中,含有P(磷)或Sb(銻)等第15族的元素作為施體(donor)元素。 Further, in the above-described p-type diffusion layer and method for producing a solar cell element, in order to form an n-type diffusion layer on a germanium substrate as a p-type semiconductor substrate, phosphorus oxychloride (POCl 3 ), nitrogen, and oxygen are used. The mixed gas, but a composition forming an n-type diffusion layer may also be used to form the n-type layer. In the composition for forming the n-type diffusion layer, an element of Group 15 such as P (phosphorus) or Sb (antimony) is contained as a donor element.
於將形成n型擴散層的組成物用於n型擴散層的形成的方法中,首先,於作為p型半導體基板的表面的受光面塗佈形成n型擴散層的組成物,於背面塗佈本發明的形成p型擴散層的組成物,然後於600℃~1200℃下進行熱擴散處理。藉由該熱擴散處理,施體元素於表面向p型半導體基板中擴散而形成n型擴散層,受體元素則於背面擴散而形成p+型擴散層。除該步驟以外,藉由與上述方法相同的步驟來製作太陽電池元件。 In the method of forming a composition for forming an n-type diffusion layer for the formation of an n-type diffusion layer, first, a composition for forming an n-type diffusion layer is applied to a light-receiving surface of a surface of a p-type semiconductor substrate, and is coated on the back surface. The composition for forming a p-type diffusion layer of the present invention is then subjected to thermal diffusion treatment at 600 ° C to 1200 ° C. By this thermal diffusion treatment, the donor element diffuses into the p-type semiconductor substrate to form an n-type diffusion layer, and the acceptor element diffuses on the back surface to form a p + -type diffusion layer. In addition to this step, the solar cell element was fabricated by the same steps as the above method.
再者,藉由參照而將日本申請案2010-100225中所揭示的全部內容引用於本說明書中。 In addition, the entire contents disclosed in Japanese Patent Application No. 2010-100225 are hereby incorporated by reference.
本說明書中所記載的所有文獻、專利申請案、及技術規格是以與具體地且個別地記載藉由參照而引用各個文獻、專利申請案、及技術規格時相同的程度,藉由參照而引用於本說明書中。 All of the documents, patent applications, and technical specifications described in the specification are the same as those which are specifically and individually described by reference to the respective documents, patent applications, and technical specifications, and are cited by reference. In this manual.
以下,更具體地說明本發明的實例,但本發明並不受該些實例限制。再者,只要事先無特別記述,則化學品全部使用了試劑。另外,只要事先無說明,則「%」表示「質量%」。 Hereinafter, examples of the invention will be more specifically described, but the invention is not limited by the examples. Further, as long as there is no special description in advance, the reagents are all used in the chemicals. In addition, "%" means "% by mass" as long as there is no explanation in advance.
使用自動乳缽混練裝置將粒子形狀為大致球狀,平均粒徑為3.1μm,軟化溫度為491℃的B2O3-SiO2體系玻璃(B2O3:10%)粉末20g與乙基纖維素3g、乙酸2-(2-丁氧基乙氧基)乙酯77g加以混合並膏化,製成形成p型擴散層的組成物。 B 2 O 3 -SiO 2 system glass (B 2 O 3 : 10%) powder 20 g and ethyl group having a particle shape of a substantially spherical shape, an average particle diameter of 3.1 μm, and a softening temperature of 491 ° C using an automatic mortar mixing device 3 g of cellulose and 77 g of 2-(2-butoxyethoxy)ethyl acetate were mixed and pasteified to prepare a composition for forming a p-type diffusion layer.
再者,玻璃粒子形狀是使用日立高科技(Hitachi High-Technologies)(股份)製造的TM-1000型掃描型電子顯微鏡進行觀察並判定。玻璃的平均粒徑是使用Beckman Coulter(股份)製造的LS 13 320型雷射散射繞射法粒度分布測定裝置(測定波長:632nm)來算出。玻璃的軟化點是使用島津製作所(股份)製造的DTG-60H型示差熱.熱重量同步測定裝置,根據示差熱(DTA)曲線而求出。 Further, the glass particle shape was observed and judged using a TM-1000 scanning electron microscope manufactured by Hitachi High-Technologies Co., Ltd. The average particle diameter of the glass was calculated using a LS 13 320 laser scattering diffraction particle size distribution measuring apparatus (measuring wavelength: 632 nm) manufactured by Beckman Coulter Co., Ltd. The softening point of the glass is DTG-60H type differential heat manufactured by Shimadzu Corporation. The thermal weight synchronization measuring device was obtained from the differential heat (DTA) curve.
繼而,藉由網版印刷將所製備的膏狀物塗佈於p型矽基板的表面,並於150℃的加熱板上乾燥5分鐘。繼而,利用設定成1000℃的電爐進行10分鐘熱擴散處理,然後,為了去除玻璃層而將基板浸漬於氫氟酸中5分鐘,然後進行流水清洗,其後進行乾燥。 Then, the prepared paste was applied to the surface of the p-type ruthenium substrate by screen printing, and dried on a hot plate at 150 ° C for 5 minutes. Then, the film was subjected to thermal diffusion treatment for 10 minutes in an electric furnace set at 1000 ° C, and then the substrate was immersed in hydrofluoric acid for 5 minutes in order to remove the glass layer, and then washed with running water, followed by drying.
塗佈有形成p型擴散層的組成物之側的表面的薄片電阻為90Ω/□,B(硼)擴散而形成p型擴散層。背面的薄片電阻為1000000Ω/□以上而無法測定,判斷為實質上未形成p型擴散層。另外,未產生基板的翹曲。 The sheet resistance of the surface on the side on which the composition on which the p-type diffusion layer was formed was 90 Ω/□, and B (boron) was diffused to form a p-type diffusion layer. The sheet resistance of the back surface was 1,000,000 Ω/□ or more and could not be measured, and it was judged that the p-type diffusion layer was not substantially formed. In addition, warpage of the substrate did not occur.
再者,薄片電阻是使用三菱化學(股份)製造的Loresta-EP MCP-T360型低電阻率計並藉由四探針法來測定。 Further, the sheet resistance was measured by a four-probe method using a Loresta-EP MCP-T360 type low resistivity meter manufactured by Mitsubishi Chemical Corporation.
除將熱擴散處理時間設定為20分鐘以外,以與實例1相同的方式形成p型擴散層。塗佈有形成p型擴散層的組成物之側的表面的薄片電阻為87Ω/□,B(硼)擴散而形成p型擴散層。 A p-type diffusion layer was formed in the same manner as in Example 1 except that the thermal diffusion treatment time was set to 20 minutes. The sheet resistance of the surface on the side on which the composition on which the p-type diffusion layer was formed was 87 Ω/□, and B (boron) was diffused to form a p-type diffusion layer.
背面的薄片電阻為1000000Ω/□以上而無法測定,判斷為實質上未形成p型擴散層。另外,未產生基板的翹曲。 The sheet resistance of the back surface was 1,000,000 Ω/□ or more and could not be measured, and it was judged that the p-type diffusion layer was not substantially formed. In addition, warpage of the substrate did not occur.
除將熱擴散處理的時間設定為30分鐘以外,以與實例1相同的方式形成p型擴散層。塗佈有形成p型擴散層的組成物之側的表面的薄片電阻為79Ω/□,B(硼)擴散而形成p型擴散層。 A p-type diffusion layer was formed in the same manner as in Example 1 except that the time of the thermal diffusion treatment was set to 30 minutes. The sheet resistance of the surface on the side on which the composition on which the p-type diffusion layer was formed was 79 Ω/□, and B (boron) was diffused to form a p-type diffusion layer.
另一方面,背面的薄片電阻為1000000Ω/□以上而無法測定,判斷為實質上未形成p型擴散層。另外,未產生基板的翹曲。 On the other hand, the sheet resistance of the back surface was 1,000,000 Ω/□ or more and could not be measured, and it was judged that the p-type diffusion layer was not substantially formed. In addition, warpage of the substrate did not occur.
將玻璃粉末替換成粒子形狀為大致球狀,平均粒徑為3.1μm,軟化溫度為515℃的B2O3-SiO2體系玻璃粉末(B2O3含量:30%),除此以外,以與實例1相同的方式製備形成p型擴散層的組成物,並使用該形成p型擴散層的組成物形成p型擴散層。塗佈有形成p型擴散層的組成物之側的表面的薄片電阻為77Ω/□,B(硼)擴散而形成p型擴散層。 The glass powder was replaced with a B 2 O 3 -SiO 2 system glass powder (B 2 O 3 content: 30%) having a particle shape of a substantially spherical shape, an average particle diameter of 3.1 μm, and a softening temperature of 515 ° C. A composition for forming a p-type diffusion layer was prepared in the same manner as in Example 1, and a p-type diffusion layer was formed using the composition forming the p-type diffusion layer. The sheet resistance of the surface on the side on which the composition on which the p-type diffusion layer was formed was 77 Ω/□, and B (boron) was diffused to form a p-type diffusion layer.
另一方面,背面的薄片電阻為1000000Ω/□以上而無法測定,判斷為實質上未形成p型擴散層。另外,未產生基板的翹曲。 On the other hand, the sheet resistance of the back surface was 1,000,000 Ω/□ or more and could not be measured, and it was judged that the p-type diffusion layer was not substantially formed. In addition, warpage of the substrate did not occur.
將玻璃粉末替換成粒子形狀為大致球狀,平均粒徑為3.1μm,軟化溫度為605℃的B2O3-SiO2體系玻璃粉末(B2O3含量:50%),除此以外,以與實例1相同的方式製備形成p型擴散層的組成物,並使用該形成p型擴散層的組成物形成p型擴散層。塗佈有形成p型擴散層的組成物之側的表面的薄片電阻為74Ω/□,B(硼)擴散而形成p型擴散層。 The glass powder was replaced with a B 2 O 3 -SiO 2 system glass powder (B 2 O 3 content: 50%) having a particle shape of a substantially spherical shape, an average particle diameter of 3.1 μm, and a softening temperature of 605 ° C. A composition for forming a p-type diffusion layer was prepared in the same manner as in Example 1, and a p-type diffusion layer was formed using the composition forming the p-type diffusion layer. The sheet resistance of the surface on the side on which the composition on which the p-type diffusion layer was formed was 74 Ω/□, and B (boron) was diffused to form a p-type diffusion layer.
另一方面,背面的薄片電阻為1000000Ω/□以上而無法測定,判斷為實質上未形成p型擴散層。另外,未產生基板的翹曲。 On the other hand, the sheet resistance of the back surface was 1,000,000 Ω/□ or more and could not be measured, and it was judged that the p-type diffusion layer was not substantially formed. In addition, warpage of the substrate did not occur.
將玻璃粉末替換成粒子形狀為大致球狀,平均粒徑為3.1μm,軟化溫度為644℃的B2O3-SiO2體系玻璃粉末(B2O3含量:60%),除此以外,以與實例1相同的方式製備形成p型擴散層的組成物,並使用該形成p型擴散層的組成物形成p型擴散層。塗佈有形成p型擴散層的組成物之側的表面的薄片電阻為76Ω/□,B(硼)擴散而形成p型擴散層。 The glass powder was replaced with a B 2 O 3 -SiO 2 system glass powder (B 2 O 3 content: 60%) having a substantially spherical shape, an average particle diameter of 3.1 μm, and a softening temperature of 644 ° C. A composition for forming a p-type diffusion layer was prepared in the same manner as in Example 1, and a p-type diffusion layer was formed using the composition forming the p-type diffusion layer. The sheet resistance of the surface on the side on which the composition on which the p-type diffusion layer was formed was 76 Ω/□, and B (boron) was diffused to form a p-type diffusion layer.
另一方面,背面的薄片電阻為1000000Ω/□以上而無法測定,判斷為實質上未形成p型擴散層。另外,未產生基板的翹曲。 On the other hand, the sheet resistance of the back surface was 1,000,000 Ω/□ or more and could not be measured, and it was judged that the p-type diffusion layer was not substantially formed. In addition, warpage of the substrate did not occur.
將玻璃粉末替換成粒子形狀為大致球狀,平均粒徑為3.1μm,軟化溫度為702℃的B2O3-SiO2體系玻璃粉末(B2O3含量:70%),除此以外,以與實例1相同的方式製備形成p型擴散層的組成物,並使用該形成p型擴散層的組成物形成p型擴散層。塗 佈有形成p型擴散層的組成物之側的表面的薄片電阻為72Ω/□,B(硼)擴散而形成p型擴散層。 The glass powder was replaced with a B 2 O 3 -SiO 2 system glass powder (B 2 O 3 content: 70%) having a substantially spherical shape, an average particle diameter of 3.1 μm, and a softening temperature of 702 ° C. A composition for forming a p-type diffusion layer was prepared in the same manner as in Example 1, and a p-type diffusion layer was formed using the composition forming the p-type diffusion layer. The sheet resistance of the surface on the side on which the composition on which the p-type diffusion layer was formed was 72 Ω/□, and B (boron) was diffused to form a p-type diffusion layer.
另一方面,背面的薄片電阻為1000000Ω/□以上而無法測定,判斷為實質上未形成p型擴散層。另外,未產生基板的翹曲。 On the other hand, the sheet resistance of the back surface was 1,000,000 Ω/□ or more and could not be measured, and it was judged that the p-type diffusion layer was not substantially formed. In addition, warpage of the substrate did not occur.
將玻璃粉末替換成粒子形狀為大致球狀,平均粒徑為3.1μm,軟化溫度為775℃的B2O3-SiO2體系玻璃粉末(B2O3含量:85%),除此以外,以與實例1相同的方式製備形成p型擴散層的組成物,並使用該形成p型擴散層的組成物形成p型擴散層。塗佈有形成p型擴散層的組成物之側的表面的薄片電阻為75Ω/□,B(硼)擴散而形成p型擴散層。 The glass powder was replaced with a B 2 O 3 -SiO 2 system glass powder (B 2 O 3 content: 85%) having a substantially spherical shape, an average particle diameter of 3.1 μm, and a softening temperature of 775 ° C. A composition for forming a p-type diffusion layer was prepared in the same manner as in Example 1, and a p-type diffusion layer was formed using the composition forming the p-type diffusion layer. The sheet resistance of the surface on the side on which the composition on which the p-type diffusion layer was formed was 75 Ω/□, and B (boron) was diffused to form a p-type diffusion layer.
另一方面,背面的薄片電阻為1000000Ω/□以上而無法測定,判斷為實質上未形成p型擴散層。另外,未產生基板的翹曲。 On the other hand, the sheet resistance of the back surface was 1,000,000 Ω/□ or more and could not be measured, and it was judged that the p-type diffusion layer was not substantially formed. In addition, warpage of the substrate did not occur.
將玻璃粉末替換成粒子形狀為大致球狀,平均粒徑為3.1μm,軟化溫度為505℃的B2O3-ZnO體系玻璃粉末(B2O3含量:10%),除此以外,以與實例1相同的方式製備形成p型擴散層的組成物,並使用該形成p型擴散層的組成物形成p型擴散層。塗佈有形成p型擴散層的組成物之側的表面的薄片電阻為88Ω/□,B(硼)擴散而形成p型擴散層。 The glass powder was replaced with a B 2 O 3 -ZnO system glass powder (B 2 O 3 content: 10%) having a particle shape of a substantially spherical shape, an average particle diameter of 3.1 μm, and a softening temperature of 505 ° C, in addition to A composition for forming a p-type diffusion layer was prepared in the same manner as in Example 1, and a p-type diffusion layer was formed using the composition forming the p-type diffusion layer. The sheet resistance of the surface on the side on which the composition on which the p-type diffusion layer was formed was 88 Ω/□, and B (boron) was diffused to form a p-type diffusion layer.
另一方面,背面的薄片電阻為1000000Ω/□以上而無法測定,判斷為實質上未形成p型擴散層。另外,未產生基板的翹曲。 On the other hand, the sheet resistance of the back surface was 1,000,000 Ω/□ or more and could not be measured, and it was judged that the p-type diffusion layer was not substantially formed. In addition, warpage of the substrate did not occur.
將玻璃粉末替換成粒子形狀為大致球狀,平均粒徑為3.1μm,軟化溫度為559℃的B2O3-PbO體系玻璃粉末(B2O3含量:40%),除此以外,以與實例1相同的方式製備形成p型擴散層的組成物,並使用該形成p型擴散層的組成物形成p型擴散層。塗佈有形成p型擴散層的組成物之側的表面的薄片電阻為68Ω/□,B(硼)擴散而形成p型擴散層。 The glass powder was replaced with a B 2 O 3 -PbO system glass powder (B 2 O 3 content: 40%) having a particle shape of a substantially spherical shape, an average particle diameter of 3.1 μm, and a softening temperature of 559 ° C, in addition to A composition for forming a p-type diffusion layer was prepared in the same manner as in Example 1, and a p-type diffusion layer was formed using the composition forming the p-type diffusion layer. The sheet resistance of the surface on the side on which the composition on which the p-type diffusion layer was formed was 68 Ω/□, and B (boron) was diffused to form a p-type diffusion layer.
另一方面,背面的薄片電阻為1000000Ω/□以上而無法測定,判斷為實質上未形成p型擴散層。另外,未產生基板的翹曲。 On the other hand, the sheet resistance of the back surface was 1,000,000 Ω/□ or more and could not be measured, and it was judged that the p-type diffusion layer was not substantially formed. In addition, warpage of the substrate did not occur.
使用自動乳缽混練裝置將B2O3-SiO2體系玻璃(B2O3含量:10%)粉末19.7g與Ag0.3g、乙基纖維素0.3g、乙酸2-(2-丁氧基乙氧基)乙酯7g加以混合並膏化,製成形成p型擴散層的組成物。其後,實施與實例1相同之操作。 B 2 O 3 -SiO 2 system glass (B 2 O 3 content: 10%) powder 19.7 g and Ag 0.3 g, ethyl cellulose 0.3 g, 2-(2-butoxyl acetate) using an automatic mortar mixing device 7 g of ethoxy)ethyl ester was mixed and pasteified to prepare a composition for forming a p-type diffusion layer. Thereafter, the same operation as in Example 1 was carried out.
其結果,於清洗後的基板上無玻璃的附著物,該附著物已被容易地去除。另外,表面的薄片電阻為85Ω/□,且判斷為於背面實質上未形成p型擴散層。另外,未產生基板的翹曲。 As a result, there is no deposit of glass on the cleaned substrate, and the deposit has been easily removed. Further, the sheet resistance of the surface was 85 Ω/□, and it was judged that the p-type diffusion layer was not substantially formed on the back surface. In addition, warpage of the substrate did not occur.
將玻璃粉末替換成粒子形狀為大致球狀,平均粒徑為3.1μm,軟化溫度為466℃的B2O3-SiO2體系玻璃粉末(B2O3含量:0.5%),除此以外,以與實例1相同的方式製備形成p型擴散層的組成物,並使用該形成p型擴散層的組成物進行熱擴散處理。塗 佈有形成p型擴散層的組成物之側的表面的薄片電阻為1000000Ω/□以上而無法測定,判斷為實質上未形成p型擴散層。 The glass powder was replaced with a B 2 O 3 -SiO 2 system glass powder (B 2 O 3 content: 0.5%) having a substantially spherical shape, an average particle diameter of 3.1 μm, and a softening temperature of 466 ° C. A composition for forming a p-type diffusion layer was prepared in the same manner as in Example 1, and the composition for forming the p-type diffusion layer was subjected to thermal diffusion treatment. The sheet resistance of the surface on the side on which the composition on which the p-type diffusion layer was formed was 1,000,000 Ω/□ or more and could not be measured, and it was judged that the p-type diffusion layer was not substantially formed.
將玻璃粉末替換成粒子形狀為大致球狀,平均粒徑為3.1μm,軟化溫度為805℃的B2O3-SiO2體系玻璃粉末(B2O3含量:95%),除此以外,以與實例1相同的方式製備形成p型擴散層的組成物,並使用該形成p型擴散層的組成物進行熱擴散處理。塗佈有形成p型擴散層的組成物之側的表面的薄片電阻為70Ω/□,B(硼)擴散而形成p型擴散層。 The glass powder was replaced with a B 2 O 3 —SiO 2 system glass powder (B 2 O 3 content: 95%) having a particle shape of a substantially spherical shape, an average particle diameter of 3.1 μm, and a softening temperature of 805° C., A composition for forming a p-type diffusion layer was prepared in the same manner as in Example 1, and the composition for forming the p-type diffusion layer was subjected to thermal diffusion treatment. The sheet resistance of the surface on the side on which the composition on which the p-type diffusion layer was formed was 70 Ω/□, and B (boron) was diffused to form a p-type diffusion layer.
但是,背面的薄片電阻為123Ω/□,於背面亦形成有p型擴散層。 However, the sheet resistance of the back surface was 123 Ω/□, and a p-type diffusion layer was also formed on the back surface.
雖然本發明已以較佳實施例揭露如上,然其並非用以限定本發明,任何熟習此技藝者,在不脫離本發明之精神和範圍內,當可作些許之更動與潤飾,因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。 While the present invention has been described in its preferred embodiments, the present invention is not intended to limit the invention, and the present invention may be modified and modified without departing from the spirit and scope of the invention. The scope of protection is subject to the definition of the scope of the patent application.
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