TW202236691A - Electrode-forming composition, solar cell element and aluminum/silver laminated electrode - Google Patents
Electrode-forming composition, solar cell element and aluminum/silver laminated electrode Download PDFInfo
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- TW202236691A TW202236691A TW111104925A TW111104925A TW202236691A TW 202236691 A TW202236691 A TW 202236691A TW 111104925 A TW111104925 A TW 111104925A TW 111104925 A TW111104925 A TW 111104925A TW 202236691 A TW202236691 A TW 202236691A
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- aluminum
- silver
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- 239000000203 mixture Substances 0.000 title claims abstract description 160
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 160
- 239000004332 silver Substances 0.000 title claims abstract description 160
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Abstract
Description
本揭示是有關於一種電極形成用組成物、太陽電池元件及鋁/銀積層電極。The disclosure relates to a composition for electrode formation, a solar cell element, and an aluminum/silver laminated electrode.
近年來，對以全球變暖、大氣污染等為首的環境問題的關注正在提高。其中，作為全球變暖問題的對策，代替化石燃料的可再生能源的需求正在提高。作為可再生能源，可列舉：太陽光、地熱、風力、波力、潮力及生物量（biomass）等。特別是太陽光發電在利用取之不盡的太陽光能源的同時，作為發電時不排放二氧化碳的清潔自然能源受到關注，被期待成為日益嚴重的能源問題的有效解決方案。In recent years, interest in environmental issues such as global warming and air pollution has been increasing. Among them, as a countermeasure against the problem of global warming, the demand for renewable energy that replaces fossil fuels is increasing. Examples of renewable energy include sunlight, geothermal energy, wind power, wave power, tidal power, biomass, and the like. In particular, solar power generation is attracting attention as a clean natural energy that does not emit carbon dioxide during power generation while utilizing inexhaustible sunlight energy, and is expected to be an effective solution to increasingly serious energy problems.
作為太陽電池，一般為使用矽（Si）基板作為半導體基板的結晶矽系太陽電池。在使用Si基板的太陽電池單元（太陽電池元件）的受光面及背面（與受光面相反的面）分別形成用於回收載子的集電用電極、及用於將載子作為輸出而取出的輸出取出電極（匯流條電極）。受光面的集電用電極特別稱為指狀電極。在受光面電極的形成中，使用銀（Ag）電極形成用組成物，指狀電極及匯流條電極部的印刷分別或一併進行。對於背面，匯流條電極的形成使用銀電極形成用組成物，集電用電極使用鋁（Al）電極形成用組成物。各電極形成用組成物中含有導電性金屬粒子、玻璃粒子、各種添加劑等。A solar cell is generally a crystalline silicon-based solar cell using a silicon (Si) substrate as a semiconductor substrate. On the light-receiving surface and the back surface (the surface opposite to the light-receiving surface) of a solar cell (solar cell element) using a Si substrate, a collector electrode for collecting carriers and an electrode for taking out carriers as an output are respectively formed. Output take-out electrodes (bus bar electrodes). The current-collecting electrode on the light-receiving surface is particularly called a finger electrode. In the formation of the light-receiving surface electrode, the printing of the finger electrode and the bus bar electrode portion is performed separately or collectively using a composition for forming a silver (Ag) electrode. On the rear surface, a composition for forming a silver electrode was used for forming the bus bar electrode, and a composition for forming an aluminum (Al) electrode was used for the electrode for current collection. Each electrode-forming composition contains conductive metal particles, glass particles, various additives, and the like.
在用於形成受光面電極及背面匯流條電極的銀電極形成用組成物中，作為所述導電性金屬粒子，一般使用銀粒子。作為其理由，可列舉：銀的體積電阻率低（1.47×10 -6Ωcm）、銀粒子在所述熱處理條件下自還原而燒結、銀粒子與矽基板形成良好的歐姆接觸、及由銀粒子形成的電極的焊料材料的潤濕性優異，能夠較佳地接著將太陽電池元件間電連接的配線材料（接合線（tab line）等）。 In the composition for forming a silver electrode for forming a light-receiving surface electrode and a back bus bar electrode, silver particles are generally used as the conductive metal particles. The reasons include: the volume resistivity of silver is low (1.47×10 -6 Ωcm), the silver particles are self-reduced and sintered under the above heat treatment conditions, the silver particles form a good ohmic contact with the silicon substrate, and the silver particles The solder material of the formed electrode has excellent wettability, and can be preferably bonded to a wiring material (tab line, etc.) that electrically connects solar cell elements.
使用鋁電極形成用組成物形成背面的集電用電極時，鋁電極形成用組成物中的鋁經過與矽的共晶反應而在背面的表面形成高濃度擴散層（p +-Si層、背面場（Back Surface Field，BSF））。藉此，賦予使p型矽基板中的少數載子即電子向受光面側返回的結構，能夠降低載子複合的概率。 但是，在現有的使用鋁電極形成用組成物的背面電極/BSF結構中，背面的少數載子複合速度快至3×10 3cm/s左右，可能成為使太陽電池元件的發電性能降低的因素。 When the current collecting electrode on the back is formed using a composition for forming an aluminum electrode, the aluminum in the composition for forming an aluminum electrode undergoes a eutectic reaction with silicon to form a high-concentration diffusion layer (p + -Si layer, back surface field (Back Surface Field, BSF)). This provides a structure for returning electrons, which are minority carriers in the p-type silicon substrate, to the light-receiving surface side, thereby reducing the probability of carrier recombination. However, in the conventional back electrode/BSF structure using a composition for forming an aluminum electrode, the minority carrier recombination speed on the back is as fast as about 3×10 3 cm/s, which may be a factor that reduces the power generation performance of the solar cell element .
作為降低背面複合損失的對策，鈍化射極-背面電池（Passivated Emitter，Rear Cell，PERC）結構備受關注（例如，參照專利文獻1）。PERC結構的特徵是將背面複合的原因之一的背面電極與Si基板之間的歐姆接觸部限制為點狀或線狀，除背面電極的接觸部以外全部被鈍化膜覆蓋。作為可用於PERC結構的背面鈍化膜，可列舉藉由原子層沈積法（Atomic Layer Deposition，ALD）或化學氣相沈積法（Chemical Vapor Deposition，CVD）而得的非晶氧化鋁（AlO X）膜。已知藉由ALD法或CVD法而得的AlO X膜具有大的負的固定電荷，且已知應用了該膜的PERC結構太陽電池元件顯示出高的發電性能。 As a countermeasure to reduce the back recombination loss, a Passivated Emitter, Rear Cell, PERC (Passivated Emitter, Rear Cell, PERC) structure has attracted attention (for example, refer to Patent Document 1). The characteristic of the PERC structure is that the ohmic contact between the back electrode and the Si substrate, which is one of the causes of back recombination, is limited to dots or lines, and all but the contact part of the back electrode is covered with a passivation film. As the rear passivation film that can be used in the PERC structure, an amorphous aluminum oxide (AlO x ) film obtained by atomic layer deposition (Atomic Layer Deposition, ALD) or chemical vapor deposition (Chemical Vapor Deposition, CVD) can be cited . It is known that the AlO X film obtained by the ALD method or the CVD method has a large negative fixed charge, and it is known that a PERC structure solar cell device to which the film is applied exhibits high power generation performance.
在PERC結構中，背面電極與矽基板的接觸部受限，因此能夠實現雙面受光（bifacial）型的太陽電池元件。作為bifacial-PERC結構的優點，可列舉能夠有效利用射入背面的光等。In the PERC structure, the contact portion between the back electrode and the silicon substrate is limited, so a bifacial solar cell element can be realized. As an advantage of the bifacial-PERC structure, it is possible to effectively use the light incident on the back surface, and the like.
在所述的包括bifacial-PERC結構、多主柵（Multi Busbar，MBB）-bifacial-PERC結構等的PERC結構中，形成背面電極時，一般將包含銀的電極形成用組成物及包含鋁的電極形成用組成物分別印刷到基板的規定區域，並進行乾燥後，一併進行熱處理。 在所述結構中，由於在鋁電極的表面形成的氧化鋁（Al 2O 3）皮膜與被覆配線材料的焊料的潤濕性差，故無法在鋁電極上直接接合配線材料。另外，在背面，與受光面側同樣，在連接配線材料的部位需要形成作為輸出取出電極的銀電極，因此在背面電極製程中，在成膜的鈍化膜上首先塗佈銀電極形成用組成物。此時，在藉由以往的製程形成的背面電極中，由於鋁電極與作為背面輸出取出電極的銀電極的階差（厚度的差），有可能產生配線材料的連接不良，或者損害作為太陽電池的可靠性。 In the PERC structure including the bifacial-PERC structure, the Multi Busbar (MBB)-bifacial-PERC structure, etc., when forming the back electrode, the composition for forming the electrode containing silver and the electrode containing aluminum are generally used The forming composition is printed on predetermined regions of the substrate, dried, and then heat-treated at the same time. In this structure, since the aluminum oxide (Al 2 O 3 ) film formed on the surface of the aluminum electrode has poor wettability with the solder covering the wiring material, the wiring material cannot be directly bonded to the aluminum electrode. In addition, on the back surface, like the light-receiving surface side, it is necessary to form a silver electrode as an output extraction electrode at the part where the wiring material is connected. Therefore, in the back electrode process, the composition for forming a silver electrode is first coated on the formed passivation film. . At this time, in the back electrode formed by the conventional process, due to the step difference (difference in thickness) between the aluminum electrode and the silver electrode as the output extraction electrode on the back, poor connection of the wiring material may occur, or damage to the solar cell may occur. reliability.
這例如可如以下般考慮。就降低銀電極形成用組成物的使用量等觀點而言，背面電極中的作為輸出取出電極的銀電極有時不沿著配線材料的連接方向連續形成，而是沿著配線材料的連接方向，在銀電極與銀電極之間形成鋁電極。熱處理（煆燒後）的鋁電極的厚度一般為20 μm～40 μm，作為背面輸出取出電極的銀電極的厚度一般為2 μm～5 μm。在此種情況下，配線材料的一部分配置在鋁電極上，但若鋁電極與銀電極的階差大，則配線材料的變形無法追隨階差，認為銀電極上的配線材料的連接變得不充分。另外，即使能夠在銀電極上連接配線材料，由於配線材料根據階差而形成凹凸的同時進行變形，故認為會施加由熱引起的內部應力以外的應力。在此種情況下，在對太陽電池構件賦予溫度變化的試驗或環境（例如溫度循環試驗）中，由於在連接部產生龜裂等，發電性能的降低率會變大。This can be considered as follows, for example. From the viewpoint of reducing the amount of silver electrode-forming composition used, etc., the silver electrode as an output extraction electrode in the back electrode may not be formed continuously along the connection direction of the wiring material, but along the connection direction of the wiring material. An aluminum electrode is formed between the silver electrode and the silver electrode. The thickness of the heat-treated (after sintered) aluminum electrode is generally 20 μm to 40 μm, and the thickness of the silver electrode used as the output output electrode on the back is generally 2 μm to 5 μm. In this case, part of the wiring material is placed on the aluminum electrode, but if the level difference between the aluminum electrode and the silver electrode is large, the deformation of the wiring material cannot follow the level difference, and it is considered that the connection of the wiring material on the silver electrode becomes difficult. full. In addition, even if the wiring material can be connected to the silver electrode, since the wiring material deforms while being uneven due to the step difference, it is considered that stress other than internal stress due to heat is applied. In such a case, in a test or an environment (for example, a temperature cycle test) in which temperature changes are applied to the solar cell member, the rate of decrease in power generation performance increases due to cracks or the like occurring at the connection portion.
作為解決所述課題的方法，認為並非在基板上分別形成鋁電極及銀電極，而是形成將在基板上形成的鋁電極與在其上形成的銀電極積層的狀態的電極（以下亦稱為鋁/銀積層電極）是有效的。 作為形成鋁/銀積層電極的方法，例如，考慮將包含鋁粒子的電極形成用組成物以期望的圖案塗佈在基板的背面，形成含鋁粒子的膜後，將包含銀的電極形成用組成物以期望的圖案印刷在含鋁粒子的膜上，一併進行熱處理。 [現有技術文獻] [專利文獻] As a method of solving the above-mentioned problems, it is considered that instead of forming the aluminum electrode and the silver electrode separately on the substrate, an electrode in a state in which the aluminum electrode formed on the substrate and the silver electrode formed thereon are laminated (hereinafter also referred to as Al/Ag laminated electrodes) are effective. As a method of forming an aluminum/silver laminated electrode, for example, it is conceivable to coat an electrode-forming composition containing aluminum particles on the back surface of a substrate in a desired pattern, form a film containing aluminum particles, and then apply an electrode-forming composition containing silver to The material is printed on the film containing aluminum particles in a desired pattern and heat-treated at the same time. [Prior art literature] [Patent Document]
[專利文獻1]日本專利第6203990號公報[Patent Document 1] Japanese Patent No. 6203990
[發明所欲解決之課題][Problem to be Solved by the Invention]
當形成鋁/銀積層電極時，有時鈍化膜會被蝕刻，PERC結構的太陽電池元件的發電性能下降。因此，要求一種在形成鋁/銀積層電極時，抑制鈍化膜的蝕刻的電極形成用組成物。 另外，在藉由所述方法形成鋁/銀積層電極的情況下，由於鋁電極與銀電極的接觸面積大，因此在熱處理（煆燒）中，在銀電極與鋁電極之間鋁原子與銀原子的相互擴散過度進行，有時銀電極中的鋁濃度變高。其結果，配線材料的連接性等鋁/銀積層電極的作為背面輸出取出電極的功能有可能受損。 本揭示是鑒於所述以往的情況而完成，本揭示的一實施方式的課題在於提供一種能夠抑制鈍化膜的蝕刻且形成與配線材料的連接強度優異的電極的電極形成用組成物、以及使用該電極形成用組成物而獲得的太陽電池元件及鋁/銀積層電極。 [解決課題之手段] When an aluminum/silver laminated electrode is formed, the passivation film may be etched, and the power generation performance of the PERC structure solar cell element may decrease. Therefore, there is a demand for an electrode-forming composition that suppresses etching of a passivation film when forming an aluminum/silver laminated electrode. In addition, in the case of forming an aluminum/silver laminated electrode by the above-mentioned method, since the contact area between the aluminum electrode and the silver electrode is large, during the heat treatment (sintering), the aluminum atom and the silver electrode are separated between the silver electrode and the aluminum electrode. Interdiffusion of atoms progresses excessively, and the aluminum concentration in the silver electrode may become high. As a result, there is a possibility that the function of the aluminum/silver laminated electrode as the output extraction electrode on the rear surface, such as the connectivity of the wiring material, is impaired. The present disclosure has been made in view of the above-mentioned conventional circumstances, and an object of one embodiment of the present disclosure is to provide an electrode-forming composition capable of suppressing etching of a passivation film and forming an electrode excellent in connection strength with a wiring material, and to provide an electrode-forming composition using the present disclosure. A solar cell element and an aluminum/silver laminated electrode obtained from a composition for electrode formation. [Means to solve the problem]
用於實現所述課題的具體方式如下。 ＜1＞一種電極形成用組成物，包含含銀粒子、含鉍粒子、及玻璃粒子， 所述玻璃粒子包含含有釩（vanadium）及碲（tellurium）的玻璃粒子、及含有硼的玻璃粒子。 ＜2＞如＜1＞所述的電極形成用組成物，其中，在構成所述含有釩及碲的玻璃粒子的玻璃的組成中，氧化釩（vanadium oxide）的含有率為10.0質量%～50.0質量%。 ＜3＞如＜1＞或＜2＞所述的電極形成用組成物，其中，在構成所述含有釩及碲的玻璃粒子的玻璃的組成中，氧化碲的含有率為35.0質量%～65.0質量%。 ＜4＞如＜1＞～＜3＞中任一項所述的電極形成用組成物，其中，所述含有釩及碲的玻璃粒子在所述玻璃粒子整體中所佔的比例為10.0質量%～50.0質量%。 ＜5＞如＜1＞～＜4＞中任一項所述的電極形成用組成物，其中，在構成所述含有硼的玻璃粒子的玻璃的組成中，氧化硼的含有率為3.0質量%～25.0質量%。 ＜6＞如＜1＞～＜5＞中任一項所述的電極形成用組成物，其中，所述含有硼的玻璃粒子在所述玻璃粒子整體中所佔的比例為30.0質量%～80.0質量%。 ＜7＞如＜1＞～＜6＞中任一項所述的電極形成用組成物，其中，所述玻璃粒子更包含含有磷的玻璃粒子。 ＜8＞如＜7＞所述的電極形成用組成物，其中，在構成所述含有磷的玻璃粒子的玻璃的組成中，氧化磷的含有率為20.0質量%～50.0質量%。 ＜9＞如＜7＞或＜8＞所述的電極形成用組成物，其中，所述含有磷的玻璃粒子在所述玻璃粒子整體中所佔的比例為40.0質量%以下。 ＜10＞如＜1＞～＜9＞中任一項所述的電極形成用組成物，其中，所述含鉍粒子包含選自由金屬鉍粒子、鉍合金粒子及氧化鉍粒子所組成的群組中的至少一種。 ＜11＞如＜1＞～＜10＞中任一項所述的電極形成用組成物，其中，所述含鉍粒子的含量相對於所述含銀粒子的含量的質量比（Bi/Ag比）為0.30～1.40。 ＜12＞如＜1＞～＜11＞中任一項所述的電極形成用組成物，其中，所述含鉍粒子的含量相對於所述玻璃粒子的含量的質量比（Bi/G比）為0.5～15.0。 ＜13＞如＜1＞～＜12＞中任一項所述的電極形成用組成物，其中，所述玻璃粒子的含有率為所述電極形成用組成物整體的1.0質量%～10.0質量%。 ＜14＞如＜1＞～＜13＞中任一項所述的電極形成用組成物，其中，更包含選自由溶劑及樹脂所組成的群組中的至少一種。 ＜15＞如＜1＞～＜14＞中任一項所述的電極形成用組成物，用於形成鋁/銀積層電極。 ＜16＞一種太陽電池元件，包括：半導體基板、設置在所述半導體基板上的鈍化膜（passivation film）、設置在所述鈍化膜上的包含如＜1＞～＜15＞中任一項所述的電極形成用組成物的熱處理物的鋁/銀積層電極。 ＜17＞一種鋁/銀積層電極，包含如＜1＞～＜15＞中任一項所述的電極形成用組成物的熱處理物，且 所述鋁/銀積層電極包括包含鋁的第一電極及配置在所述第一電極上的包含銀的第二電極，所述第一電極更包含氧化鉍相及玻璃相。 [發明的效果] A specific means for achieving the above-mentioned problems is as follows. <1> A composition for electrode formation, comprising silver-containing particles, bismuth-containing particles, and glass particles, The glass particles include glass particles containing vanadium (vanadium) and tellurium (tellurium), and glass particles containing boron. <2> The electrode-forming composition according to <1>, wherein the content of vanadium oxide (vanadium oxide) in the composition of the glass constituting the glass particles containing vanadium and tellurium is 10.0% by mass to 50.0% by mass. quality%. <3> The electrode-forming composition according to <1> or <2>, wherein the content of tellurium oxide in the composition of the glass constituting the glass particles containing vanadium and tellurium is 35.0% by mass to 65.0% by mass. quality%. <4> The electrode-forming composition according to any one of <1> to <3>, wherein the ratio of the glass particles containing vanadium and tellurium to the entire glass particles is 10.0% by mass ~50.0% by mass. <5> The electrode-forming composition according to any one of <1> to <4>, wherein the content of boron oxide in the composition of the glass constituting the boron-containing glass particles is 3.0% by mass ~25.0% by mass. <6> The electrode-forming composition according to any one of <1> to <5>, wherein the ratio of the boron-containing glass particles to the entire glass particles is 30.0% by mass to 80.0% by mass. quality%. <7> The electrode-forming composition according to any one of <1> to <6>, wherein the glass particles further include glass particles containing phosphorus. <8> The electrode-forming composition according to <7>, wherein the content of phosphorus oxide in the composition of the glass constituting the phosphorus-containing glass particles is 20.0% by mass to 50.0% by mass. <9> The electrode-forming composition according to <7> or <8>, wherein the ratio of the phosphorus-containing glass particles to the entire glass particles is 40.0% by mass or less. <10> The electrode-forming composition according to any one of <1> to <9>, wherein the bismuth-containing particles are selected from the group consisting of metallic bismuth particles, bismuth alloy particles, and bismuth oxide particles. at least one of the <11> The electrode-forming composition according to any one of <1> to <10>, wherein the mass ratio of the content of the bismuth-containing particles to the content of the silver-containing particles (Bi/Ag ratio ) is 0.30 to 1.40. <12> The electrode-forming composition according to any one of <1> to <11>, wherein the mass ratio of the content of the bismuth-containing particles to the content of the glass particles (Bi/G ratio) 0.5 to 15.0. <13> The electrode-forming composition according to any one of <1> to <12>, wherein the content of the glass particles is 1.0% by mass to 10.0% by mass of the entire electrode-forming composition . <14> The electrode-forming composition according to any one of <1> to <13>, further comprising at least one selected from the group consisting of a solvent and a resin. <15> The electrode-forming composition according to any one of <1> to <14>, which is used to form an aluminum/silver laminated electrode. <16> A solar cell element, comprising: a semiconductor substrate, a passivation film provided on the semiconductor substrate, and a passivation film provided on the passivation film according to any one of <1> to <15>. An aluminum/silver laminated electrode that is a heat-treated product of the above-mentioned electrode-forming composition. <17> An aluminum/silver laminated electrode comprising a heat-treated product of the electrode-forming composition according to any one of <1> to <15>, and The aluminum/silver laminated electrode includes a first electrode including aluminum and a second electrode including silver disposed on the first electrode, and the first electrode further includes a bismuth oxide phase and a glass phase. [Effect of the invention]
根據本揭示的一實施方式，提供一種可抑制鈍化膜的蝕刻且形成與配線材料的連接強度優異的電極的電極形成用組成物、以及使用該電極形成用組成物而獲得的太陽電池元件及鋁/銀積層電極。According to one embodiment of the present disclosure, there are provided an electrode-forming composition capable of suppressing etching of a passivation film and forming an electrode excellent in connection strength with a wiring material, and a solar cell element and an aluminum alloy obtained using the electrode-forming composition. /Silver laminated electrodes.
以下，對用以實施本揭示的形態進行詳細說明。其中，本揭示並不限定於以下的實施方式。於以下的實施方式中，除特別明示的情況以外，其結構要素（亦包括要素步驟等）並非必需。數值及其範圍亦同樣如此，並不限制本揭示。Hereinafter, the form for carrying out this indication is demonstrated in detail. However, this indication is not limited to the following embodiment. In the following embodiments, unless otherwise specified, the constituent elements (including element steps and the like) are not essential. The same applies to numerical values and their ranges, and do not limit the present disclosure.
於本揭示中，「步驟」的用語中，除包含與其他步驟獨立的步驟以外，即便於無法與其他步驟明確區別的情況下，只要達成該步驟的目的，則亦包含該步驟。 於本揭示中，使用「～」所表示的數值範圍中包含「～」的前後所記載的數值分別作為最小值及最大值。 於本揭示中階段性記載的數值範圍中，一個數值範圍中所記載的上限值或下限值亦可置換為其他階段性記載的數值範圍的上限值或下限值。另外，於本揭示中所記載的數值範圍中，該數值範圍的上限值或下限值亦可置換為實施例中所示的值。 於本揭示中，可包含多種與各成分相當的物質。於在組成物中存在多種與各成分相當的物質的情況下，只要無特別說明，則各成分的含有率或含量是指組成物中所存在的該多種物質的合計含有率或含量。 於本揭示中，與各成分相當的粒子可包含多種粒子。於在組成物中存在多種與各成分相當的粒子的情況下，只要無特別說明，則各成分的粒徑是指關於組成物中所存在的該多種粒子的混合物的值。 於本揭示中，「層」或「膜」的用語中，當觀察該層或膜所存在的區域時，除包含形成於該區域的整體的情況以外，亦包含僅形成於該區域的一部分的情況。 於本揭示中，「積層」的用語表示將層重疊，兩層以上的層可結合，兩層以上的層亦能夠拆裝。 於本揭示中，層或膜的平均厚度設為測定作為對象的層或膜的五點的厚度並以其算術平均值的形式給出的值。 於本揭示中，「剖面」的用語是指垂直於半導體基板的面方向切斷太陽電池元件而獲得的面。 於本揭示中，「熱處理」的用語包括在熱處理的對象物中包含的粒子燒結或熔融的條件下進行的加熱（煆燒等）。 層或膜的厚度可使用測微計等進行測定。在本揭示中，在可直接測定層或膜的厚度的情況下，使用測微計進行測定。另一方面，在測定一層的厚度或多層的總厚度的情況下，亦可藉由使用電子顯微鏡觀察測定對象的剖面來進行測定。 In the present disclosure, the term "step" includes not only a step independent of other steps, but also includes the step as long as the purpose of the step is achieved even when it cannot be clearly distinguished from other steps. In this disclosure, the numerical values described before and after including "-" in the numerical range represented by "-" are used as the minimum value and the maximum value, respectively. In the numerical ranges described step by step in this disclosure, the upper limit or lower limit described in one numerical range may also be replaced by the upper limit or lower limit of other numerical ranges described step by step. In addition, in the numerical range described in this indication, the upper limit or the lower limit of the numerical range may be replaced with the value shown in an Example. In this disclosure, various substances corresponding to each component may be included. When a plurality of substances corresponding to each component exist in the composition, unless otherwise specified, the content or content of each component refers to the total content or content of the plurality of substances present in the composition. In the present disclosure, the particles corresponding to each component may include a plurality of kinds of particles. In the case where a plurality of types of particles corresponding to each component exist in the composition, unless otherwise specified, the particle size of each component refers to a value for a mixture of the plurality of types of particles present in the composition. In the present disclosure, the term "layer" or "film" includes not only the case where the layer or film is formed in the entirety of the region but also the case where it is formed in only a part of the region when looking at the region where the layer or film exists. Condition. In this disclosure, the term "lamination" means that layers are stacked, two or more layers can be combined, and two or more layers can also be detached. In this indication, the average thickness of a layer or a film shall be the value which measured the thickness of the target layer or film at five points, and gave it as the arithmetic mean value. In the present disclosure, the term "cross section" refers to a surface obtained by cutting a solar cell element perpendicular to the surface direction of a semiconductor substrate. In the present disclosure, the term "heat treatment" includes heating (sintering, etc.) performed under the conditions that the particles contained in the object to be heat treated are sintered or melted. The thickness of a layer or film can be measured using a micrometer or the like. In the present disclosure, when the thickness of a layer or film can be directly measured, it is measured using a micrometer. On the other hand, when measuring the thickness of one layer or the total thickness of multiple layers, it can also be measured by observing the cross-section of the object to be measured using an electron microscope.
＜電極形成用組成物＞ 本揭示的電極形成用組成物包含含銀粒子、含鉍粒子、及玻璃粒子，所述玻璃粒子包含含有釩及碲的玻璃粒子及含有硼的玻璃粒子。以下，有時將含有釩及碲的玻璃粒子稱為含釩-碲玻璃粒子，將含有硼的玻璃粒子稱為含硼玻璃粒子。 根據包含含銀粒子、含鉍粒子、作為玻璃粒子的含釩-碲玻璃粒子及含硼玻璃粒子的電極形成用組成物，可抑制鈍化膜的蝕刻且形成與配線材料的連接強度優異的電極。其理由未必明確，推測如下。 ＜Electrode formation composition＞ The electrode-forming composition of the present disclosure includes silver-containing particles, bismuth-containing particles, and glass particles, and the glass particles include glass particles containing vanadium and tellurium, and glass particles containing boron. Hereinafter, glass particles containing vanadium and tellurium may be referred to as vanadium-tellurium-containing glass particles, and glass particles containing boron may be referred to as boron-containing glass particles. According to the composition for electrode formation containing silver-containing particles, bismuth-containing particles, vanadium-tellurium-containing glass particles as glass particles, and boron-containing glass particles, etching of a passivation film can be suppressed and an electrode excellent in connection strength with a wiring material can be formed. The reason for this is not necessarily clear, but it is presumed as follows.
包含含銀粒子及含鉍粒子的電極形成用組成物被賦予在形成於基板上的含鋁粒子的膜上的期望區域，根據需要進行乾燥後，進行熱處理。藉此，在鋁電極上形成銀電極。 藉由熱處理，電極形成用組成物中所含的含銀粒子燒結而形成銀電極，含鋁粒子的膜中所含的鋁粒子燒結而形成鋁電極。此時，含鉍粒子中所含的鉍氧化而形成的氧化鉍相表現出抑制銀電極與鋁電極的介面處的相互擴散的性質（以下亦稱為擴散阻擋性）。另一方面，鉍具有蝕刻鈍化膜的性質。 在對電極形成用組成物進行熱處理時，熔融的含釩-碲玻璃粒子具有難以滲透至含鋁粒子的膜中所含的鋁粒子之間的性質。因此，隨著熔融的玻璃粒子成分滲透至鋁粒子之間，鉍透過含鋁粒子的膜到達鈍化膜的現象有藉由使用含釩-碲玻璃粒子而被防止的傾向。另外，含釩-碲玻璃粒子幾乎不蝕刻鈍化膜。因此，即使熔融的含釩-碲玻璃粒子的一部分滲透至鋁粒子之間而到達鈍化膜，鈍化膜的蝕刻亦得到抑制。 另一方面，若熔融的玻璃粒子不滲透到鋁粒子之間，則在鋁電極中的鋁粒子之間不會填充玻璃成分，有時難以確保電極的強度，進而難以確保與配線材料的連接強度。與含釩-碲玻璃粒子相比，含硼玻璃粒子有容易滲透至鋁電極中的鋁粒子之間的傾向。藉由熔融的含硼玻璃粒子滲透至鋁粒子之間，可確保與配線材料的連接強度。 由以上而推測，根據本揭示的電極形成用組成物，可抑制鈍化膜的蝕刻，且形成與配線材料的連接強度優異的電極。 The electrode-forming composition containing silver-containing particles and bismuth-containing particles is applied to a desired region on the aluminum particle-containing film formed on the substrate, dried if necessary, and then heat-treated. Thereby, a silver electrode was formed on the aluminum electrode. By heat treatment, the silver-containing particles contained in the electrode-forming composition are sintered to form a silver electrode, and the aluminum particles contained in the aluminum particle-containing film are sintered to form an aluminum electrode. At this time, the bismuth oxide phase formed by oxidation of bismuth contained in the bismuth-containing particles exhibits a property of suppressing interdiffusion at the interface between the silver electrode and the aluminum electrode (hereinafter also referred to as diffusion barrier property). On the other hand, bismuth has a property of etching a passivation film. When the composition for forming an electrode is heat-treated, molten vanadium-tellurium-containing glass particles have a property that it is difficult to penetrate between aluminum particles contained in an aluminum particle-containing film. Therefore, the phenomenon that bismuth permeates through the film containing aluminum particles to reach the passivation film as molten glass particle components permeate between the aluminum particles tends to be prevented by using the vanadium-tellurium containing glass particles. In addition, vanadium-tellurium-containing glass particles hardly etch the passivation film. Therefore, even if a part of the molten vanadium-tellurium-containing glass particles penetrates between the aluminum particles and reaches the passivation film, etching of the passivation film is suppressed. On the other hand, if the molten glass particles do not permeate between the aluminum particles, the glass component will not be filled between the aluminum particles in the aluminum electrode, and it may be difficult to ensure the strength of the electrode, and furthermore, it is difficult to ensure the connection strength with the wiring material. . Compared with vanadium-tellurium-containing glass particles, boron-containing glass particles tend to penetrate more easily between the aluminum particles in the aluminum electrode. By infiltrating the molten boron-containing glass particles between the aluminum particles, the connection strength with the wiring material can be ensured. From the above, according to the composition for electrode formation of this indication, etching of a passivation film can be suppressed, and the electrode excellent in the connection strength with a wiring material can be formed.
以下，對本揭示的電極形成用組成物中含有的各成分進行說明。本揭示的電極形成用組成物包含含銀粒子、含鉍粒子及玻璃粒子，亦可包含其他成分。另外，本揭示的電極形成用組成物中，作為玻璃粒子，包含含釩-碲玻璃粒子及含硼玻璃粒子，亦可包含其他玻璃粒子。Hereinafter, each component contained in the electrode-forming composition of this disclosure is demonstrated. The electrode-forming composition disclosed herein includes silver-containing particles, bismuth-containing particles, and glass particles, and may also contain other components. In addition, the electrode-forming composition of the present disclosure contains vanadium-tellurium-containing glass particles and boron-containing glass particles as glass particles, and may contain other glass particles.
（含銀粒子） 電極形成用組成物包含含銀粒子。電極形成用組成物中所含的含銀粒子可僅為一種，亦可為兩種以上。 (with silver particles) The electrode-forming composition contains silver-containing particles. The silver-containing particle contained in the composition for electrode formation may be only 1 type, and may be 2 or more types.
含銀粒子只要是包含銀的粒子就並無特別限制。其中，較佳為選自由銀粒子及銀合金粒子所組成的群組中的至少一種，更佳為選自由銀粒子及銀含有率為50.0質量%以上的銀合金粒子所組成的群組中的至少一種。The silver-containing particles are not particularly limited as long as they contain silver. Among them, it is preferably at least one selected from the group consisting of silver particles and silver alloy particles, more preferably selected from the group consisting of silver particles and silver alloy particles with a silver content of 50.0% by mass or more. at least one.
銀粒子中銀的含有率並無特別限制。例如，可設為銀粒子整體的95.0質量%以上，較佳為97.0質量%以上，更佳為99.0質量%以上。The content of silver in the silver particles is not particularly limited. For example, it can be 95.0 mass % or more of the whole silver particle, Preferably it is 97.0 mass % or more, More preferably, it is 99.0 mass % or more.
銀合金粒子只要是包含銀的合金的粒子就並無特別限制。其中，就銀合金粒子的熔點及燒結性的觀點而言，銀的含有率較佳為粒子整體的50.0質量%以上，更佳為60.0質量%以上，進而佳為70.0質量%以上，特佳為80.0質量%以上。所述含有率可為95.0質量%以下。The silver alloy particles are not particularly limited as long as they are particles of an alloy containing silver. Among them, from the viewpoint of the melting point and sinterability of the silver alloy particles, the silver content is preferably at least 50.0% by mass of the entire particle, more preferably at least 60.0% by mass, still more preferably at least 70.0% by mass, particularly preferably at least 70.0% by mass. 80.0% by mass or more. The content rate may be 95.0% by mass or less.
作為銀合金，可列舉Ag-Pd系合金、Ag-Pd-Au系合金、Ag-Pd-Cu系合金、Ag-Pd-In系合金、Ag-In系合金、Ag-Sn系合金、Ag-Zn系合金、Ag-Sn-Zn系合金等。 含銀粒子可不包含不相當於銀及銀合金的成分，亦可包含。 在含銀粒子包含不相當於銀及銀合金的成分的情況下，其含有率在含銀粒子中可設為3.0質量%以下，較佳為1.0質量%以下。 Examples of silver alloys include Ag-Pd-based alloys, Ag-Pd-Au-based alloys, Ag-Pd-Cu-based alloys, Ag-Pd-In-based alloys, Ag-In-based alloys, Ag-Sn-based alloys, Ag- Zn-based alloys, Ag-Sn-Zn-based alloys, etc. The silver-containing particles may not contain components corresponding to silver and silver alloys, or may contain them. When the silver-containing particles contain components other than silver and silver alloys, the content of the silver-containing particles may be 3.0% by mass or less, preferably 1.0% by mass or less.
含銀粒子的粒徑並無特別限制，作為在利用雷射繞射-散射法獲得的體積基準的粒度分佈中自小徑側起的累積為50%時的粒徑（體積平均粒徑），較佳為0.1 μm～50.0 μm，更佳為0.15 μm～40.0 μm，進而佳為0.2 μm～30.0 μm。含銀粒子的體積平均粒徑為0.1 μm以上時，能夠充分提高鋁/銀積層電極的表面的銀濃度，配線材料的連接強度提高。含銀粒子的體積平均粒徑為50.0 μm以下時，鋁/銀積層電極內的電阻有降低的傾向。The particle size of the silver-containing particles is not particularly limited, and as the particle size (volume average particle size) when the accumulation from the small diameter side is 50% in the volume-based particle size distribution obtained by the laser diffraction-scattering method, It is preferably 0.1 μm to 50.0 μm, more preferably 0.15 μm to 40.0 μm, and still more preferably 0.2 μm to 30.0 μm. When the volume average particle diameter of the silver-containing particles is 0.1 μm or more, the silver concentration on the surface of the aluminum/silver laminated electrode can be sufficiently increased, and the connection strength of the wiring material can be improved. When the volume average particle diameter of the silver-containing particles is 50.0 μm or less, the electrical resistance in the aluminum/silver laminated electrode tends to decrease.
含銀粒子的粒徑藉由雷射繞射式粒度分佈計（例如貝克曼-庫爾特（Beckman-Coulter）（股）、LS 13 320型雷射散射繞射法粒度分佈測定裝置）進行測定。具體而言，在溶劑（萜品醇）125 g中，在0.01質量%～0.3質量%的範圍內添加含銀粒子，製備分散液。將該分散液的約100 ml左右注入單元中，在25℃下進行測定。粒度分佈以溶媒的折射率為1.48進行測定。The particle size of the silver-containing particles is measured by a laser diffraction particle size distribution meter (for example, Beckman-Coulter (Beckman-Coulter) (stock),
含銀粒子的形狀並無特別限制，可為大致球狀、扁平狀、塊狀、板狀、鱗片狀等。就含銀粒子彼此的燒結性的觀點而言，較佳為大致球狀、扁平狀或板狀。The shape of the silver-containing particles is not particularly limited, and may be approximately spherical, flat, massive, plate-like, scale-like, or the like. From the viewpoint of the sinterability of silver-containing particles, it is preferably approximately spherical, flat or plate-shaped.
（含鉍粒子） 電極形成用組成物包含含鉍粒子。電極形成用組成物中所含的含鉍粒子可僅為一種，亦可為兩種以上。 (with bismuth particles) The electrode-forming composition contains bismuth-containing particles. The bismuth-containing particles contained in the composition for electrode formation may be only one kind, or two or more kinds.
含鉍粒子只要是包含鉍的粒子就並無特別限制。其中，較佳為選自由金屬鉍粒子、鉍合金粒子及氧化鉍粒子所組成的群組中的至少一種，更佳為選自由金屬鉍粒子、鉍含有率為40.0質量%以上的鉍合金粒子及氧化鉍粒子所組成的群組中的至少一種。 本揭示中，在含鉍粒子為玻璃狀的情況（包含鉍的玻璃粒子）下，設為不相當於含鉍粒子。 The bismuth-containing particles are not particularly limited as long as they contain bismuth. Among them, it is preferably at least one selected from the group consisting of metal bismuth particles, bismuth alloy particles, and bismuth oxide particles, more preferably selected from metal bismuth particles, bismuth alloy particles with a bismuth content of 40.0% by mass or more, and At least one of the group consisting of bismuth oxide particles. In the present disclosure, when the bismuth-containing particles are glassy (glass particles containing bismuth), it is not assumed to correspond to the bismuth-containing particles.
金屬鉍粒子中的鉍的含有率並無特別限制。例如，可設為金屬鉍粒子整體的95.0質量%以上，較佳為97.0質量%以上，更佳為99.0質量%以上。The bismuth content in the metal bismuth particles is not particularly limited. For example, it can be 95.0 mass % or more of the whole metallic bismuth particle, Preferably it is 97.0 mass % or more, More preferably, it is 99.0 mass % or more.
鉍合金粒子只要是包含鉍的合金的粒子就並無特別限制。其中，就鉍合金粒子的熔點及擴散阻擋性的觀點而言，鉍合金粒子的鉍的含有率較佳為粒子整體的40.0質量%以上，更佳為50.0質量%以上，進而佳為60.0質量%以上，特佳為70.0質量%以上。鉍合金粒子的鉍的含有率可為95.0質量%以下。The bismuth alloy particles are not particularly limited as long as they are particles of an alloy containing bismuth. Among them, from the viewpoint of the melting point and diffusion barrier properties of the bismuth alloy particles, the content of bismuth in the bismuth alloy particles is preferably at least 40.0% by mass of the entire particle, more preferably at least 50.0% by mass, and still more preferably 60.0% by mass. Above, especially preferably 70.0% by mass or more. The bismuth content of the bismuth alloy particles may be 95.0% by mass or less.
作為鉍合金，可列舉Bi-Sn系合金、Bi-Sn-Cu系合金、Bi-Pb-Sn系合金、Bi-Cd系合金等。Bismuth alloys include Bi—Sn alloys, Bi—Sn—Cu alloys, Bi—Pb—Sn alloys, Bi—Cd alloys, and the like.
作為氧化鉍粒子，可列舉三氧化鉍（Bi 2O 3）的粒子。就發揮充分的擴散阻擋性及鋁/銀積層電極自身的低電阻化的觀點而言，氧化鉍粒子較佳為與金屬鉍粒子併用。 含鉍粒子可不包含不相當於金屬鉍、鉍合金及氧化鉍的成分，亦可包含。 在含鉍粒子包含不相當於金屬鉍、鉍合金及氧化鉍的成分的情況下，就氧化鉍相的形成及擴散阻擋性的觀點而言，其含有率在含鉍粒子中可設為3.0質量%以下，較佳為1.0質量%以下。 Bismuth oxide particles include particles of bismuth trioxide (Bi 2 O 3 ). Bismuth oxide particles are preferably used in combination with metal bismuth particles from the viewpoint of exerting sufficient diffusion barrier properties and reducing the resistance of the aluminum/silver laminated electrode itself. The bismuth-containing particles may contain components other than metallic bismuth, bismuth alloys, and bismuth oxide, or may contain them. In the case where the bismuth-containing particles contain components other than metal bismuth, bismuth alloy, and bismuth oxide, from the viewpoint of the formation of a bismuth oxide phase and diffusion barrier properties, the content of the bismuth-containing particles can be set to 3.0 mass % or less, preferably 1.0 mass % or less.
含鉍粒子的粒徑並無特別限制，但體積平均粒徑較佳為0.1 μm～50.0 μm，更佳為0.15 μm～40.0 μm，進而佳為0.2 μm～30.0 μm。含鉍粒子的粒徑為0.1 μm以上時，會促進向含鋁粒子的膜的轉移及氧化鉍相的形成。含鉍粒子的粒徑為50.0 μm以下時，有效果地發揮擴散阻擋性。 含鉍粒子的體積平均粒徑與含銀粒子的體積平均粒徑同樣地測定。 The particle size of the bismuth-containing particles is not particularly limited, but the volume average particle size is preferably from 0.1 μm to 50.0 μm, more preferably from 0.15 μm to 40.0 μm, and still more preferably from 0.2 μm to 30.0 μm. When the particle size of the bismuth-containing particles is 0.1 μm or more, the transfer to the film of the aluminum-containing particles and the formation of the bismuth oxide phase are promoted. When the particle size of the bismuth-containing particles is 50.0 μm or less, the diffusion barrier properties are effectively exhibited. The volume average particle diameter of the bismuth-containing particles is measured in the same manner as the volume average particle diameter of the silver-containing particles.
含鉍粒子的形狀並無特別限制，可為大致球狀、扁平狀、塊狀、板狀、鱗片狀等。就擴散阻擋性的觀點而言，較佳為大致球狀、扁平狀或板狀。The shape of the bismuth-containing particles is not particularly limited, and may be approximately spherical, flat, massive, plate-like, and scaly. From the viewpoint of diffusion barrier property, it is preferably approximately spherical, flat or plate-shaped.
電極形成用組成物中的含鉍粒子的含量相對於含銀粒子的含量的質量比（Bi/Ag比）較佳為0.30～1.40，更佳為0.35～1.30，進而佳為0.40～1.20，特佳為0.45～1.10。藉由使Bi/Ag比為0.30以上，有鋁與銀的相互擴散被有效果地抑制的傾向。藉由使Bi/Ag比為1.40以下，有充分確保鋁/銀積層電極表面的銀濃度、良好地維持連接材料的連接強度（焊料的潤濕性）的傾向。The mass ratio (Bi/Ag ratio) of the content of the bismuth-containing particles to the content of the silver-containing particles in the electrode-forming composition is preferably from 0.30 to 1.40, more preferably from 0.35 to 1.30, still more preferably from 0.40 to 1.20, especially Preferably it is 0.45-1.10. There exists a tendency for the mutual diffusion of aluminum and silver to be suppressed effectively by making Bi/Ag ratio 0.30 or more. By setting the Bi/Ag ratio to 1.40 or less, the silver concentration on the surface of the aluminum/silver laminated electrode is sufficiently secured, and the connection strength (solder wettability) of the connection material tends to be maintained favorably.
（玻璃粒子） 電極形成用組成物包含玻璃粒子，作為玻璃粒子包含含釩-碲玻璃粒子及含硼玻璃粒子。 (glass particles) The electrode-forming composition includes glass particles, and the glass particles include vanadium-tellurium-containing glass particles and boron-containing glass particles.
-含釩-碲玻璃粒子- 作為含釩-碲玻璃粒子，可列舉包含氧化釩（V 2O 5）及氧化碲（TeO 2）的玻璃粒子。 在構成含釩-碲玻璃粒子的玻璃的組成中，氧化釩的含有率較佳為10.0質量%～50.0質量%，更佳為15.0質量%～40.0質量%，進而佳為20.0質量%～30.0質量%。 在構成含釩-碲玻璃粒子的玻璃的組成中，氧化碲的含有率較佳為35.0質量%～65.0質量%，更佳為40.0質量%～60.0質量%，進而佳為45.0質量%～55.0質量%。 構成含釩-碲玻璃粒子的氧化釩與氧化碲的質量基準的比率（氧化釩/氧化碲）較佳為20/80～60/40，更佳為25/75～55/45，進而佳為30/70～50/50。 -Vadium-tellurium-containing glass particles- Examples of the vanadium-tellurium-containing glass particles include glass particles containing vanadium oxide (V 2 O 5 ) and tellurium oxide (TeO 2 ). In the composition of the glass constituting the vanadium-tellurium-containing glass particles, the content of vanadium oxide is preferably from 10.0 mass % to 50.0 mass %, more preferably from 15.0 mass % to 40.0 mass %, still more preferably from 20.0 mass % to 30.0 mass % %. In the composition of the glass constituting the vanadium-tellurium-containing glass particles, the content of tellurium oxide is preferably from 35.0 mass % to 65.0 mass %, more preferably from 40.0 mass % to 60.0 mass %, still more preferably from 45.0 mass % to 55.0 mass % %. The mass ratio of vanadium oxide and tellurium oxide constituting the vanadium-tellurium-containing glass particles (vanadium oxide/tellurium oxide) is preferably 20/80 to 60/40, more preferably 25/75 to 55/45, and still more preferably 30/70～50/50.
含釩-碲玻璃粒子可包含氧化釩、氧化碲、以及氧化釩及氧化碲以外的其他氧化物。 作為構成含釩-碲玻璃粒子的玻璃中所含的其他氧化物，例如可列舉：二氧化矽（SiO 2）、氧化磷（P 2O 5）、氧化鋁（Al 2O 3）、氧化鉀（K 2O）、氧化鉍（Bi 2O 3）、氧化鈉（Na 2O）、氧化鋰（Li 2O）、氧化鋇（BaO）、氧化鍶（SrO）、氧化鈣（CaO）、氧化鎂（MgO）、氧化鈹（BeO）、氧化鋅（ZnO）、氧化鎘（CdO）、氧化錫（SnO）、氧化鋯（ZrO 2）、氧化鎢（WO 3）、氧化鉬（MoO 3）、氧化鑭（La 2O 3）、氧化鈮（Nb 2O 3）、氧化鉭（Ta 2O 5）、氧化釔（Y 2O 3）、氧化鈦（TiO 2）、氧化鍺（GeO 2）、氧化鎦（Lu 2O 3，Lutetium oxide）、氧化銻（Sb 2O 3）、氧化銅（CuO）、氧化鐵（Fe 2O 3）、氧化銀（Ag 2O）及氧化錳（MnO）。 該些中，作為其他氧化物，可列舉氧化鋅（ZnO）、氧化銅（CuO）、氧化銀（Ag 2O）、氧化鋰（Li 2O）等。 其他氧化物在構成含釩-碲玻璃粒子的玻璃整體中所佔的比例較佳為10.0質量%～40.0質量%，更佳為15.0質量%～35.0質量%，進而佳為20.0質量%～30.0質量%。 The vanadium-tellurium-containing glass particles may include vanadium oxide, tellurium oxide, and oxides other than vanadium oxide and tellurium oxide. Examples of other oxides contained in the glass constituting vanadium-tellurium-containing glass particles include silicon dioxide (SiO 2 ), phosphorus oxide (P 2 O 5 ), aluminum oxide (Al 2 O 3 ), potassium oxide (K 2 O), bismuth oxide (Bi 2 O 3 ), sodium oxide (Na 2 O), lithium oxide (Li 2 O), barium oxide (BaO), strontium oxide (SrO), calcium oxide (CaO), oxide Magnesium (MgO), beryllium oxide (BeO), zinc oxide (ZnO), cadmium oxide (CdO), tin oxide (SnO), zirconium oxide (ZrO 2 ), tungsten oxide (WO 3 ), molybdenum oxide (MoO 3 ), Lanthanum oxide (La 2 O 3 ), niobium oxide (Nb 2 O 3 ), tantalum oxide (Ta 2 O 5 ), yttrium oxide (Y 2 O 3 ), titanium oxide (TiO 2 ), germanium oxide (GeO 2 ), Lutetium oxide (Lu 2 O 3 , Lutetium oxide), antimony oxide (Sb 2 O 3 ), copper oxide (CuO), iron oxide (Fe 2 O 3 ), silver oxide (Ag 2 O) and manganese oxide (MnO). Among these, zinc oxide (ZnO), copper oxide (CuO), silver oxide (Ag 2 O), lithium oxide (Li 2 O) and the like are exemplified as other oxides. The proportion of other oxides in the entire glass constituting the vanadium-tellurium-containing glass particles is preferably 10.0 mass % to 40.0 mass %, more preferably 15.0 mass % to 35.0 mass %, and still more preferably 20.0 mass % to 30.0 mass % %.
-含硼玻璃粒子- 含硼玻璃粒子較佳為包含硼酸鹽玻璃。本揭示中硼酸鹽玻璃是指包含氧化硼（B 2O 3）作為網眼形成氧化物的玻璃。 -Boron-containing glass particles- The boron-containing glass particles preferably contain borate glass. Borate glass in this disclosure refers to glass comprising boron oxide (B 2 O 3 ) as the network-forming oxide.
作為構成含硼玻璃粒子的玻璃的組成，就玻璃的功能上的觀點而言，氧化硼的含有率較佳為3.0質量%～25.0質量%，更佳為5.0質量%～20.0質量%，進而佳為10.0質量%～15.0質量%。As the composition of the glass constituting the boron-containing glass particles, from the functional viewpoint of the glass, the content of boron oxide is preferably from 3.0% by mass to 25.0% by mass, more preferably from 5.0% by mass to 20.0% by mass, and still more preferably It is 10.0 mass % - 15.0 mass %.
含硼玻璃粒子可包含氧化硼及氧化硼以外的氧化物。 作為構成含硼玻璃粒子的玻璃中所含的氧化硼以外的氧化物，可列舉作為構成含釩-碲玻璃粒子的玻璃中可包含的氧化物而例示的氧化物。 含硼玻璃粒子較佳不包含氧化磷，或者氧化磷的含有率低於氧化硼的含有率。 The boron-containing glass particles may contain boron oxide and oxides other than boron oxide. Examples of oxides other than boron oxide contained in the glass constituting the boron-containing glass particles include oxides exemplified as oxides that may be contained in the glass constituting the vanadium-tellurium-containing glass particles. The boron-containing glass particles preferably do not contain phosphorus oxide, or the content of phosphorus oxide is lower than that of boron oxide.
含硼玻璃粒子較佳為包含選自由氧化矽、氧化鋁、氧化鋅、氧化鉍、氧化銅以及氧化鋰所組成的群組中的至少一種，更佳為包含氧化鉍，含鉍硼酸鹽玻璃（B 2O 3-Bi 2O 3系）等可列舉為較佳的例子。此種組成的玻璃的軟化點低，熱處理後獲得的電極對基板的密接性有進一步提高的傾向。 The boron-containing glass particles preferably include at least one selected from the group consisting of silicon oxide, aluminum oxide, zinc oxide, bismuth oxide, copper oxide, and lithium oxide, more preferably include bismuth oxide, bismuth-containing borate glass ( B 2 O 3 -Bi 2 O 3 system) etc. are mentioned as preferable examples. Glass with such a composition has a low softening point, and the adhesion between the electrode and the substrate obtained after the heat treatment tends to be further improved.
在含硼玻璃粒子包含氧化鉍的情況下，氧化鉍的含有率較佳為整體的70.0質量%～97.0質量%，更佳為75.0質量%～95.0質量%，進而佳為80.0質量%～90.0質量%。When the boron-containing glass particles contain bismuth oxide, the content of bismuth oxide is preferably 70.0% by mass to 97.0% by mass of the whole, more preferably 75.0% by mass to 95.0% by mass, further preferably 80.0% by mass to 90.0% by mass %.
電極形成用組成物可包含含釩-碲玻璃粒子及含硼玻璃粒子兩種作為玻璃粒子，亦可包含含釩-碲玻璃粒子及含硼玻璃粒子以外的其他玻璃粒子。 含釩-碲玻璃粒子在玻璃粒子整體中所佔的比例較佳為10.0質量%～50.0質量%，更佳為15.0質量%～45.0質量%，進而佳為20.0質量%～40.0質量%。 含硼玻璃粒子在玻璃粒子整體中所佔的比例較佳為30.0質量%～80.0質量%，更佳為35.0質量%～75.0質量%，進而佳為40.0質量%～70.0質量%。 The composition for electrode formation may contain both vanadium-tellurium-containing glass particles and boron-containing glass particles as glass particles, or may contain glass particles other than vanadium-tellurium-containing glass particles and boron-containing glass particles. The ratio of the vanadium-tellurium-containing glass particles to the total glass particles is preferably 10.0% by mass to 50.0% by mass, more preferably 15.0% by mass to 45.0% by mass, and still more preferably 20.0% by mass to 40.0% by mass. The ratio of the boron-containing glass particles to the whole glass particles is preferably from 30.0% by mass to 80.0% by mass, more preferably from 35.0% by mass to 75.0% by mass, still more preferably from 40.0% by mass to 70.0% by mass.
作為其他玻璃粒子，較佳為含有磷的玻璃粒子。以下，有時將含有磷的玻璃粒子稱為含磷玻璃粒子。作為含有磷的玻璃，可列舉包含氧化磷（P 2O 5）的玻璃，較佳為磷酸鹽玻璃。 本揭示中，磷酸鹽玻璃是指包含氧化磷（P 2O 5）作為網眼形成氧化物的玻璃。 As other glass particles, phosphorus-containing glass particles are preferable. Hereinafter, glass particles containing phosphorus may be referred to as phosphorus-containing glass particles. Glass containing phosphorus includes glass containing phosphorus oxide (P 2 O 5 ), preferably phosphate glass. In the present disclosure, phosphate glass refers to glass containing phosphorus oxide (P 2 O 5 ) as a network-forming oxide.
在構成含磷玻璃粒子的玻璃的組成中，就玻璃的功能上的觀點而言，氧化磷的含有率較佳為20.0質量%～50.0質量%，更佳為30.0質量%～45.0質量%，進而佳為35.0質量%～40.0質量%。In the composition of the glass constituting the phosphorus-containing glass particles, the content of phosphorus oxide is preferably from 20.0% by mass to 50.0% by mass, more preferably from 30.0% by mass to 45.0% by mass, from the functional viewpoint of the glass, and further Preferably, it is 35.0 mass % - 40.0 mass %.
含磷玻璃粒子可包含氧化磷及氧化磷以外的其他氧化物。作為其他氧化物的具體例，可列舉作為構成含釩-碲玻璃粒子的玻璃中所含的其他氧化物而列舉的氧化物。 含磷玻璃粒子較佳為包含選自由氧化鋁、氧化錫及氧化鋅所組成的群組中的至少一種。藉由使用此種組成的玻璃，鋁/銀積層電極在高溫高濕環境下的可靠性有進一步提高的傾向。 The phosphorus-containing glass particles may contain phosphorus oxide and other oxides other than phosphorus oxide. Specific examples of other oxides include oxides listed as other oxides contained in glass constituting vanadium-tellurium-containing glass particles. The phosphorus-containing glass particles preferably include at least one selected from the group consisting of aluminum oxide, tin oxide, and zinc oxide. By using a glass having such a composition, the reliability of the aluminum/silver laminated electrode in a high-temperature and high-humidity environment tends to be further improved.
在構成含磷玻璃粒子的玻璃包含氧化錫的情況下，氧化錫的含有率較佳為20.0質量%～80.0質量%，更佳為30.0質量%～70.0質量%，進而佳為40.0質量%～60.0質量%。 含磷玻璃粒子較佳為不包含氧化硼，或者氧化硼的含有率低於氧化磷的含有率。 When the glass constituting the phosphorus-containing glass particles contains tin oxide, the content of tin oxide is preferably from 20.0% by mass to 80.0% by mass, more preferably from 30.0% by mass to 70.0% by mass, still more preferably from 40.0% by mass to 60.0% by mass. quality%. The phosphorus-containing glass particles preferably do not contain boron oxide, or the content of boron oxide is lower than that of phosphorus oxide.
含磷玻璃粒子在玻璃粒子整體中所佔的比例可為40.0質量%以下，較佳為5.0質量%～40.0質量%，更佳為10.0質量%～35.0質量%，進而佳為15.0質量%～30.0質量%。The ratio of phosphorus-containing glass particles to the total glass particles may be 40.0% by mass or less, preferably 5.0% by mass to 40.0% by mass, more preferably 10.0% by mass to 35.0% by mass, and still more preferably 15.0% by mass to 30.0% by mass. quality%.
在SiN X膜上形成鋁/銀積層電極的情況下，較佳為使用實質上不含鉛的無鉛玻璃。作為無鉛玻璃，可列舉日本專利特開2006-313744號公報的段落號0024～段落號0025中記載的無鉛玻璃、日本專利特開2009-188281號公報等中記載的無鉛玻璃等。 When forming an aluminum/silver laminated electrode on a SiNx film, it is preferable to use lead-free glass which does not contain lead substantially. Examples of the lead-free glass include lead-free glasses described in paragraphs 0024 to 0025 of JP-A-2006-313744, lead-free glasses described in JP-A-2009-188281, and the like.
構成各玻璃粒子的玻璃的軟化點並無特別限制，較佳為650℃以下，更佳為500℃以下。玻璃的軟化點可由使用示差熱-熱重量同時測定裝置測定的示差熱（示差熱分析（Differential Thermal Analysis，DTA））曲線求出。The softening point of glass constituting each glass particle is not particularly limited, but is preferably 650°C or lower, more preferably 500°C or lower. The softening point of glass can be calculated|required from the differential heat (differential thermal analysis (Differential Thermal Analysis, DTA)) curve measured using a differential heat-thermogravimetry simultaneous measurement apparatus.
玻璃粒子的形狀並無特別限制，可為大致球狀、扁平狀、塊狀、板狀、鱗片狀等。就與含銀粒子及含鉍粒子的潤濕性的觀點而言，玻璃粒子的形狀較佳為大致球狀、扁平狀或板狀。The shape of the glass particles is not particularly limited, and may be approximately spherical, flat, massive, plate-like, scaly, or the like. From the viewpoint of wettability with silver-containing particles and bismuth-containing particles, the shape of the glass particles is preferably approximately spherical, flat or plate-like.
各玻璃粒子的體積平均粒徑分別較佳為0.5 μm～15.0 μm，更佳為0.7 μm～12.0 μm，進而佳為0.9 μm～10.0 μm。 藉由使玻璃粒子的體積平均粒徑為0.5 μm以上，有在對電極形成用組成物進行熱處理而獲得的銀電極的表面形成由玻璃粒子引起的凹凸形狀的傾向。其結果，配線材料與銀電極的接觸呈點接觸，因此應力緩和，有高溫高濕環境下的可靠性提高的傾向。 藉由使玻璃粒子的體積平均粒徑為15.0 μm以下，電極形成用組成物中的玻璃粒子的分散性良好，有在銀電極的表面形成的凹凸形狀的分佈不均得到抑制的傾向。 玻璃粒子的體積平均粒徑與含銀粒子的體積平均粒徑同樣地測定。 The volume average particle diameter of each glass particle is preferably 0.5 μm to 15.0 μm, more preferably 0.7 μm to 12.0 μm, and still more preferably 0.9 μm to 10.0 μm. When the volume average particle diameter of the glass particles is 0.5 μm or more, unevenness due to the glass particles tends to be formed on the surface of the silver electrode obtained by heat-treating the electrode-forming composition. As a result, since the contact between the wiring material and the silver electrode is point contact, the stress is relaxed, and the reliability in a high-temperature, high-humidity environment tends to be improved. By setting the volume average particle diameter of the glass particles to 15.0 μm or less, the dispersibility of the glass particles in the electrode-forming composition becomes favorable, and uneven distribution of unevenness formed on the surface of the silver electrode tends to be suppressed. The volume average particle diameter of the glass particles is measured in the same manner as the volume average particle diameter of the silver-containing particles.
電極形成用組成物中所含的玻璃粒子的含有率較佳為電極形成用組成物整體的1.0質量%～10.0質量%，更佳為1.5質量%～9.0質量%，進而佳為2.0質量%～8.0質量%。 藉由使玻璃粒子的含有率為1.0質量%以上，有維持高溫高濕環境下的良好的可靠性的傾向。藉由使玻璃粒子的含有率為10.0質量%以下，充分確保形成在鋁電極上的銀電極的表面的銀濃度，而有良好地維持連接材料的連接強度（焊料的潤濕性）的傾向。 The content of the glass particles contained in the electrode-forming composition is preferably from 1.0% by mass to 10.0% by mass of the entire electrode-forming composition, more preferably from 1.5% by mass to 9.0% by mass, still more preferably from 2.0% by mass to 8.0% by mass. By making the glass particle content rate 1.0 mass % or more, it exists in the tendency which maintains favorable reliability in a high-temperature, high-humidity environment. By making the content of glass particles 10.0% by mass or less, the silver concentration on the surface of the silver electrode formed on the aluminum electrode is sufficiently ensured, and the connection strength (solder wettability) of the connection material tends to be maintained well.
電極形成用組成物中所含的含鉍粒子的含量相對於玻璃粒子的含量的質量比（Bi/G比）較佳為0.5～15.0，更佳為1.0～12.0，進而佳為1.5～10.0。藉由使Bi/G比為0.5以上，有氧化鉍相的擴散阻擋性有效果地表現出來的傾向。藉由使Bi/G比為15.0以下，有高溫高濕環境下的可靠性有效果地提高的傾向。The mass ratio (Bi/G ratio) of the content of the bismuth-containing particles contained in the composition for electrode formation to the content of the glass particles is preferably from 0.5 to 15.0, more preferably from 1.0 to 12.0, still more preferably from 1.5 to 10.0. By making the Bi/G ratio 0.5 or more, the diffusion barrier property of the bismuth oxide phase tends to be effectively expressed. By making the Bi/G ratio 15.0 or less, the reliability in a high-temperature, high-humidity environment tends to be effectively improved.
（溶劑及樹脂） 電極形成用組成物可包含選自由有溶劑及樹脂所組成的群組中的至少一種。 藉由使電極形成用組成物包含選自由溶劑及樹脂所組成的群組中的至少一種，可將電極形成用組成物的液狀性（黏度、表面張力等）調整到適合於賦予基板等時的賦予方法的範圍內。 電極形成用組成物中所含的溶劑或樹脂可分別僅為一種，亦可為兩種以上。 (solvent and resin) The electrode-forming composition may contain at least one selected from the group consisting of solvents and resins. By making the electrode-forming composition contain at least one selected from the group consisting of solvents and resins, the liquid properties (viscosity, surface tension, etc.) of the electrode-forming composition can be adjusted to be suitable for application to substrates, etc. within the scope of the assigned method. The solvent or resin contained in the electrode-forming composition may be only one kind, or two or more kinds.
作為溶劑，可列舉：己烷、環己烷、甲苯等烴溶劑，二氯乙烯、二氯乙烷、二氯苯等鹵化烴溶劑，四氫呋喃、呋喃、四氫吡喃、吡喃、二噁烷、1,3-二氧雜環戊烷（1,3-dioxolane）、三噁烷等環狀醚溶劑，N,N-二甲基甲醯胺、N,N-二甲基乙醯胺等醯胺溶劑，二甲基亞碸、二乙基亞碸等亞碸溶劑，丙酮、甲基乙基酮、二乙基酮、環己酮等酮溶劑，乙醇、2-丙醇、1-丁醇、二丙酮醇等醇溶劑，2,2,4-三甲基-1,3-戊二醇單乙酸酯、2,2,4-三甲基-1,3-戊二醇單丙酸酯、2,2,4-三甲基-1,3-戊二醇單丁酸酯、乙二醇單丁醚乙酸酯、二乙二醇單丁醚乙酸酯等多元醇的酯溶劑，丁基溶纖劑、二乙二醇單丁醚、二乙二醇二***等多元醇的醚溶劑，α-萜品烯、萜品醇、月桂油烯、別羅勒烯、檸檬烯、雙戊烯、α-蒎烯、β-蒎烯、香旱芹酮、羅勒烯、水芹烯等萜烯溶劑等。Examples of solvents include hydrocarbon solvents such as hexane, cyclohexane, and toluene; halogenated hydrocarbon solvents such as dichloroethylene, dichloroethane, and dichlorobenzene; tetrahydrofuran, furan, tetrahydropyran, pyran, and dioxane. , 1,3-dioxolane (1,3-dioxolane), trioxane and other cyclic ether solvents, N,N-dimethylformamide, N,N-dimethylacetamide, etc. Amide solvents, dimethyl sulfide, diethyl sulfide and other sulfide solvents, acetone, methyl ethyl ketone, diethyl ketone, cyclohexanone and other ketone solvents, ethanol, 2-propanol, 1-butanol Alcohol solvents such as alcohol and diacetone alcohol, 2,2,4-trimethyl-1,3-pentanediol monoacetate, 2,2,4-trimethyl-1,3-pentanediol monopropane Esters of polyols such as acid esters, 2,2,4-trimethyl-1,3-pentanediol monobutyrate, ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, etc. Solvents, butyl cellosolve, diethylene glycol monobutyl ether, diethylene glycol diethyl ether and other polyhydric alcohol ether solvents, α-terpinene, terpineol, laurene, alloocimene, limonene, dipentene , α-pinene, β-pinene, carvone, ocimene, phellandrene and other terpene solvents.
就電極形成用組成物的賦予性（例如，塗佈性或印刷性）的觀點而言，溶劑較佳為包含選自由多元醇的酯溶劑、萜烯溶劑及多元醇的醚溶劑所組成的群組中的至少一種，更佳為包含選自由多元醇的酯溶劑及萜烯溶劑所組成的群組中的至少一種。From the viewpoint of imparting properties (for example, coatability or printability) of the composition for electrode formation, the solvent is preferably a solvent selected from the group consisting of ester solvents of polyols, terpene solvents, and ether solvents of polyols. At least one of the group, more preferably at least one selected from the group consisting of polyol ester solvents and terpene solvents.
樹脂只要是可藉由熱處理進行熱分解的樹脂就並無特別限制，可為天然高分子，亦可為合成高分子。具體而言，可列舉：甲基纖維素、乙基纖維素、羧基甲基纖維素、硝基纖維素等纖維素樹脂，聚乙烯醇化合物，聚乙烯吡咯啶酮化合物，丙烯酸樹脂，乙酸乙烯酯-丙烯酸酯共聚物，聚乙烯丁醛等丁醛樹脂，酚改質醇酸樹脂、蓖麻油脂肪酸改質醇酸樹脂等醇酸樹脂，環氧樹脂，酚樹脂，松香酯樹脂等。The resin is not particularly limited as long as it can be thermally decomposed by heat treatment, and may be a natural polymer or a synthetic polymer. Specifically, cellulose resins such as methylcellulose, ethylcellulose, carboxymethylcellulose, and nitrocellulose, polyvinyl alcohol compounds, polyvinylpyrrolidone compounds, acrylic resins, vinyl acetate - Acrylate copolymers, butyral resins such as polyvinyl butyral, alkyd resins such as phenol-modified alkyd resins, castor oil fatty acid-modified alkyd resins, epoxy resins, phenol resins, rosin ester resins, etc.
就利用熱處理的熱分解性的觀點而言，樹脂較佳為包含選自由纖維素樹脂及丙烯酸樹脂所組成的群組中的至少一種。From the viewpoint of thermal decomposability by heat treatment, the resin preferably contains at least one selected from the group consisting of cellulose resins and acrylic resins.
樹脂的重量平均分子量並無特別限制。其中樹脂的重量平均分子量較佳為5,000～500,000，更佳為10,000～300,000。樹脂的重量平均分子量為5,000以上時，有能夠抑制電極形成用組成物的黏度增加的傾向。可認為其原因例如在於，樹脂吸附於粒子時的立體的排斥作用變得充分，該些樹脂彼此的凝聚得到抑制。另一方面，樹脂的重量平均分子量為500,000以下時，有抑制樹脂彼此在溶劑中凝聚，而能夠抑制電極形成用組成物的黏度增加的傾向。另外，樹脂的重量平均分子量為500,000以下時，有如下傾向：抑制樹脂的燃燒溫度過高而在對電極形成用組成物進行熱處理時不燃燒而作為異物殘留，從而能夠形成更低電阻率的電極。The weight average molecular weight of the resin is not particularly limited. Among them, the weight average molecular weight of the resin is preferably from 5,000 to 500,000, more preferably from 10,000 to 300,000. When the weight average molecular weight of resin is 5,000 or more, it exists in the tendency which can suppress the viscosity increase of the composition for electrode formation. This is considered to be because, for example, the three-dimensional repulsion effect when the resin is adsorbed to the particles becomes sufficient, and the aggregation of these resins is suppressed. On the other hand, when the weight average molecular weight of the resin is 500,000 or less, aggregation of the resins in the solvent is suppressed, and an increase in the viscosity of the electrode-forming composition tends to be suppressed. In addition, when the weight-average molecular weight of the resin is 500,000 or less, there is a tendency that the combustion temperature of the resin is suppressed from being too high, and the composition for forming an electrode is not burned and remains as a foreign substance during heat treatment, so that an electrode with a lower resistivity can be formed. .
重量平均分子量是根據利用凝膠滲透層析法（Gel Permeation Chromatography，GPC）所測定的分子量分佈，使用標準聚苯乙烯的校準曲線進行換算來求出。校準曲線是使用標準聚苯乙烯的5個樣品套組（PStQuick MP-H、PStQuick B，東曹（Tosoh）（股份））並以三維來近似。GPC的測定條件如下所述。 ·裝置：（泵：L-2130型[日立先端科技（Hitachi High-technologies）（股）]）、（檢測器：L-2490型RI[日立先端科技（Hitachi High-technologies）（股）]）、（管柱烘箱：L-2350[日立先端科技（Hitachi High-technologies）（股）]） ·管柱：Gelpack GL-R440+Gelpack GL-R450+Gelpack GL-R400M（共計3根）（昭和電工材料（Materials）（股）） ·管柱尺寸：10.7 mm×300 mm（內徑） ·溶離液：四氫呋喃 ·試樣濃度：10 mg/2 mL ·注入量：200 μL ·流量：2.05 mL/min ·測定溫度：25℃ The weight average molecular weight is obtained by converting the molecular weight distribution measured by gel permeation chromatography (Gel Permeation Chromatography, GPC) using a calibration curve of standard polystyrene. The calibration curve was approximated three-dimensionally using a set of 5 samples of standard polystyrene (PStQuick MP-H, PStQuick B, Tosoh (stock)). The measurement conditions of GPC are as follows. Device: (Pump: L-2130 type [Hitachi High-technologies (Hitachi High-technologies) (stock)]), (Detector: L-2490 type RI [Hitachi High-technologies (Hitachi High-technologies) (stock)]) , (column oven: L-2350 [Hitachi High-technologies (stock)]) ·Column: Gelpack GL-R440+Gelpack GL-R450+Gelpack GL-R400M (3 pieces in total) (Showa Denko Materials (Materials) (stock)) ·Tube size: 10.7 mm×300 mm (inner diameter) Eluent: Tetrahydrofuran ·Sample concentration: 10 mg/2 mL ・Injection volume: 200 μL ·Flow rate: 2.05 mL/min ·Measurement temperature: 25℃
在電極形成用組成物包含溶劑及樹脂的情況下，溶劑及樹脂的含有率可根據電極形成用組成物的所期望的液體物性、所使用的溶劑及樹脂的種類等進行選擇。 例如，溶劑及樹脂的合計含有率較佳為電極形成用組成物整體的3.0質量%～70.0質量%，更佳為20.0質量%～55.0質量%，進而佳為30.0質量%～50.0質量%。 藉由使溶劑及樹脂的合計含有率為所述範圍內，對基板賦予電極形成用組成物時的賦予適應性變得良好，有能夠更容易地形成具有所期望的寬度及高度的電極的傾向。 在電極形成用組成物包含溶劑及樹脂的情況下，溶劑及樹脂的含有比能夠根據所使用的溶劑及樹脂的種類適當選擇，以使電極形成用組成物達到所期望的液體物性。 When the electrode-forming composition contains a solvent and a resin, the contents of the solvent and the resin can be selected according to the desired liquid properties of the electrode-forming composition, the types of solvent and resin used, and the like. For example, the total content of the solvent and the resin is preferably 3.0% by mass to 70.0% by mass of the entire electrode-forming composition, more preferably 20.0% by mass to 55.0% by mass, still more preferably 30.0% by mass to 50.0% by mass. By setting the total content of the solvent and the resin within the above range, the applicability of the application of the electrode-forming composition to the substrate becomes better, and it tends to be easier to form an electrode having a desired width and height. . When the electrode-forming composition contains a solvent and a resin, the content ratio of the solvent and the resin can be appropriately selected according to the types of the solvent and resin used so that the electrode-forming composition has desired liquid properties.
就含銀粒子的燒結性、含鉍粒子的擴散阻擋性、玻璃粒子所帶來的鋁電極的強度及密接性的提高效果等觀點而言，電極形成用組成物中，含銀粒子、含鉍粒子及玻璃粒子的合計含有率較佳為電極形成用組成物整體的30.0質量%～97.0質量%，更佳為45.0質量%～80.0質量%，進而佳為50.0質量%～70.0質量%。In terms of the sinterability of silver-containing particles, the diffusion barrier properties of bismuth-containing particles, and the effect of improving the strength and adhesion of aluminum electrodes by glass particles, in the composition for electrode formation, silver particles, bismuth-containing The total content of particles and glass particles is preferably from 30.0% by mass to 97.0% by mass of the entire electrode-forming composition, more preferably from 45.0% by mass to 80.0% by mass, still more preferably from 50.0% by mass to 70.0% by mass.
（其他成分） 電極形成用組成物除了含有所述成分以外，亦可更含有在該技術領域中通常使用的其他成分。作為其他成分，可列舉塑化劑、分散劑、界面活性劑、增稠劑、無機結合劑、金屬氧化物（氧化鉍除外）、陶瓷、有機金屬化合物等。 (other ingredients) The composition for electrode formation may further contain other components generally used in this technical field in addition to the above-mentioned components. Examples of other components include plasticizers, dispersants, surfactants, thickeners, inorganic binders, metal oxides (excluding bismuth oxide), ceramics, organometallic compounds, and the like.
（電極形成用組成物的製造方法） 電極形成用組成物的製造方法並無特別限制。例如，可藉由將含銀粒子、含鉍粒子、玻璃粒子及根據需要使用的其他成分分散及混合來製造。分散及混合的方法並無特別限制，可自通常使用的方法中選擇來應用。 (Manufacturing method of composition for electrode formation) The method for producing the electrode-forming composition is not particularly limited. For example, it can be produced by dispersing and mixing silver-containing particles, bismuth-containing particles, glass particles, and other components used as necessary. The method of dispersing and mixing is not particularly limited, and can be selected from commonly used methods.
＜鋁/銀積層電極＞ 本揭示的鋁/銀積層電極包含所述本揭示的電極形成用組成物的熱處理物，包括包含鋁的第一電極及配置在所述第一電極上的包含銀的第二電極，所述第一電極更包含氧化鉍相及玻璃相。 ＜Aluminum/Silver Laminated Electrode＞ The aluminum/silver laminated electrode of the present disclosure includes a heat-treated product of the electrode-forming composition of the present disclosure, and includes a first electrode containing aluminum and a second electrode containing silver disposed on the first electrode. An electrode further includes a bismuth oxide phase and a glass phase.
第一電極是否包含氧化鉍相及玻璃相可使用透射型電子顯微鏡來確認。具體而言，藉由結晶Bi 2O 3的格子花紋（原子的排列）的存在可確認氧化鉍相的存在，藉由非晶特有的組織的存在可確認玻璃相的存在。透射型電子顯微鏡的放大倍率例如設定為幾十萬倍。 Whether or not the first electrode contains a bismuth oxide phase and a glass phase can be confirmed using a transmission electron microscope. Specifically, the presence of a bismuth oxide phase can be confirmed by the presence of a lattice pattern (arrangement of atoms) of crystalline Bi 2 O 3 , and the presence of a glass phase can be confirmed by the presence of an amorphous structure. The magnification of the transmission electron microscope is set to several hundred thousand times, for example.
所述結構的鋁/銀積層電極較佳為配置在構成太陽電池元件的基板上，更佳為配置在相當於太陽電池元件的背面的一側。 本揭示中，「基板上」亦包括形成在基板表面上的鈍化膜、鈍化膜的保護膜等膜上。 The aluminum/silver laminated electrode of the above structure is preferably arranged on the substrate constituting the solar cell element, more preferably on the side corresponding to the back side of the solar cell element. In the present disclosure, "on the substrate" also includes a passivation film formed on the surface of the substrate, a protective film of the passivation film, and the like.
包含鋁的第一電極的厚度（在厚度不固定的情況下為最小厚度）例如可為0.5 μm～50.0 μm的範圍。 包含銀的第二電極的厚度（在厚度不固定的情況下為最小厚度）例如可為0.5 μm～30.0 μm的範圍。 The thickness (minimum thickness if the thickness is not fixed) of the first electrode containing aluminum may be in the range of 0.5 μm to 50.0 μm, for example. The thickness (minimum thickness if the thickness is not constant) of the second electrode containing silver may be, for example, in the range of 0.5 μm to 30.0 μm.
所述結構的鋁/銀積層電極例如可使用所述的電極形成用組成物來製造。
利用圖1對使用電極形成用組成物製造的鋁/銀積層電極及包含該鋁/銀積層電極的太陽電池元件的結構的一例進行說明。再者，鋁/銀積層電極的實施方式不限於此。
另外，各圖中的構件的大小為概念性，構件之間的大小的相對關係不限定於此。再者，在所有附圖中對實質上具有相同功能的構件標注相同的符號，並且有時省略重複的說明。
圖1是使用電極形成用組成物製作的PERC結構的太陽電池元件的背面電極的剖面示意圖。如圖1所示，在半導體基板1的表面依次形成鈍化膜18及保護膜19（SiN
X），在其上形成有鋁電極（亦稱為鋁粒子燒結部）5及鋁/銀積層電極8。
鋁/銀積層電極8包括鋁電極與銀電極（亦稱為銀粒子燒結部）積層的部位。例如，可在鋁/銀積層電極8的最表面形成銀粒子燒結部。另外，鋁電極5與構成鋁/銀積層電極8的鋁電極可同時形成。
An aluminum/silver laminated electrode having the above-mentioned structure can be produced, for example, using the above-mentioned electrode-forming composition. An example of the structure of an aluminum/silver laminated electrode manufactured using the electrode-forming composition and a solar cell element including the aluminum/silver laminated electrode will be described with reference to FIG. 1 . In addition, the embodiments of the aluminum/silver laminated electrode are not limited thereto. In addition, the size of members in each figure is conceptual, and the relative relationship of sizes between members is not limited thereto. In addition, in all drawings, the same code|symbol is attached|subjected to the member which has substantially the same function, and duplicative description may be abbreviate|omitted. FIG. 1 is a schematic cross-sectional view of a rear surface electrode of a PERC-structured solar cell element fabricated using an electrode-forming composition. As shown in FIG. 1, a
（鋁/銀積層電極的製造方法） 使用電極形成用組成物製造鋁/銀積層電極的方法並無特別限制。 例如，可列舉依次實施如下步驟的方法：在半導體基板上形成含鋁粒子的膜的步驟、將電極形成用組成物賦予在含鋁粒子的膜上並根據需要進行乾燥的步驟、對含鋁粒子的膜及電極形成用組成物進行熱處理的步驟。 (Manufacturing method of aluminum/silver laminated electrode) The method of producing an aluminum/silver laminated electrode using the electrode-forming composition is not particularly limited. For example, a method of sequentially implementing the following steps: a step of forming a film containing aluminum particles on a semiconductor substrate; The step of heat-treating the film and electrode-forming composition.
含鋁粒子的膜可形成在成膜有鈍化膜及保護膜（SiN X）的半導體基板上。另外，含鋁粒子的膜可將賦予到半導體基板上的鋁電極形成組成物乾燥而形成。半導體基板可為矽（Si）基板。作為使用鋁電極形成用組成物在半導體基板上形成含鋁粒子的膜時的、賦予鋁電極形成用組成物的方法，可列舉網版印刷法、噴墨法、分注器法（dispenser method）等，就生產率的觀點而言，較佳為網版印刷法。作為賦予鋁電極形成用組成物後的乾燥條件，可適用本技術領域中通常使用的熱處理條件。 A film containing aluminum particles can be formed on a semiconductor substrate on which a passivation film and a protective film (SiN x ) are formed. In addition, the film containing aluminum particles can be formed by drying the aluminum electrode-forming composition provided on the semiconductor substrate. The semiconductor substrate may be a silicon (Si) substrate. Examples of the method of applying the composition for forming an aluminum electrode when forming a film containing aluminum particles on a semiconductor substrate using the composition for forming an aluminum electrode include a screen printing method, an inkjet method, and a dispenser method. etc. From the viewpoint of productivity, the screen printing method is preferable. As drying conditions after applying the composition for forming an aluminum electrode, heat treatment conditions generally used in this technical field can be applied.
作為將電極形成用組成物賦予到含鋁粒子的膜上的方法，可列舉網版印刷法、噴墨法、分注器法等，就生產率的觀點而言，較佳為網版印刷法。Examples of methods for applying the electrode-forming composition to the aluminum particle-containing film include screen printing, inkjet, and dispenser methods, and screen printing is preferred from the viewpoint of productivity.
當藉由網版印刷法將電極形成用組成物賦予至含鋁粒子的膜上時，電極形成用組成物較佳為膏狀。膏狀的電極形成用組成物較佳為具有20 Pa·s～1000 Pa·s的範圍的黏度。再者，電極形成用組成物的黏度是使用布魯克菲爾德（Brookfield）HBT黏度計於25℃下進行測定。When the composition for electrode formation is applied to the film containing aluminum particles by a screen printing method, the composition for electrode formation is preferably in the form of a paste. The paste-like electrode-forming composition preferably has a viscosity in the range of 20 Pa·s to 1000 Pa·s. In addition, the viscosity of the composition for electrode formation was measured at 25 degreeC using the Brookfield (Brookfield) HBT viscometer.
電極形成用組成物對含鋁粒子的膜的賦予量可根據形成的電極的大小適當選擇。例如，作為電極形成用組成物的賦予量，可設為1.0 mg/cm 2～20.0 mg/cm 2，較佳為2.0 mg/cm 2～15.0 mg/cm 2。 The amount of the electrode-forming composition to be applied to the aluminum particle-containing film can be appropriately selected according to the size of the electrode to be formed. For example, the amount of the composition for electrode formation can be set at 1.0 mg/cm 2 to 20.0 mg/cm 2 , preferably 2.0 mg/cm 2 to 15.0 mg/cm 2 .
另外，作為使用電極形成用組成物形成鋁/銀積層電極時的熱處理條件，可應用本技術領域中通常使用的熱處理條件。作為熱處理溫度，可較佳地使用製造一般的結晶矽系太陽電池元件時使用的700℃～900℃的範圍。 另外，熱處理時間可根據熱處理溫度適當選擇，例如可設為1秒～20秒。 In addition, as heat treatment conditions when forming an aluminum/silver laminated electrode using the composition for electrode formation, the heat treatment conditions normally used in this technical field can be applied. As the heat treatment temperature, the range of 700° C. to 900° C. used in the production of general crystalline silicon-based solar cell elements can be preferably used. In addition, the heat treatment time can be appropriately selected according to the heat treatment temperature, and can be set to, for example, 1 second to 20 seconds.
作為熱處理裝置，只要是可加熱至所述溫度的裝置，則可適宜採用，可列舉紅外線加熱爐、隧道式爐等。紅外線加熱爐因將電能以電磁波的形式投入至加熱材料中，並將電能轉換成熱能，故效率高，另外，可進行更短時間內的快速加熱。進而，由燃燒所生成的產物少，另外，其為非接觸加熱，因此可抑制所生成的電極的污染。隧道式爐自動地將試樣自入口連續地朝出口搬送，並進行熱處理，因此可藉由爐體的劃分與搬送速度的控制來更均勻地進行熱處理。就太陽電池元件的發電性能的觀點而言，適宜的是藉由隧道式爐來進行熱處理。As the heat treatment device, any device that can be heated to the above-mentioned temperature can be suitably employed, and an infrared heating furnace, a tunnel furnace, and the like are exemplified. Infrared heating furnaces are highly efficient because they input electric energy into the heating material in the form of electromagnetic waves and convert the electric energy into heat energy. In addition, they can perform rapid heating in a shorter period of time. Furthermore, there are few products generated by combustion, and since this is non-contact heating, contamination of generated electrodes can be suppressed. The tunnel furnace automatically and continuously transports the sample from the entrance to the exit for heat treatment, so the heat treatment can be performed more uniformly by dividing the furnace body and controlling the transport speed. From the viewpoint of the power generation performance of the solar cell element, it is preferable to perform heat treatment in a tunnel furnace.
以下，參照附圖說明鋁/銀積層電極的製造方法的具體例。其中，本揭示不限於此。代表性的鋁/銀積層電極的製造方法的一例如圖2A～圖2C所示。Hereinafter, a specific example of a method for manufacturing an aluminum/silver laminated electrode will be described with reference to the drawings. However, the present disclosure is not limited thereto. An example of a typical manufacturing method of an aluminum/silver laminated electrode is shown in FIGS. 2A to 2C .
首先，如圖2A所示，在成膜有鈍化膜18及保護膜（SiN
X）19的半導體基板1的其中一個面上，利用網版印刷法塗佈膏狀的鋁電極形成用組成物2。將其在150℃左右的溫度下加熱，除去鋁電極形成用組成物2中的溶劑。藉此，如圖2B所示，在成膜有鈍化膜18及保護膜（SiN
X）19的半導體基板1上形成含鋁粒子的膜3。
其次，在含鋁粒子的膜3上的期望的區域塗佈電極形成用組成物4，將其在150℃左右的溫度下加熱，進行乾燥。再者，在電極形成用組成物4為膏狀的情況下，與鋁電極形成用組成物2同樣，利用網版印刷法來塗佈。然後，在所述條件下對其進行熱處理。藉此，如圖2C所示，鋁/銀積層電極8形成在成膜有鈍化膜18及保護膜（SiN
X）19的半導體基板1上。
鋁/銀積層電極8在最表面配置銀粒子燒結部7，在銀粒子燒結部7與成膜有鈍化膜18及保護膜（SiN
X）19的半導體基板1之間配置鋁粒子燒結部/氧化鉍相混合部6。
First, as shown in FIG. 2A , on one surface of a
圖3放大地示出了圖2C中的鋁/銀積層電極的形成部位。如圖3所示，鋁粒子燒結部/氧化鉍相混合部6包含鋁粒子燒結部5及填充在鋁粒子燒結部5的空隙部的氧化鉍相9。鋁粒子燒結部/氧化鉍相混合部6之所以具有此種結構的原因在於，如上所述，電極形成用組成物4中的含鉍粒子的一部分或整體藉由熱處理轉移至含鋁粒子的膜3。FIG. 3 is an enlarged view showing the formation site of the aluminum/silver laminated electrode in FIG. 2C. As shown in FIG. 3 , the aluminum particle sintered part/bismuth oxide phase
氧化鉍相9可以隔開銀粒子燒結部7與鋁粒子燒結部5的方式配置，亦可部分地形成鋁粒子燒結部5中的鋁粒子與銀粒子燒結部7接觸的部位。在此種情況下，較佳為以抑制鋁粒子與銀粒子的過度相互擴散的程度，以隔開銀粒子燒結部7與鋁粒子燒結部5的方式配置氧化鉍相9。
在圖3中，鋁粒子燒結部/氧化鉍相混合部6相當於包含鋁的第一電極，銀粒子燒結部7相當於包含銀的第二電極。另外，氧化鉍相9中亦包含玻璃相。
The
＜太陽電池元件＞ 本揭示的太陽電池元件具有半導體基板、設置在所述半導體基板上的鈍化膜、及設置在所述鈍化膜上的所述本揭示的包含電極形成用組成物的熱處理物的鋁/銀積層電極。 ＜Solar Cell Elements＞ The solar cell element of the present disclosure has a semiconductor substrate, a passivation film provided on the semiconductor substrate, and an aluminum/silver laminated electrode of the present disclosure that includes a heat-treated product of an electrode-forming composition provided on the passivation film .
根據需要，所述太陽電池元件亦可包括用於保護設置在半導體基板上的鈍化膜的保護膜。作為鈍化膜，具體可列舉氧化鋁膜（AlO X）。作為保護膜具體可列舉氮化矽膜（SiN X）。 所述太陽電池元件的鋁/銀積層電極亦可設置在半導體基板的背面。另外，所述太陽電池元件亦可具有PERC結構。 If necessary, the solar cell element may also include a protective film for protecting a passivation film provided on the semiconductor substrate. As a passivation film, an aluminum oxide film ( AlOx ) is mentioned specifically. Specific examples of the protective film include silicon nitride films (SiN x ). The aluminum/silver laminated electrode of the solar cell element can also be arranged on the back of the semiconductor substrate. In addition, the solar cell element may also have a PERC structure.
以下，參照附圖說明太陽電池元件的結構的具體例，但本揭示不限於此。將代表性的太陽電池元件的一例示於圖4、圖5A、圖5B、圖6A、圖6B及圖6C。Hereinafter, specific examples of the structure of the solar cell element will be described with reference to the drawings, but the present disclosure is not limited thereto. An example of a typical solar cell element is shown in FIG. 4, FIG. 5A, FIG. 5B, FIG. 6A, FIG. 6B, and FIG. 6C.
圖4是太陽電池元件的受光面側的概略平面圖。圖4所示的受光面電極14一般使用銀電極膏形成。具體而言，在防反射膜13上以期望的圖案賦予銀電極膏並乾燥後，在大氣中以700℃～900℃左右進行熱處理，形成受光面電極14。Fig. 4 is a schematic plan view of the light-receiving surface side of the solar cell element. The light-receiving
圖5A是太陽電池元件的背面的概略平面圖。在圖5A所示的太陽電池元件的背面，整面地形成有鋁電極5。圖5B是太陽電池元件的背面中、鋁指狀電極20及鋁匯流條電極21形成於背面的一部分的情況下的概略平面圖。
在太陽電池元件的背面，如上所述，在鋁電極形成用組成物的賦予及乾燥後，以期望的圖案賦予本揭示的電極形成用組成物並進行乾燥。其次，將其在大氣中以700℃～900℃左右進行熱處理，形成鋁/銀積層電極。熱處理可與所述用於形成受光面電極14的熱處理一併進行。
Fig. 5A is a schematic plan view of the back surface of the solar cell element. On the back surface of the solar cell element shown in FIG. 5A , an
如圖6A～圖6C的概略剖面圖所示，在半導體基板1的其中一個面的表面附近形成n
+型擴散層12，在n
+型擴散層12上形成有輸出取出電極14及防反射膜13。
As shown in the schematic cross-sectional views of FIGS. 6A to 6C , an n +
圖6A是圖5A中的A-A'部的切斷面。當A-A'剖面不橫穿背面鈍化膜的開口部時，背面具有圖6A所示的結構。圖6B是圖5B中的B-B'部的切斷面。當B-B'剖面不橫穿背面鈍化膜的開口部時，背面具有圖6B所示的結構。圖6C是圖5B中的C-C'部的切斷面。當C-C'剖面橫穿背面鈍化膜的開口部（鋁指狀電極20）時，背面具有圖6C所示的結構。Fig. 6A is a cross section of AA' portion in Fig. 5A. When the AA' section does not cross the opening of the rear passivation film, the rear surface has the structure shown in FIG. 6A . Fig. 6B is a cross section of the BB' portion in Fig. 5B. When the BB' section does not cross the opening of the rear passivation film, the rear surface has the structure shown in FIG. 6B . FIG. 6C is a cross section of CC' portion in FIG. 5B . When the CC' section crosses the opening of the passivation film (the aluminum finger electrodes 20 ) on the back, the back has the structure shown in FIG. 6C .
如圖6A～圖6C所示，在受光面側，藉由熱處理形成受光面電極14的銀電極膏中所含的玻璃粒子與防反射膜13進行反應（燒穿），受光面電極14與n
+型擴散層12電連接（歐姆接觸）。
在背面側，藉由熱處理，鋁電極5、鋁指狀電極20或鋁匯流條電極21中的鋁擴散到半導體基板1的背面的一部分（利用雷射等除去背面鈍化膜成膜部後的部分），形成p
+型擴散層15，藉此在半導體基板1與鋁電極5之間部分地形成歐姆接觸。
[實施例]
As shown in FIGS. 6A to 6C , on the light-receiving surface side, the glass particles contained in the silver electrode paste that forms the light-receiving
以下，使用實施例及比較例更詳細地說明本揭示的內容，但是本揭示的範圍不限於以下的實施例。Hereinafter, the contents of the present disclosure will be described in more detail using examples and comparative examples, but the scope of the present disclosure is not limited to the following examples.
在以下的實施例中，玻璃粒子的形狀使用掃描型電子顯微鏡（日立先端科技公司（Hitachi High-technologies）、TM-1000）進行觀察來判定。玻璃粒子的體積平均粒徑使用雷射散射繞射法粒度分佈測定裝置（貝克曼-庫爾特（Beckman-Coulter）公司、LS 13 320型、測定波長：632 nm）算出。玻璃粒子的軟化點由使用示差熱-熱重量同時測定裝置（島津製作所股份有限公司，DT-60H）測定的示差熱（DTA）曲線求出。具體而言，在DTA曲線中，可由吸熱部估計軟化點。In the following examples, the shape of the glass particles was observed and determined using a scanning electron microscope (Hitachi High-technologies, TM-1000). The volume average particle diameter of the glass particles was calculated using a laser scattering diffraction particle size distribution analyzer (Beckman-Coulter,
（含硼玻璃粒子的製備） 獲得包含二氧化矽（SiO 2）1.6質量%、氧化硼（B 2O 3）13.4質量%、氧化鉍（Bi 2O 3）84.1質量%及氧化鋰（Li 2O）0.9質量%的含硼玻璃。所獲得的含硼玻璃的軟化點為440℃。 使用所獲得的含硼玻璃，獲得體積平均粒徑為1.1 μm的含硼玻璃粒子。粒子的形狀為大致球狀。 （含磷玻璃粒子的製備） 獲得包含氧化磷（P 2O 5）38.0質量%、氧化錫（SnO）57.0質量%、氧化鋅（ZnO）3.5質量%及氧化鋁（Al 2O 3）1.5質量%的含磷玻璃。所獲得的含磷玻璃的軟化點為340℃。使用含磷玻璃，獲得體積平均粒徑為8.0 μm的含磷玻璃粒子。粒子的形狀為大致球狀。 （含釩-碲玻璃粒子的製備） 獲得包含氧化釩（V 2O 5）24.0質量%、氧化碲（TeO 2）51.2質量%及氧化銀（Ag 2O）24.8質量%的含釩-碲玻璃。所獲得的含釩-碲玻璃的軟化點為270℃。使用含釩-碲玻璃，獲得體積平均粒徑為1.6 μm的含釩-碲玻璃粒子。粒子的形狀為大致球狀。 (Preparation of Boron-Containing Glass Particles) 1.6 mass % of silicon dioxide (SiO 2 ), 13.4 mass % of boron oxide (B 2 O 3 ), 84.1 mass % of bismuth oxide (Bi 2 O 3 ) and lithium oxide (Li 2 O) 0.9% by mass boron-containing glass. The softening point of the obtained boron-containing glass was 440°C. Using the obtained boron-containing glass, boron-containing glass particles having a volume average particle diameter of 1.1 μm were obtained. The shape of the particles was substantially spherical. (Preparation of Phosphorus-Containing Glass Particles) A glass particle containing 38.0% by mass of phosphorus oxide (P 2 O 5 ), 57.0% by mass of tin oxide (SnO), 3.5% by mass of zinc oxide (ZnO), and 1.5% by mass of aluminum oxide (Al 2 O 3 ) was obtained. % phosphorous glass. The softening point of the obtained phosphorus-containing glass was 340°C. Phosphorus-containing glass was used to obtain phosphorous-containing glass particles with a volume average particle diameter of 8.0 μm. The shape of the particles was substantially spherical. (Preparation of vanadium-tellurium-containing glass particles) Vanadium-tellurium-containing glass containing 24.0% by mass of vanadium oxide (V 2 O 5 ), 51.2% by mass of tellurium oxide (TeO 2 ), and 24.8% by mass of silver oxide (Ag 2 O) was obtained. . The obtained vanadium-tellurium-containing glass had a softening point of 270°C. The vanadium-tellurium-containing glass was used to obtain vanadium-tellurium-containing glass particles with a volume average particle diameter of 1.6 μm. The shape of the particles was substantially spherical.
（電極形成用組成物的製備） 以表1所示的量調配表1中記載的成分，使用輥磨機（阿伊麥克（AIMEX）股份有限公司，BR-150HCV）進行混合，製備實施例1～實施例3及比較例的膏狀的電極形成用組成物。表1中記載的成分的詳細情況如以下般。表1的數值為質量份。 (Preparation of composition for electrode formation) The ingredients described in Table 1 were blended in the amounts shown in Table 1, and mixed using a roll mill (AIMEX Co., Ltd., BR-150HCV) to prepare pastes of Examples 1 to 3 and Comparative Examples A composition for forming an electrode. Details of the components described in Table 1 are as follows. The numerical values in Table 1 are parts by mass.
Ag：銀粒子（體積平均粒徑：0.6 μm、銀含有率：99.9質量%） Bi：金屬鉍粒子（體積平均粒徑：1.5 μm、鉍含有率：99.5質量%） Bi 2O 3：氧化鉍粒子（體積平均粒徑：2.2 μm） B玻璃：所述的含硼玻璃粒子 V-Te玻璃：所述的含釩-碲玻璃粒子 P玻璃：所述的含磷玻璃粒子 TPO：萜品醇 乙基纖維素：日新化成股份有限公司，STD-10 Ag: Silver particles (volume average particle diameter: 0.6 μm, silver content: 99.9% by mass) Bi: metallic bismuth particles (volume average particle diameter: 1.5 μm, bismuth content: 99.5% by mass) Bi 2 O 3 : bismuth oxide Particles (volume average particle diameter: 2.2 μm) B glass: the boron-containing glass particles V-Te glass: the vanadium-tellurium-containing glass particles P glass: the phosphorus-containing glass particles TPO: terpineol B Base cellulose: Nisshin Chemical Co., Ltd., STD-10
使用所述獲得的電極形成用組成物，藉由以下方法製作太陽電池元件。
準備在受光面上形成n
+型擴散層、紋理及防反射（SiN
X）膜，在與受光面相反一側的面（以下，亦稱為「背面」）上依次形成有作為鈍化膜的氧化鋁（AlO
X）膜及保護膜（SiN
X）膜、厚度160 μm的p型矽單結晶基板，並切成158.75 mm×158.75 mm的大小。其次，對於背面的鈍化膜/保護膜的一部分，如圖5B所示，利用雷射去除形成鋁指狀電極的部位，使矽基板露出。在受光面上，以成為如圖4所示的電極圖案的方式藉由網版印刷賦予包含銀粒子及鉛玻璃粒子的銀電極形成用組成物（杜邦（Dupont）公司製造、PV20）。實際上，將受光面輸出取出電極14的根數設為9根。將其在250℃的設定溫度及240吋/分鐘的輸送速度的條件下加熱的隧道爐（蒂斯邦（Despatch）公司）中加熱，藉由蒸發除去溶劑。
Using the obtained composition for electrode formation, a solar cell element was produced by the following method. Prepare to form an n + -type diffusion layer, texture, and anti-reflection (SiN X ) film on the light receiving surface. On the surface opposite to the light receiving surface (hereinafter, also referred to as "rear surface"), an oxide film as a passivation film is sequentially formed. Aluminum (AlO X ) film and protective film (SiN X ) film, p-type silicon single crystal substrate with a thickness of 160 μm, and cut into a size of 158.75 mm×158.75 mm. Next, for a part of the passivation film/protective film on the back, as shown in FIG. 5B , the part where the aluminum finger electrodes are formed is removed by laser to expose the silicon substrate. On the light-receiving surface, a composition for forming a silver electrode (manufactured by Dupont, PV20) containing silver particles and lead glass particles was applied by screen printing so as to form an electrode pattern as shown in FIG. 4 . Actually, the number of
繼而，藉由網版印刷將鋁電極形成用組成物（如星（Ruxing）公司、RX8401）及所述獲得的電極形成用組成物以圖5B所示的電極圖案的形狀賦予至矽基板的背面側。實際上，將鋁匯流條電極21的根數設為9根，將每一根鋁匯流條電極21的鋁/銀積層電極的形成部位設為6處。
具體而言，將鋁電極形成用組成物印刷為鋁指狀電極20及鋁匯流條電極21的細線圖案的形狀，進行乾燥而形成含鋁粒子的膜。然後，在含鋁粒子的膜上印刷電極形成用組成物。
鋁指狀電極的形成部位與矽基板露出的部分一致。鋁電極形成用組成物的印刷條件調節成使熱處理後的鋁電極的厚度成為30 μm。使用排列有1.6 mm×8.0 mm尺寸的焊盤形狀的圖案，以8.0 mg/cm
2的塗佈量進行電極形成用組成物的印刷。
分別印刷鋁電極形成用組成物及電極形成用組成物後，在250℃的設定溫度及240吋/分鐘的輸送速度的條件下，在隧道爐（蒂斯邦（Despatch）公司）中加熱，藉由蒸發除去溶劑。
Then, the aluminum electrode-forming composition (such as Ruxing, RX8401) and the obtained electrode-forming composition were applied to the back surface of the silicon substrate in the shape of the electrode pattern shown in FIG. 5B by screen printing. side. Actually, the number of aluminum
繼而，使用隧道爐（蒂斯邦（Despatch）公司）在大氣氣氛下，在最高溫度870℃的設定溫度及240吋/分鐘的輸送速度的條件下進行熱處理，製作了形成有作為背面輸出取出電極的鋁/銀積層電極的太陽電池元件。Then, a tunnel furnace (Despatch Company) was used to conduct heat treatment under the conditions of the maximum temperature of 870°C and the conveying speed of 240 inches/min under the atmospheric atmosphere, and the output electrode formed on the back was fabricated. Aluminum/silver laminated electrodes for solar cell components.
-背面側電極的表面觀察- 根據下述基準，藉由目視觀察所獲得的太陽電池元件的背面側的鋁/銀積層電極的表面狀態。觀察結果如表1所示。若評價為A或B，則可說是能夠作為電極發揮功能的狀態。 A：整體呈現銀白色的狀態 B：在約80%以上的面積中呈現銀白色的狀態 C：銀白色的面積小於80%的狀態 -Surface Observation of Back Side Electrode- The surface state of the aluminum/silver laminated electrode on the back side of the obtained solar cell element was observed visually according to the following criteria. The observation results are shown in Table 1. If the evaluation is A or B, it can be said that it is in a state that can function as an electrode. A: The overall appearance is silvery white B: silvery white in about 80% or more of the area C: A state where the silver-white area is less than 80%
-PL明暗比- 用光致發光（Photoluminescence）法映射所獲得的太陽電池元件的缺陷，進行數值化處理，而計算出PL明暗比。具體而言，以太陽電池元件的受光面側為上表面，使用EL·PL圖像觀察系統（梯愛司（ITES）公司製造的PVX100及可選單元 POPLI V2R）拍攝PL圖像。利用圖像處理軟體（國立衛生研究所（National Institutes of Health）開發的ImageJ），自PL圖像中的鋁/銀積層電極形成部位及電極非形成部位，分別任意對28部位導出了濃淡值。將由下述式（A）獲得的值作為各太陽電池元件的PL明暗比。 （鋁/銀積層電極形成部位的濃淡值的28部位平均值）÷（電極非形成部位的濃淡值的28部位平均值）…式（A） 將由比較例的太陽電池元件求出的PL明暗比的值作為基準（1.00），將由各實施例的太陽電池元件求出的PL明暗比的值除以由比較例的太陽電池元件求出的PL明暗比而得到的值（PL比）示於表1。 -PL light and dark ratio- The defects of the obtained solar cell elements are mapped by the photoluminescence method, and numerically processed to calculate the PL light-dark ratio. Specifically, PL images were captured using an EL·PL image observation system (PVX100 manufactured by ITES and an optional unit POPLI V2R) with the light-receiving surface side of the solar cell element as the upper surface. Using image processing software (ImageJ developed by the National Institutes of Health), shading values were arbitrarily derived for 28 locations from the aluminum/silver laminate electrode formation and electrode non-formation locations in the PL image. Let the value obtained by the following formula (A) be the PL light-dark ratio of each solar cell element. (Average value of 28 parts of the shading value of the aluminum/silver laminated electrode formation part) ÷ (28 part average value of the shading value of the electrode non-forming part)...Formula (A) Taking the value of the PL light-dark ratio obtained from the solar cell element of the comparative example as a reference (1.00), the value of the PL light-dark ratio obtained from the solar cell element of each example was divided by the PL value obtained from the solar cell element of the comparative example. Table 1 shows the values (PL ratio) obtained from the light-to-dark ratio.
-連接強度- 在所獲得的太陽電池元件的鋁/銀積層電極上連接配線材料，藉由剝離試驗測定配線材料的連接強度。 具體而言，將配線材料（奧博銳（Ulbrich）公司、多重接合線（Multi-Tabbing wire）、Sn-Pb系共晶焊料被覆、Cu芯材的尺寸為直徑0.4 mm）載置在鋁/銀積層電極上，自配線材料上按壓烙鐵使焊料熔融，藉此進行連接。其次，使用台式剝離試驗機（島津製作所股份有限公司，EZ-S），將配線材料的拉伸速度設為300 mm/min，將在180°的方向上自鋁/銀積層電極剝離配線材料時的強度設為連接強度（N）。若連接強度為1N以上，則可說在實用上確保了充分的連接強度（焊料的潤濕性）。 連接強度為1N以上時評價為OK（合格），低於1N時評價為NG（不合格）。評價結果如表1所示。 -Connection Strength- A wiring material was connected to the aluminum/silver laminated electrode of the obtained solar cell element, and the connection strength of the wiring material was measured by a peel test. Specifically, a wiring material (Ulbrich, Multi-Tabbing wire, Sn-Pb eutectic solder coating, Cu core material with a diameter of 0.4 mm) was placed on an aluminum/ On the silver-laminated electrode, a soldering iron is pressed from the wiring material to melt the solder, thereby making a connection. Next, using a table-top peeling tester (Shimadzu Corporation, EZ-S), set the tensile speed of the wiring material to 300 mm/min, and peel the wiring material from the aluminum/silver laminated electrode in the direction of 180°. The strength of is set to the connection strength (N). When the connection strength is 1 N or more, it can be said that sufficient connection strength (solder wettability) is practically ensured. When the connection strength was 1N or more, it was evaluated as OK (pass), and when it was less than 1N, it was evaluated as NG (failure). The evaluation results are shown in Table 1.
[表1]
如表1所示，相對於比較例的太陽電池元件，各實施例的太陽電池元件的PL比有所提高。PL比的結果表明，與比較例的太陽電池元件相比，抑制了設置在各實施例的太陽電池元件背面的鈍化層的蝕刻。 另外，可知連接強度在各實施例及比較例中都確保了1N以上，在實用上確保了充分的連接強度（焊料的潤濕性）。 As shown in Table 1, the PL ratio of the solar cell element of each Example was improved compared with the solar cell element of the comparative example. The results of the PL ratio showed that the etching of the passivation layer provided on the back surface of the solar cell element of each example was suppressed compared with the solar cell element of the comparative example. In addition, it can be seen that the connection strength was secured at 1N or more in each of the Examples and Comparative Examples, and a practically sufficient connection strength (solder wettability) was ensured.
將2021年2月16日提出申請的日本專利申請案2021-022878號的揭示的整體藉由參照而併入本說明書中。 關於本說明書中所記載的所有文獻、專利申請案、及技術規格，與具體且各個地記載有藉由參照而併入各個文獻、專利申請案、及技術規格的情況同等程度地，援引並併入本說明書中。 The entire disclosure of Japanese Patent Application No. 2021-022878 for which it applied on February 16, 2021 is incorporated in this specification by reference. All documents, patent applications, and technical specifications described in this specification are cited and incorporated by reference to the same extent as if they were specifically and individually stated to be incorporated by reference. into this manual.
1:半導體基板 2:鋁電極形成用組成物（膏狀） 3:含鋁粒子的膜 4:電極形成用組成物（乾燥前後） 5:鋁粒子燒結部、鋁電極 6:鋁粒子燒結部/氧化鉍相混合部 7:銀粒子燒結部 8:鋁/銀積層電極 9:氧化鉍相 12:n +型擴散層 13:防反射膜 14:受光面電極及輸出取出電極 15:p +型擴散層 18:鈍化膜 19:保護膜（SiN X） 20:鋁指狀電極 21:鋁匯流條電極 1: Semiconductor substrate 2: Aluminum electrode formation composition (paste) 3: Aluminum particle-containing film 4: Electrode formation composition (before and after drying) 5: Aluminum particle sintered part, aluminum electrode 6: Aluminum particle sintered part/ Bismuth oxide phase mixed part 7: silver particle sintered part 8: aluminum/silver laminated electrode 9: bismuth oxide phase 12: n + type diffusion layer 13: antireflection film 14: light receiving surface electrode and output extraction electrode 15: p + type diffusion Layer 18: passivation film 19: protective film (SiN X ) 20: aluminum finger electrodes 21: aluminum bus bar electrodes
圖1是示出太陽電池元件背面的鋁電極及鋁/銀積層電極的剖面的一例的圖。 圖2A是示出鋁/銀積層電極的製造方法的一例的剖面示意圖。 圖2B是示出鋁/銀積層電極的製造方法的一例的剖面示意圖。 圖2C是示出鋁/銀積層電極的製造方法的一例的剖面示意圖。 圖3是鋁/銀積層電極的剖面示意圖。 圖4是示出太陽電池元件的受光面的一例的概略平面圖。 圖5A是示出太陽電池元件的背面的一例的概略平面圖。 圖5B是示出太陽電池元件的背面的一例的概略平面圖。 圖6A是示出太陽電池元件的一例的剖面示意圖（圖5A的A-A'部的切斷面）。 圖6B是示出太陽電池元件的一例的剖面示意圖（圖5B的B-B'部的切斷面）。 圖6C是示出太陽電池元件的一例的剖面示意圖（圖5B的C-C'部的切斷面）。 FIG. 1 is a diagram showing an example of a cross-section of an aluminum electrode and an aluminum/silver laminated electrode on the back surface of a solar cell element. FIG. 2A is a schematic cross-sectional view illustrating an example of a method of manufacturing an aluminum/silver laminated electrode. 2B is a schematic cross-sectional view illustrating an example of a method of manufacturing an aluminum/silver laminated electrode. 2C is a schematic cross-sectional view illustrating an example of a method of manufacturing an aluminum/silver laminated electrode. Fig. 3 is a schematic cross-sectional view of an aluminum/silver laminated electrode. Fig. 4 is a schematic plan view showing an example of a light-receiving surface of a solar cell element. Fig. 5A is a schematic plan view showing an example of the back surface of a solar cell element. 5B is a schematic plan view showing an example of the back surface of the solar cell element. FIG. 6A is a schematic cross-sectional view showing an example of a solar cell element (the cross-sectional plane of portion AA′ in FIG. 5A ). FIG. 6B is a schematic cross-sectional view showing an example of a solar cell element (a cross-section at BB′ in FIG. 5B ). FIG. 6C is a schematic cross-sectional view showing an example of a solar cell element (cross-section along line CC′ in FIG. 5B ).
Claims (17)
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| JP5041323B2 (en) * | 2005-05-09 | 2012-10-03 | 日本電気硝子株式会社 | Powder material and paste material |
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| WO2014014109A1 (en) * | 2012-07-19 | 2014-01-23 | 日立化成株式会社 | Passivation-layer-forming composition, semiconductor substrate having passivation layer, method for manufacturing semiconductor substrate having passivation layer, solar-cell element, method for manufacturing solar-cell element, and solar cell |
| WO2015030199A1 (en) * | 2013-08-30 | 2015-03-05 | 京セラ株式会社 | Solar cell element and method for manufacturing same |
| US9349883B2 (en) * | 2014-06-19 | 2016-05-24 | E I Du Pont De Nemours And Company | Conductor for a solar cell |
| KR102379829B1 (en) * | 2018-02-23 | 2022-03-28 | 엘지전자 주식회사 | Lead-free low temperature calcined glass frit, paste and vacuum glass assembly using the same |
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