TWI743683B - Conductive paste for hjt solar cell, hjt solar cell, and electrode structure - Google Patents

Conductive paste for hjt solar cell, hjt solar cell, and electrode structure Download PDF

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TWI743683B
TWI743683B TW109104646A TW109104646A TWI743683B TW I743683 B TWI743683 B TW I743683B TW 109104646 A TW109104646 A TW 109104646A TW 109104646 A TW109104646 A TW 109104646A TW I743683 B TWI743683 B TW I743683B
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conductive paste
solar cell
metal salt
heterojunction solar
cell according
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TW109104646A
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TW202131355A (en
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陳星君
郭懷仁
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碩禾電子材料股份有限公司
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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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Abstract

A conductive paste for HJT (heterojunction technology) solar cell, a HJT solar cell, and an electrode structure are provided. The conductive paste includes a plurality of conductive particles, a polymerizable resin, and a metal salt. Based on the total weight of the conductive paste, the content of the conductive particles is 75-97 wt%, the content of the polymerizable resin is 2-20 wt%, and the content of the metal salt is 0.05-5 wt%. The metal salt includes a Group IA metal salt, a Group IIA metal salt, or a combination thereof.

Description

用於HJT太陽能電池的導電漿料、HJT太陽能電池與電極結構Conductive paste for HJT solar cell, HJT solar cell and electrode structure

本發明是有關於一種導電漿料，且特別是有關於一種用於異質接面(HJT)太陽能電池的導電漿料、HJT太陽能電池與電極結構。 The present invention relates to a conductive paste, and in particular to a conductive paste used for heterojunction (HJT) solar cells, HJT solar cells and electrode structures.

太陽能電池是一種將太陽光能轉換為電能的裝置，其藉由照射可見光於基板來產生電子與電洞，並透過基板兩側的正、負電極分別引導電子與電洞來形成電流。 A solar cell is a device that converts solar energy into electrical energy. It generates electrons and holes by irradiating visible light on a substrate, and guides the electrons and holes through the positive and negative electrodes on both sides of the substrate to form an electric current.

異質接面太陽能電池是在基板的表面形成有整面透明導電氧化物(TCO)，再經由集線(金屬)電極完成電流的傳遞與輸送，因此如何進一步降低電極本身的電阻、增加其導電率並降低電極與TCO之間的接觸電阻，已成為目前所需研究的重要課題。 Hetero-junction solar cells are formed on the surface of the substrate with a transparent conductive oxide (TCO) on the entire surface, and then through the collector (metal) electrode to complete the current transmission and transportation, so how to further reduce the resistance of the electrode itself, increase its conductivity and Reducing the contact resistance between the electrode and the TCO has become an important subject of current research.

本發明提供一種用於異質接面(HJT)太陽能電池的導電 漿料，其中包含IA族或IIA族金屬鹽，能提高由此種漿料製得的電極的導電性質及電極與TCO的附著力。 The invention provides a conductive material for heterojunction (HJT) solar cells The slurry, which contains the IA or IIA metal salt, can improve the conductivity of the electrode made from the slurry and the adhesion between the electrode and the TCO.

本發明另提供一種異質接面太陽能電池，具有低電阻率與低接觸電阻率之電極，進而提高電極之電性連結並提供高效率之太陽能電池。 The present invention also provides a heterogeneous junction solar cell, which has electrodes with low resistivity and low contact resistivity, thereby improving the electrical connection of the electrodes and providing a high-efficiency solar cell.

本發明再提供一種電極結構，具有優異的導電性及附著力。 The present invention further provides an electrode structure with excellent conductivity and adhesion.

本發明的用於異質接面(HJT)太陽能電池的導電漿料，包括：75wt%~97wt%的導電粒子、2wt%~20wt%的聚合性樹脂與0.05wt%~5wt%的金屬鹽。所述金屬鹽包括IA族金屬鹽、IIA族金屬鹽或其組合。 The conductive paste for heterojunction (HJT) solar cells of the present invention includes: 75wt% to 97wt% of conductive particles, 2wt% to 20wt% of polymerizable resin and 0.05wt% to 5wt% of metal salt. The metal salt includes a group IA metal salt, a group IIA metal salt, or a combination thereof.

在本發明的一實施例中，上述金屬鹽包括有機金屬鹽或無機金屬鹽。 In an embodiment of the present invention, the above-mentioned metal salt includes an organic metal salt or an inorganic metal salt.

在本發明的一實施例中，上述有機金屬鹽包括飽和脂族金屬鹽或不飽和脂族金屬鹽。 In an embodiment of the present invention, the aforementioned organic metal salt includes a saturated aliphatic metal salt or an unsaturated aliphatic metal salt.

在本發明的一實施例中，上述飽和脂族金屬鹽包括2-乙基己酸銫、2-乙基己酸鋇、2-乙基己酸鈣、硬脂酸銫、2-乙基己酸鉀或其組合。 In an embodiment of the present invention, the above-mentioned saturated aliphatic metal salt includes cesium 2-ethylhexanoate, barium 2-ethylhexanoate, calcium 2-ethylhexanoate, cesium stearate, 2-ethylhexanoate Potassium acid or a combination thereof.

在本發明的一實施例中，上述不飽和脂族金屬鹽包括油酸銫、油酸鉀、油酸鋰、油酸鈉、巴豆酸銫或其組合。 In an embodiment of the present invention, the aforementioned unsaturated aliphatic metal salt includes cesium oleate, potassium oleate, lithium oleate, sodium oleate, cesium crotonate, or a combination thereof.

在本發明的一實施例中，上述無機金屬鹽包括金屬氫氧化物、金屬氯化物、金屬碳酸鹽或其組合。 In an embodiment of the present invention, the above-mentioned inorganic metal salt includes metal hydroxide, metal chloride, metal carbonate, or a combination thereof.

在本發明的一實施例中，上述金屬氫氧化物包括氫氧化鋰、氫氧化鉀、氫氧化銫、氫氧化鋇或其組合。 In an embodiment of the present invention, the aforementioned metal hydroxide includes lithium hydroxide, potassium hydroxide, cesium hydroxide, barium hydroxide, or a combination thereof.

在本發明的一實施例中，上述金屬氯化物包括氯化銫。 In an embodiment of the present invention, the aforementioned metal chloride includes cesium chloride.

在本發明的一實施例中，上述金屬碳酸鹽包括碳酸鋰、碳酸鈉、碳酸鉀、碳酸銫、碳酸鋇、碳酸鈣或其組合。 In an embodiment of the present invention, the aforementioned metal carbonate includes lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, barium carbonate, calcium carbonate, or a combination thereof.

在本發明的一實施例中，每100重量份的上述聚合性樹脂中所含的上述金屬鹽之重量份為1.5~25。 In an embodiment of the present invention, the weight part of the metal salt contained in 100 weight parts of the polymerizable resin is 1.5-25.

在本發明的一實施例中，上述導電粒子包括銀、銅、鉑、鈀、金、錫、銦、鋁、鉍、鎳、鋅或其組合。 In an embodiment of the present invention, the aforementioned conductive particles include silver, copper, platinum, palladium, gold, tin, indium, aluminum, bismuth, nickel, zinc, or a combination thereof.

在本發明的一實施例中，上述導電粒子具有0.1μm~10μm的平均粒徑。 In an embodiment of the present invention, the above-mentioned conductive particles have an average particle diameter of 0.1 μm-10 μm.

在本發明的一實施例中，上述聚合性樹脂包括具有單個或多個環氧基團的樹脂、具有羥基的樹脂或其組合。 In an embodiment of the present invention, the above-mentioned polymerizable resin includes a resin having a single or multiple epoxy groups, a resin having a hydroxyl group, or a combination thereof.

在本發明的一實施例中，上述導電漿料還可包括溶劑，且以導電漿料的總重量計，所述溶劑的含量為1wt%~10wt%。 In an embodiment of the present invention, the aforementioned conductive paste may further include a solvent, and based on the total weight of the conductive paste, the content of the solvent is 1 wt% to 10 wt%.

在本發明的一實施例中，上述導電漿料還可包括添加劑，且以導電漿料的總重量計，所述添加劑的含量在5wt%以下。 In an embodiment of the present invention, the aforementioned conductive paste may further include an additive, and the content of the additive is less than 5 wt% based on the total weight of the conductive paste.

在本發明的一實施例中，上述添加劑包括增敏劑(sensitizing agent)、偶合劑(coupling agent)、分散劑(dispersant)、流平劑(levelling agent)、黏度調節劑(viscosity adjuster)、消泡劑(defoaming agent)、觸變劑(thixotropic agent)、安定劑(stabilizer)、介面活性劑(surfactant)、硬化劑(curing agent)、流變助劑(Rheology additive)、樹脂稀釋劑或其組合。 In an embodiment of the present invention, the above-mentioned additives include a sensitizing agent, a coupling agent, a dispersant, a levelling agent, a viscosity adjuster, and a vanishing agent. Defoaming agent, thixotropic agent, stabilizer, surfactant, curing agent agent), rheology additive, resin diluent or a combination thereof.

本發明的異質接面太陽能電池，包括一基板與電極。基板包括至少一透明導電層，電極則形成於透明導電層上，且所述電極為固化上述導電漿料所形成。 The heterojunction solar cell of the present invention includes a substrate and electrodes. The substrate includes at least one transparent conductive layer, the electrode is formed on the transparent conductive layer, and the electrode is formed by curing the above-mentioned conductive paste.

本發明的電極結構，是由上述導電漿料固化所形成。 The electrode structure of the present invention is formed by curing the above-mentioned conductive paste.

在本發明的再一實施例中，上述電極結構，適用於異質接面太陽能電池、觸控面板等裝置。 In still another embodiment of the present invention, the above-mentioned electrode structure is suitable for devices such as heterojunction solar cells and touch panels.

在本發明的上述實施例中，所述固化的溫度例如100℃~350℃。 In the above embodiment of the present invention, the curing temperature is, for example, 100°C to 350°C.

在本發明的上述實施例中，所述固化的時間例如1分鐘至2小時。 In the above-mentioned embodiment of the present invention, the curing time is, for example, 1 minute to 2 hours.

基於上述，本發明的導電漿料包含特定比例範圍的特定成分，因此能降低以此種導電漿料固化得到的電極的電阻率，進而增加導電率。而且，在上述電極與透明導電層之間的接觸電阻也能被降低。此外，經實驗發現部分導電漿料還具有增加電極與透明導電層之間的附著性的特性。具有上述低電阻率與低接觸電阻率之電極的異質接面太陽能電池也因此能提高其效率。另外，上述電極結構也可應用於其他領域中，如觸控面板等。 Based on the above, the conductive paste of the present invention contains specific components in a specific ratio range, and therefore can reduce the electrical resistivity of the electrode obtained by curing the conductive paste, thereby increasing the electrical conductivity. Furthermore, the contact resistance between the above-mentioned electrode and the transparent conductive layer can also be reduced. In addition, it is found through experiments that some conductive pastes also have the characteristic of increasing the adhesion between the electrode and the transparent conductive layer. The heterojunction solar cell with the above-mentioned electrodes with low resistivity and low contact resistivity can also improve its efficiency. In addition, the above-mentioned electrode structure can also be applied to other fields, such as touch panels.

為讓本發明的上述特徵和優點能更明顯易懂，下文特舉實施例，並配合所附圖式作詳細說明如下。 In order to make the above-mentioned features and advantages of the present invention more comprehensible, the following specific embodiments are described in detail in conjunction with the accompanying drawings.

100:異質接面太陽能電池 100: Heterojunction solar cell

102:基板 102: substrate

104a、104b:透明導電層 104a, 104b: transparent conductive layer

106a、106b:電極 106a, 106b: electrodes

108:n型單晶矽基板 108: n-type monocrystalline silicon substrate

110a、110b:i型非晶矽層 110a, 110b: i-type amorphous silicon layer

112:p+型非晶矽層 112: p+ type amorphous silicon layer

114:n+型非晶矽層 114: n+ type amorphous silicon layer

圖1是依照本發明的一實施例的一種異質接面太陽能電池的剖面示意圖。 FIG. 1 is a schematic cross-sectional view of a heterojunction solar cell according to an embodiment of the present invention.

本發明的用於異質接面(HJT)太陽能電池的導電漿料，包括：75wt%~97wt%的導電粒子、2wt%~20wt%的聚合性樹脂與0.05wt%~5wt%的金屬鹽。所述金屬鹽包括IA族金屬鹽、IIA族金屬鹽或其組合。以下將針對本發明的用於HJT太陽能電池的導電漿料中的各成分進行詳細說明。 The conductive paste for heterojunction (HJT) solar cells of the present invention includes: 75wt% to 97wt% of conductive particles, 2wt% to 20wt% of polymerizable resin and 0.05wt% to 5wt% of metal salt. The metal salt includes a group IA metal salt, a group IIA metal salt, or a combination thereof. Hereinafter, each component in the conductive paste for HJT solar cells of the present invention will be described in detail.

〈金屬鹽〉〈Metal Salt〉

在本實施例中，金屬鹽包括IA族金屬鹽、IIA族金屬鹽或其組合。因此，金屬鹽內所含金屬離子包括鋰(Li+)、鈉(Na+)、鉀(K+)、銣(Rb+)、銫(Cs+)、鍅(Fr+)、鈹(Be2+)、鎂(Mg2+)、鈣(Ca2+)、鍶(Sr2+)、鋇(Ba2+)、鐳(Ra2+)。 In this embodiment, the metal salt includes a group IA metal salt, a group IIA metal salt, or a combination thereof. Therefore, the metal ions contained in the metal salt include lithium (Li + ), sodium (Na + ), potassium (K + ), rubidium (Rb + ), cesium (Cs + ), thium (Fr + ), beryllium (Be 2 + ), magnesium (Mg 2+ ), calcium (Ca 2+ ), strontium (Sr 2+ ), barium (Ba 2+ ), radium (Ra 2+ ).

上述金屬鹽可包括有機金屬鹽或無機金屬鹽。若以有機金屬鹽為例，則可列舉但不限於飽和脂族金屬鹽或不飽和脂族金屬鹽，其中不飽和脂族金屬鹽又包含單元不飽和脂族金屬鹽或多元不飽和脂族金屬鹽，從導電漿料的安定性來說，飽和脂族金屬鹽相較於不飽和脂族金屬鹽少了反應性官能基，擁有較穩定的特質及較長的保存期。飽和脂族金屬鹽可列舉但不限於醋酸鈉(Sodium Acetate)、醋酸鉀(Potassium Acetate)、醋酸銫(Cesium Acetate)、醋酸鈣(Calcium Acetate)、醋酸鋇(Barium Acetate)、2-乙基己酸銫(Cesium 2-Ethylhexanoate)、2-乙基己酸鋇(Barium 2-Ethylhexanoate)、2-乙基己酸鉀(Potassium 2-Ethylhexanoate)、2-乙基己酸鈣(Calcium 2-Ethylhexanoate)、棕櫚酸鈉(Sodium Palmitate)、棕櫚酸鉀(Potassium Palmitate)、棕櫚酸銫(Cesium Palmitate)、棕櫚酸鈣(Calcium Palmitate)、棕櫚酸鋇(Barium Palmitate)、硬脂酸銫(Cesium Stearate)、硬脂酸鈣(Calcium Stearate)、硬脂酸鋇(Barium Stearate)、硬脂酸鈉(Sodium Stearate)、硬脂酸鉀(Potassium Stearate)等及其衍生物；更具體而言，飽和脂族金屬鹽較佳為2-乙基己酸銫、2-乙基己酸鋇、2-乙基己酸鈣、硬脂酸銫、2-乙基己酸鉀或其組合。不飽和脂族金屬鹽可列舉但不限於油酸銫(Cesium Oleate)、油酸鉀(Potassium Oleate)、油酸鋰(Lithium Oleate)、油酸鎂(Magnesium Oleate)、油酸鈉(Sodium Oleate)、亞油酸銫(Linoleic acid Cesium)、亞油酸鉀(Linoleic acid Potassium)、亞油酸鋰(Linoleic acid Lithium)、亞油酸鎂(Linoleic acid Magnesium)、亞油酸鈉(Linoleic acid Sodium)、α-亞麻酸銫(α-Linoleic acid Cesium)、α-亞麻酸鉀(α-Linoleic acid Potassium)、α-亞麻酸鋰(α-Linoleic acid Lithium)、α-亞麻酸鎂(α-Linoleic acid Magnesium)、α-亞麻酸鈉(α-Linoleic acid Sodium)、巴豆酸銫(Cesium Crotonate)、巴豆酸鈉(Sodium Crotonate)等及其衍生物；更具體而言，不飽和脂族金屬鹽較佳為油酸銫、油酸鉀、油酸鋰、油酸鈉、巴豆酸 銫或其組合。 The aforementioned metal salt may include an organic metal salt or an inorganic metal salt. If the organic metal salt is taken as an example, it can be exemplified but not limited to saturated aliphatic metal salt or unsaturated aliphatic metal salt, wherein the unsaturated aliphatic metal salt contains unit unsaturated aliphatic metal salt or polyunsaturated aliphatic metal Salt, in terms of the stability of the conductive paste, the saturated aliphatic metal salt has fewer reactive functional groups than the unsaturated aliphatic metal salt, and has more stable characteristics and a longer shelf life. Saturated aliphatic metal salts include but are not limited to sodium acetate (Sodium Acetate), potassium acetate (Potassium Acetate), cesium acetate (Cesium Acetate) Acetate), Calcium Acetate, Barium Acetate, Cesium 2-Ethylhexanoate, Barium 2-Ethylhexanoate, 2-Ethylhexanoate Potassium 2-Ethylhexanoate, Calcium 2-Ethylhexanoate, Sodium Palmitate, Potassium Palmitate, Cesium Palmitate, Calcium Palmitate (Calcium Palmitate), Barium Palmitate, Cesium Stearate, Calcium Stearate, Barium Stearate, Sodium Stearate, Hard Potassium Stearate, etc. and its derivatives; more specifically, the saturated aliphatic metal salt is preferably cesium 2-ethylhexanoate, barium 2-ethylhexanoate, calcium 2-ethylhexanoate, Cesium stearate, potassium 2-ethylhexanoate, or a combination thereof. Unsaturated aliphatic metal salts include, but are not limited to, Cesium Oleate, Potassium Oleate, Lithium Oleate, Magnesium Oleate, Sodium Oleate , Linoleic acid Cesium, Linoleic acid Potassium, Linoleic acid Lithium, Linoleic acid Magnesium, Linoleic acid Sodium , Α-Linoleic acid Cesium, α-Linoleic acid Potassium, α-Linoleic acid Lithium, α-Linoleic acid magnesium (α-Linoleic acid) Magnesium, α-Linoleic acid Sodium, Cesium Crotonate, Sodium Crotonate, etc. and their derivatives; more specifically, unsaturated aliphatic metal salts are preferred Cesium oleate, potassium oleate, lithium oleate, sodium oleate, crotonic acid Cesium or a combination thereof.

上述無機金屬鹽可列舉但不限於金屬氫氧化物(MXOH)、金屬氯化物(MXCl)、金屬碳酸鹽(MXCO3)或其組合，其中M為IA族金屬或IIA族金屬，x則為0.5~2。金屬氫氧化物可列舉但不限於氫氧化鋰、氫氧化鈉、氫氧化鉀、氫氧化銣、氫氧化銫、氫氧化鍅、氫氧化鈹、氫氧化鎂、氫氧化鈣、氫氧化鍶、氫氧化鋇、氫氧化鐳等及其衍生物；更具體而言，金屬氫氧化物較佳為氫氧化鋰、氫氧化鉀、氫氧化銫、氫氧化鋇或其組合。金屬氯化物可列舉但不限於氯化鋰、氯化鈉、氯化鉀、氯化銣、氯化銫、氯化鍅、氯化鈹、氯化鎂、氯化鈣、氯化鍶、氯化鋇、氯化鐳等及其衍生物；更具體而言，金屬氯化物較佳為氯化銫。金屬碳酸鹽可列舉但不限於碳酸鋰、碳酸鈉、碳酸鉀、碳酸銣、碳酸銫、碳酸鍅、碳酸鈹、碳酸鎂、碳酸鈣、碳酸鍶、碳酸鋇、碳酸鐳等及其衍生物；更具體而言，金屬碳酸鹽較佳為碳酸鋰、碳酸鈉、碳酸鉀、碳酸銫、碳酸鋇、碳酸鈣或其組合。無機金屬鹽不限於水溶液，也能溶於醇類等其他溶劑。 The above-mentioned inorganic metal salts include, but are not limited to, metal hydroxides (M X OH), metal chlorides (M X Cl), metal carbonates (M X CO 3 ) or combinations thereof, where M is a group IA metal or a group IIA For metals, x is 0.5~2. Metal hydroxides include but are not limited to lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, thorium hydroxide, beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, hydrogen Barium oxide, radium hydroxide, etc. and their derivatives; more specifically, the metal hydroxide is preferably lithium hydroxide, potassium hydroxide, cesium hydroxide, barium hydroxide or a combination thereof. Metal chlorides include, but are not limited to, lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, thorium chloride, beryllium chloride, magnesium chloride, calcium chloride, strontium chloride, barium chloride, Radium chloride, etc. and its derivatives; more specifically, the metal chloride is preferably cesium chloride. Metal carbonates include, but are not limited to, lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, thorium carbonate, beryllium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, radium carbonate, etc. and their derivatives; Specifically, the metal carbonate is preferably lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, barium carbonate, calcium carbonate, or a combination thereof. Inorganic metal salts are not limited to aqueous solutions, but can also be dissolved in other solvents such as alcohols.

而且，有機金屬鹽可直接使用市售品或者利用上述無機金屬鹽與有機酸混合反應得到，且可適時添加溶劑進行混合。在一實施例中，有機酸可含2~26個碳的有機酸，更佳是含有8~20個碳的有機酸。前述有機酸可列舉但不限於飽和脂肪酸類的棕櫚酸、醋酸、硬脂酸；或者不飽和脂肪酸類的2-乙基己酸、油酸、亞油酸、α-亞麻酸、巴豆酸等。 Furthermore, the organic metal salt can be obtained by directly using a commercially available product or by mixing and reacting the above-mentioned inorganic metal salt with an organic acid, and a solvent can be added and mixed at an appropriate time. In one embodiment, the organic acid may be an organic acid containing 2 to 26 carbons, and more preferably an organic acid containing 8 to 20 carbons. The aforementioned organic acids include, but are not limited to, palmitic acid, acetic acid, and stearic acid of saturated fatty acids; or 2-ethylhexanoic acid, oleic acid, linoleic acid, α-linolenic acid, and crotonic acid of unsaturated fatty acids.

以導電漿料的總重量計，金屬鹽的含量是在0.05wt%~5wt%之間，例如有機金屬鹽是0.1wt%~2wt%之間或無機金屬鹽是0.05wt%~1wt%之間。若是以每100重量份的上述聚合性樹脂中所含的上述金屬鹽之重量份(即PHR)來看，例如是在1.5~25之間。 Based on the total weight of the conductive paste, the content of the metal salt is between 0.05wt% and 5wt%, for example, the organic metal salt is between 0.1wt% and 2wt% or the inorganic metal salt is between 0.05wt% and 1wt%. . If viewed in terms of parts by weight (ie PHR) per 100 parts by weight of the above-mentioned metal salt contained in the above-mentioned polymerizable resin, it is, for example, between 1.5-25.

〈聚合性樹脂〉〈Polymerizable resin〉

在本實施例中，聚合性樹脂在導電漿料固化後仍會存在於固化物中，其可作為黏結導電粒子與導電粒子以及/或者導電粒子與其下方基板的黏合劑。以導電漿料的總重量計，聚合性樹脂的含量是2wt%~20wt%之間，較佳是2.5wt%~10wt%之間，例如是3wt%~5wt%之間。更詳細而言，聚合性樹脂可列舉但不限於具有單個或多個環氧基團的樹脂、具有羥基的樹脂或其組合。 In this embodiment, the polymerizable resin will still exist in the cured product after the conductive paste is cured, and it can be used as an adhesive for bonding the conductive particles and the conductive particles and/or the conductive particles and the underlying substrate. Based on the total weight of the conductive paste, the content of the polymerizable resin is between 2wt% and 20wt%, preferably between 2.5wt% and 10wt%, for example between 3wt% and 5wt%. In more detail, the polymerizable resin includes, but is not limited to, a resin having a single or multiple epoxy groups, a resin having a hydroxyl group, or a combination thereof.

上述具有單個或多個環氧基團的樹脂是熱固性樹脂，可列舉但不限於雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚A酚醛環氧樹脂、苯酚醛環氧樹脂、鄰甲酚醛環氧樹脂、多官能基環氧樹脂、聚氨酯改性環氧樹脂、矽改性環氧樹脂等；若是使用市售品，則可選自長春化工的BE系列、BFE系列、BNE系列、PNE系列、CNE系列、TFE系列等；或選自南亞化工的NPEL系列、NPEF系列、NPPN系列、NPPN系列、NPCN系列等。 The above-mentioned resins with single or multiple epoxy groups are thermosetting resins, including but not limited to bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol A novolac epoxy resins, and phenol novolac epoxy resins. , O-cresol epoxy resin, multifunctional epoxy resin, polyurethane modified epoxy resin, silicon modified epoxy resin, etc.; if commercially available products are used, they can be selected from the BE series, BFE series, and BNE of Changchun Chemical Industry Series, PNE series, CNE series, TFE series, etc.; or selected from Nanya Chemical's NPEL series, NPEF series, NPPN series, NPPN series, NPCN series, etc.

上述具有羥基的樹脂可列舉但不限於聚乙烯醇縮丁醛樹脂(PVB)、聚乙烯醇(PVA)、聚甲基丙烯酸甲酯樹脂(PMMA)、甲基丙烯酸甲酯(MMA)、苯酚甲醛樹脂(PF)、萜烯酚醛樹脂、醛酮樹 脂等；若是使用市售品，則可選自Mowital的PVB樹脂；或選自長春化工的PF系列。添加具有羥基的樹脂能增加導電漿料之穩定性與導電性。 The above-mentioned resins with hydroxyl groups include but are not limited to polyvinyl butyral resin (PVB), polyvinyl alcohol (PVA), polymethyl methacrylate resin (PMMA), methyl methacrylate (MMA), phenol formaldehyde Resin (PF), terpene phenolic resin, aldehyde ketone tree Grease, etc.; if commercially available products are used, they can be selected from Mowital's PVB resin; or from Changchun Chemical's PF series. Adding a resin with hydroxyl groups can increase the stability and conductivity of the conductive paste.

此外，除上述聚合性樹脂之外，還可添加其他樹脂，如三聚氰胺樹脂、尿素甲醛樹脂、聚酯樹脂、醇酸樹脂等，但本發明並不限於此。 In addition, other resins such as melamine resin, urea-formaldehyde resin, polyester resin, alkyd resin, etc. may be added in addition to the above-mentioned polymerizable resin, but the present invention is not limited to this.

〈導電粒子〉〈Conductive particles〉

在本實施例中，導電粒子例如銀、銅、鉑、鈀、金、錫、銦、鋁、鉍、鎳、鋅或其組合；較佳為銀粒子。導電粒子例如具有0.1μm~10μm的平均粒徑。導電粒子的形狀可包含片狀、球形、柱狀、塊狀或符合尺寸之無特定形狀。以導電漿料的總重量計，導電粒子的含量例如75wt%~97wt%之間，較佳是85wt%~95wt%之間。 In this embodiment, the conductive particles are, for example, silver, copper, platinum, palladium, gold, tin, indium, aluminum, bismuth, nickel, zinc or a combination thereof; preferably silver particles. The conductive particles have, for example, an average particle diameter of 0.1 μm to 10 μm. The shape of the conductive particles may include flake, spherical, columnar, massive or non-specific shapes corresponding to the size. Based on the total weight of the conductive paste, the content of conductive particles is, for example, between 75 wt% and 97 wt%, preferably between 85 wt% and 95 wt%.

〈溶劑〉〈Solvent〉

在本實施例中，導電漿料還可包括溶劑，且以導電漿料的總重量計，溶劑的含量例如1wt%~10wt%。溶劑的作用為溶解聚合性樹脂與金屬鹽，以使導電漿料均勻混合並具有黏度，溶劑可列舉但不限於醇類溶劑、醚類溶劑、酯類溶劑、醚醇類溶劑等，例如二乙二醇單丁醚(Diethylene Glycol Monobutyl Ether，DB)、三乙二醇單丁醚(Triethylene glycol monobutyl ether，TB)、二乙二醇丁醚醋酸酯(Butyl Carbitol Acetate，BCA)、松油醇(Terpineol)、Texanol、乙酸丁酯(Butyl Acetate)、二甘醇二*** (Diethylene glycol diethyl ether)、乙二醇單丁醚(2-Butoxyethanol)或其組合。 In this embodiment, the conductive paste may further include a solvent, and based on the total weight of the conductive paste, the content of the solvent is, for example, 1 wt% to 10 wt%. The role of the solvent is to dissolve the polymerizable resin and the metal salt, so that the conductive paste is uniformly mixed and has viscosity. The solvent can include but is not limited to alcohol solvents, ether solvents, ester solvents, ether alcohol solvents, etc., such as diethyl Diethylene Glycol Monobutyl Ether (DB), Triethylene glycol monobutyl ether (TB), Butyl Carbitol Acetate (BCA), Terpineol ( Terpineol), Texanol, Butyl Acetate, Diethylene Glycol Diethyl Ether Diethylene glycol diethyl ether, 2-Butoxyethanol, or a combination thereof.

〈添加劑〉<additive>

在本實施例中，導電漿料還可包括添加劑。添加劑的作用為改善導電漿料的性質，且以導電漿料的總重量計，添加劑的含量例如在5wt%以下，如1wt%~5wt%。添加劑可列舉但不限於增敏劑、偶合劑、分散劑、流平劑、黏度調節劑、消泡劑、觸變劑、安定劑、介面活性劑、硬化劑、流變助劑、樹脂稀釋劑或其組合。 In this embodiment, the conductive paste may further include additives. The role of the additive is to improve the properties of the conductive paste, and based on the total weight of the conductive paste, the content of the additive is, for example, below 5 wt%, such as 1 wt% to 5 wt%. Additives include, but are not limited to, sensitizers, coupling agents, dispersants, leveling agents, viscosity regulators, defoamers, thixotropic agents, stabilizers, interface active agents, hardeners, rheology additives, resin diluents Or a combination.

上述偶合劑可列舉但不限於含乙烯基、環氧基、苯乙烯、甲基丙烯醯氧基、丙烯醯氧基、氨基、異氰酸鹽等的矽烷偶合劑。若是使用市售品，則可選自信越的KBM-1003、KBE-1003、KBM-403、KBE-403、KBM-503、KBE-502等；或者選自道康寧的OFS-6300、OFS-6020、OFS-6030、OFS-6040、OFS-6011等。 The above-mentioned coupling agents include, but are not limited to, silane coupling agents containing vinyl groups, epoxy groups, styrene, methacryloxy groups, acryloxy groups, amino groups, and isocyanates. If you are using commercially available products, you can choose more confident KBM-1003, KBE-1003, KBM-403, KBE-403, KBM-503, KBE-502, etc.; or from Dow Corning's OFS-6300, OFS-6020, OFS-6030, OFS-6040, OFS-6011, etc.

上述介面活性劑可列舉但不限於脂肪酸類的油酸、亞油酸、α-亞麻酸、亞麻油、2-乙基己酸、氫化蓖麻油、蓖麻油、硬脂酸、棕櫚酸等。 The above-mentioned surfactants include, but are not limited to, fatty acids such as oleic acid, linoleic acid, α-linolenic acid, linseed oil, 2-ethylhexanoic acid, hydrogenated castor oil, castor oil, stearic acid, palmitic acid, and the like.

上述硬化劑可列舉但不限於咪唑(imidazole)型硬化劑、胺(amine)型硬化劑、酐類(anhydrides)硬化劑等的環氧樹脂硬化劑；若是使用市售品，則可選自四國化成的2E4MZ-CN、雙氰胺等。 The above-mentioned hardeners include, but are not limited to, imidazole-type hardeners, amine-type hardeners, anhydrides-type hardeners, and other epoxy resin hardeners; if commercially available products are used, they can be selected from four Guohua Cheng's 2E4MZ-CN, dicyandiamide, etc.

上述樹脂稀釋劑可列舉但不限於己二醇二縮水甘油醚等的環氧樹脂稀釋劑。 Examples of the above-mentioned resin diluent include, but are not limited to, epoxy resin diluents such as hexanediol diglycidyl ether.

圖1是依照本發明的一實施例的一種異質接面太陽能電池的剖面示意圖。而且，圖式僅以說明為目的，並未依照原尺寸比例作圖。 FIG. 1 is a schematic cross-sectional view of a heterojunction solar cell according to an embodiment of the present invention. Moreover, the drawings are for illustrative purposes only, and are not drawn in accordance with the original scale.

請參照圖1，異質接面太陽能電池100包括一基板102與在基板102兩面的電極106a、106b。基板102例如以n型單晶矽基板108為中心，其上下分別具有i型非晶矽層110a與110b，並在i型非晶矽層110a表面具有p+型非晶矽層112、在i型非晶矽層110b表面具有n+型非晶矽層114、在p+型非晶矽層112表面具有透明導電層104a、在n+型非晶矽層114表面具有透明導電層104b。然而，本發明並不限於此，基板102也可以由不同導電態或結晶態的半導體材料構成，或透明導電層可僅設置在基板102的一面，例如用於背接觸式太陽能電池(Back Contact Solar Cell)。 Please refer to FIG. 1, the heterojunction solar cell 100 includes a substrate 102 and electrodes 106 a and 106 b on both sides of the substrate 102. The substrate 102, for example, is centered on an n-type single crystal silicon substrate 108, which has i-type amorphous silicon layers 110a and 110b above and below, respectively, and has a p+-type amorphous silicon layer 112 on the surface of the i-type amorphous silicon layer 110a. The amorphous silicon layer 110b has an n+ type amorphous silicon layer 114 on the surface, a transparent conductive layer 104a on the surface of the p+ type amorphous silicon layer 112, and a transparent conductive layer 104b on the surface of the n+ type amorphous silicon layer 114. However, the present invention is not limited to this. The substrate 102 may also be composed of semiconductor materials with different conductivity or crystalline states, or the transparent conductive layer may only be provided on one side of the substrate 102, for example, used for back contact solar cells (Back Contact Solar). Cell).

透明導電層104a、104b，指具有優異透明性及導電性材料所製成之薄膜，例如金屬粒子、金屬奈米線、導電性聚合物、或碳材料，具體範例例如金屬粒子為銦錫氧化物(ITO)或其他適合的材料，金屬奈米線例如為銀奈米線或其他適合材料，碳材料例如為奈米碳管或石墨烯等其他適合材料。在另一實施例中，透明導電層104a與n型單晶矽基板108之間還可根據需求增加其他功能性膜層，譬如鈍化層或抗反射層等。 The transparent conductive layers 104a and 104b refer to films made of materials with excellent transparency and conductivity, such as metal particles, metal nanowires, conductive polymers, or carbon materials. Specific examples are indium tin oxide. (ITO) or other suitable materials, the metal nanowires are, for example, silver nanowires or other suitable materials, and the carbon materials are, for example, carbon nanotubes or other suitable materials such as graphene. In another embodiment, between the transparent conductive layer 104a and the n-type single crystal silicon substrate 108, other functional layers, such as a passivation layer or an anti-reflection layer, can be added as required.

電極106a和106b則分別形成於透明導電層104a與104b上。在本實施例中，電極106a和106b是經由固化上一實施例中的導電漿料所形成的，且固化的溫度可約為100℃~350℃，較佳 為150℃~300℃；固化的時間可為1分鐘至2小時，例如30分鐘至1小時。另外，固化的方式可列舉但不限於熱風循環式固化或紅外線固化。若為熱風循環式固化，製程參數可為150℃~250℃以及20分鐘至60分鐘；若為紅外線固化，製程參數可為200℃~300℃以及1分鐘至10分鐘。 The electrodes 106a and 106b are formed on the transparent conductive layers 104a and 104b, respectively. In this embodiment, the electrodes 106a and 106b are formed by curing the conductive paste in the previous embodiment, and the curing temperature may be about 100°C to 350°C, preferably It is 150°C~300°C; the curing time can be 1 minute to 2 hours, for example, 30 minutes to 1 hour. In addition, the curing method may include, but is not limited to, hot air circulation curing or infrared curing. If it is hot air circulation curing, the process parameters can be 150℃~250℃ and 20 minutes to 60 minutes; if it is infrared curing, the process parameters can be 200℃~300℃ and 1 minute to 10 minutes.

在其他實施例中，上述透明導電層104a、104b與電極106a、106b也可形成於其他裝置的表面作為電極結構，例如觸控面板等。由於電極106a、106b是經由固化上述實施例中的導電漿料所形成的，所以能降低電極106a、106b的電阻率，進而增加導電率。而且，在電極106a與透明導電層104a/電極106b與透明導電層104b之間的接觸電阻都會被降低。而且，電極106a透明導電層104a之間以及電極106b透明導電層104b之間的附著性也有改善的機會。 In other embodiments, the transparent conductive layers 104a, 104b and the electrodes 106a, 106b can also be formed on the surface of other devices as electrode structures, such as touch panels. Since the electrodes 106a and 106b are formed by curing the conductive paste in the above embodiment, the resistivity of the electrodes 106a and 106b can be reduced, thereby increasing the conductivity. Moreover, the contact resistance between the electrode 106a and the transparent conductive layer 104a/the electrode 106b and the transparent conductive layer 104b will be reduced. Moreover, the adhesion between the transparent conductive layers 104a of the electrodes 106a and the transparent conductive layers 104b of the electrodes 106b may also be improved.

以下列舉實驗來驗證本發明的功效，但本發明並不侷限於以下的內容。 The following experiments are listed to verify the efficacy of the present invention, but the present invention is not limited to the following content.

〈原料〉<raw material>

1.聚合性樹脂 1. Polymerizable resin

聚合性樹脂1：長春化工所售的酚醛環氧樹脂CNE200ELF。 Polymeric resin 1: Novolac epoxy resin CNE200ELF sold by Changchun Chemical Industry.

聚合性樹脂2：長春化工所售的線性酚醛樹脂PF-5090。 Polymerizable resin 2: Novolac resin PF-5090 sold by Changchun Chemical Industry.

2.導電粒子 2. Conductive particles

導電粒子1：平均粒徑為3μm~5μm的片狀銀粉 Conductive particles 1: flake silver powder with an average particle size of 3μm~5μm

導電粒子2：平均粒徑為2μm的球狀銀粉 Conductive particles 2: Spherical silver powder with an average particle size of 2μm

導電粒子3：平均粒徑為0.8μm~1μm的球狀銀粉 Conductive particles 3: Spherical silver powder with an average particle size of 0.8μm~1μm

3-1.無機金屬鹽 3-1. Inorganic metal salt

AQS-1：10wt%的氫氧化鉀水溶液 AQS-1: 10wt% potassium hydroxide aqueous solution

AQS-2：10wt%的氫氧化銫水溶液 AQS-2: 10wt% cesium hydroxide aqueous solution

AQS-3：10wt%的氫氧化鋇水溶液 AQS-3: 10wt% barium hydroxide aqueous solution

AQS-4：22.5wt%的氫氧化鉀水溶液 AQS-4: 22.5wt% potassium hydroxide aqueous solution

AQS-5：22.5wt%的氫氧化銫水溶液 AQS-5: 22.5wt% cesium hydroxide aqueous solution

AQS-6：0.5wt%的氯化銫水溶液 AQS-6: 0.5wt% cesium chloride aqueous solution

AQS-7：40wt%的碳酸銫水溶液 AQS-7: 40wt% cesium carbonate aqueous solution

3-2.有機金屬鹽(以下有機金屬鹽若未加異丙醇(IPA)，則以Thinky ARM-310行星式攪拌機，轉速2000rpm進行5分鐘混合得到；若所選脂肪酸於室溫下為固體時，另加異丙醇將其溶解以促進反應，並在室溫磁石攪拌4小時後，置於熱風循環烘箱60℃烘乾48小時，以去除異丙醇) 3-2. Organometallic salt (If the following organometallic salt is not added with isopropyl alcohol (IPA), it can be obtained by mixing with Thinky ARM-310 planetary mixer at 2000rpm for 5 minutes; if the selected fatty acid is solid at room temperature At the time, add isopropanol to dissolve it to promote the reaction, and after stirring at room temperature for 4 hours, place it in a hot air circulating oven at 60°C for 48 hours to remove the isopropanol)

FAS-1：10克 碳酸鋰+80克 油酸 FAS-1: 10 grams of lithium carbonate + 80 grams of oleic acid

FAS-2：10克 碳酸鉀+40克 油酸 FAS-2: 10 grams of potassium carbonate + 40 grams of oleic acid

FAS-3：10克 碳酸銫+20克 油酸 FAS-3: 10 grams of cesium carbonate + 20 grams of oleic acid

FAS-4：20克 碳酸銫+10克 油酸 FAS-4: 20 grams of cesium carbonate + 10 grams of oleic acid

FAS-5：20克 碳酸銫+10克 硬脂酸+30克 異丙醇 FAS-5: 20g cesium carbonate+10g stearic acid+30g isopropanol

FAS-6：20克 碳酸銫+10克 2-乙基己酸 FAS-6: 20 grams of cesium carbonate + 10 grams of 2-ethylhexanoic acid

FAS-7：10克 碳酸銫+20克 巴豆酸+30克 異丙醇 FAS-7: 10g cesium carbonate+20g crotonic acid+30g isopropanol

FAS-8：10克 碳酸鉀+20克 2-乙基己酸 FAS-8: 10 grams of potassium carbonate + 20 grams of 2-ethylhexanoic acid

FAS-9：30克 碳酸鋇+40克 2-乙基己酸 FAS-9: 30 grams of barium carbonate + 40 grams of 2-ethylhexanoic acid

FAS-10：10克 碳酸鈣+20克 2-乙基己酸 FAS-10: 10 grams of calcium carbonate + 20 grams of 2-ethylhexanoic acid

FAS-11：油酸鈉(97%)，售自Sigma Aldrich FAS-11: Sodium oleate (97%), sold from Sigma Aldrich

FAS-12：10克 碳酸鈉+50克 油酸 FAS-12: 10 grams of sodium carbonate + 50 grams of oleic acid

FAS-13：10克 醋酸銀+20克 硬脂酸+40克 異丙醇 FAS-13: 10g silver acetate+20g stearic acid+40g isopropanol

〈實驗例〉<Experimental example>

將上述原料根據表1~表6的比例先將溶劑、樹脂、金屬鹽及添加劑以行星式攪拌機預先混合，再加入導電粒子重新以行星式攪拌機均勻混合，然後以三滾筒進行分散研磨，即可得到不同的導體漿料。計算混合後的導體漿料的金屬離子濃度時，包含其可能產生的二氧化碳與水。而且，有添加異丙醇配製的導體漿料，計算金屬離子濃度時，包含其可能產生的二氧化碳與水但不含異丙醇。因此，據以上條件計算所得之金屬離子濃度略低於實際值，一併將其記載於表1。 Pre-mix the solvent, resin, metal salt and additives with a planetary mixer according to the ratio of the above raw materials according to Table 1 to Table 6, then add conductive particles and mix them evenly with a planetary mixer, and then disperse and grind with three drums. Different conductive pastes are obtained. When calculating the metal ion concentration of the mixed conductive paste, the carbon dioxide and water that may be generated are included. In addition, there is a conductive paste prepared with isopropanol. When calculating the metal ion concentration, it contains the carbon dioxide and water that it may generate, but does not contain isopropanol. Therefore, the metal ion concentration calculated based on the above conditions is slightly lower than the actual value, and it is recorded in Table 1.

Figure 109104646-A0305-02-0016-1
Figure 109104646-A0305-02-0017-3
 表1~6中的PHR是每100重量份的樹脂所含的金屬鹽重量份。
Figure 109104646-A0305-02-0016-1
Figure 109104646-A0305-02-0017-3
 The PHR in Tables 1 to 6 is the weight part of the metal salt per 100 parts by weight of the resin.

Figure 109104646-A0305-02-0017-4
Figure 109104646-A0305-02-0017-4

Figure 109104646-A0305-02-0017-5
Figure 109104646-A0305-02-0017-5
Figure 109104646-A0305-02-0018-6
Figure 109104646-A0305-02-0018-6

Figure 109104646-A0305-02-0018-7
Figure 109104646-A0305-02-0018-7
Figure 109104646-A0305-02-0019-8
Figure 109104646-A0305-02-0019-8

Figure 109104646-A0305-02-0019-9
Figure 109104646-A0305-02-0019-9

Figure 109104646-A0305-02-0019-10
Figure 109104646-A0305-02-0019-10
Figure 109104646-A0305-02-0020-11
Figure 109104646-A0305-02-0020-11

〈電性分析〉〈Electrical Analysis〉

將上述實驗例製備的導電漿料網印塗佈於表面為SiNx之單晶矽晶圓基板上並乾燥後，再以熱風循環200℃的溫度持續30分鐘進行固化得到細線電極。細線電極的圖案規格是中間線段寬度50μm長度4.6cm，頭尾接觸墊(contact pad)為2mm×2mm大小，然後使用HIOKI 3540微電阻計測量細線電極電阻，並使用Zeta 20 3D立體顯微鏡量測細線電極截面積，以便藉由「電阻率=細線電極電阻×細線電極截面積÷細線電極長度」的公式得到電阻率(ρ)，並記載於下表7。 The conductive paste prepared in the above experimental example was screen-printed coated on a single crystal silicon wafer substrate with SiNx on the surface and dried, and then cured by circulating hot air at a temperature of 200° C. for 30 minutes to obtain a thin wire electrode. The pattern specification of the thin wire electrode is 50μm in the middle and 4.6cm in length, and the contact pads are 2mm×2mm in size. Then the resistance of the thin wire electrode is measured with a HIOKI 3540 micro-resistance meter, and the thin wire is measured with a Zeta 20 3D stereo microscope. The cross-sectional area of the electrode is used to obtain the resistivity (ρ) by the formula of "resistivity = thin wire electrode resistance x thin wire electrode cross-sectional area ÷ thin wire electrode length", and record it in Table 7 below.

另外，將上述實驗例製備的導電漿料塗佈於基板之TCO上並乾燥後，再以熱風循環200℃的溫度持續30分鐘進行固化得到電極圖案。電極圖案是由5條線寬為0.7mm長度為40mm的線型電極組成，且線距為3.3mm，然後以HIOKI 3540微電阻計測量不同間距線型電極之間的電阻後，電阻值搭配線型電極間距離，以傳輸線模型法(TLM)求得與基板之接觸電阻率(ρC)，並記載於下 表7。因接觸電阻率會隨測試圖案的大小、間距等而有不同數值，所以此處傾向以相對值而非實際值來呈現。 In addition, the conductive paste prepared in the above experimental example was coated on the TCO of the substrate and dried, and then cured by circulating hot air at a temperature of 200° C. for 30 minutes to obtain an electrode pattern. The electrode pattern is composed of 5 linear electrodes with a line width of 0.7mm and a length of 40mm, and the line spacing is 3.3mm. After measuring the resistance between the line electrodes at different spacings with a HIOKI 3540 micro-resistance meter, the resistance value is matched between the line electrodes The distance is calculated by the transmission line model method (TLM) to obtain the contact resistivity (ρ C ) with the substrate, and is recorded in Table 7 below. Since the contact resistivity will have different values depending on the size and spacing of the test pattern, it tends to be presented here as relative values rather than actual values.

〈附著性分析〉<Adhesion Analysis>

將上述實驗例製備的導電漿料塗佈於基板上並乾燥後，再以熱風循環200℃的溫度持續30分鐘進行固化得到測試電極。測試電極的圖案規格是長度5cm寬度0.2cm，然後將寬度為0.9mm的鍍錫銅焊帶焊接到測試電極上。將基板固定於拉力計平台上進行剝離強度的測試，其中拉力計型號是AIKOH RX-20電子式推拉力計，測試條件是以角度180°速度300mm/min剝離焊帶並取得拉力值，每0.2秒紀錄一個數值。所得拉力為5cm長度電極之平均值，結果同樣記載於下表7。其中，所得拉力值大於拉力機最小測試值(0.1N)者以所測得數值表示；拉力測試時焊帶未直接脫落，平均剝離強度小於拉力機最小測試值者以「+」表示；一經拉動即整條焊帶脫落者以「-」表示。 After the conductive paste prepared in the above experimental example was coated on the substrate and dried, the hot air was circulated at a temperature of 200° C. for 30 minutes for curing to obtain a test electrode. The pattern specification of the test electrode is 5 cm in length and 0.2 cm in width, and then a tin-plated copper solder tape with a width of 0.9 mm is welded to the test electrode. Fix the substrate on the tension meter platform to test the peel strength. The model of the tension meter is AIKOH RX-20 electronic push-pull meter. The test condition is to peel off the solder tape at an angle of 180° at a speed of 300mm/min and obtain a tensile force value, every 0.2 Record a value every second. The obtained tensile force is the average value of 5 cm length electrodes, and the results are also described in Table 7 below. Among them, the obtained tensile force value is greater than the minimum test value of the tensile machine (0.1N) is represented by the measured value; the welding tape does not fall off directly during the tensile test, and the average peel strength is less than the minimum test value of the tensile machine is represented by "+"; once pulled That is, if the entire welding strip falls off, it is indicated by "-".

Figure 109104646-A0305-02-0021-12
Figure 109104646-A0305-02-0022-13
 比較例2因對ITO的附著力極差，致無法量測其接觸電阻率的程度。
Figure 109104646-A0305-02-0021-12
Figure 109104646-A0305-02-0022-13
 Comparative Example 2 has extremely poor adhesion to ITO, so the degree of contact resistivity cannot be measured.

從表7可得到，與不含金屬鹽或含其他族金屬鹽的導電漿料相比，含有IA族金屬鹽或IIA族金屬鹽的導電漿料能明顯降低電阻率(ρ)與接觸電阻率(ρC)，甚至有部分含有IA或IIA族金屬鹽的導電漿料能增加其所製得的電極的附著性。 It can be seen from Table 7 that compared with the conductive paste containing no metal salt or other group metal salt, the conductive paste containing the IA group metal salt or the IIA group metal salt can significantly reduce the resistivity (ρ) and contact resistivity (ρ C ), even some conductive pastes containing IA or IIA metal salts can increase the adhesion of the electrodes made by them.

〈HJT太陽能電池效率〉〈HJT solar cell efficiency〉

製作一個六吋N型HJT太陽能基板，係將實驗例14和17的導電漿料塗佈於ITO層表面，經由溫度為200℃、時間為0.5小時的熱風循環固化，於基板表面形成電極。正面電極是由5條寬0.7mm的主柵加上101條寬28μm的細柵所組成；背面電極是由5條寬0.9mm的主柵加上180條寬70μm的細柵所組成。 A six-inch N-type HJT solar substrate was fabricated. The conductive pastes of Experimental Examples 14 and 17 were coated on the surface of the ITO layer and cured by hot air circulation at a temperature of 200°C for 0.5 hours to form electrodes on the surface of the substrate. The front electrode is composed of 5 main grids with a width of 0.7mm and 101 thin grids with a width of 28μm; the back electrode is composed of 5 main grids with a width of 0.9mm and 180 thin grids with a width of 70μm.

然後，進行光電轉換效率的測試，並將測得的開路電壓(VOC，open circuit voltage)、短路電流(ISC，short circuit current)、填充因子(FF，fill factor)以及光電轉換效率(NCell)的結果記載於下表8。 Then, the photoelectric conversion efficiency test is performed, and the measured open circuit voltage (V OC , open circuit voltage), short circuit current (I SC , short circuit current), fill factor (FF, fill factor), and photoelectric conversion efficiency (NCell ) The results are shown in Table 8 below.

Figure 109104646-A0305-02-0023-14
Figure 109104646-A0305-02-0023-14

從表8可得到，本發明的導電漿料可使HJT太陽能電池具有高開路電壓、高短路電流、高填充因子及高光電轉換效率。 It can be obtained from Table 8 that the conductive paste of the present invention can make HJT solar cells have high open circuit voltage, high short circuit current, high fill factor and high photoelectric conversion efficiency.

綜上所述，本發明提供一種用於HJT太陽能電池的導電漿料，其中包含特定含量範圍的成分，因此將其形成於透明導電層表面，可改善電極結構的電性，進而提升HJT太陽能電池的光電轉換效率。 In summary, the present invention provides a conductive paste for HJT solar cells, which contains a specific content range of ingredients, so it is formed on the surface of the transparent conductive layer, which can improve the electrical properties of the electrode structure, thereby enhancing the HJT solar cell The photoelectric conversion efficiency.

雖然本發明已以實施例揭露如上，然其並非用以限定本發明，任何所屬技術領域中具有通常知識者，在不脫離本發明的 精神和範圍內，當可作些許的更動與潤飾，故本發明的保護範圍當視後附的申請專利範圍所界定者為準。 Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention. Anyone with ordinary knowledge in the relevant technical field will not depart from the present invention. Within the spirit and scope, some changes and modifications can be made, so the scope of protection of the present invention shall be subject to those defined by the attached patent scope.

100:異質接面太陽能電池100: Heterojunction solar cell

102:基板102: substrate

104a、104b:透明導電層104a, 104b: transparent conductive layer

106a、106b:電極106a, 106b: electrodes

108:n型單晶矽基板108: n-type monocrystalline silicon substrate

110a、110b:i型非晶矽層110a, 110b: i-type amorphous silicon layer

112:p型非晶矽層112: p-type amorphous silicon layer

114:n型非晶矽層114: n-type amorphous silicon layer

Claims (23)

一種用於異質接面(HJT)太陽能電池的導電漿料，包括：75wt%~97wt%的導電粒子；2wt%~20wt%的聚合性樹脂；以及0.05wt%~5wt%的金屬鹽，所述金屬鹽內所含金屬離子包括鋰、鈉、鉀、銫、鈣、鋇或其組合。 A conductive paste for heterojunction (HJT) solar cells, comprising: 75wt%~97wt% conductive particles; 2wt%~20wt% polymerizable resin; and 0.05wt%~5wt% metal salt. The metal ions contained in the metal salt include lithium, sodium, potassium, cesium, calcium, barium or a combination thereof. 如請求項1所述的異質接面太陽能電池的導電漿料，其中所述金屬鹽包括有機金屬鹽或無機金屬鹽。 The conductive paste for a heterojunction solar cell according to claim 1, wherein the metal salt includes an organic metal salt or an inorganic metal salt. 如請求項2所述的異質接面太陽能電池的導電漿料，其中所述有機金屬鹽包括飽和脂族金屬鹽或不飽和脂族金屬鹽。 The conductive paste for a heterojunction solar cell according to claim 2, wherein the organic metal salt includes a saturated aliphatic metal salt or an unsaturated aliphatic metal salt. 如請求項3所述的異質接面太陽能電池的導電漿料，其中所述飽和脂族金屬鹽包括2-乙基己酸銫(Cesium 2-Ethylhexanoate)、2-乙基己酸鋇(Barium 2-Ethylhexanoate)、2-乙基己酸鈣(Caleium 2-Ethylhexanoate)、硬脂酸銫(Cesium Stearate)、2-乙基己酸鉀(Potassium 2-Ethylhexanoate)或其組合。 The conductive paste for a heterojunction solar cell according to claim 3, wherein the saturated aliphatic metal salt includes cesium 2-Ethylhexanoate (Cesium 2-Ethylhexanoate), barium 2-ethylhexanoate (Barium 2 -Ethylhexanoate, Caleium 2-Ethylhexanoate, Cesium Stearate, Potassium 2-Ethylhexanoate, or a combination thereof. 如請求項3所述的異質接面太陽能電池的導電漿料，其中所述不飽和脂族金屬鹽包括油酸銫(Cesium Oleate)、油酸鉀(Potassium Oleate)、油酸鋰(Lithium Oleate)、油酸鈉(Sodium Oleate)、巴豆酸銫(Cesium Crotonate)或其組合。 The conductive paste for a heterojunction solar cell according to claim 3, wherein the unsaturated aliphatic metal salt includes cesium oleate (Cesium Oleate), potassium oleate (Potassium Oleate), lithium oleate (Lithium Oleate) , Sodium Oleate, Cesium Crotonate, or a combination thereof. 如請求項2所述的異質接面太陽能電池的導電漿料，其中所述無機金屬鹽包括金屬氫氧化物、金屬氯化物、金屬碳酸鹽或其組合。 The conductive paste for a heterojunction solar cell according to claim 2, wherein the inorganic metal salt includes metal hydroxide, metal chloride, metal carbonate, or a combination thereof. 如請求項6所述的異質接面太陽能電池的導電漿料，其中所述金屬氫氧化物包括氫氧化鋰、氫氧化鉀、氫氧化銫、氫氧化鋇或其組合。 The conductive paste for a heterojunction solar cell according to claim 6, wherein the metal hydroxide includes lithium hydroxide, potassium hydroxide, cesium hydroxide, barium hydroxide, or a combination thereof. 如請求項6所述的異質接面太陽能電池的導電漿料，其中所述金屬氯化物包括氯化銫。 The conductive paste for a heterojunction solar cell according to claim 6, wherein the metal chloride includes cesium chloride. 如請求項6所述的異質接面太陽能電池的導電漿料，其中所述金屬碳酸鹽包括碳酸鋰、碳酸鈉、碳酸鉀、碳酸銫、碳酸鋇、碳酸鈣或其組合。 The conductive paste for a heterojunction solar cell according to claim 6, wherein the metal carbonate includes lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, barium carbonate, calcium carbonate, or a combination thereof. 如請求項1所述的異質接面太陽能電池的導電漿料，其中每100重量份的所述聚合性樹脂中所含的所述金屬鹽的重量份為1.5~25。 The conductive paste for a heterojunction solar cell according to claim 1, wherein the weight part of the metal salt contained in 100 parts by weight of the polymerizable resin is 1.5-25. 如請求項1所述的異質接面太陽能電池的導電漿料，其中所述導電粒子包括銀、銅、鉑、鈀、金、錫、銦、鋁、鉍、鎳、鋅或其組合。 The conductive paste for a heterojunction solar cell according to claim 1, wherein the conductive particles include silver, copper, platinum, palladium, gold, tin, indium, aluminum, bismuth, nickel, zinc, or a combination thereof. 如請求項1所述的異質接面太陽能電池的導電漿料，其中所述導電粒子具有0.1μm~10μm的平均粒徑。 The conductive paste for a heterojunction solar cell according to claim 1, wherein the conductive particles have an average particle diameter of 0.1 μm to 10 μm. 如請求項1所述的異質接面太陽能電池的導電漿料，其中所述聚合性樹脂包括具有單個或多個環氧基團的樹脂、具有羥基的樹脂或其組合。 The conductive paste for a heterojunction solar cell according to claim 1, wherein the polymerizable resin includes a resin having a single or multiple epoxy groups, a resin having a hydroxyl group, or a combination thereof. 如請求項1所述的異質接面太陽能電池的導電漿料，更包括溶劑，且以所述導電漿料的總重量計，所述溶劑的含量為1wt%~10wt%。 The conductive paste for a heterojunction solar cell according to claim 1, further comprising a solvent, and based on the total weight of the conductive paste, the content of the solvent is 1 wt% to 10 wt%. 如請求項1所述的異質接面太陽能電池的導電漿料，更包括添加劑，且以所述導電漿料的總重量計，所述添加劑的含量在5wt%以下。 The conductive paste for a heterojunction solar cell according to claim 1, further comprising an additive, and based on the total weight of the conductive paste, the content of the additive is less than 5 wt%. 如請求項15所述的異質接面太陽能電池的導電漿料，其中所述添加劑包括增敏劑、偶合劑、分散劑、流平劑、黏度調節劑、消泡劑、觸變劑、安定劑、介面活性劑、硬化劑、流變助劑、樹脂稀釋劑或其組合。 The conductive paste for heterojunction solar cells according to claim 15, wherein the additives include sensitizers, coupling agents, dispersants, leveling agents, viscosity regulators, defoamers, thixotropic agents, stabilizers , Interface surfactants, hardeners, rheology additives, resin diluents or combinations thereof. 一種異質接面太陽能電池，包括：一基板，所述基板包括至少一透明導電層；以及電極，形成於所述透明導電層上，且所述電極為固化如請求項1~16中任一所述的導電漿料所形成。 A heterogeneous junction solar cell, comprising: a substrate, the substrate comprising at least one transparent conductive layer; and an electrode formed on the transparent conductive layer, and the electrode is cured according to any one of claims 1-16 The conductive paste is formed. 如請求項17所述的異質接面太陽能電池，其中所述固化的溫度為100℃~350℃。 The heterojunction solar cell according to claim 17, wherein the curing temperature is 100°C to 350°C. 如請求項17所述的異質接面太陽能電池，其中所述固化的時間為1分鐘至2小時。 The heterojunction solar cell according to claim 17, wherein the curing time is 1 minute to 2 hours. 一種電極結構，係由如請求項1~16中任一所述的導電漿料固化所形成。 An electrode structure formed by curing the conductive paste as described in any one of claims 1-16. 如請求項20所述的電極結構，適用於異質接面太陽能電池或觸控面板。 The electrode structure described in claim 20 is suitable for heterojunction solar cells or touch panels. 如請求項20所述的電極結構，其中所述固化的溫度為100℃~350℃。 The electrode structure according to claim 20, wherein the curing temperature is 100°C to 350°C. 如請求項20所述的電極結構，其中所述固化的時間為1分鐘至2小時。 The electrode structure according to claim 20, wherein the curing time is 1 minute to 2 hours.
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