TWI673726B - Conductive composition, semiconductor element and solar cell element - Google Patents
Conductive composition, semiconductor element and solar cell element Download PDFInfo
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- TWI673726B TWI673726B TW105100219A TW105100219A TWI673726B TW I673726 B TWI673726 B TW I673726B TW 105100219 A TW105100219 A TW 105100219A TW 105100219 A TW105100219 A TW 105100219A TW I673726 B TWI673726 B TW I673726B
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- conductive composition
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/40—Glass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier
- H01L31/068—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells
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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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/547—Monocrystalline silicon PV cells
Abstract
本發明提供一種導電性組成物，其可進行印刷時的電極圖案的細線化以及高縱橫比化，且電極圖案的斷線或意外的電阻上升得到抑制。藉由本發明來提供用以形成電極的導電性組成物。該導電性組成物包含導電性粉末、玻璃料、矽酮樹脂、有機黏合劑、以及分散介質。而且，玻璃料的經氧化物換算時的SiO2成分的比例為0質量%以上、5質量%以下。 The present invention provides a conductive composition capable of thinning and high aspect ratio of an electrode pattern during printing, and suppressing disconnection of the electrode pattern or an unexpected increase in resistance. The present invention provides a conductive composition for forming an electrode. The conductive composition includes a conductive powder, a glass frit, a silicone resin, an organic binder, and a dispersion medium. In addition, the ratio of the SiO 2 component at the time of oxide conversion of the glass frit is 0 mass% or more and 5 mass% or less.
Description
本發明是有關於一種導電性組成物。更詳細而言，是有關於一種可用於形成太陽電池的電極圖案的導電性組成物。 The present invention relates to a conductive composition. More specifically, the present invention relates to a conductive composition that can be used to form an electrode pattern of a solar cell.
本申請案主張基於2015年1月7日提出申請的日本專利申請2015-001855號的優先權，所述申請案的全部內容作為參照而併入本說明書中。 This application claims priority based on Japanese Patent Application No. 2015-001855 filed on January 7, 2015, and the entire contents of the application are incorporated herein by reference.
就近年來的環境意識的提高或省能量的觀點而言，太陽電池的普及急速推進，隨之，要求較先前而言更高性能的單元結構、即光電轉換效率良好且高功率的單元結構的太陽電池。作為用以實現該要求的一個方案，可列舉擴大太陽電池的每單元單位面積的受光面積的方法。例如，作為用以擴大受光面積的一個方法，期望形成於受光面上的線狀電極的細線化(細實線(fine line)化)。 From the standpoint of improvement of environmental awareness or energy saving in recent years, the spread of solar cells is rapidly advancing, and as a result, a higher-performance cell structure, that is, a solar cell with a high photoelectric conversion efficiency and a high-power cell structure, is required. battery. One way to achieve this requirement is a method of increasing the light receiving area per unit area of a solar cell. For example, as one method for increasing the light-receiving area, thinning (fine line) of linear electrodes formed on the light-receiving surface is desired.
於目前成為主流的所謂結晶矽型太陽電池的受光面上，典型而言，設置有包含由銀等電導體所形成的細線的指狀(集電用)電極、以及與該指狀電極連接的匯流排電極。以下，亦將該些電極統稱為受光面電極。此種受光面電極含有作為導體成分的銀等導電性粉末、以及包含有機黏合劑及溶劑的有機媒液(vehicle)成分，藉由將製備成膏狀(包含漿料狀、油墨狀)的 材料(以下亦稱為「導電性組成物」，簡稱為「組成物」等)，利用網版印刷法等方法，以既定的電極圖案印刷於太陽電池(單元)的受光面上，進行煅燒而形成。作為與為了形成此種太陽電池的受光面電極而使用的導電性組成物相關的現有技術，例如可列舉專利文獻1~專利文獻3。 On the light-receiving surface of a so-called crystalline silicon solar cell that is currently in the mainstream, typically, a finger-like (collecting) electrode including a thin wire formed of an electrical conductor such as silver, and a finger electrode connected to the finger-like electrode are provided. Bus electrode. Hereinafter, these electrodes are collectively referred to as a light-receiving surface electrode. Such a light-receiving surface electrode contains a conductive powder such as silver as a conductive component, and an organic vehicle component containing an organic binder and a solvent, and is prepared in a paste form (including a slurry form and an ink form). Materials (hereinafter also referred to as "conductive composition", abbreviated as "composition", etc.) are printed on a light-receiving surface of a solar cell (cell) with a predetermined electrode pattern by a method such as screen printing, and then calcined. form. As a related art related to the electroconductive composition used for forming the light-receiving surface electrode of such a solar cell, patent document 1-patent document 3 are mentioned, for example.
[專利文獻1]日本專利特開2010-087251號公報 [Patent Document 1] Japanese Patent Laid-Open No. 2010-087251
[專利文獻2]日本專利特開2012-023095號公報 [Patent Document 2] Japanese Patent Laid-Open No. 2012-023095
[專利文獻3]日本專利特表2012-508812號公報 [Patent Document 3] Japanese Patent Publication No. 2012-508812
但，太陽電池的電極形成用的導電性組成物中，除了所述的構成材料以外，有時還包含玻璃料(glass frit)。玻璃料可作為於煅燒中軟化或熔融而實現基板與電極的良好結合的無機黏合劑來發揮功能。而且，於太陽電池的製造中，藉由導電性組成物包含玻璃料，而表現出良好的經火(fire through)特性。即，製造太陽電池時，典型而言，首先，於矽基板的受光面的大致整個面上形成抗反射膜，於該抗反射膜上以所需的電極圖案來供給受光面電極形成用的導電性組成物，進行煅燒。此時，導電性組成物中的玻璃料於煅燒中與抗反射膜反應而將其取入玻璃中。藉此，導電性組成物中的導電性粉末通過(經火)抗反射膜，實現 與矽基板的良好的電性連接(歐姆接觸(ohmic contact))。若如上所述利用導電性組成物的經火特性，則於形成微細的受光面電極時，不再需要部分性地去除抗反射膜等，較為簡便，而且不再擔憂於抗反射膜的去除部分與受光面電極的形成位置之間產生間隙或重疊而較佳。 However, the conductive composition for forming an electrode of a solar cell may contain a glass frit in addition to the above-mentioned constituent materials. The glass frit can function as an inorganic adhesive that softens or melts during firing to achieve a good combination of a substrate and an electrode. In addition, in the manufacture of solar cells, the conductive composition contains a glass frit, which exhibits good fire through characteristics. That is, when manufacturing a solar cell, typically, an anti-reflection film is formed on substantially the entire surface of the light-receiving surface of a silicon substrate, and the conductive material for light-receiving surface electrode formation is provided on the anti-reflection film with a desired electrode pattern The sexual composition is calcined. At this time, the glass frit in the conductive composition reacts with the antireflection film during firing and takes it into the glass. Thereby, the conductive powder in the conductive composition is passed through the (anti-reflective) anti-reflection film to realize Good electrical connection (ohmic contact) with silicon substrate. If the fire-resistance property of the conductive composition is used as described above, when forming a fine light-receiving surface electrode, it is not necessary to partially remove the anti-reflection film, etc., which is simpler, and there is no longer any concern about the removal portion of the anti-reflection film. It is preferable that a gap or overlap is formed between the light receiving surface electrode and the formation position.
另外，於太陽電池的受光面上，形成有受光面電極的部分成為遮光部分(非受光部分)。因此，若使受光面電極較先前而言更細線化(細實線化)，則每單元單位面積的受光面積擴大，可提高每單元單位面積的功率。然而，此時，若僅於經細線化的部分使電極成為大體積(厚)，則電極的線路電阻(line resistance)增加，造成太陽電池的功率特性下降。因此，為了受光面電極的細實線化，同時要求電極厚度的提高、即高縱橫比(電極的厚度與線寬的比：厚度/線寬大；以下相同)。 In addition, on the light-receiving surface of the solar cell, a portion where the light-receiving surface electrode is formed becomes a light-shielding portion (non-light-receiving portion). Therefore, if the light-receiving surface electrode is made thinner (thin solid line) than before, the light-receiving area per unit unit area is enlarged, and the power per unit unit area can be increased. However, at this time, if the electrode is made bulky (thick) only in the thinned portion, the line resistance of the electrode increases, resulting in a decrease in the power characteristics of the solar cell. Therefore, in order to make the light-receiving electrode thin and solid, it is required to increase the thickness of the electrode, that is, a high aspect ratio (the ratio of the thickness of the electrode to the line width: the thickness / line width is large; the same applies hereinafter).
然而，關於現有的導電性組成物，就使所述電極的良好歐姆接觸以及細實線化併存的觀點而言，期待進一步的改善。 However, regarding the conventional conductive composition, further improvement is expected from the viewpoint of coexistence of good ohmic contact and fine solid wire of the electrode.
本發明是鑒於所述情況而形成，其主要目的在於提供一種電極形成用的導電性組成物，其可實現電極圖案的細線化以及高縱橫比化，且可良好地形成電極與基板的接點。另外，其他目的在於提供一種可藉由採用該導電性組成物而實現的功能或性能提高的半導體元件，例如太陽電池元件。 The present invention has been made in view of the above circumstances, and a main object thereof is to provide a conductive composition for electrode formation, which can realize thinning of an electrode pattern and a high aspect ratio, and can form a good contact between an electrode and a substrate. . In addition, another object is to provide a semiconductor element, such as a solar cell element, which can improve functions or performance by using the conductive composition.
為了實現所述目的，藉由本發明來提供可適合用於形成 電極(電極圖案)的導電性組成物。該導電性組成物的特徵在於：包含導電性粉末、玻璃料、矽酮樹脂、有機黏合劑、以及分散介質，並且所述玻璃料的經氧化物換算時的SiO2成分的比例為O質量%以上、5質量%以下。 To achieve the above object, the present invention provides a conductive composition that can be suitably used for forming an electrode (electrode pattern). This conductive composition is characterized in that it includes a conductive powder, a glass frit, a silicone resin, an organic binder, and a dispersion medium, and the proportion of the SiO 2 component when the glass frit is converted by oxide is O mass%. Above 5 mass%.
此處所揭示的導電性組成物由於包含玻璃料，故而可形成與基板的接合性良好的電極，另外，形成太陽電池用電極時，即便是供給至抗反射膜上的情況，亦可藉由經火而適當地形成電極與基板的接點。而且可實現良好的歐姆接觸。進而，該導電性組成物由於包含矽酮樹脂，故而可穩定地形成微細且高縱橫比的電極。此處，由玻璃料或矽酮樹脂而來的SiO2成分於在電極中使絕緣性的電阻成分增大的方面欠佳。因此，此處所揭示的技術中，藉由玻璃料不包含SiO2成分，或者如上所述來限制玻璃料中的SiO2成分的比例，則不會損及電極特性，而以高水準使良好的經火特性、電極形狀穩定性併存。 The conductive composition disclosed herein can form an electrode with good adhesion to the substrate because it contains a glass frit. In addition, when the electrode for a solar cell is formed, it can be supplied to an antireflection film by The contact between the electrode and the substrate is appropriately formed by fire. And good ohmic contact can be achieved. Furthermore, since this conductive composition contains a silicone resin, a fine and high aspect ratio electrode can be stably formed. Here, the SiO 2 component derived from a glass frit or a silicone resin is not good in that the insulating resistance component is increased in the electrode. Therefore, in the technology disclosed here, by not including the SiO 2 component in the glass frit, or by limiting the ratio of the SiO 2 component in the glass frit as described above, the electrode characteristics are not impaired, and a good quality is achieved at a high level. The fire characteristics and electrode shape stability coexist.
此處所揭示的導電性組成物的較佳一形態中，特徵在於：相對於所述導電性粉末100質量份的所述矽酮樹脂的比例為0.005質量份以上、0.9質量份以下。藉由此種構成，不僅可形成高縱橫比的電極，而且可形成電氣特性更良好的電極。 In a preferred aspect of the conductive composition disclosed herein, the ratio of the silicone resin to 100 parts by mass of the conductive powder is 0.005 part by mass or more and 0.9 part by mass or less. With this configuration, not only an electrode having a high aspect ratio can be formed, but also an electrode having better electrical characteristics can be formed.
此處所揭示的導電性組成物的較佳一形態中，特徵在於：所述矽酮樹脂的重量平均分子量為3000以上、90000以下。藉由此種構成，與不添加矽酮樹脂的情況相比較，可進一步提高電極的線路電阻等電氣特性。 In a preferred embodiment of the conductive composition disclosed herein, the weight average molecular weight of the silicone resin is 3,000 or more and 90,000 or less. With this configuration, it is possible to further improve the electrical characteristics such as the line resistance of the electrode, as compared with the case where no silicone resin is added.
此處所揭示的導電性組成物的較佳一形態中，特徵在於：構成所述導電性粉末的金屬種包含選自由鎳、鉑、鈀、銀、銅及鋁所組成的組群中的任意一種或兩種以上的元素。藉由此種構成，可構成導電性優異的電極。 In a preferred aspect of the conductive composition disclosed herein, the metal species constituting the conductive powder includes any one selected from the group consisting of nickel, platinum, palladium, silver, copper, and aluminum. Or two or more elements. With this configuration, an electrode having excellent conductivity can be configured.
本發明於用以實現所述目的其他方面，亦提供包括使用所述任一項所記載的導電性組成物來形成的電極的半導體元件。典型而言，該半導體元件可為包括使用所述導電性組成物來形成的受光面電極的太陽電池元件。 According to another aspect of the present invention for achieving the object, a semiconductor element including an electrode formed using the conductive composition according to any one of the aspects is provided. Typically, the semiconductor element may be a solar cell element including a light-receiving surface electrode formed using the conductive composition.
具體而言，本發明的導電性組成物例如於利用網版印刷法等而供給至半導體基板的受光面上的情況下，可大體積地(以高縱橫比)形成線寬更微細的電極圖案以及電極。因此，例如可於各種半導體元件的電極圖案的印刷中實現進一步的細實線化，從而實現達成半導體元件的進一步小型化以及高積體化的高性能半導體元件。另外，例如藉由應用於形成太陽電池元件的受光面電極，可增大受光面的每單位面積的受光量，產生更多的電力，因此特佳。 Specifically, when the conductive composition of the present invention is supplied to a light-receiving surface of a semiconductor substrate by, for example, a screen printing method, an electrode pattern with a finer line width can be formed in a large volume (with a high aspect ratio). And electrodes. Therefore, for example, further thinning and solid lines can be realized in printing electrode patterns of various semiconductor elements, thereby realizing high-performance semiconductor elements that achieve further miniaturization and high integration of semiconductor elements. In addition, for example, it is particularly preferable to apply the light-receiving surface electrode of a solar cell element to increase the amount of light received per unit area of the light-receiving surface and generate more power.
10‧‧‧太陽電池元件(單元) 10‧‧‧solar cell element (unit)
11‧‧‧半導體基板(矽基板) 11‧‧‧Semiconductor substrate (silicon substrate)
11A‧‧‧受光面 11A‧‧‧ Light receiving surface
11B‧‧‧背面 11B‧‧‧Back
12‧‧‧匯流排電極(受光面電極) 12‧‧‧Bus electrode (light receiving surface electrode)
13‧‧‧指狀電極(受光面電極) 13‧‧‧finger electrode (light receiving surface electrode)
14‧‧‧抗反射膜 14‧‧‧Anti-reflective film
16‧‧‧n-Si層 16‧‧‧n-Si layer
18‧‧‧p-Si層 18‧‧‧p-Si layer
20‧‧‧背面鋁電極 20‧‧‧ back aluminum electrode
22‧‧‧背面側外部連接用電極 22‧‧‧ Electrodes for external connection on the back side
24‧‧‧p+層 24‧‧‧p + layer
圖1是示意性表示太陽電池的結構的一例的剖面圖。 FIG. 1 is a cross-sectional view schematically showing an example of the structure of a solar cell.
圖2是示意性表示形成於太陽電池的受光面上的電極的圖案的平面圖。 FIG. 2 is a plan view schematically showing a pattern of an electrode formed on a light receiving surface of a solar cell.
圖3是表示一實施形態中的導電性組成物中的矽酮樹脂的重 量平均分子量、與所形成的電極的斷線數及縱橫比的關係的圖表。 FIG. 3 shows the weight of the silicone resin in the conductive composition in one embodiment. A graph showing the relationship between the weight average molecular weight, the number of broken wires, and the aspect ratio of the formed electrode.
圖4是表示一實施形態中的導電性組成物中的矽酮樹脂的重量平均分子量、與所形成的電極的線路電阻的關係的圖表。 FIG. 4 is a graph showing the relationship between the weight average molecular weight of the silicone resin in the conductive composition and the line resistance of the formed electrode in one embodiment.
以下，對本發明的較佳實施形態進行說明。此外，本說明書中特別提及的內容以外的技術事項且本發明的實施所需要的事項可作為基於現有技術的本領域技術人員的設計事項來把握。本發明可基於本說明書所揭示的技術內容及該領域中的技術常識來實施。 Hereinafter, preferred embodiments of the present invention will be described. In addition, technical matters other than those specifically mentioned in the present specification and matters necessary for the implementation of the present invention can be grasped as design matters for those skilled in the art based on the prior art. The present invention can be implemented based on the technical content disclosed in this specification and technical common sense in the field.
此處所揭示的導電性組成物典型而言為可藉由煅燒而形成電極的導電性組成物。該導電性組成物在本質上與現有的此種導電性組成物同樣，藉由包含導電性粉末、玻璃料、以及用以使該些構成要素分散的有機媒液成分(後述，有機黏合劑與分散劑的混合物)，進而包含矽酮樹脂作為必需的構成要素來構成。以下，對該些各構成要素進行說明。 The conductive composition disclosed here is typically a conductive composition capable of forming an electrode by firing. The conductive composition is essentially the same as the conventional conductive composition, and includes a conductive powder, a glass frit, and an organic vehicle liquid component (to be described later, an organic binder and A mixture of dispersants), and further includes a silicone resin as an essential constituent element. Each of these constituent elements will be described below.
成為該膏的固體成分的主體的導電性粉末可考慮包含具備與用途對應的所需導電性以及其他物性等的各種金屬或者其合金等的粉末。構成所述導電性粉末的材料的一例可例示：金(Au)、銀(Ag)、銅(Cu)、鉑(Pt)、鈀(Pd)、釕(Ru)、銠(Rh)、銥(Ir)、鋨(Os)、鎳(Ni)及鋁(Al)等金屬以及它們的合金；碳黑等碳質材料；表示為LaSrCoFeO3系氧化物(例如LaSrCoFeO3)、LaMnO3系氧化物(例如LaSrGaMgO3)、LaFeO3 系氧化物(例如LaSrFeO3)、LaCoO3系氧化物(例如LaSrCoO3)等的過渡金屬鈣鈦礦(perovskite)型氧化物所代表的導電性陶瓷等。其中，可列舉包含鉑、鈀、銀等貴金屬的單體及它們的合金(Ag-Pd合金、Pt-Pd合金等)，以及鎳、銅、鋁及其合金等者來作為特佳的構成導電性粉末的材料。此外，就成本比較低廉、導電度高等觀點而言，特佳為使用包含銀及其合金的粉末(以下亦簡稱為「Ag粉末」)。以下，對於本案發明的導電性組成物，以使用Ag粉末作為導電性粉末的情況為例來進行說明。 It is conceivable that the conductive powder that is the main component of the solid content of the paste contains powders of various metals or alloys thereof having the required conductivity and other physical properties according to the application. Examples of the material constituting the conductive powder include gold (Au), silver (Ag), copper (Cu), platinum (Pt), palladium (Pd), ruthenium (Ru), rhodium (Rh), and iridium ( Ir), osmium (Os), nickel (Ni), aluminum (Al) and other metals and their alloys; carbonaceous materials such as carbon black; expressed as LaSrCoFeO 3 based oxides (such as LaSrCoFeO 3 ), LaMnO 3 based oxides ( For example, conductive ceramics represented by transition metal perovskite type oxides such as LaSrGaMgO 3 ), LaFeO 3 -based oxides (for example, LaSrFeO 3 ), and LaCoO 3 -based oxides (for example, LaSrCoO 3 ). Among them, monomers containing noble metals such as platinum, palladium, and silver, and alloys thereof (Ag-Pd alloy, Pt-Pd alloy, etc.), and nickel, copper, aluminum, and alloys thereof can be cited as particularly preferable constituents for conduction. Powder material. In addition, from the viewpoint of relatively low cost and high conductivity, it is particularly preferable to use a powder containing silver and its alloy (hereinafter also simply referred to as "Ag powder"). Hereinafter, the conductive composition of the present invention will be described using an example where a Ag powder is used as the conductive powder.
對於Ag粉末以外的導電性粉末的粒徑並無特別限制，可使用與用途對應的各種粒徑的粉末。典型而言，適宜為基於雷射．散射繞射法的平均子粒徑為5μm以下者，較佳為使用平均粒子徑為3μm以下(典型而言為1μm~3μm，例如為1μm~2μm)者。 The particle diameter of the conductive powder other than the Ag powder is not particularly limited, and powders having various particle diameters according to the application can be used. Typically, laser-based is suitable. The scattering diffraction method has an average particle diameter of 5 μm or less, and preferably uses an average particle diameter of 3 μm or less (typically 1 μm to 3 μm, for example, 1 μm to 2 μm).
構成導電性粉末的粒子的形狀並無特別限定。典型而言，可適合使用球狀、鱗片狀(薄片狀)、圓錐狀、棒狀者等。就容易形成填充性良好且緻密的受光面電極等原因而言，較佳為使用球狀或鱗片狀的粒子。所使用的導電性粉末較佳為粒度分佈尖銳(狹窄)者。例如，較佳為使用實質上不包含粒子徑為10μm以上的粒子之類的粒度分佈尖銳的導電性粉末。作為該指標，可採用基於雷射散射繞射法的粒度分佈中的累積體積10%時的粒徑(D10)與累積體積90%時的粒徑(D90)的比(D10/D90)。於構成粉末的粒徑全部相等的情況下，D10/D90的值成為1，相反，粒 度分佈變得越廣，該D10/D90的值越接近於0。較佳為使用D10/D90的值為0.2以上(例如0.2以上、0.5以下)的粒度分佈比較狹窄的粉末。 The shape of the particles constituting the conductive powder is not particularly limited. Typically, those having a spherical shape, a scaly shape (flaky shape), a conical shape, or a rod shape can be suitably used. For reasons such as easy formation of a dense and light-receiving surface electrode, it is preferable to use spherical or scaly particles. The conductive powder used is preferably one having a sharp (narrow) particle size distribution. For example, it is preferable to use a conductive powder having a sharp particle size distribution such as particles having a particle diameter of 10 μm or more. As this index, a ratio (D10 / D90) of a particle diameter (D10) at a cumulative volume of 10% and a particle diameter (D90) at a cumulative volume of 90% in a particle size distribution by a laser scattering diffraction method can be used. When the particle sizes of the constituent powders are all equal, the value of D10 / D90 becomes 1, whereas The wider the degree distribution becomes, the closer this D10 / D90 value is to zero. It is preferable to use a powder having a relatively narrow particle size distribution with a D10 / D90 value of 0.2 or more (for example, 0.2 or more and 0.5 or less).
使用具有此種平均粒子徑及粒子形狀的導電性粉末的導電性組成物的導電性粉末的填充性良好，可形成緻密的電極。這在以良好的形狀精度來形成細的電極圖案時有利。 The conductive powder using a conductive composition having a conductive powder having such an average particle diameter and particle shape has good filling properties and can form a dense electrode. This is advantageous when forming a thin electrode pattern with good shape accuracy.
此外，Ag粉末等導電性粉末的製造方法等並無特別限定。例如可將利用眾所周知的濕式還原法、氣相反應法、氣體還原法等來製造的導電性粉末(典型而言為Ag粉末)視需要進行分級而使用。所述分級例如可使用利用離心分離法的分級設備等而實施。 Moreover, the manufacturing method of conductive powders, such as Ag powder, etc. are not specifically limited. For example, a conductive powder (typically, an Ag powder) produced by a well-known wet reduction method, a gas phase reaction method, a gas reduction method, or the like can be classified and used as necessary. The classification can be performed using, for example, a classification device using a centrifugation method.
玻璃料是可作為所述導電性粉末的無機黏合劑而發揮功能的成分，發揮使構成導電性粉末的導電性粒子彼此、或導電性粒子與基板(形成有電極的對象)的結合性提高的作用。另外，於該導電性組成物用於形成例如太陽電池的受光面電極的情況下，藉由該玻璃料的存在，導電性組成物可於煅燒中貫通作為下層的抗反射膜，可實現與基板的良好黏接以及電性接觸。 The glass frit is a component that can function as an inorganic binder of the conductive powder, and is used to improve the bonding between the conductive particles constituting the conductive powder, or the conductive particles and the substrate (the object on which the electrode is formed). effect. In addition, when the conductive composition is used to form, for example, a light-receiving surface electrode of a solar cell, the presence of the glass frit allows the conductive composition to pass through an anti-reflection film as a lower layer during firing, and can be realized with a substrate. Good adhesion and electrical contact.
此種玻璃料較佳為調整為與導電性粉末同等或其以下的大小。例如，基於雷射．散射繞射法的平均粒子徑較佳為4μm以下，適合為2μm以下，典型而言更佳為0.1μm以上、3μm以下左右。 Such a glass frit is preferably adjusted to a size equal to or smaller than the conductive powder. For example, based on lasers. The average particle diameter of the scattering diffraction method is preferably 4 μm or less, preferably 2 μm or less, and typically more preferably about 0.1 μm to 3 μm.
此外，關於玻璃料的組成，可使用經氧化物換算時的SiO2成分的比例為0質量%以上、5質量%以下(例如小於5質量 %)者。就提高系統的穩定性，另外可調整經火時的侵蝕性的方面而言，SiO2成分較佳為包含於玻璃料中。然而，此處所揭示的技術中，包含後述的矽酮樹脂作為必需的構成成分，該矽酮樹脂於煅燒中形成SiO2成分。過剩的SiO2成分可提高玻璃料的軟化點，降低經火時的導電性組成物的侵蝕性。另外，若無法藉由更低溫的煅燒來形成電極，則亦可對電極性能造成不良影響。因此，此處所揭示的技術中，將玻璃料的SiO2成分的比例如上所述限制為極少的量。玻璃料中的SiO2成分較佳為4質量%以下，例如可設為3質量%以下。此外，玻璃料中的SiO2成分亦可為0質量%(即不包含SiO2成分)。 As for the composition of the glass frit, an oxide-converted SiO 2 component having a ratio of 0% by mass to 5% by mass (for example, less than 5% by mass) can be used. In terms of improving the stability of the system and adjusting the aggressiveness during fire, the SiO 2 component is preferably contained in the glass frit. However, the technology disclosed here includes a silicone resin described later as an essential constituent, and the silicone resin forms a SiO 2 component during firing. The excessive SiO 2 component can increase the softening point of the glass frit and reduce the corrosiveness of the conductive composition during fire. In addition, if the electrode cannot be formed by firing at a lower temperature, the electrode performance may be adversely affected. Therefore, in the technique disclosed here, the ratio of the SiO 2 component of the glass frit is limited to an extremely small amount as described above. The SiO 2 component in the glass frit is preferably 4% by mass or less, and may be, for example, 3% by mass or less. In addition, the SiO 2 component in the glass frit may be 0% by mass (that is, the SiO 2 component is not included).
對於玻璃料中所含的其他成分並無特別限制，可使用各種組成的玻璃。例如，作為大體上的玻璃組成，亦可為本領域技術人員所慣用表述的稱呼，即，所謂的鉛系玻璃、鉛鋰系玻璃、鋅系玻璃、硼酸鹽系玻璃、矽酸硼系玻璃(其中Si量受到限制)、鹼系玻璃、無鉛系玻璃、碲系玻璃、以及含有氧化鋇或氧化鉍等的玻璃等。不言而喻，該些玻璃除了包含所述稱呼中出現的主要玻璃構成元素以外，亦可包含選自由Si(其中Si量受到限制)、Pb、Zn、Ba、Bi、B、Al、Li、Na、K、Rb、Te、Ag、Zr、Sn、Ti、W、Cs、Ge、Ga、In、Ni、Ca、Cu、Mg、Sr、Se、Mo、Y、As、La、Nd、C、Pr、Gd、Sm、Dy、Eu、Ho、Yb、Lu、Ta、V、Fe、Hf、Cr、Cd、Sb、F、Mn、P、Ce及Nb所組成的組群中的一種或者多種元素。此種玻璃料例如除了一般的非晶質玻璃以外， 亦可為一部分中包含結晶的結晶化玻璃。另外，玻璃料若如上所述來調整作為總體的SiO2成分，則可單獨使用一種的組成的玻璃料，亦可將兩種以上的組成的玻璃料混合使用。 The other components contained in the glass frit are not particularly limited, and glasses of various compositions can be used. For example, as a general glass composition, it is also commonly used by those skilled in the art, that is, so-called lead-based glass, lead-lithium-based glass, zinc-based glass, borate-based glass, boron silicate-based glass ( Among them, the amount of Si is limited), alkali-based glass, lead-free glass, tellurium-based glass, and glass containing barium oxide or bismuth oxide. It goes without saying that, in addition to the main glass constituent elements appearing in the title, these glasses may also be selected from the group consisting of Si (wherein the amount of Si is restricted), Pb, Zn, Ba, Bi, B, Al, Li, Na, K, Rb, Te, Ag, Zr, Sn, Ti, W, Cs, Ge, Ga, In, Ni, Ca, Cu, Mg, Sr, Se, Mo, Y, As, La, Nd, C, One or more elements in the group consisting of Pr, Gd, Sm, Dy, Eu, Ho, Yb, Lu, Ta, V, Fe, Hf, Cr, Cd, Sb, F, Mn, P, Ce, and Nb . Such a glass frit may be, for example, a crystal glass including crystals in part in addition to general amorphous glass. Further, when the glass frit as described above to adjust the SiO 2 component as a whole, may be used alone glass frit composition, the glass frit composition may be a mixture of two or more types.
構成玻璃料的玻璃的軟化點並無特別限定，較佳為300℃~600℃左右(例如400℃~500℃)。如上所述軟化點可調整為300℃以上、600℃以下的範圍內的玻璃具體而言，例如可列舉組合包含以下所示的元素的玻璃。B-Si-Al系玻璃、Pb-B-Si系玻璃、Si-Pb-Li系玻璃、Si-Al-Mg系玻璃、Ge-Zn-Li系玻璃、B-Si-Zn-Sn系玻璃、B-Si-Zn-Ta系玻璃、B-Si-Zn-Ta-Ce系玻璃、B-Zn-Pb系玻璃、B-Si-Zn-Pb系玻璃、B-Si-Zn-Pb-Cu系玻璃、B-Si-Zn-Al系玻璃、Pb-B-Si-Ti-Bi系玻璃、Pb-B-Si-Ti系玻璃、Pb-B-Si-Al-Zn-P系玻璃、Pb-Li-Bi-Te系玻璃、Pb-Si-Al-Li-Zn-Te系玻璃、Pb-B-Si-Al-Li-Ti-Zn系玻璃、Pb-B-Si-Al-Li-Ti-P-Te系玻璃、Pb-Si-Li-Bi-Te系玻璃、Pb-Si-Li-Bi-Te-W系玻璃、P-Pb-Zn系玻璃、P-Al-Zn系玻璃、P-Si-Al-Zn系玻璃、P-B-Al-Si-Pb-Li系玻璃、P-B-Al-Mg-F-K系玻璃、Te-Pb系玻璃、Tr-Pb-Li系玻璃、V-P-Ba-Zn系玻璃、V-P-Na-Zn系玻璃、AgI-Ag2O-B-P系玻璃、Zn-B-Si-Li系玻璃、Si-Li-Zn-Bi-Mg-W-Te系玻璃、Si-Li-Zn-Bi-Mg-Mo-Te系玻璃、Si-Li-Zn-Bi-Mg-Cr-Te系玻璃等。含有具有所述軟化點的玻璃料的導電性組成物例如若於形成太陽電池元件的受光面電極時使用，則表現出良好的經火特性而有助於形成高性能的電極，因此較佳。 The softening point of the glass constituting the glass frit is not particularly limited, but is preferably about 300 ° C to 600 ° C (for example, 400 ° C to 500 ° C). As mentioned above, the glass whose softening point can be adjusted to the range of 300 degreeC or more and 600 degreeC or less specifically, the glass which combined the element shown below for example is mentioned. B-Si-Al-based glass, Pb-B-Si-based glass, Si-Pb-Li-based glass, Si-Al-Mg-based glass, Ge-Zn-Li-based glass, B-Si-Zn-Sn-based glass, B-Si-Zn-Ta-based glass, B-Si-Zn-Ta-Ce-based glass, B-Zn-Pb-based glass, B-Si-Zn-Pb-based glass, B-Si-Zn-Pb-Cu-based Glass, B-Si-Zn-Al-based glass, Pb-B-Si-Ti-Bi-based glass, Pb-B-Si-Ti-based glass, Pb-B-Si-Al-Zn-P-based glass, Pb- Li-Bi-Te-based glass, Pb-Si-Al-Li-Zn-Te-based glass, Pb-B-Si-Al-Li-Ti-Zn-based glass, Pb-B-Si-Al-Li-Ti- P-Te-based glass, Pb-Si-Li-Bi-Te-based glass, Pb-Si-Li-Bi-Te-W-based glass, P-Pb-Zn-based glass, P-Al-Zn-based glass, P- Si-Al-Zn based glass, PB-Al-Si-Pb-Li based glass, PB-Al-Mg-FK based glass, Te-Pb based glass, Tr-Pb-Li based glass, VP-Ba-Zn based Glass, VP-Na-Zn-based glass, AgI-Ag 2 OBP-based glass, Zn-B-Si-Li-based glass, Si-Li-Zn-Bi-Mg-W-Te-based glass, Si-Li-Zn- Bi-Mg-Mo-Te-based glass, Si-Li-Zn-Bi-Mg-Cr-Te-based glass, and the like. A conductive composition containing a glass frit having the softening point is preferred, for example, when it is used when forming a light-receiving surface electrode of a solar cell element because it exhibits good fire resistance characteristics and contributes to the formation of a high-performance electrode.
矽酮樹脂作為此處揭示的導電性組成物中所含的必需構成成分而具有特徵性。藉由含有該矽酮樹脂，所述導電性組成物例如可自印刷至煅燒時一直穩定地保持形狀，可穩定地形成更微細且高縱橫比的電極。另外，矽酮樹脂可藉由煅燒而於電極中生成SiO2成分。所述SiO2成分在並非直接提高玻璃料的軟化點，而是可提高系統的穩定性以及電極與基板的黏結性的方面較佳。 The silicone resin has characteristics as an essential constituent component contained in the conductive composition disclosed herein. By containing the silicone resin, the conductive composition can stably maintain a shape from printing to firing, for example, and can form a finer electrode with a high aspect ratio stably. In addition, the silicone resin can generate a SiO 2 component in the electrode by firing. The SiO 2 component is preferred in that it does not directly increase the softening point of the glass frit, but improves the stability of the system and the adhesion between the electrode and the substrate.
該矽酮樹脂(亦可簡稱為矽酮(silicone))可無特別限制地使用包含矽(Si)的有機化合物。典型而言，矽酮樹脂作為液狀或油狀的組成物而均勻地分散或溶解於導電性組成物中。矽酮樹脂可較佳地使用例如具有藉由矽氧烷鍵(Si-O-Si)的主骨架的有機化合物。例如，可為於主骨架中的未結合鍵(側鏈、末端)上導入有烷基或苯基等的直鏈型矽酮。另外，亦可為將聚醚基、環氧基、胺基、羧基、芳烷基、羥基等其他的取代基導入至側鏈、末端、或者兩者上的直鏈改質矽酮，亦可為使聚醚與矽酮交替鍵結而成的直鏈狀的嵌段共聚物。 The silicone resin (also simply referred to as silicone) may be an organic compound containing silicon (Si) without any particular limitation. Typically, a silicone resin is uniformly dispersed or dissolved in a conductive composition as a liquid or oily composition. As the silicone resin, for example, an organic compound having a main skeleton through a siloxane bond (Si-O-Si) can be preferably used. For example, it may be a linear silicone in which an alkyl group, a phenyl group, or the like is introduced into an unbound bond (side chain, terminal) in the main skeleton. In addition, it may be a linear modified silicone in which other substituents such as polyether group, epoxy group, amine group, carboxyl group, aralkyl group, and hydroxyl group are introduced into a side chain, a terminal, or both, or It is a linear block copolymer formed by alternately bonding polyether and silicone.
此種矽酮樹脂的重量平均分子量(以下，有僅表示為「Mw」的情況)變得越高，可形成越高縱橫比的電極，因此較佳。然而，若Mw成為11萬左右，則導致所獲得的電極的斷線等缺陷，或者提高電阻，因此欠佳。就此種觀點而言，例如，Mw較佳為9萬以下，更佳為7萬以下，特佳為6萬以下。Mw的下限並無特別限制，例如可設為千以上，較佳為3千以上，更佳為5千以上，特佳為1萬以上，例如2萬以上。 The higher the weight-average molecular weight of such a silicone resin (hereinafter, sometimes referred to as "Mw" only), the higher the aspect ratio electrode can be formed. However, if Mw is about 110,000, defects such as disconnection of the obtained electrode may be caused, or resistance may be increased, which is not preferable. From this viewpoint, for example, Mw is preferably 90,000 or less, more preferably 70,000 or less, and particularly preferably 60,000 or less. The lower limit of Mw is not particularly limited, and may be, for example, 1,000 or more, preferably 3,000 or more, more preferably 5,000 or more, and particularly preferably 10,000 or more, such as 20,000 or more.
使以上的導電性粉末等構成要素分散的有機媒液成分可根據所需的目的，無特別限制地使用先前用於此種導電性組成物中的各種媒液。典型而言，媒液包含多種組成的有機黏合劑及有機溶劑。所述有機媒液成分中，有機黏合劑可全部溶解於有機溶劑中，亦可僅一部分溶解或分散(可為所謂的乳膠類型的有機媒液)。 The organic vehicle component in which the above-mentioned conductive powder and other constituent elements are dispersed can be used without any particular limitation depending on the intended purpose, and various vehicle solutions previously used in such a conductive composition. Typically, the vehicle contains organic binders and organic solvents of various compositions. Among the organic vehicle components, the organic binder may be completely dissolved in the organic solvent, or may be dissolved or dispersed only partially (it may be a so-called latex-type organic vehicle).
作為有機黏合劑，例如適合使用將乙基纖維素，羥基乙基纖維素等纖維素系高分子，聚甲基丙烯酸丁酯、聚甲基丙烯酸甲酯、聚甲基丙烯酸乙酯等丙烯酸系樹脂，環氧樹脂、酚樹脂、醇酸樹脂、聚乙烯醇、聚乙烯丁醛等作為基礎的有機黏合劑。特佳為纖維素系高分子(例如乙基纖維素)，可實現能夠進行特別良好的網版印刷的黏度特性。 As the organic binder, for example, cellulose polymers such as ethyl cellulose and hydroxyethyl cellulose, and acrylic resins such as polybutyl methacrylate, polymethyl methacrylate, and polyethyl methacrylate are suitably used. , Epoxy resin, phenol resin, alkyd resin, polyvinyl alcohol, polyvinyl butyral and other organic binders as the basis. Particularly preferred is a cellulose-based polymer (for example, ethyl cellulose), which can achieve particularly good viscosity characteristics that can be used for screen printing.
作為構成有機媒液的溶媒，較佳為沸點為約200℃以上(典型而言為約200℃~260℃)的有機溶媒。更佳為使用沸點為約230℃以上(典型而言為大致230℃~260℃)的有機溶媒。此種有機溶劑可適合使用：丁基溶纖劑乙酸酯，丁基卡必醇乙酸酯(BCA(butyl carbitol acetate)：二乙二醇單丁醚乙酸酯)等酯系溶劑，丁基卡必醇(BC(butyl carbitol)：二乙二醇單丁醚)等醚系溶劑，乙二醇及二乙二醇衍生物、甲苯、二甲苯、礦油精(mineral spirit)、松油醇(terpineol)、薄荷腦(menthanol)、醇酯(texanol)等有機溶媒。特佳的溶劑成分可列舉：丁基卡必醇(BC)、丁基卡必醇乙酸酯(BCA)、2,2,4-三甲基-1,3-戊二醇單異丁酸酯等。 The solvent constituting the organic vehicle is preferably an organic solvent having a boiling point of about 200 ° C. or higher (typically about 200 ° C. to 260 ° C.). More preferably, an organic solvent having a boiling point of about 230 ° C. or higher (typically approximately 230 ° C. to 260 ° C.) is used. This organic solvent can be suitably used: butyl cellosolve acetate, butyl carbitol acetate (BCA (butyl carbitol acetate): diethylene glycol monobutyl ether acetate) and other ester solvents, butyl card Ether solvents such as BC (butyl carbitol): diethylene glycol monobutyl ether; ethylene glycol and diethylene glycol derivatives, toluene, xylene, mineral spirit, terpineol ( organic solvents such as terpineol, menthanol, and texanol. Examples of particularly good solvent components include: butylcarbitol (BC), butylcarbitol acetate (BCA), 2,2,4-trimethyl-1,3-pentanediol monoisobutyric acid Esters, etc.
導電性組成物中所含的各構成成分的調配比例可根據電極的形成方法，典型而言為印刷方法等而有所不同，大致可設為以先前所採用的組成的導電性組成物為準的調配比例。作為一例，例如能夠將以下的調配作為標準來決定各構成成分的比例。 The blending ratio of each constituent contained in the conductive composition may vary depending on the method of forming the electrode, typically the printing method, etc., and it can be roughly set to the conductive composition of the composition previously used. Deployment ratio. As an example, the ratio of each component can be determined using the following formulation as a standard.
即，當將膏總體設為100質量%時，導電性組成物中所佔的導電性粉末的含有比例適宜設為約70質量%以上(典型而言為70質量%~95質量%)，更佳為設為80質量%~90質量%左右，例如較佳為設為85質量%左右。就形成形狀精度良好且緻密的電極的圖案的觀點而言，較佳為提高導電性粉末的含有比例。另一方面，若該含有比例過高，則存在膏的操作性、或對各種印刷性的適應性等下降。 That is, when the total paste content is 100% by mass, the content of the conductive powder in the conductive composition is suitably set to about 70% by mass or more (typically 70% to 95% by mass), and more It is preferably set to about 80% by mass to 90% by mass, and is preferably set to about 85% by mass, for example. From the viewpoint of forming a pattern of a dense electrode with good shape accuracy, it is preferable to increase the content ratio of the conductive powder. On the other hand, if the content ratio is too high, there is a decrease in the operability of the paste, the adaptability to various printability, and the like.
矽酮樹脂即便對導電性粉末添加極少量，亦可藉此使電極形成為更高縱橫比者，因此較佳。例如，當將導電性粉末設為100質量份時，典型而言，矽酮樹脂的添加量可設為0.005質量份以上，較佳為設為0.01質量份以上，更佳為設為0.1質量份以上。此外，過剩的添加會提高所形成的電極的電阻，因此欠佳。因此，當將導電性粉末設為100質量份時，典型而言，矽酮樹脂的添加量為可設為1.2質量份以下，較佳為設為0.9質量份以下，更佳為設為0.8質量份以下。 Even if a silicone resin is added to the conductive powder in a small amount, it can form an electrode with a higher aspect ratio, and therefore, it is preferable. For example, when the conductive powder is 100 parts by mass, typically, the addition amount of the silicone resin can be 0.005 parts by mass or more, preferably 0.01 parts by mass or more, and more preferably 0.1 parts by mass. the above. In addition, the excessive addition increases the resistance of the formed electrode, and is therefore not preferable. Therefore, when the conductive powder is 100 parts by mass, the amount of the silicone resin added is typically 1.2 parts by mass or less, preferably 0.9 parts by mass or less, and more preferably 0.8 parts by mass. The following.
玻璃料相對於導電性粉末的比例由於亦存在與矽酮樹脂的關係，故而無法一概而言，但為了獲得良好的經火特性，當將導電性粉末設為100質量份時，典型而言可設為0.1質量份以 上，較佳為設為0.5質量份以上，更佳為設為1質量份以上。此外，過剩的添加會提高所形成的電極的電阻，因此欠佳，典型而言可設為12質量份以下，較佳為設為10質量份以下，更佳為設為8質量份以下。 The ratio of the glass frit to the conductive powder cannot be generalized because it also has a relationship with the silicone resin. However, in order to obtain good fire resistance characteristics, when the conductive powder is 100 parts by mass, it is typically Set to 0.1 parts by mass or more In the above, it is preferably 0.5 parts by mass or more, and more preferably 1 part by mass or more. In addition, the excessive addition increases the resistance of the formed electrode, which is not satisfactory. Typically, it can be 12 parts by mass or less, preferably 10 parts by mass or less, and more preferably 8 parts by mass or less.
此外，所述的矽酮樹脂與玻璃料是電極內中所含的SiO2成分的來源。而且，就該SiO2成分抑制經火特性，或可於電極中成為絕緣性的電阻成分的方面而言，可互補地考慮其含量。更具體而言，此處所揭示的導電性組成物由於包含矽酮樹脂，故而可將玻璃料中的SiO2成分抑制為少量。然而，例如若矽酮樹脂量為大致超過0.15質量份的(例如0.2質量份以上的)範圍，則該導電性組成物可貫通抗反射膜，或形成與基板的良好接觸，因此較佳為與矽酮樹脂量對應來確保充分的玻璃料量。例如，玻璃料相對於矽酮樹脂的質量比(玻璃料的質量/矽酮樹脂的質量)較佳為7.5以上，更佳為8以上，特佳為8.3以上，例如10以上。然而，矽酮樹脂與玻璃料如上所述，其本身可成為電極的電阻成分。就所述觀點而言，玻璃料相對於矽酮樹脂的質量比較佳為例如大致18以下，更佳為16.5以下，例如可設為15以下，尤佳為設為12以下。例如，如上所述，藉由將玻璃料相對於矽酮樹脂的量比限定於既定的範圍內，可有效地降低串聯電阻Rs。 In addition, the silicone resin and the glass frit are a source of the SiO 2 component contained in the electrode. In addition, the content of the SiO 2 component can be considered in a complementary manner in terms of suppressing warp resistance characteristics, or as a resistance component that can be insulated in the electrode. More specifically, since the conductive composition disclosed herein contains a silicone resin, the SiO 2 component in the glass frit can be suppressed to a small amount. However, for example, if the amount of the silicone resin is more than approximately 0.15 parts by mass (for example, 0.2 parts by mass or more), the conductive composition can penetrate the antireflection film or form a good contact with the substrate. The amount of silicone resin corresponds to ensure a sufficient amount of glass frit. For example, the mass ratio of glass frit to silicone resin (mass of glass frit / mass of silicone resin) is preferably 7.5 or more, more preferably 8 or more, particularly preferably 8.3 or more, such as 10 or more. However, as described above, the silicone resin and the glass frit may themselves become the resistance component of the electrode. From this viewpoint, the quality of the glass frit relative to the silicone resin is preferably about 18 or less, more preferably 16.5 or less, for example, 15 or less, and particularly preferably 12 or less. For example, as described above, by limiting the amount ratio of the glass frit to the silicone resin within a predetermined range, the series resistance Rs can be effectively reduced.
而且，有機媒液成分中，當將導電性粉末的質量設為100質量%時，有機黏合劑較佳為以約15質量%以下、典型而言為1質量%~10質量%左右的比例來含有。特佳為相對於導電性粉末 100質量%，而以2質量%~6質量%的比例來含有。此外，所述有機黏合劑亦可包含例如溶解於有機溶劑中的有機黏合劑成分、以及不溶解於有機溶劑中的有機黏合劑成分。於包含溶解於有機溶劑中的有機黏合劑成分、以及不溶解的有機黏合劑成分的情況下，對它們的比例並無特別限制，但例如可使溶解於有機溶劑中的有機黏合劑成分佔(4成~10成)。 In addition, when the mass of the conductive powder is 100% by mass in the organic vehicle liquid component, the organic binder is preferably at a ratio of about 15% by mass or less, typically about 1% to 10% by mass. contain. Especially preferred for conductive powder It is 100% by mass and is contained in a proportion of 2% to 6% by mass. In addition, the organic binder may include, for example, an organic binder component dissolved in an organic solvent, and an organic binder component not dissolved in an organic solvent. When the organic binder component is dissolved in an organic solvent and the insoluble organic binder component is contained, the ratio thereof is not particularly limited, but the organic binder component dissolved in the organic solvent may be used for example ( 40% to 10%).
此外，作為所述有機媒液的總體的含有比例可根據所獲得的膏的性狀而變化，作為大致的標準，當將導電性組成物總體設為100質量%時，例如適宜為成為5質量%~30質量%的量，較佳為5質量%~20質量%，更佳為成為5質量%~15質量%(特別是7質量%~12質量%)的量。 In addition, the overall content ratio of the organic vehicle can be changed according to the properties of the obtained paste. As a rough guideline, when the total conductive composition is set to 100% by mass, for example, it is preferably 5% by mass. The amount of 30 mass% is preferably 5 mass% to 20 mass%, and more preferably an amount of 5 mass% to 15 mass% (particularly 7 mass% to 12 mass%).
另外，此處所揭示的導電性組成物可於不脫離本發明的目的的範圍內，包含所述以外的各種無機添加劑及/或有機添加劑。作為無機添加劑的較佳例，可列舉所述以外的陶瓷粉末(ZnO2、Al2O3等)、除此以外的各種填料。另外，作為有機添加劑的較佳例，例如可列舉界面活性劑、消泡劑、抗氧化劑、分散劑、黏度調整劑等添加劑。 In addition, the conductive composition disclosed herein may include various inorganic additives and / or organic additives other than those described above within a range not departing from the object of the present invention. As preferred examples of the inorganic additives include ceramic powder other than said (ZnO 2, Al 2 O 3, etc.), except that various fillers. Moreover, as a preferable example of an organic additive, additives, such as a surfactant, a defoamer, an antioxidant, a dispersing agent, and a viscosity modifier, are mentioned, for example.
以上的導電性組成物由於具有形狀穩定性，故而適合作為例如應用於網版印刷、凹版印刷、平版印刷及噴墨印刷等的印刷用組成物(亦存在稱為膏、漿料或油墨等的情況)。而且，當形成要求細線化及高縱橫比化的電極圖案時，可於使用如上所述的通用的印刷方法的情況下特佳地採用所述導電性組成物。因此， 例如以作為半導體元件的一例的太陽電池元件為例，不僅示出藉由網版印刷而形成於該受光面上包含更微細的指狀電極的梳型電極圖案的例子，而且對此處所揭示的作為半導體元件的太陽電池元件進行說明。此外，關於太陽電池元件，除了本發明的特徵性的受光面電極的構成以外，可與現有的太陽電池同樣，對於與先前同樣的構成以及和與先前同樣的材料的使用有關的部分，並非本發明的特徵性者，因此省略詳細的說明。 The above conductive composition is suitable as a printing composition (such as a paste, a paste, or an ink, etc.) suitable for use in, for example, screen printing, gravure printing, lithography, and inkjet printing due to its shape stability. Happening). Furthermore, when forming an electrode pattern requiring thinning and high aspect ratio, the conductive composition can be particularly preferably used when a general printing method as described above is used. therefore, For example, taking a solar cell element as an example of a semiconductor element, not only an example of a comb-shaped electrode pattern including finer finger electrodes formed on the light-receiving surface by screen printing is shown, but also the example disclosed here A solar cell element as a semiconductor element will be described. In addition, the solar cell element may be the same as the existing solar cell except for the constitution of the characteristic light-receiving surface electrode of the present invention, and it is not the same as the conventional solar cell. Since it is a characteristic of the invention, detailed description is omitted.
圖1及圖2是示意性圖示出可藉由本發明的實施而適當製造的太陽電池元件(單元)10的一例的圖，是利用包含單結晶或多結晶或者非晶型的矽(Si)的晶圓作為半導體基板11的所謂矽型太陽電池元件10。圖1所示的單元10為一般的單面受光類型的太陽電池元件10。具體而言，此種太陽電池元件10於矽基板(Si晶圓)11的p-Si層(p型結晶矽)18的受光面側具備藉由形成pn接合而形成的n-Si層16，且於其表面具備藉由化學氣相沈積(chemical vapor deposition，CVD)等而形成的包含氧化鈦或氮化矽的抗反射膜14、以及由包含Ag粉末等作為主體的導電性組成物所形成的受光面電極12、受光面電極13。 FIGS. 1 and 2 are diagrams schematically illustrating an example of a solar cell element (cell) 10 that can be appropriately manufactured by the implementation of the present invention, and are made of silicon (Si) containing single crystal, polycrystal, or amorphous type. The so-called silicon-type solar cell element 10 is a semiconductor wafer 11. The unit 10 shown in FIG. 1 is a general single-sided light-receiving type solar cell element 10. Specifically, such a solar cell element 10 includes an n-Si layer 16 formed by forming a pn junction on a light-receiving surface side of a p-Si layer (p-type crystalline silicon) 18 of a silicon substrate (Si wafer) 11. The surface is provided with an anti-reflection film 14 containing titanium oxide or silicon nitride formed by chemical vapor deposition (CVD) or the like, and a conductive composition containing Ag powder as a main body. Light-receiving surface electrode 12 and light-receiving surface electrode 13.
另一方面，於p-Si層18的背面側具備：與受光面電極12同樣地由既定的導電性組成物(典型而言，導電性粉末為Ag粉末的導體性膏)所形成的背面側外部連接用電極22、以及發揮所謂的背面電場(BSF；Back Surface Field)效果的背面鋁電極20。鋁電極20藉由將以鋁粉末作為主體的導電性組成物進行印刷．煅 燒而形成於背面的大致整個面上。於該煅燒時形成未圖示的Al-Si合金層，鋁於p-Si層18上擴散而形成p+層24。藉由形成所述的p+層24、即BSF層，而防止光生成的載子於背面電極附近進行再結合，例如實現短路電流或開放電壓(Voc)的提高。 On the other hand, the back surface side of the p-Si layer 18 includes a back surface side made of a predetermined conductive composition (typically, a conductive paste in which the conductive powder is an Ag powder) similarly to the light receiving surface electrode 12. The external connection electrode 22 and the back aluminum electrode 20 exhibiting a so-called back surface field (BSF; Back Surface Field) effect. The aluminum electrode 20 is printed with a conductive composition mainly composed of aluminum powder. It is fired and formed on substantially the entire back surface. During this firing, an Al-Si alloy layer (not shown) is formed, and aluminum diffuses on the p-Si layer 18 to form a p + layer 24. By forming the p + layer 24, that is, the BSF layer, the carriers generated by light are prevented from being recombined near the back electrode, for example, to improve the short-circuit current or the open voltage (Voc).
如圖2所示，於太陽電池元件10的矽基板11的受光面11A側，作為受光面電極12、受光面電極13，形成有數根(例如1根~3根左右)的相互平行的直線狀的匯流排(連接用)電極12、以及以與該匯流排電極12交叉的方式連接的相互平行的多根的(例如60根~90根左右)條紋狀的指狀(集電用)電極13。 As shown in FIG. 2, on the light-receiving surface 11A side of the silicon substrate 11 of the solar cell element 10, as the light-receiving surface electrode 12 and the light-receiving surface electrode 13, a plurality of (for example, about one to three) parallel linear shapes are formed. Bus electrodes (for connection) electrodes 12 and a plurality of parallel (for example, about 60 to about 90) stripe-shaped finger-like (collector) electrodes 13 connected to intersect with the bus electrodes 12 .
為了收集藉由受光而生成的光生成載子(電洞及電子)而形成有多根的指狀電極13。匯流排電極12是用以將由指狀電極13收集的載子進行集電的連接用電極。形成有此種受光面電極12、受光面電極13的部分於太陽電池元件的受光面11A上形成非受光部分(遮光部分)。因此，藉由使設置於所述受光面11A側的匯流排電極12與指狀電極13(特別是數量多的指狀電極13)僅可能地細實線化，則與其對應的程度的非受光部分(遮光部分)減少，每單元單位面積的受光面積擴大。這可極其簡單地提高太陽電池元件10的每單位面積的功率。 A plurality of finger electrodes 13 are formed in order to collect light-generating carriers (holes and electrons) generated by receiving light. The bus bar electrode 12 is a connection electrode for collecting the carriers collected by the finger electrodes 13. The portion where the light receiving surface electrode 12 and the light receiving surface electrode 13 are formed forms a non-light receiving portion (light shielding portion) on the light receiving surface 11A of the solar cell element. Therefore, by making the busbar electrodes 12 and the finger electrodes 13 (especially a large number of finger electrodes 13) provided on the light-receiving surface 11A side as thin as possible, the corresponding amount of non-light-receiving The portion (light-shielding portion) is reduced, and the light-receiving area per unit area is increased. This makes it extremely easy to increase the power per unit area of the solar cell element 10.
此時，只要經細線化的電極的高度高且均勻即可，但例如，只要於其一部分上產生鬆弛或凹陷，則所述鬆弛或凹陷的部位導致電阻的增大，造成集電產生損耗。而且，另外，只要於經細線化的電極的一部分產生斷線，則無法通過所述斷線部位而使 發電電流集電(於高電阻的基板中流通的電流於產生集電損耗的狀態下集電)。因此，為了形成太陽電池元件的受光面電極，要求電氣特性當然要高，而且印刷的形狀穩定性優異的導電性組成物。 At this time, as long as the height of the thinned electrode is high and uniform, for example, as long as a slack or depression is generated in a part thereof, the slack or depressed portion leads to an increase in resistance and a loss in current collection. In addition, as long as a disconnection occurs in a part of the thinned electrode, the disconnection portion cannot cause the disconnection. Power generation current collection (current flowing through a high-resistance substrate is collected in a state where a collection loss is generated). Therefore, in order to form a light-receiving surface electrode of a solar cell element, it is of course required to have a conductive composition having high electrical characteristics and excellent printed shape stability.
概略而言，此種太陽電池元件10是經過如下所述的製程來製造。 Roughly, such a solar cell element 10 is manufactured through a process described below.
即，準備適宜的矽晶圓，利用熱擴散法或離子植入(ion plantation)等一般的技法，摻雜既定的雜質來形成所述p-Si層18或n-Si層16，藉此製作所述矽基板(半導體基板)11。繼而，例如利用電漿CVD等技法來形成包含氮化矽等的抗反射膜14。 That is, a suitable silicon wafer is prepared, and the p-Si layer 18 or the n-Si layer 16 is formed by doping a predetermined impurity by a general technique such as a thermal diffusion method or an ion plantation, thereby fabricating the silicon wafer. The silicon substrate (semiconductor substrate) 11. Then, the anti-reflection film 14 containing silicon nitride or the like is formed by a technique such as plasma CVD.
然後，於所述矽基板11的背面11B側，首先，使用既定的導電性組成物(典型而言，導電性粉末為Ag粉末的導電性組成物)而網版印刷為既定的圖案，進行乾燥，藉此於煅燒後形成成為背面側外部連接用電極22(參照圖1)的背面側導體塗佈物。繼而，於背面側的整個面上，利用網版印刷法等來塗佈(供給)以鋁粉末作為導體成分的導電性組成物，進行乾燥，藉此形成鋁膜。 Then, on the back surface 11B side of the silicon substrate 11, first, a predetermined conductive composition (typically, a conductive powder is a conductive composition of Ag powder) is used to screen-print a predetermined pattern and dried. Thereby, a back-surface-side conductor coating material to be the back-surface-side external connection electrode 22 (see FIG. 1) is formed after firing. Then, a conductive composition containing aluminum powder as a conductive component is applied (supplied) to the entire surface of the back surface by a screen printing method or the like, and dried to form an aluminum film.
繼而，於形成於所述矽基板11的表面側的抗反射膜14上，典型而言，基於網版印刷法，以如圖2所示的配線圖案來印刷(供給)本發明的導電性組成物。所印刷的線寬並無特別限定，藉由採用本發明的導電性組成物，而形成具備線寬為70μm左右或其以下(較佳為50μm~60μm左右的範圍，更佳為40μm~50μm左右的範圍)的指狀電極的電極圖案的塗膜(印刷體)。繼而，於適宜的溫度域(典型而言為100℃~200℃，例如120℃~150℃ 左右)下使基板乾燥。關於較佳的網版印刷法的內容如後所述。 Next, on the antireflection film 14 formed on the surface side of the silicon substrate 11, the conductive composition of the present invention is typically printed (supplied) with a wiring pattern as shown in FIG. 2 based on a screen printing method. Thing. The printed line width is not particularly limited, and the conductive composition of the present invention is used to form a line width of about 70 μm or less (preferably in a range of about 50 μm to 60 μm, more preferably about 40 μm to 50 μm) Range) of the electrode pattern of the finger electrode (printed body). Then, in an appropriate temperature range (typically 100 ° C to 200 ° C, such as 120 ° C to 150 ° C) Left and right) to dry the substrate. The content of a preferable screen printing method is mentioned later.
於大氣環境中使用例如近紅外線高速煅燒爐之類的煅燒爐，將如上所述於兩面分別形成有膏塗佈物(乾燥膜狀的塗佈物)的矽基板11於適當的煅燒溫度(例如700℃~900℃)下進行煅燒。 Using a calcining furnace such as a near-infrared high-speed calcining furnace in an atmospheric environment, the silicon substrate 11 having the paste coating material (dry film coating material) formed on both sides as described above at an appropriate calcination temperature (for example, 700 ° C ~ 900 ° C).
藉由所述煅燒，與受光面電極(典型而言為Ag電極)12、受光面電極13以及背面側外部連接用電極(典型而言為Ag電極)22一併，形成煅燒鋁電極20，另外，同時形成未圖示的Al-Si合金層，而且鋁於p-Si層18上擴散而形成所述的p+層(BSF層)24，製作太陽電池元件10。 By the firing described above, the calcined aluminum electrode 20 is formed together with the light-receiving surface electrode (typically an Ag electrode) 12, the light-receiving surface electrode 13, and the backside external connection electrode (typically an Ag electrode) 22. At the same time, an Al-Si alloy layer (not shown) is formed at the same time, and aluminum is diffused on the p-Si layer 18 to form the p + layer (BSF layer) 24 to produce a solar cell element 10.
此外，替代如上所述般同時進行煅燒，亦可分別實施例如用以形成受光面11A側的受光面電極(典型而言為Ag電極)12、受光面電極13的煅燒，與用以形成背面11B側的鋁電極20以及外部連接用電極22的煅燒。 In addition, instead of performing simultaneous firing as described above, for example, firing to form the light-receiving surface electrode (typically an Ag electrode) 12 and the light-receiving surface electrode 13 on the light-receiving surface 11A side and to form the back surface 11B, respectively The aluminum electrode 20 on the side and the electrode 22 for external connection are fired.
依據此處所揭示的導電性組成物，例如可藉由網版印刷，以所需的電極圖案將導電性組成物供給(印刷)於矽基板11上。所述導電性組成物由於形狀穩定性優異，故而例如對於煅燒後獲得的電極，可於大幅度減少線的變細或斷線的產生的狀態下，高品質地形成線寬為60μm以下且厚度為20μm以上(較佳為線寬為40μm以上、50μm以下且厚度為20μm以上)的指狀電極13。關於匯流排電極，基本上不存在因線的變細或斷線等所引起的影響，因此雖不需要使用所述的導電性組成物，但亦可高 品質地形成例如線寬1000μm~3000μm左右的匯流排電極。如上所述，若實現電極線的細線化及高縱橫比化，例如可不提高每一根指狀電極的電阻，而是提高每單位面積的功率。另外，即便於電極線的電阻值稍有上升的情況下，亦可將作為電極圖案總體的線路電阻值抑制為低值。因此，藉由將指狀電極13的寬度與根數設計為最佳組合者，而提供光電轉換效率高的太陽電池元件。 According to the conductive composition disclosed herein, for example, the conductive composition can be supplied (printed) on the silicon substrate 11 with a desired electrode pattern by screen printing. The conductive composition is excellent in shape stability. For example, for electrodes obtained after firing, the thickness of the wire can be reduced to 60 μm and the thickness can be formed with high quality in a state where the thinning of the wire or the occurrence of disconnection is greatly reduced. The finger electrode 13 is 20 μm or more (preferably a line width of 40 μm or more, 50 μm or less, and a thickness of 20 μm or more). As for the bus electrode, there is basically no influence caused by thinning or disconnection of the wire, so although the above-mentioned conductive composition is not required, it can be high. For example, a bus bar electrode having a line width of about 1000 μm to 3000 μm is formed with good quality. As described above, if the electrode line is thinned and the aspect ratio is increased, for example, the power per unit area can be increased without increasing the resistance of each finger electrode. In addition, even when the resistance value of the electrode line slightly increases, the line resistance value as a whole of the electrode pattern can be suppressed to a low value. Therefore, by designing the width and the number of the finger electrodes 13 as an optimal combination, a solar cell element with high photoelectric conversion efficiency is provided.
以下，對與本發明有關的若干實施例進行說明，但並未意圖將本發明限定為所述實施例所示者。 Hereinafter, several embodiments related to the present invention will be described, but it is not intended to limit the present invention to those shown in the embodiments.
(實施形態1) (Embodiment 1)
[導電性組成物的製備] [Preparation of conductive composition]
藉由以下所示的順序來製備電極形成用的導電性組成物。即，導電性粉末是使用平均粒子徑為2μm的銀(Ag)粉末。玻璃料是使用下述表1所示的十二種玻璃粉末(平均粒子徑：0.5μm~1.6μm)。矽酮樹脂是使用重量平均分子量Mw為5萬的聚二甲基矽氧烷。另外，界面活性劑是使用硬化蓖麻油。有機媒液成分是使用作為有機黏合劑成分的乙基纖維素(ethyl cellulose，EC)分散於作為分散介質的醇酯中而成的媒液。 A conductive composition for electrode formation was prepared by the procedure shown below. That is, the conductive powder is a silver (Ag) powder having an average particle diameter of 2 μm. As the glass frit, twelve glass powders (average particle diameter: 0.5 μm to 1.6 μm) shown in Table 1 below were used. As the silicone resin, polydimethylsiloxane having a weight average molecular weight Mw of 50,000 was used. As the surfactant, hardened castor oil was used. The organic vehicle component is a vehicle liquid in which ethyl cellulose (EC), which is an organic binder component, is dispersed in an alcohol ester as a dispersion medium.
此外，表1中，表示玻璃料的構成的記號為：將包含Pb的有鉛系玻璃表示為「A」，將不包含Pb而含有鉍(Bi)等的無鉛系玻璃表示為「B」，將不包含Pb而含有硼(B)或矽(Si)等的其他無鉛系玻璃表示為「C」，而且附記有表示各玻璃組成中的SiO2成分的含量的數字。該些玻璃料藉由調整組成，而如表1所示般使 軟化點於300℃以上、600℃以下的範圍內變化。 In addition, in Table 1, the symbol showing the composition of the glass frit is: "A" is a leaded glass containing Pb, and "B" is a lead-free glass containing bismuth (Bi) and the like without Pb, Other lead-free glasses containing boron (B), silicon (Si), and the like that do not contain Pb are indicated as "C", and a number indicating the content of the SiO 2 component in each glass composition is added. By adjusting the composition of these glass frits, as shown in Table 1, the softening point was changed in a range of 300 ° C or higher and 600 ° C or lower.
接著，將該些材料以如下方式進行調配：當將銀粉末設為100質量份時，玻璃料成為2.50質量份，矽酮樹脂成為0質量份、0.0050質量份、0.30質量份的任一者，乙基纖維素成為1.00質量份，硬化蓖麻油成為0.80質量份；一邊使用三輥磨機來充分混練，一邊利用醇酯進行調整，以使黏度成為約190Pa．s，藉此製備例1~例21的導電性組成物。將各例的導電性組成物中使用的玻璃料的種類、矽酮樹脂的調配量、以及所獲得的導電性組成物的黏度的實測值示於下述表2中。此外，表2中，各例中使用的玻璃料的組成是由表1所示的記號來表示。另外，矽酮樹脂量的欄的「-」表示不調配矽酮樹脂(0質量份)。而且，各例的導電性 組成物的黏度是使用HBT類型的布氏(Brookfield)型黏度計，於25℃下以20rpm的條件來測量的值。 Next, these materials are prepared in such a manner that when the silver powder is 100 parts by mass, the glass frit becomes 2.50 parts by mass, and the silicone resin becomes any of 0 parts by mass, 0.0050 parts by mass, and 0.30 parts by mass, Ethylcellulose becomes 1.00 parts by mass, and hardened castor oil becomes 0.80 parts by mass; while using a three-roll mill to fully knead, the alcohol ester is used to adjust the viscosity to approximately 190 Pa. In this way, the conductive compositions of Examples 1 to 21 were prepared. The type of the glass frit used in each example of the conductive composition, the blending amount of the silicone resin, and the measured values of the viscosity of the obtained conductive composition are shown in Table 2 below. In addition, in Table 2, the composition of the glass frit used in each example is represented by the symbol shown in Table 1. In addition, the "-" in the column of the amount of silicone resin indicates that no silicone resin (0 parts by mass) was blended. Moreover, the conductivity of each example The viscosity of the composition is a value measured using a Brookfield viscometer of HBT type at 25 rpm and 20 rpm.
[試驗用太陽電池元件(受光面電極)的製作] [Manufacture of solar cell elements (light-receiving surface electrodes) for testing]
使用所述獲得的例1~例21的導電性組成物來形成受光面電極(即，包含指狀電極及匯流排電極的梳型電極)，藉此製作例1~例21的太陽電池元件。 The obtained conductive composition of Examples 1 to 21 was used to form a light-receiving surface electrode (that is, a comb-type electrode including a finger electrode and a bus electrode), thereby fabricating the solar cell elements of Examples 1 to 21.
具體而言，首先，準備市售的156mm四方(6英吋見方)的尺寸的太陽電池用p型單結晶矽基板(板厚為180μm)，對其表面(受光面)，使用氫氟酸及硝酸的混酸進行蝕刻，藉此去除損壞層，並且形成凹凸的紋理結構。繼而，藉由對於所述紋理結構面塗佈含磷溶液，實施熱處理，而於該矽基板的受光面上形成厚度為約0.5μm的n-Si層(n+層)。繼而，於該n-Si層上，利用電漿CVD(Plasma Enhanced Chemical Vapor Deposition，PECVD)法來製成厚度為約80nm左右的氮化矽膜，作為抗反射膜。 Specifically, first, a commercially available p-type single crystal silicon substrate (plate thickness: 180 μm) for a solar cell with a size of 156 mm square (6 inches square) was prepared, and a hydrofluoric acid and a surface thereof were used. The mixed acid of nitric acid is etched, thereby removing the damaged layer and forming an uneven texture structure. Then, by applying a phosphorus-containing solution to the textured structure surface and performing heat treatment, an n-Si layer (n + layer) having a thickness of about 0.5 μm is formed on the light-receiving surface of the silicon substrate. Then, a plasma nitride CVD (Plasma Enhanced Chemical Vapor Deposition, PECVD) method is used to form a silicon nitride film with a thickness of about 80 nm on the n-Si layer as an anti-reflection film.
繼而，於矽基板的背面側，使用既定的銀電極形成用膏，然後以成為背面側外部連接用電極的方式以既定的圖案進行網版印刷，使其乾燥，藉此形成背面側電極圖案。接著，於背面側的整個面上網版印刷鋁電極形成用膏，進行乾燥，藉此形成鋁膜。 Next, a predetermined silver electrode-forming paste is used on the back surface side of the silicon substrate, and then screen-printed in a predetermined pattern so as to become the back-side external connection electrode and dried to form a back-side electrode pattern. Next, an aluminum electrode forming paste is screen-printed on the entire surface of the back surface and dried to form an aluminum film.
然後，使用所準備的例1~例21的導電性組成物，於大氣環境中，於室溫條件下利用網版印刷法，於所述抗反射膜上印刷受光面電極(Ag電極)用的電極圖案，於120℃下進行乾燥。 具體而言，如圖2所示，藉由網版印刷而形成包含3根相互平行的直線狀匯流排電極、以及與該匯流排電極正交而相互平行的90根指狀電極的電極圖案。作為目標的指狀電極圖案的煅燒後的尺寸為線寬成為45μm~55μm、膜厚成為15μm~25μm的範圍。另外，匯流排電極是以煅燒後的線寬成為約1.5mm的方式來設定。 Then, the prepared conductive composition of Examples 1 to 21 was used to print a light-receiving surface electrode (Ag electrode) on the antireflection film by screen printing in the atmospheric environment at room temperature. The electrode pattern was dried at 120 ° C. Specifically, as shown in FIG. 2, an electrode pattern including three linear bus electrodes that are parallel to each other and 90 finger electrodes that are orthogonal to the bus electrodes and parallel to each other is formed by screen printing. The size of the target finger electrode pattern after firing is in a range of a line width of 45 μm to 55 μm and a film thickness of 15 μm to 25 μm. In addition, the bus bar electrode was set so that the line width after firing might become about 1.5 mm.
於大氣環境中，使用近紅外線高速煅燒爐，於煅燒溫度700℃~800℃下將如上所述於兩面分別印刷有電極圖案的基板進行煅燒，藉此製作評價用的太陽電池。 In the atmospheric environment, a near-infrared high-speed calcining furnace was used to calcinate the substrate on which the electrode patterns were printed on both sides as described above at a calcination temperature of 700 ° C. to 800 ° C. to produce a solar cell for evaluation.
[評價] [Evaluation]
對於以所述方式製作的太陽電池的受光面電極(指狀電極)，藉由以下的順序來測定膜厚、線寬、串聯電阻Rs以及能量轉換效率Eff。 With respect to the light-receiving surface electrode (finger electrode) of the solar cell produced in the manner described above, the film thickness, line width, series resistance Rs, and energy conversion efficiency Eff were measured in the following procedures.
關於電極的膜厚及線寬，利用形狀分析雷射顯微鏡(基恩斯(Keyence)股份有限公司製造)來測定各例的太陽電池的受光面電極的任意位置的厚度(高度)及線寬。將其結果作為對100處測定的值的平均值而示於表2中。 Regarding the film thickness and line width of the electrode, a shape analysis laser microscope (manufactured by Keyence Co., Ltd.) was used to measure the thickness (height) and line width of the light receiving surface electrode of each example of the solar cell. The results are shown in Table 2 as an average value of the values measured at 100 points.
電極的串聯電阻Rs以及能量轉換效率Eff是根據使用太陽模擬器(貝格(Beger)公司製造，PSS10)，對各例的太陽電池所獲得的I-V曲線，且基於JIS C8913中規定的「結晶系太陽電池單元功率測定方法」來算出。將其結果作為利用太陽模擬器來獲得的100個資料的平均值而示於表2中。 The series resistance Rs of the electrodes and the energy conversion efficiency Eff are based on the IV curve obtained for each example of the solar cell using a solar simulator (Beger Corporation, PSS10), and based on the "crystalline system" specified in JIS C8913 Solar cell power measurement method ". The results are shown in Table 2 as an average of 100 data obtained by a solar simulator.
如表2所示，例5、例12及例19是雖於導電性組成物中使用SiO2含量比較多，為7質量%的玻璃料，但未調配矽酮樹脂的例子。使用該些導電性組成物來形成的電極並不依存於玻璃料的組成，確認與其他例的電極相比較，膜厚有意地變薄。即可知，不包含矽酮樹脂的導電性組成物的印刷體(塗膜)鬆弛，形狀穩定性低。 As shown in Table 2, Example 5, Example 12, and Example 19 are examples in which a glass frit having a relatively high SiO 2 content of 7% by mass was used in the conductive composition, but a silicone resin was not blended. The electrode formed using these conductive compositions does not depend on the composition of the glass frit, and it was confirmed that the film thickness is intentionally thin compared to the electrodes of other examples. That is, it is understood that the printed body (coating film) of the conductive composition not containing a silicone resin is loosened, and the shape stability is low.
與此相對，可知使用SiO2的比例為0質量%、3質量%及5質量%的玻璃料且包含矽酮樹脂的例1~例4、例8~例11及例15~例18的導電性組成物可形成較所述的例5、例12及例19而言膜厚更厚的電極。即可確認，煅燒中的形狀穩定性提高，可不依存於玻璃料的組成而形成縱橫比高的電極。另外可確認，使用該導電性組成物來製作的太陽電池的串聯電阻Rs大致低，轉換效率Eff高，隨著縱橫比的提高而發電性能得到改善。 On the other hand, it can be seen that the conductivity of Examples 1 to 4, Example 8 to Example 11, and Example 15 to Example 18 using a glass frit containing SiO 2 at 0% by mass, 3% by mass, and 5% by mass, and containing a silicone resin is known The sexual composition can form electrodes having a thicker film thickness than those of Examples 5, 12, and 19. That is, it was confirmed that the shape stability during firing is improved, and an electrode having a high aspect ratio can be formed without depending on the composition of the glass frit. In addition, it was confirmed that the series resistance Rs of a solar cell produced using this conductive composition is substantially low, the conversion efficiency Eff is high, and the power generation performance is improved as the aspect ratio is increased.
此外，關於玻璃料中的SiO2的比例為7質量%且包含矽酮樹脂的例6、例7、例13、例14、例20及例21的導電性組成物，與不包含矽酮樹脂的例5、例12及例19相比較，所形成的電極的膜厚變厚，但另一方面，關於串聯電阻以及轉換效率確認到惡化。認為其原因在於：雖可藉由矽酮樹脂的作用而形成大體積的電極，但於煅燒後的電極中存在來源於玻璃料及矽酮樹脂的SiO2，該比較大量的SiO2作為電阻成分而發揮作用。因此可知，於在導電性組成物中調配矽酮樹脂的情況下，玻璃料中的SiO2的比例較佳為設為小於7質量%，例如設為5質量%以下。 In addition, the conductive compositions of Examples 6, 7, 7, 13, 14, 20, and 21 that contained a silicone resin in a proportion of 7 mass% of SiO 2 in the glass frit and did not contain a silicone resin As compared with Examples 5, 12, and 19, the film thickness of the formed electrode became thicker, but on the other hand, deterioration in series resistance and conversion efficiency was confirmed. The reason is considered to be that although a large volume electrode can be formed by the action of a silicone resin, SiO 2 derived from a glass frit and a silicone resin exists in the calcined electrode, and the relatively large amount of SiO 2 is used as a resistance component. Play a role. Therefore, when the silicone resin is blended in the conductive composition, it is found that the proportion of SiO 2 in the glass frit is preferably less than 7 mass%, for example, 5 mass% or less.
另外，包含矽酮樹脂的導電性組成物中，例1、例8及例15為使用不包含SiO2成分的玻璃料的例子。若依據現有的常識，該些例子預計於煅燒時無法與Si基板充分反應，不會形成Si基板/電極界面的良好接觸。然而，與使用包含SiO2成分的玻璃料的例子相比較，例1、例8及例15的太陽電池的串聯電阻以及轉換效率均為同等或更良好的結果。因此認為，藉由在導電性組成物中調配矽酮樹脂，該矽酮樹脂於煅燒中表現出與玻璃料中的SiO2同等的作用，作為SiO2的代替品而發揮功能。而且可確認，藉由在導電性組成物中調配矽酮樹脂，可使玻璃料中的SiO2的比例削減或成為零。不包含SiO2的玻璃料由於能夠大幅度降低軟化點，故而認為可藉由使用包含此種玻璃料的導電性組成物來降低電極形成時的煅燒溫度。 In the conductive composition containing a silicone resin, Examples 1, 8 and 15 are examples using a glass frit that does not contain a SiO 2 component. If based on existing common sense, these examples are not expected to fully react with the Si substrate during firing, and will not form a good contact between the Si substrate / electrode interface. However, compared with the example using the glass frit containing the SiO 2 component, the series resistance and conversion efficiency of the solar cells of Examples 1, 8, and 15 were all the same or better results. So that, by the deployment of one silicone resin in the conductive composition, the silicone resin exhibits a ketone in the firing in the same role and SiO 2 glass frit, a substitute for the SiO 2 functions. In addition, it was confirmed that by blending the silicone resin in the conductive composition, the proportion of SiO 2 in the glass frit can be reduced or reduced to zero. Since a glass frit not containing SiO 2 can greatly reduce the softening point, it is considered that the use of a conductive composition containing such a glass frit can reduce the firing temperature during electrode formation.
進而，包含矽酮樹脂的導電性組成物中，例3、例10及例17是將矽酮樹脂抑制為極少量的例子。即便是此種極少量的矽酮樹脂的添加，與使用SiO2含量為7質量%的玻璃料的例5、例12及例19相比較，亦不僅可形成膜厚較厚的電極，而且太陽電池的串聯電阻以及轉換效率為同等或更良好的結果。因此可知，藉由在導電性組成物中調配即便是極少量的矽酮樹脂，亦獲得使印刷或煅燒中的導電性組成物(塗佈物)的形狀穩定性提高的效果，可形成縱橫比得到改善的電極。 Furthermore, in the conductive composition containing a silicone resin, Examples 3, 10, and 17 are examples in which the silicone resin was suppressed to a very small amount. Even if such a very small amount of silicone resin is added, compared with Examples 5, 12, and 19 in which a glass frit having an SiO 2 content of 7% by mass is used, not only a thicker electrode can be formed, but also the sun The battery's series resistance and conversion efficiency are the same or better results. Therefore, it can be seen that by blending even a very small amount of a silicone resin in the conductive composition, the effect of improving the shape stability of the conductive composition (coated product) during printing or firing can be obtained, and an aspect ratio can be formed. Improved electrodes.
(實施形態2) (Embodiment 2)
[導電性組成物的製備] [Preparation of conductive composition]
藉由以下的順序，對於矽酮樹脂的重量平均分子量對導電性組成物的特性造成的影響進行評價。即，使用實施形態1中的A5作為玻璃料。另外，使用重量平均分子量Mw為(S1)3000、(S2)1萬、(S3)2萬、(S4)5萬、(S5)7萬、(S6)9萬及(S7)11萬的七種聚二甲基矽氧烷作為矽酮樹脂。而且，相對於銀粉末100質量份而調配0.3質量份的該些矽酮樹脂的任一者，其他條件設為與所述實施形態1相同，來製備S1~S7的導電性組成物。此外，為了進行比較，亦準備不調配矽酮樹脂的S0的導電性組成物。 The influence of the weight average molecular weight of the silicone resin on the characteristics of the conductive composition was evaluated by the following procedure. That is, A5 in Embodiment 1 was used as the glass frit. In addition, the weight average molecular weight Mw is (S1) 3000, (S2) 10,000, (S3) 20,000, (S4) 50,000, (S5) 70,000, (S6) 90,000 and (S7) 110,000. A polydimethylsiloxane is used as the silicone resin. In addition, 0.3 mass parts of any of these silicone resins were blended with respect to 100 mass parts of silver powder, and other conditions were set to be the same as those in the first embodiment to prepare conductive compositions S1 to S7. In addition, for comparison, a conductive composition of S0 in which a silicone resin is not prepared is also prepared.
繼而，使用如上所述所準備的S0~S7的導電性組成物，以與所述實施形態1相同的方式，利用網版印刷法來形成S0~S7的太陽電池元件。 Then, using the conductive compositions S0 to S7 prepared as described above, the solar cell elements S0 to S7 were formed by the screen printing method in the same manner as in the first embodiment.
[評價] [Evaluation]
對於以所述方式形成的受光面電極(指狀電極)，藉由以下的順序來測定斷線數、縱橫比以及線路電阻RL。 With respect to the light-receiving surface electrode (finger electrode) formed as described above, the number of disconnections, the aspect ratio, and the line resistance R L were measured in the following procedure.
關於電極的斷線數，使用太陽電池電致發光(Electro Luminescence，EL)檢查裝置，對100塊的各基板指定電極的斷線部位(龜裂部分)，來測定其數量。將其結果作為每1塊基板的斷線部位數的平均值而示於圖3中。 With regard to the number of electrode disconnections, a solar cell electroluminescence (EL) inspection device was used to specify the electrode disconnection locations (cracked portions) of each of the 100 substrates, and the number was measured. The result is shown in FIG. 3 as an average value of the number of disconnected portions per one substrate.
電極的縱橫比是藉由利用形狀分析雷射顯微鏡(基恩斯(Keyence)股份有限公司製造)來測定各例的受光面電極的寬度W及厚度(高度)H，以(H/W)的形式算出縱橫比來求出。將其結果作為對受光面電極100處測定的值的平均值而示於圖3中。 The aspect ratio of the electrodes was calculated by measuring the width W and thickness (height) H of the light-receiving surface electrode of each example using a shape analysis laser microscope (manufactured by Keyence Co., Ltd.). Find the aspect ratio. The results are shown in FIG. 3 as an average value of the values measured at the light-receiving surface electrode 100.
電極的線路電阻值是使用電阻計(日置電機股份有限公司製造，數位萬用錶(digital hitester))，作為指狀電極表面的任意間隔(24mm)的電阻值(Ω)來測定。將其結果作為對受光面電極100處測定的值的平均值而示於圖4中。 The electrode line resistance value was measured using a resistance meter (manufactured by Hitachi Electric Co., Ltd., a digital multimeter (digital hitester)) as the resistance value (Ω) at an arbitrary interval (24 mm) on the surface of the finger electrode. The results are shown in FIG. 4 as an average value of the values measured at the light-receiving surface electrode 100.
圖3及圖4的圖表中的標記是依據X軸(即重量平均分子量Mw)，自左側起依次表示S0~S7的結果。 The marks in the graphs of FIGS. 3 and 4 are based on the X axis (that is, the weight average molecular weight Mw), and the results of S0 to S7 are shown in order from the left.
如圖3所明示，可確認，藉由在導電性組成物中添加矽酮樹脂，電極的縱橫比大幅度提高。另外，所添加的矽酮樹脂的重量平均分子量變得越大，可形成越高縱橫比的電極，預計矽酮樹脂中所含的Si有助於維持電極的形狀。 As clearly shown in FIG. 3, it was confirmed that by adding a silicone resin to the conductive composition, the aspect ratio of the electrode was significantly improved. In addition, as the weight average molecular weight of the added silicone resin becomes larger, an electrode having a higher aspect ratio can be formed, and it is expected that Si contained in the silicone resin will help maintain the shape of the electrode.
另外，根據圖3可確認，在導電性組成物中添加矽酮樹脂，另外，根據所述添加的矽酮樹脂的重量平均分子量，電極的斷線數變化。即可確認，本實施形態中，藉由將重量平均分子量例如為9萬以下的矽酮樹脂添加於導電性組成物中，則與不添加矽酮樹脂的情況相比，可減少電極的斷線數。然而可知，若使用重量平均分子量超過9萬，例如為11萬的矽酮樹脂，則存在斷線數增大的傾向。 In addition, it was confirmed from FIG. 3 that a silicone resin was added to the conductive composition, and that the number of disconnections of the electrode changed according to the weight average molecular weight of the added silicone resin. That is, in this embodiment, by adding a silicone resin having a weight-average molecular weight of, for example, 90,000 or less to the conductive composition, it is possible to reduce the disconnection of the electrode compared to the case where no silicone resin is added. number. However, it was found that when a silicone resin having a weight average molecular weight exceeding 90,000, for example, 110,000, is used, the number of broken wires tends to increase.
如圖4所明示，可知，電極的線路電阻受到導電性組成物中的矽酮樹脂的重量平均分子量的影響。該結果顯示出與斷線數的結果相似的傾向。即，就使電極形狀進行高縱橫比化的觀點而言，較佳為於導電性組成物中添加矽酮樹脂。然而，若含有過剩的Si成分，則會導致電極的斷線，因此可成為電阻成分。根據 該些情況可知，為了使電極的高縱橫比化與低電阻特性併存，較佳為使用重量平均分子量適當的矽酮樹脂。還可知，本實施形態中，添加於導電性組成物中的矽酮樹脂較佳為使用例如重量平均分子量小於11萬、更佳為大致9萬以下左右者。 As is clear from FIG. 4, it is understood that the line resistance of the electrode is affected by the weight average molecular weight of the silicone resin in the conductive composition. This result shows a tendency similar to the result of the number of broken lines. That is, it is preferable to add a silicone resin to a conductive composition from a viewpoint of making an electrode shape high aspect ratio. However, if an excessive Si component is contained, the electrode may be disconnected, and thus it may become a resistance component. according to In these cases, it was found that in order to coexist the high aspect ratio of the electrode and the low resistance characteristics, it is preferable to use a silicone resin having a suitable weight average molecular weight. It can also be seen that in the present embodiment, the silicone resin added to the conductive composition is preferably one having a weight average molecular weight of less than 110,000 and more preferably approximately 90,000 or less.
(實施形態3) (Embodiment 3)
[導電性組成物的製備] [Preparation of conductive composition]
藉由以下的順序來製備導電性組成物，對組成物內的矽酮樹脂與串聯電阻Rs的關係進行評價。此處，玻璃料是使用作為有鉛系玻璃且SiO2成分的含量為5質量%的「A5」、作為無鉛系玻璃1且SiO2成分的含量為5質量%的「B5」。另外，使用重量平均分子量Mw為5萬的聚二甲基矽氧烷作為矽酮樹脂。而且，使該些玻璃料與矽酮樹脂相對於100質量份銀粉末的比例以下述表3所示的組合來變化，其他條件設為與所述實施形態1相同，來製備導電性組成物。另外，藉由使用該些導電性組成物形成受光面電極，來製作太陽電池元件。 A conductive composition was prepared by the following procedure, and the relationship between the silicone resin in the composition and the series resistance Rs was evaluated. Here, the glass frit is "A5" which is a leaded glass and whose content of SiO 2 component is 5 mass%, and "P5" which is a lead-free glass 1 and whose content of SiO 2 component is 5 mass%. In addition, as the silicone resin, polydimethylsiloxane having a weight average molecular weight Mw of 50,000 was used. In addition, the ratio of the glass frit and the silicone resin to 100 parts by mass of silver powder was changed in a combination shown in Table 3 below, and other conditions were set to be the same as in the first embodiment to prepare a conductive composition. In addition, a solar cell element is produced by forming a light-receiving surface electrode using these conductive compositions.
測定以所述方式準備的太陽電池元件的串聯電阻Rs，示於表3中。此外已知，與使用無鉛系玻璃料B5的導電性組成物相比較，使用有鉛系玻璃料A5的導電性組成物可形成串聯電阻Rs等特性高的電極。因此，下述表3中，於使用玻璃料A5的情況下將Rs≦3.73時判斷為電阻低而良好，於使用玻璃料B5的情況下將Rs≦3.91時判斷為電阻低而良好。而且，將表3中的電阻低而良好的結果以粗體字表示。 Table 3 shows the measurement of the series resistance Rs of the solar cell element prepared as described above. In addition, it is known that, compared with a conductive composition using a lead-free glass frit B5, a conductive composition using a lead-based glass frit A5 can form an electrode having high characteristics such as series resistance Rs. Therefore, in the following Table 3, when the glass frit A5 is used, Rs ≦ 3.73 is determined to be low and the resistance is good, and when the glass frit B5 is used, Rs ≦ 3.91 is determined to be low and the resistance is good. In addition, the results with low resistance in Table 3 are shown in bold.
另外，根據表3所示的玻璃料與矽酮樹脂的調配量來算出玻璃料相對於矽酮樹脂的比例，示於表4中。此外，表4中，對於表3中電阻變得良好的玻璃料與矽酮樹脂的調配量的組合，將結果以粗體字表示。 In addition, Table 4 shows the ratio of the glass frit to the silicone resin based on the blending amounts of the glass frit and the silicone resin shown in Table 3. Moreover, in Table 4, the result of the combination of the compounding quantity of the glass frit and silicone resin which became favorable in Table 3 is shown in bold.
[評價] [Evaluation]
如表3所示，可知，本實施形態中，若導電性組成物中所含的矽酮樹脂量大致為0.2質量份以下的範圍，則可藉由將玻璃料的添加量限定於既定的範圍內，來有效地降低串聯電阻Rs。例如可知，不論玻璃組成如何，均可藉由將玻璃料的添加量限定為1.875質量份~3.125質量份，來有效地降低串聯電阻Rs。 As shown in Table 3, it can be seen that, in the present embodiment, if the amount of the silicone resin contained in the conductive composition is within a range of approximately 0.2 parts by mass or less, the amount of the glass frit to be added can be limited to a predetermined range. To effectively reduce the series resistance Rs. For example, it can be seen that the series resistance Rs can be effectively reduced by limiting the addition amount of the glass frit to 1.875 parts by mass to 3.125 parts by mass regardless of the composition of the glass.
另一方面可知，若導電性組成物中所含的矽酮樹脂量為大致超過0.15質量份的(例如0.2質量份以上的)範圍，則可藉由將玻璃料量相對於矽酮樹脂量的比(玻璃料質量/矽酮樹脂質量)限定於既定的範圍內，來有效地降低串聯電阻Rs。例如可知，不論玻璃組成如何，均可藉由將所述玻璃料量的比限定於大致7.5~18左右、較佳為8.33~16.67左右的範圍內，來有效地降低串聯電阻Rs。認為其原因在於：例如，若使導電性組成物中所含的矽酮樹脂量增大，則為了使所形成的電極的串聯電阻Rs保持為低值，需要增加玻璃料的添加量。即，若於導電性組成物中包含矽酮樹脂，則可於電極煅燒中由該矽酮樹脂來生成SiO2成分。該SiO2成分與玻璃料中的SiO2成分同樣地，顯示出抑制電極與抗反射膜或基板的界面的侵蝕的作用。因此，可以說為了表現出良好的經火特性，而且實現電極及基板的良好接觸，較佳為將玻璃料的添加量預先調整為與添加於導電性組成物中的矽酮樹脂量相適應的值。 On the other hand, it was found that if the amount of the silicone resin contained in the conductive composition is in the range of more than 0.15 parts by mass (for example, 0.2 parts by mass or more), the amount of the glass frit relative to the amount of the silicone resin The ratio (glass frit mass / silicone resin mass) is limited to a predetermined range to effectively reduce the series resistance Rs. For example, it can be seen that, regardless of the glass composition, the series resistance Rs can be effectively reduced by limiting the ratio of the frit amount to approximately 7.5 to 18, preferably 8.33 to 16.67. This is considered to be because, for example, if the amount of the silicone resin contained in the conductive composition is increased, in order to keep the series resistance Rs of the formed electrode to a low value, it is necessary to increase the amount of glass frit added. That is, when a silicone resin is included in the conductive composition, a SiO 2 component can be generated from the silicone resin during electrode firing. Like the SiO 2 component in the glass frit, this SiO 2 component exhibits the effect of suppressing the erosion of the interface between the electrode and the antireflection film or the substrate. Therefore, it can be said that in order to exhibit good fire resistance characteristics and achieve good contact between the electrode and the substrate, it is preferable to adjust the amount of the glass frit added in advance to be compatible with the amount of the silicone resin added to the conductive composition. value.
以上，已藉由較佳的實施形態對本發明進行了說明，但所述記述並非限定事項，當然可進行各種改變。 The present invention has been described above with reference to the preferred embodiments, but the description is not a limitation and it is needless to say that various changes can be made.
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| US10741300B2 (en) | 2016-10-07 | 2020-08-11 | E I Du Pont De Nemours And Company | Conductive paste composition and semiconductor devices made therewith |
| US10593439B2 (en) | 2016-10-21 | 2020-03-17 | Dupont Electronics, Inc. | Conductive paste composition and semiconductor devices made therewith |
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| CN112509727B (en) * | 2020-11-10 | 2022-08-12 | 广东工业大学 | Inner electrode copper paste for low-temperature co-fired ceramic and preparation method and application thereof |
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