TW201247416A - Layered material and assembly joined by the same - Google Patents

Layered material and assembly joined by the same Download PDF

Info

Publication number
TW201247416A
TW201247416A TW101106223A TW101106223A TW201247416A TW 201247416 A TW201247416 A TW 201247416A TW 101106223 A TW101106223 A TW 101106223A TW 101106223 A TW101106223 A TW 101106223A TW 201247416 A TW201247416 A TW 201247416A
Authority
TW
Taiwan
Prior art keywords
layer
metal
sintered
metal nanoparticle
bonding
Prior art date
Application number
TW101106223A
Other languages
Chinese (zh)
Other versions
TWI556973B (en
Inventor
Kazuhiko Yamasaki
Fuyumi Mawatari
Original Assignee
Mitsubishi Materials Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Materials Corp filed Critical Mitsubishi Materials Corp
Publication of TW201247416A publication Critical patent/TW201247416A/en
Application granted granted Critical
Publication of TWI556973B publication Critical patent/TWI556973B/en

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/58—Optical field-shaping elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/58—Optical field-shaping elements
    • H01L33/60—Reflective elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
    • H01L2224/838—Bonding techniques
    • H01L2224/8384—Sintering
    • 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

Landscapes

  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • General Physics & Mathematics (AREA)
  • Photovoltaic Devices (AREA)
  • Led Device Packages (AREA)
  • Laminated Bodies (AREA)
  • Conductive Materials (AREA)
  • Die Bonding (AREA)
  • Powder Metallurgy (AREA)

Abstract

A layered material 1 comprises a metal nanoparticles sintered layer 11 and a junction layer 12 containing metal particles or metal oxide particles. An assembly joined by a layered material is able to utilize the layered material which significantly reduces manufacturing cost and is able to utilize an LED device which includes the layered material. The assembly joined by a layered material is provided by using a metal paste such as metal particles and solvent as major components and therefore, the manufacturing process is simplified.

Description

201247416 六、發明說明： 【發明所屬之技術領域】 本發明係關於用以接合一對被接合體之接合用積層體 ，以及含有該接合用積層體之接合體。該接合用積層體及 接合體，尤其適合於發光元件和太陽能電池。 【先前技術】 近年來，發光元件，尤其是led光源，乃伴隨著高 亮度化等而應用在各種領域中。特別是由於可實現白色 LED光源，而使用在照明器具和液晶顯示器的背光等用途 〇 爲了進一步提高LED光源的亮度等，係探討可有效 率地應用來自LED元件的發光之做法，而揭示有一種具 備有：支撐基板、裝載於該支撐基板上之LED元件、以 及含有螢光劑之封合劑，在基板與LED元件之間具備有 用以使LED元件的發光反射之鍍Ag電極膜，並且在鍍 Ag電極膜上具有鈦薄膜之LED光源（專利文獻1 )。 該LED光源，是藉由在支撐基板與LED元件之間設 置導電性反射膜層而有效率地使來自發光體的光反射以增 加發光強度。在此’ Ag薄膜與鈦薄膜係藉由電鍍法或真 空成膜法所形成。 然而’電鍍法會令人預想到其繁瑣的步驟和廢液的產 生，而真空成膜法則爲了維持大型的真空成膜裝置並使其 運轉1而耗費大量成本。上述LED光源，僅依據鍍Ag電 201247416 極膜者，會產生熱劣化或光劣化，故需形成鈦薄膜而須倂 用電鍍法及真空成膜法。 此外，LED光源須採用將基板與LED元件接合之構 造，一般而言，較多是採用金屬膏或焊錫等來接合。尤其 當使用Au-Sn合金焊錫等時，可得到良好的散熱特性（專 利文獻2 )。 然而，該方法中，爲了防止LED元件電極的「焊錫 侵蝕」，且爲了防止金屬從電極的擴散，必須以電鍍法或 真空成膜法來設置Ni、Ti等之複數層接合層，而具有花 費極大的成膜成本之缺點。用以防止該焊錫侵蝕之接合層 ，在Au-Sn合金焊錫以外的無鉛焊錫等情況中亦爲必要。 再者，當使用先前的濺鍍法或真空成膜法，將由複數 層透明膜所構成之具有增強反射構造的反射膜設置在LED 元件的內面，並且設置散熱特性高之金屬接合構造時，由 於前述透明膜與接合用的金屬膜間之接合不良，因而亦產 生難以提高密著性之問題。 除此之外’依據Au-Sn合金焊錫所形成之接合，一般 是在2 70~40 0°C ’較多情形是在300~35(TC的高溫中進行 ’但就抑制LED元件的劣化和降低製造時的能量之觀點 來看，乃期望可在更低溫下進行接合。 [先前技術文獻] [專利文獻] [專利文獻1]日本特開2009-231568號公報 201247416 [專利文獻2]日本特開2008-10545號公報 【發明內容】 (發明所欲解決之課題） 本發明之課題在於提供一種相對於以電鍍法或真空成 膜法所成膜之昂貴的Ni接合層，藉由採用以金屬粒子與 溶劑爲主成分之金屬膏等來取而代之，可簡化製造步驟並 大幅地改善運轉成本，並且可在低溫下進行接合之接合用 積層體，以及含有該接合用積層體之可使用在LED元件 等發光元件之接合體。該接合用積層體，亦可應用在其他 用途的接合體，尤其適合於用作爲使用反射膜之太陽能電 池之接合體。 (用以解決課題之手段） 本發明係關於藉由以下所示之型態來解決上述課題之 接合用積層體及接合體。 (1) 一種接合用積層體，其特徵爲具備有：金屬奈 米粒子燒結體層，以及積層於該金屬奈米粒子燒結體層上 之含有金屬粒子或金屬氧化物粒子之接合層。 (2) 如上述（1)之接合用積層體，其中前述金屬奈 米粒子燒結體層，具備有積層於與前述接合體爲相反側之 透明層。 (3) 如上述（1)或（2)之接合用積層體，其係進 一步具備有：形成於前述金屬奈米粒子燒結體層與前述接 201247416 合層之間之黏合劑層。 (4) 如上述（1)至（3)中任一項之揆合用積層體 ，其中前述金屬奈米粒子燒結體層含有75質量％以上的 銀，並且含有金、銅、錫 '鋅、鉬及錳之至少1種的第2 金屬。 (5) 如上述（1)至（4)中任一項之接合用積層體 ，其中前述金屬奈米粒子燒結體層含有黏合劑。 (6) 如上述（1)至（5)中任一項之接合用積層體 ，其中前述金屬奈米粒子燒結體層的厚度爲〇.〇1〜〇.5/zm 〇 (7) 如上述（1)至（6)中任一項之揆合用積層體 ，其中前述各層是在藉由濕式塗佈法成膜後，在130~2 50 °C中燒結之層。 (8) 如上述（3)至（7)中任一項之接合用積層體 ’其中前述透明層及前述黏合劑層，含有藉由加熱而硬化 之聚合物型黏合劑及非聚合物型黏合劑的至少1種。 (9) 如上述（7)或（8)之接合用積層體，其中前 述濕式塗佈法，爲噴霧塗佈法、分注塗佈法、旋轉塗佈法 、刮刀塗佈法、狹縫塗佈法、噴墨塗佈法、網版印刷法、 平版印刷法、轉印法及壓鑄模塗佈法中的任—種。 (10) —種接合體，其特徵係具備有：第1被接合體 ，上述（1)至（9)中任一項之接合用積層體，以及第2 被接合體。 (11) 如上述（10)之接合體，其中前述第1被接合 -8- 201247416 體爲可發光或可光電轉換之元件，前述金屬奈米粒子燒結 體層可使來自前述第1被接合體的光反射，前述第2被接 合體爲基板。 (12) 如上述（11)之接合體，其中前述第1被接合 體爲可發光之元件，並使用作爲發光源。 (13) 如上述（11)之接合體，其中前述第1被接合 體爲可光電轉換之元件，並使用作爲太陽能電池。 發明之效果： 根據本發明之型態（1 )，可在低溫下對被接合體進 行接合，且可得到高接合可靠度。此外，成膜層數少，不 需昂貴的成膜裝置，可達到大幅度的低成本化。此外，本 發明之型態（2)的透明層，與電鍍法或真空成膜法相比 ，透明層可使用之材料的自由度高，可任意地設定透明層 的折射率，而能夠控制因金屬奈米粒子燒結體層所帶來之 增強反射效果。 根據本發明之型態（1 0 )，可容易地提供可在低溫下 對被接合體進行接合，且具有高接合可靠度之接合體。此 外，根據本發明之型態（1 2 )，可提供一種LED元件所 發光之光的應用效率高之發光源，根據本發明之型態（13 )’可提供一種光電轉換效率高之太陽能電池。 【實施方式】 以下係根據實施形態來具體地說明本發明。「％」在 -9 - 201247416 未特別表示時，且在數値固有以外的情形下’爲「質量％ [接合用積層體] 本實施形態之接合用積層體，係具備有：金屬奈米粒 子燒結體層，以及直接或間接積層於該金屬奈米粒子燒結 體層上之含有金屬粒子或金屬氧化物粒子之接合層。以下 依序說明金屬奈米粒子燒結體層及接合層。 《金屬奈米粒子燒結體層》 金屬奈米粒子燒結體，係將導電性或反射性及密著性 賦予至接合層。金屬奈米粒子燒結體層，可藉由濕式塗佈 法使金屬奈米粒子燒結體層用組成物成膜，並在乾燥後進 行燒結而形成。 金屬奈米粒子燒結體層，較佳係含有75質量％以上 的銀，並且含有選自由金、鉑、鈀、釕、鎳、銅、錫、銦 、鋅、鐵、鉻、鉬及錳所組成之群組的至少1種第2金屬 。爲上述組成時，導電性、反射性佳。前述第2金屬，尤 佳爲選自由金、銅、錫、鋅、鉬及錳所組成之群組的至少 1種。特佳爲錫。 前述金屬奈米粒子燒結體層’鄰接之金屬奈米粒子相 互擴散並形成粒成長，粒成長後之粒子彼此間成爲殘留氣 孔之狀態。如此，藉由使用奈米粒子，可形成緊密的膜。 前述金屬奈米粒子燒結體層，就導電性之觀點來看， -10- 201247416 該厚度較佳爲0.01〜0.5/Z m。厚度尤佳爲0.05-0.2以m。 前述金屬奈米粒子燒結體層的氣孔率，較佳爲 1〜20vol%，尤佳爲l~10vol%。位於該範圍時，不僅可在 低溫下形成，並且可得到良好的導電性及反射率。 前述金屬奈米粒子燒結體層用組成物，含有金屬奈米 粒子，前述金屬奈米粒子，較佳係含有75質量％以上的 銀奈米粒子，尤佳含有8 0質量％以上的銀奈米粒子。銀 奈米粒子的含量相對於金屬奈米粒子燒結體層：1〇〇質量 %而言較佳含有75質量％以上之理由，是由於未達75質 量％時，使用該組成物所形成之電極的導電性及反射率會 降低之故。 前述金屬奈米粒子燒結體層用組成物中的金屬奈米粒 子，較佳是以碳骨架爲碳數1~3的有機分子主鏈之保護劑 進行化學改質者。此時，當爲了形成金屬奈米粒子燒結體 層而在基材上塗佈金屬奈米粒子燒結體層用組成物後進行 燒結時，保護金屬奈米粒子的表面之保護劑中的有機分子 會脫離或分解，或是脫離並分解。藉此，可容易得到實質 上不含有對電極的導電性及反射率造成不良影響之有機物 殘渣之以金屬爲主成分的電極之故。將對金屬奈米粒子進 行化學改質之保護劑的有機分子主鏈之碳骨架的碳數設爲 1〜3的範圍者，是由於當碳數爲4以上時，難以藉由燒結 時的熱使保護劑脫離或分解（分離並燃燒），而在金屬奈 米粒子燒結體層內容易殘留對金屬奈米粒子燒結體層的導 電性及反射率造成不良影響之有機物殘渣之故。 -11 - 201247416 再者，尤佳者係保護劑，亦即將金屬奈米粒子表面進 行化學改質之保護分子，含有羥基（-OH)及羰基（-C = 0 )中的任一方或兩者。當將銀奈米粒子等之金屬奈米粒子 進行化學改質之保護劑含有羥基（-OH )時，組成物的分 散穩定性佳，對於塗膜的低溫燒結亦可有效地作用，當將 銀奈米粒子等之金屬奈米粒子進行化學改質之保護劑中含 有羰基（-C = 0 )時，金屬奈米粒子燒結體層用組成物的 分散穩定性佳，對於金屬奈米粒子燒結體層的低溫燒結亦 可有效地作用。 前述金屬奈米粒子燒結體層用組成物中的金屬奈米粒 子，較佳是以數量平均計含有70 %以上；t 一次粒徑： 10~5 0nm範圍內的金屬奈米粒子，尤佳爲含有75%以上 » 10〜50nm範圍內的金屬奈米粒子之含量相對於全部金屬 奈米粒子100%而言較佳以數量平均計含有70%以上之理 由如下。當前述含量未達70%時，金屬奈米粒子的比表 面積增大，使保護劑所佔之比率增大，即使是容易藉由燒 結時的熱使使保護劑脫離或分解（分離並燃燒）之有機分 子，亦會在電極內殘留多量來自保護材之有機殘渣。當該 有機殘渣變質或劣化時，會產生電極的導電性及反射率降 低之疑慮》此外，當金屬奈米粒子的粒度分布過廣時，電 極的密度容易降低，容易使電極的導電性及反射率降低。 上述金屬奈米粒子的一次粒徑較佳設爲l〇~50nm範圍內 之理由，是由於金屬奈米粒子隨時間經過之穩定性（長年 穩定性）良好之故。在此，一次粒徑可藉由依據堀場製作 -12- 201247416 所公司製的LB-550所進行之動態光散射法來 ，除了特別記載之情況外，平均粒徑是藉由相 定。 前述第2金屬的金屬奈米粒子’相對於含 金屬奈米粒子：1〇〇質量％而言’較佳爲〇.02 且未達25質量％，尤佳爲〇.〇3質量％〜2 0質 第2金屬的含量相對於全部金屬奈米粒子1 00 較佳設爲0.02質量％以上且未達25質量％之 於耐候性試驗（保持在溫度l〇〇°C且濕度50% 槽1 000小時之試驗）後之金屬奈米粒子燒結 性及反射率與耐候性試驗前相比不會惡化之故 25質量％以上時，燒結不久後之金屬奈米粒 的導電性及反射率會降低，且耐候性試驗後之 子燒結體層的導電性及反射率與耐候性試驗前 〇 金屬奈米粒子燒結體層用組成物，可進一 由金屬氧化物、金屬氫氧化物、有機金屬化合 所組成之群組的1種或2種以上添加物。藉由 粒子燒結體層用組成物中進一步含有1種或2 述種類的添加物，可賦予進一步抑制因金屬奈 燒結所導致之粒成長之效果，故可製作出因應 形狀。添加物的添加比率，相對於金屬奈米粒 用組成物：100質量％而言，較佳爲0.1質量 %的範圍內。當中尤佳爲1〜5質量％的範圍內 測定。以下 同方法來測 有銀之全部 質量％以上 量％。前述 質量％而言 理由，是由 的恆溫恆濕 體層的導電 。前述値爲 子燒結體層 金屬奈米粒 相比爲降低 步含有選自 物、及矽油 在金屬奈米 種以上之上 米粒子間的 目的的表面 子燒結體層 % ~20質量 -13- 201247416 用作爲添加物之金屬氧化物，較佳爲含有選自由鋁、 矽、鈦、鉻、錳、鐵、鈷、鎳、銀、銅、鋅、鉬、錫、銦 、及銻所組成之群組的至少1種之氧化物或複合氧化物。 複合氧化物，具體爲氧化銦-氧化錫系複合氧化物（ Indium Tin Oxide: ITO)、氧化錄-氧化錫系複合氧化物 (Antimony Tin Oxide: ΑΤΟ)、氧化銦-氧化鋅系複合氧 化物（Indium Zinc Oxide : ΙΖΟ)等。 用作爲添加物之金屬氫氧化物，較佳爲含有選自由鋁 、矽、鈦、鉻、錳、鐵、鈷、鎳、銀、銅、鋅、鉬、錫、 銦、及銻所組成之群組的至少1種之氫氧化物。 用作爲添加物之有機金屬化合物，較佳爲矽、鈦、鉻 、錳、鐵、鈷、鎳、銀、銅、鋅、鉬、及錫之金屬皂、金 屬錯合物或烷氧化金屬》例如，金屬皂可使用乙酸鉻、甲 酸錳、檸檬酸鐵、甲酸鈷、乙酸鎳、檸檬酸銀、乙酸銅、 檸檬酸銅、乙酸錫、乙酸鋅、草酸鋅、乙酸鉬等。此外， 金屬錯合物可列舉出乙醯丙酮鋅錯合物、乙醯丙酮鉻錯合 物、乙醯丙酮鎳錯合物等。再者，烷氧化金屬可使用異丙 氧化鈦 '甲基矽酸鹽、異氰酸丙基三甲氧矽烷、胺丙基三 甲氧矽烷等。 用作爲添加物之矽油，可使用純矽油與改質矽油兩者 。改質矽油，可使用進一步將有機基導入於聚矽氧烷之側 鏈的一部分者（側鏈型）、將有機基導入於聚矽氧烷的兩 末端者（兩末端型）、將有機基導入於聚矽氧烷的兩末端 中之任一方者（單末端型）、以及將有機基導入於聚矽氧 -14- 201247416 烷之側鏈的一部分與兩末端者（側鏈兩末端型）。改質矽 油，有反應性矽油與非反應性矽油，該兩種均可使用。所 謂反應性矽油，係表示胺改質、環氧改質、羧改質、甲醇 改質、锍改質、及異種官能基改質（例如環氧基、胺基、 聚醚基），非反應性矽油，係表示聚醚改質、甲基苯乙烯 改質、烷基改質、高級脂肪酸酯改質、氟改質、及親水特 殊改質》 金屬奈米粒子燒結體層用組成物中之金屬奈米粒子的 含量，相對於由金屬奈米粒子與分散介質所構成之分散體 :100質量％而言’較佳係含有2.5〜9 5.0質量％，尤佳含 有3.5-90.0質量％。當金屬奈米粒子的含量相對於由金 屬奈米粒子與分散介質所構成之分散體：100質量％而言 未達2.5質量％時，雖然對燒結後之電極的特性不會造成 影響，但難以得到必要厚度的電極。另一方面，超過95.0 質量％時，組成物於濕式塗佈時，匯市去作爲油墨或膏的 必要流動性。 此外，構成金屬奈米粒子燒結體層用組成物之分散介 質，相對於全部的分散介質100質量％而言含有1質量％ 以上，較佳爲2質量％以上的水，以及2質量％以上，較 佳爲3質量％以上的醇類。例如，當分散介質僅由水及醇 所構成時，含有2質量％的水時，則含有98質量％的醇 ，含有2質量％的醇時，則含有98質量％的水。當水的 含量相對於全部的分散介質100質量％而言未達1質量％ 時，藉由濕式塗佈法塗佈組成物所得之膜，難以在低溫下 -15- 201247416 進行燒結，此外，燒結後之金屬奈米粒子燒結體層的導電 性及反射率亦降低。另一方面，當醇類的含量相對於全部 的分散介質100質量％而言未達2質量％時，與上述相同 ，藉由濕式塗佈法塗佈組成物所得之膜，難以在低溫下進 行燒結，此外，燒結後之電極的導電性及反射率亦降低。 分散介質中所使用之醇類，較佳係使用選自由甲醇、乙醇 、丙醇、丁醇、乙二醇、丙二醇、二乙二醇、甘油、異莰 基己醇及赤藻糖醇所組成之群組的1種或2種以上。 醇類的添加，係用以改善與基材之潤濕性，可配合基 材的種類自由地改變水與醇類之混合比率》 前述金屬奈米粒子燒結體層用組成物，可藉由一般方 法，藉由塗料搖動器、球磨機、砂磨機、稚磨機、三軋輥 等，將期望成分混合，並使金屬奈米粒子等分散而製造出 。當然亦可藉由通常的攪拌操作來製造。 用以使金屬奈米粒子燒結體層用組成物成膜之濕式塗 佈法，較佳爲噴霧塗佈法、分注塗佈法、旋轉塗佈法、刮 刀塗佈法、狹縫塗佈法、噴墨塗佈法、網版印刷法、平版 印刷法、轉印法以及壓鑄模塗佈法中的任一項，但並不限 定於此，可應用任意方法。 噴霧塗佈法，爲藉由壓縮空氣將金屬奈米粒子燒結體 層用組成物形成爲霧狀而塗佈於基材之方法。分注塗佈法 ，例如將金屬奈米粒子燒結體層用組成物裝入於注射器， 並藉由按壓該注射器的活塞，使分散體從注射器前端的細 微噴嘴中吐出，而塗佈於基材之方法。旋轉塗佈法，爲將 -16- 201247416 金屬奈米粒子燒結體層用組成物滴下至旋轉中的基材上， 藉由該離心力將滴下後的金屬奈米粒子燒結體層用組成物 擴散至基材周緣之方法。刮刀塗佈法，係將與刮刀前端隔 著既定空隙之基材，設置爲可在水平方向上移動，並從該 刮刀將金屬奈米粒子燒結體層用組成物供給至上游側的基 材，然後使基材朝下游側水平地移動之方法。狹縫塗佈法 ，爲使金屬奈米粒子燒結體層用組成物從狹窄的狹縫中流 出而塗佈於基材上之方法。噴墨塗佈法，爲將金屬奈米粒 子燒結體層用組成物充塡於市售之噴墨印表機的墨水匣， 而噴墨印刷於基材上之方法。網版印刷法，係使用薄紗作 爲圖形指示材料，並通過該上方所製作之版畫像而將金屬 奈米粒子燒結體層用組成物轉移至基材之方法。平版印刷 法，爲將附著於版上之金屬奈米粒子燒結體層用組成物， 不直接附著於基材，而是從版上先轉印至橡膠薄片，然後 再從橡膠薄片轉移至基材，以應用金屬奈米粒子燒結體層 用組成物的撥水性之印刷方法。壓鑄模塗佈法，係藉由歧 管來分配被供給至壓鑄模之金屬奈米粒子燒結體層用組成 物’並從狹縫中擠壓至薄膜上，而塗佈行進中之基材的表 面之方法。壓鑄模塗佈法，有狹縫塗佈方式或斜板塗佈方 式、淋幕塗佈方式。轉印法可列舉出銷轉印法等。 成膜後之金屬奈米粒子燒結體層用組成物的塗膜乾燥 溫度’較佳爲不會對作爲被接合體的led元件等造成影 響之溫度以下，例如爲6(TC以下，尤佳爲40~50°c。 乾燥後之塗膜的燒結溫度，較佳位於130〜250。(：的範 -17- 201247416 圍。此係由於當未達130 °C時，金屬奈米粒子燒結體層上 會產生硬化不足的缺失之故。此外，超過25〇°C時，無法 活用低溫製程之生產上的優勢，亦即使製造成本上升而使 生產性降低。此外，作爲被接合體的候選物之LED元件 或非晶矽、微晶矽、或使用此等之混成型矽太陽能電池， 其耐熱性相對較弱，會因燒結步驟而使轉換效率降低之故 ^尤佳爲1 30〜200°C。 塗膜的燒結時間較佳爲5〜60分鐘的範圍。此係由於 當燒結時間未達下限値時，金屬奈米粒子燒結體層上會產 生燒結不足的缺失之故。當燒結時間超過上限値時，會使 製造成本上升超過所需而導致生產性降低，此外，亦會產 生LED元件的發光效率或太陽能電池的轉換效率降低之 缺失。 《接合層》 前述接合層，係用以介於前述金屬奈米粒子燒結體層 ，在低溫下將被接合體彼此接合者。該接合層，可藉由濕 式塗佈法使接合層用組成物成膜，並在乾燥後進行燒結而 形成。 前述接合層，就黏著強度、密著性之觀點來看，該厚 度較佳爲0.01〜l〇#m。厚度尤佳爲2〜10&quot; m。 接合層用組成物，可使用金屬奈米粒子基質的接合層 用組成物及金屬化合物基質的接合層用組成物中的任一方 或兩者。以下係依序說明（A)金屬奈米粒子基質的接合 -18- 201247416 層用組成物、（B)金屬化合物基質的接合層用組成物。 (A)金屬奈米粒子基質的接合層用組成物 (A)金屬奈米粒子基質的接合層用組成物係含有金 屬奈米粒子，構成該金屬奈米粒子之金屬，例如可列舉出 鐵、鎳、鈷、釕、铑、鈀、銥、鉑等之週期表第8族金屬 :鈦、鉻、給等之週期表第4A族金屬；釩、鈮、鉬等之 週期表第5A族金屬；鉻、鉬、鎢等之週期表第6A族金 屬；錳等之週期表第7A族金屬；銅、銀、金等之週期表 第1B族金屬；鋅、鎘等之週期表第2B族金屬；鋁、鎵 、銦等之週期表第3B族金屬；鍺、錫、鉛等之週期表第 4B族金屬；銻、鉍等之週期表第5B族金屬等。金屬奈米 粒子，可爲此等金屬的單體、此等金屬的混合物、及此等 金屬的合金中之任一種’但就接合強度之觀點來看’特佳 爲選自鐵、鎳、鈷、釕、鍺、鈀 '銥、鉑等之週期表第8 族金屬；銅、銀、金等之週期表第1B族金屬之一種或2 種以上。可從此等金屬或該合金中’因應接合溫度、接合 強度等來適當地選擇。例如在低溫接合用途中’較佳爲銀 。金屬奈米粒子，可單獨使用或組合兩種以上而使用。 金屬奈米粒子爲奈米等級的大小。例如’金屬奈米粒 子的平均粒徑（平均一次粒徑），較佳爲l~l〇〇nm’尤佳 爲1.5〜80nm，更佳爲2~70nm，特佳爲3〜50nm，通常在 約l~40nm (例如2~30nm)內使用。 金屬奈米粒子，由保護膠體被覆時’室溫下的分散性 -19- 201247416 、保存穩定性良好，故較佳，該保護膠體可列舉出有機化 合物或高分子分散劑。 用作爲保護膠體之有機化合物，較佳爲具有1〜3個羧 基之有機化合物，尤佳爲單羧酸、多羧酸、羥基羧酸等之 羧酸。 用作爲保護膠體之高分子分散劑，可列舉出含有由親 水性單體所構成之親水性單元（或親水性嵌段）之樹脂（ 或水溶性樹脂、水分散性樹脂）。親水性單體，例如可列 舉出含羧基或酸酐基單體（丙烯酸、甲基丙烯酸等之（甲 基）丙烯酸系單體、馬來酸等之不飽和多元羧酸、馬來酸 酐等）、含羥基單體（（甲基）丙烯酸2-羥乙酯等之（ 甲基）丙烯酸羥烷酯、乙烯基酚等）等之加成聚合系單體 ;環氧烷（環氧乙烷等）等之縮合系單體等。 金屬奈米粒子基質的接合層用組成物，就濕式塗佈法 中的塗佈容易度之觀點來看，較佳係含有分散介質。分散 介質，只要是可藉由與金屬奈米粒子或保護膠體之組合來 產生充分黏度之溶劑者即可，並無特別限定，可使用泛用 的溶劑。溶劑可列舉出水、醇類。分散介質的比率，可因 應濕式塗佈法中的塗佈容易度等來適當地選擇。 金屬奈米粒子相對於金屬奈米粒子基質的接合層用組 成物中之固體成分全體之比率，可因應濕式塗佈法中的塗 佈容易度、金屬奈米粒子的燒結密度等來適當地選擇，例 子之一，較佳爲7〇~99質量％，尤佳爲85〜99質量％，更 佳爲90〜99質量％。 -20- 201247416 保護膠體的比率，可因應金屬奈米粒子的分散性等來 適當地選擇，例如相對於金屬奈米粒子：100質量份而言 ，較佳爲〇.5~2 0質量份，尤佳爲1~15質量份。有機化合 物與高分子分散劑之比率，亦可因應金屬奈米粒子的分散 性等來適當地選擇。 金屬奈米粒子基質的接合層用組成物’可使藉由—般 所知的方法所製造之金屬奈米粒子等，與金屬奈米粒子燒 結體層用組成物相同地分散而製造出。 (B)金屬化合物基質的接合層用組成物 接著，（B)金屬化合物基質的接合層用組成物係含 有金屬化合物。金屬化合物可列舉出金屬氧化物、金屬氫 氧化物、金屬硫化物、金屬碳化物、金屬氮化物、金屬硼 化物等。構成金屬化合物之金屬，與上述（A)金屬奈米 粒子基質的金屬相同。此等金屬化合物，可單獨使用或組 合兩種以上而使用。構成金屬化合物之金屬，較佳爲至少 含有銀等之貴金屬（尤其是週期表第1B族金屬）之金屬 (金屬單體及金屬合金），特佳爲貴金屬單體（例如銀單 體等）。以下說明銀化合物之情形。 銀化合物，可列舉出一氧化二銀、氧化銀、碳酸銀、 乙酸銀、乙醯丙酮銀錯合物等。此等銀化合物，可單獨使 用或組合兩種以上而使用。銀化合物可使用市售者。 銀化合物的平均粒徑，較佳爲〇.〇1〜l#m，尤佳爲 0.01~0.5/zm的範圍，可因應還原反應條件或加熱溫度等 -21 - 201247416 來適當地選擇。 金屬化合物基質的接合層用組成物，亦含有分散介質 。分散介質可使用水、乙醇、甲醇、丙醇等醇類、異佛爾 酮、松油醇、三乙二醇單丁醚、乙酸2 -乙氧丁酯等之有 機溶劑。分散介質的比率，可因應濕式塗佈法中的塗佈容 易度等來適當地選擇。 此外，爲了使銀化合物良好地分散於分散介質，較佳 係加入分散劑。分散劑可使用羥丙基纖維素、聚乙烯吡咯 啶酮、聚乙烯醇等，該含量，一般而言，相對於銀化合物 :1 〇〇質量份而言爲〇~3 00質量份。 此外，金屬化合物基質的接合層用組成物，爲了提升 濕式塗佈法中的塗佈容易度，可含有黏合劑樹脂。黏合劑 樹脂可列舉出丙烯酸樹脂、乙烯樹脂、聚酯樹脂、胺基甲 酸酯樹脂、酚樹脂、環氧樹脂等，亦可爲此等之單體》 再者，金屬化合物基質的接合層用組成物，可含有能 夠使金屬化合物還原之還原劑。還原劑可列舉出乙二醇、 福馬林、肼、維生素C、各種醇等。 金屬化合物基質的接合層用組成物，可使市售的金屬 化合物等，與金屬奈米粒子燒結體層用組成物相同地分散 而製造出。 (接合層） 藉由濕式塗佈法使（A)金屬奈米粒子基質的接合層 用組成物' (B)金屬化合物基質的接合層用組成物成膜 -22- 201247416 之方法、乾燥之方法及燒結之方法，係與金屬奈米粒子燒 結體層用組成物相同。 《接合用積層體》 第1圖係顯示接合用積層體的剖面之示意圖。從第1 圖中可得知，接合用積層體1係具備有金屬奈米粒子燒結 體層1 〇與接合層1 1。 接合用積層體，當金屬奈米粒子燒結體層於接合層的 相反面上具備有透明層時，可控制由金屬奈米粒子燒結體 層所形成之增強反射效果，故較佳。透明層的厚度，就反 射性提升之觀點來看，較佳爲0.01〜0.5 /z m。第2圖係顯 示含有透明層之接合用積層體的剖面之示意圖的一例。從 第2圖中可得知，透明層23，在金屬奈米粒子燒結體層 21上形成於與接合層22爲相反面。 此外，接合用積層體，在金屬奈米粒子燒結體層與接 合層之間進一步具備有黏合劑層時，可提升金屬奈米粒子 燒結體層的黏著性，故較佳。黏合劑層的厚度’就密著性 提升之觀點來看，較佳爲0.001〜lVm。第3圖係顯示含 有黏合劑層之接合用積層體的剖面之示意圖的一例。從第 3圖中可得知，黏合劑層3 4係形成於金屬奈米粒子燒結 體層31與接合層32之間。 (透明層及黏合劑層） 透明層及黏合劑層，可藉由濕式塗佈法使黏合劑組成 -23- 201247416 物成膜，並在乾燥後進行燒結而形成。在此，透明層及黏 合劑層，當含有黏合劑，且含有藉由加熱而硬化之聚合物 型黏合劑及非聚合物型黏合劑的至少1種時，可容易地藉 由濕式塗佈法來製造，故較佳。 聚合物型黏合劑，可使用丙烯酸樹脂、聚碳酸酯、聚 酯、醇酸樹脂、聚胺基甲酸酯、丙烯酸胺基甲酸酯、聚苯 乙烯、聚縮醛、聚醯胺、聚乙烯醇、聚乙酸乙烯酯、纖維 素、及矽氧烷聚合物。此外，聚合物型黏合劑，較佳係含 有選自由鋁、矽、鈦、鉻、錳、鐵、鈷、鎳、銀、銅、鋅 、鉬及錫的金屬皂、金屬錯合物、烷氧化金屬及烷氧化金 屬的水解物所組成之群組的至少1種。 非聚合物型黏合劑，可使用金屬皂、金屬錯合物、烷 氧化金屬、烷氧矽烷、鹵矽烷類、2-烷氧3醇、β -二酮 、及乙酸烷酯等。此外’金屬皂、金屬錯合物、或烷氧化 金屬中所含有之金屬，較佳爲鋁、矽、鈦、鉻、錳、鐵、 姑、鎳、銀、銅、辞、鉬、錫、銦或鍊，尤佳爲砂、欽的 烷氧化物（例如四乙氧矽烷、四甲氧矽烷、丁氧矽烷）^ 鹵矽烷類可使用三氯矽烷。此等聚合物型黏合劑、非聚合 物型黏合劑’藉由加熱而硬化，可形成具有高密著性之抗 反射膜。 使烷氧化金屬硬化時，除了用以使水解反應進行之水 分之外，較佳亦含有鹽酸、硝酸、磷酸（Η3ρ〇4)、硫酸 等之酸，或是氨水、氫氧化鈉等之鹼作爲催化劑，就加熱 硬化後催化劑容易揮發而不易殘存，不會殘存鹵素，亦不 -24 - 201247416 會殘存耐水性弱之p等，且硬化後之密著性等之觀點來看 ，尤佳爲硝酸。 黏合劑組成物中之黏合劑的含有比率，相對於扣除分 散介質之黏合劑組成物：100質量份而言，較佳爲10〜90 質量份，尤佳爲30~80質量份。爲10質量份以上時，與 透明導電膜之接著力良好，爲90質量份以下時，成膜時 不易產生膜不均。此外，當使用烷氧化金屬作爲黏合劑並 使用硝酸作爲催化劑時，相對於烷氧化金屬：1 00質量份 而言，硝酸1〜10質量份者，就黏合劑的硬化速度、硝酸 的殘存量之觀點來看爲較佳。 再者，當黏合劑組成物含有透明氧化物微粒時，可調 整透明層的折射率，並控制金屬奈米粒子燒結體層所形成 之增強反射效果，故較佳。當該透明氧化物微粒爲高折射 率時，可容易藉由透明氧化物微粒的含量來調整燒結或硬 化後之透明膜的折射率，故尤佳。透明氧化物微粒，可列 舉出 Si〇2、Ti〇2、Zr〇2、ITO( Indium Tin Oxide:氧化 銦錫）、ZnO、ΑΤΟ、（ Antimony Tin Oxide :摻雜錄的 氧化錫）等的微粉末，就折射率之觀點來看，較佳爲ITO 或Ti〇2。此外，透明氧化物微粒的平均粒徑，爲了在分 散介質中保持穩定性，較佳係位於10〜100nm的範圍內， 當中尤佳係位於20〜60nm的範圍內。在此，平均粒徑是 藉由動態光散射法來測定。透明氧化物微粒，就透明氧化 物微粒的均一分散性之觀點來看，較佳係在預先分散於分 散介質中後，再與黏合劑組成物的其他成分混合。 -25- 201247416 透明氧化物微粒，相對於扣除分散介質 物：100質量份而言，較佳爲10〜90質J 2 0〜70質量份。爲10質量份以上時，可期 導電膜的返回光往透明導電膜側回射之效果 份以下時，可維持透明層本身的強度，以及 奈米粒子燒結體層之接著力、透明層與被接 〇 此外，黏合劑組成物，較佳係因應所使 而添加偶合劑。此係由於可達成透明層的低 透明層與金屬奈米粒子燒結體層之接著力、 合體之接著力，並且在含有透明氧化物微粒 透明氧化物微粒與透光系黏合劑之密著性之 使用矽烷偶合劑、鋁偶合劑及鈦偶合劑等。 矽烷偶合劑，可列舉出乙烯基三乙氧ί 丙氧基丙基三甲氧矽烷、r-甲基丙烯氧基 烷等。鋁偶合劑可列舉出由式（1 )表示之 基之鋁偶合劑。此外，鈦偶合劑可列舉出S )表示之具有二烷基焦磷酸基之鈦偶合劑， )表示之具有二烷基磷酸基之鈦偶合劑》 之黏合劑組成 豪份，尤佳爲 待使來自透明 ，爲90質量 透明層與金屬 合體之接著力 用之其他成分 基質化，提升 透明層與被接 時，亦可提升 故。偶合劑可 S7院、7 -環氧 丙基三甲氧矽 含有乙醯烷氧 丨式（2 )〜（4 或是由式（5 -26- 201247416 【化1 ch3201247416 VI. [Technical Field] The present invention relates to a laminated body for joining a pair of joined bodies, and a joined body including the laminated body for bonding. The bonding laminate and the bonding body are particularly suitable for a light-emitting element and a solar cell. [Prior Art] In recent years, light-emitting elements, particularly LED light sources, have been used in various fields with high brightness and the like. In particular, since a white LED light source can be realized and used for backlights of lighting fixtures and liquid crystal displays, etc., in order to further improve the brightness of the LED light source, etc., it is possible to efficiently apply light emission from LED elements, and to disclose a method. A support substrate, an LED element mounted on the support substrate, and a sealant containing a fluorescent agent are provided, and an Ag-plated electrode film for reflecting light emission of the LED element is provided between the substrate and the LED element, and is plated. An LED light source having a titanium thin film on the Ag electrode film (Patent Document 1). In the LED light source, by providing a conductive reflective film layer between the support substrate and the LED element, light from the illuminant is efficiently reflected to increase the luminescence intensity. Here, the 'Ag film and the titanium film are formed by a plating method or a vacuum film forming method. However, the electroplating method envisions the cumbersome steps and the generation of waste liquid, and the vacuum film forming process consumes a large amount of cost in order to maintain a large vacuum film forming apparatus and operate it. The above LED light source is only subjected to thermal degradation or photodegradation depending on the Ag-plated 201247416 polar film. Therefore, a titanium film is required to be formed by electroplating and vacuum film formation. Further, the LED light source is constructed by bonding a substrate to an LED element, and in general, it is often joined by a metal paste or solder. In particular, when Au-Sn alloy solder or the like is used, good heat dissipation characteristics can be obtained (Patent Document 2). However, in this method, in order to prevent "solder erosion" of the LED element electrode and to prevent diffusion of metal from the electrode, it is necessary to provide a plurality of layer bonding layers of Ni, Ti, etc. by electroplating or vacuum film formation. The disadvantage of great filming costs. The bonding layer for preventing the solder from being etched is also necessary in the case of lead-free solder other than the Au-Sn alloy solder. Further, when a reflective film having a reinforced reflective structure composed of a plurality of transparent films is provided on the inner surface of the LED element and a metal bonded structure having high heat dissipation characteristics is provided, using a previous sputtering method or a vacuum film forming method, Since the joint between the transparent film and the metal film for bonding is poor, it is difficult to improve the adhesion. In addition, the bonding formed by the Au-Sn alloy solder is generally at 2 70 to 40 ° C. In many cases, it is performed at 300 to 35 (the high temperature of TC), but the deterioration of the LED element is suppressed. From the viewpoint of reducing the energy at the time of the production, it is desirable to perform the bonding at a lower temperature. [Prior Art] [Patent Document] [Patent Document 1] Japanese Laid-Open Patent Publication No. 2009-231568 No. 201247416 [Patent Document 2] SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION An object of the present invention is to provide an expensive Ni bonding layer formed by a plating method or a vacuum film forming method by using a metal A metal paste having a particle and a solvent as a main component, and the like, the manufacturing process can be simplified, the running cost can be greatly improved, and the laminated body for joining at a low temperature and the laminated body containing the bonding can be used for the LED element. The bonded body of the light-emitting element. The laminated body for bonding can also be applied to a bonded body for other uses, and is particularly suitable for use as a bonded body of a solar cell using a reflective film. The present invention relates to a laminated body for joining and a joined body which solve the above-described problems by the following modes. (1) A laminated body for joining, comprising: a sintered layer of a metal nanoparticle; And a bonding layer containing metal particles or metal oxide particles laminated on the sintered layer of the metal nanoparticles. (2) The bonding layer according to the above (1), wherein the sintered metal nanoparticle layer has a buildup layer (3) The laminated body for bonding according to the above (1) or (2), further comprising: a sintered body layer formed on the metal nanoparticles, which is combined with the above-mentioned 201247416 (4) The laminated body for a composite according to any one of (1) to (3), wherein the sintered body layer of the metal nanoparticles contains 75% by mass or more of silver, and contains gold, The bonding layer for bonding of any one of the above-mentioned (1) to (4), wherein the metal nanoparticle sintered body layer contains a bonding layer. (6) as above (1) to (5) engaged with any one of the laminate, wherein the thickness of the metal nanoparticle sintered body layers is square. 〇1~〇. (5) The laminated body according to any one of the above (1) to (6), wherein the respective layers are formed at 130 to 2 50 ° C after being formed by a wet coating method. Sintered layer. (8) The bonding layer for bonding according to any one of the above (3) to (7) wherein the transparent layer and the binder layer contain a polymer type binder which is hardened by heating and a non-polymer type bonding. At least one of the agents. (9) The bonding layered body according to the above (7) or (8), wherein the wet coating method is a spray coating method, a dispensing coating method, a spin coating method, a knife coating method, or a slit Any of a coating method, an inkjet coating method, a screen printing method, a lithography method, a transfer method, and a die-casting method. (10) A bonded body, characterized in that the first joined body, the joining laminated body according to any one of the above (1) to (9), and the second joined body. (11) The joined body according to the above (10), wherein the first bonded 8-800474470 body is an element that can emit light or photoelectrically convertible, and the sintered metal nanoparticle sintered body layer can be derived from the first joined body. The light is reflected, and the second joined body is a substrate. (12) The joined body according to the above (11), wherein the first joined body is a light-emitting element and is used as a light-emitting source. (13) The joined body according to the above (11), wherein the first joined body is a photoelectrically convertible element and is used as a solar cell. EFFECTS OF THE INVENTION According to the aspect (1) of the present invention, the joined body can be joined at a low temperature, and high joint reliability can be obtained. Further, since the number of film formation layers is small, an expensive film forming apparatus is not required, and a large cost can be achieved. Further, in the transparent layer of the form (2) of the present invention, the transparent layer can be used with a higher degree of freedom than the electroplating method or the vacuum film forming method, and the refractive index of the transparent layer can be arbitrarily set, and the metal can be controlled. The enhanced reflection effect brought about by the sintered body layer of nanoparticles. According to the form (10) of the present invention, it is possible to easily provide a joined body which can join the joined body at a low temperature and has high joint reliability. Further, according to the form (12) of the present invention, it is possible to provide an illumination source having high application efficiency of light emitted from the LED element, and the type (13)' according to the present invention can provide a solar cell having high photoelectric conversion efficiency. . [Embodiment] Hereinafter, the present invention will be specifically described based on the embodiments. "%" is not particularly indicated in the case of -9 - 201247416, and is "% by mass in the case of the number of layers". [The laminated body for bonding] The laminated body for bonding of the present embodiment is provided with metal nanoparticles. a sintered body layer and a bonding layer containing metal particles or metal oxide particles directly or indirectly laminated on the sintered body layer of the metal nanoparticles. Hereinafter, the sintered body layer and the bonding layer of the metal nanoparticles are sequentially described. Body layer: A sintered body of a metal nanoparticle imparts conductivity, reflectivity, and adhesion to the bonding layer. The sintered body layer of the metal nanoparticle can be used to form a sintered body layer of a metal nanoparticle by a wet coating method. Forming a film and sintering it after drying. The sintered body layer of the metal nanoparticle preferably contains 75 mass% or more of silver, and contains a metal selected from the group consisting of gold, platinum, palladium, rhodium, nickel, copper, tin, indium, At least one second metal of the group consisting of zinc, iron, chromium, molybdenum, and manganese. When the composition is the above, electrical conductivity and reflectivity are good. The second metal is preferably selected from the group consisting of gold and copper. At least one of a group consisting of tin, zinc, molybdenum, and manganese. Particularly preferably tin. The metal nanoparticle sintered body layer of the metal nanoparticle sintered particles mutually diffuse and form a grain growth, and the particles after the grain growth are mutually In the state of the residual pores, a dense film can be formed by using the nanoparticles. The sintered metal nanoparticle sintered body layer is preferably 0. 01~0. 5/Z m. The thickness is particularly preferably 0. 05-0. 2 to m. The porosity of the sintered body layer of the metal nanoparticles is preferably from 1 to 20% by volume, particularly preferably from 1 to 10% by volume. When it is in this range, it can be formed not only at a low temperature but also with good electrical conductivity and reflectance. The metal nanoparticle sintered body layer composition contains metal nanoparticles, and the metal nanoparticle preferably contains 75% by mass or more of silver nanoparticles, and more preferably 80% by mass or more of silver nanoparticles. . The content of the silver nanoparticles is preferably 75% by mass or more based on the sintered body layer of the metal nanoparticles: 1% by mass or less, and the electrode formed using the composition is less than 75% by mass. Conductivity and reflectivity are reduced. The metal nanoparticles in the composition for sintering a metal nanoparticle sintered body layer are preferably chemically modified by a protective agent of an organic molecular main chain having a carbon skeleton of 1 to 3 carbon atoms. In this case, when the composition for sintering the metal nanoparticle sintered body layer is applied to the substrate in order to form the sintered body layer of the metal nanoparticles, the organic molecules in the protective agent for protecting the surface of the metal nanoparticles are detached or Decompose, or break away and break down. As a result, it is possible to easily obtain an electrode containing a metal as a main component which does not substantially contain an organic substance residue which adversely affects the conductivity and reflectance of the electrode. When the carbon number of the carbon skeleton of the organic molecular main chain of the protective agent for chemically modifying the metal nanoparticles is in the range of 1 to 3, when the carbon number is 4 or more, it is difficult to heat by sintering. When the protective agent is detached or decomposed (separated and burned), an organic residue which adversely affects the conductivity and reflectance of the sintered body layer of the metal nanoparticle is likely to remain in the sintered layer of the metal nanoparticle. -11 - 201247416 Furthermore, a better protective agent is a protective molecule that chemically reforms the surface of metal nanoparticles, and contains either or both of a hydroxyl group (-OH) and a carbonyl group (-C = 0). . When the protective agent for chemically modifying the metal nanoparticles such as silver nanoparticles contains a hydroxyl group (-OH), the dispersion stability of the composition is good, and the low-temperature sintering of the coating film can also effectively act when silver is used. When the protective agent for chemical modification of the metal nanoparticles such as nano particles contains a carbonyl group (-C = 0), the dispersion stability of the composition for the sintered body layer of the metal nanoparticle is good, and for the sintered body layer of the metal nanoparticle Low temperature sintering can also work effectively. The metal nanoparticles in the composition for sintering a metal nanoparticle sintered body layer preferably contain 70% or more of the number average; t primary particle diameter: metal nanoparticles in the range of 10 to 50 nm, particularly preferably The reason why the content of the metal nanoparticles in the range of 75% or more and the range of 10 to 50 nm is preferably 100% or more in terms of the number average of the total of the metal nanoparticles is 100% or more. When the aforementioned content is less than 70%, the specific surface area of the metal nanoparticles increases, and the ratio of the protective agent increases, even if the protective agent is easily detached or decomposed (separated and burned) by the heat during sintering. The organic molecules also leave a large amount of organic residue from the protective material in the electrode. When the organic residue is deteriorated or deteriorated, there is a concern that the conductivity and the reflectance of the electrode are lowered. Further, when the particle size distribution of the metal nanoparticles is too wide, the density of the electrode is easily lowered, and the conductivity and reflection of the electrode are easily caused. The rate is reduced. The reason why the primary particle diameter of the above metal nanoparticles is preferably in the range of 10 Å to 50 nm is because the stability of the metal nanoparticles over time (long-term stability) is good. Here, the primary particle diameter can be determined by dynamic light scattering according to LB-550 manufactured by Horiba, -12-201247416, and the average particle diameter is determined by the basis of the case. The metal nanoparticle ' of the second metal is preferably 〇 with respect to the metal-containing nanoparticle: 1% by mass. 02 and less than 25% by mass, especially good for 〇. 〇3质量%~2 0 The content of the second metal is preferably set to 0 with respect to all the metal nanoparticles 1 00. Sinterability and reflectivity and weatherability test of metallic nanoparticles after 02% by mass and less than 25% by mass in weather resistance test (tested at temperature l〇〇°C and humidity 50% tank 1 000 hours) When the amount is not more than 25% by mass, the conductivity and reflectance of the metal nanoparticles after sintering are lowered, and the conductivity and reflectance of the sintered body layer after the weather resistance test and the weather resistance test are performed. The metal nanoparticle sintered body layer composition may be one or more additives selected from the group consisting of metal oxides, metal hydroxides, and organometallic compounds. By further containing one or two types of additives in the composition for a sintered layer of the particles, it is possible to impart an effect of further suppressing grain growth due to sintering of the metal naphthalene, and it is possible to produce a corresponding shape. The addition ratio of the additive is preferably 0% with respect to the metal nanoparticle composition: 100% by mass. Within 1% by mass. It is particularly preferably measured in the range of 1 to 5 mass%. The following method is used to measure the total mass% or more of silver. The reason for the aforementioned mass % is that the constant temperature and humidity layer is electrically conductive. The above-mentioned niobium is a sub-sintered layer of metal nano-particles, and is a surface-sintered body layer containing a selected material and an eucalyptus oil between the metal nanoparticles and the above-mentioned rice particles. The metal oxide of the substance preferably contains at least 1 selected from the group consisting of aluminum, ruthenium, titanium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum, tin, indium, and antimony. Oxide or composite oxide. The composite oxide is specifically an indium tin oxide-based composite oxide (Indium Tin Oxide: ITO), an oxide-tin oxide composite oxide (Antimony Tin Oxide: yttrium), an indium oxide-zinc oxide composite oxide ( Indium Zinc Oxide : ΙΖΟ) and so on. The metal hydroxide used as an additive preferably contains a group selected from the group consisting of aluminum, bismuth, titanium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum, tin, indium, and antimony. A group of at least one hydroxide. As the organometallic compound of the additive, preferably a metal soap of a ruthenium, titanium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum, and tin, a metal complex or an alkoxylated metal, for example, As the metal soap, chromium acetate, manganese formate, iron citrate, cobalt formate, nickel acetate, silver citrate, copper acetate, copper citrate, tin acetate, zinc acetate, zinc oxalate, molybdenum acetate or the like can be used. Further, examples of the metal complex include acetonitrile acetonitrile complex, acetamyl acetonate complex, acetamacetone nickel complex, and the like. Further, as the alkoxide metal, isopropylidene titanate "methyl phthalate", isocyanate propyl trimethoxide, amine propyl trimethoxide or the like can be used. As the eucalyptus oil as an additive, both pure eucalyptus oil and modified eucalyptus oil can be used. In the modified eucalyptus oil, a part of the side chain of the polyoxyalkylene (lateral chain type) may be further introduced, and the organic group may be introduced into both ends of the polyoxyalkylene (both end type), and the organic group may be used. Introduced into either of the two ends of the polyoxyalkylene (single-terminal type), and a part of the side chain of the polyoxyl-14-201247416 alkane and the both ends (both side chain type) . Modified 矽 oil, reactive oyster oil and non-reactive eucalyptus oil, both of which can be used. The term "reactive eucalyptus" means amine modification, epoxy modification, carboxy modification, methanol upgrading, hydrazine modification, and modification of heterogeneous functional groups (eg, epoxy group, amine group, polyether group), non-reactive Sexual eucalyptus oil, which means polyether modification, methyl styrene modification, alkyl modification, higher fatty acid ester modification, fluorine modification, and hydrophilic special modification. The content of the metal nanoparticle is preferably 2. in relation to the dispersion composed of the metal nanoparticle and the dispersion medium: 100% by mass. 5~9 5. 0% by mass, especially good with 3. 5-90. 0% by mass. When the content of the metal nanoparticle is less than 2.5% by mass of the dispersion composed of the metal nanoparticle and the dispersion medium: 100% by mass. At 5 mass%, although the characteristics of the electrode after sintering are not affected, it is difficult to obtain an electrode having a necessary thickness. On the other hand, more than 95. When the mass is 0% by mass, the composition is required to be used as an ink or a paste at the time of wet coating. In addition, the dispersion medium constituting the composition for the sintered body layer of the metal nanoparticles contains 1% by mass or more, preferably 2% by mass or more, and 2% by mass or more, based on 100% by mass of the entire dispersion medium. It is preferably an alcohol of 3 mass% or more. For example, when the dispersion medium is composed only of water and alcohol, when 2% by mass of water is contained, 98% by mass of alcohol is contained, and when 2% by mass of alcohol is contained, 98% by mass of water is contained. When the content of the water is less than 1% by mass based on 100% by mass of the entire dispersion medium, the film obtained by coating the composition by the wet coating method is difficult to be sintered at a low temperature of -15 to 201247416, and further, The electrical conductivity and reflectance of the sintered body layer of the sintered metal nanoparticles are also lowered. On the other hand, when the content of the alcohol is less than 2% by mass based on 100% by mass of the entire dispersion medium, it is difficult to apply the film obtained by the wet coating method to the film at a low temperature as described above. Sintering is performed, and the conductivity and reflectance of the electrode after sintering are also lowered. The alcohol used in the dispersion medium is preferably selected from the group consisting of methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, diethylene glycol, glycerin, isodecyl hexanol and erythritol. One or two or more of the groups. The alcohol is added to improve the wettability with the substrate, and the mixing ratio of water and alcohol can be freely changed in accordance with the type of the substrate. The composition for the sintered body layer of the metal nanoparticle can be obtained by a general method. The desired components are mixed by a paint shaker, a ball mill, a sand mill, a grinder, a three-roller, or the like, and metal nanoparticles or the like are dispersed and produced. Of course, it can also be manufactured by a usual stirring operation. The wet coating method for forming a composition for sintering a metal nanoparticle sintered body layer is preferably a spray coating method, a dispensing coating method, a spin coating method, a knife coating method, or a slit coating method. In any of the inkjet coating method, the screen printing method, the lithography method, the transfer method, and the die casting method, the method is not limited thereto, and any method can be applied. The spray coating method is a method in which a metal nanoparticle sintered body layer composition is formed into a mist by a compressed air and applied to a substrate. In the dispensing method, for example, a composition for sintering a metal nanoparticle sintered body layer is placed in a syringe, and by pressing a piston of the syringe, the dispersion is discharged from a fine nozzle at the tip end of the syringe, and is applied to the substrate. method. In the spin coating method, a composition for sintering a layer of the -16474474 metal nanoparticle sintered body layer is dropped onto a rotating substrate, and the composition of the sintered metal nanoparticle sintered body layer is diffused to the substrate by the centrifugal force. The method of the periphery. The blade coating method is configured to move the substrate with a predetermined gap between the tip end of the blade so as to be movable in the horizontal direction, and to supply the metal nanoparticle sintered body layer composition from the blade to the substrate on the upstream side, and then A method of moving the substrate horizontally toward the downstream side. The slit coating method is a method in which a composition for sintering a metal nanoparticle sintered body layer is discharged from a narrow slit and applied to a substrate. The inkjet coating method is a method in which an ink cartridge of a commercially available ink jet printer is charged on a substrate by charging a composition of a sintered metal nanoparticle body layer on a substrate. The screen printing method is a method in which a tissue of a metal nanoparticle sintered body layer is transferred to a substrate by using a tissue as a pattern indicating material and a pattern image produced thereon. The lithographic method is a composition for sintering a metal nanoparticle sintered body layer attached to a plate, and is not directly attached to a substrate, but is transferred from a plate to a rubber sheet, and then transferred from a rubber sheet to a substrate. A printing method using a water repellency of a composition for sintering a metal nanoparticle sintered body layer. The die-casting method is a method of distributing a composition for a sintered metal layer of a metal nanoparticle supplied to a die-casting mold by a manifold and extruding it from a slit onto a film to coat a surface of the substrate in progress The method. The die casting method has a slit coating method, a swash plate coating method, and a curtain coating method. The transfer method may be a pin transfer method or the like. The drying temperature of the coating film of the composition for forming a sintered body layer of the metal nanoparticle after the film formation is preferably not more than a temperature which does not affect the LED element or the like as the bonded body, and is, for example, 6 (TC or less, particularly preferably 40). ~50°c. The sintering temperature of the coated film after drying is preferably 130~250. (: Fan-17-201247416. This is because when it is less than 130 °C, the sintered layer of metal nanoparticles will be on the layer In addition, when the temperature exceeds 25 ° C, the production advantage of the low-temperature process cannot be utilized, and the productivity is lowered even if the manufacturing cost is increased. Further, the LED element as a candidate for the bonded body is used. Or an amorphous germanium, a microcrystalline germanium, or a mixed-molded solar cell using the same, the heat resistance is relatively weak, and the conversion efficiency is lowered by the sintering step, so it is preferably 1 30 to 200 ° C. The sintering time of the film is preferably in the range of 5 to 60 minutes. This is because when the sintering time is less than the lower limit, there is a lack of sintering deficiency on the sintered body layer of the metal nanoparticle. When the sintering time exceeds the upper limit, Will make the manufacturing cost If it exceeds the demand, the productivity is lowered, and the luminous efficiency of the LED element or the conversion efficiency of the solar cell is also reduced. "Joining layer" The bonding layer is used to form the sintered layer of the metal nanoparticle. The joined bodies are bonded to each other at a low temperature. The bonding layer can be formed by forming a film for a bonding layer by a wet coating method, and sintering after drying. The bonding layer is adhesive and dense. From the viewpoint of sex, the thickness is preferably 0. 01~l〇#m. The thickness is particularly preferably 2 to 10&quot; m. As the composition for the bonding layer, either one or both of the composition for a bonding layer of a metal nanoparticle substrate and the composition for a bonding layer of a metal compound substrate can be used. The following is a description of the composition of the bonding layer of (A) metal nanoparticle matrix, -18-201247416 layer composition, and (B) metal compound matrix. (A) Metallic Nanoparticles of the Metallic Nanoparticles in the Metallic Nanoparticles, and Metallic Nanoparticles, and Metallic Nanoparticles, and the metal of the metal nanoparticles, for example, iron, Metals of Group 8 of the periodic table of nickel, cobalt, ruthenium, rhodium, palladium, iridium, platinum, etc.: metals of Group 4A of the periodic table of titanium, chromium, etc.; Group 5A of the periodic table of vanadium, niobium, molybdenum, etc.; Metals of Group 6A of the periodic table such as chromium, molybdenum and tungsten; metals of Group 7A of the periodic table of manganese; metals of Group 1B of the periodic table of copper, silver and gold; metals of Group 2B of the periodic table of zinc, cadmium, etc.; Metals of Group 3B of the periodic table such as aluminum, gallium, and indium; metals of Group 4B of the periodic table such as bismuth, tin, and lead; metals of Group 5B of the periodic table of lanthanum, cerium, and the like. The metal nanoparticle may be any one of such a metal monomer, a mixture of such metals, and an alloy of such metals 'but from the viewpoint of joint strength', it is particularly preferably selected from the group consisting of iron, nickel, and cobalt. , lanthanum, cerium, palladium 'palladium, platinum, etc., Group 8 metals; copper, silver, gold, etc., one or more of the Group 1B metals of the periodic table. From such metals or alloys, it can be appropriately selected in accordance with the bonding temperature, the bonding strength, and the like. For example, in low temperature bonding applications, 'preferably silver'. The metal nanoparticles may be used singly or in combination of two or more. Metal nanoparticles are the size of the nanoscale. For example, the average particle diameter (average primary particle diameter) of the metal nanoparticles is preferably from 1 to 10 nm. 5 to 80 nm, more preferably 2 to 70 nm, particularly preferably 3 to 50 nm, and usually used in about 1 to 40 nm (for example, 2 to 30 nm). When the metal nanoparticles are coated with a protective colloid, the dispersibility at room temperature is -19-201247416, and the storage stability is good. The protective colloid is preferably an organic compound or a polymer dispersant. The organic compound to be used as the protective colloid is preferably an organic compound having 1 to 3 carboxyl groups, and more preferably a carboxylic acid such as a monocarboxylic acid, a polycarboxylic acid or a hydroxycarboxylic acid. The polymer dispersing agent used as the protective colloid may, for example, be a resin (or a water-soluble resin or a water-dispersible resin) containing a hydrophilic unit (or a hydrophilic block) composed of a hydrophilic monomer. Examples of the hydrophilic monomer include a carboxyl group-containing or acid anhydride group-containing monomer (a (meth)acrylic monomer such as acrylic acid or methacrylic acid, an unsaturated polycarboxylic acid such as maleic acid, or maleic anhydride). An addition polymerization monomer such as a hydroxyl group-containing monomer (hydroxyalkyl (meth) acrylate such as 2-hydroxyethyl methacrylate or a vinyl phenol); an alkylene oxide (such as ethylene oxide) The condensation is a monomer or the like. The composition for a bonding layer of the metal nanoparticle matrix preferably contains a dispersion medium from the viewpoint of easiness of coating in the wet coating method. The dispersion medium is not particularly limited as long as it can form a solvent having a sufficient viscosity by a combination with a metal nanoparticle or a protective colloid, and a general-purpose solvent can be used. Examples of the solvent include water and alcohol. The ratio of the dispersion medium can be appropriately selected depending on the ease of coating in the wet coating method and the like. The ratio of the metal nanoparticles to the total solid content in the composition for the bonding layer of the metal nanoparticle matrix can be appropriately determined depending on the ease of coating in the wet coating method, the sintered density of the metal nanoparticles, and the like. Alternatively, one of the examples is preferably from 7 to 99% by mass, particularly preferably from 85 to 99% by mass, more preferably from 90 to 99% by mass. -20- 201247416 The ratio of the protective colloid can be appropriately selected depending on the dispersibility of the metal nanoparticles, for example, relative to the metal nanoparticles: 100 parts by mass, preferably 〇. 5 to 20 parts by mass, particularly preferably 1 to 15 parts by mass. The ratio of the organic compound to the polymer dispersant can be appropriately selected in accordance with the dispersibility of the metal nanoparticles. The metal nanoparticle or the like which is produced by a generally known method can be produced by dispersing the metal nanoparticle or the like which is produced by a generally known method, in the same manner as the metal nanoparticle sintered layer composition. (B) Composition for a bonding layer of a metal compound substrate Next, the composition for a bonding layer of the (B) metal compound substrate contains a metal compound. The metal compound may, for example, be a metal oxide, a metal hydroxide, a metal sulfide, a metal carbide, a metal nitride or a metal boron compound. The metal constituting the metal compound is the same as the metal of the above (A) metal nanoparticle matrix. These metal compounds may be used singly or in combination of two or more. The metal constituting the metal compound is preferably a metal (metal monomer and metal alloy) containing at least a noble metal such as silver (particularly a metal of Group 1B of the periodic table), and particularly preferably a noble metal monomer (e.g., a silver monomer). The case of the silver compound will be described below. Examples of the silver compound include silver oxychloride, silver oxide, silver carbonate, silver acetate, silver acetylacetate complex, and the like. These silver compounds may be used singly or in combination of two or more. Silver compounds can be used commercially. The average particle diameter of the silver compound is preferably 〇. 〇1~l#m, especially good 0. 01~0. The range of 5/zm can be appropriately selected in accordance with the reduction reaction conditions or the heating temperature, etc. -21 - 201247416. The composition for the bonding layer of the metal compound matrix also contains a dispersion medium. As the dispersion medium, an organic solvent such as water, ethanol, methanol or propanol, isophorone, terpineol, triethylene glycol monobutyl ether or 2-ethoxybutyl acetate can be used. The ratio of the dispersion medium can be appropriately selected in accordance with the coating ease in the wet coating method and the like. Further, in order to disperse the silver compound well in the dispersion medium, it is preferred to add a dispersant. As the dispersing agent, hydroxypropylcellulose, polyvinylpyrrolidone, polyvinyl alcohol or the like can be used, and the content is generally 〇~300 parts by mass based on 1 part by mass of the silver compound. Further, the composition for a bonding layer of the metal compound substrate may contain a binder resin in order to improve the ease of coating in the wet coating method. Examples of the binder resin include an acrylic resin, a vinyl resin, a polyester resin, a urethane resin, a phenol resin, an epoxy resin, and the like, and a monomer such as this may be used. The composition may contain a reducing agent capable of reducing the metal compound. Examples of the reducing agent include ethylene glycol, formalin, hydrazine, vitamin C, and various alcohols. The composition for the bonding layer of the metal compound substrate can be produced by dispersing the commercially available metal compound or the like in the same manner as the composition for sintering the metal nanoparticle sintered body layer. (Joining layer) The method for forming a bonding layer of (A) a metal nanoparticle matrix by a wet coating method, and forming a composition for a bonding layer of a metal compound matrix, -22-201247416, drying The method and the method of sintering are the same as those of the sintered body layer of the metal nanoparticle. <<Laminated laminated body>> Fig. 1 is a schematic view showing a cross section of a laminated body for joining. As is apparent from Fig. 1, the bonding layer 1 for bonding is provided with the sintered metal layer 1 〇 and the bonding layer 11 of the metal nanoparticles. In the laminated body for bonding, when the sintered layer of the metal nanoparticle is provided with a transparent layer on the opposite surface of the bonding layer, the effect of enhancing the reflection formed by the sintered body layer of the metal nanoparticles can be controlled, which is preferable. The thickness of the transparent layer is preferably 0. from the viewpoint of improvement in reflectivity. 01~0. 5 /z m. Fig. 2 is a view showing an example of a schematic view of a cross section of a laminate for a transparent layer. As is apparent from Fig. 2, the transparent layer 23 is formed on the metal nanoparticle sintered body layer 21 on the opposite side to the bonding layer 22. Further, when the adhesive layer is further provided between the sintered metal layer of the metal nanoparticles and the bonding layer, the bonding layer for bonding can improve the adhesion of the sintered layer of the metal nanoparticles, which is preferable. The thickness of the adhesive layer is preferably 0 in terms of adhesion improvement. 001~lVm. Fig. 3 is a view showing an example of a schematic view of a cross section of a bonding layer containing a binder layer. As is apparent from Fig. 3, the adhesive layer 34 is formed between the sintered metal oxide layer 31 and the bonding layer 32. (Transparent Layer and Adhesive Layer) The transparent layer and the adhesive layer can be formed by forming a film of a binder composition -23-201247416 by a wet coating method and sintering it after drying. Here, when the transparent layer and the adhesive layer contain at least one of a polymer type binder and a non-polymer type binder which are cured by heating, the transparent layer and the adhesive layer can be easily wet-coated. It is better to manufacture by law. Polymer type adhesive, acrylic resin, polycarbonate, polyester, alkyd resin, polyurethane, urethane acrylate, polystyrene, polyacetal, polyamide, polyethylene Alcohol, polyvinyl acetate, cellulose, and siloxane polymers. Further, the polymer type binder preferably contains a metal soap selected from the group consisting of aluminum, bismuth, titanium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum and tin, a metal complex, and alkoxylation. At least one of the group consisting of a hydrolyzate of a metal and an alkoxylated metal. As the non-polymer type binder, a metal soap, a metal complex, an alkoxide, an alkoxysilane, a halogenated alkane, a 2-alkoxy-3-ol, a β-diketone, an alkyl acetate or the like can be used. Further, the metal contained in the 'metal soap, the metal complex, or the alkoxide metal is preferably aluminum, bismuth, titanium, chromium, manganese, iron, austenite, nickel, silver, copper, rhenium, molybdenum, tin, indium. Or a chain, particularly preferably an alkoxide of sand or chin (for example, tetraethoxy decane, tetramethoxy decane, butoxy oxane), and a chlorodecane may be used. These polymer type binders and non-polymer type binders are hardened by heating to form an antireflection film having high adhesion. When the alkoxide metal is hardened, it preferably contains hydrochloric acid, nitric acid, phosphoric acid (Η3ρ〇4), sulfuric acid or the like, or a base such as ammonia water or sodium hydroxide, in addition to moisture for carrying out the hydrolysis reaction. When the catalyst is heated and hardened, the catalyst is easily volatilized and does not easily remain, and no halogen remains, and it is not preferable that the -24 - 201247416 remains weak in p-resistance, and the adhesion after hardening is particularly preferable. . The content ratio of the binder in the binder composition is preferably from 10 to 90 parts by mass, particularly preferably from 30 to 80 parts by mass, per 100 parts by mass of the binder composition excluding the dispersion medium. When the amount is 10 parts by mass or more, the adhesion to the transparent conductive film is good, and when it is 90 parts by mass or less, film unevenness is less likely to occur at the time of film formation. In addition, when an alkoxide metal is used as a binder and nitric acid is used as a catalyst, the curing rate of the binder and the residual amount of nitric acid are 1 to 10 parts by mass of the nitric acid metal: 100 parts by mass of the metal oxide. The point of view is better. Further, when the binder composition contains transparent oxide fine particles, it is preferable to adjust the refractive index of the transparent layer and control the effect of enhancing the reflection formed by the sintered body layer of the metal nanoparticles. When the transparent oxide fine particles have a high refractive index, the refractive index of the sintered or hardened transparent film can be easily adjusted by the content of the transparent oxide fine particles, which is particularly preferable. Examples of the transparent oxide fine particles include micro sized particles such as Si 〇 2, Ti 〇 2, Zr 〇 2, ITO (Indium Tin Oxide), ZnO, ruthenium, and (Antimony Tin Oxide). The powder is preferably ITO or Ti〇2 from the viewpoint of the refractive index. Further, the average particle diameter of the transparent oxide fine particles is preferably in the range of 10 to 100 nm in order to maintain stability in the dispersion medium, and particularly preferably in the range of 20 to 60 nm. Here, the average particle diameter is measured by a dynamic light scattering method. The transparent oxide fine particles are preferably mixed with other components of the binder composition in view of uniform dispersibility of the transparent oxide fine particles before being dispersed in the dispersion medium. -25-201247416 The transparent oxide fine particles are preferably 10 to 90 parts by mass of J 2 0 to 70 parts by mass based on 100 parts by mass of the dispersion medium. When the amount of return light of the conductive film is less than or equal to the effect of the retroreflective film on the side of the transparent conductive film, the strength of the transparent layer itself and the adhesion of the sintered layer of the nanoparticle, the transparent layer and the connection are obtained. Further, the binder composition is preferably added with a coupling agent as it is. This is because the adhesion between the low-transparent layer of the transparent layer and the sintered layer of the metal nanoparticle can be achieved, and the adhesion of the composite, and the adhesion of the transparent oxide fine particles and the light-transmitting adhesive can be achieved. A decane coupling agent, an aluminum coupling agent, a titanium coupling agent, and the like. Examples of the decane coupling agent include vinyltriethoxymethoxypropyltrimethoxysilane and r-methacryloxyalkylene. The aluminum coupling agent may, for example, be an aluminum coupling agent represented by the formula (1). Further, the titanium coupling agent may be a binder of a titanium coupling agent having a dialkyl pyrophosphate group represented by S), and a binder of a titanium coupling agent having a dialkyl phosphate group, which is particularly preferable. From the transparent, the other components used for the adhesion of the 90-millimeter transparent layer and the metal composite are matrixed, and the transparent layer can be lifted when it is connected. The coupling agent can be S7, 7-epoxypropyltrimethoxy oxime containing acetal oxide 丨 (2)~(4 or by formula (5 -26- 201247416 [chemical 1 ch3

ChU CH3-CH-0-AI—O-CH—CH3 o 0 h3c C18H35ChU CH3-CH-0-AI—O-CH—CH3 o 0 h3c C18H35

H lit, 2] oII . C-O-Tr h2c——o 【化3】H lit, 2] oII . C-O-Tr h2c——o 【化3】

o o II II / -ο P 0 P-(〇C8H17i OH '2 o oII II / ' H2C-0-Ti-0 P O P-f〇C8H17 I I V &gt;2 H2c—-o L 6h (2) 2 2 【化4】 CH, 「00I 3 II II / \ H3C-CH-O-T1--O p o P-f〇C8H17)II 、 ’2 OH 【化5】 2 (3) (4) (C8H170)4Ti[P(0C13H27)20H] 偶合劑，相對於黏合劑組成物：100 J 佳爲0.01〜5質量份，尤佳爲0.1〜2質量份 份以上時，可顯現出透明層與金屬奈米粒1 著力的提升、透明層與被接合體之接著力白 (5) 量份而言，較 。爲0.0 1質量 燒結體層之接 提升，或是顯 -27- 201247416 著之粒子分散性的提升效果，多於5質量份時，容易產生 膜不均。 黏合劑組成物，爲了良好地成膜，較佳係含有分散介 質。分散介質，可列舉出水；甲醇、乙醇、異丙醇、丁醇 等之醇類：丙酮、丁酮、環己酮、異佛爾酮等之酮類；甲 苯、二甲苯、己烷、環己烷等之烴類；N，N-二甲基甲醯胺 、N，N-二甲基乙醯胺等之醯胺類；二甲基亞楓等之亞颯類 或乙二醇等之二醇類；2-乙氧乙醇等之二醇醚類等。分散 介質的含量，爲了得到良好的成膜性，相對於黏合劑組成 物：100質量份而言，較佳爲80〜99質量份。 此外，較佳可因應所使用之成分而添加水溶性纖維素 衍生物。水溶性纖維素衍生物，爲非離子化界面活性劑， 且與其他界面活性劑相比，即使少量添加，使導電性氧化 物粉末分散之能力亦極高，此外，藉由水溶性纖維素衍生 物的添加，亦可提升所形成之透明層的透明性。水溶性纖 維素衍生物，可列舉出羥丙基纖維素、羥丙基甲基纖維素 等。水溶性纖維素衍生物的添加量，相對於黏合劑組成物 :100質量份而言，較佳爲0.2〜5質量份。 再者，較佳亦可在黏合劑組成物中添加低電阻化劑。 低電阻化劑，可使用選自 Co、Fe、In、Ni、Pb ' Sn、Ti 、及Zn的礦酸鹽及有機酸鹽之金屬鹽。礦酸鹽可列舉出 鹽酸鹽、硫酸鹽、硝酸鹽等，有機酸鹽可列舉出乙酸鹽、 丙酸鹽、丁酸鹽、辛酸鹽、乙醯乙酸鹽、環烷酸鹽、苯甲 酸鹽等。低電阻化劑的添加量，相對於黏合劑組成物： -28- 201247416 100質量份而言，較佳爲0·5~10質量份。 製造黏合劑組成物之方法、藉由濕式塗佈法使黏合劑 組成物成膜之方法、乾燥方法、及燒結方法，係與金屬奈 米粒子燒結體層用組成物相同。 當金屬奈米粒子燒結體層具有空孔時，將黏合劑組成 物塗佈於金屬奈米粒子燒結體層上時’黏合劑組成物可滲 透於金屬奈米粒子燒結體層的空孔’並且在黏合劑組成物 硬化後，可使金屬奈米粒子燒結體層含有黏合劑。含有該 黏合劑之金屬奈米粒子燒結體層，可提升金屬奈米粒子燒 結體層本身的機械強度，及金屬奈米粒子燒結體層的接合 強度，故較佳。 [接合體] 本發明之接合體的特徵，在於依序具備有：第1被接 合體、上述接合用積層體、以及第2被接合體。 第4圖爲本發明之接合體的剖面之示意圖的一例。第 4圖爲具備有透明層及黏合劑層之例子。從第4圖中可得 知，接合體4依序具備有：第1被接合體45、接合用積 層體40、以及第2被接合體46。接合用積層體40具備有 金屬奈米粒子燒結體層41及接合層42，金屬奈米粒子燒 結體層41在與接合層42的相反面上具備有透明層43, 再者，於金屬奈米粒子燒結體層41與接合層42之間進一 步具備有黏合劑層44。 在此，爲了將接合體應用在光學用途上，第1被接合 -29- 201247416 體爲可發光或可光電轉換之元件，金屬奈米粒子燒結體層 可使來自第1被接合體的光反射，且第2被接合體爲基板 者，乃爲適合。具體而言，當第1被接合體爲可發光之元 件時，乃適合用在用作爲LED等的發光源之接合體，當 第1被接合體爲可光電轉換之元件時，乃適合用在用作爲 太陽能電池之接合體。 [實施例] 以下藉由實施例來詳細地說明本發明，但本發明並不 限定於此等。 [材料1 -1的調製] 將非聚合物型黏合劑之2-正丁氧乙醇與3-異丁基-2,4 戊二酮的混合液（質量比5:5) : 10質量份，與作爲分 散劑的異丙醇：90質量份混合，於室溫下藉由轉子以轉 速2 0〇rpm攪拌1小時，而調製出材料：i〇g。 [材料1-2的調製] 將非聚合物型黏合劑之2-正丙氧乙醇10質量份，與 作爲分散劑之異丙醇與丁醇的混合液（質量比40 : 60 ) :90質量份混合，於室溫下藉由轉子以轉速200rpm攪拌 1小時，而調製出材料1-2 : 10g。 [材料1-3的調製] -30- 201247416 將Si02黏結劑：1 0質量份，與作爲分散劑之乙醇與 丁醇的混合液（質量比98 : 2 ) : 90質量份混合，調製出 材料1-3 : 10g。用作爲黏合劑之Si02黏結劑，可使用 5 00cm3之玻璃製的四頸燒瓶，加入四乙氧矽烷：140g與 乙醇：240g，一邊攪拌，使12N-HC1: l.Og溶解於25g的 純水並一次加入，然後在8(TC中反應6小時，而調製出 材料 1 -3 : 1 0g。 [材料4-1的調製] 將 Ag80%、Au20%的混合金屬奈米粒子分散液混合 作爲（A)金屬奈米粒子基質的接合層用組成物後，對金 屬奈米粒子分散液進行離心分離。以相對於金屬奈米粒子 :95質量份而言成爲聚乙二醇：5質量份之方式，將聚乙 二醇加入於離心分離後的沉澱物中，並藉由行星攪拌型混 合機，調製出材料4-1 : 10g。在此，Ag80%、Au20%的 混合金屬奈米粒子分散液係以下列方式製作， 《銀奈米粒子分散液的製作》 將硝酸銀溶解於脫離子水，調製出濃度25質量％的 金屬鹽水溶液。此外，將檸檬酸鈉溶解於脫離子水，調製 出濃度26質量％的檸檬酸鈉水溶液。在保持於35°C之氮 氣氣流中，將粒狀的硫酸亞鐵直接加入於該檸檬酸鈉水溶 液並溶解’而調製出以3: 2的莫耳比計含有檸檬酸離子 與亞鐵離子之還原劑水溶液。 -31 - 201247416 接著將上述氮氣氣流保持於35 °C，並敢入磁力攪拌 器的攪拌件於還原劑水溶液，一邊以攪拌件的轉速： lOOrpm攪拌，一邊將上述金屬鹽水溶液滴入於該還原劑 水溶液並混合。在此，以使金屬鹽水溶液相對於還原劑水 溶液之添加量成爲還原劑水溶液的量的1 /1 Φ以下之方式 ，調整各溶液的濃度，並且即使在滴入室溫的金屬鹽水溶 液，亦將反應溫度保持在40 °C。此外，還原劑水溶液與 金屬鹽水溶液之混合比，係設爲還原劑水溶液的檸檬酸離 子與亞鐵離子，相對於金屬鹽水溶液中之金屬離子的總原 子價數之莫耳比均成爲3倍莫耳。結束將金屬鹽水溶液滴 入於該還原劑水溶液後，再持續攪拌混合液15分鐘，藉 此於混合液中產生銀奈米粒子，而得到分散有銀奈米粒子 之銀奈米粒子分散液：100cm3»銀奈米粒子分散液的PH 爲5.5，分散液中之銀奈米粒子的計量化學生成量爲5g/ 升。 將所得之銀奈米粒子分散液放置在室溫，藉此使分散 液中的銀奈米粒子沉降，並藉由傾析來分離沉降後之銀奈 米粒子的凝聚物。將脫離子水加入於分離後之銀奈米粒子 凝聚物而形成分散體，藉由超過濾進行脫鹽處理後，再以 甲醇進行取代洗淨，使銀的含量成爲50質暈％。然後使 用離心分離機，調整該離心分離機的離心力，來分離粒徑 超過lOOnm之相對較大的銀粒子，藉此調整爲以數量平 均計含有71%之一次粒徑位於10〜5 Onm的範圍內之銀奈 米粒子。亦即調整爲，以數量平均計一次粒徑位於 -32- 201247416 10〜5 Onm的範圍內之銀奈米粒子相對於全部銀奈米粒子 1 0 〇 %所佔之比率爲7 1 % ’而得銀奈米粒子分散液。所得 之銀奈米粒子’係經檸檬酸鈉的保護劑進行化學改質。 《金奈米粒子分散液的製作》 除了使用氯金酸來取代硝酸銀之外’其他與銀奈米粒 子的製作相同’而得到含有5質量％之平均粒徑1 0nm的 金奈米粒子之金奈米粒子分散液：1 00cm3。 《混合金屬奈米粒子分散液的製作》 以使質量比計成爲Ag80%、Au20%之方式來混合所 得之銀奈米粒子分散液與金奈米粒子分散液，而得混合金 屬奈米粒子分散液：100cm3。 [材料4 - 2的調製] 將Ag粒子（平均徑· 70重量份、一氧化 二銀（平均粒徑：〇 ·1 M m) : 5重量份、碳酸銀（平均粒 徑：0 ·4 // m ) : 5重量份、松油醇：2 0重量份混合作爲（ B)金屬化合物基質的接合層用組成物。將各原料預備混 合後，藉由行星攪拌型混合機，調製出材料4-2 : 10g。 [金屬奈米粒子燒結體層用組成物] 以第1表所不之組成來混合材料，並與材料4 -1相同 地調製出金屬奈米粒子燒結體層用組成物。在此，使用氯 -33- 201247416 金酸作爲Au的原料，使用硝酸銀作爲Ag的原料，使用 氯化錫作爲Sn的原料’使用硫酸錳作爲Mn的原料。 [實施例1] 首先製備使發光層成膜於長：5mm、寬：5mm、厚： 5mm的藍寶石基板上之元件。並且製備長：2〇mm、寬： 20mm、厚.〇.5mm且表面形成有Ni/Au鍍層之Si製基板 作爲支擦基板。首先藉由旋轉塗佈法，將金廓奈米粒子燒 結體層用組成物塗佈於元件的接合處理面上，在13〇乞下 燒結10分鐘’而形成厚度：〇.3//m的金屬奈米粒子燒結 體層。接著藉由網版印刷法，將材料4-1印刷於支撐基板 側’設置藍寶石基板，並在室溫下以1 Μ P a加壓1 〇秒後 ，於烘烤爐內，在2 0 0 °C下燒結2 0分鐘。 [實施例2] 製備與實施例1相同之元件及基板。首先藉由壓鑄模 塗佈法，將材料1-1塗佈於元件的接合處理面上，在130 °C下燒結30分鐘，而形成厚度：〇.〇1 a m的透明層。接 著藉由網版印刷法，將金屬奈米粒子燒結體層用組成物塗 佈於該透明層上，在200°C下燒結20分鐘，而形成厚度 :0.5 v m的金屬奈米粒子燒結體層。接著藉由銷轉印法 ，使材料4-1成膜於支撐基板側，設置藍寶石基板’並在 室溫下以IMPa加壓10秒後，於烘烤爐內，在200°C下燒 結20分鐘。 -34- 201247416 [實施例3] 以第1表所記載之條件，與實施例1相同地製作出實 施例3。在此，黏合劑層是藉由壓鑄模塗佈法所塗佈。 [實施例4、5] 以第1表所記載之條件，與實施例2相同地製作出實 施例4、5。在此，黏合劑層是藉由壓鑄模塗佈法所塗佈 [比較例1 ] 以第1表所記載之條件，未形成金屬奈米粒子燒結體 層，而與實施例2相同地製作出比較例1。 [比較例2] 以第1表所記載之條件，使用信越化學公司製的Ag-聚矽氧烷樹脂（品名：SMP-2 8 00 )來製作出比較例2。 [接合強度的評估] 係以精密萬能試驗機Autograph AG-XplUS來測定實 施例1〜5、比較例1、2之接合強度（剪切強度）。測定 條件係依據JIS Z3 198-5來進行。 [發光強度的評估] -35- 201247416 係以Labsphere公司製的LSA-3000裝置來測定實施 例1 ~5、比較例1、2之發光強度（相對強度）。 [第1表】 分類 ST施例1 Η施例2 资施例3 R施例4 瘺施例3 比較例Ί 比校例2 材料 無 1-1 m 1-2 :1-3 1-2 無 - 0.01 - 0.1 :0.4 0.06 - 规結酿τ) - 130 - 200 220 170 - 依結時問(分） - 30 - 20 :10 5 - 金層»米粒子 供結舰 材料 As 100012% As 99!Tfi% PVP〇.9«a% Si〇2 0.1ΠΑ% Ag 89Qfi% Au 5H*% 甲基纖維索 zmA〇 mis% As 95.8ΏΞ% Sn 0.2SS% 抒丙孩甲越纖雄索3霣£1% ZoO Ag9iS.8iJ*% Mn PVP20*% 乙 BlcJulB*% 無 無 0.3 0.5 0.1 0.2 ;〇.4 - - 焼結沮度CC) 130 200 150 t70 220 - — 問汾） 10 20 5 M :15 - - «料 無 無 1-1 1-2 Ί-3 無 無 u 合 m/s 6U9 ΐ m) - — 0.01 0.02 0.03 - - 堍結S度(1C) - - 130 200 220 - - flMSRra(分） - - 30 20 :10 - - ίί料 4-1 4-1 4-1 4-2 4-2 4-2 Α8·Κ矽铒烷餌脂 0.01 0.5 2 5 ：i〇 10 10 供結度rc) 200 200 200 250 250 300 200 坊挪問⑼ 20 20 20 60 60 60 30 接合強度 53切強度（N/mm1) 20 20 26 30 ：40 30 20 發光強度 相對強度 130 140 120 135 | 145 103 100 從第1表中可得知，實施例1~5中，接合強度及發光 強度均高。尤其在具備有透明層之實施例2、4、5中，發 光強度極高，此外，具備有透明層與黏合劑層之實施例4 、5中，接合強度較其他實施例更高。相對於此，未形成 金屬奈米粒子燒結體層之比較例1及2中，發光強度低。 本發明之接合用積層體，相對於以往昂貴的Ni接合 層，藉由採用以金屬粒子與溶劑爲主成分之金屬膏等來取 而代之，可簡化製造步驟並大幅地改善運轉成本，並且可 在低溫下進行接合。 【圖式簡單說明】 -36- 201247416 第I圖爲本發明的一項實施形態之接合用積層體的剖 面圖。 第2圖爲本發明的其他實施形態之含有透明層之接合 用積層體的剖面圖。 第3圖爲本發明的其他實施形態之含有黏合劑層之接 $用積層體的剖面圖。 第4圖爲本發明的其他實施形態之接合體的剖面圖。 f i要元件符號說明】 I、 2、3:接合用積層體 4 :接合體 II、 21、31、41 :金屬奈米粒子燒結體層 12、22、32、42:接合層 23 ' 43 :透明層 3 4、44 :黏合劑層 45 :第〗被接合體 46 :第2被接合體 -37-Oo II II / -ο P 0 P-(〇C8H17i OH '2 o oII II / ' H2C-0-Ti-0 PO Pf〇C8H17 IIV &gt;2 H2c—o L 6h (2) 2 2 】 CH, "00I 3 II II / \ H3C-CH-O-T1--O po Pf〇C8H17)II , '2 OH 【化5】 2 (3) (4) (C8H170)4Ti[P(0C13H27) 20H] coupler, relative to the binder composition: 100 J is preferably 0.01 to 5 parts by mass, particularly preferably 0.1 to 2 parts by mass or more, and the transparent layer and the metal nanoparticle 1 can be visually enhanced, and the transparent layer In comparison with the white (5) parts of the bonded body, the adhesion of the sintered body layer of 0.01 mass is improved, or the effect of improving the dispersibility of the particles by -27-201247416 is more than 5 parts by mass. It is easy to cause film unevenness. The binder composition preferably contains a dispersion medium in order to form a film well. The dispersion medium may, for example, be water; methanol, ethanol, isopropanol, butanol or the like: acetone, butyl Ketones such as ketone, cyclohexanone and isophorone; hydrocarbons such as toluene, xylene, hexane and cyclohexane; N,N-dimethylformamide, N,N-dimethyl B Amidoxime, such as guanamine; dimethyl sulfoxide, etc. a diol such as an anthracene or an ethylene glycol; a glycol ether such as 2-ethoxyethanol; etc. The content of the dispersion medium is 100 parts by mass based on the binder composition in order to obtain good film formability. Preferably, it is preferably 80 to 99 parts by mass. Further, it is preferred to add a water-soluble cellulose derivative in accordance with the components to be used. The water-soluble cellulose derivative is a nonionic surfactant and has other interfacial activity. Compared with the agent, even if added in a small amount, the ability to disperse the conductive oxide powder is extremely high, and the transparency of the formed transparent layer can be improved by the addition of the water-soluble cellulose derivative. The derivative may, for example, be hydroxypropylcellulose or hydroxypropylmethylcellulose. The amount of the water-soluble cellulose derivative to be added is preferably 0.2 to 5 with respect to 100 parts by mass of the binder composition. Further, it is preferable to add a low-resistance agent to the binder composition. For the low-resistance agent, a mineral acid selected from the group consisting of Co, Fe, In, Ni, Pb 'Sn, Ti, and Zn can be used. Metal salts of salts and organic acid salts. Hydrochloride, sulfate, nitrate, etc., and examples of the organic acid salt include acetate, propionate, butyrate, octoate, acetoacetate, naphthenate, benzoate, etc. The amount of the agent to be added is preferably from 0.5 to 10 parts by mass relative to the binder composition: -28 to 201247416, 100 parts by mass. A method of producing a binder composition, which is bonded by a wet coating method The method of forming a film of the agent composition, the drying method, and the sintering method are the same as those for the sintered body layer of the metal nanoparticle. When the sintered body layer of the metal nanoparticle has pores, when the binder composition is coated on the sintered layer of the metal nanoparticle, the 'adhesive composition can penetrate the pores of the sintered layer of the metal nanoparticle' and is in the binder After the composition is hardened, the sintered body layer of the metal nanoparticles may contain a binder. The sintered body layer of the metal nanoparticles containing the binder can improve the mechanical strength of the sintered body layer of the metal nanoparticles and the bonding strength of the sintered layer of the metal nanoparticles. [Joined body] The joined body of the present invention is characterized in that the first joined body, the joined laminated body, and the second joined body are provided in this order. Fig. 4 is a view showing an example of a schematic view of a cross section of the joined body of the present invention. Figure 4 is an example with a transparent layer and a binder layer. As can be seen from Fig. 4, the joined body 4 is provided with the first joined body 45, the joined laminated body 40, and the second joined body 46 in this order. The bonding layer body 40 includes a sintered metal layer 41 and a bonding layer 42. The sintered metal layer 41 has a transparent layer 43 on the surface opposite to the bonding layer 42, and is sintered in the metal nanoparticles. Further, an adhesive layer 44 is provided between the bulk layer 41 and the bonding layer 42. Here, in order to apply the bonded body to an optical use, the first bonded -29-201247416 body is an element that can emit light or be photoelectrically converted, and the sintered metal layer of the metal nanoparticles can reflect light from the first joined body. It is suitable that the second joined body is a substrate. Specifically, when the first to-be-joined body is a light-emitting element, it is suitable for use as a bonding body for a light-emitting source such as an LED, and is suitable for use when the first object to be bonded is a photoelectrically convertible element. Used as a joint of solar cells. [Examples] Hereinafter, the present invention will be specifically described by way of examples, but the invention is not limited thereto. [Preparation of Material 1-1] A mixture of 2-n-butoxyethanol and 3-isobutyl-2,4-pentanedione (mass ratio: 5:5) of a non-polymer type binder: 10 parts by mass, The mixture was mixed with 90 parts by mass of isopropyl alcohol as a dispersing agent, and stirred at a rotation speed of 20 rpm for 1 hour at room temperature to prepare a material: i〇g. [Preparation of Material 1-2] 10 parts by mass of non-polymeric binder 2-n-propoxyethanol, and a mixture of isopropanol and butanol as a dispersing agent (mass ratio 40:60): 90 mass The mixture was mixed and stirred at a rotation speed of 200 rpm for 1 hour at room temperature to prepare a material of 1-2:10 g. [Preparation of materials 1-3] -30- 201247416 SiO 2 bonding agent: 10 parts by mass, mixed with ethanol and butanol as a dispersing agent (mass ratio: 98:2): 90 parts by mass to prepare a material 1-3 : 10g. For the SiO 2 bonding agent as a binder, a four-necked flask made of glass of 500 cm 3 can be used, and tetraethoxy oxane: 140 g and ethanol: 240 g are added, and 12 N-HC1: 1.0 g is dissolved in 25 g of pure water. It was added in one time, and then reacted in 8 (TC for 6 hours to prepare a material of 1-3: 10 g. [Preparation of Material 4-1] Ag80%, Au20% mixed metal nanoparticle dispersion was mixed as ( A) The metal nanoparticle dispersion liquid is centrifuged after the composition of the bonding layer of the metal nanoparticle matrix, and is polyethylene glycol: 5 parts by mass with respect to 95 parts by mass of the metal nanoparticles. The polyethylene glycol was added to the precipitate after centrifugation, and a material of 4-1 : 10 g was prepared by a planetary stirring type mixer. Here, Ag 80%, Au 20% mixed metal nanoparticle dispersion liquid It is produced in the following manner, "Preparation of silver nanoparticle dispersion liquid". Silver nitrate was dissolved in deionized water to prepare a metal salt aqueous solution having a concentration of 25% by mass. Further, sodium citrate was dissolved in deionized water to prepare a concentration. 26% by mass aqueous sodium citrate solution. The ferrous sulfate was directly added to the aqueous sodium citrate solution and dissolved in a nitrogen gas stream maintained at 35 ° C to prepare a reduction of citrate ions and ferrous ions in a molar ratio of 3:2. -31 - 201247416 Then, the above-mentioned nitrogen gas flow was maintained at 35 ° C, and the stirring agent of the magnetic stirrer was used in the reducing agent aqueous solution while stirring at the rotation speed of the stirring member: 100 rpm, and the above aqueous metal salt solution was dropped. The aqueous solution of the reducing agent is mixed and mixed. The concentration of each solution is adjusted so that the amount of the metal salt aqueous solution added to the reducing agent aqueous solution is less than 1 / 1 Φ of the amount of the reducing agent aqueous solution, and even if it is dropped The room temperature aqueous metal salt solution also maintains the reaction temperature at 40 ° C. In addition, the mixing ratio of the reducing agent aqueous solution and the metal salt aqueous solution is set as the citrate ion and ferrous ion of the reducing agent aqueous solution, with respect to the metal salt aqueous solution. The molar ratio of the total valence of the metal ion in the metal ion is 3 times the molar amount. After the aqueous solution of the metal salt is dropped into the aqueous solution of the reducing agent, it continues. The mixture was mixed for 15 minutes to produce silver nanoparticles in the mixed solution, and a silver nanoparticle dispersion in which silver nanoparticles were dispersed was obtained: the pH of the 100 cm3»silver nanoparticle dispersion was 5.5, in the dispersion. The metered chemical production amount of the silver nanoparticles is 5 g / liter. The obtained silver nanoparticle dispersion is allowed to stand at room temperature, whereby the silver nanoparticles in the dispersion are sedimented, and sedimentation is separated by decantation. Agglomerates of silver nanoparticles after the addition. The deionized water is added to the separated silver nanoparticle aggregates to form a dispersion, which is desalted by ultrafiltration, and then washed with methanol instead of silver. The content becomes 50% halo%. Then, using a centrifugal separator, the centrifugal force of the centrifugal separator is adjusted to separate relatively large silver particles having a particle diameter of more than 100 nm, thereby adjusting to a range of 71% of the primary particle diameter of 10 to 5 Onm. Silver nanoparticle inside. That is, the ratio of the silver nanoparticles in the range of -32 to 201247416 10 to 5 Onm with respect to the total silver particle size of the silver nanoparticles is 71%. A silver nanoparticle dispersion is obtained. The obtained silver nanoparticles were chemically modified with a protective agent of sodium citrate. "Preparation of a gold nanoparticle dispersion liquid" In addition to the use of chloroauric acid instead of silver nitrate, "others are the same as the production of silver nanoparticle", and gold having a mass particle size of 10 nm% of gold nanoparticles having an average particle diameter of 10 nm is obtained. Nanoparticle dispersion: 1 00cm3. <<Preparation of mixed metal nanoparticle dispersion liquid>> The obtained silver nanoparticle dispersion liquid and the gold nanoparticle dispersion liquid are mixed so that the mass ratio is 80% of Ag and 20% of Au, and the mixed metal nanoparticle dispersion is obtained. Liquid: 100cm3. [Preparation of Material 4 - 2] Ag particles (average diameter: 70 parts by weight, diammonium oxychloride (average particle diameter: 〇·1 M m): 5 parts by weight, silver carbonate (average particle diameter: 0 · 4 / / m ) : 5 parts by weight, terpineol: 20 parts by weight of a composition for a bonding layer of (B) a metal compound matrix. After mixing the raw materials, the material 4 is prepared by a planetary agitating mixer. -2 : 10g [Metal composition for sintered metal oxide layer] The material is mixed with the composition of the first table, and the composition for the sintered body layer of the metal nanoparticle is prepared in the same manner as the material 4-1. Chlorine-33-201247416 gold acid was used as a raw material of Au, silver nitrate was used as a raw material of Ag, and tin chloride was used as a raw material of Sn'. Manganese sulfate was used as a raw material of Mn. [Example 1] First, a light-emitting layer was formed. Yu Chang: 5mm, width: 5mm, thickness: 5mm on the sapphire substrate. And preparation length: 2〇mm, width: 20mm, thickness. 5.5mm and Si-based substrate with Ni/Au plating on the surface as a branch Wiping the substrate. First, the gold-coated nanoparticle sintered body layer is used by the spin coating method. The material was applied to the joint-treated surface of the element and sintered at 13 Torr for 10 minutes to form a sintered layer of a metal nanoparticle having a thickness of 〇3/m. Then, the material was 4-by screen printing. 1 Printed on the side of the support substrate 'Set a sapphire substrate, and pressurize at room temperature for 1 〇 P at 1 Μ P a, and then sinter at 20 ° C for 20 minutes in a baking oven. [Example 2 The same elements and substrates as in Example 1 were prepared. First, the material 1-1 was applied onto the joint-treated surface of the element by a die-casting method, and sintered at 130 ° C for 30 minutes to form a thickness: 〇 a transparent layer of 〇1 am. The metal nanoparticle sintered body layer composition was applied onto the transparent layer by screen printing, and sintered at 200 ° C for 20 minutes to form a thickness of 0.5 vm. The metal nanoparticle sintered body layer, and then the material 4-1 is formed on the support substrate side by a pin transfer method, and the sapphire substrate ′ is placed and pressurized at 10 MPa for 10 seconds at room temperature in the baking furnace. Sintering at 200 ° C for 20 minutes. -34 - 201247416 [Example 3] According to the conditions described in Table 1, it was the same as Example 1. Example 3 was produced. Here, the adhesive layer was applied by a die-casting method. [Examples 4 and 5] The same conditions as in Example 2 were carried out in the same manner as in Example 2. Examples 4 and 5. Here, the adhesive layer was applied by a die casting method [Comparative Example 1] The sintered metal layer of the metal nanoparticles was not formed under the conditions described in the first table, and Example 2 was Comparative Example 1 was prepared in the same manner. [Comparative Example 2] Comparative Example 2 was produced using Ag-polysiloxane resin (product name: SMP-2 8 00) manufactured by Shin-Etsu Chemical Co., Ltd. under the conditions described in the first table. . [Evaluation of Bonding Strength] The joint strength (shear strength) of Examples 1 to 5 and Comparative Examples 1 and 2 was measured by a precision universal testing machine Autograph AG-XplUS. The measurement conditions were carried out in accordance with JIS Z3 198-5. [Evaluation of Luminous Intensity] -35-201247416 The luminous intensity (relative intensity) of Examples 1 to 5 and Comparative Examples 1 and 2 was measured using an LSA-3000 apparatus manufactured by Labsphere. [Table 1] Classification ST Example 1 Η Example 2 Capital Example 3 R Example 4 瘘 Example 3 Comparative Example Ί Comparative Example 2 Material No 1-1 m 1-2 : 1-3 1-2 No - 0.01 - 0.1 :0.4 0.06 - Specification τ) - 130 - 200 220 170 - Dependent on time (minutes) - 30 - 20 :10 5 - Gold layer » Rice particle supply material As 100012% As 99!Tfi % PVP〇.9«a% Si〇2 0.1ΠΑ% Ag 89Qfi% Au 5H*% methyl fiber cable zmA〇mis% As 95.8ΏΞ% Sn 0.2SS% 抒丙儿甲越纤雄索3霣£1% ZoO Ag9iS.8iJ*% Mn PVP20*% B BlcJulB*% No 0.3 0.5 0.1 0.2 ; 〇.4 - - 焼 沮 CC CC) 130 200 150 t70 220 - — 汾 汾 ) 10 20 5 M : 15 - - «料无无1-1 1-2 Ί-3 无无乌合m/s 6U9 ΐ m) - — 0.01 0.02 0.03 - - 堍 knot S degree (1C) - - 130 200 220 - - flMSRra (minutes) - - 30 20 :10 - - ίί 4-1 4-1 4-1 4-2 4-2 4-2 Α8· decane bait 0.01 0.5 2 5 :i〇10 10 Supply degree rc) 200 200 200 250 250 300 200 Workshop (9) 20 20 20 60 60 60 30 Joint strength 53 Shear strength (N/mm1) 20 20 26 30 : 40 30 20 Relative intensity of luminous intensity 130 140 120 135 | 145 103 100 It can be seen from the first table that in Examples 1 to 5, the joint strength and the light-emitting intensity were both high. In particular, in Examples 2, 4, and 5 having a transparent layer, the light-emitting intensity was extremely high, and in Examples 4 and 5 in which the transparent layer and the adhesive layer were provided, the joint strength was higher than that of the other examples. On the other hand, in Comparative Examples 1 and 2 in which the sintered body layer of the metal nanoparticles was not formed, the emission intensity was low. The laminated body for bonding of the present invention can be replaced by a metal paste containing metal particles and a solvent as a main component, and the manufacturing process can be simplified, and the running cost can be greatly improved, and the temperature can be lowered at a low temperature. Engage under. [Brief Description of the Drawings] -36-201247416 Fig. 1 is a cross-sectional view showing a laminated body for bonding according to an embodiment of the present invention. Fig. 2 is a cross-sectional view showing a laminated body including a transparent layer according to another embodiment of the present invention. Fig. 3 is a cross-sectional view showing a laminated body including a pressure-sensitive adhesive layer according to another embodiment of the present invention. Fig. 4 is a cross-sectional view showing a joined body according to another embodiment of the present invention. Fi element reference symbol] I, 2, 3: bonding layer body 4: joint body II, 21, 31, 41: metal nanoparticle sintered body layer 12, 22, 32, 42: bonding layer 23 ' 43 : transparent layer 3 4, 44: adhesive layer 45: the first joined body 46: the second joined body - 37-

Claims (1)

201247416 七、申請專利範圍： 1. —種接合用積層體，其特徵爲 具備有：以金屬奈米粒子爲主原料燒結而成之金屬奈 米粒子燒結體層，以及 積層於前述金屬奈米粒子燒結體層上之食有金屬粒子 或金屬氧化物粒子之接合層。 2. 如申請專利範圍第1項之接合用積層體，其中前 述金屬奈米粒子燒結體層，具備有積層於與前述接合層爲 相反側之透明層。 3. 如申請專利範圍第1項之接合用積層體，其係具 備有：形成於前述金屬奈米粒子燒結體層與前述接合層之 間之黏合劑層。 4. 如申請專利範圍第1項之接合用積層體，其中前 述金屬奈米粒子燒結體層含有75質量％以上的銀，並且 含有金、銅、錫、鋅、鉬及錳之至少1種的第2金屬。 5. 如申請專利範圍第1項之接合用積層體，其中前 述金屬奈米粒子燒結體層含有黏合劑。 6. 如申請專利範圍第1項之接合用積層體，其中前 述金屬奈米粒子燒結體層的厚度爲〇.〇1〜0.5 # m ° 7. 如申請專利範圍第1項之接合用積層體，其中前 述各層是在藉由濕式塗佈法成膜後’在130〜250°C中燒結 之層。 8. 如申請專利範圍第3項之接合用積層體’其中前 述透明層及前述黏合劑層’含有藉由加熱而硬化之聚合物 -38 - 201247416 型黏合劑及非聚合物型黏合劑的至少1種。 9.如申請專利範圍第7項之接合用積層體，其中前 述濕式塗佈法，爲噴霧塗佈法、分注塗佈法、旋轉塗佈法 、刮刀塗佈法、狹縫塗佈法、噴墨塗佈法、網版印刷法、 平版印刷法 '轉印法及壓鑄模塗佈法中的任一種。 10·如申請專利範圍第4項之接合用積層體，其中前 述金屬奈米粒子燒結體層中之前述第2金屬的含量，相對 於前述金屬奈米粒子燒結體層中之全部金屬的總量，爲 〇.〇2質量％以上且未達25質量％。 11. 一種接合體，其特徵爲 具備有：第1被接合體，第2被接合體，以及設置在 前述第1及第2被接合體之間之如申請專利範圍第丨至 10項中任一項之接合用積層體。 12. 如申請專利範圍第11項之接合體，其中前述第 1被接合體爲可發光或可光電轉換之元件，前述金屬奈米 粒子燒結體層可使來自前述第1被接合體的光反射，前述 第2被接合體爲基板。 1 3 .如申請專利範圍第1 2項之接合體，其中前述第 1被接合體爲可發光之元件，並使用作爲發光源。 1 4 ·如申請專利範圍第1 2項之接合體，其中前述第 1被接合體爲可光電轉換之元件，並使用作爲太陽能電池 〇 I5. —種接合體的製造方法，其係藉由接合用積層體 將第1及第2被接合體接合而製造接合體之方法，其特徵 -39- 201247416 爲包含 將含有金屬奈米粒子之金屬奈米粒子燒結體層用組成 物塗佈於前述第1被接合體’並進行燒,結而形成金屬奈米 粒子燒結體層之步驟’ 將含有金屬粒子或金屬化合物的粒子之接合層用組成 物塗佈於前述第2被接合體之步驟’ 使前述金麗奈米粒子燒結體層朝向前述撞佈後之接合 層用組成物的層，而重疊前述第1被接合體及前述第2被 接合體之步驟； 藉由加熱前述重疊後之第1及第2被接合體，燒結前 述塗佈後之接合層用組成物的層來形成接合層，而將第1 及第2被接合體接合之步驟。 16. 如申請專利範圍第15項之接合體的製造方法， 其中前述塗佈方法，爲選自噴霧塗佈法、分注塗佈法、旋 轉塗佈法、刮刀塗佈法、狹縫塗佈法、噴墨塗佈法、網版 印刷法、平版印刷法、轉印法及壓鑄模塗佈法中的任—種 之濕式塗佈法。 17. 如申請專利範圍第15或16項之接合體的製造方 &amp; ’前述金屬奈米粒子燒結體層用組成物及前述接合 層用組成物的燒結溫度，均爲130〜250〇C。 -40-201247416 VII. Patent application scope: 1. A laminated body for bonding, comprising: a sintered layer of a metal nanoparticle sintered by using a metal nanoparticle as a main raw material, and a laminated layer of the metal nanoparticle sintered The layer on the body layer has a bonding layer of metal particles or metal oxide particles. 2. The joint laminated body according to the first aspect of the invention, wherein the sintered metal nanoparticle sintered body layer is provided with a transparent layer laminated on the opposite side to the joint layer. 3. The bonding layered body according to the first aspect of the invention, wherein the bonding layer formed between the sintered metal nanoparticle sintered body layer and the bonding layer is provided. 4. The joint laminated body according to the first aspect of the invention, wherein the sintered body layer of the metal nanoparticle contains 75 mass% or more of silver, and contains at least one of gold, copper, tin, zinc, molybdenum and manganese. 2 metal. 5. The joint laminated body according to claim 1, wherein the sintered metal nanoparticle sintered body layer contains a binder. 6. The bonding layer according to the first aspect of the invention, wherein the thickness of the sintered body layer of the metal nanoparticle is 〇.〇1 to 0.5 #m° 7. The bonding layer according to item 1 of the patent application scope, The foregoing layers are layers which are sintered at 130 to 250 ° C after film formation by a wet coating method. 8. The joint laminate according to claim 3, wherein the transparent layer and the adhesive layer contain at least a polymer which is hardened by heating-38 - 201247416 type adhesive and a non-polymer type adhesive 1 species. 9. The bonding layer according to claim 7, wherein the wet coating method is a spray coating method, a dispensing coating method, a spin coating method, a knife coating method, or a slit coating method. Any one of an inkjet coating method, a screen printing method, a lithographic printing method, a transfer method, and a die-casting method. The bonding layered body according to the fourth aspect of the invention, wherein the content of the second metal in the sintered body layer of the metal nanoparticle is relative to the total amount of all the metals in the sintered body layer of the metal nanoparticle 〇.〇 2% by mass or more and less than 25% by mass. 11. A joined body, comprising: a first joined body, a second joined body, and a first to second joined body disposed between the first and second joined bodies as claimed in claims 10 to 10 A joint laminate. 12. The joined body of claim 11, wherein the first joined body is an element that is illuminable or photoelectrically convertible, and the sintered metal nanoparticle layer reflects light from the first joined body. The second joined body is a substrate. The bonded body of claim 12, wherein the first joined body is a light-emitting element and is used as a light-emitting source. The joint body of claim 12, wherein the first joined body is a photoelectrically convertible element, and a method of manufacturing a solar cell 〇I5. A method of producing a joined body by joining the first and second joined bodies with a laminate, and the method of 39-201247416 is to apply the composition for sintering a metal nanoparticle containing body layer containing metal nanoparticles to the first one. Step of forming a sintered body layer of a metal nanoparticle by firing the bonded body', and forming a composition of a bonding layer containing particles of a metal particle or a metal compound on the second bonded body. a step of superimposing the first joined body and the second joined body toward the layer of the bonding layer composition after the collision of the lining particles, and heating the first and second conditioned by the overlapping In the bonded body, a step of forming the bonding layer by sintering the layer of the composition for the bonding layer after the coating, and bonding the first and second bonded bodies. 16. The method for producing a joined body according to claim 15, wherein the coating method is selected from the group consisting of a spray coating method, a dispensing coating method, a spin coating method, a knife coating method, and a slit coating method. Any of the wet coating methods of the method, the inkjet coating method, the screen printing method, the lithography method, the transfer method, and the die casting method. 17. The manufacturer of the joined body of the invention of claim 15 or 16 and the sintering temperature of the composition for the sintered metal nanoparticle sintered body layer and the composition for the bonding layer are both 130 to 250 °C. -40-
TW101106223A 2011-02-28 2012-02-24 Layered material and assembly joined by the same TWI556973B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2011041515A JP5810553B2 (en) 2011-02-28 2011-02-28 Laminate for bonding and bonded body

Publications (2)

Publication Number Publication Date
TW201247416A true TW201247416A (en) 2012-12-01
TWI556973B TWI556973B (en) 2016-11-11

Family

ID=46691521

Family Applications (1)

Application Number Title Priority Date Filing Date
TW101106223A TWI556973B (en) 2011-02-28 2012-02-24 Layered material and assembly joined by the same

Country Status (4)

Country Link
JP (1) JP5810553B2 (en)
KR (1) KR101752931B1 (en)
CN (1) CN102649330B (en)
TW (1) TWI556973B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3508891A4 (en) * 2016-08-30 2019-11-06 Panasonic Intellectual Property Management Co., Ltd. Color conversion element
TWI683322B (en) * 2015-12-07 2020-01-21 日商哈利瑪化成股份有限公司 Method for producing conductive paste

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5830302B2 (en) * 2011-08-11 2015-12-09 古河電気工業株式会社 Heat bonding material, heat bonding sheet, and heat bonding molded body
AT513747B1 (en) 2013-02-28 2014-07-15 Mikroelektronik Ges Mit Beschränkter Haftung Ab Assembly process for circuit carriers and circuit carriers
JP2015188035A (en) * 2014-03-27 2015-10-29 セイコーエプソン株式会社 Manufacturing method of light-emitting device, light-emitting device, and projector
JP6815133B2 (en) * 2016-08-31 2021-01-20 日東電工株式会社 Sheet for heat bonding and sheet for heat bonding with dicing tape
JP2019065229A (en) * 2017-10-04 2019-04-25 コニカミノルタ株式会社 Manufacturing method of mixed liquid, system for manufacturing mixture, ink composition, image formation method and image formation article
KR102046225B1 (en) * 2017-11-20 2019-11-19 동국대학교 산학협력단 Side Light transmitting System
CN111033703A (en) 2018-04-12 2020-04-17 松下知识产权经营株式会社 Mounting structure and nanoparticle mounting material
KR102243472B1 (en) * 2018-12-17 2021-04-26 주식회사 경동원 Sintering paste composition for bonding power semiconductor
US12103073B2 (en) 2019-03-18 2024-10-01 Hewlett-Packard Development Company, L.P. Three-dimensional object formation
CN110640354B (en) * 2019-08-27 2022-03-04 北京康普锡威科技有限公司 Preformed solder and preparation method thereof

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE60326760D1 (en) * 2002-09-18 2009-04-30 Ebara Corp PROCESS FOR CONNECTING
JP2005205696A (en) * 2004-01-21 2005-08-04 Ebara Corp Joining article
JP5012239B2 (en) * 2007-06-13 2012-08-29 株式会社デンソー Joining method and joined body
US8921688B2 (en) * 2007-09-12 2014-12-30 Mitsubishi Materials Corporation Composite film for superstrate solar cell having conductive film and electroconductive reflective film formed by applying composition containing metal nanoparticles and comprising air pores of preset diameter in contact surface
JP5515499B2 (en) * 2008-08-08 2014-06-11 三菱マテリアル株式会社 Composite film for substrate type solar cell and manufacturing method thereof
JP5370372B2 (en) * 2009-01-23 2013-12-18 日亜化学工業株式会社 Semiconductor device and manufacturing method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI683322B (en) * 2015-12-07 2020-01-21 日商哈利瑪化成股份有限公司 Method for producing conductive paste
EP3508891A4 (en) * 2016-08-30 2019-11-06 Panasonic Intellectual Property Management Co., Ltd. Color conversion element

Also Published As

Publication number Publication date
CN102649330A (en) 2012-08-29
JP2012178507A (en) 2012-09-13
KR20120098461A (en) 2012-09-05
JP5810553B2 (en) 2015-11-11
KR101752931B1 (en) 2017-07-03
CN102649330B (en) 2015-10-14
TWI556973B (en) 2016-11-11

Similar Documents

Publication Publication Date Title
TW201247416A (en) Layered material and assembly joined by the same
JP5899623B2 (en) Laminate for solder joint and joined body
TWI399759B (en) Composition for forming electrode of solar cell, method for forming same electrode, and solar cell employing electrode formed by same method
JP5309440B2 (en) Composition for forming electrode of solar cell, method for forming the electrode, and method for producing solar cell using the electrode obtained by the forming method
TWI580075B (en) Composition for reflective film of light emitting element, light emitting element, and method of producing same
JP5741811B2 (en) Composition for enhanced reflective transparent film for light emitting device, light emitting device, and method for producing light emitting device
JP2014088550A (en) Metal particle-dispersed body, article and sintered film using the metal particle-dispersed body, and method for producing the sintered film
JP5637196B2 (en) Composite film for super straight type thin film solar cell and manufacturing method thereof
JP2013045752A (en) Organic electroluminescent element and method for manufacturing the same
JP5741810B2 (en) REFLECTIVE FILM COMPOSITION FOR LIGHT EMITTING ELEMENT, LIGHT EMITTING ELEMENT, AND METHOD FOR PRODUCING LIGHT EMITTING ELEMENT
JP2011109069A (en) Conductive reflecting film and method of manufacturing the same
JP2010087480A (en) Composite film for substraight type solar cell and method of manufacturing the same
JP2010087477A (en) Composite film for super straight type solar cell and method of manufacturing the same
JP5407989B2 (en) Method for forming composite film for solar cell
WO2017086453A1 (en) Connecting material and connection structure
TW201335952A (en) Reflector film with electrical conductivity and production method thereof
JP2013045751A (en) Organic electroluminescent element and method for manufacturing the same
JP2013045749A (en) Organic electroluminescent element and method for manufacturing the same