JP2015168803A - 導電性接着剤組成物、接続体、太陽電池モジュール及びその製造方法 - Google Patents
導電性接着剤組成物、接続体、太陽電池モジュール及びその製造方法 Download PDFInfo
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- JP2015168803A JP2015168803A JP2014046744A JP2014046744A JP2015168803A JP 2015168803 A JP2015168803 A JP 2015168803A JP 2014046744 A JP2014046744 A JP 2014046744A JP 2014046744 A JP2014046744 A JP 2014046744A JP 2015168803 A JP2015168803 A JP 2015168803A
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- KEROTHRUZYBWCY-UHFFFAOYSA-N tridecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C(C)=C KEROTHRUZYBWCY-UHFFFAOYSA-N 0.000 description 1
- XOALFFJGWSCQEO-UHFFFAOYSA-N tridecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C=C XOALFFJGWSCQEO-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/048—Encapsulation of modules
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/05—Electrical interconnection means between PV cells inside the PV module, e.g. series connection of PV cells
- H01L31/0504—Electrical interconnection means between PV cells inside the PV module, e.g. series connection of PV cells specially adapted for series or parallel connection of solar cells in a module
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
Description
本実施形態に係る導電性接着剤組成物は、(A)融点が220℃以下の金属を含む導電性粒子と、(B)熱硬化性樹脂と、(C)熱カチオン重合開始剤と、を含有する。
(A)導電性粒子は、融点が220℃以下である金属を含む。このような導電性粒子を導電性接着剤組成物において用いると、金属が溶融してなる金属部が強固な導電パスを形成できるため、銀粒子等の粒子同士の接触による比較的細く脆弱なパスと比較して、低抵抗に伴う発電効率の向上、及び、温度サイクル試験での熱歪に対する耐性の向上を図ることができる。
(B)熱硬化性樹脂は、被着体を接着する作用を有すると共に、導電性接着剤組成物中の導電性粒子、及び、必要に応じて添加されるフィラーを互いに結合するバインダ成分として作用する。このような熱硬化性樹脂としては、例えば、エポキシ樹脂、(メタ)アクリル樹脂、マレイミド樹脂、シアネート樹脂等の熱硬化性の有機高分子化合物、及び、それらの前駆体が挙げられる。ここで、「(メタ)アクリル樹脂」とは、メタクリル樹脂及びアクリル樹脂を示す。これらの中では、エポキシ樹脂、及び、重合可能な炭素−炭素二重結合を有する化合物に由来する構造単位を有する重合体(例えば(メタ)アクリル樹脂及びマレイミド樹脂)が好ましい。これらの熱硬化性樹脂は、耐熱性及び接着性に更に優れると共に、必要に応じて有機溶剤中に溶解又は分散させれば液体の状態で取り扱うことができるため作業性に優れている。また、入手容易性、及び、被着体との接着性に更に優れる観点から、エポキシ樹脂がより好ましい。(B)熱硬化性樹脂は、1種単独又は2種以上を組み合わせて用いられる。
[式(I)中、n1は、1〜5の整数を示す。]
本実施形態に係る導電性接着剤組成物は、加熱により酸等を発生して重合を開始する(C)熱カチオン重合開始剤を含有する。(C)熱カチオン重合開始剤は、カチオン重合開始剤の中でも、加熱プロセス適用性及び熱硬化性に優れている。(C)熱カチオン重合開始剤は、(B)熱硬化性樹脂の重合を促進して充分な接続強度を与える効果に加え、(C)熱カチオン重合開始剤から発生する遊離酸が導電性粒子及び接続部の表面酸化膜を除去することにより導電性粒子の溶融及び凝集が促進されると共に接続部に対する充分な濡れ性が発現することによって導通パスを形成する効果を有する。
本実施形態に係る導電性接着剤組成物は、電気導通性が更に向上する観点から、(C)熱カチオン重合開始剤の他に(D)フラックス活性剤を更に含有していてもよい。(D)フラックス活性剤は、(A)導電性粒子の表面に形成された酸化膜の除去能を示すものである。このようなフラックス活性剤を用いることにより、(A)導電性粒子の溶融及び凝集の妨げとなる酸化膜の除去が更に促進され、電気導通性が更に向上する。(D)フラックス活性剤は、(C)熱カチオン重合開始剤の硬化反応を阻害しない化合物であれば、特に制限なく公知の化合物を使用することができる。
本実施形態に係る導電性接着剤組成物は、紫外線等のエネルギー線の照射によりカチオン重合を開始することのできる酸を発生する光カチオン重合開始剤(熱カチオン重合開始剤としても用いられる化合物を除く)を含有していてもよい。光カチオン重合開始剤としては、例えば、芳香族スルホニウム塩、芳香族ヨードニウム塩、芳香族ジアゾニウム塩及び芳香族アンモニウム塩が挙げられる。
次に、本実施形態に係る接続体、太陽電池モジュール及びこれらの製造方法を説明する。本実施形態に係る接続体は、太陽電池セルと、本実施形態に係る導電性接着剤組成物又はその硬化物を介して、太陽電池セルの電極面に配置された電極と電気的に接続された配線部材と、を備え、本実施形態に係る導電性接着剤組成物を用いて太陽電池セルの電極と配線部材とを電気的に接続することにより得ることができる。本実施形態に係る接続体は、太陽電池セルを複数備えていてもよく、配線部材を介して複数の太陽電池セルを互いに接続することにより得られてもよい。
実施例及び比較例で用いた材料は、下記の方法で作製したもの、あるいは、入手したものである。導電性接着剤の調製方法の詳細を実施例1に示すが、その他の実施例及び比較例の樹脂組成、配合比は表1及び表2に示すとおりであり、調製方法に関しては実施例1と同様である。
YL−980(三菱化学株式会社製、ビスフェノールA型エポキシ樹脂の商品名)27.3質量部と、サンエイドSI−60L(三新化学工業株式会社製、商品名、熱カチオン重合開始剤)2.7質量部とを混合した後、3本ロールを3回通して接着剤成分を調製した。
表1及び表2に示す組成とした以外は実施例1と同様にして、導電性接着剤として、実施例2〜10及び比較例1〜7の導電性接着剤組成物を得た。表1及び表2中の各材料の配合割合の単位は質量部である。表1及び表2中の成分の詳細は下記のとおりである。
YDF−170:ビスフェノールF型エポキシ樹脂、東都化成株式会社製
630LSD:アミン型エポキシ樹脂、三菱化学株式会社製
サンエイドSI−80L:熱カチオン重合開始剤、三新化学工業株式会社製
サンエイドSI−100L:熱カチオン重合開始剤、三新化学工業株式会社製
2P4MHZ−PW:イミダゾール化合物、四国化成工業株式会社製
2PZ−CN:イミダゾール化合物、四国化成工業株式会社製
BHPA(2,2−ビス(ヒドロキシメチル)プロピオン酸)
Sn42−Bi57−Ag1はんだ粒子:平均粒子径20μm、三井金属鉱業株式会社製、融点139℃
Sn96.5−Ag3−Cu0.5はんだ粒子:平均粒子径20μm、三井金属鉱業株式会社製、融点217℃
Sn99.3−Cu0.7はんだ粒子:平均粒子径20μm、三井金属鉱業株式会社製、融点227℃
比較例8では、導電性接続剤として、市販のSn42−Bi58クリームはんだを用いた。比較例9では、導電性接続剤として、市販のAgペーストを用いた。なお、これらの導電接着剤は、熱カチオン重合開始剤を含有していない。
上記実施例及び比較例の導電性接着剤の特性を下記の方法で評価した。
(実施例1〜8、比較例1〜9)
10個のヘテロ接合型太陽電池セル(125mm×125mm、厚さ210μm)を準備した。次に、実施例1〜8及び比較例1〜9の液状の導電性接着剤を、ヘテロ接合型太陽電池セル(125mm×125mm、厚さ210μm)の受光面上に形成された表面電極(材質:銀ペースト、2mm×125mm)上にメタルマスク(厚み100μm、開口寸法1.2mm×125mm)を用いて印刷した後、配線部材としてはんだ被覆タブ線(日立電線株式会社製、商品名:A−TPS)を配置した。同様の処理を太陽電池セルの裏面電極に行い、はんだ被覆タブ線を配置した。そして、太陽電池用ホットエア加熱接続装置(株式会社エヌ・ピー・シー製、商品名:NTS−150−M)を用いて、加熱部分の温度が160℃となるように設定して30秒間加熱し、太陽電池の表面電極とはんだ被覆タブ線、及び、太陽電池の裏面電極とはんだ被覆タブ線のそれぞれが導電性接着剤を介して接続された10連の太陽電池ストリングを作製した。また、ホットエア加熱の条件を160℃/10秒、160℃/2秒、220℃/2秒へ変更して、上記と同様に太陽電池ストリングを作製した。
ヘテロ接合型太陽電池セルに代えて結晶シリコン型太陽電池セルを用いると共に、実施例9〜10の導電性接着剤を用いて、上記と同様に太陽電池ストリングスを作製した。
上記方法で作製した太陽電池ストリングスのはんだ被覆タブ線部分のみを持ち、太陽電池ストリングスの水平面に対して垂直に引き上げる方法を用いて、接続部の接続強度を評価した。はんだ被覆タブ線と太陽電池ストリングスとが引き上げ時に自重によって剥がれない場合を、充分な接続強度を維持しているとみなして「A」と評価した。自重によって端部のみが剥がれる場合を「B」と評価した。はんだ被覆タブ線を引き上げたときに、太陽電池ストリングスが持ち上がることなく、自重によって接続部からタブ線が完全に剥離する場合を「C」と評価した。結果を表1及び表2に示す。
上記方法で作製した太陽電池ストリングス(比較例2を除く)の表面電極と配線部材との間の導電性接着剤中の金属の凝集状態をX線透過装置(株式会社島津製作所製、マクロフォーカスX線透視装置、SMX−1000)で観察した(観察写真である図4参照)。導電性粒子が完全に溶融及び凝集している場合を「A」と評価し、溶融金属パス間に樹脂の噛み込みがある場合を「B」と評価し、導電性粒子が溶融及び凝集していない場合を「C」と評価した。導電性粒子が溶融及び凝集していない場合(非凝集)は、図4に示すように、X線透過装置像で黒い粒状の金属粒子が観測される。また、導電性粒子が溶融及び凝集している場合は、非凝集の時に見られた黒い粒状の金属粒子が観測されず、導電性粒子が溶融してできたバルク状の金属凝集体が一面の黒い影となって見られる。なお、完全溶融の「A」、及び、樹脂が噛み込んだ「B」の場合は、導電パス面積が本質的に変わらないため、導通性に関して差は見られない。結果を表1及び表2に示す。
上記方法で作製した太陽電池ストリングスに関して、太陽電池セルの裏面に封止樹脂(三井化学ファブロ株式会社製、商品名:ソーラーエバSC50B)及び保護フィルム(株式会社コバヤシ製、商品名:コバテックPV)を積層し、太陽電池セルの表面(受光面)に封止樹脂(三井化学ファブロ株式会社製、ソーラーエバSC50B)及びガラス部材(200×200×3mm)を積層して積層体を得た。次に、真空ラミネータ(株式会社エヌ・ピー・シー製、商品名:LM−50×50−S)の熱板側にガラス部材が接するように積層体を搭載して5分間0.1MPaの減圧下に置いた後、真空ラミネータの真空を解放した状態で140℃、10分間加熱して太陽電池モジュールを作製した。この際、140℃に到達するまでの時間は8分であった。
上記方法で作製した太陽電池モジュールのI−V曲線を、ソーラシミュレータ(ワコム電創社製、商品名:WXS−155S−10、AM:1.5G)を用いて測定した。また、太陽電池モジュールを85℃、85%RHの高温高湿雰囲気下で1500時間静置した後、同様にI−V曲線を測定した。それぞれのI−V曲線から、太陽電池の電気特性を示す曲線因子(Fill Factor:以下、「F.F」と略す)を各々導出した。高温高湿雰囲気下に静置する前のF.F(0h)と、高温高湿雰囲気下に静置した後のF.F(1500h)の変化率ΔF.F(=[F.F(1500h)×100/F.F(0h)]、単位「%」)を評価指標として算出した。なお、一般にΔF.Fの値が95%以上となると接続信頼性が良好であると判断される。結果を表1及び表2に示す。
Claims (12)
- 融点が220℃以下の金属を含む導電性粒子と、熱硬化性樹脂と、熱カチオン重合開始剤と、を含有する、導電性接着剤組成物。
- 前記導電性粒子の含有量が導電性接着剤組成物の全量に対して5〜95質量%である、請求項1に記載の導電性接着剤組成物。
- 前記導電性粒子の前記金属が、ビスマス、インジウム、スズ及び亜鉛からなる群より選ばれる少なくとも一種を含む、請求項1又は2に記載の導電性接着剤組成物。
- フラックス活性剤を更に含有する、請求項1〜3のいずれか一項に記載の導電性接着剤組成物。
- 前記フラックス活性剤が水酸基及びカルボキシル基を有する、請求項4に記載の導電性接着剤組成物。
- 前記熱硬化性樹脂がエポキシ樹脂を含む、請求項1〜5のいずれか一項に記載の導電性接着剤組成物。
- 前記熱カチオン重合開始剤が、加熱により、アンチモン原子を含む無機酸イオン、リン原子を含む無機酸イオン、及び、ホウ素原子を含む有機酸イオンからなる群より選ばれる少なくとも一種を放出する、請求項1〜6のいずれか一項に記載の導電性接着剤組成物。
- 前記熱硬化性樹脂と前記熱カチオン重合開始剤との反応開始温度が30〜200℃である、請求項1〜7のいずれか一項に記載の導電性接着剤組成物。
- 太陽電池セルの電極と配線部材とを電気的に接続するために用いられる、請求項1〜8のいずれか一項に記載の導電性接着剤組成物。
- 太陽電池セルと、請求項1〜9のいずれか一項に記載の導電性接着剤組成物又はその硬化物を介して前記太陽電池セルの電極と電気的に接続された配線部材と、を備える、接続体。
- 請求項1〜9のいずれか一項に記載の導電性接着剤組成物を介して太陽電池セルの電極と配線部材とを相対向するように配置する工程と、
前記太陽電池セルの受光面側と、当該受光面とは反対側の裏面側とに封止材を積層する工程と、
前記太陽電池セルの前記受光面側の前記封止材にガラス部材を積層する工程と、
前記太陽電池セルの前記裏面側の前記封止材に保護フィルムを積層する工程と、
前記ガラス部材及び前記保護フィルムを有する積層体を加熱することで、前記太陽電池セルの電極と前記配線部材とを電気的に接続すると共に前記太陽電池セルを封止する工程と、を備える、太陽電池モジュールの製造方法。 - 太陽電池セルと、請求項1〜9のいずれか一項に記載の導電性接着剤組成物又はその硬化物を介して前記太陽電池セルの電極と電気的に接続された配線部材と、前記太陽電池セルの受光面側、及び、当該受光面とは反対側の裏面側にそれぞれ積層された封止材と、前記太陽電池セルの前記受光面側の前記封止材に積層されたガラス部材と、前記太陽電池セルの前記裏面側の前記封止材に積層された保護フィルムと、を備える、太陽電池モジュール。
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