JP6714275B2 - 導電性ペースト及び太陽電池 - Google Patents
導電性ペースト及び太陽電池 Download PDFInfo
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- JP6714275B2 JP6714275B2 JP2016162915A JP2016162915A JP6714275B2 JP 6714275 B2 JP6714275 B2 JP 6714275B2 JP 2016162915 A JP2016162915 A JP 2016162915A JP 2016162915 A JP2016162915 A JP 2016162915A JP 6714275 B2 JP6714275 B2 JP 6714275B2
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- conductive paste
- electrode
- solar cell
- back surface
- passivation film
- Prior art date
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
- C03C8/18—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing free metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/288—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L24/50—Tape automated bonding [TAB] connectors, i.e. film carriers; Manufacturing methods related thereto
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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
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- 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
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
- H01L31/02168—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells the coatings being antireflective or having enhancing optical properties for the solar cells
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Description
本発明の構成1は、太陽電池セルのパッシベーション膜上に形成される導電性ペーストであって、
(A)銀粒子と、
(B)有機ビヒクルと、
(C)TeO2を1.0〜20mol%、及びBi2O3を10〜30mol%含むガラスフリットと
を含む、導電性ペーストである。
本発明の構成2は、(A)銀粒子の比表面積が0.4〜1.5m2/gである、構成1に記載の導電性ペーストである。
本発明の構成3は、(B)有機ビヒクルが、エチルセルロース、ロジンエステル、ブチラール、アクリル又は有機溶剤を少なくとも1つ含む、構成1又は2の導電性ペーストである。
本発明の構成4は、(C)ガラスフリットが、SiO2を5〜30mol%、さらに含むことを特徴とする構成1〜3のいずれかの導電性ペーストである。
本発明の構成5は、(C)ガラスフリットが、ZnOを10〜30mol%、さらに含む、構成1〜4のいずれかの導電性ペーストである。
本発明の構成5は、(C)ガラスフリットが、Al2O3を1〜10mol%、さらに含む、構成1〜5のいずれかの導電性ペーストである。
本発明の構成7は、(C)ガラスフリットが、TiO2を1〜20mol%、さらに含む、請求項1〜6のいずれか1項に記載の導電性ペーストである。
本発明の構成6は、チタンレジネート、酸化チタン、酸化コバルト、酸化セリウム、窒化ケイ素、銅マンガン錫、アルミノケイ酸塩及びケイ酸アルミニウムの少なくとも1つの添加物を含むことを特徴とする構成1〜7のいずれかの導電性ペーストである。
本発明の構成9は、導電性ペーストが、裏面TAB電極形成用の導電性ペーストである、構成1〜8のいずれかの導電性ペーストである。
本発明の構成10は、構成1〜9のいずれかの導電性ペーストを用いて電極形成された太陽電池である。
実施例及び比較例の太陽電池製造に用いた導電性ペーストの組成は、下記のとおりである。
実施例1〜23及び比較例1〜3に用いた銀粒子(100重量部)の形状は球状である。表1〜表6に、銀粒子のBET比表面積を示す。BET比表面積の測定には、全自動比表面積測定装置Macsoeb(MOUNTEC社製)を用いた。BET比表面積は、100℃で予備乾燥し、10分間窒素ガスを流したのち、窒素ガス吸着によるBET1点法により測定した。
実施例1〜23及び比較例1〜3のそれぞれに、表1〜表6に示す配合のガラスフリットを用いた。実施例及び比較例の導電性ペースト中の、銀粒子100重量部に対するガラスフリットの添加量は、表1〜表6に示すとおりである。なお、ガラスフリットの平均粒子径(D50)は2μmとした。平均粒子径(D50)は、マイクロトラック法(レーザー回折散乱法)にて粒度分布測定を行い、粒度分布測定の結果からメジアン径(D50)の値を得ることにより求めた。他の粒子の平均粒径(D50)についても同様である。
エチルセルロース(1重量部)を用いた。エトキシ含有量48〜49.5重量%のものを用いた。
ブチルカルビトールアセテート(11重量部)を用いた。
本発明の導電性ペーストの評価の一つとして、調製した導電性ペーストを用いて太陽電池を模擬したはんだ付け接着強度測定用基板を試作し、はんだ付け接着強度を測定した。なお、はんだ付け接着強度試験では、パッシベーション膜を含む測定用基板と電極との間の接着強度、及び金属リボンと電極との間の接着強度の両方を測定していることになるが、電極に含まれる金属粒子はAgなので、金属リボンと電極との間の接着強度は比較的高い。したがって、はんだ付け接着強度の測定により、パッシベーション膜を含む測定用基板と電極との間の接着強度を評価することができる。
導電性ペーストのパッシベーション膜に対する反応性の評価を、フォトルミネッセンスイメージング法(「PL法」という。)により行った。PL法は、非破壊・非接触かつ、短時間で、導電性ペーストのパッシベーション膜に対する反応性を評価することが可能である。具体的には、PL法は、試料に対して禁制帯幅より大きいエネルギーの光を照射して発光させ、その発光の状況から、結晶中の欠陥及び表面・界面欠陥の様子を評価する方法である。試料が単結晶シリコン基板中の欠陥及び表面・界面欠陥を有する場合には、欠陥が、光を照射により発生した電子−正孔対の再結合中心として働き、これと対応してフォトルミネッセンスによるバンド端発光強度が低下する。つまり、印刷/焼成された電極によりパッシベーション膜が侵食され、パッシベーション膜と単結晶シリコン基板との界面(すなわち、単結晶シリコン基板の表面)に表面欠陥が形成された場合、表面欠陥が形成された部分(すなわち、試料に形成された電極の部分)のフォトルミネッセンスの発光強度が低下する。このフォトルミネッセンスの発光強度の強弱により、試作ペーストのパッシベーションとの反応性を評価することができる。
表1〜表6に示す配合のガラスフリットを、表1〜表6に示す添加量になるように添加した導電性ペーストを用意した。これらの導電性ペーストを、はんだ付け接着強度測定用基板及びフォトルミネッセンスイメージング法(PL法)測定用基板の作製のために用いて、上述のような方法で、実施例1〜23及び比較例1〜3のはんだ付け接着強度測定用基板及びPL法測定用基板を作製した。表1〜表6に、これらのはんだ付け接着強度試験及びPL法の測定結果を示す。
2 反射防止膜
4 不純物拡散層(n型不純物拡散層)
14 裏面パッシベーション膜
15 裏面電極
15a 裏面TAB電極(裏面バスバー電極)
15b 裏面電極(裏面全面電極)
16 不純物拡散層(p型不純物拡散層)
18 不純物拡散部(p型不純物拡散部)
20 光入射側電極(表面電極)
20a 光入射側バスバー電極
20b 光入射側フィンガー電極
32 銀
34 ガラスフリット
Claims (4)
- 太陽電池セルのパッシベーション膜上に形成される裏面TAB電極形成用の導電性ペーストであって、
(A)銀粒子と、
(B)有機ビヒクルと、
(C)TeO2を1.0〜20mol%、及びBi2O3を10〜30mol%含むガラスフリットと
を含み、
(A)銀粒子の比表面積が0.4〜1.5m 2 /gであり、
(C)ガラスフリットが、さらに、SiO 2 を15〜25mol%、ZnOを15〜27mol%、Al 2 O 3 を2〜7mol%、及びTiO 2 を3〜5mol%含む、導電性ペースト。 - (B)有機ビヒクルが、エチルセルロース、ロジンエステル、ブチラール、アクリル又は有機溶剤を少なくとも1つ含む、請求項1に記載の導電性ペースト。
- チタンレジネート、酸化チタン、酸化コバルト、酸化セリウム、窒化ケイ素、銅マンガン錫、アルミノケイ酸塩及びケイ酸アルミニウムの少なくとも1つの添加物を含む請求項1又は2に記載の導電性ペースト。
- 請求項1〜3のいずれか1項に記載の導電性ペーストを用いて電極形成された太陽電池。
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