JP2716630B2 - Current collecting electrode of photovoltaic element and method of manufacturing the same - Google Patents
Current collecting electrode of photovoltaic element and method of manufacturing the sameInfo
- Publication number
- JP2716630B2 JP2716630B2 JP4273972A JP27397292A JP2716630B2 JP 2716630 B2 JP2716630 B2 JP 2716630B2 JP 4273972 A JP4273972 A JP 4273972A JP 27397292 A JP27397292 A JP 27397292A JP 2716630 B2 JP2716630 B2 JP 2716630B2
- Authority
- JP
- Japan
- Prior art keywords
- layer
- solder
- conductive
- collecting electrode
- current collecting
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired - Fee Related
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/548—Amorphous silicon PV cells
Description
【０００１】[0001]
【産業上の利用分野】本発明は、高い光電変換効率を有
する光発電素子に係わり、特に光起電力素子の集電電極
及びその製造方法に関する。The present invention has a high photoelectric conversion efficiency.
Related to photovoltaic elements
And its manufacturing method .
【０００２】[0002]
【従来の技術】従来より、光発電素子の集電電極は、図
７に示すように、ポリエステル系、ポリイミド系、エポ
キシ系、フェノール系等の熱硬化性樹脂、もしくはガラ
スフリットに、直径１〜１０μｍ程度の銀の微粒子を単
分散させ、さらに粘性を整えるためにセルソルブ等の有
機溶剤を混ぜた導電ペースト材料７４をステンシルスク
リーン等を用いて、光発電素子の電極形成面７１に印刷
し、その後加熱硬化したものがよく用いられている。こ
の方法のメリットは極めて大きな面積を持つ材料に対
し、高い生産性と高い材料収率で電極形成を行える点に
あり、現在光発電素子の最大の問題である製造コストの
低減に大きく寄与している。2. Description of the Related Art Conventionally, as shown in FIG. 7, a current collecting electrode of a photovoltaic element is made of a thermosetting resin such as polyester, polyimide, epoxy or phenol, or a glass frit, and has a diameter of 1 to 4. Using a stencil screen or the like, a conductive paste material 74 mixed with an organic solvent such as Cellsolve is printed on the electrode forming surface 71 of the photovoltaic element by monodispersing silver fine particles of about 10 μm, and then adjusting the viscosity. Heat cured products are often used. The advantage of this method is that the electrode can be formed with a high productivity and a high material yield for a material having an extremely large area, which greatly contributes to the reduction of the manufacturing cost, which is currently the biggest problem of the photovoltaic device. I have.
【０００３】しかしながら、近年の光発電素子の光電変
換効率の向上や光発電素子の大面積化により、従来に比
べ、より損失の少ない集電電極が求められるようになり
導電ペーストだけで構成する集電電極ではこれらのニー
ズに答えられなくなってきている。例えば、前記熱硬化
性樹脂を用いた導電ペーストは、比抵抗が３〜５×１０
-5Ωｃｍであり、更に電極により生じる遮光ロスを低減
するために微細な印刷を行うとそれに応じて印刷むらの
増大や膜厚の減少が発生し、集電電極の抵抗による発電
ロスが大幅に増大するという問題がある。しかも、これ
ら導電ペーストは、硬化のために長時間加熱する必要が
あるため、重ね塗り等により厚盛りすることは実際上困
難である。However, recent improvements in photoelectric conversion efficiency of photovoltaic elements and enlargement of photovoltaic elements have resulted in the need for current-collecting electrodes with less loss than in the past. Electrodes are no longer able to meet these needs. For example, the conductive paste using the thermosetting resin has a specific resistance of 3 to 5 × 10
-5 Ωcm, and when fine printing is performed to reduce the shading loss caused by the electrodes, the printing unevenness increases and the film thickness decreases accordingly. There is a problem of increasing. In addition, since these conductive pastes need to be heated for a long time for curing, it is practically difficult to thickly build them by overcoating or the like.
【０００４】これに対し、例えば図８に示すように、半
田等の低い比抵抗を有す材料８７を前記導電ペースト８
４上に載せた構造の電極が提案されている。しかしこの
場合、半田層の接着性を高めるため導電性ペーストとし
て半田とぬれ性のよい材料を用いる必要があるが、そう
すると半田材料の曲率は小さくなり、その結果膜厚は薄
くなってしまうという問題がある。On the other hand, as shown in FIG. 8, for example, a material 87 having a low specific resistance such as solder is applied to the conductive paste 8.
4 has been proposed. However, in this case, it is necessary to use a material having good wettability with solder as a conductive paste in order to enhance the adhesiveness of the solder layer. However, in such a case, the curvature of the solder material becomes small, and as a result, the film thickness becomes thin. There is.
【０００５】この他に電極形成法としては、蒸着やスパ
ッタリングによる方法も知られているが、その製造コス
トが高くなることから大面積素子においてはほとんど使
用されていない。[0005] In addition, as a method of forming an electrode, a method of vapor deposition or sputtering is also known, but it is hardly used in a large-area element because of its high manufacturing cost.
【０００６】[0006]
【発明が解決しようとする課題】以上の現状に鑑み、本
発明は、細線でかつ低抵抗の集電電極を有し、高性能・
低価格の光発電素子を提供することを目的とする。DISCLOSURE OF THE INVENTION In view of the above situation, the present invention has a thin wire and a low-resistance current collecting electrode, and has high performance and high performance.
An object is to provide a low-cost photovoltaic element.
【０００７】[0007]
【課題を解決するための手段】本発明の光起電力素子の
集電電極は、半導体層上に、少なくとも金属粉体と結着
材とからなる線状の導電層、Ｐｄ、Ｚｎ、Ａｇ、Ｃｕ、
Ｃｕ合金、Ｎｉから選ばれる導電性粉体、及びクリーム
半田を硬化させてなる半田層を有し、該導電性粉体は前
記半田層の下部に偏在し、且つ前記半田層は前記導電層
の表面を全長に亘って被覆しており、該半田層の平均厚
みは該導電層の平均厚みより厚いことを特徴とする。 According to the present invention, there is provided a photovoltaic device comprising:
The collecting electrode is bonded to at least the metal powder on the semiconductor layer.
Linear conductive layer made of a material, Pd, Zn, Ag, Cu,
Conductive powder and cream selected from Cu alloy and Ni
It has a solder layer obtained by curing the solder, and the conductive powder is
The solder layer is unevenly distributed below the solder layer, and the solder layer is the conductive layer
Is coated over the entire length, and the average thickness of the solder layer
The feature is that the thickness is larger than the average thickness of the conductive layer.
【０００８】本発明の光起電力素子の集電電極は半導体
層上に、少なくとも金属粉体と結着材とからなる線状の
導電層、Ｐｄ、Ｚｎ、Ａｇ、Ｃｕ、Ｃｕ合金、Ｎｉから
選ばれる導電性粉体、及びクリーム半田を硬化させてな
る半田層を有し、該導電性粉体は前記半田層の上部に偏
在し、且つ前記半田層は前記導電層の表面を全長に亘っ
て被覆しており、該半田層の平均厚みは該導電層の平均
厚みより厚いことを特徴とする。 [0008] The current collecting electrode of the photovoltaic element of the present invention is a semiconductor.
On the layer, at least a linear shape consisting of a metal powder and a binder
From conductive layer, Pd, Zn, Ag, Cu, Cu alloy, Ni
Harden the selected conductive powder and cream solder
And the conductive powder is biased on top of the solder layer.
And the solder layer extends over the entire surface of the conductive layer.
The average thickness of the solder layer is the average thickness of the conductive layer.
It is characterized by being thicker than the thickness.
【０００９】本発明の光起電力素子の集電電極の製造方
法は、半導体層を有する基体上に少なくとも金属粉体と
結着材とからなる導電性ペーストを線状に塗布する工程
と、該導電性ペースト上にＰｄ、Ｚｎ、Ａｇ、Ｃｕ、Ｃ
ｕ合金、Ｎｉから選ばれる導電性粉体を載置し加熱する
工程と、クリーム半田を塗布し、熱溶融させることによ
り半田層を形成する工程とを有し、且つ前記半田層は前
記導電層の表面を全長に亘って被覆しており、該半田層
の平均厚みは該導電層の平均厚みより厚いことを特徴と
する。 Method for manufacturing current collecting electrode of photovoltaic device of the present invention
The method comprises at least metal powder on a substrate having a semiconductor layer.
Step of linearly applying a conductive paste comprising a binder
And Pd, Zn, Ag, Cu, C on the conductive paste.
Place and heat conductive powder selected from u alloy and Ni
Process and applying cream solder and heat melting
Forming a solder layer, and the solder layer is
The surface of the conductive layer is covered over the entire length, and the solder layer
Characterized in that the average thickness of the conductive layer is larger than the average thickness of the conductive layer.
I do.
【００１０】本発明の光起電力素子の集電電極の製造方
法は、半導体層を有する基体上に少なくとも金属粉体と
結着材とからなる導電性ぺーストを線状に塗布し熱硬化
する工程と、クリーム半田を塗布し、該クリーム半田上
にＰｄ、Ｚｎ、Ａｇ、Ｃｕ、Ｃｕ合金、Ｎｉから選ばれ
る導電性粉体を載置し熱溶融させることにより半田層を
形成する工程とを有し、且つ前記半田層は前記導電層の
表面を全長に亘って被覆しており、該半田層の平均厚み
は該導電層の平均厚みより厚いことを特徴とする。 Method for manufacturing current collecting electrode of photovoltaic device of the present invention
The method comprises at least metal powder on a substrate having a semiconductor layer.
Conductive paste consisting of a binder is applied in a line and heat-cured
And applying cream solder on the cream solder
Selected from Pd, Zn, Ag, Cu, Cu alloy and Ni
The conductive layer is placed and thermally melted to form a solder layer.
And forming the solder layer on the conductive layer.
The surface is covered over the entire length, and the average thickness of the solder layer
Is characterized by being thicker than the average thickness of the conductive layer.
【００１１】[0011]
【作用】本発明の導電性粉体は、半田材料等の低融点金
属または合金または混合物（以後、低融点金属という）
を吸着する効果を有しており、低融点金属の電極層を形
成する際、溶融金属の流動性を抑え半導体層（または透
明導電層）上により多くの低融点金属を固定する役割を
果たす。このことにより、一層厚盛りの低融点金属の層
を形成することが可能となる。The conductive powder of the present invention is a low melting point metal such as a solder material, an alloy or a mixture thereof (hereinafter referred to as a low melting point metal).
When the electrode layer of the low melting point metal is formed, it plays a role of suppressing the flowability of the molten metal and fixing more low melting point metal on the semiconductor layer (or the transparent conductive layer). This makes it possible to form a thicker low-melting-point metal layer.
【００１２】また、低融点金属の表面近傍に比較的距離
の接近した導電性粉体の集合体を設けることにより、集
電電極のより一層の低抵抗化が達成される。Further, by providing an aggregate of conductive powders relatively close to each other in the vicinity of the surface of the low melting point metal, the resistance of the current collecting electrode can be further reduced.
【００１３】以上の結果、電極の抵抗を下げることがで
き、光発電素子の効率を上げることができる。更に、厚
盛りによる抵抗減少分を細線化に振り向ければ、集電電
極による遮光ロスをより減少させることができ、更に光
発電素子の発電効率をあげることが可能となる。As a result, the resistance of the electrode can be reduced, and the efficiency of the photovoltaic device can be increased. Furthermore, if the decrease in resistance due to the thick embossing is directed to thinning, the light-shielding loss due to the current collecting electrode can be further reduced, and the power generation efficiency of the photovoltaic element can be further increased.
【００１４】本発明の光起電力素子の構成を図１及び図
２を用いて詳細に説明する。The structure of the photovoltaic element of the present invention will be described in detail with reference to FIGS.
【００１５】図１において、１１は透明導電膜、１２は
半導体層、１３は基板、１４は導電性粉体１５を固定す
る導電層、１７は低融点金属層である。In FIG. 1, 11 is a transparent conductive film, 12 is a semiconductor layer, 13 is a substrate, 14 is a conductive layer for fixing a conductive powder 15, and 17 is a low melting point metal layer.
【００１６】図２において、２１は透明導電膜、２２は
半導体層、２４は導電層、２５は、導電性粉体、２７は
低融点金属層である。In FIG. 2, 21 is a transparent conductive film, 22 is a semiconductor layer, 24 is a conductive layer, 25 is a conductive powder, and 27 is a low melting point metal layer.
【００１７】本発明の低融点金属は、半導体にダメージ
を与えない温度範囲で導電性粉体よりも低い融点のもの
であれば、いずれの金属または合金を用いることができ
るが、導電性粉体と融点の違いが１００℃以上あるもの
が、より厚盛りの電極層が形成でき好ましいものであ
る。低融点金属の具体例としては、例えば半田があげら
れる。半田材料は、例えばＳｎ−Ｐｂ系、Ｓｎ−Ａｇ
系，Ｐｂ基，Ｉｎ基のものがあげられる。また、クリー
ム半田を用いることも可能であり、その場合は半田の盛
り量のコントロールができるメリットがあるため、より
好ましいものである。As the low melting point metal of the present invention, any metal or alloy can be used as long as it has a lower melting point than the conductive powder within a temperature range that does not damage the semiconductor. It is preferable that the difference between the melting point and the melting point is 100 ° C. or more because a thicker electrode layer can be formed. Specific examples of the low melting point metal include, for example, solder. The solder material is, for example, Sn-Pb, Sn-Ag
System, Pb group and In group. It is also possible to use cream solder, and in that case, it is more preferable since there is an advantage that the amount of solder can be controlled.
【００１８】本発明の導電性粉体で、半導体層側に固定
される導電体粉体１４はパラジウム、銀、銅、銅合金、
ニッケルまたは亜鉛からなる粉体またはこれらの金属を
含む粉体が好適に用いられる。これらの金属を用いるこ
とにより、熱溶融時の導電性粉体の吸着作用により、半
田の流動性が抑えられ単位面積当りの半田量が増加し、
集電電極の電気抵抗を一層低下させることができる。The conductive powder of the present invention, which is fixed on the semiconductor layer side, includes palladium, silver, copper, copper alloy,
A powder made of nickel or zinc or a powder containing these metals is preferably used. By using these metals, the fluidity of the solder is suppressed and the amount of solder per unit area increases due to the adsorption action of the conductive powder during heat melting,
The electric resistance of the current collecting electrode can be further reduced.
【００１９】また、低融点金属層の表面または／及び表
面近傍に設けられる導電体粉体２５としては、パラジウ
ム、金、銀、銅、銅合金、亜鉛またはニッケルからなる
粉体またはこれらの金属を含む粉体が好適に用いられ
る。これらの金属は、他の金属に比べ比抵抗及び半田材
料との結着性が優れ、集電電極の抵抗を一層低下させる
ことができる。The conductive powder 25 provided on or near the surface of the low-melting metal layer may be a powder made of palladium, gold, silver, copper, copper alloy, zinc or nickel, or a powder of these metals. The powder containing is preferably used. These metals are superior in specific resistance and binding property to a solder material as compared with other metals, and can further reduce the resistance of the current collecting electrode.
【００２０】本発明の導電性粉体粒子の形状は、球状に
限るものではなく、例えば、りん片状や針状のものも使
用できる、また大きさは形成する集電電極の幅によって
異なるが、通常０．１〜１００μｍ程度のものが用いら
れる。The shape of the conductive powder particles of the present invention is not limited to a spherical shape, and for example, a flaky or needle-like shape can be used. The size varies depending on the width of the current collecting electrode to be formed. Usually, those having a thickness of about 0.1 to 100 μm are used.
【００２１】本発明の導電層１４、２４は、半導体層
（または透明導電膜）及び低融点金属との結合力の大き
なものであればいずれの材料も用いられ、例えば金、
銀、銅、ニッケル、鉄等の金属粒子を、エポキシ樹脂、
フェノール樹脂、ポリエステル樹脂、ポリイミド樹脂等
の有機樹脂等の結着剤に分散した導電性ペーストが好適
に用いられる。また比較的高温処理が許される場合に
は、前記金属材料とガラスフリットを混成した焼成ペー
スト等も用いることができる。As the conductive layers 14 and 24 of the present invention, any material having a large bonding force with the semiconductor layer (or the transparent conductive film) and the low melting point metal can be used.
Metal particles such as silver, copper, nickel, iron, etc., epoxy resin,
A conductive paste dispersed in a binder such as an organic resin such as a phenol resin, a polyester resin, and a polyimide resin is preferably used. If a relatively high temperature treatment is permitted, a baked paste obtained by mixing the above-mentioned metal material and glass frit can be used.
【００２２】[0022]
【実施例】以下に実施例を挙げて本発明を詳細に説明す
るが、本発明がこれら実施例に限定されないことは言う
までもない。EXAMPLES The present invention will be described in detail below with reference to examples, but it goes without saying that the present invention is not limited to these examples.
【００２３】（実施例１）図１に示した構成の光発電素
子の製造方法を図３を用いて説明する。Example 1 A method for manufacturing a photovoltaic device having the structure shown in FIG. 1 will be described with reference to FIG.
【００２４】図３（ａ）は、電極形成面となるアモルフ
ァス太陽電池を示し、ステンレス基板３３上に、アモル
ファスシリコン層３２、透明導電膜３１形成されてい
る。本実施例の透明導電膜は厚さ６４０〜７００ÅのＩ
ＴＯである。FIG. 3A shows an amorphous solar cell serving as an electrode forming surface. An amorphous silicon layer 32 and a transparent conductive film 31 are formed on a stainless steel substrate 33. The transparent conductive film of this embodiment has an I-thickness of 640 to 700 °.
It is TO.
【００２５】ＩＴＯは、金属と比べ比抵抗が１×１０-3
Ωｃｍ程度と高いため、その上に比抵抗値の低い銀のポ
リマーペースト材料を用いて集電電極を形成する。本実
施例で用いた銀のポリマーペーストは、ロールミル装置
を用い、粒径３〜５μｍのりん片状銀粉と１〜２μｍの
球状銀粉をエポキシ樹脂に混成したものである。ここ
で、粒径は、沈降法で求めた値である。ITO has a specific resistance of 1 × 10 −3 as compared with metal.
Since it is as high as about Ωcm, a current collecting electrode is formed thereon using a silver polymer paste material having a low specific resistance. The silver polymer paste used in this example is obtained by mixing a scaly silver powder having a particle size of 3 to 5 μm and a spherical silver powder having a particle size of 1 to 2 μm with an epoxy resin using a roll mill apparatus. Here, the particle size is a value obtained by the sedimentation method.
【００２６】なお、粉体の作製方法は、例えば電気分解
により粉体を陰極に析出させる方法（電解法）、ボール
ミル、クラッシャーなどの粉砕機や搗砕機を用い、金属
を粉砕して作製する方法（粉砕法）、溶けた金属を細い
ノズルを通して流出させ、この溶湯流に圧縮ガスや水流
ジェットに当てて噴霧状に吹き飛ばすと同時に冷却させ
て作製する方法（アトマイズ法）等があげられる。本実
施例のりん片状及び球状銀粉はそれぞれアトマイズ法で
作製したものである。The method of producing the powder is, for example, a method of depositing the powder on the cathode by electrolysis (electrolysis method), a method of pulverizing metal using a pulverizer or a pulverizer such as a ball mill or a crusher. (Pulverization method), a method in which a molten metal is caused to flow out through a thin nozzle, and the molten metal stream is blown out in a spray form by applying a compressed gas or a water jet to the molten metal stream, and simultaneously cooled (atomizing method). The scaly and spherical silver powders of the present example were each produced by an atomizing method.
【００２７】図３（ｂ）に示すように、透明導電層３１
上に銀のポリマーペースト３４のパターンを、ステンレ
ス紗４００メッシュ、エマルジョン厚１０μｍの刷板を
使用してスクリーン印刷で形成した。この条件で、線幅
１００μｍ、厚さ３０μｍ程度のパターンが形成でき
た。なお、この時点で銀のポリマーペーストは導電性は
なく、また粘性を有している。熱硬化後では厚さは２０
μｍ程度となる。As shown in FIG. 3B, the transparent conductive layer 31
A pattern of the silver polymer paste 34 was formed on the upper surface by screen printing using a printing plate having a stainless steel screen of 400 mesh and an emulsion thickness of 10 μm. Under these conditions, a pattern having a line width of about 100 μm and a thickness of about 30 μm was formed. At this point, the silver polymer paste is not conductive and has viscosity. After heat curing, the thickness is 20
It is about μm.
【００２８】次に、アトマイズ法により作製した粒径３
０μｍ〜７０μｍのＮｉ粒子３５を、圧縮空気による粉
体スプレー法により、ポリマーペースト上に吹きつけて
トッピングした。このときＩＴＯ表面は十分に乾燥して
おいた。図３（ｃ）にその様子を示す。吹きつけられた
Ｎｉ粒子３５はポリマーペースト３４上だけでなく、透
明導電膜３１上にも付着した。本実施例では、圧縮空気
による粉体スプレー法でＮｉ粒子をペースト上に吹き付
けたが、例えばマイクロディスペンサーで塗布してもよ
いことはいうまでもない。Next, a particle size of 3 prepared by the atomizing method
The Ni particles 35 of 0 μm to 70 μm were sprayed on the polymer paste by a powder spray method using compressed air and topped. At this time, the ITO surface was sufficiently dried. FIG. 3C shows this state. The sprayed Ni particles 35 adhered not only on the polymer paste 34 but also on the transparent conductive film 31. In this embodiment, Ni particles are sprayed on the paste by the powder spray method using compressed air, but it goes without saying that the paste may be applied by a micro dispenser, for example.
【００２９】そして空気流を吹きつけ、ポリマーペース
ト上以外のＮｉ粒子を吹きとばして除去した。その後、
赤外加熱乾燥炉を用い１６０℃で乾燥して、ポリマーペ
ーストを硬化した。加熱によりポリマーペーストは収縮
しながらＮｉ粒子を巻き込み硬化した。図３（ｄ）にそ
の様子を示す。ペーストの表面は比較的粒径の大きなＮ
ｉ粒子が銀の微粒子にまきこまれた形で硬化し、このＮ
ｉ粒子が半田層を形成する際の土台となる。Then, a stream of air was blown to blow and remove Ni particles other than those on the polymer paste. afterwards,
The polymer paste was dried at 160 ° C. using an infrared heating drying oven to cure the polymer paste. While heating, the polymer paste shrinked and entrained Ni particles while shrinking. FIG. 3D shows this state. The surface of the paste has a relatively large particle size of N
The i-particles are cured in the form of being engulfed by silver fine particles, and this N
The i-particles serve as a basis for forming the solder layer.
【００３０】次に電極形成面全体にフラックス３６をス
プレー法により塗布した（図３（ｅ））。フラックスの
塗布方法としては、このスプレー法の他、刷毛による塗
布、フラックス溶液への浸漬、噴流法、滴下法等を用い
ることができる。Next, a flux 36 was applied to the entire surface on which the electrodes were formed by a spray method (FIG. 3E). As a method of applying the flux, in addition to the spray method, application by a brush, immersion in a flux solution, a jet method, a dropping method, and the like can be used.
【００３１】更にフラックスを塗布された電極形成面上
に、噴流半田槽を用いて半田層を形成した。ここで、一
方向に流れるＳｎ６０％Ｐｂ３８％Ａｇ２％の溶融半田
流をつくり、この半田流を電極形成面と接触させた。光
発電素子自体もこの半田流との接触前後で加熱されてお
り、半田が固化して電極以外の部分に付着しないように
した。半田流を通る時間は、２〜３０秒程度とした。フ
ラックスを塗布することにより、ポリマーペースト及び
金属粒子と半田の濡れを促進させる他、ポリマーペース
トのない電極形成面への半田の付着をより一層防止する
ことができる。Further, a solder layer was formed on the surface of the electrode on which the flux was applied, using a jet solder bath. Here, a molten solder flow of Sn60% Pb38% Ag2% flowing in one direction was created, and this solder flow was brought into contact with the electrode formation surface. The photovoltaic element itself is also heated before and after contact with the solder flow, so that the solder is solidified and does not adhere to portions other than the electrodes. The time for passing through the solder flow was about 2 to 30 seconds. The application of the flux not only promotes the wetting of the solder with the polymer paste and the metal particles, but also further prevents the solder from adhering to the electrode forming surface without the polymer paste.
【００３２】図３（ｆ）は半田層形成後の電極形成面で
あり、この状態ではポリマーペースト３４上に半田層３
７が形成され、電極形成面には多量のフラックス３６が
残存する。残存するフラックスを温水によるシャワー水
洗で洗浄除去した。洗浄終了後、乾燥して集電電極の作
製を終了した（図３（ｇ））。FIG. 3F shows an electrode forming surface after the formation of the solder layer. In this state, the solder layer 3 is formed on the polymer paste 34.
7 is formed, and a large amount of flux 36 remains on the electrode forming surface. The remaining flux was washed and removed by shower water washing with warm water. After completion of the washing, the substrate was dried to complete the production of the current collecting electrode (FIG. 3 (g)).
【００３３】フラックスには前記空気流でとりきれなか
った残存金属粒子も含まれており、またフラックスは酸
性もしくはアルカリ性でありため、放置しておくと透明
導電膜を浸食したり、入射光を遮光することから洗浄を
行う必要がある。The flux contains residual metal particles that could not be removed by the air flow, and the flux is acidic or alkaline. Cleaning is required.
【００３４】以上のようにして、１００μｍ細線であり
ながら中心高さ５０μｍ、平均厚さ４０μｍの低抵抗な
集電電極が精度良く作製できることが確認された。As described above, it was confirmed that a low-resistance current-collecting electrode having a center height of 50 μm and an average thickness of 40 μm could be produced with high accuracy even though it was a 100 μm thin wire.
【００３５】（実施例２）本実施例では、導電性粉体と
して粒径３０〜１００μｍの銀（純度９９．９％）粒子
を用いた他は、実施例１と同様にして集電電極を作製し
た。Example 2 In this example, a current collecting electrode was used in the same manner as in Example 1 except that silver (purity: 99.9%) particles having a particle size of 30 to 100 μm were used as the conductive powder. Produced.
【００３６】本実施例においても、実施例１と同様、１
００μｍ細線でありながら平均厚さ４０μｍの低抵抗な
集電電極が精度良く作製できることが確認された。In this embodiment, as in Embodiment 1, 1
It was confirmed that a low-resistance current collecting electrode having an average thickness of 40 μm, which is a thin wire having a thickness of 00 μm, can be accurately produced.
【００３７】（実施例３）本実施例では、導電性粉体と
して粒径３０〜６０μｍの銅粒子を用いた他は、実施例
１と同様にして集電電極を作製した。Example 3 In this example, a current-collecting electrode was produced in the same manner as in Example 1 except that copper particles having a particle size of 30 to 60 μm were used as the conductive powder.
【００３８】本実施例においても、実施例１と同様、１
００μｍ細線でありながら平均厚さ４０μｍの低抵抗な
集電電極が精度良く作製できることが確認された。In this embodiment, as in Embodiment 1, 1
It was confirmed that a low-resistance current collecting electrode having an average thickness of 40 μm, which is a thin wire having a thickness of 00 μm, can be accurately produced.
【００３９】（実施例４）図１に示す構成の光発電素子
の製造方法を図４を用いて説明する。Example 4 A method for manufacturing a photovoltaic device having the structure shown in FIG. 1 will be described with reference to FIG.
【００４０】図４は、クリーム半田ペーストを用いた電
極形成工程を示している。図４（ａ）において、４４は
フェノール系樹脂に粒径１０〜２０μｍの銅粒子を単分
散させた銅ペーストを用いて形成したパターンである。
４１は透明導電膜ＩＴＯ、４２は光発電層であるアモル
ファスシリコン層である。ここで、電極形成面はＩＴＯ
膜４１表面である。FIG. 4 shows an electrode forming process using a cream solder paste. In FIG. 4A, reference numeral 44 denotes a pattern formed using a copper paste in which copper particles having a particle size of 10 to 20 μm are monodispersed in a phenolic resin.
41 is a transparent conductive film ITO and 42 is an amorphous silicon layer which is a photovoltaic layer. Here, the electrode formation surface is ITO
This is the surface of the film 41.
【００４１】よく洗浄乾燥された表面に、まずスクリー
ン印刷機により線幅約１００μｍの線を銅ペーストで形
成した。First, a line having a line width of about 100 μm was formed with a copper paste on a well-washed and dried surface by a screen printer.
【００４２】次に、図４（ｂ）に示すように、電極形成
面に粒径３０〜７０μｍの亜鉛粒子４５を吹きつけた。
亜鉛粒子は電極形成面全体に散乱した状態で吹き付けら
れた。Next, as shown in FIG. 4B, zinc particles 45 having a particle size of 30 to 70 μm were sprayed on the surface on which the electrodes were formed.
The zinc particles were sprayed in a scattered state over the entire surface on which the electrode was formed.
【００４３】この散乱した電極形成面に対して水平に空
気流を流し、ポリマーペースト上以外の亜鉛粒子を除去
し、ポリマーペースト上に亜鉛粒子に残した。図４
（ｃ）はこの状態を示している。An air stream was caused to flow horizontally to the scattered electrode forming surface to remove zinc particles other than on the polymer paste, leaving the zinc particles on the polymer paste. FIG.
(C) shows this state.
【００４４】続いて、熱乾燥炉で加熱した。銅ペースト
は収縮し、亜鉛粒子をまきこんだ形で硬化した。ここで
は硬化条件としては１６０℃、３０分とした。硬化後の
状態を図４（ｄ）に示す。Subsequently, it was heated in a heat drying oven. The copper paste shrinks and hardens in a manner that envelops the zinc particles. Here, the curing conditions were 160 ° C. and 30 minutes. The state after curing is shown in FIG.
【００４５】こうして亜鉛粒子をちりばめた集電電極上
に、スクリーン印刷によりクリーム半田ペースト４７’
を付着させた（図４（ｅ））。The cream solder paste 47 ′ is screen-printed on the current collecting electrode on which the zinc particles are studded.
(FIG. 4 (e)).
【００４６】クリーム半田ペースト４７’にはフラック
ス４６も含まれており、また、電極形成面であるＩＴＯ
は半田との濡れ性が悪いためこのまま赤外加熱炉等で２
２０℃に加熱すると、図４（ｆ）に示すように、半田は
半田濡れ性を良い導電ペースト側に集まり、更に導電性
ペースト上にある亜鉛粒子は半田材料を吸着し、導電ペ
ースト上に盛りあがった状態となった。The solder paste 47 ′ also contains the flux 46.
Is poor in wettability with solder, so that
When heated to 20 ° C., as shown in FIG. 4F, the solder collects on the conductive paste side having good solder wettability, and the zinc particles on the conductive paste adsorb the solder material and swell on the conductive paste. It was in a state of being.
【００４７】最後に、にじみでたフラックス４６は温水
洗浄等により洗浄され、乾燥されて、工程は終了した
（図４（ｇ））。Finally, the oozed flux 46 was washed by hot water washing and the like, and dried to complete the process (FIG. 4 (g)).
【００４８】以上のようにして、１００μｍ幅、平均厚
さ４０μｍの集電電極が精度良く作製できることが確認
された。また、クリーム半田ペーストを用いることによ
り、半田層の厚さの均一性は一層増加した。As described above, it was confirmed that a current collecting electrode having a width of 100 μm and an average thickness of 40 μm could be produced with high accuracy. Further, by using the cream solder paste, the uniformity of the thickness of the solder layer was further increased.
【００４９】（実施例５）本実施例では、導電性粉体と
して、粒径 ３０〜７０μｍの銀粒子を用いた他は、実
施例４と同様にして集電電極を形成した。Example 5 In this example, a current collecting electrode was formed in the same manner as in Example 4, except that silver particles having a particle size of 30 to 70 μm were used as the conductive powder.
【００５０】本実施例においても、実施例４と同様、１
００μｍ幅、平均厚さ４０μｍの集電電極が精度良く作
製できることが確認された。In this embodiment, as in Embodiment 4, 1
It was confirmed that a current collecting electrode having a width of 00 μm and an average thickness of 40 μm could be produced with high accuracy.
【００５１】（実施例６）本実施例では、導電性粉体と
して、粒径３０〜７０μｍの銅粒子を用い、また導電性
ペーストとして、粒径３〜５μｍのりん片状銀粉と１〜
２μｍの球状銀粉をエポキシ樹脂に混成したものを用い
た以外は、実施例４と同様にして集電電極を形成した。Example 6 In this example, copper particles having a particle size of 30 to 70 μm were used as the conductive powder, and flaky silver powder having a particle size of 3 to 5 μm was used as the conductive paste.
A current collecting electrode was formed in the same manner as in Example 4, except that a mixture of 2 μm spherical silver powder and an epoxy resin was used.
【００５２】本実施例においても、実施例４と同様、１
００μｍ幅、平均厚さ４０μｍの集電電極が精度良く作
製できることが確認された。In this embodiment, as in Embodiment 4, 1
It was confirmed that a current collecting electrode having a width of 00 μm and an average thickness of 40 μm could be produced with high accuracy.
【００５３】（実施例７）図２に示す構成の光発電素子
の製造方法を図５を用いて説明する。(Embodiment 7) A method for manufacturing the photovoltaic element having the structure shown in FIG. 2 will be described with reference to FIG.
【００５４】図５（ａ）は、スクリーン印刷工程であ
り、光発電素子の電極形成面に導電ペーストを付着す
る。本実施例では導電ペーストとして、粒径３〜５μｍ
の銀粒子をエポキシ系樹脂に分散したものを用い、スク
リーン版には、ステンレス紗３００メッシュ、開口率６
０％、エマルジョン厚１５μｍのものを用いた。これに
より、線幅１００μｍ、厚さ２０〜３０μｍの導電ペー
ストのパターンが形成された。FIG. 5A shows a screen printing step in which a conductive paste is attached to the electrode forming surface of the photovoltaic element. In this embodiment, the conductive paste has a particle size of 3 to 5 μm.
Silver particles dispersed in an epoxy resin were used. The screen plate had a stainless steel screen of 300 mesh and an aperture ratio of 6
0% and an emulsion thickness of 15 μm were used. As a result, a conductive paste pattern having a line width of 100 μm and a thickness of 20 to 30 μm was formed.
【００５５】図５（ｂ）は、導電ペーストの硬化工程で
あり、強制循環式の熱乾燥炉を用い、導電性ペーストを
１６０℃で３０分加熱した。加熱処理により、導電ペー
ストは収縮して、厚さは１５〜２０μｍとなった。FIG. 5B shows a step of curing the conductive paste. The conductive paste was heated at 160 ° C. for 30 minutes using a forced circulation type heat drying furnace. By the heat treatment, the conductive paste shrunk to have a thickness of 15 to 20 μm.
【００５６】図５（ｃ）は、クリーム半田ペーストの印
刷工程である。本実施例では、Ｓｎ６３％Ｐｂ３５％Ａ
ｇ２％の共晶合金の半田微粒子からなる半田ペーストを
用い、メタル版による印刷を行った。メタル版は、厚さ
１００μｍの金属版に印刷パターンをエッチングしたも
のであり、粒径１〜５０μｍの半田微粒子を含むクリー
ム半田ペースト用いて、硬化した導電ペーストを覆うよ
うに幅１５０〜２００μｍのクリーム半田層を形成し
た。FIG. 5C shows a printing process of the cream solder paste. In this embodiment, Sn 63% Pb 35% A
Using a solder paste composed of g2% eutectic alloy solder fine particles, printing was performed using a metal plate. The metal plate is obtained by etching a printing pattern on a metal plate having a thickness of 100 μm, and using a cream solder paste containing solder fine particles having a particle size of 1 to 50 μm, a cream having a width of 150 to 200 μm so as to cover the cured conductive paste. A solder layer was formed.
【００５７】図５（ｄ）は、導電性粒子の吹き付け工程
であり、乾燥した空気流により粒径０．１〜１００μｍ
の金粒子をクリーム半田層上に分散付着させた。クリー
ム半田ペースト中には、粘性を生み出すためにフラック
ス材料やチキソトロピック材料等が添加されており、金
粒子は図５（ｄ）に示すように、クリーム半田上に付着
する。FIG. 5D shows a step of spraying the conductive particles.
Was dispersed and attached on the cream solder layer. A flux material, a thixotropic material, or the like is added to the cream solder paste to generate viscosity, and the gold particles adhere to the cream solder as shown in FIG.
【００５８】図５（ｅ）は、導電性粉体粒子の吹き付け
工程において、クリーム半田層以外に残った余剰の金粒
子を除去する工程であり、吹き付け工程で用いた空気流
を用い余剰粒子を吹き飛ばす。余剰粒子を完全に取り除
くためには、前記印刷工程で例えば溶剤等の不純物が電
極形成面に付着しないように注意する必要がある。また
導電性粉体粒子の吹き付けする際、電極形成面及び吹き
付け雰囲気を十分に乾燥することが重要である。FIG. 5 (e) shows a step of removing excess gold particles remaining in the conductive powder particle spraying step other than the cream solder layer. The surplus particles are removed by using the air flow used in the spraying step. Blow it away. In order to completely remove the surplus particles, care must be taken so that impurities such as a solvent do not adhere to the electrode forming surface in the printing step. When spraying the conductive powder particles, it is important to sufficiently dry the electrode forming surface and the spraying atmosphere.
【００５９】図５（ｆ）は、クリーム半田ペーストの加
熱溶融工程である。赤外加熱炉を用いて半田ペーストを
加熱した。半田ペーストは溶融し、半田濡れ性の高い導
電ペースト上に凝集した。一方金粒子は初め表面張力に
よりはじかれ、中央付近に集まり、続いて半田となじ
み、その後半田の固化にともない、半田の表面層に固定
された。半田の周辺には半田ペーストに含まれていたフ
ラックス材料が残った。FIG. 5F shows a step of heating and melting the cream solder paste. The solder paste was heated using an infrared heating furnace. The solder paste melted and aggregated on the conductive paste having high solder wettability. On the other hand, the gold particles were first repelled by the surface tension, gathered near the center, subsequently adapted to the solder, and then fixed to the surface layer of the solder as the solder solidified. The flux material contained in the solder paste remained around the solder.
【００６０】図５（ｇ）は、フラックスの洗浄除去工程
であり、電極表面に残されたフラックスはここで溶剤等
によるシャワー洗浄され、乾燥して集電電極の形成を終
えた。FIG. 5 (g) shows a step of cleaning and removing the flux. The flux remaining on the electrode surface was subjected to shower cleaning with a solvent or the like and dried to complete the formation of the current collecting electrode.
【００６１】以上により、線幅１００μｍ、平均厚さ４
０μｍで、半田層の表面層に金粒子が固定された集電電
極が形成された。As described above, the line width is 100 μm and the average thickness is 4
At 0 μm, a current collecting electrode having gold particles fixed on the surface layer of the solder layer was formed.
【００６２】（実施例８）本実施例では、導電性粉体と
して、金粒子の代わりに銀粒子を用いた以外は実施例７
と同様にして集電電極を作製した。(Embodiment 8) In this embodiment, except that silver particles were used in place of the gold particles as the conductive powder, the embodiment 7
A current collecting electrode was produced in the same manner as described above.
【００６３】実施例７と同様に、線幅１００μｍ、平均
厚さ４０μｍで、半田層の表面層に銀粒子が固定された
集電電極が形成された。As in Example 7, a current collecting electrode having a line width of 100 μm and an average thickness of 40 μm and having silver particles fixed on the surface layer of the solder layer was formed.
【００６４】（実施例９）本実施例では、導電性粉体と
して、金粒子の代わりに銅粒子を用いた以外は実施例７
と同様にして集電電極を作製した。(Embodiment 9) In this embodiment, except that copper particles were used instead of gold particles as the conductive powder, the embodiment 7
A current collecting electrode was produced in the same manner as described above.
【００６５】実施例７と同様に、線幅１００μｍ、平均
厚さ４０μｍで、半田層の表面層に銅粒子が固定された
集電電極が形成された。As in the case of Example 7, a current collecting electrode having a line width of 100 μm and an average thickness of 40 μm and having copper particles fixed on the surface layer of the solder layer was formed.
【００６６】（実施例１０）本実施例では、導電性粉体
として、金粒子の代わりにニッケル粒子を用いた以外は
実施例７と同様にして集電電極を作製した。Example 10 In this example, a current-collecting electrode was produced in the same manner as in Example 7, except that nickel particles were used instead of gold particles as the conductive powder.
【００６７】実施例７と同様に、線幅１００μｍ、平均
厚さ４０μｍで、半田層の表面層にニッケル粒子が固定
された集電電極が形成された。As in the case of Example 7, a current collecting electrode having a line width of 100 μm and an average thickness of 40 μm and having nickel particles fixed on the surface layer of the solder layer was formed.
【００６８】（実施例１１）図２に示す構成の光発電素
子の製造方法を図６を用いて説明する。(Embodiment 11) A method for manufacturing a photovoltaic element having the structure shown in FIG. 2 will be described with reference to FIG.
【００６９】図６（ａ）は、スクリーン印刷工程であ
り、光発電素子の電極形成面に導電ペーストを付着す
る。本実施例では導電ペーストとして、粒径５〜８μｍ
の銅粒子をフェノール系樹脂に分散したものを用い、ス
クリーン版には、ステンレス紗３００メッシュ、開口率
６０％のものを用いた。これにより、線幅１００μｍ、
厚さ３０μｍ程度の導電ペーストのパターンを形成し
た。FIG. 6A shows a screen printing process, in which a conductive paste is attached to the electrode forming surface of the photovoltaic element. In this embodiment, the conductive paste has a particle size of 5 to 8 μm.
The copper plate was prepared by dispersing copper particles in a phenolic resin, and the screen plate was made of stainless steel 300 mesh and an aperture ratio of 60%. Thereby, the line width is 100 μm,
A conductive paste pattern having a thickness of about 30 μm was formed.
【００７０】次に、熱乾燥炉を用い、導電性ペーストを
窒素雰囲気で、１６０℃で３０分加熱硬化処理を行った
（図６（ｂ））。加熱硬化処理により、導電ペーストは
収縮して、厚さは２０μｍ程度となった。硬化処理方法
としては、この他例えばフロリナート沸騰気中で硬化さ
せるベーパフェーズ炉を用いてもよい。Next, the conductive paste was heated and cured at 160 ° C. for 30 minutes in a nitrogen atmosphere using a heat drying furnace (FIG. 6B). The conductive paste shrunk by the heat curing treatment, and the thickness became about 20 μm. As a curing treatment method, for example, a vapor phase furnace for curing in boiling Fluorinert may be used.
【００７１】図６（ｃ）は、クリーム半田ペーストの印
刷工程である。本実施例では、粒子径２０〜３０μｍの
Ｓｎ６０％Ｐｂ４０％の共晶合金の半田微粒子からなる
半田ペーストを用い、スクリーン印刷を行った。スクリ
ーン版は、ステンレス紗２００メッシュのものを用い、
硬化した導電ペーストを覆うように幅１５０μｍのクリ
ーム半田層を形成した。FIG. 6C shows a printing process of the cream solder paste. In this example, screen printing was performed using a solder paste composed of solder particles of a eutectic alloy of Sn60% Pb40% with a particle diameter of 20 to 30 μm. The screen plate is made of stainless steel 200 mesh,
A 150 μm-wide cream solder layer was formed so as to cover the cured conductive paste.
【００７２】図６（ｄ）は、導電性粒子の吹き付け工程
であり、粒径０．１〜１００μｍの金粒子をフラックス
に単分散したものを、ディスペンサーによりクリーム半
田ペースト上に吹き付けた。FIG. 6 (d) shows a step of spraying conductive particles, in which gold particles having a particle size of 0.1 to 100 μm monodispersed in a flux were sprayed onto a cream solder paste by a dispenser.
【００７３】図６（ｅ）は、クリーム半田ペーストの加
熱溶融工程である。赤外加熱リフローを用いてクリーム
半田ペーストを加熱した。クリーム半田ペーストは溶融
し、フラックス中に混合した金粒子を吸着し、そして固
化した。この際余剰のフラックスは余剰となった金粒子
を含んで電極周辺にあふれた。FIG. 6E shows a step of heating and melting the cream solder paste. The cream solder paste was heated using infrared heating reflow. The cream solder paste melted, adsorbed the gold particles mixed in the flux, and solidified. At this time, the excess flux overflowed around the electrodes, including the excess gold particles.
【００７４】図６（ｆ）は、フラックスの洗浄除去工程
であり、電極表面に残されたフラックスはここで溶剤等
によるシャワー洗浄され、乾燥して集電電極の形成を終
えた。FIG. 6F shows a step of cleaning and removing the flux. The flux remaining on the electrode surface was washed with a solvent or the like in a shower and dried to complete the formation of the current collecting electrode.
【００７５】以上により、線幅１００μｍ、平均厚さ４
０μｍで、半田層の表面層に金粒子が固定された集電電
極が形成された。As described above, the line width is 100 μm and the average thickness is 4
At 0 μm, a current collecting electrode having gold particles fixed on the surface layer of the solder layer was formed.
【００７６】（実施例１２）本実施例では、導電性粉体
として、金粒子の代わりに銀粒子を用いた以外は実施例
１１と同様にして集電電極を作製した。Example 12 In this example, a current collecting electrode was produced in the same manner as in Example 11, except that silver particles were used instead of gold particles as the conductive powder.
【００７７】実施例１１と同様に、線幅１００μｍ、平
均厚さ４０μｍで、半田層の表面層に銀粒子が固定され
た集電電極が形成された。As in the case of Example 11, a current collecting electrode having a line width of 100 μm and an average thickness of 40 μm and having silver particles fixed on the surface layer of the solder layer was formed.
【００７８】（実施例１３）本実施例では、導電性粉体
として、金粒子の代わりに銅粒子を用いた以外は実施例
１１と同様にして集電電極を作製した。Example 13 In this example, a current collecting electrode was produced in the same manner as in Example 11, except that copper particles were used instead of gold particles as the conductive powder.
【００７９】実施例１１と同様に、線幅１００μｍ、平
均厚さ４０μｍで、半田層の表面層に銅粒子が固定され
た集電電極が形成された。As in the case of Example 11, a current collecting electrode having a line width of 100 μm and an average thickness of 40 μm and having copper particles fixed on the surface layer of the solder layer was formed.
【００８０】（実施例１４）本実施例では、導電性粉体
として、金粒子の代わりに亜鉛粒子を用いた以外は実施
例１１と同様にして集電電極を作製した。Example 14 In this example, a current-collecting electrode was produced in the same manner as in Example 11, except that zinc particles were used instead of gold particles as the conductive powder.
【００８１】実施例１１と同様に、線幅１００μｍ、平
均厚さ４０μｍで、半田層の表面層に亜鉛粒子が固定さ
れた集電電極が形成された。As in Example 11, a current collecting electrode having a line width of 100 μm and an average thickness of 40 μm and having zinc particles fixed on the surface layer of the solder layer was formed.
【００８２】[0082]
【発明の効果】本発明によれば、細線でありながら厚盛
りの集電電極を形成することが可能となり、その結果、
集電電極の抵抗を大幅に下げることができ、光電変換効
率の高い光発電素子を安価に提供することが可能とな
る。 According to the present invention, it is possible to form a thick current collector electrode while being a thin wire.
The resistance of the current collecting electrode can be significantly reduced, and a photovoltaic element having high photoelectric conversion efficiency can be provided at low cost.
【００８３】本発明によれば、低融点金属層の最上部に
比較的距離が接近した金属粒子の集合体を形成でき、そ
の結果、集電電極の抵抗をより一層下げることができ、
光電変換効率の高い光発電素子を安価に提供することが
可能となる。更に長期間にわたり抵抗が安定するため出
力の経時変化の少ない、高い変換効率を有す光発電素子
を提供することが可能となる。 According to the present invention, an aggregate of metal particles having a relatively short distance can be formed at the uppermost portion of the low melting point metal layer, and as a result, the resistance of the current collecting electrode can be further reduced.
A photovoltaic element having high photoelectric conversion efficiency can be provided at low cost. Furthermore, since the resistance is stable for a long period of time, it is possible to provide a photovoltaic element having a high conversion efficiency with little change in output over time.
【図１】本発明の光発電素子を示す概念図。FIG. 1 is a conceptual diagram showing a photovoltaic device of the present invention.
【図２】本発明の光発電素子を示す概念図。FIG. 2 is a conceptual diagram showing a photovoltaic element of the present invention.
【図３】本発明の実施例１の光発電素子の製造プロセス
を説明する概念図。FIG. 3 is a conceptual diagram illustrating a manufacturing process of the photovoltaic device according to the first embodiment of the present invention.
【図４】本発明の実施例４の光発電素子の製造プロセス
を説明する概念図。FIG. 4 is a conceptual diagram illustrating a manufacturing process of a photovoltaic device according to a fourth embodiment of the present invention.
【図５】本発明の実施例７の光発電素子の製造プロセス
を説明する概念図。FIG. 5 is a conceptual diagram illustrating a manufacturing process of a photovoltaic device according to a seventh embodiment of the present invention.
【図６】本発明の実施例１１の光発電素子の製造プロセ
スを説明する概念図。FIG. 6 is a conceptual diagram illustrating a manufacturing process of a photovoltaic device according to Embodiment 11 of the present invention.
【図７】従来の光発電素子の一例を示す概念図。FIG. 7 is a conceptual diagram showing an example of a conventional photovoltaic element.
【図８】従来の光発電素子の他の例を示す概念図。FIG. 8 is a conceptual diagram showing another example of a conventional photovoltaic element.
１１、２１、３１、４１、５１、６１、７１、８１ 透
明導電膜、 １２、２２、３２、４２、５２、６２ アモルファスシ
リコン層、 １３、３３ ステンレス基板、 １４、２４、３４、４４、５４、６４、７４、８４ ポ
リマーペースト、 １５、２５、３５、４５、５５、６５ 導電性粒子、 １７、２７、３７、４７、５７、６７、８７ 半田、 ３６、４６、５６、６６ フラックス、 ４７’、５７’、６７’ クリーム半田。11, 21, 31, 41, 51, 61, 71, 81 transparent conductive film, 12, 22, 32, 42, 52, 62 amorphous silicon layer, 13, 33 stainless steel substrate, 14, 24, 34, 44, 54, 64, 74, 84 polymer paste, 15, 25, 35, 45, 55, 65 conductive particles, 17, 27, 37, 47, 57, 67, 87 solder, 36, 46, 56, 66 flux, 47 ′, 57 ', 67' cream solder.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平３−283472（ＪＰ，Ａ) 特開 平２−7476（ＪＰ，Ａ) 特開 平３−94078（ＪＰ，Ａ) 特開 平１−319992（ＪＰ，Ａ) 特開 平３−58427（ＪＰ，Ａ) 特開 平４−22595（ＪＰ，Ａ) 実開 昭61−186255（ＪＰ，Ｕ) ────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-3-283472 (JP, A) JP-A-2-7476 (JP, A) JP-A-3-94078 (JP, A) JP-A-1- 319992 (JP, A) JP-A-3-58427 (JP, A) JP-A-4-22595 (JP, A) JP-A-61-186255 (JP, U)
Claims (5)
着材とからなる線状の導電層、Ｐｄ、Ｚｎ、Ａｇ、Ｃ
ｕ、Ｃｕ合金、Ｎｉから選ばれる導電性粉体、及びクリ
ーム半田を硬化させてなる半田層を有し、該導電性粉体
は前記半田層の下部に偏在し、且つ前記半田層は前記導
電層の表面を全長に亘って被覆しており、該半田層の平
均厚みは該導電層の平均厚みより厚いことを特徴とする
光起電力素子の集電電極。1. A linear conductive layer comprising at least a metal powder and a binder, Pd, Zn, Ag, C on a semiconductor layer.
u, a Cu alloy, a conductive powder selected from Ni, and a solder layer obtained by curing cream solder, the conductive powder is unevenly distributed below the solder layer, and the solder layer is A current collecting electrode for a photovoltaic element, wherein the surface of the layer is covered over the entire length, and the average thickness of the solder layer is larger than the average thickness of the conductive layer.
着材とからなる線状の導電層、Ｐｄ、Ｚｎ、Ａｇ、Ｃ
ｕ、Ｃｕ合金、Ｎｉから選ばれる導電性粉体、及びクリ
ーム半田を硬化させてなる半田層を有し、該導電性粉体
は前記半田層の上部に偏在し、且つ前記半田層は前記導
電層の表面を全長に亘って被覆しており、該半田層の平
均厚みは該導電層の平均厚みより厚いことを特徴とする
光起電力素子の集電電極。2. A linear conductive layer comprising at least a metal powder and a binder, Pd, Zn, Ag, C on a semiconductor layer.
u, a Cu alloy, a conductive powder selected from Ni, and a solder layer obtained by curing cream solder, the conductive powder is unevenly distributed on the upper portion of the solder layer, and the solder layer is A current collecting electrode for a photovoltaic element, wherein the surface of the layer is covered over the entire length, and the average thickness of the solder layer is larger than the average thickness of the conductive layer.
属粉体と結着材とからなる導電性ペーストを線状に塗布
する工程と、該導電性ペースト上にＰｄ、Ｚｎ、Ａｇ、
Ｃｕ、Ｃｕ合金、Ｎｉから選ばれる導電性粉体を載置し
加熱する工程と、クリーム半田を塗布し、熱溶融させる
ことにより半田層を形成する工程とを有し、且つ前記半
田層は前記導電層の表面を全長に亘って被覆しており、
該半田層の平均厚みは該導電層の平均厚みより厚いこと
を特徴とする光起電力素子の集電電極の製造方法。3. A step of linearly applying a conductive paste comprising at least a metal powder and a binder on a substrate having a semiconductor layer, and forming Pd, Zn, Ag, and Pb on the conductive paste.
A step of placing and heating a conductive powder selected from Cu, Cu alloy, and Ni; and applying a cream solder and forming a solder layer by heat melting, and the solder layer is Covering the entire surface of the conductive layer,
The method for manufacturing a current collecting electrode of a photovoltaic element, wherein the average thickness of the solder layer is larger than the average thickness of the conductive layer.
属粉体と結着材とからなる導電性ぺーストを線状に塗布
し熱硬化する工程と、クリーム半田を塗布し、該クリー
ム半田上にＰｄ、Ｚｎ、Ａｇ、Ｃｕ、Ｃｕ合金、Ｎｉか
ら選ばれる導電性粉体を載置し熱溶融させることにより
半田層を形成する工程とを有し、且つ前記半田層は前記
導電層の表面を全長に亘って被覆しており、該半田層の
平均厚みは該導電層の平均厚みより厚いことを特徴とす
る光起電力素子の集電電極の製造方法。4. A step of linearly applying a conductive paste composed of at least a metal powder and a binder on a base having a semiconductor layer and thermally curing the same, applying cream solder, and applying the cream solder on the base. Placing a conductive powder selected from Pd, Zn, Ag, Cu, Cu alloy, and Ni, and thermally melting the solder powder to form a solder layer, and the solder layer covers the surface of the conductive layer. A method for manufacturing a current collecting electrode of a photovoltaic element, wherein the current collecting electrode is covered over the entire length, and the average thickness of the solder layer is larger than the average thickness of the conductive layer.
よりも幅広に塗布することを特徴とする請求項３又は４
記載の光起電力素子の集電電極の製造方法。5. The solder paste according to claim 3, wherein the cream solder is applied wider than the conductive paste.
A method for producing a current collecting electrode of the photovoltaic element according to the above.
Priority Applications (11)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4273972A JP2716630B2 (en) | 1992-10-13 | 1992-10-13 | Current collecting electrode of photovoltaic element and method of manufacturing the same |
| US08/089,585 US5428249A (en) | 1992-07-15 | 1993-07-12 | Photovoltaic device with improved collector electrode |
| DE69332933T DE69332933T2 (en) | 1992-07-15 | 1993-07-14 | Photovoltaic device and process for its manufacture |
| AU41959/93A AU671639B2 (en) | 1992-07-15 | 1993-07-14 | Photovoltaic device and method of manufacturing the same |
| AT93111278T ATE207244T1 (en) | 1992-07-15 | 1993-07-14 | PHOTOVOLTAIC DEVICE AND METHOD OF PRODUCTION THEREOF |
| DE69330925T DE69330925T2 (en) | 1992-07-15 | 1993-07-14 | Photovoltaic device and its manufacturing process |
| EP97103454A EP0778624B1 (en) | 1992-07-15 | 1993-07-14 | Photovoltaic device and method of manufacturing the same |
| AT97103454T ATE239303T1 (en) | 1992-07-15 | 1993-07-14 | PHOTOVOLTAIC DEVICE AND METHOD FOR PRODUCING THE SAME |
| EP93111278A EP0579199B1 (en) | 1992-07-15 | 1993-07-14 | photovoltaic device and method of manufacturing the same |
| KR1019930013319A KR100190800B1 (en) | 1992-07-15 | 1993-07-15 | Photovoltaic device and method of manufacturing the same |
| US08/999,790 US6214636B1 (en) | 1992-07-15 | 1997-10-29 | Photovoltaic device with improved collector electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4273972A JP2716630B2 (en) | 1992-10-13 | 1992-10-13 | Current collecting electrode of photovoltaic element and method of manufacturing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06125100A JPH06125100A (en) | 1994-05-06 |
| JP2716630B2 true JP2716630B2 (en) | 1998-02-18 |
Family
ID=17535147
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4273972A Expired - Fee Related JP2716630B2 (en) | 1992-07-15 | 1992-10-13 | Current collecting electrode of photovoltaic element and method of manufacturing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2716630B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5428249A (en) * | 1992-07-15 | 1995-06-27 | Canon Kabushiki Kaisha | Photovoltaic device with improved collector electrode |
| JP5323307B2 (en) * | 2005-12-21 | 2013-10-23 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Solar cell electrode paste |
| US8721931B2 (en) | 2005-12-21 | 2014-05-13 | E I Du Pont De Nemours And Company | Paste for solar cell electrode, solar cell electrode manufacturing method, and solar cell |
-
1992
- 1992-10-13 JP JP4273972A patent/JP2716630B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06125100A (en) | 1994-05-06 |
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