JP3097805B2 - Solar cell, method of manufacturing the same, and plating method - Google Patents
Solar cell, method of manufacturing the same, and plating methodInfo
- Publication number
- JP3097805B2 JP3097805B2 JP06238730A JP23873094A JP3097805B2 JP 3097805 B2 JP3097805 B2 JP 3097805B2 JP 06238730 A JP06238730 A JP 06238730A JP 23873094 A JP23873094 A JP 23873094A JP 3097805 B2 JP3097805 B2 JP 3097805B2
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- JP
- Japan
- Prior art keywords
- plating
- copper
- indium
- layer
- selenium
- Prior art date
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Classifications
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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
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- Photovoltaic Devices (AREA)
Description
【0001】[0001]
【産業上の利用分野】本発明は、CuInSe2 を吸収
層として有する薄膜太陽電池とその製造方法並びに薄膜
太陽電池の製造に用いられるめっき方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thin-film solar cell having CuInSe 2 as an absorbing layer, a method of manufacturing the same, and a plating method used for manufacturing a thin-film solar cell.
【0002】[0002]
【従来の技術】最近、優れた光電変換効率を有し、大面
積の薄膜太陽電池を低コストで製造できるものとして周
期律表の1B族−3B族−6B族の元素からなる化合物
半導体が注目されており、特にCuInSe2 は、
(1)吸収係数αが105 /cm程度と高く、2μm程
度の薄膜でも十分に太陽光を吸収できること、(2)禁
止帯幅が1.1eVであり、太陽光の光電変換に適して
いること、(3)光劣化がアモルファス・シリコンと比
べて著しく小さいこと等の特徴を有していることから最
も注目されている。大面積の薄膜太陽電池を低コストで
製造するため、特表平5−506334号(国際公開W
O92/05586号)公報に開示されているように、
分散めっき法を利用した太陽電池の製造方法が提案され
ている。2. Description of the Related Art Recently, compound semiconductors comprising elements of groups 1B-3B-6B of the periodic table have attracted attention as thin-film solar cells having excellent photoelectric conversion efficiency and large area can be manufactured at low cost. In particular, CuInSe 2 is
(1) The absorption coefficient α is as high as about 10 5 / cm, and it is possible to sufficiently absorb sunlight even with a thin film of about 2 μm. (2) The band gap is 1.1 eV, which is suitable for photoelectric conversion of sunlight. (3) It has received the most attention because it has features such as light degradation significantly smaller than that of amorphous silicon. To manufacture a large-area thin-film solar cell at low cost, Japanese Patent Application Laid-Open No. Hei 5-506334 (International Publication W
O92 / 05586) publication,
A method for manufacturing a solar cell using a dispersion plating method has been proposed.
【0003】図9は従来の薄膜太陽電池の製造方法の第
1の例を説明するための工程順に示した断面図である。FIG. 9 is a cross-sectional view illustrating a first example of a conventional method of manufacturing a thin-film solar cell in the order of steps for explaining the method.
【0004】まず、下記の表1に示す割合で調合しため
っき液を用意し、めっき槽に入れる。Se粉末は、水と
の親和性がよくないので、表面活性剤を添加することも
行われる。[0004] First, a plating solution prepared at a ratio shown in Table 1 below is prepared and put into a plating tank. Since the Se powder has poor affinity for water, a surfactant may be added.
【0005】[0005]
【表1】 [Table 1]
【0006】次に、図9(a)に示すように、ガラス基
板1の上に蒸着、スパッタなどの方法によりMo膜2を
形成した基板を用意する。この基板を、トリクロロエチ
レン、エタノール、アルカリ脱脂液に順々に浸漬して良
く洗浄し、次に純水にて良く洗浄した後、乾燥させる。
この洗浄ではすべて超音波洗浄機を用いる。Next, as shown in FIG. 9A, a substrate on which a Mo film 2 is formed on a glass substrate 1 by a method such as vapor deposition or sputtering is prepared. The substrate is immersed in trichloroethylene, ethanol, and an alkaline degreasing solution in order to wash well, then thoroughly washed with pure water, and dried.
In this cleaning, an ultrasonic cleaner is used.
【0007】次に、図9(b)に示すように、Mo膜2
を陰極として電流密度3A/dm2で電着を行なってC
u−In/Se分散めっき層3を形成する。このめっき
中にSe粉末が沈殿するので、めっき液を攪拌しながら
めっきを行う。[0007] Next, as shown in FIG.
Electrodeposited at a current density of 3 A / dm 2 using
The u-In / Se dispersed plating layer 3 is formed. Since Se powder precipitates during this plating, plating is performed while stirring the plating solution.
【0008】次に、図9(c)に示すように、Arガス
とH2 Seガスを混合したAr+H 2 Seガス雰囲気中
またはArガスとSe蒸気を混合したAr+Seガス雰
囲気中で熱処理してCuInSe2 合金層4に転換す
る。熱処理は、図10に示すように、室温から30℃/
分の速度で200℃〜250℃に上げ、この温度に約3
0〜60分保持し、次に30℃/分の速度で400℃〜
450℃に上げ、この温度に約2〜4時間保持し、次に
室温まで冷却する条件で行われる。200℃〜250℃
の温度は合金化が始まる温度、400℃〜450℃はC
uInSe2 の結晶が成長する温度といわれている。Next, as shown in FIG.
And HTwoAr + H mixed with Se gas TwoIn Se gas atmosphere
Or an Ar + Se gas atmosphere in which Ar gas and Se vapor are mixed.
CuInSe by heat treatment in atmosphereTwoConvert to alloy layer 4
You. As shown in FIG. 10, the heat treatment is performed from room temperature to 30 ° C. /
At a rate of 200 minutes to 200 ° C to 250 ° C.
Hold for 0-60 minutes, then at 400C at a rate of 30C / min.
Raise to 450 ° C and hold at this temperature for about 2-4 hours, then
It is performed under the condition of cooling to room temperature. 200 ° C to 250 ° C
Is the temperature at which alloying starts, and 400 ° C to 450 ° C is C
uInSeTwoIt is said that the temperature at which the crystal grows.
【0009】図11は従来の薄膜太陽電池の製造方法の
第2の例を説明するための工程順に示した断面図であ
る。FIG. 11 is a cross-sectional view illustrating a second example of a conventional method of manufacturing a thin-film solar cell in the order of steps for explaining the second example.
【0010】図11(a)に示すように、ソーダライム
ガラス製のガラス基板1の上にCr膜5を形成し、その
上にMo膜2を形成した基板を用意する。Cr膜5を設
けるのは、Moとガラス基板との熱膨張率の差による剥
がれを防止するためである。ソーダライムガラス、M
o、Crの熱膨張率は、表2に示す通りである。すなわ
ち、Crはソーダライムガラスとほぼ同じ熱膨張率をも
っており、ソーダライムガラスとなじみも良く、剥がれ
を生ずることは殆どない。CrとMoの熱膨張率はかな
りはなれているが、共に熱膨張率差に起因する応力を吸
収する柔軟性を有し、かつ金属間結合も強いので両者の
間で剥がれを生ずることは殆どない。この理由によりC
rをMoとガラスの間に挟むのである。この基板を第1
の例と同じ方法で良く洗浄する。As shown in FIG. 11A, a substrate is prepared in which a Cr film 5 is formed on a glass substrate 1 made of soda lime glass, and a Mo film 2 is formed thereon. The Cr film 5 is provided to prevent peeling due to a difference in thermal expansion coefficient between Mo and the glass substrate. Soda lime glass, M
The thermal expansion coefficients of o and Cr are as shown in Table 2. That is, Cr has almost the same coefficient of thermal expansion as soda lime glass, is well compatible with soda lime glass, and hardly peels off. Although the thermal expansion coefficients of Cr and Mo are far apart, both have the flexibility to absorb the stress caused by the difference in the thermal expansion coefficient, and the bonding between the metals is strong, so there is almost no peeling between the two. . For this reason C
r is sandwiched between Mo and glass. This substrate is
Wash well with the same method as in the example.
【0011】[0011]
【表2】 [Table 2]
【0012】次に、図11(b)に示すように、Mo膜
2を陰極として、電流密度3A/dm2 で電着を行なっ
てCu−In/Se分散めっき層3を形成する。このめ
っき中にめっき液を攪拌するのも第1の例と同じであ
る。Next, as shown in FIG. 11B, a Cu—In / Se dispersed plating layer 3 is formed by performing electrodeposition at a current density of 3 A / dm 2 using the Mo film 2 as a cathode. The stirring of the plating solution during the plating is the same as in the first example.
【0013】次に、第1の例と同じように、Seガスを
含む雰囲気中で熱処理して、図11(c)に示すよう
に、CuInSe2 合金層4を形成する。Next, as in the first example, heat treatment is performed in an atmosphere containing Se gas to form a CuInSe 2 alloy layer 4 as shown in FIG.
【0014】[0014]
【発明が解決しようとする課題】上記二つの例におい
て、CuInSe2 合金化の熱処理を行うと、Mo膜2
とCuInSe2 合金層4との間、またはMo膜2とガ
ラス基板1との間に剥がれが発生することがある。Mo
膜2とガラス基板1との間の剥がれはCr層5を設ける
ことにより大幅に低減できるが、Mo膜2とCuInS
e2 合金層4との間の剥がれを低減するのは中々難しい
という問題がある。In the above two examples, when the heat treatment for alloying CuInSe 2 is performed, the Mo film 2
Peeling may occur between the Cu film and the CuInSe 2 alloy layer 4 or between the Mo film 2 and the glass substrate 1. Mo
The peeling between the film 2 and the glass substrate 1 can be greatly reduced by providing the Cr layer 5, but the Mo film 2 and the CuInS
there is a problem that the medium s difficult to reduce the peeling between e 2 alloy layer 4.
【0015】剥がれが起こる原因は種々あるが、Mo膜
2とCu−In/Se分散めっき層3中のSe粒子が接
触し、MoとSeとが反応してMo−Se化合物を生成
すること、Mo膜2中にピンホールがあって、ピンホー
ル中に存在していた水分やガスが熱処理によって気化ま
たは熱膨張してピンホールの上のCuInSe2 合金層
4を押し退けて外へ出ようとすること、熱処理時の熱に
よってSeが気化してピンホールの中に入り、Moやそ
の下のCrと反応すること等が主な原因と考えられる。Although there are various causes of the peeling, the Mo film 2 and the Se particles in the Cu—In / Se dispersed plating layer 3 come into contact with each other and react with Mo and Se to form a Mo—Se compound. There is a pinhole in the Mo film 2, and moisture or gas existing in the pinhole is vaporized or thermally expanded by heat treatment to push out the CuInSe 2 alloy layer 4 on the pinhole and try to go outside. It is considered that the main cause is that Se evaporates due to heat during the heat treatment, enters into the pinhole, and reacts with Mo and Cr underneath.
【0016】さらに詳しく説明すると、図12(a)に
示すように、ピンホール42があるMo膜2の上にCu
−In/Se分散めっき層3が被着されているとする。
Cu−In/Se分散めっき層3の中にはSe粒子41
が分散しており、Se粒子41の内のいくつかはMo膜
2と接触している。この状態で熱処理すると、図12
(b)に示すように、Mo−Se化合物43が生成し、
生成化合物は体積をもつためその上のCuInSe2 合
金層4が押し上げられて剥がれる。また、ピンホール4
2中に存在していた水分やガスが熱処理によって気化ま
たは熱膨張してピンホール42の上のCuInSe2 合
金層4を押し退けて外へ出ようとするためCuInSe
2 合金層4が剥がれる。さらにまた、図12(c)に示
すように、熱処理時の熱によってSeが気化してピンホ
ール42の中に入り、Moやその下のCrと反応して、
例えばCr−Se化合物44が生成し、CuInSe2
合金層4押し上げ、CuInSe2 合金層4が剥がれ
る。剥がれは、それ程多く発生するわけではないが、た
とえ小量であっても剥がれが起こる以上は全製品につい
て検査し、剥がれ不良品を取り除かねばならないので、
検査と選別に工数を要し、製品歩留りの低下もあるの
で、太陽電池のコストが高くなるという問題があった。More specifically, as shown in FIG. 12A, a Cu film is
-Assume that the In / Se dispersed plating layer 3 is applied.
Se particles 41 are contained in the Cu—In / Se dispersed plating layer 3.
Are dispersed, and some of the Se particles 41 are in contact with the Mo film 2. When heat treatment is performed in this state, FIG.
As shown in (b), a Mo-Se compound 43 is generated,
Since the generated compound has a volume, the CuInSe 2 alloy layer 4 thereon is pushed up and peeled off. In addition, pinhole 4
2 is vaporized or thermally expanded by the heat treatment to push out the CuInSe 2 alloy layer 4 on the pinhole 42 and try to go outside.
2 The alloy layer 4 peels off. Further, as shown in FIG. 12C, Se is vaporized by the heat during the heat treatment, enters the pinhole 42, and reacts with Mo and Cr under the Mo.
For example, a Cr—Se compound 44 is generated, and CuInSe 2
When the alloy layer 4 is pushed up, the CuInSe 2 alloy layer 4 is peeled off. Peeling does not occur very much, but even if it is a small amount, as long as peeling occurs, all products must be inspected and peeling defective products must be removed,
Inspection and sorting require man-hours, and the product yield is reduced, so that there is a problem that the cost of the solar cell is increased.
【0017】本発明の目的は、熱処理してもCuInS
e2 合金層が剥がれない構造を有する太陽電池とその製
造方法を提供することにある。An object of the present invention is to provide a CuInS
An object of the present invention is to provide a solar cell having a structure in which an e 2 alloy layer does not peel off and a method for manufacturing the same.
【0018】本発明の目的は、めっき装置の設備費、設
備設置面積が低減でき、太陽電池の製造に効率良く使用
できるめっき方法を提供することにある。An object of the present invention is to provide a plating method which can reduce the equipment cost and equipment installation area of a plating apparatus and can be used efficiently in the manufacture of solar cells.
【0019】[0019]
【0020】[0020]
【0021】[0021]
【0022】[0022]
【0023】[0023]
【課題を解決するための手段】本発明は、銅イオンとイ
ンジウムイオンとを溶解させた溶液にセレン粒子を添加
しためっき液にモリブデン導電膜を表面に有する基板を
浸漬する工程と、前記セレン粒子が沈殿している状態
で、前記モリブデン導電膜に銅のみが析出する電位を印
加して前記モリブデン導電膜の上に銅層を形成する工程
と、前記めっき液を攪拌して前記セレン粒子が前記めっ
き液中に分散した状態で、前記モリブデン導電膜に銅と
インジウムが析出する電位を印加して前記銅層の上に銅
−インジウム−セレンめっき層を形成する工程と、熱処
理して少なくとも前記銅−インジウム−セレンめっき層
を銅−インジウム−セレン合金層に変換する工程とを備
えたことを特徴とする。SUMMARY OF THE INVENTION The present invention comprises a step of immersing a substrate having a molybdenum conductive film on a surface thereof in a plating solution obtained by adding selenium particles to a solution in which copper ions and indium ions are dissolved; In a state where is precipitated, a step of forming a copper layer on the molybdenum conductive film by applying a potential at which only copper is deposited on the molybdenum conductive film, and the selenium particles are stirred by stirring the plating solution. In a state of being dispersed in the plating solution, a step of applying a potential at which copper and indium are deposited on the molybdenum conductive film to form a copper-indium-selenium plating layer on the copper layer, and heat-treating at least the copper -Converting the indium-selenium plating layer to a copper-indium-selenium alloy layer.
【0024】本発明は、銅イオンとインジウムイオンと
を溶解させた溶液にセレン粒子を添加しためっき液にモ
リブデン導電膜を表面に有する基板を浸漬する工程と、
前記セレン粒子が沈殿している状態で、前記モリブデン
導電膜に銅とインジウムが析出する電位を印加して前記
モリブデン導電膜の上に銅−インジウム合金層を形成す
る工程と、前記めっき液を攪拌して前記セレン粒子が前
記めっき液中に分散した状態で、前記モリブデン導電膜
に銅とインジウムが析出する電位を印加して前記銅−イ
ンジウム合金層の上に銅−インジウム−セレンめっき層
を形成する工程と、熱処理して少なくとも前記銅−イン
ジウム−セレンめっき層を銅−インジウム−セレン合金
層に変換する工程とを備えたことを特徴とする。The present invention comprises a step of immersing a substrate having a molybdenum conductive film on its surface in a plating solution obtained by adding selenium particles to a solution in which copper ions and indium ions are dissolved;
In the state where the selenium particles are precipitated, a step of applying a potential at which copper and indium are deposited on the molybdenum conductive film to form a copper-indium alloy layer on the molybdenum conductive film, and stirring the plating solution. Then, in a state where the selenium particles are dispersed in the plating solution, a potential at which copper and indium are deposited on the molybdenum conductive film is applied to form a copper-indium-selenium plating layer on the copper-indium alloy layer. And a step of converting at least the copper-indium-selenium plating layer into a copper-indium-selenium alloy layer by heat treatment.
【0025】本発明は、銅イオンとインジウムイオンと
を少なくとも含むめっき液に導電膜を表面に有する基板
を浸漬する工程と、銅のみが析出する電位を前記導電膜
に印加して前記導電膜の上に銅層を形成する工程と、銅
とインジウムが析出する電位を前記導電膜に印加して前
記銅層の上に銅−インジウムを少なくとも含むめっき層
を形成する工程とを備えたことを特徴とする。The present invention comprises a step of immersing a substrate having a conductive film on a surface thereof in a plating solution containing at least copper ions and indium ions, and a step of applying a potential at which only copper is deposited to the conductive film. Forming a plating layer containing at least copper-indium on the copper layer by applying a potential at which copper and indium are deposited to the conductive film. And
【0026】[0026]
【作用】導電性中間層は、モリブデン導電膜とセレンと
が直接接触するのを防ぎ、モリブデンとセレンとが反応
するのを阻止し、銅−インジウム−セレン合金層が剥が
れるのを防止する作用を有する。The conductive intermediate layer prevents the molybdenum conductive film from directly contacting selenium, prevents the reaction between molybdenum and selenium, and prevents the copper-indium-selenium alloy layer from peeling off. Have.
【0027】導電性中間層として銅層が選ばれる。銅
は、モリブデンと合金を作り難く、銅−インジウム−セ
レン合金層の組成元素であるので、銅−インジウム−セ
レン合金層と強固に接着するからである。A copper layer is selected as the conductive intermediate layer. This is because copper is difficult to form an alloy with molybdenum and is a constituent element of the copper-indium-selenium alloy layer, and thus strongly adheres to the copper-indium-selenium alloy layer.
【0028】導電性中間層としてインジウム層が選ばれ
る。インジウムは、モリブデンと合金を作り難く、銅−
インジウム−セレン合金層の組成元素であるので、銅−
インジウム−セレン合金層と強固に接着するからであ
る。An indium layer is selected as the conductive intermediate layer. Indium is difficult to form an alloy with molybdenum,
Since it is a constituent element of the indium-selenium alloy layer, copper-
This is because it firmly adheres to the indium-selenium alloy layer.
【0029】導電性中間層として銅−インジウム合金層
が選ばれる。銅−インジウム合金は、モリブデンと合金
を作り難く、銅−インジウム−セレン合金層の組成元素
であるので、銅−インジウム−セレン合金層と強固に接
着するからである。A copper-indium alloy layer is selected as the conductive intermediate layer. This is because the copper-indium alloy hardly forms an alloy with molybdenum and is a constituent element of the copper-indium-selenium alloy layer, so that it is firmly bonded to the copper-indium-selenium alloy layer.
【0030】銅イオンとインジウムイオンとは、還元電
位が異なるので、銅のみが析出する電位を印加すること
によりモリブデン導電膜の上に銅層のみを形成すること
ができ、続いてめっき液を攪拌することによって沈殿し
ていたセレン粒子を浮き上がらせ、銅とインジウムが析
出する電位を印加することにより銅層の上に銅−インジ
ウム−セレンめっき層を形成することができる。銅層を
形成するめっきにおいてセレン粒子がめっき液中に浮遊
分散していると、銅と一緒にセレン粒子も析出するの
で、銅めっき時には攪拌せずセレン粒子をめっき槽の底
部に沈殿させておく。このように、一つのめっき槽、一
種類のめっき液で銅層と銅−インジウム−セレンめっき
層を形成できるようにすると、めっき装置の設備費が安
くつき、設備設置面積が広くならず、工数が低減でき、
しかも銅−インジウム−セレン合金層の剥がれもなくな
るので、低コストで太陽電池を製造することができる。Since the copper ion and the indium ion have different reduction potentials, only the copper layer can be formed on the molybdenum conductive film by applying a potential at which only copper is deposited, and then the plating solution is stirred. By doing so, the precipitated selenium particles are lifted up, and a copper-indium-selenium plating layer can be formed on the copper layer by applying a potential at which copper and indium are deposited. If selenium particles are suspended and dispersed in the plating solution during plating to form a copper layer, selenium particles also precipitate together with copper, so that the selenium particles are allowed to settle at the bottom of the plating tank without stirring during copper plating. . As described above, if the copper layer and the copper-indium-selenium plating layer can be formed with one plating tank and one kind of plating solution, the equipment cost of the plating apparatus is reduced, the equipment installation area is not increased, and the man-hour is reduced. Can be reduced,
Moreover, since the copper-indium-selenium alloy layer does not peel off, the solar cell can be manufactured at low cost.
【0031】セレン粒子をめっき槽の底部に沈殿させて
おき、上澄み液を用いてめっきするとセレン粒子を含ま
ないめっき層が得られることを利用すると、モリブデン
導電膜の上に銅−インジウム合金層を形成することがで
き、続いてめっき液を攪拌することによって沈殿してい
たセレン粒子を浮き上がらせ、銅とインジウムが析出す
る電位を印加することにより銅−インジウム合金層の上
に銅−インジウム−セレンめっき層を形成することがで
きる。このようにすると、一つのめっき槽、一種類のめ
っき液で銅−インジウム合金層と銅−インジウム−セレ
ンめっき層を形成でき、設備費、設備設置面積、工数を
低減でき、しかも銅−インジウム−セレン合金層の剥が
れもなくなるので、低コストで太陽電池を製造すること
ができる。By making use of the fact that selenium particles are settled at the bottom of the plating tank and plating is performed using a supernatant to obtain a plating layer containing no selenium particles, a copper-indium alloy layer is formed on the molybdenum conductive film. Then, the selenium particles that have precipitated are lifted by stirring the plating solution, and a copper-indium-selenium is deposited on the copper-indium alloy layer by applying a potential at which copper and indium are deposited. A plating layer can be formed. In this way, a copper-indium alloy layer and a copper-indium-selenium plating layer can be formed with one plating tank and one kind of plating solution, and equipment costs, equipment installation area, man-hours can be reduced, and copper-indium- Since the selenium alloy layer does not peel off, a solar cell can be manufactured at low cost.
【0032】上記製造方法は、銅イオンとインジウムイ
オンとの還元電位が異なることを利用しためっき方法に
基づいている。このめっき方法は、銅イオンとインジウ
ムイオンとを少なくとも含みセレンを含まないめっき液
にも適用できるものである。このめっき方法を用いる
と、前記と同様に、めっき装置の設備費、設備設置面積
を低減でき、かつ工数も低減できるので、低コストでめ
っきを行うことができる。The above manufacturing method is based on a plating method utilizing the fact that copper ions and indium ions have different reduction potentials. This plating method can be applied to a plating solution containing at least copper ions and indium ions and not containing selenium. When this plating method is used, similarly to the above, the equipment cost and equipment installation area of the plating apparatus can be reduced, and the number of steps can be reduced, so that plating can be performed at low cost.
【0033】[0033]
(実施例1)まず、Cu下地めっき液を下記の割合で調
合する。 硫酸銅 160g/l(1.0M) 硫酸 49g/l(0.5M) 次に、表1に示した組成のCu−In/Se分散めっき
液を調合する。(Example 1) First, a Cu base plating solution is prepared at the following ratio. Copper sulfate 160 g / l (1.0 M) Sulfuric acid 49 g / l (0.5 M) Next, a Cu—In / Se dispersed plating solution having the composition shown in Table 1 is prepared.
【0034】めっき槽は二つ用意し、上記のめっき液を
別々のめっき槽に入れ、Cu下地めっき浴およびCu−
In/Se分散めっき浴とする。Two plating tanks were prepared, and the above plating solutions were put into separate plating tanks, and a Cu base plating bath and a Cu-
In / Se dispersion plating bath.
【0035】図1は本発明の太陽電池の第1の実施例の
製造方法を説明するための工程順に示した断面図であ
る。FIG. 1 is a sectional view showing a method of manufacturing a solar cell according to a first embodiment of the present invention in order of steps.
【0036】まず、図1(a)に示すように、ガラス基
板1の上にCr膜5、Mo膜2を形成したものを用意す
る。これをCu下地めっき浴に入れ、電流密度3A/d
m2で1分間めっきを行い、Mo膜2の上に厚さ約0.
2μmのCu層6を形成した。First, as shown in FIG. 1A, a glass substrate 1 having a Cr film 5 and a Mo film 2 formed thereon is prepared. This was put into a Cu base plating bath, and the current density was 3 A / d
m 2 for 1 minute, and a thickness of about 0.1 mm on the Mo film 2.
A 2 μm Cu layer 6 was formed.
【0037】次に、図1(b)に示すように、これをC
u−In/Se分散めっき浴に入れ、電流密度3A/d
m2 で5分間めっきを行い、厚さ1.5μmのCu−I
n/Se分散めっき層3を形成した。この分散めっき層
3を分析したところ、原子%で Cu:In:Se=30:35:35 であった。Next, as shown in FIG.
Put in u-In / Se dispersion plating bath, current density 3A / d
plating for 5 minutes at m 2 , and 1.5 μm thick Cu-I
The n / Se dispersed plating layer 3 was formed. When this dispersed plating layer 3 was analyzed, it was Cu: In: Se = 30: 35: 35 in atomic%.
【0038】次に、図1(c)に示すように、Arガス
とSe蒸気を混合したAr+Seガス雰囲気中で熱処理
してCuInSe2 膜4に転換した。熱処理は、図10
に示すように、室温から30℃/分の速度で250℃に
上げ、この温度に約30分保持し、次に30℃/分の速
度で450℃に上げ、この温度に約2時間保持し、次に
室温まで冷却する条件で行った。このCuInSe2 膜
4を分析したところ、原子%で Cu:In:Se=25.3:24.4:50.3 であった。また、CuInSe2 膜4を目視で検査した
が膜の剥がれは観察されなかった。Next, as shown in FIG. 1C, the CuInSe 2 film 4 was formed by heat treatment in an Ar + Se gas atmosphere in which Ar gas and Se vapor were mixed. Heat treatment is shown in FIG.
As shown in the figure, the temperature is raised from room temperature to 250 ° C. at a rate of 30 ° C./min and held at this temperature for about 30 minutes, then raised to 450 ° C. at a rate of 30 ° C./min and held at this temperature for about 2 hours And then cooled to room temperature. When this CuInSe 2 film 4 was analyzed, it was Cu: In: Se = 25.3: 24.4: 50.3 in atomic%. The CuInSe 2 film 4 was visually inspected, but no peeling of the film was observed.
【0039】このように、Mo膜2とCu−In/Se
分散めっき層3との間にCu層6を設けると、MoとS
eとが直接接触することがなくなるので、図12に示し
たような、Mo−Se化合物が生成したり、あるいはS
eが気化してMo膜2のピンホールの中に入り、Moや
その下のCrと反応して、Cr−Se化合物が生成し、
CuInSe2 合金層4押し上げ、CuInSe2 合金
層4が剥がれるというような不良発生を防ぐことがで
き、従って歩留りを向上させ、コストを低減することが
できる。As described above, the Mo film 2 and the Cu-In / Se
When the Cu layer 6 is provided between the dispersed plating layer 3 and Mo, S
e does not come into direct contact with the Mo-Se compound, as shown in FIG.
e evaporates into the pinholes of the Mo film 2 and reacts with Mo and Cr under the Mo to form a Cr—Se compound,
CuInSe 2 alloy layer 4 pushed, it is possible to prevent occurrence of defects such as that CuInSe 2 alloy layer 4 is peeled off, thus to improve the yield, the cost can be reduced.
【0040】(実施例2)まず、In下地めっき液を下
記の割合で調合する。このめっき液をめっき槽に入れ、
In下地めっき浴とする。 硫酸インジウム 300g/l(0.6M) Cu−In/Se分散めっき液は実施例1で用いためっ
き液と同じである。(Example 2) First, an In base plating solution is prepared at the following ratio. Put this plating solution in the plating tank,
In plating bath. The indium sulfate 300 g / l (0.6 M) Cu-In / Se dispersion plating solution is the same as the plating solution used in Example 1.
【0041】図2は本発明の太陽電池の第2の実施例の
製造方法を説明するための工程順に示した断面図であ
る。FIG. 2 is a sectional view illustrating a method of manufacturing a solar cell according to a second embodiment of the present invention in the order of steps.
【0042】まず、図2(a)に示すように、ガラス基
板1の上にCr膜5、Mo膜2を形成したものを用意す
る。これをIn下地めっき浴に入れ、電流密度3A/d
m2で1分間めっきを行い、厚さ約0.2μmのIn層
7をMo膜2の上に形成した。First, as shown in FIG. 2A, a glass substrate 1 having a Cr film 5 and a Mo film 2 formed thereon is prepared. This was put into an In base plating bath, and the current density was 3 A / d.
Plating was performed at m 2 for 1 minute, and an In layer 7 having a thickness of about 0.2 μm was formed on the Mo film 2.
【0043】次に、実施例1と同様に、Cu−In/S
e分散めっき浴に入れ、電流密度3A/dm2 で5分間
めっきを行い、図2(b)に示すように、Cu−In/
Se分散めっき層3を形成した。Cu−In/Se分散
めっき層3の厚さおよび組成は実施例1と同様である。Next, Cu-In / S
e, and placed in a dispersion plating bath, plating was performed at a current density of 3 A / dm 2 for 5 minutes, and as shown in FIG.
The Se dispersion plating layer 3 was formed. The thickness and composition of the Cu—In / Se dispersed plating layer 3 are the same as in Example 1.
【0044】次に、実施例1と同様に、Ar+Seガス
雰囲気中で熱処理して、図2(c)に示すように、Cu
InSe2 膜4に転換した。Next, similarly to the first embodiment, a heat treatment is performed in an Ar + Se gas atmosphere, and as shown in FIG.
The film was converted to an InSe 2 film 4.
【0045】実施例2においても、Mo膜2とCu−I
n/Se分散めっき層3とはIn層7で分離されている
から、MoとSeとが直接接触することがなく、図12
に示したような、Mo−Se化合物あるいはCr−Se
化合物が生成したりすることはなく、CuInSe2 合
金層4が剥がれるというような不良発生を防ぐことがで
き、従って歩留りを向上させ、コストを低減することが
できる。In the second embodiment, the Mo film 2 and the Cu-I
Since the n / Se dispersed plating layer 3 is separated from the n / Se dispersed plating layer 3 by the In layer 7, Mo and Se do not come into direct contact with each other.
Mo-Se compound or Cr-Se as shown in
No compound is generated, and defects such as peeling of the CuInSe 2 alloy layer 4 can be prevented. Therefore, the yield can be improved and the cost can be reduced.
【0046】(実施例3)まず、Cu−In下地めっき
液を表3に示す割合で調合する。このめっき液をめっき
槽に入れ、Cu−In下地めっき浴とする。Cu−In
/Se分散めっき液は、実施例1で用いためっき液(表
1参照)と同じである。(Example 3) First, a Cu-In base plating solution is prepared at a ratio shown in Table 3. This plating solution is put into a plating bath to form a Cu-In base plating bath. Cu-In
The / Se dispersion plating solution is the same as the plating solution used in Example 1 (see Table 1).
【0047】[0047]
【表3】 [Table 3]
【0048】図3は本発明の太陽電池の第3の実施例の
製造方法を説明するための工程順に示した断面図であ
る。FIG. 3 is a sectional view showing a method of manufacturing a solar cell according to a third embodiment of the present invention in the order of steps.
【0049】まず、図3(a)に示すように、ガラス基
板1の上にCr膜5、Mo膜2を形成したものを用意す
る。これをCu−In下地めっき浴に入れ、電流密度6
A/dm2 で1分間めっきを行い、厚さ0.5μmのC
u−In合金層8を得た。このCu−In合金層8を分
析したところ、原子%で Cu:In=60:40 であった。First, as shown in FIG. 3A, a glass substrate 1 having a Cr film 5 and a Mo film 2 formed thereon is prepared. This was put into a Cu-In base plating bath, and a current density of 6
A / dm 2 plating for 1 minute, 0.5μm thick C
The u-In alloy layer 8 was obtained. When this Cu—In alloy layer 8 was analyzed, it was Cu: In = 60: 40 in atomic%.
【0050】次に、実施例1と同様に、Cu−In/S
e分散めっき浴に入れ、電流密度3A/dm2 で5分間
めっきを行い、図3(b)に示すように、Cu−In/
Se分散めっき層3を形成した。Cu−In/Se分散
めっき層3の厚さおよび組成は実施例1と同様である。Next, as in the first embodiment, Cu-In / S
e, and placed in a dispersion plating bath, plating was performed at a current density of 3 A / dm 2 for 5 minutes, and as shown in FIG.
The Se dispersion plating layer 3 was formed. The thickness and composition of the Cu—In / Se dispersed plating layer 3 are the same as in Example 1.
【0051】次に、実施例1と同様に、Ar+Seガス
雰囲気中で熱処理して、図3(c)に示すように、Cu
InSe2 膜4に転換した。Next, as in the first embodiment, a heat treatment is performed in an Ar + Se gas atmosphere, and as shown in FIG.
The film was converted to an InSe 2 film 4.
【0052】実施例3においても、Mo膜2とCu−I
n/Se分散めっき層3とはCu−In合金層8で分離
されているから、MoとSeとが直接接触することがな
く、図12に示したような、Mo−Se化合物あるいは
Cr−Se化合物が生成したりすることはなく、CuI
nSe2 合金層4が剥がれるというような不良発生を防
ぐことができ、従って歩留りを向上させ、コストを低減
することができる。In the third embodiment, the Mo film 2 and the Cu-I
Since the n / Se dispersed plating layer 3 is separated from the n-Se dispersed plating layer 3 by the Cu-In alloy layer 8, Mo and Se do not come into direct contact with each other, and the Mo-Se compound or the Cr-Se as shown in FIG. No compound is formed and CuI
It is possible to prevent the occurrence of defects such as the nSe 2 alloy layer 4 being peeled off, thereby improving the yield and reducing the cost.
【0053】以上説明した三つの実施例では、いずれも
下地めっき浴とCu−In/Se分散めっき浴とを分け
て行っていた。めっき浴を別々にすると、めっき浴の設
備費と設備設置面積が2倍になり、被めっき体の移し替
えと洗浄に工数がかかり、コストが高くなる。一つのめ
っき槽と一種類のめっき液で連続作業で下地めっきとC
u−In/Se分散めっきとができれば、設備費、設置
面積が半分になり、工数も低減でき、コストダウンが図
れることになる。本発明は、この問題を解決したので、
以下これについて説明する。In each of the three embodiments described above, the underlying plating bath and the Cu-In / Se dispersed plating bath were separately used. Separating the plating baths doubles the equipment cost and the installation area of the plating bath, and takes a lot of man-hours to transfer and clean the object to be plated, thus increasing the cost. Undercoating and C in continuous operation with one plating tank and one kind of plating solution
If u-In / Se dispersion plating can be performed, equipment costs and installation area can be halved, man-hours can be reduced, and costs can be reduced. The present invention has solved this problem,
This will be described below.
【0054】図4は本発明のめっきに使用するめっき浴
の側面図である。FIG. 4 is a side view of a plating bath used for plating of the present invention.
【0055】めっき槽11は、直方体に作られ、上方が
開いている。この槽の中にめっき液12を入れ、液内に
作用電極としての被めっき体13と対向電極14と参照
電極REを浸漬し、被めっき体13と対向電極14と参
照電極REをポテンシオスタット15に接続し、被めっ
き体13に負電位、対向電極14に正電位、参照電極R
Eに参照電位を印加する。参照電位は、作用電極(被め
っき体13)の電位を目的とする電位に一定に保つため
の電位で、基準として通常SSE(Saturated
Sulfate Electrode、硫酸第一水銀
電極)またはNHE(Normal Hydrogen
Electrode、標準水素電極)の電位が採用さ
れている。ここでは、めっき液が強酸性であるので、S
SEを基準電位に採用する。参照電極REは、作用電極
(被めっき体13)を目的とする電位に変化させるため
にも使用される。参照電極REの電位を基準としてこれ
にある電圧を加算または減算して作用電極(被めっき体
13)を目的とする電位に変化させる。さらに、ポテン
シオスタット15は、作用電極(被めっき体13)と参
照電極REとの間の電位を一定に保つのにも使用され
る。The plating tank 11 is formed in a rectangular parallelepiped, and is open at the top. The plating solution 12 is put into this tank, and the plate 13 as a working electrode, the counter electrode 14 and the reference electrode RE are immersed in the solution, and the plate 13, the counter electrode 14 and the reference electrode RE are placed in a potentiostat. 15, a negative potential is applied to the plate 13, a positive potential is applied to the counter electrode 14, and the reference electrode R
A reference potential is applied to E. The reference potential is a potential for keeping the potential of the working electrode (plated object 13) constant at a target potential, and is usually a reference SSE (Saturated) as a reference.
Sulfate Electrode (mercuric sulfate electrode) or NHE (Normal Hydrogen)
Electrode, a standard hydrogen electrode). Here, since the plating solution is strongly acidic,
SE is used as the reference potential. The reference electrode RE is also used for changing the working electrode (plated object 13) to a target potential. The working electrode (plated object 13) is changed to a target potential by adding or subtracting a certain voltage with reference to the potential of the reference electrode RE. Further, the potentiostat 15 is also used to keep the potential between the working electrode (plated object 13) and the reference electrode RE constant.
【0056】めっきにおいては、還元電位が重要であ
る。CuとInの還元反応と還元電位は数1に示す通り
である。数1において、還元電位Vは、SSE(Sat
urated Sulfate Electrode)
を基準として、これに対する電位で示されている。In plating, the reduction potential is important. The reduction reaction and reduction potential of Cu and In are as shown in Formula 1. In Equation 1, the reduction potential V is SSE (Sat
urated Sulfate Electrode)
, The potential is shown with respect to this.
【0057】[0057]
【数1】 (Equation 1)
【0058】図5は還元電位差によるCuとCu−In
の析出開始の差を説明する図、図6は被めっき体の設定
電位とCuおよびCu−Inの析出量との関係を説明す
る図である。FIG. 5 shows Cu and Cu-In due to the reduction potential difference.
And FIG. 6 is a diagram for explaining the relationship between the set potential of the object to be plated and the amounts of Cu and Cu-In deposited.
【0059】実施例3で用いたCu−In下地めっき液
と同じ組成のめっき液をめっき槽11に入れ、Cu−I
n下地めっき浴とする。被めっき体13に負電位を印加
し、被めっき体13の電位を下げていくと、ある電圧a
でCuが析出し始め、ある電圧bでCuとInが析出し
始める。CuとInと合金を作っている。電圧bより高
い電圧ではInは析出しない。電圧bと電圧aの最小差
は還元電位の差0.675Vに等しい。図5,図6に示
すように、被めっき体13の電位を段々下げていくと、
─0.278VでCuが析出し始め、電位の低下に伴っ
てCuの析出量が増加し、−0.953VになるとIn
も析出し始め、Cu−In合金が析出するようになる。A plating solution having the same composition as that of the Cu-In base plating solution used in Example 3 was put into the plating tank 11 and Cu-I
Use n base plating bath. When a negative potential is applied to the plated body 13 and the potential of the plated body 13 is reduced, a certain voltage a
Then, Cu starts to precipitate, and at a certain voltage b, Cu and In start to precipitate. An alloy is made with Cu and In. At a voltage higher than the voltage b, In does not precipitate. The minimum difference between voltage b and voltage a is equal to the reduction potential difference 0.675V. As shown in FIGS. 5 and 6, when the potential of the body to be plated 13 is gradually lowered,
Cu starts to precipitate at 0.278V, and the amount of Cu increases with a decrease in potential.
Also starts to precipitate, and a Cu—In alloy starts to precipitate.
【0060】図7は設定電位と析出するCu/In比と
の関係を説明する図である。FIG. 7 is a diagram for explaining the relationship between the set potential and the Cu / In ratio that precipitates.
【0061】Cuのみが析出しInが析出していない間
はCu/In比は無限大であるが、設定電位を下げてい
くと−0.953VでInが析出し始め、Cu/In比
は急速に低下してある値に近づいていく。図7はその様
子を示している。The Cu / In ratio is infinite while only Cu is precipitated and In is not deposited, but as the set potential is lowered, In starts to precipitate at -0.953 V, and the Cu / In ratio becomes It rapidly decreases and approaches a certain value. FIG. 7 shows this state.
【0062】(実施例4)実施例3で用いたCu−In
下地めっき液と同じ組成のめっき液をめっき槽に入れめ
っき浴とする。ガラス基板1の上にCr膜5、Mo膜2
を形成したものをめっき浴に入れ被めっき体とする。被
めっき体の電位を−0.7Vに設定して1分間めっきを
行い、図1(a)に示すような厚さ0.6μmのCu層
6をMo膜2の上に形成した。(Example 4) Cu-In used in Example 3
A plating solution having the same composition as the base plating solution is placed in a plating tank to form a plating bath. Cr film 5 and Mo film 2 on glass substrate 1
Is formed in a plating bath to obtain a plated object. Plating was performed for 1 minute while the potential of the object to be plated was set to −0.7 V, and a Cu layer 6 having a thickness of 0.6 μm was formed on the Mo film 2 as shown in FIG.
【0063】次に、被めっき体の電圧を−1.5Vに下
げて5分間めっきを行い、厚さ1.2μmのCu−In
合金層を得た。このCu−In合金層を分析したとこ
ろ、原子%で Cu:In=44:56 であった。Next, the voltage of the object to be plated was lowered to -1.5 V, and plating was performed for 5 minutes.
An alloy layer was obtained. When this Cu-In alloy layer was analyzed, it was found that Cu: In = 44: 56 in atomic%.
【0064】以上説明したように、CuとInの還元電
位が離れていることを利用すれば、一つのめっき槽と一
種類のめっき液でCu下地めっきとCu−Inめっきを
連続作業で行うことができることが分かった。この原理
をCu−In/Se分散めっきに適用して、一つのめっ
き槽と一種類のめっき液でCuまたはCu−In下地め
っきとCu−In/Se分散めっきとを連続作業で形成
できれば設備費、設備設置面積、工数を低減することが
でき、低コストでめっきを行うことができるので好都合
であるが、Cu−In/Se分散めっき液にはSe粒子
が分散されているから、CuまたはCu−In下地めっ
き層中にSeが混入する恐れがある。Seが混入すれ
ば、Mo膜とSeが接触し、中間層を設ける意味がなく
なるからである。それ故、CuまたはCu−In下地め
っき層中にSeが混入しないように工夫する必要があ
る。As described above, by utilizing the fact that the reduction potentials of Cu and In are distant from each other, it is possible to perform Cu base plating and Cu-In plating in a continuous operation using one plating tank and one kind of plating solution. I knew I could do it. Applying this principle to Cu-In / Se dispersion plating, if one plating tank and one kind of plating solution can form Cu or Cu-In base plating and Cu-In / Se dispersion plating in a continuous operation, equipment cost This is advantageous because the equipment installation area and man-hour can be reduced, and plating can be performed at low cost. However, since Se particles are dispersed in the Cu-In / Se dispersed plating solution, Cu or Cu There is a possibility that Se may be mixed into the -In base plating layer. This is because if Se is mixed, the Mo film comes into contact with Se, and there is no point in providing an intermediate layer. Therefore, it is necessary to take measures to prevent Se from being mixed into the Cu or Cu-In base plating layer.
【0065】図8はCu−In/Se分散めっきにおけ
る攪拌流量とSe析出量との関係を示す図である。FIG. 8 is a diagram showing the relationship between the stirring flow rate and the Se deposition amount in Cu—In / Se dispersion plating.
【0066】実施例1で用いためっき液と同じ組成のC
u−In/Se分散めっき液を用い、攪拌機を作動させ
ないでSe粉末をめっき槽の底部に沈殿させておく。従
って、上澄み液はCuイオンとInイオンのみを含有す
る液となっている。この状態でガラス基板1の上にCr
膜5、Mo膜2を形成したものをめっき浴に入れて被め
っき体とし、被めっき体の電圧を−0.7Vに設定し、
電流密度0.2A/dm2 でめっき時間を種々変えてめ
っきを行い、図1(a)に示すようにCu層6をMo膜
2の上に形成したサンプルを10個作り、Cu層6中の
Se量を分析したが、Seは検出されなかった。C having the same composition as the plating solution used in Example 1
Using a u-In / Se dispersed plating solution, Se powder is allowed to settle at the bottom of the plating tank without operating a stirrer. Therefore, the supernatant liquid is a liquid containing only Cu ions and In ions. In this state, Cr is placed on the glass substrate 1.
The film 5 and the Mo film 2 formed were placed in a plating bath to form a body to be plated, and the voltage of the body to be plated was set to −0.7 V;
Plating was performed by changing the plating time at a current density of 0.2 A / dm 2 , and as shown in FIG. 1A, ten samples in which a Cu layer 6 was formed on the Mo film 2 were formed. Was analyzed, but no Se was detected.
【0067】次に、Inが析出するように被めっき体の
電圧を−1.5Vに下げ、電流密度を2A/dm2 に保
ち、めっき液の攪拌を開始し、種々の攪拌流量でめっき
を行い、図1(b)に示すようにCu層6の上にCu−
In/Se分散めっき層3を形成したサンプルを10個
作り、層3中のSe量を分析し、図8に示す結果を得
た。図8から、めっき液の攪拌の無い時はSeの析出が
無く、攪拌を開始するとSe析出量は攪拌流量の増加と
共に急速に増加し、やがて飽和状態になることが分か
る。Next, the voltage of the object to be plated was lowered to -1.5 V so that In was deposited, the current density was kept at 2 A / dm 2 , stirring of the plating solution was started, and plating was performed at various stirring flow rates. Then, as shown in FIG. 1B, Cu-
Ten samples on which the In / Se dispersed plating layer 3 was formed were prepared, and the amount of Se in the layer 3 was analyzed, and the results shown in FIG. 8 were obtained. From FIG. 8, it can be seen that when there is no stirring of the plating solution, there is no precipitation of Se, and when stirring is started, the Se deposition amount increases rapidly with an increase in the stirring flow rate, and eventually becomes saturated.
【0068】(実施例5)実施例1で用いためっき液と
同じCu−In/Se分散めっき液(表1参照)をめっ
き槽に入れめっき浴とする。このとき、攪拌機は作動さ
せないでSe粉末をめっき槽の底部に沈殿させておく。
この状態でガラス基板1の上にCr膜5、Mo膜2を形
成したものをめっき浴に入れ被めっき体とする。Cuの
みが析出し、Inが析出しない電圧となるように、被め
っき体の電圧を─0.7Vに設定し、電流密度0.2A
/dm2 で5分間めっきを行い、図1(a)に示すよう
な厚さ1.5μmのCu層6をMo膜2の上に形成し
た。Cu層6中のSe量を分析したが、Seは検出され
なかった。(Example 5) The same Cu-In / Se dispersed plating solution (see Table 1) as the plating solution used in Example 1 was placed in a plating tank to form a plating bath. At this time, the Se powder is settled at the bottom of the plating tank without operating the stirrer.
In this state, the one in which the Cr film 5 and the Mo film 2 are formed on the glass substrate 1 is placed in a plating bath to be a plated object. The voltage of the object to be plated was set at 0.7 V so that only Cu was deposited and In was not deposited, and the current density was 0.2 A.
/ Dm 2 for 5 minutes to form a Cu layer 6 having a thickness of 1.5 μm on the Mo film 2 as shown in FIG. The Se content in the Cu layer 6 was analyzed, but no Se was detected.
【0069】次に、攪拌機を作動させて、単位時間当た
りの流量3リットル/分で攪拌してめっき槽の底部に沈
殿していたSe粉末を浮き上がらせてめっき液中に分散
させ、この状態で被めっき体の電圧を−1.5Vに下
げ、電流密度を3A/dm2 に保って5分間めっきを行
い、図1(b)に示すように、厚さ1.5μmのCu−
In/Se分散めっき層3を得た。このCu−In/S
e分散めっき層3を分析したところ、原子%で Cu:In:Se=33:37:30 であった。Next, the stirrer was operated to stir at a flow rate of 3 liters / minute per unit time to float the Se powder precipitated at the bottom of the plating tank and disperse it in the plating solution. The voltage of the object to be plated was reduced to -1.5 V, plating was performed for 5 minutes while maintaining the current density at 3 A / dm 2 , and as shown in FIG.
In / Se dispersed plating layer 3 was obtained. This Cu-In / S
When the e-dispersion plating layer 3 was analyzed, it was Cu: In: Se = 33: 37: 30 in atomic%.
【0070】次に、実施例1と同様に、Seガスを含む
雰囲気中で熱処理して、図1(c)に示すように、Cu
InSe2 膜4に転換する。これにより実施例1と同等
の太陽電池が得られた。Next, as in the first embodiment, a heat treatment is performed in an atmosphere containing Se gas, and as shown in FIG.
Convert to InSe 2 film 4. As a result, a solar cell equivalent to that of Example 1 was obtained.
【0071】(実施例6)実施例5と同じCu−In/
Se分散めっき浴を作る。実施例5と同様に、攪拌機は
作動させないでSe粉末をめっき槽の底部に沈殿させて
おく。この状態でガラス基板1の上にCr膜5、Mo膜
2を形成したものをめっき浴に入れ被めっき体とする。
CuとInの両方が析出するように、被めっき体の電圧
を─1.0Vに設定し、電流密度を0.7A/dm2 に
保って1分間めっきを行い、図3(a)に示すような厚
さ0.2μmのCu−In合金層8をMo膜2の上に形
成した。Cu−In合金層8中のSe量を分析したが、
Seは検出されなかった。(Embodiment 6) The same Cu-In /
Make a Se dispersion plating bath. As in Example 5, the Se powder is settled at the bottom of the plating tank without operating the stirrer. In this state, the one in which the Cr film 5 and the Mo film 2 are formed on the glass substrate 1 is placed in a plating bath to be a plated object.
The plating was performed for 1 minute while setting the voltage of the object to be plated at ─1.0 V and maintaining the current density at 0.7 A / dm 2 so that both Cu and In were precipitated, as shown in FIG. The Cu—In alloy layer 8 having a thickness of 0.2 μm was formed on the Mo film 2. The Se content in the Cu—In alloy layer 8 was analyzed.
Se was not detected.
【0072】次に、攪拌機を作動させて、単位時間当た
りの流量3リットル/分で攪拌してめっき槽の底部に沈
殿していたSe粉末を浮き上がらせてめっき液中に分散
させ、この状態で被めっき体の電圧を−1.5Vに下
げ、電流密度3A/dm2 で5分間めっきを行い、図3
(b)に示すように、厚さ1.5μmのCu−In/S
e分散めっき層3をCu−In合金層8の上に形成し
た。このCu−In/Se分散めっき層3を分析したと
ころ、原子%で Cu:In:Se=32:39:29 であった。Next, the stirrer was operated to stir at a flow rate of 3 liters / minute per unit time to float the Se powder precipitated at the bottom of the plating tank and disperse it in the plating solution. The voltage of the object to be plated was reduced to -1.5 V, and plating was performed at a current density of 3 A / dm 2 for 5 minutes.
As shown in (b), Cu-In / S of 1.5 μm thickness
The e-dispersion plating layer 3 was formed on the Cu-In alloy layer 8. When the Cu—In / Se dispersed plating layer 3 was analyzed, it was Cu: In: Se = 32: 39: 29 in atomic%.
【0073】次に、実施例1と同様に、Seガスを含む
雰囲気中で熱処理して、図1(c)に示すように、Cu
InSe2 膜4に転換する。これにより実施例3と同等
の太陽電池が得られた。Next, as in the first embodiment, a heat treatment is performed in an atmosphere containing Se gas, and as shown in FIG.
Convert to InSe 2 film 4. As a result, a solar cell equivalent to that of Example 3 was obtained.
【0074】[0074]
【発明の効果】以上説明したように、本発明では、モリ
ブデン導電膜と銅−インジウム−セレン分散めっき層と
の間に導電性中間層を設けたので、モリブデン導電膜と
セレンとが直接接触するのを防ぎ、モリブデンとセレン
とが反応するのを阻止し、銅−インジウム−セレン合金
層が剥がれるのを防止することができ、歩留りを上げ、
コストを低減した太陽電池を得ることができる。As described above, in the present invention, since the conductive intermediate layer is provided between the molybdenum conductive film and the copper-indium-selenium dispersed plating layer, the molybdenum conductive film and selenium come into direct contact. To prevent the reaction of molybdenum and selenium, prevent the copper-indium-selenium alloy layer from peeling off, increase the yield,
A solar cell with reduced cost can be obtained.
【0075】本発明では、銅イオンとインジウムイオン
との還元電位が異なることを利用して印加する電位を変
えることにより一つのめっき槽、一種類のめっき液で銅
層と銅−インジウム−セレンめっき層とを形成できるよ
うにしたので、めっき装置の設備費が安くつき、設備設
置面積が広くならず、かつ工数も低減することができ、
低コストで太陽電池を製造することができる。In the present invention, the copper layer and the copper-indium-selenium plating can be performed in one plating tank and one kind of plating solution by changing the applied potential by utilizing the difference in the reduction potential between copper ions and indium ions. Since the layer can be formed, the equipment cost of the plating apparatus can be reduced, the installation area of the equipment cannot be increased, and the number of steps can be reduced.
A solar cell can be manufactured at low cost.
【0076】銅イオンとインジウムイオンとの還元電位
が異なることを利用するめっき方法は、太陽電池の製造
のみならず、一般の銅−インジウムめっきに適用でき、
設備費、設備設置面積、工数を低減することができ、低
コストでめっきを行うことができる。The plating method utilizing the difference in the reduction potential between copper ions and indium ions can be applied not only to the production of solar cells but also to general copper-indium plating.
Equipment costs, equipment installation area, and man-hours can be reduced, and plating can be performed at low cost.
【図1】本発明の太陽電池の製造方法の第1の実施例を
説明するための工程順に示した断面図である。FIG. 1 is a cross-sectional view illustrating a method of manufacturing a solar cell according to a first embodiment of the present invention in the order of steps for explaining the same.
【図2】本発明の太陽電池の製造方法の第2の実施例を
説明するための工程順に示した断面図である。FIG. 2 is a cross-sectional view illustrating a solar cell manufacturing method according to a second embodiment of the present invention in the order of steps for explaining the second embodiment.
【図3】本発明の太陽電池の製造方法の第3の実施例を
説明するための工程順に示した断面図である。FIG. 3 is a cross-sectional view illustrating a method of manufacturing a solar cell according to a third embodiment of the present invention in the order of steps for explaining the third embodiment.
【図4】本発明の分散めっきに使用するめっき浴の側面
図である。FIG. 4 is a side view of a plating bath used for the dispersion plating of the present invention.
【図5】還元電位差によるCuとCu−Inの析出開始
の差を説明する図である。FIG. 5 is a diagram illustrating a difference in the initiation of precipitation of Cu and Cu—In due to a reduction potential difference.
【図6】被めっき体の電位とCuおよびCu−Inの析
出量との関係を説明する図である。FIG. 6 is a diagram for explaining the relationship between the potential of an object to be plated and the amounts of Cu and Cu—In deposited.
【図7】設定電位と析出するCu/In比との関係を説
明する図である。FIG. 7 is a diagram for explaining a relationship between a set potential and a Cu / In ratio deposited.
【図8】Cu−In/Se分散めっきにおける攪拌流量
とSe析出量との関係を示す図である。FIG. 8 is a diagram showing the relationship between the stirring flow rate and the Se deposition amount in Cu—In / Se dispersion plating.
【図9】従来の太陽電池の製造方法の第1の例を説明す
るための工程順に示した断面図である。FIG. 9 is a cross-sectional view illustrating a first example of a conventional method of manufacturing a solar cell in the order of steps for explaining the example.
【図10】従来の薄膜太陽電池の製造において実施する
熱処理条件を示す温度プロファィル図である。FIG. 10 is a temperature profile diagram showing heat treatment conditions performed in manufacturing a conventional thin-film solar cell.
【図11】従来の太陽電池の製造方法の第2の例を説明
するための工程順に示した断面図である。FIG. 11 is a cross-sectional view illustrating a second example of a conventional method of manufacturing a solar cell in the order of steps for explaining the second example.
【図12】従来の太陽電池の製造における不良発生の機
構を説明する断面図である。FIG. 12 is a cross-sectional view illustrating a mechanism of occurrence of a defect in a conventional solar cell manufacturing.
1 ガラス基板 2 Mo膜 3 Cu−In/Se分散めっき層 4 CuInSe2 合金層 5 Cr層 6 Cu層 7 In層 8 Cu−In合金層 11 めっき槽 12 めっき液 13 被めっき体 14 対向電極 15 ポテンシオスタット RE 参照電極DESCRIPTION OF SYMBOLS 1 Glass substrate 2 Mo film 3 Cu-In / Se dispersion plating layer 4 CuInSe 2 alloy layer 5 Cr layer 6 Cu layer 7 In layer 8 Cu-In alloy layer 11 Plating tank 12 Plating solution 13 Plated object 14 Counter electrode 15 Potency Ostat RE Reference electrode
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7,DB名) H01L 31/04 - 31/078 ──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. 7 , DB name) H01L 31/04-31/078
Claims (3)
せた溶液にセレン粒子を添加しためっき液にモリブデン
導電膜を表面に有する基板を浸漬する工程と、 前記セレン粒子が沈殿している状態で、前記モリブデン
導電膜に銅のみが析出する電位を印加して前記モリブデ
ン導電膜の上に銅層を形成する工程と、 前記めっき液を攪拌して前記セレン粒子が前記めっき液
中に分散した状態で、前記モリブデン導電膜に銅とイン
ジウムが析出する電位を印加して前記銅層の上に銅−イ
ンジウム−セレンめっき層を形成する工程と、 熱処理して少なくとも前記銅−インジウム−セレンめっ
き層を銅−インジウム−セレン合金層に変換する工程と
を備えたことを特徴とする太陽電池の製造方法。A step of immersing a substrate having a molybdenum conductive film on its surface in a plating solution in which selenium particles are added to a solution in which copper ions and indium ions are dissolved; Applying a potential at which only copper is deposited on the molybdenum conductive film to form a copper layer on the molybdenum conductive film, and stirring the plating solution while the selenium particles are dispersed in the plating solution. Applying a potential at which copper and indium are deposited on the molybdenum conductive film to form a copper-indium-selenium plating layer on the copper layer; and heat treating at least the copper-indium-selenium plating layer with copper. Converting the indium-selenium alloy layer into an indium-selenium alloy layer.
せた溶液にセレン粒子を添加しためっき液にモリブデン
導電膜を表面に有する基板を浸漬する工程と、 前記セレン粒子が沈殿している状態で、前記モリブデン
導電膜に銅とインジウムが析出する電位を印加して前記
モリブデン導電膜の上に銅−インジウム合金層を形成す
る工程と、 前記めっき液を攪拌して前記セレン粒子が前記めっき液
中に分散した状態で、前記モリブデン導電膜に銅とイン
ジウムが析出する電位を印加して前記銅−インジウム合
金層の上に銅−インジウム−セレンめっき層を形成する
工程と、 熱処理して少なくとも前記銅−インジウム−セレンめっ
き層を銅−インジウム−セレン合金層に変換する工程と
を備えたことを特徴とする太陽電池の製造方法。2. a step of immersing a substrate having a molybdenum conductive film on a surface thereof in a plating solution in which selenium particles are added to a solution in which copper ions and indium ions are dissolved; Applying a potential at which copper and indium are deposited on the molybdenum conductive film to form a copper-indium alloy layer on the molybdenum conductive film, and stirring the plating solution so that the selenium particles are contained in the plating solution. Forming a copper-indium-selenium plating layer on the copper-indium alloy layer by applying a potential at which copper and indium are deposited on the molybdenum conductive film in a dispersed state; Converting the indium-selenium plating layer into a copper-indium-selenium alloy layer.
とも含むめっき液に導電膜を表面に有する基板を浸漬す
る工程と、 銅のみが析出する電位を前記導電膜に印加して前記導電
膜の上に銅層を形成する工程と、 銅とインジウムが析出する電位を前記導電膜に印加して
前記銅層の上に銅−インジウムを少なくとも含むめっき
層を形成する工程とを備えたことを特徴とするめっき方
法。3. A step of immersing a substrate having a conductive film on a surface thereof in a plating solution containing at least copper ions and indium ions, and applying a potential at which only copper is deposited to the conductive film by applying a potential to the conductive film. Forming a copper layer, and applying a potential at which copper and indium are deposited to the conductive film to form a plating layer containing at least copper-indium on the copper layer. Plating method.
Priority Applications (1)
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JP06238730A JP3097805B2 (en) | 1994-10-03 | 1994-10-03 | Solar cell, method of manufacturing the same, and plating method |
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JP06238730A JP3097805B2 (en) | 1994-10-03 | 1994-10-03 | Solar cell, method of manufacturing the same, and plating method |
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KR101172132B1 (en) * | 2009-09-30 | 2012-08-10 | 엘지이노텍 주식회사 | Solar cell and method of fabricating the same |
KR101221394B1 (en) * | 2011-04-11 | 2013-01-16 | (주) 다쓰테크 | Method for producing CIGS solar battery |
FR2983642B1 (en) * | 2011-12-05 | 2014-01-03 | Nexcis | IMPROVED INTERFACE BETWEEN A LAYER I-III-VI2 AND A REAR CONTACT LAYER IN A PHOTOVOLTAIC CELL. |
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