JPH0897450A - Thin film solar cell manufacturing method - Google Patents
Thin film solar cell manufacturing methodInfo
- Publication number
- JPH0897450A JPH0897450A JP6229516A JP22951694A JPH0897450A JP H0897450 A JPH0897450 A JP H0897450A JP 6229516 A JP6229516 A JP 6229516A JP 22951694 A JP22951694 A JP 22951694A JP H0897450 A JPH0897450 A JP H0897450A
- Authority
- JP
- Japan
- Prior art keywords
- film
- heat treatment
- group
- solar cell
- temperature
- 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.)
- Pending
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
- Y02E10/541—CuInSe2 material PV cells
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、周期律表の１Ｂ族、３
Ｂ族、及び６Ｂ族の元素からなる化合物半導体を用いて
形成された薄膜太陽電池の製造方法に関する。BACKGROUND OF THE INVENTION The present invention relates to 1B group of the periodic table, 3
The present invention relates to a method for manufacturing a thin-film solar cell formed by using a compound semiconductor composed of Group B and Group 6B elements.
【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、特開平５−２６７７０４号公報、特表平
５−５０６３３４号（国際公開ＷＯ９２／０５５８６
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。ＣｕＩｎＳ
ｅ三元合金膜を製造する方法が提案されている。2. Description of the Related Art Recently, a compound semiconductor composed of an element of Group 1B-3B-6B of the periodic table has attracted attention as a thin-film solar cell having a large photoelectric conversion efficiency and a large area, which can be manufactured at low cost. In particular, CuInSe 2 is
(1) Absorption coefficient α is as high as about 10 5 / cm, and even a thin film of about 2 μm can sufficiently absorb sunlight. (2) Forbidden band width is 1.1 eV, which is suitable for photoelectric conversion of sunlight. In particular, (3) photodegradation has the feature that it is significantly smaller than that of amorphous silicon, and therefore, it is most noticed. In order to manufacture a large-area thin film solar cell at low cost, JP-A-5-267704 and JP-A-5-506334 (International Publication WO92 / 05586).
As disclosed in Japanese Laid-Open Patent Publication No. 1989-163, a method of manufacturing a solar cell using a dispersion plating method has been proposed. CuInS
A method for producing a ternary alloy film has been proposed.
【０００３】図６は従来の化合物半導体を用いた薄膜太
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。この製造方法は、前記特開平５−
２６７７０４号公報に開示された方法である。6A to 6C are sectional views showing a first example of a method of manufacturing a conventional thin film solar cell using a compound semiconductor in the order of steps for explaining. This manufacturing method is described in the above-mentioned JP-A-5-
This is the method disclosed in Japanese Patent No. 267704.
【０００４】まず、図６（ａ）に示すように、Ｔｉ板４
１の上に電着法によりＣｕ膜４２、Ｉｎ膜４３をＣｕ／
Ｉｎのモル比が１となるように、そして膜厚が約１μｍ
になるように形成する。First, as shown in FIG. 6 (a), a Ti plate 4
Cu film 42 and In film 43 on top of No. 1 by Cu /
The molar ratio of In is 1 and the film thickness is about 1 μm
To be formed.
【０００５】次に、図７に示すような温度プロファイル
で熱処理を行う。まず、Ｎ2 ＋Ｈ2混合ガス中で室温か
ら５℃／分の速度で３００℃まで上げ、この温度に約３
０分保持した後、Ｓｅガスを導入して２時間保持し、次
にＳｅガスを停止してさらに１時間保持して残留Ｓｅガ
スを除去する。次いで、５℃／分の速度で５００℃まで
上げ、この温度に１時間保持した後、冷却する。この熱
処理により図６（ｂ）に示すようなＣｕＩｎＳｅ2 膜４
４を得る。Next, heat treatment is performed with a temperature profile as shown in FIG. First, the temperature was raised from room temperature to 300 ° C. at a rate of 5 ° C./min in a mixed gas of N 2 + H 2 and the temperature was raised to about 3
After holding for 0 minutes, Se gas is introduced and held for 2 hours, then Se gas is stopped and held for another hour to remove residual Se gas. Then, the temperature is raised to 500 ° C. at a rate of 5 ° C./minute, and this temperature is maintained for 1 hour, and then cooled. By this heat treatment, the CuInSe 2 film 4 as shown in FIG.
Get 4.
【０００６】図８は従来の化合物半導体を用いた薄膜太
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。この製造方法は、前記特表平５−
５０６３３４号公報に開示された方法である。FIG. 8 is a sectional view showing the order of steps for explaining a second example of a conventional method for manufacturing a thin film solar cell using a compound semiconductor. This manufacturing method is based on
This is the method disclosed in Japanese Patent No. 506334.
【０００７】まず、図８（ａ）に示すように、ガラス基
板５１の上に蒸着、スパッタなどの方法によりＭｏ膜５
２を形成したものを用意する。First, as shown in FIG. 8A, a Mo film 5 is formed on a glass substrate 51 by a method such as vapor deposition or sputtering.
Prepare what formed 2.
【０００８】めっき液は、次の割合で調合する。 スルファミン酸銅 ０．０１ Ｍ スルファミン酸インジウム ０．５ Ｍ スルファミン酸 ０．１０４Ｍ Ｓｅ粉末 ５０ｇ／ｌ（０．６３３Ｍ） ここで、Ｍはモル／リットルを示す。このめっき液を用
い、Ｍｏ膜５２を陰極として電流密度３Ａ／ｄｍ2 で電
着を行なってＣｕ−Ｉｎ／Ｓｅ分散めっき膜５３を形成
する。特表平５−５０６３３４号公報に開示されている
データによれば、このめっき膜の組成は、重量比（ｗｔ
％）で、 Ｃｕ：Ｉｎ：Ｓｅ＝２０．５：４４．１：３５．４ である。原子比（ａｔ％）に直して示すと、 Ｃｕ：Ｉｎ：Ｓｅ＝２８．０：３３．２：３８．８ となる。The plating solution is prepared in the following ratio. Copper sulfamate 0.01 M Indium sulfamate 0.5 M Sulfamic acid 0.104 M Se powder 50 g / l (0.633 M) Here, M represents mol / liter. Using this plating solution, electrodeposition is performed at a current density of 3 A / dm 2 using the Mo film 52 as a cathode to form a Cu-In / Se dispersed plating film 53. According to the data disclosed in Japanese Laid-Open Patent Publication No. 5-506334, the composition of this plating film has a weight ratio (wt).
%), Cu: In: Se = 20.5: 44.1: 35.4. When converted to the atomic ratio (at%), it becomes Cu: In: Se = 28.0: 33.2: 38.8.
【０００９】次に、図８（ｂ）に示すように、Ｓｅを含
むガス雰囲気中で熱処理してＣｕＩｎＳｅ2 膜５４を得
る。特表平５−５０６３３４号公報には熱処理について
開示されていないが、熱処理は、通常、図９に示すよう
に、ＡｒガスとＨ2 Ｓｅガスを混合したＡｒ＋Ｈ2 Ｓｅ
ガス雰囲気中またはＡｒガスとＳｅ蒸気を混合したＡｒ
＋Ｓｅガス雰囲気中で室温から３０℃／分の速度で２０
０℃〜２５０℃に上げ、この温度に約３０分〜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ＣｕＩｎＳｅ2
の結晶が成長する温度といわれている。Next, as shown in FIG. 8B, heat treatment is performed in a gas atmosphere containing Se to obtain a CuInSe 2 film 54. Although the heat treatment is not disclosed in JP-A-5-506334, the heat treatment is usually performed by mixing Ar gas and H 2 Se gas with Ar + H 2 Se as shown in FIG. 9.
Ar in gas atmosphere or mixed Ar gas and Se vapor
20 at room temperature + 30 ° C / min in + Se gas atmosphere
Raise to 0 ° C-250 ° C, hold at this temperature for about 30-60 minutes, then raise to 400 ° C-450 ° C at a rate of 30 ° C / min, hold at this temperature for about 2-4 hours, then It is performed under the condition of cooling to room temperature. The temperature of 200 ° C. to 250 ° C. is the temperature at which alloying begins, and the temperature of 400 ° C. to 450 ° C. is CuInSe 2
Is said to be the temperature at which the crystals grow.
【００１０】[0010]
【発明が解決しようとする課題】上記第１の例ではＣｕ
膜とＩｎ膜を別々にを形成した後に、第２の例ではＣｕ
−Ｉｎ／Ｓｅ分散めっき膜を形成した後に、Ｓｅを含む
ガス雰囲気中で熱処理してＣｕＩｎＳｅ2 膜を得ている
が、この熱処理では、図１０に示すように、Ｃｕ−Ｉｎ
合金化は均一に行われていない。図１０は第２の例のＣ
ｕＩｎＳｅ2 膜５４をオージェ電子分光器でＣｕＩｎＳ
ｅ2 膜を深さ方向に濃度測定をしたもので、横軸に深さ
を、縦軸に相対濃度をとっている。図１０から分かるよ
うに、下地（Ｍｏ膜５２）付近にＩｎが多く、膜表面付
近はＩｎが少ないという組成勾配がついてしまう。さら
にＣｕは下地に近づくに従って濃度が減少している。こ
のようにＣｕとＩｎの濃度分布が均一でないと良好なカ
ルコパイライト型のＣｕＩｎＳｅ2 結晶が得られず、Ｃ
ｕＩｎＳｅ2 膜の上に形成されるＣｄＳとの間に良好な
ｐ−ｎ接合が形成されず、従って光電変換効率が低下
し、製造歩留りが低下するという問題があった。In the above first example, Cu is used.
After forming the film and the In film separately, in the second example, Cu
After forming the -In / Se dispersed plating film, a CuInSe 2 film is obtained by heat treatment in a gas atmosphere containing Se. In this heat treatment, as shown in FIG.
The alloying is not uniform. FIG. 10 shows C of the second example.
The uInSe 2 film 54 is CuInS by Auger electron spectroscopy.
The concentration of the e 2 film was measured in the depth direction, where the horizontal axis represents the depth and the vertical axis represents the relative concentration. As can be seen from FIG. 10, there is a composition gradient in which a large amount of In is present near the base (Mo film 52) and a small amount of In is present near the film surface. Further, the concentration of Cu decreases as it gets closer to the base. If the concentration distribution of Cu and In is not uniform in this way, a good chalcopyrite type CuInSe 2 crystal cannot be obtained, and C
There is a problem that a good pn junction is not formed with CdS formed on the uInSe 2 film, so that the photoelectric conversion efficiency is lowered and the manufacturing yield is lowered.
【００１１】本発明の目的は、周期律表の１Ｂ族、３Ｂ
族、及び６Ｂ族の元素を含む膜を熱処理により合金化し
て光吸収膜とする薄膜太陽電池の製造において、均一組
成の合金膜が得られ、高光電変換効率を有する薄膜太陽
電池を高い製造歩留りで製造することのできる薄膜太陽
電池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 group 1B, 3B of the periodic table.
In the manufacture of a thin film solar cell in which a film containing a Group 6 element and a Group 6B element is alloyed by heat treatment to form a light absorbing film, an alloy film having a uniform composition is obtained, and a thin film solar cell having high photoelectric conversion efficiency is manufactured at a high yield Another object of the present invention is to provide a method for manufacturing a thin-film solar cell that can be manufactured by.
【００１２】[0012]
【課題を解決するための手段】本発明は、表面に導電膜
を有する基板の上に周期律表の１Ｂ族、３Ｂ族、及び６
Ｂ族の元素を含む膜を形成する工程と、前記膜を６Ｂ族
元素を含むガス雰囲気中で熱処理して１Ｂ族−３Ｂ族−
６Ｂ族元素の合金膜に転換する合金化熱処理工程とを有
する薄膜太陽電池の製造方法において、前記合金化熱処
理を行う前に前記膜に含まれる１Ｂ族−３Ｂ族元素の均
一分布化熱処理を行うことを特徴とする。According to the present invention, a 1B group, 3B group, and 6 group of the periodic table are provided on a substrate having a conductive film on its surface.
Forming a film containing a group B element, and subjecting the film to heat treatment in a gas atmosphere containing a group 6B element to form a group 1B-3B group-
In the method for manufacturing a thin-film solar cell, which comprises a step of alloying heat treatment for converting to an alloy film of a group 6B element, a heat treatment for uniform distribution of the group 1B-3B elements contained in the film is performed before the alloying heat treatment. It is characterized by
【００１３】本発明は、前記均一分布化熱処理が非酸化
雰囲気中で行われることを特徴とする。The present invention is characterized in that the uniform distribution heat treatment is performed in a non-oxidizing atmosphere.
【００１４】本発明は、前記均一分布化熱処理が真空中
で行われることを特徴とする。The present invention is characterized in that the heat treatment for uniform distribution is performed in a vacuum.
【００１５】本発明は、前記均一分布化熱処理が前記膜
を構成している元素の融点の内最も低い融点以上で、か
つ前記合金化熱処理の最低温度よりも１０℃低い温度以
下の範囲内で行われることを特徴とする。According to the present invention, the uniform distribution heat treatment is performed within a range of the lowest melting point of the elements constituting the film or higher, and 10 ° C. or lower than the lowest temperature of the alloying heat treatment. It is characterized by being performed.
【００１６】本発明は、前記１Ｂ族、３Ｂ族、及び６Ｂ
族の元素を含む膜が銅−インジウム−セレンを含む膜で
あることを特徴とする。The present invention provides the above-mentioned 1B group, 3B group, and 6B
The film containing a group element is a film containing copper-indium-selenium.
【００１７】本発明は、前記均一分布化熱処理が１５７
℃以上で、かつ１９０℃以下の温度範囲内で行われるこ
とを特徴とする。In the present invention, the uniform heat treatment for distribution is 157.
It is characterized in that it is carried out within a temperature range of not lower than 0 ° C and not higher than 190 ° C.
【００１８】[0018]
【作用】薄膜太陽電池の光吸収膜としての１Ｂ族、３Ｂ
族、及び６Ｂ族の元素を含む膜をめっき法で形成し、熱
処理してこの膜を合金膜に変換すると、膜の深さ方向の
組成分布が均一にならない。これは、いきなり高温熱処
理すると膜の組成元素が拡散する暇がなく、その場で合
金を作ってしまうためと考えられる。それ故、高温で合
金化熱処理する前にこの温度より低い温度で均一分布化
熱処理を行い、膜の組成元素が十分に拡散して均一に分
布するようにする。[Function] Group 1B, 3B as a light absorbing film of a thin film solar cell
When a film containing a Group 6 element and a Group 6B element is formed by a plating method and heat treated to convert the film into an alloy film, the composition distribution in the depth direction of the film is not uniform. It is considered that this is because when the high temperature heat treatment is suddenly performed, the composition elements of the film do not have time to diffuse and an alloy is formed on the spot. Therefore, before the alloying heat treatment at a high temperature, the uniform distribution heat treatment is performed at a temperature lower than this temperature so that the composition elements of the film are sufficiently diffused and uniformly distributed.
【００１９】この均一分布化熱処理において、１Ｂ族、
３Ｂ族、及び６Ｂ族の元素を含む膜が酸化してはいけな
いので、均一分布化熱処理は非酸化雰囲気中で行う。In this uniform distribution heat treatment, 1B group,
Since the film containing the 3B group and 6B group elements should not be oxidized, the uniform distribution heat treatment is performed in a non-oxidizing atmosphere.
【００２０】この均一分布化熱処理は、真空中で行うと
効率がよい。This uniform distribution heat treatment is efficient when performed in a vacuum.
【００２１】均一分布化熱処理は、膜の組成元素が十分
に拡散して均一に分布するようにする熱処理であるか
ら、膜を構成している元素の融点の内最も低い融点以上
の温度で熱処理すると効率がよい。また、合金化が始ま
ると溶融している元素が余り拡散しなくなるので、合金
化処理の最低温度より１０℃低い温度以下で行うのがよ
い。Since the uniform distribution heat treatment is a heat treatment for sufficiently diffusing the constituent elements of the film so that the constituent elements are uniformly distributed, the heat treatment is performed at a temperature equal to or higher than the lowest melting point of the melting points of the elements constituting the film. Then it is efficient. Further, when alloying starts, molten elements do not diffuse much, so it is preferable to carry out at a temperature 10 ° C. lower than the lowest temperature of alloying treatment.
【００２２】本発明の方法は、周期律表の１Ｂ族、３Ｂ
族、及び６Ｂ族の元素を含む膜をめっき法を利用して作
ったすべての薄膜太陽電池に適用されるのであるが、そ
の中でもＣｕ−Ｉｎ−Ｓｅ三元合金が優れた光電変換効
率を有するので、特にＣｕ−Ｉｎ−Ｓｅを含む膜に適用
すると効果的である。The method of the present invention is carried out according to the groups 1B and 3B of the periodic table.
It is applied to all thin-film solar cells prepared by using a plating method to form a film containing a Group 6 element and a Group 6B element. Among them, a Cu-In-Se ternary alloy has excellent photoelectric conversion efficiency. Therefore, it is particularly effective when applied to a film containing Cu-In-Se.
【００２３】光電変換性半導体膜がＣｕ−Ｉｎ−Ｓｅを
含む膜である場合、最も融点が低いのはＩｎであり、そ
の融点は１５６．６℃であるので、均一分布化熱処理
は、１５７℃室温以上で、かつ合金化処理の最低温度２
００℃より１０℃低い１９０℃以下で行うのがよい。When the photoelectric conversion semiconductor film is a film containing Cu—In—Se, In has the lowest melting point and its melting point is 156.6 ° C., so the uniform distribution heat treatment is 157 ° C. At room temperature or above and minimum temperature of alloying process 2
It is preferable to carry out at 190 ° C or lower, which is 10 ° C lower than 00 ° C.
【００２４】[0024]
【実施例】図１は本発明の一実施例を説明するための工
程順に示した断面図である。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS FIGS. 1A to 1D are sectional views showing steps in order to explain one embodiment of the present invention.
【００２５】まず、図１（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
形成したものを用意する。First, as shown in FIG. 1A, a glass substrate 1 having a Mo film 2 formed thereon by a method such as vapor deposition and sputtering is prepared.
【００２６】分散めっき液は下記組成で調合した。 スルファミン酸銅 ０．０１ Ｍ スルファミン酸インジウム ０．５ Ｍ スルファミン酸 ０．１０４Ｍ Ｓｅ粉末 ５０ｇ／ｌ（０．６３３Ｍ） ここで、Ｍはモル／リットルを示す。The dispersion plating solution was prepared with the following composition. Copper sulfamate 0.01 M Indium sulfamate 0.5 M Sulfamic acid 0.104 M Se powder 50 g / l (0.633 M) Here, M represents mol / liter.
【００２７】このめっき液を用い、Ｍｏ膜２を陰極とし
て電流密度２Ａ／ｄｍ2 で２分間分散めっきを行って、
図１（ａ）に示すように、厚さ約２μｍのＣｕ−Ｉｎ／
Ｓｅ分散めっき膜３を形成する。Using this plating solution, dispersion plating was performed at a current density of 2 A / dm 2 for 2 minutes with the Mo film 2 as a cathode,
As shown in FIG. 1A, Cu-In / having a thickness of about 2 μm is used.
The Se dispersed plating film 3 is formed.
【００２８】図４は図１（ａ）に示すＣｕ−Ｉｎ／Ｓｅ
分散めっき膜の深さ方向の相対濃度分布図である。FIG. 4 shows the Cu-In / Se shown in FIG.
FIG. 5 is a relative concentration distribution diagram in the depth direction of the dispersion plated film.
【００２９】図１（ａ）のＣｕ−Ｉｎ／Ｓｅ分散めっき
膜３の深さ方向の組成分布をオージェ電子分析器で調べ
た。図４に示されるように、Ｉｎは膜表面付近で少な
く、下地（Ｍｏ膜２）に近づくに従って多くなってい
る。これに対してＣｕは膜表面付近でＩｎより多く、下
地に近づくに従ってＩｎより少なくなっている。The composition distribution in the depth direction of the Cu-In / Se dispersed plating film 3 of FIG. 1 (a) was examined by an Auger electron analyzer. As shown in FIG. 4, In is small in the vicinity of the film surface and increases as it approaches the base (Mo film 2). On the other hand, Cu is larger than In in the vicinity of the film surface and is smaller than In as it gets closer to the base.
【００３０】ＣｕとＩｎを同時にめっきするとき、この
ような現象が起こるのはＣｕとＩｎの還元電位が離れて
いてＩｎがＣｕよりも析出しにくいことに起因すると考
えられる。ＣｕとＩｎの還元反応は次式で表される。 Ｃｕ++ ＋２ｅ- → Ｃｕ（還元電位Ｖ＝＋０．３３７Ｖ） …（１） Ｉｎ+++ ＋３ｅ- → Ｉｎ（還元電位Ｖ＝−０．３３８Ｖ） …（２） ここで、還元電位Ｖは、ＮＨＥ（Ｎｏｒｍａｌ Ｈｙｄ
ｒｏｇｅｎ Ｅｌｅｃｔｒｏｄｅ、標準水素電極）を基
準として、これに対する電位で示されている。When Cu and In are plated at the same time, it is considered that such a phenomenon occurs because the reduction potentials of Cu and In are apart from each other and In is less likely to precipitate than Cu. The reduction reaction of Cu and In is represented by the following equation. Cu ++ + 2e − → Cu (reduction potential V = + 0.337V) (1) In +++ + 3e − → In (reduction potential V = −0.338V) (2) Here, the reduction potential V is NHE (Normal Hyd
Rogen Electrode (standard hydrogen electrode) is used as a reference, and the potential is shown.
【００３１】このようにＩｎの還元電位はＣｕよりも
０．６７５Ｖも低いので、同時めっきではＩｎはＣｕよ
りも析出しにくいことになる。これを補うために、めっ
き液ではＩｎイオンをＣｕイオンの５０倍も多く加えて
Ｉｎ析出量がＣｕ析出量とほぼ同じになるようにしてい
る。しかし、平均値ではＣｕとＩｎとがほぼ同量に析出
するようにしても、深さ方向に均一に析出する訳ではな
い。それは、めっき初期にはＩｎイオン濃度が高く、Ｉ
ｎが多く析出するが、Ｉｎの析出に伴ってめっき液中の
Ｉｎイオン濃度が段々低くなり、Ｉｎ析出量が段々減っ
てくるからである。Ｉｎ析出量の減少に伴って相対的に
Ｃｕ析出量が増加する。図４はこのことを示している。Since the reduction potential of In is 0.675 V lower than that of Cu, In is less likely to precipitate than Cu in simultaneous plating. In order to compensate for this, the plating solution is added with 50 times more In ions than Cu ions so that the In precipitation amount becomes substantially the same as the Cu precipitation amount. However, even if Cu and In are deposited in the same amount in the average value, they are not uniformly deposited in the depth direction. At the beginning of plating, the In ion concentration is high and I
Although a large amount of n is deposited, the concentration of In ions in the plating solution is gradually lowered as the In is deposited, and the amount of In deposited is gradually reduced. The Cu precipitation amount relatively increases as the In precipitation amount decreases. FIG. 4 illustrates this.
【００３２】図４に示す組成分布をもったまま、図９で
説明した合金化熱処理を行うと、Ｉｎが余り拡散するこ
となくその場でＣｕと合金を作るので、図１０に示した
ような組成分布となる。そこで、本発明では、合金化熱
処理を行う前に、ＩｎがＣｕの中に拡散して均一組成と
なるように均一分布化熱処理を行う。均一分布化熱処理
は、拡散を効率良く行わせるため、化合物半導体膜を構
成している元素の融点の内最も低い融点以上で、かつ合
金化熱処理の最低温度よりも１０℃低い温度以下の範囲
内で行う。拡散は融点より低い温度でも行われるが、温
度が低いと拡散に時間がかかり、効率がよくない。膜組
成元素の一つが溶融状態にあるとき、拡散が効率良く行
われるので、熱処理温度は、膜組成元素の内最も低い融
点以上にする。また、合金化が始まると溶融した組成元
素が余り拡散しない内に合金を作ってしまうので、熱処
理温度は合金化熱処理温度より低くしなければならな
い。拡散が効率良く行われためには合金化熱処理温度よ
りも１０℃低い温度が上限となる。このような理由か
ら、均一分布化熱処理の温度範囲を、化合物半導体膜を
構成している元素の融点の内最も低い融点以上で、かつ
合金化熱処理の最低温度よりも１０℃低い温度以下と定
める。When the alloying heat treatment described with reference to FIG. 9 is performed with the composition distribution shown in FIG. 4 being formed, an alloy is formed with Cu on the spot without much diffusion of In. Therefore, as shown in FIG. It has a composition distribution. Therefore, in the present invention, prior to the alloying heat treatment, the uniform distribution heat treatment is performed so that In diffuses into Cu and has a uniform composition. The uniform distribution heat treatment is performed in a range of not less than the lowest melting point of the elements constituting the compound semiconductor film and not more than 10 ° C. lower than the lowest temperature of the alloying heat treatment in order to efficiently perform the diffusion. Done in. Diffusion occurs even at a temperature lower than the melting point, but if the temperature is low, the diffusion takes time and is not efficient. When one of the film composition elements is in a molten state, the diffusion is efficiently performed, and therefore the heat treatment temperature is set to be the lowest melting point or higher of the film composition elements. Further, when alloying starts, a molten composition element forms an alloy before being diffused so much, so the heat treatment temperature must be lower than the alloying heat treatment temperature. For efficient diffusion, the upper limit is a temperature 10 ° C. lower than the alloying heat treatment temperature. For this reason, the temperature range of the uniform distribution heat treatment is set to a temperature that is equal to or higher than the lowest melting point of the melting points of the elements forming the compound semiconductor film and is 10 ° C. or lower than the lowest temperature of the alloying heat treatment. .
【００３３】この熱処理において、膜組成物が酸化して
はいけないので、熱処理は非酸化雰囲気中で行う。非酸
化雰囲気として真空、Ｈ2 、Ｈ2 ＋Ｎ2 等を用いること
ができるが、均一分布化熱処理の後で行われる合金化熱
処理との関連から、真空が最も好ましい。Since the film composition should not be oxidized in this heat treatment, the heat treatment is performed in a non-oxidizing atmosphere. As the non-oxidizing atmosphere, vacuum, H 2 , H 2 + N 2 or the like can be used, but vacuum is most preferable in relation to the alloying heat treatment performed after the uniform distribution heat treatment.
【００３４】図２は本発明の実施例で行う均一分布化熱
処理の条件を説明する温度プロファィル図である。FIG. 2 is a temperature profile diagram for explaining the conditions of the uniform distribution heat treatment performed in the embodiment of the present invention.
【００３５】均一分布化熱処理する対象物がＣｕ−Ｉｎ
／Ｓｅ分散めっき膜である場合、最も融点が低いのはＩ
ｎであり、その融点は１５６．６℃であるので、均一分
布化熱処理の下限温度を１５７℃に設定し、上限温度を
合金化熱処理の最低温度２００℃よりも１０℃低い１９
０℃に設定する。室温から３０℃／分の速度で１５７℃
〜１９０℃に上げ、この温度に約３０〜６０分保持して
ＩｎをＣｕ中に拡散させる。The object of the uniform heat treatment is Cu-In.
/ Se dispersed plating film has the lowest melting point I
n and its melting point is 156.6 ° C., so the lower limit temperature of the uniform distribution heat treatment is set to 157 ° C. and the upper limit temperature is 10 ° C. lower than the minimum temperature 200 ° C. of the alloying heat treatment.
Set to 0 ° C. 157 ° C at a rate of 30 ° C / min from room temperature
Raise to 190 ° C. and hold at this temperature for about 30 to 60 minutes to diffuse In into Cu.
【００３６】以上の均一分布化熱処理が終了すると、従
来と同じ合金化処理を続けて行う。すなわち、Ａｒガス
とＨ2 Ｓｅガスを混合したＡｒ＋Ｈ2 Ｓｅガス雰囲気中
またはＡｒガスとＳｅ蒸気を混合したＡｒ＋Ｓｅガスを
導入して、この雰囲気中で３０℃／分の速度で２００℃
〜２５０℃に上げ、この温度に約３０〜６０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時間保持して合金化処理を行い、その
後室温まで冷却する。以上の熱処理を行うには真空加熱
がてきる熱処理炉が最も好ましい。When the above uniform distribution heat treatment is completed, the same alloying treatment as the conventional one is continuously performed. That is, an Ar + H 2 Se gas atmosphere in which Ar gas and H 2 Se gas are mixed or an Ar + Se gas in which Ar gas and Se vapor are mixed are introduced, and 200 ° C. at a rate of 30 ° C./min in this atmosphere.
Up to 250 ° C and hold at this temperature for about 30-60 minutes,
Next, the temperature is raised to 400 ° C. to 450 ° C. at a rate of 30 ° C./minute, and this temperature is maintained for about 2 to 4 hours for alloying treatment, and then cooled to room temperature. In order to carry out the above heat treatment, a heat treatment furnace capable of vacuum heating is most preferable.
【００３７】図３は本発明の実施例で使用する熱処理炉
の構成図である。FIG. 3 is a block diagram of a heat treatment furnace used in the embodiment of the present invention.
【００３８】めっきで形成された膜を有するガラス基板
１（これをサンプル１１と称する）を炉室２１に入れ、
リーク弁２４、主弁２７、ガス導入弁２８を閉じ、弁２
９を開け、三方弁２５を炉室２１側に切替え、油回転ポ
ンプ２２を起動させる。炉室２１内の気圧が約１Ｐａ以
下になったら三方弁２５を油拡散ポンプ２３側に切替
え、油拡散ポンプ２３を起動させ、主弁２７を開く。ヒ
ータ３０に通電してサンプル１１を加熱する。サンプル
１１の加熱温度の制御は温度センサ３２と温度制御装置
３３を用いて行う。A glass substrate 1 having a film formed by plating (this is referred to as sample 11) is placed in a furnace chamber 21,
The leak valve 24, the main valve 27, and the gas introduction valve 28 are closed, and the valve 2
9, the three-way valve 25 is switched to the furnace chamber 21 side, and the oil rotary pump 22 is started. When the atmospheric pressure in the furnace chamber 21 becomes about 1 Pa or less, the three-way valve 25 is switched to the oil diffusion pump 23 side, the oil diffusion pump 23 is activated, and the main valve 27 is opened. The heater 30 is energized to heat the sample 11. The heating temperature of the sample 11 is controlled by using the temperature sensor 32 and the temperature control device 33.
【００３９】均一分布化熱処理が終了したら、主弁２７
を閉じ、ガス導入弁２８を開き、ＡｒガスとＨ2 Ｓｅガ
スを混合したＡｒ＋Ｈ2 Ｓｅガス雰囲気中またはＡｒガ
スとＳｅ蒸気を混合したＡｒ＋Ｓｅガスを導入して、こ
の雰囲気中で３０℃／分の速度で２００℃〜２５０℃に
上げ、この温度に約３０〜６０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時間保持して合金化処理を行う。ヒータ３０の通電
を停止し、ガス導入弁２８を閉じ、主弁２７を開いてＳ
ｅを含むガスを排気する。サンプル１１が室温まで冷却
したら弁２９を閉じ、炉室２１からサンプル１１を取り
出す。When the uniform distribution heat treatment is completed, the main valve 27
Closed, the gas introduction valve 28 is opened, and an Ar + H 2 Se gas atmosphere in which Ar gas and H 2 Se gas are mixed or an Ar + Se gas in which Ar gas and Se vapor are mixed are introduced and 30 ° C./min in this atmosphere. At a rate of 200 ° C to 250 ° C, hold at this temperature for about 30 to 60 minutes, then at 30 ° C /
Raise to 400-450 ℃ at the speed of a minute, and at this temperature about 2
Hold for 4 hours to perform alloying treatment. The heater 30 is de-energized, the gas introduction valve 28 is closed, the main valve 27 is opened and S
The gas containing e is exhausted. When the sample 11 is cooled to room temperature, the valve 29 is closed and the sample 11 is taken out from the furnace chamber 21.
【００４０】以上説明した均一分布化熱処理およびそれ
に続く合金化処理を行って、図１（ｂ）に示すＣｕＩｎ
Ｓｅ2 膜４を形成した。The uniform distribution heat treatment described above and the subsequent alloying treatment are performed to obtain CuIn shown in FIG. 1 (b).
The Se 2 film 4 was formed.
【００４１】図５は均一分布化熱処理したＣｕ−Ｉｎ／
Ｓｅ分散めっき膜の深さ方向の相対濃度分布図である。FIG. 5 shows Cu-In / which has been heat-treated for uniform distribution.
FIG. 6 is a relative concentration distribution diagram in the depth direction of the Se-dispersed plating film.
【００４２】温度１９０℃で３０分の均一分布化熱処理
したＣｕ−Ｉｎ／Ｓｅ分散めっき膜の深さ方向の組成分
布をオージェ電子分析器で調べ。図５に示されるよう
に、Ｉｎは膜全体に均一に分布しており、均一分布化熱
処理が組成の均一化に非常に有効であることが証明され
た。なお、Ｓｅの相対濃度が低いのは、この試料がＳｅ
ガス雰囲気中での合金化熱処理を行う前の試料だからで
ある。The composition distribution in the depth direction of the Cu-In / Se dispersion-plated film which was heat-treated for uniform distribution for 30 minutes at a temperature of 190 ° C. was examined by an Auger electron analyzer. As shown in FIG. 5, In was uniformly distributed throughout the film, and it was proved that the heat treatment for uniform distribution was very effective for uniforming the composition. The relative concentration of Se is low because this sample is Se
This is because it is a sample before alloying heat treatment in a gas atmosphere.
【００４３】上記実施例はＣｕ−Ｉｎ−Ｓｅを含む膜に
ついて行ったが、本発明はこれに限定されず、周期律表
の１Ｂ族、３Ｂ族、及び６Ｂ族の元素を含む膜をめっき
法で作ったすべての薄膜太陽電池に適用されるものであ
る。Although the above embodiment was carried out on a film containing Cu-In-Se, the present invention is not limited to this, and a film containing elements of 1B group, 3B group and 6B group of the periodic table is plated. It is applied to all thin-film solar cells made in.
【００４４】[0044]
【発明の効果】以上説明したように、本発明では、めっ
き法で形成されている光電変換性半導体の先駆生成物膜
を合金膜に変換して光電変換性半導体膜とする合金化熱
処理を行う前に膜組成元素を均一に分布させる均一分布
化熱処理を行うようにしたので、ＣｕとＩｎとが膜全体
に均一に分布し、良好なカルコパイライト型の結晶が形
成され、良好なｐ−ｎ接合が形成されることによって光
電変換効率が向上し、高い製造歩留りと低コストで薄膜
太陽電池を製造することができる。As described above, in the present invention, alloying heat treatment is performed to convert a precursor product film of a photoelectric conversion semiconductor formed by a plating method into an alloy film to form a photoelectric conversion semiconductor film. Since the uniform distribution heat treatment for uniformly distributing the film composition elements is performed before, Cu and In are uniformly distributed in the entire film, and a good chalcopyrite type crystal is formed, and a good pn By forming the junction, the photoelectric conversion efficiency is improved, and the thin film solar cell can be manufactured with high manufacturing yield and low cost.
【図面の簡単な説明】[Brief description of drawings]
【図１】本発明の薄膜太陽電池の製造方法の一実施例を
説明するための工程順に示した断面図である。1A to 1D are cross-sectional views showing a process sequence for explaining an example of a method for manufacturing a thin-film solar cell of the present invention.
【図２】本発明の実施例で行う均一分布化熱処理の条件
を説明する温度プロファィル図である。FIG. 2 is a temperature profile diagram for explaining conditions of uniform distribution heat treatment performed in an example of the present invention.
【図３】本発明の実施例で使用する熱処理炉の構成図で
ある。FIG. 3 is a configuration diagram of a heat treatment furnace used in an example of the present invention.
【図４】図１（ａ）に示すＣｕ−Ｉｎ／Ｓｅ分散めっき
膜の深さ方向の相対濃度分布図である。FIG. 4 is a relative concentration distribution diagram in the depth direction of the Cu—In / Se dispersed plating film shown in FIG.
【図５】均一分布化熱処理したＣｕ−Ｉｎ／Ｓｅ分散め
っき膜の深さ方向の相対濃度分布図である。FIG. 5 is a relative concentration distribution diagram in the depth direction of a Cu—In / Se dispersed plating film subjected to uniform distribution heat treatment.
【図６】従来の化合物半導体を用いた薄膜太陽電池の製
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. 6 is a cross-sectional view showing the order of steps for explaining a first example of a method for manufacturing a thin-film solar cell using a conventional compound semiconductor.
【図７】従来の第１の例の薄膜太陽電池の製造において
実施する熱処理の条件を説明する温度プロファィル図で
ある。FIG. 7 is a temperature profile diagram for explaining the conditions of heat treatment performed in the manufacture of the conventional first example thin-film solar cell.
【図８】従来の化合物半導体を用いた薄膜太陽電池の製
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. 8 is a cross-sectional view showing the order of steps for explaining a second example of a method for manufacturing a thin-film solar cell using a conventional compound semiconductor.
【図９】従来の第２の例の薄膜太陽電池の製造において
実施する熱処理の条件を説明する温度プロファィル図で
ある。FIG. 9 is a temperature profile diagram for explaining conditions of heat treatment carried out in the production of the conventional thin-film solar cell of the second example.
【図１０】従来の第２の例のＣｕＩｎＳｅ2 膜の深さ方
向の相対濃度分布図である。FIG. 10 is a relative concentration distribution diagram in the depth direction of a CuInSe 2 film of a second conventional example.
１ ガラス基板 ２ Ｍｏ膜 ３ Ｃｕ−Ｉｎ／Ｓｅ分散めっき膜 ４ ＣｕＩｎＳｅ2 膜1 Glass substrate 2 Mo film 3 Cu-In / Se dispersed plating film 4 CuInSe 2 film
Claims (6)
表の１Ｂ族、３Ｂ族、及び６Ｂ族の元素を含む膜を形成
する工程と、前記膜を６Ｂ族元素を含むガス雰囲気中で
熱処理して１Ｂ族−３Ｂ族−６Ｂ族元素の合金膜に転換
する合金化熱処理工程とを有する薄膜太陽電池の製造方
法において、 前記合金化熱処理を行う前に前記膜に含まれる１Ｂ族−
３Ｂ族元素の均一分布化熱処理を行うことを特徴とする
薄膜太陽電池の製造方法。1. A step of forming a film containing elements of the 1B group, 3B group and 6B group of the periodic table on a substrate having a conductive film on the surface thereof, and the film in a gas atmosphere containing the 6B group element. In the method for manufacturing a thin film solar cell, the method comprises: an alloying heat treatment step of converting the alloy film of a 1B group-3B group-6B group element by heat treatment at 1B-group contained in the film before the alloying heat treatment.
A method for manufacturing a thin-film solar cell, characterized by performing heat treatment for uniform distribution of a Group 3B element.
で行われることを特徴とする請求項１記載の薄膜太陽電
池の製造方法。2. The method for manufacturing a thin film solar cell according to claim 1, wherein the uniform distribution heat treatment is performed in a non-oxidizing atmosphere.
ることを特徴とする請求項１または請求項２記載の薄膜
太陽電池の製造方法。3. The method for manufacturing a thin film solar cell according to claim 1, wherein the heat treatment for uniform distribution is performed in a vacuum.
ている元素の融点の内最も低い融点以上で、かつ前記合
金化熱処理の最低温度よりも１０℃低い温度以下の範囲
内で行われることを特徴とする請求項１または請求項２
または請求項３記載の薄膜太陽電池の製造方法。4. The uniform distribution heat treatment is performed within a range of the lowest melting point of the elements constituting the film or higher and 10 ° C. or lower than the lowest temperature of the alloying heat treatment. Claim 1 or claim 2 characterized in that
Or the manufacturing method of the thin film solar cell of Claim 3.
を含む膜が銅−インジウム−セレンを含む膜であること
を特徴とする請求項１記載の薄膜太陽電池の製造方法。5. The method for manufacturing a thin-film solar cell according to claim 1, wherein the film containing the elements of 1B group, 3B group, and 6B group is a film containing copper-indium-selenium.
で、かつ１９０℃以下の温度範囲内で行われることを特
徴とする請求項１または請求項２または請求項３または
請求項４記載の薄膜太陽電池の製造方法。6. The thin film according to claim 1, wherein the heat treatment for uniform distribution is performed within a temperature range of 157 ° C. or higher and 190 ° C. or lower. Method for manufacturing solar cell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6229516A JPH0897450A (en) | 1994-09-26 | 1994-09-26 | Thin film solar cell manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6229516A JPH0897450A (en) | 1994-09-26 | 1994-09-26 | Thin film solar cell manufacturing method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0897450A true JPH0897450A (en) | 1996-04-12 |
Family
ID=16893403
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6229516A Pending JPH0897450A (en) | 1994-09-26 | 1994-09-26 | Thin film solar cell manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0897450A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012109559A (en) * | 2010-10-29 | 2012-06-07 | Kyocera Corp | Photoelectric conversion device |
| JP2014022562A (en) * | 2012-07-18 | 2014-02-03 | Kyocera Corp | Method for manufacturing photoelectric conversion device |
| WO2017187871A1 (en) * | 2016-04-28 | 2017-11-02 | 国立研究開発法人産業技術総合研究所 | High power generation efficiency compound semiconductor thin-film solar cell, and method for manufacturing same |
-
1994
- 1994-09-26 JP JP6229516A patent/JPH0897450A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012109559A (en) * | 2010-10-29 | 2012-06-07 | Kyocera Corp | Photoelectric conversion device |
| JP2014022562A (en) * | 2012-07-18 | 2014-02-03 | Kyocera Corp | Method for manufacturing photoelectric conversion device |
| WO2017187871A1 (en) * | 2016-04-28 | 2017-11-02 | 国立研究開発法人産業技術総合研究所 | High power generation efficiency compound semiconductor thin-film solar cell, and method for manufacturing same |
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