JP3007179B2 - Semiconductor thick film fabrication method - Google Patents
Semiconductor thick film fabrication methodInfo
- Publication number
- JP3007179B2 JP3007179B2 JP3073875A JP7387591A JP3007179B2 JP 3007179 B2 JP3007179 B2 JP 3007179B2 JP 3073875 A JP3073875 A JP 3073875A JP 7387591 A JP7387591 A JP 7387591A JP 3007179 B2 JP3007179 B2 JP 3007179B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- cuinse
- thickness
- thick film
- present
- 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
- Y02E10/541—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
Description
【０００１】[0001]
【産業上の利用分野】本発明は、光センサーや太陽電池
などに応用されるCuInSe2 膜の作製方法に関し、さらに
詳しくはMo膜上にMo膜との密着性に富むCuInSe2 の厚膜
を作製する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a CuInSe 2 film applied to an optical sensor or a solar cell, and more particularly to a method for forming a thick film of CuInSe 2 on a Mo film, which has high adhesion to the Mo film. It relates to a manufacturing method.
【０００２】[0002]
【従来の技術】CuInSe2 系太陽電池において、CuInSe2
はｐ形半導体として利用されている。一方、CuInSe2 の
オーミック電極としては、接触抵抗がAuやPtよりも小さ
いことから、通常Moが用いられている（例えば雑誌 J.
Vac. Sci. Technol. A7, 837,1989）。 2. Description of the Related Art CuInSe 2 based solar cells include CuInSe 2
Are used as p-type semiconductors. On the other hand, Mo is usually used as an ohmic electrode of CuInSe 2 because contact resistance is smaller than Au or Pt (for example, magazine J.
Vac. Sci. Technol. A7, 837, 1989).
【０００３】しかしながら、Mo膜からCuInSe2 膜が剥離
する現象がしばしば認められるという問題があり、これ
を防止する手段として、Mo膜とCuInSe2 膜との間にGaを
含む層を入れることなどが提案されている（例えば特開
平2-94669 号）[0003] However, there is a problem that the phenomenon that the CuInSe 2 film is peeled off from the Mo film is often recognized. As a means for preventing this, for example, a Ga-containing layer is inserted between the Mo film and the CuInSe 2 film. It has been proposed (for example, JP-A-2-94669)
【０００４】[0004]
【発明が解決しようとする課題】上述のようにGaを含む
層をMo膜とCuInSe2 膜との間に挟むには、Mo膜上にGaを
含有する層をスパッターや蒸着などによって作製する工
程を要するため、これらの装置や材料を新たに準備しな
ければならず、工程の複雑化とコストの上昇という問題
があった。In order to sandwich a Ga-containing layer between a Mo film and a CuInSe 2 film as described above, a step of forming a Ga-containing layer on the Mo film by sputtering, vapor deposition, or the like. Therefore, these devices and materials must be newly prepared, and there has been a problem that the process becomes complicated and the cost increases.
【０００５】そこで、本発明は、Mo膜とCuInSe2 膜間の
密着性を改善するに当り、上記提案のようにGa層等の第
３の金属層を形成する方法を用いずに、Mo膜上に直接Cu
InSe2 膜を形成する既存の技術を改良することによって
両者の密着性を高め、安定なCuInSe2 半導体厚膜を作製
する方法の提供を目的としている。In order to improve the adhesion between a Mo film and a CuInSe 2 film, the present invention does not use a method of forming a third metal layer such as a Ga layer as described above, but uses a Mo film. Cu directly on top
It is an object of the present invention to provide a method for producing a stable CuInSe 2 semiconductor thick film by improving the existing technology for forming an InSe 2 film to enhance the adhesion between the two and improve the existing technology.
【０００６】[0006]
【課題を解決するための手段】本発明者は斯る課題を解
決するために鋭意研究した結果、Mo膜上に形成するCuIn
Se2 膜の厚さが 0.2μｍ以下であると「しわ」の発生が
まったくないことに記がつき、本発明のように密着性に
富み、所望の膜厚を有する半導体膜を作製することがで
きることを見い出し、本発明法を提供できた。Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, have found that CuIn
When the thickness of the Se 2 film is 0.2 μm or less, it is noted that generation of “wrinkles” does not occur at all, and as in the present invention, it is possible to produce a semiconductor film having high adhesion and a desired film thickness. They found what they could do and could provide the method of the present invention.
【０００７】すなわち本発明は、Mo膜上に 0.2μｍ以上
の厚さを有するCuInSe2 膜を作製する方法において、予
め 0.2μｍ以下のCuInSe2 膜を設けた後に、順次CuInSe
2膜を積層することにより所望の厚膜となすことを特徴
とする半導体厚膜の作製方法に関するものである。ただ
し、上述の初期形成薄膜の下限値は0.01μｍ程度である
と認められる。[0007] The present invention provides a method of making a CuInSe 2 film having more than 0.2μm thickness on the Mo film, after providing a pre 0.2μm following CuInSe 2 film, sequentially CuInSe
The present invention relates to a method for manufacturing a semiconductor thick film, characterized in that a desired thickness is obtained by laminating two films. However, it is recognized that the lower limit of the above-mentioned initially formed thin film is about 0.01 μm.
【０００８】[0008]
【作用】通常、半導体膜はガラスなどの絶縁体基板上に
Moのオーミック電極を有するｐ形CuInSe2 膜を作製する
場合、基板上にスパッタ法や電子ビーム蒸着法でMo膜を
作製し、その上にCuInSe2 膜を作製する。[Function] Usually, a semiconductor film is formed on an insulating substrate such as glass.
When manufacturing a p-type CuInSe 2 film having an ohmic electrode of Mo, a Mo film is formed on a substrate by a sputtering method or an electron beam evaporation method, and a CuInSe 2 film is formed thereon.
【０００９】この場合、CuInSe2 膜の作製法としては、
Cu、In、Seの同時蒸着法や、Cu、In、Se（Seを除く場合
もある）を蒸着などによって積層し、Seガス雰囲気下で
熱処理するセレン化法などが知られている。In this case, as a method for producing the CuInSe 2 film,
There are known a co-evaporation method of Cu, In, and Se, and a selenization method in which Cu, In, and Se (sometimes excluding Se) are stacked by evaporation and heat-treated in a Se gas atmosphere.
【００１０】本発明法の実施例ではSeソースを用いての
熱処理によるセレン化法を用いたが、その他、Cu、In、
Seの積層膜を加熱してセレン化するCuInSe2 膜の成膜方
法によっても同様な効果を得ることができることを確認
している。In the embodiment of the method of the present invention, a selenization method by heat treatment using a Se source is used.
It has been confirmed that a similar effect can be obtained by a method of forming a CuInSe 2 film, which is formed by heating a stacked film of Se to be selenized.
【００１１】上記の方法によりMo膜上に厚いCuInSe2 膜
を作製しようとした場合、「しわ」の発生や膜の剥離等
がしばしば見られるが、これらをよく観察したところ、
「しわ」の発生や膜の剥離がまったく見られないグルー
プの膜厚はすべて 0.2μｍ以下にあることが本発明者の
試験によって判明した。そしてMo膜上に予め 0.2μｍ以
下のCuInSe2 膜を設けた後、順次CuInSe2 膜を積層させ
ることによって所望の厚膜を有する半導体膜を作製する
ことができたものである。When an attempt is made to form a thick CuInSe 2 film on a Mo film by the above-described method, occurrence of “wrinkles” and peeling of the film are often observed.
The test by the present inventors has revealed that the film thicknesses of all the groups in which generation of “wrinkles” and peeling of the film are not observed are all 0.2 μm or less. Then, a semiconductor film having a desired thickness can be produced by providing a CuInSe 2 film of 0.2 μm or less in advance on the Mo film and then sequentially laminating the CuInSe 2 film.
【００１２】以下、実施例をもって詳細に説明する。Hereinafter, the present invention will be described in detail with reference to embodiments.
【００１３】[0013]
【実施例１】図１に示すように、厚さ１μｍのMo膜２を
面上に有するガラス板１をCuInSe2 の成膜用基板とし
た。まず基板上に、Cuを 250Ａ（オングストローム）、
その上にInを 550Ａの厚さでそれぞれ真空蒸着法で積層
した。EXAMPLE 1 As shown in FIG. 1, a glass plate 1 having a Mo film 2 having a thickness of 1 μm on its surface was used as a substrate for forming CuInSe 2 . First, 250A (Angstrom) of Cu on the substrate,
In was laminated thereon by vacuum evaporation at a thickness of 550 A, respectively.
【００１４】次いで上記積層体をSeソースを有する炉に
入れ、 400℃に加熱して、Seガス雰囲気下でセレン化反
応を行ったところ、図１に示すようにMo層上に、厚さ20
00ＡのCuInSe2 膜３の成膜を得た。Next, the above laminate was placed in a furnace having a Se source, heated to 400 ° C., and subjected to a selenization reaction in an Se gas atmosphere. As shown in FIG.
The formation of the CuInSe 2 film 3 of 00A was obtained.
【００１５】得られたCuInSe2 膜には、膜剥離や「し
わ」の発生は一切見られず、Mo膜との密着性は良好であ
った。The resulting CuInSe 2 film did not show any peeling or "wrinkles", and had good adhesion to the Mo film.
【００１６】なお、この成膜をＸ線回折によって調べた
ところ、基板のMoに関するピークと共に、カルコパイラ
イト形CuInSe2 に関するピークがあり、このセレン化に
よってMo上にCuInSe2 半導体膜が成膜されていることを
確認できた。When this film was examined by X-ray diffraction, a peak related to chalcopyrite-type CuInSe 2 was found together with a peak related to Mo on the substrate, and a CuInSe 2 semiconductor film was formed on Mo by selenization. I was able to confirm that
【００１７】[0017]
【実施例２】実施例１で得た2000ＡのCuInSe2 膜を用い
て、実施例１と同様な手段でCuを 250Ａ、その上にInを
550Ａ、それぞれ真空蒸着によってさらに積層し、Seソ
ースを用いたSeガス雰囲気下でセレン化反応を行ったと
ころ、膜剥離や「しわ」などの発生がまったくなく、図
２に示すようにMo膜２との密着性の良好な厚さ4000Ａの
CuInSe2 膜３を得ることができた。[Embodiment 2] Using the 2000A CuInSe 2 film obtained in Embodiment 1, Cu was used for 250A by the same means as in Embodiment 1, and In was further added thereon.
550A, each of which was further laminated by vacuum evaporation and selenized in a Se gas atmosphere using a Se source. As a result, there was no occurrence of film peeling or "wrinkles", and as shown in FIG. 4000A thickness with good adhesion to
A CuInSe 2 film 3 was obtained.
【００１８】なお、この成膜をＸ線回折によって調べた
ところ、基板のMoに関するピークと共に、カルコパイラ
イト形CuInSe2 に関するピークがあり、Mo膜上に密着性
が良好な厚さ4000ＡのCuInSe2 半導体膜を成膜できたこ
とを確認した。[0018] Incidentally, were examined the deposition by X-ray diffraction, with peak for Mo substrate, there is a peak for a chalcopyrite type CuInSe 2, CuInSe 2 semiconductor thick 4000A adhesion good on the Mo film It was confirmed that the film could be formed.
【００１９】[0019]
【比較例１】図３に示すような厚さ１μｍのMo膜２を面
上に有するガラス板１を基板とし、基板上にCuを1200
Ａ、その上にInを2700Ａ、それぞれ真空蒸着により積層
した。Comparative Example 1 A glass plate 1 having a Mo film 2 having a thickness of 1 μm on its surface as shown in FIG.
A, and 2700 A of In were stacked thereon by vacuum evaporation.
【００２０】次いで上記積層体をSeソースをを有する炉
に入れ、 400℃に加熱して、Seガス雰囲気下でセレン化
反応を行ったところ、図３に示すように、Mo層上に厚さ
約１μｍのCuInSe2 膜３が作製されたが、図から明らか
なように、Mo膜との間に大きな空隙４が所々見られる
他、Mo膜上から剥離している部分や、膜に「しわ」がよ
っている部分があり、Mo膜との密着性が不良であること
が確認できた。Next, the laminate was placed in a furnace having a Se source, heated to 400 ° C., and subjected to a selenization reaction in a Se gas atmosphere. As shown in FIG. A CuInSe 2 film 3 having a thickness of about 1 μm was produced. As is clear from the drawing, large voids 4 were observed in some places between the Mo film and the MoIn film. ", And it was confirmed that the adhesion to the Mo film was poor.
【００２１】なお、この密着性不良な膜をＸ線回折で調
べたところ、実施例１、実施例２と同様なカルコパイラ
イト形CuInSe2 であった。When the film having poor adhesion was examined by X-ray diffraction, it was found to be chalcopyrite-type CuInSe 2 similar to those in Examples 1 and 2.
【００２２】[0022]
【発明の効果】本発明法は上述のように、Mo膜との密着
性を損なわずに所望の厚さのCuInSe2 膜をMo膜上に成膜
するため、CuInSe2 膜を 0.2μｍ（2000Ａ）以下の厚さ
で繰り返し作製するだけでよい。The present invention method according to the present invention, as described above, for forming a CuInSe 2 film of a desired thickness on the Mo film without impairing the adhesion to the Mo film, CuInSe 2 film 0.2 [mu] m (2000A It is only necessary to repeatedly produce the following thickness.
【００２３】したがって、従来法にようにCuInSe2 と関
係のない第３の金属を媒介する必要もないため、これら
に要する新たな装置の導入も不要で、コスト的に安価に
作製できるものである。Therefore, unlike the conventional method, there is no need to mediate a third metal irrelevant to CuInSe 2 , so that it is not necessary to introduce a new device required for these, and the device can be manufactured at a low cost. .
【図１】本発明法でMo膜上にCuInSe2 膜を膜厚2000Ａに
積層して得た実施例１の積層膜の断面のＳＥＭ写真をイ
メージ化した図である。FIG. 1 is an image of an SEM photograph of a cross section of a laminated film of Example 1 obtained by laminating a CuInSe 2 film on a Mo film to a thickness of 2000 A by a method of the present invention.
【図２】本発明法でMo膜上にCuInSe2 膜を膜厚2000Ａず
つ２回積層した実施例２の積層膜の断面のＳＥＭ写真を
イメージ化した図である。FIG. 2 is a diagram in which a SEM photograph of a cross section of a laminated film of Example 2 in which a CuInSe 2 film is laminated twice on a Mo film by a thickness of 2000 A by a method of the present invention is shown.
【図３】従来法によってMo膜上に厚さ約１μｍのCuInSe
2 膜を積層した比較例の積層膜の断面のＳＥＭ写真をイ
メージ化した図である。FIG. 3 shows a CuInSe layer having a thickness of about 1 μm formed on a Mo film by a conventional method.
FIG. 9 is a diagram in which an SEM photograph of a cross section of a laminated film of a comparative example in which two films are laminated is imaged.
１ ガラス板 ２ Mo膜 ３ CuInSe2 膜 ４ 空隙1 Glass plate 2 Mo film 3 CuInSe 2 film 4 Void
───────────────────────────────────────────────────── フロントページの続き (72)発明者 伊藤 和人 東京都千代田区丸の内１丁目８番２号 同和鉱業株式会社内 (56)参考文献 特開 平４−56172（ＪＰ，Ａ) 特開 平２−94669（ＪＰ，Ａ) 特開 昭61−237476（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01L 31/04 - 31/078 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Kazuto Ito 1-8-2 Marunouchi, Chiyoda-ku, Tokyo Dowa Mining Co., Ltd. (56) References JP-A-4-56172 (JP, A) JP-A-Hei 2-94669 (JP, A) JP-A-61-237476 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) H01L 31/04-31/078
Claims (1)
上の厚さを有するCuInSe2 膜を作製する方法において、
予め 0.2μｍ以下のCuInSe2 膜を設けた後に、順次CuIn
Se2 膜を積層することにより所望の厚膜となすことを特
徴とする半導体厚膜の作製方法。1. A method for producing a CuInSe 2 film having a thickness of 0.2 μm or more on a Mo film by a selenization method,
After providing a CuInSe 2 film of 0.2 μm or less in advance,
A method for manufacturing a semiconductor thick film, wherein a desired thick film is formed by stacking Se 2 films.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3073875A JP3007179B2 (en) | 1991-03-12 | 1991-03-12 | Semiconductor thick film fabrication method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3073875A JP3007179B2 (en) | 1991-03-12 | 1991-03-12 | Semiconductor thick film fabrication method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04283969A JPH04283969A (en) | 1992-10-08 |
| JP3007179B2 true JP3007179B2 (en) | 2000-02-07 |
Family
ID=13530812
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3073875A Expired - Fee Related JP3007179B2 (en) | 1991-03-12 | 1991-03-12 | Semiconductor thick film fabrication method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3007179B2 (en) |
-
1991
- 1991-03-12 JP JP3073875A patent/JP3007179B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04283969A (en) | 1992-10-08 |
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