JPH08330613A - Manufacture of thin film solar cell - Google Patents
Manufacture of thin film solar cellInfo
- Publication number
- JPH08330613A JPH08330613A JP7137668A JP13766895A JPH08330613A JP H08330613 A JPH08330613 A JP H08330613A JP 7137668 A JP7137668 A JP 7137668A JP 13766895 A JP13766895 A JP 13766895A JP H08330613 A JPH08330613 A JP H08330613A
- Authority
- JP
- Japan
- Prior art keywords
- selenium
- layer
- indium
- solar cell
- copper
- 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.)
- Granted
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
Landscapes
- Electrodes Of Semiconductors (AREA)
- Physical Deposition Of Substances That Are Components Of Semiconductor Devices (AREA)
- Photovoltaic Devices (AREA)
- Physical Vapour Deposition (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、銅−インジウム−セレ
ン三元合金層を有する薄膜太陽電池の製造方法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a thin film solar cell having a copper-indium-selenium ternary alloy layer.
【０００２】[0002]
【従来の技術】太陽電池は、光エネルギーを電気エネル
ギーに変換する装置であり、導電性基板上に、光電変換
性半導体からなる吸収層と光透過性電極層とを順次積層
して構成されるのが普通である。このような光電変換性
半導体層としては、原子の存在比が１：１：２である銅
−インジウム−セレン三元合金（ＣｕＩｎＳｅ2 ）の薄
膜が最も優れた光電変換効率を示すものと考えられてい
る。この三元合金の製造方法としては特開昭６１−２３
７４７６号公報で知られている方法があった。この方法
は、導電性基板上に銅及びインジウムを順次電着させて
プリカーサーを形成した後、セレン化水素を含んだ不活
性ガスを流しながら加熱処理を行い、銅−インジウム−
セレン三元合金（ＣｕＩｎＳｅ2 ）層を形成する方法で
あった。2. Description of the Related Art A solar cell is a device for converting light energy into electric energy, and is constructed by sequentially laminating an absorbing layer made of a photoelectric conversion semiconductor and a light transmitting electrode layer on a conductive substrate. Is normal. As such a photoelectric conversion semiconductor layer, a thin film of a copper-indium-selenium ternary alloy (CuInSe 2 ) having an atomic abundance ratio of 1: 1: 2 is considered to exhibit the best photoelectric conversion efficiency. ing. As a method for producing this ternary alloy, Japanese Patent Application Laid-Open No. 61-23
There was a method known from Japanese Patent No. 7476. In this method, copper and indium are sequentially electrodeposited on a conductive substrate to form a precursor, and then heat treatment is performed while an inert gas containing hydrogen selenide is flowed to form copper-indium-
It was a method of forming a selenium ternary alloy (CuInSe 2 ) layer.
【０００３】しかしこの方法では、導電性基板と生成し
た三元合金層との密着性が悪く、剥がれが生じ、そのた
め太陽電池を作成した場合に特性が悪くなる。また、セ
レン化水素を含んだ不活性ガスを流しながら加熱処理を
行うため、セレン化水素が本来化学量論的に必要な量の
数１０倍〜数１００倍程度必要である。また、このセレ
ン化水素は極めて毒性が高いためその取り扱い性にも問
題があり、同時に、高価な不活性ガスを用いるためコス
ト高になる等の多くの問題があった。However, according to this method, the adhesiveness between the conductive substrate and the ternary alloy layer formed is poor and peeling occurs, which results in poor properties when a solar cell is produced. Further, since the heat treatment is carried out while flowing an inert gas containing hydrogen selenide, the amount of hydrogen selenide required is approximately several tens to several hundreds of the stoichiometrically required amount. Further, since hydrogen selenide is extremely toxic, it has a problem in handleability, and at the same time, there are many problems such as an increase in cost because an expensive inert gas is used.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、上記従来技
術の問題点、即ち、剥がれのない良好な銅−インジウム
−セレン三元合金層を、容易、安全にかつ安価に得るこ
とができる方法を提供することを目的とする。SUMMARY OF THE INVENTION The present invention is a method of obtaining the above-mentioned problem of the prior art, that is, a good copper-indium-selenium ternary alloy layer without peeling, easily, safely and inexpensively. The purpose is to provide.
【０００５】[0005]
【課題を解決するための手段】本発明の薄膜太陽電池の
製造方法は、次の４工程、即ち、(1) 基板上にスパッタ
リングによりモリブデン層を形成する工程、(2) 該モリ
ブデン層上にスパッタリングにより銅層を形成する工
程、(3) インジウムイオンを含み、かつ、セレンコロイ
ドを分散させた溶液中で該銅層上にセレン分散インジウ
ム層を電着によって形成し、プリカーサーを完成する工
程、(4) 該プリカーサーをセレンと共に容器に入れ、該
容器を密閉した後、加熱する工程、を有することを特徴
とする。Means for Solving the Problems The method for manufacturing a thin film solar cell of the present invention comprises the following four steps: (1) a step of forming a molybdenum layer on a substrate by sputtering, and (2) a step of forming the molybdenum layer on the molybdenum layer. A step of forming a copper layer by sputtering, (3) a step of forming a selenium-dispersed indium layer on the copper layer by electrodeposition in a solution containing indium ions, and dispersing a selenium colloid, to complete a precursor, (4) A step of placing the precursor together with selenium in a container, sealing the container, and then heating the container.
【０００６】ここで、基板としては、ソーダライムガラ
スを用いると、ＣｕＩｎＳｅ2 とほぼ同様の熱膨張係数
を持つため熱処理時に剥がれの発生が少なくなり、ま
た、このガラス中のアルカリ成分がＣｕＩｎＳｅ2 の結
晶性を向上させるので、好ましい。モリブデン層は導電
性を有し、太陽電池の構成上電極として必要なものであ
るが、基板との密着性の点でスパッタリングによって形
成されることが必要である。銅層も同様の理由でスパッ
タリングによって形成されることが必要である。When soda lime glass is used as the substrate, the occurrence of peeling during heat treatment is small because it has a coefficient of thermal expansion similar to that of CuInSe 2, and the alkaline component in this glass is CuInSe 2 . It is preferable because it improves the crystallinity. The molybdenum layer has conductivity and is necessary as an electrode in the structure of the solar cell, but it is necessary to be formed by sputtering in terms of adhesion to the substrate. The copper layer also needs to be formed by sputtering for the same reason.
【０００７】インジウムイオン（Ｉｎ2+）を含み、か
つ、セレンコロイドを有する溶液において、インジウム
イオンは、例えば硫酸インジウム等のインジウム塩を水
に溶解することにより得られる。またセレンコロイド
は、例えば、亜セレン酸を硫酸ヒドラジニウムによって
還元して得られる。In a solution containing indium ions (In 2+ ) and having a selenium colloid, indium ions are obtained by dissolving an indium salt such as indium sulfate in water. The selenium colloid can be obtained, for example, by reducing selenious acid with hydrazinium sulfate.
【０００８】ここで得られるセレンコロイド粒子の粒径
は１μｍ未満であることが好ましい。このコロイド粒子
の粒径が１μｍより大きいと溶液中での均一分散が困難
であり、また、電着によって形成されたインジウム層に
均一に分散されなくなる傾向がある。The particle size of the selenium colloidal particles obtained here is preferably less than 1 μm. When the particle size of the colloidal particles is larger than 1 μm, it is difficult to uniformly disperse the colloidal particles in the solution, and the colloidal particles tend not to be uniformly dispersed in the indium layer formed by electrodeposition.
【０００９】銅層とセレンコロイドを分散含有する電着
インジウム層は銅層の上に形成されることが必要であ
る。即ち、導電性基板／銅層／セレン粒子散含有インジ
ウム層の順に成層されることが必要である。これは、セ
レンと導電性基板に含まれているモリブデンとが反応し
て形成される化合物が、吸収層の銅−インジウム−セレ
ン三元合金の生成を阻害し、また、この三元合金の結晶
の発達を妨げる性質を持ち、かつ、最終的に得られる吸
収層を脱落しやすくするためである。It is necessary that the electrodeposited indium layer containing the copper layer and the selenium colloid dispersed therein is formed on the copper layer. That is, it is necessary to form the conductive substrate / copper layer / indium layer containing selenium particles in this order. This is because the compound formed by the reaction between selenium and molybdenum contained in the conductive substrate inhibits the formation of the copper-indium-selenium ternary alloy in the absorption layer, and also the crystal of this ternary alloy. This is because it has the property of hindering the development of the water and makes it easier to remove the absorption layer that is finally obtained.
【００１０】なお、電着条件として、セレンコロイド粒
子を分散含有する電着インジウム層中のインジウム原子
に対するセレン原子の存在量が１／１０００以上２／１
以下になるよう定めることが好ましい。As an electrodeposition condition, the abundance of selenium atoms with respect to indium atoms in the electrodeposited indium layer containing selenium colloidal particles dispersed therein is 1/1000 or more and 2/1.
It is preferable to set it as follows.
【００１１】インジウム原子に対するセレン原子の存在
量が１／１０００より少ない場合は、熱処理時に膜中か
らのセレン供給が不足して銅−インジウム−セレン三元
合金の生成量が減少しやすく、また、このことを防止す
るため加熱処理中に外部から大量のセレンを供給する
と、三元合金形成時の層の膨張に対応できずにひずみが
生じ、三元合金層に剥がれが生じやすい。If the amount of selenium atoms to the amount of indium atoms is less than 1/1000, the amount of selenium supplied from the film is insufficient during the heat treatment and the amount of copper-indium-selenium ternary alloy produced tends to decrease. If a large amount of selenium is supplied from the outside during the heat treatment in order to prevent this, strain cannot be dealt with due to the expansion of the layer when the ternary alloy is formed, and the ternary alloy layer is likely to peel off.
【００１２】一方、このインジウム原子に対するセレン
の存在量が２／１より多いときには、銅とセレンとが安
定な化合物を形成しやすくなり、このため、銅−インジ
ウム−セレン三元合金の生成量が減少するとともに、こ
の銅とセレンとからなる化合物が生成した銅−インジウ
ム−セレン三元合金の結晶の成長を妨げるため、発達し
た三元合金の結晶が得られにくくなる。On the other hand, when the abundance of selenium with respect to the indium atom is more than 2/1, copper and selenium are likely to form a stable compound, so that the production amount of the copper-indium-selenium ternary alloy is increased. At the same time, the growth of the copper-indium-selenium ternary alloy crystal produced by the compound of copper and selenium is reduced, and it becomes difficult to obtain the developed ternary alloy crystal.
【００１３】上記のようにセレンコロイドを分散含有す
る電着インジウム層が形成されたプリカーサーをイオン
交換水で洗浄後乾燥する。この乾燥は、優れた吸収層を
得るために、窒素ガス中、或いは不活性気体中で行うこ
とが望ましい。The precursor having the electrodeposited indium layer containing the selenium colloid dispersed therein as described above is washed with ion-exchanged water and dried. This drying is preferably performed in nitrogen gas or an inert gas in order to obtain an excellent absorption layer.
【００１４】次いで、このプリカーサーを密閉容器にセ
レン粉末と共に入れて、一旦、系をアルゴンまたは窒素
置換し、その後必要に応じて減圧した後、４００〜５５
０℃で熱処理を行う。ここで５００〜５５０℃であると
三元合金の結晶の成長が速いので好ましい。この熱処理
により吸収層として銅−インジウム−セレン合金（Ｃｕ
ＩｎＳｅ2）が形成され、かつ、その結晶が発達する。Next, this precursor was put in a closed container together with selenium powder, the system was once replaced with argon or nitrogen, and then depressurized if necessary, then 400 to 55.
Heat treatment is performed at 0 ° C. Here, it is preferable that the temperature is 500 to 550 ° C. because the ternary alloy crystals grow rapidly. By this heat treatment, a copper-indium-selenium alloy (Cu
InSe 2 ) is formed and its crystal develops.
【００１５】[0015]
【作用】本発明において、スパッタリングによって形成
されたモリブデン層の上に、同じくスパッタリングによ
って銅層を形成し、その後セレン分散インジウム層が形
成されるため、セレンとモリブデンとの化合物の生成が
なく、モリブデン層と銅−インジウム−セレン合金層と
の密着性は良好なものとなる。In the present invention, since a copper layer is similarly formed by sputtering on the molybdenum layer formed by sputtering and then a selenium-dispersed indium layer is formed, there is no formation of a compound of selenium and molybdenum. Adhesion between the layer and the copper-indium-selenium alloy layer is good.
【００１６】コロイド粒子となったセレンはメッキ液中
で安定で沈降せず、そのため、メッキ中に攪拌等の特別
な手段を必要とせずに均一に電着層に分散含有される。
また、粒子が小さいために形成されたセレン分散インジ
ウム層も剥離、脱落等の欠陥も非常に少ないものとな
る。The selenium, which has become colloidal particles, is stable and does not settle in the plating solution. Therefore, it is uniformly dispersed and contained in the electrodeposition layer without requiring special means such as stirring during plating.
Further, the selenium-dispersed indium layer formed due to the small size of the particles has very few defects such as peeling and falling off.
【００１７】また、インジウム層において、セレン粒子
が分散しているため緻密になりすぎず、加熱処理時に三
元合金が形成される場合に伴う層の膨張にも対応できる
ためや剥がれのない三元合金層が形成される。また、セ
レン及び密閉容器を用いて加熱処理を行うため、容易か
つ安全であり、高価な不活性ガスを必要としない。Further, since the selenium particles are dispersed in the indium layer, the selenium particles do not become too dense and can cope with expansion of the layer accompanying the formation of a ternary alloy during the heat treatment, and the ternary layer does not peel off. An alloy layer is formed. In addition, since heat treatment is performed using selenium and a closed container, it is easy and safe, and expensive inert gas is not required.
【００１８】[0018]
【実施例】青色ガラス板上にモリブデン、銅をそれぞれ
スパッタリングにより、２μｍ、０．３μｍの厚さにな
るよう成膜した。Example Molybdenum and copper were sputtered on a blue glass plate to form films having a thickness of 2 μm and 0.3 μm, respectively.
【００１９】セレンコロイド溶液は以下の手順で作製し
た。ゼラチン溶液（４ｇ／ l）４ml、亜セレン酸（０．
１ mol／ l）１０ml、硫酸ヒドラジニウム（０．１ mol
／ l）１０ml、純水３０mlを混合後、４０℃で４５分間
加熱した後、ｐＨを２に調整してコロイドを安定化させ
て、セレンコロイド溶液とした。ここで、ゼラチンを加
えるのはコロイドの安定のためである。The selenium colloidal solution was prepared by the following procedure. Gelatin solution (4 g / l) 4 ml, selenious acid (0.
1 ml / l) 10 ml, hydrazinium sulfate (0.1 mol / l)
/ L) 10 ml and 30 ml of pure water were mixed and heated at 40 ° C. for 45 minutes, and then the pH was adjusted to 2 to stabilize the colloid to obtain a selenium colloid solution. Here, gelatin is added to stabilize the colloid.
【００２０】このようにして作製したセレンコロイド溶
液のコロイド粒子を走査型電子顕微鏡で調べたところ、
セレンコロイド粒子の粒径は１０ｎｍ以上１００ｎｍ以
下であり、長時間放置してもセレン粒子の沈殿が生じる
ことなく、非常に安定であった。The colloidal particles of the selenium colloidal solution thus prepared were examined by a scanning electron microscope.
The particle size of the selenium colloidal particles was 10 nm or more and 100 nm or less, and the selenium particles did not precipitate even when left standing for a long time and were very stable.
【００２１】このセレンコロイド溶液を用いて、セレン
コロイド１０mmol／ l、硫酸インジウム５０mmol／ l、
硫酸ナトリウム８０mmol／ l、クエン酸ナトリウム５０
mmol／ lとなるようにメッキ液を調整した。前記薄膜板
に上記メッキ液を用いて参照電極である硫酸第一水銀電
極に対して１．５Ｖの電圧となるよう、定電圧メッキを
行った。なお、このとき対極としては、白金板を用い
た。Using this selenium colloid solution, selenium colloid 10 mmol / l, indium sulfate 50 mmol / l,
Sodium sulfate 80 mmol / l, sodium citrate 50
The plating solution was adjusted to be mmol / l. The thin film plate was subjected to constant voltage plating using the above plating solution so that the voltage was 1.5 V with respect to the mercuric sulfate electrode serving as the reference electrode. At this time, a platinum plate was used as the counter electrode.
【００２２】ここで、メッキ液は非常に安定であって、
メッキ液中のコロイド粒子は沈降しないため、攪拌は行
わなかった。このとき得られたセレン分散電着インジウ
ム層の厚さは０．７μｍであり、セレンコロイド粒子を
分散含有する電着インジウム層中のインジウム原子とセ
レン原子の存在比はエネルギー分散型Ｘ線分析装置（以
下「ＥＤＸ」と云う）による組成分析によれば１０：２
であった。なお、このセレン分散電着インジウム層は非
常に均一なものであった。Here, the plating solution is very stable,
Since the colloidal particles in the plating solution did not settle, stirring was not performed. The thickness of the selenium-dispersed electrodeposited indium layer obtained at this time was 0.7 μm, and the abundance ratio of indium atoms and selenium atoms in the electrodeposited indium layer containing selenium colloid particles dispersed therein was determined by an energy dispersive X-ray analyzer. According to the composition analysis (hereinafter referred to as “EDX”), it is 10: 2.
Met. The selenium-dispersed electrodeposited indium layer was very uniform.
【００２３】メッキ後の薄膜板を窒素下で乾燥後、図１
に示す密閉加熱炉を用いて熱処理を行った。即ち図１に
おいて、ベース１に溝があり、そこにＯリング１ａが一
部突出して収納されており、ベルジャ２はこのＯリング
１ａを介してベース１上に乗せられているため、ベルジ
ャ２内部を減圧に保つことが可能となっている。なお、
ベース１には弁５を備えた排気管３、及び弁６を備えた
ガス導入管４が付属する。After the plated thin film plate is dried under nitrogen,
Heat treatment was performed using the closed heating furnace shown in. That is, in FIG. 1, there is a groove in the base 1, and an O-ring 1a is partially projected and housed therein, and the bell jar 2 is placed on the base 1 through this O-ring 1a. It is possible to maintain a reduced pressure. In addition,
An exhaust pipe 3 having a valve 5 and a gas introducing pipe 4 having a valve 6 are attached to the base 1.
【００２４】ベース１上には支持具１０を介して、プリ
カーサーの加熱処理を行うための空間を有する加熱治具
１１が設置されており、またこの加熱治具１１を密閉す
るための蓋１２があるが、この蓋１２は開閉機構１３に
よってベルジャ２内部の減圧を保ったまま、外部からハ
ンドル１３ａを操作することで開閉することが可能とな
っている。A heating jig 11 having a space for heat treatment of the precursor is installed on the base 1 through a supporting tool 10, and a lid 12 for sealing the heating jig 11 is provided. However, the lid 12 can be opened and closed by operating the handle 13a from the outside while maintaining the decompression inside the bell jar 2 by the opening / closing mechanism 13.
【００２５】即ち、ハンドル１３ａを回転すると、その
回転は、傘歯車１３ｂ及び傘歯車１３ｃ、プーリー１３
ｄ及びベルト１３ｅを経てプーリー１３ｆに伝わる。こ
のプーリー１３ｆが回転するとその内部にあるめねじ
（図示せず）及び蓋操作軸１３ｇのおねじ１３ｈによっ
て、蓋操作軸１３ｇが上下し、それに接続された蓋１２
が開閉する。なお、開閉機構１３には、締め付け過ぎに
よって加熱治具１１や蓋１２の破壊を防ぐためのバネに
よる安全機構１３ｉが付属している。That is, when the handle 13a is rotated, the rotation thereof is caused by the bevel gear 13b, the bevel gear 13c, and the pulley 13.
It is transmitted to the pulley 13f via d and the belt 13e. When this pulley 13f rotates, the lid operating shaft 13g moves up and down by the internal thread (not shown) and the male screw 13h of the lid operating shaft 13g, and the lid 12 connected to it.
Opens and closes. The opening / closing mechanism 13 is provided with a safety mechanism 13i using a spring for preventing the heating jig 11 and the lid 12 from being broken by over-tightening.
【００２６】なお、加熱治具１１及び蓋１２はそれぞれ
炭素製であるが、外部への放熱を減少させるための遮熱
板が付属している。また、それぞれヒーター（図示せ
ず）が内蔵され、熱電対１１ａ及び１２ａが付属してい
て、ベルジャ２が閉まった状態でも加熱治具１１中に収
納されるプリカーサー２０の加熱処理を行う温度の測定
ができるようになっている。Although the heating jig 11 and the lid 12 are made of carbon, they are provided with a heat shield plate for reducing heat radiation to the outside. In addition, each heater has a built-in heater (not shown), thermocouples 11a and 12a are attached, and even if the bell jar 2 is closed, the temperature of the precursor 20 stored in the heating jig 11 is measured. You can do it.
【００２７】このような密閉加熱炉の加熱治具１１上に
上記プリカーサー２０及びセレン粉末（図示せず）を入
れ、ベルジャ２を閉め、弁６を閉じたのち、排気管３に
真空ポンプ（図示せず）を接続してベルジャ２内部を減
圧する。その後、弁５を閉じ、ガス導入管４にアルゴン
ガスボンベ（図示せず）を接続した後、ベルジャ２内部
にアルゴンガスを導入する。この動作を３回繰り返し
て、ベルジャ２内部の空気をアルゴンガスと置換した。
その後、開閉機構１３によって、蓋１２を閉め、加熱治
具１１を密閉する。The precursor 20 and selenium powder (not shown) are put on the heating jig 11 of such a closed heating furnace, the bell jar 2 is closed, the valve 6 is closed, and then the vacuum pump (see FIG. (Not shown) is connected to reduce the pressure inside the bell jar 2. Then, the valve 5 is closed, an argon gas cylinder (not shown) is connected to the gas introduction pipe 4, and then argon gas is introduced into the bell jar 2. This operation was repeated three times to replace the air inside the bell jar 2 with argon gas.
Then, the lid 12 is closed by the opening / closing mechanism 13 and the heating jig 11 is sealed.
【００２８】次いで、加熱治具１１及び蓋１２に付属す
るヒーターにより、２５℃／分の昇温速度で５５０℃ま
で昇温し、その後６０分保持した後、自然冷却させ、薄
膜太陽電池の吸収層を形成した。なお、加熱によって蒸
気となったセレン（セレン化水素よりは遥かに毒性が低
い）が、加熱治具１１及び蓋１２より多少漏出すること
も考えられるが、この場合においても、ベルジャ２外部
へ漏出することはない。Then, the heater attached to the heating jig 11 and the lid 12 was used to raise the temperature to 550 ° C. at a temperature rising rate of 25 ° C./minute, and after that, the temperature was maintained for 60 minutes and then naturally cooled to absorb the thin film solar cell. Layers were formed. It is possible that selenium (which is much less toxic than hydrogen selenide) turned into steam by heating leaks out from the heating jig 11 and the lid 12, but in this case also, it leaks out of the bell jar 2. There is nothing to do.
【００２９】得られた吸収層の銅原子、インジウム原子
及びセレン原子の存在比は、２３．５：２４．５：５
２．０とほぼ１：１：２であり、また、Ｘ線回折分析を
行ったところ、結晶の大きくかつ配向性の高いカルコパ
イライト型のＣｕＩｎＳｅ2 であることが確認された。
なお、この吸収層には剥がれ等の欠陥はなかった。The abundance ratio of copper atoms, indium atoms and selenium atoms in the obtained absorption layer was 23.5: 24.5: 5.
It was 2.0, which was about 1: 1: 2, and X-ray diffraction analysis confirmed that it was a chalcopyrite type CuInSe 2 having large crystals and high orientation.
The absorption layer did not have any defects such as peeling.
【００３０】[0030]
【発明の効果】上記のように、本発明によれば、剥がれ
のない優れたＣｕＩｎＳｅ2 合金結晶薄膜を、安全、容
易に、かつ低コストで製造することができる。As described above, according to the present invention, an excellent CuInSe 2 alloy crystal thin film without peeling can be manufactured safely, easily and at low cost.
【図１】本発明で用いる密閉加熱炉の例である。FIG. 1 is an example of a closed heating furnace used in the present invention.
１ ベース １ａ Ｏリング ２ ベルジャ ３ 排気管 ４ ガス導入管 １０ 支持具 １１ 加熱治具 １１ａ 熱電対 １２ 蓋 １２ａ 熱電対 １３ 開閉機構 １３ａ ハンドル １３ｉ 安全機構 1 base 1a O-ring 2 bell jar 3 exhaust pipe 4 gas introduction pipe 10 support tool 11 heating jig 11a thermocouple 12 lid 12a thermocouple 13 opening / closing mechanism 13a handle 13i safety mechanism
Claims (1)
４工程、即ち、(1) 基板上にスパッタリングによりモリ
ブデン層を形成する工程、(2) 該モリブデン層上にスパ
ッタリングにより銅層を形成する工程、(3) インジウム
イオンを含み、かつ、セレンコロイドを分散させた溶液
中で該銅層上にセレン分散インジウム層を電着によって
形成し、プリカーサーを完成する工程、(4) 該プリカー
サーをセレンと共に容器に入れ、該容器を密閉した後、
加熱する工程、を有することを特徴とする薄膜太陽電池
の製造方法。1. A method for manufacturing a thin-film solar cell, which comprises the following four steps: (1) a step of forming a molybdenum layer on a substrate by sputtering, and (2) a step of forming a copper layer on the molybdenum layer by sputtering. Step (3) a step of forming a selenium-dispersed indium layer on the copper layer by electrodeposition in a solution containing indium ions and having a selenium colloid dispersed therein, and completing the precursor, (4) the precursor is selenium. Put in a container with, after sealing the container,
A method of manufacturing a thin-film solar cell, comprising the step of heating.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7137668A JP3048040B2 (en) | 1995-06-05 | 1995-06-05 | Manufacturing method of thin film solar cell |
| US08/651,610 US5772431A (en) | 1995-05-22 | 1996-05-22 | Thin-film solar cell manufacturing apparatus and manufacturing method |
| US09/009,689 US6036822A (en) | 1995-05-22 | 1998-01-20 | Thin-film solar cell manufacturing apparatus and manufacturing method |
| US09/009,161 US6207219B1 (en) | 1995-05-22 | 1998-01-20 | Method for manufacturing thin-film solar cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7137668A JP3048040B2 (en) | 1995-06-05 | 1995-06-05 | Manufacturing method of thin film solar cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08330613A true JPH08330613A (en) | 1996-12-13 |
| JP3048040B2 JP3048040B2 (en) | 2000-06-05 |
Family
ID=15204030
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7137668A Expired - Fee Related JP3048040B2 (en) | 1995-05-22 | 1995-06-05 | Manufacturing method of thin film solar cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3048040B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008153690A1 (en) * | 2007-05-22 | 2008-12-18 | Miasole | High rate sputtering apparatus and method |
| JP2012077321A (en) * | 2010-09-30 | 2012-04-19 | Sumitomo Heavy Ind Ltd | Method of manufacturing film deposition substrate, film deposition substrate, and film deposition device |
| JP2013536986A (en) * | 2010-09-02 | 2013-09-26 | インターナショナル・ビジネス・マシーンズ・コーポレーション | Methods for electrodeposition of gallium and gallium alloy films and related photovoltaic structures |
-
1995
- 1995-06-05 JP JP7137668A patent/JP3048040B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008153690A1 (en) * | 2007-05-22 | 2008-12-18 | Miasole | High rate sputtering apparatus and method |
| JP2013536986A (en) * | 2010-09-02 | 2013-09-26 | インターナショナル・ビジネス・マシーンズ・コーポレーション | Methods for electrodeposition of gallium and gallium alloy films and related photovoltaic structures |
| JP2012077321A (en) * | 2010-09-30 | 2012-04-19 | Sumitomo Heavy Ind Ltd | Method of manufacturing film deposition substrate, film deposition substrate, and film deposition device |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3048040B2 (en) | 2000-06-05 |
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