JP2001053314A - Method for manufacturing compound semiconductor film - Google Patents
Method for manufacturing compound semiconductor filmInfo
- Publication number
- JP2001053314A JP2001053314A JP11230480A JP23048099A JP2001053314A JP 2001053314 A JP2001053314 A JP 2001053314A JP 11230480 A JP11230480 A JP 11230480A JP 23048099 A JP23048099 A JP 23048099A JP 2001053314 A JP2001053314 A JP 2001053314A
- Authority
- JP
- Japan
- Prior art keywords
- group
- fine powder
- compound semiconductor
- semiconductor film
- metal salt
- 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]
【発明の属する技術分野】本発明は、光電変換素子とし
て太陽電池材料に使用される化合物半導体膜、特にセレ
ン化物や硫化物を主成分とする化合物半導体膜の製造方
法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a compound semiconductor film used for a solar cell material as a photoelectric conversion element, in particular, a compound semiconductor film containing selenide or sulfide as a main component.
【０００２】[0002]
【従来の技術】ＣｕＩｎＳｅ2に代表されるＩｂーＩＩ
ＩｂーＶＩｂ2系のカルコパイライト構造を有する化合
物半導体膜を光吸収層に用いた太陽電池は光エネルギー
を直接、電気エネルギーに変換する際の高いエネルギー
変換効率を有しており、太陽光の照射によるエネルギー
変換効率の経時劣化も認められない。また、カルコパイ
ライト構造を有する化合物半導体膜はＳｉを主成分とす
るＳｉ系半導体膜と比較して光吸収係数が高く、かつ耐
放射線能も大きいことが知られている。 2. Description of the Related Art Ib-II represented by CuInSe 2
A solar cell using a compound semiconductor film having an Ib-VIb 2 chalcopyrite structure as a light absorbing layer has a high energy conversion efficiency when directly converting light energy into electric energy, and is irradiated with sunlight. No deterioration of the energy conversion efficiency with time due to aging is observed. It is also known that a compound semiconductor film having a chalcopyrite structure has a higher light absorption coefficient and a higher radiation resistance than a Si-based semiconductor film containing Si as a main component.
【０００３】Ｉｂ族元素、ＩＩＩｂ族元素およびＶＩｂ
族元素より構成される化合物半導体膜の製造方法におい
て、Ｉｂ族元素、ＩＩＩｂ族元素およびＶＩｂ族元素の
組成を制御することでカルコパイライト構造を得、太陽
電池の光吸収層として用いた場合にエネルギー変換効率
が高く、半導体としての特性が高性能な化合物半導体膜
を作製する手段は、精密な組成制御を行うことが膜厚方
向に対して可能な多元蒸着法に限定されているが、多元
蒸着法は精密な組成制御が可能な面積が狭く、必要な膜
厚形成に時間を要することから化合物半導体膜の大面積
化が著しく困難であり、量産化に適していない。[0003] Group Ib, IIIb and VIb elements
In a method for manufacturing a compound semiconductor film composed of a group III element, a chalcopyrite structure is obtained by controlling the composition of a group Ib element, a group IIIb element, and a group VIb element, and the energy is reduced when used as a light absorption layer of a solar cell. Means for producing a compound semiconductor film having high conversion efficiency and high performance as a semiconductor are limited to a multi-source vapor deposition method capable of performing precise composition control in the film thickness direction. In the method, the area where precise composition control is possible is narrow, and it takes time to form a required film thickness. Therefore, it is extremely difficult to increase the area of the compound semiconductor film, and it is not suitable for mass production.
【０００４】一方、化合物半導体膜の大面積化に対応可
能な手段としては、セレン化法や硫化法があるが、基板
上に既に形成されたＩｂ族元素とＩＩＩｂ族元素よりな
るアロイ膜に対して後からセレン化もしくは硫化を行わ
なければならないことから、膜中にマイクロボイドの発
生、および膜強度の低下を避けることが出来ない。On the other hand, as means capable of coping with an increase in the area of the compound semiconductor film, there are a selenization method and a sulfidation method. However, an alloy film made of a group Ib element and a group IIIb element already formed on a substrate can be used. However, since selenization or sulfidation must be performed later, generation of microvoids in the film and reduction in film strength cannot be avoided.
【０００５】また大面積化に対応する手段としてスパッ
タリング法が提案されているが、カルコパイライト化合
物の構成元素Ｉｂ族(例えばＣｕ)，ＩＩＩｂ族(例えば
Ｉｎ)，ＶＩｂ族（例えばＳｅ）の３種のスパッタリン
グターゲットを用意して同時にスパッタリングを行う
と、３元素各々のスパッタリング効率が大きく異なり、
スパッタリング速度が安定しないことから３元素の精密
な組成制御が難しい。並びにスパッタリング法は高価な
スパッタリング装置およびスパッタリングターゲットを
必要とする。A sputtering method has been proposed as a means for increasing the area. A chalcopyrite compound is composed of three elements, ie, a group Ib group (eg, Cu), a group IIIb (eg, In), and a group VIb (eg, Se). When the sputtering target is prepared and sputtering is performed at the same time, the sputtering efficiency of each of the three elements greatly differs,
Since the sputtering rate is not stable, it is difficult to precisely control the composition of the three elements. In addition, the sputtering method requires expensive sputtering equipment and sputtering targets.
【０００６】また同様に大面積化に対応可能で、かつエ
ネルギー変換効率が高く、半導体として高性能なカルコ
パイライト構造を有する化合物半導体膜を安定して得る
化合半導体膜の製造方法として、Ｉｂ族元素とＩＩＩｂ
族元素を含む有機金属塩溶液を導電性基板に被着して熱
分解処理をおこなって基板上にアロイ膜もしくはその部
分酸化物を形成した後、基板をＶＩｂ族元素雰囲気中で
熱処理して、カルコパイライト構造を有する化合物半導
体膜を得る製造方法が特開平１０−２１９４７２号公報
および特開平１１−４００９号公報にて提示されている
が、前述のセレン化法や硫化法と同様にマイクロボイド
の発生および構成元素の組成制御が難しいという問題点
を有している。[0006] Similarly, a method for producing a compound semiconductor film capable of stably obtaining a compound semiconductor film having a chalcopyrite structure, which can respond to a large area, has a high energy conversion efficiency, and has a high performance as a semiconductor, is described as an Ib group element. And IIIb
After applying an organic metal salt solution containing a group element to a conductive substrate and performing a thermal decomposition treatment to form an alloy film or a partial oxide thereof on the substrate, the substrate is heat-treated in a group VIb element atmosphere, Production methods for obtaining a compound semiconductor film having a chalcopyrite structure are disclosed in JP-A-10-219472 and JP-A-11-4009. There is a problem that generation and composition control of constituent elements are difficult.
【０００７】[0007]
【発明が解決しようとする課題】カルコパイライト構造
を有する化合物半導体膜を光吸収層に使用すると高いエ
ネルギー変換効率を有する太陽電池を製造することがで
きるにかかわらず、大面積化が対応可能であって構成元
素の精密な組成制御が可能であり、太陽電池の光吸収層
としての優れた膜特性が安定して得られる安価なカルコ
パライト構造を有する化合物半導体膜の製造方法が未だ
確立されていないという問題がある。本発明は太陽電池
の光吸収層として有効なカルコパイライト構造を有する
化合物半導体膜の量産技術を確立することが可能な化合
物半導体膜の製造方法を提供することを目的とする。When a compound semiconductor film having a chalcopyrite structure is used for a light absorbing layer, a solar cell having high energy conversion efficiency can be manufactured, but a large area can be accommodated. It is said that a method for producing a compound semiconductor film having an inexpensive chalcopyrite structure, which can precisely control the composition of constituent elements and can stably obtain excellent film characteristics as a light absorbing layer of a solar cell, has not yet been established. There's a problem. An object of the present invention is to provide a method of manufacturing a compound semiconductor film capable of establishing a mass production technique of a compound semiconductor film having a chalcopyrite structure effective as a light absorbing layer of a solar cell.
【０００８】[0008]
【課題を解決するための手段】本発明者は、この問題を
解決するためにカルコパイライト構造をを有する化合物
半導体膜の製造方法を検討した結果、本発明の製造方法
によって、簡単な手法であって安価に半導体膜の大面積
化、並びに構成元素の精密な組成制御を成し得る化合物
半導体膜の量産技術を確立することが可能であることが
判った。The present inventor studied a method for manufacturing a compound semiconductor film having a chalcopyrite structure in order to solve this problem. As a result, the manufacturing method of the present invention provides a simple method. It has been found that it is possible to establish a technique for mass production of a compound semiconductor film capable of achieving a large-area semiconductor film and controlling the composition of constituent elements precisely at low cost.
【０００９】即ち、本発明はＩｂ族元素の微粉末、ＶＩ
ｂ族元素の微粉末、およびＩＩＩｂ族元素の有機金属塩
を含む分散液を導電性の基板に被着する工程と非酸化性
雰囲気中で加熱処理する工程より化合物半導体膜を形成
することを特徴とする化合物半導体膜の製造方法であ
る。That is, the present invention relates to a fine powder of Group Ib element, VI
A compound semiconductor film is formed by a step of applying a dispersion containing a fine powder of a group b element and an organic metal salt of a group IIIb element to a conductive substrate and a step of performing heat treatment in a non-oxidizing atmosphere. Is a method for manufacturing a compound semiconductor film.
【００１０】更に、本発明はＩＩＩｂ族元素の微粉末、
ＶＩｂ族元素の微粉末、およびＩｂ族元素の有機金属塩
を含む分散液を導電性の基板に被着する工程と非酸化性
雰囲気中で加熱処理する工程より化合物半導体膜を形成
することを特徴とする化合物半導体膜の製造方法であ
る。Further, the present invention provides a fine powder of a group IIIb element,
A compound semiconductor film is formed by a step of applying a dispersion containing a fine powder of a Group VIb element and an organic metal salt of a Group Ib element to a conductive substrate and a step of performing heat treatment in a non-oxidizing atmosphere. Is a method for manufacturing a compound semiconductor film.
【００１１】更に、本発明はＶＩｂ族元素の微粉末、Ｉ
ｂ族元素の有機金属塩およびＩＩＩｂ族元素の有機金属
塩を含む分散液を導電性の基板に被着する工程と非酸化
性雰囲気中で加熱処理する工程より化合物半導体膜を形
成することを特徴とする化合物半導体膜の製造方法であ
る。Further, the present invention relates to a fine powder of a group VIb element,
A compound semiconductor film is formed by a step of applying a dispersion containing an organic metal salt of a group b element and an organic metal salt of a group IIIb element to a conductive substrate and a step of performing heat treatment in a non-oxidizing atmosphere. Is a method for manufacturing a compound semiconductor film.
【００１２】更に、本発明はＩｂ族元素の微粉末、ＩＩ
Ｉｂ族元素の微粉末、およびＶＩｂ族元素の微粉末にＩ
ｂ族元素の有機金属塩あるいはＩＩＩｂ族元素の有機金
属塩のうち１種以上を含む分散液を基板に被着する工程
と非酸化性雰囲気中で加熱処理する工程により化合物半
導体膜を形成することを特徴とする化合物半導体膜の製
造方法である。Further, the present invention relates to a fine powder of a group Ib element,
Group Ib element fine powder and Group VIb element fine powder
Forming a compound semiconductor film by a step of applying a dispersion containing at least one of an organic metal salt of a group b element or an organic metal salt of a group IIIb element to a substrate and a step of performing heat treatment in a non-oxidizing atmosphere. A method for manufacturing a compound semiconductor film.
【００１３】更に、本発明は請求項１から４の、いずれ
か一つに記載の化合物半導体膜の製造方法において、分
散液を基板に被着後、ＶＩｂ族元素を含む非酸化性雰囲
気中で熱処理することを特徴とする化合物半導体膜の製
造方法である。Further, according to the present invention, in the method for manufacturing a compound semiconductor film according to any one of claims 1 to 4, after the dispersion is applied to the substrate, the dispersion is applied to a non-oxidizing atmosphere containing a group VIb element. A method for producing a compound semiconductor film, characterized by performing a heat treatment.
【００１４】[0014]
【発明の実施の形態】本発明の化合物半導体膜の製造方
法は、導電性の基板上にＩｂ族元素の微粉末、ＶＩｂ族
元素の微粉末、およびＩＩＩｂ族元素の有機金属塩を含
む分散液を被着する工程と非酸化性雰囲気中で加熱処理
してＩｂーＩＩＩｂーＶＩｂ2元素構造、即ちカルコパ
イライト構造を有する化合物半導体膜を形成することを
特徴とする。BEST MODE FOR CARRYING OUT THE INVENTION A method for producing a compound semiconductor film according to the present invention is directed to a dispersion comprising a fine powder of a Group Ib element, a fine powder of a Group VIb element, and an organic metal salt of a Group IIIb element on a conductive substrate. And a heat treatment in a non-oxidizing atmosphere to form a compound semiconductor film having an Ib-IIIb-VIb two- element structure, that is, a chalcopyrite structure.
【００１５】導電性の基板上にＩｂ族元素の微粉末とＶ
Ｉｂ族元素の微粉末にＩＩＩｂ族元素の有機金属塩を含
む分散液を被着する工程に代わって、ＩＩＩｂ族元素の
微粉末、ＶＩｂ族元素の微粉末、およびＩｂ族元素の有
機金属塩を含む分散液を被着する工程、またはＩｂ族元
素の微粉末、ＩＩＩｂ族元素の微粉末、およびＩｂ族元
素、ＩＩＩｂ族元素のどちらか１種以上の有機金属塩を
含む分散液の被着工程であっても構わない。On a conductive substrate, fine powder of an Ib group element and V
Instead of applying the dispersion containing the organic metal salt of the group IIIb element to the fine powder of the group Ib element, the fine powder of the group IIIb element, the fine powder of the group VIb element, and the organic metal salt of the group Ib element are replaced with For applying a dispersion containing the same, or applying a dispersion containing a fine powder of a group Ib element, a fine powder of a group IIIb element, and an organic metal salt of at least one of a group Ib element and a group IIIb element It does not matter.
【００１６】本発明はカルコパイライト構造を有する化
合物半導体膜の形成において、Ｉｂ族元素を微粉末化し
液体中に分散状態にすること、およびＩＩＩｂ族元素の
有機金属塩を分散液への溶解状態にすることにより、導
電性基板への被着に際し組成ムラや皮膜ムラを軽減し、
かつ熱処理において微粉末材料と再析出材料を用いるこ
と、およびカルコパイライト化合物の構成元素をすべて
含有させることでカルコパイライト構造の化合物膜の形
成がより低温でより均一に得られることを特徴としてい
る。According to the present invention, in the formation of a compound semiconductor film having a chalcopyrite structure, a group Ib element is finely pulverized and dispersed in a liquid, and an organic metal salt of a group IIIb element is dissolved in a dispersion liquid. By doing so, when applying to the conductive substrate, reduce composition unevenness and film unevenness,
Further, it is characterized in that a compound film having a chalcopyrite structure can be more uniformly formed at a lower temperature by using a fine powder material and a reprecipitated material in the heat treatment and by including all the constituent elements of the chalcopyrite compound.
【００１７】本発明に使用する微粉末および有機金属塩
は、Ｉｂ族元素の有機金属塩とＩＩＩｂ族元素の微粉末
の組み合わせであっても構わない。Ｉｂ族元素の微粉末
とＩｂ族元素の有機金属塩が混在しても、ＩＩＩｂ族元
素の微粉末とＩＩＩｂ族元素の有機金属塩が混在しても
構わない。The fine powder and the organic metal salt used in the present invention may be a combination of an organic metal salt of a Group Ib element and a fine powder of a Group IIIb element. The fine powder of the group Ib element and the organic metal salt of the group Ib element may be mixed, or the fine powder of the group IIIb element and the organic metal salt of the group IIIb element may be mixed.
【００１８】本発明に使用する微粉末はＩｂ族元素の単
体、ＩＩＩｂ族元素の単体、もしくはＩｂ族元素とＩＩ
Ｉｂ族元素のアロイであっても構わない。微粉末の粒径
は０．０１〜５μｍ、特に１μｍ以下が好ましい。この
金属微粉末表面に界面活性剤等で表面処理が施されたも
のを本発明に使用して問題はない。The fine powder used in the present invention may be a simple substance of a group Ib element, a simple substance of a group IIIb element, or a simple substance of a group Ib element and a group II element.
It may be an alloy of an Ib group element. The particle size of the fine powder is preferably 0.01 to 5 μm, particularly preferably 1 μm or less. There is no problem in using the metal fine powder surface-treated with a surfactant or the like in the present invention.
【００１９】本発明に使用する有機金属塩は有機酸塩、
樹脂酸塩、金属アルコキシド、および金属アセチルアセ
トン錯体から選択することが可能であり、使用する分散
液に溶解することが重要である。有機金属塩は金属微粉
末やＶＩｂ族元素単体あるいはＶＩｂ族元素の化合物と
共存することから、金属微粉末やＶＩｂ族元素単体ある
いはＶＩｂ族元素の化合物と反応して系が著しく不均一
化したりする有機金属塩は本発明に適していない。The organic metal salt used in the present invention is an organic acid salt,
It is possible to choose from resinates, metal alkoxides, and metal acetylacetone complexes, and it is important that they dissolve in the dispersion used. Since the organic metal salt coexists with the metal fine powder, the single group VIb element, or the compound of the group VIb element, the organic metal salt reacts with the metal fine powder, the single element of the group VIb, or the compound of the group VIb element, and the system becomes extremely uneven. Organometallic salts are not suitable for the present invention.
【００２０】本発明に使用するＶＩｂ族元素単体あるい
はＶＩｂ族元素の有機金属塩は、Ｉｂ族元素とＩＩＩｂ
族元素が共存する状態で、Ｉｂ族元素単体、Ｉｂ族元素
の有機金属塩、ＩＩＩｂ族元素の単体、およびＩＩＩｂ
族元素の有機金属塩と熱処理時に簡単に反応してカルコ
パイライト化合物を形成することから、その粒径は微粉
末ほどの小さな粒径は必要ない。但し分散液の一部を形
成することから製造に支障を来たさない程度の粒径であ
る100μｍ以下であることが好ましい。またこのＶＩｂ
族元素は単体のみならず例えば硫化セレンのカルコゲン
物でも、分散液中でコロイド状態であっても構わない。The Group VIb element alone or the organometallic salt of the Group VIb element used in the present invention comprises a Group Ib element and a IIIb element.
A group Ib element, an organic metal salt of a group Ib element, a simple substance of a group IIIb element,
Since it easily reacts with an organic metal salt of a group element during heat treatment to form a chalcopyrite compound, its particle size does not need to be as small as a fine powder. However, it is preferable that the particle size is not more than 100 μm, which is a particle size that does not hinder the production since a part of the dispersion is formed. Also this VIb
The group element may be not only a simple substance but also a chalcogen substance of selenium sulfide, for example, or may be in a colloidal state in the dispersion.
【００２１】本発明で用いる分散液、即ち金属微粉末の
分散および有機金属塩の溶解を行う液体は有機溶剤、例
えば脂肪族炭化水素系、芳香族炭化水素系、テルペン
系、アルコール系、ケトン系、あるいはエステル系溶剤
いずれでも良く、本発明で使用する金属微粉末を分散
し、および有機金属塩を溶解しうるものであればよい。The dispersion used in the present invention, that is, the liquid for dispersing the fine metal powder and dissolving the organic metal salt, is an organic solvent such as an aliphatic hydrocarbon, an aromatic hydrocarbon, a terpene, an alcohol or a ketone. Alternatively, any solvent may be used as long as it can disperse the fine metal powder used in the present invention and dissolve the organic metal salt.
【００２２】本発明において導電性の基板に被着させる
分散液に分散助剤として界面活性剤や増粘剤を加えるこ
とができる。例えばセルロース系、脂肪酸エステル重合
体、ポリエーテル、ＰＶＡ系およびベントナイト系等、
即ち沈降抑制剤として働くものであれば、加熱処理後の
カルコパイライト化合物の半導体としての特性を損なわ
ない限り、本発明への使用は妨げるものではない。また
消泡剤の添加も、加熱処理後のカルコパイライト化合物
の半導体としての特性を損なわない限り、本発明で使用
する分散液に加えても構わない。In the present invention, a surfactant or a thickener can be added as a dispersing aid to the dispersion to be adhered to the conductive substrate. For example, cellulose type, fatty acid ester polymer, polyether, PVA type and bentonite type,
That is, as long as it acts as a precipitation inhibitor, use of the chalcopyrite compound after heat treatment in the present invention is not hindered as long as the semiconductor properties are not impaired. The defoaming agent may be added to the dispersion used in the present invention as long as the properties of the chalcopyrite compound after the heat treatment as a semiconductor are not impaired.
【００２３】本発明で使用する分散液の被着方法は、例
えば一般的な塗布方法、ディッピング法、ロールコート
法、バーコート法、スピンコーター法、スプレー法、イ
ンクジェット法、スクリーン印刷法等がその手段として
選択できるが、ディッピング法、ロールコートあるいは
バーコート法が本発明への使用において分散液の性質や
被着後の状態による材料の歩留まりを考慮するとより好
ましい被着方法である。被着時の分散液の分散状態の安
定性は長期にわたって安定である必要はなく、例えば、
ディッピング法においてディッピング時のみ分散した状
態が保持できればよく、例えば基板搬送時に分散液の攪
拌あるいは循環を、本発明で使用する分散液におこなっ
ても何ら差し支えない。The method of applying the dispersion used in the present invention includes, for example, a general coating method, dipping method, roll coating method, bar coating method, spin coater method, spray method, ink jet method, screen printing method and the like. Although it can be selected as a means, dipping, roll coating or bar coating is a more preferable deposition method in consideration of the properties of the dispersion and the yield of the material depending on the state after deposition in the use of the present invention. The stability of the dispersion state of the dispersion at the time of deposition does not need to be stable for a long time, for example,
In the dipping method, it is sufficient that the dispersed state can be maintained only at the time of dipping. For example, stirring or circulation of the dispersion during the transport of the substrate may be performed on the dispersion used in the present invention.
【００２４】本発明において導電性の基板に被着した後
の分散液の加熱処理は、分散液を被着した導電性基板を
最初に大気中で常温〜１５０℃以下で乾燥させて溶剤
が殆どなくなった後、非酸化性雰囲気中で２５０℃以
上、７００℃以下で加熱処理を行う。In the present invention, the heat treatment of the dispersion after it is applied to the conductive substrate is performed by first drying the conductive substrate on which the dispersion is applied at room temperature to 150 ° C. or less in the atmosphere to remove most of the solvent. After the disappearance, heat treatment is performed in a non-oxidizing atmosphere at a temperature of 250 ° C. or more and 700 ° C. or less.
【００２５】本発明において、加熱処理時の非酸化性雰
囲気とは、不活性ガス雰囲気、窒素ガス雰囲気、あるい
は水素ガス雰囲気等の還元性雰囲気であり、該雰囲気中
にＶＩｂ族元素もしくはＶＩｂ族元素の化合物が存在し
ても構わない。ＶＩｂ族元素もしくはＶＩｂ族元素の化
合物が存在すると、Ｉｂ族元素とＩＩＩｂ族元素による
アロイ膜と速やかに化合する。In the present invention, the non-oxidizing atmosphere at the time of the heat treatment is a reducing atmosphere such as an inert gas atmosphere, a nitrogen gas atmosphere, or a hydrogen gas atmosphere, in which a VIb group element or a VIb group element is contained. May be present. When a group VIb element or a compound of a group VIb element is present, it quickly combines with the alloy film of the group Ib element and the group IIIb element.
【００２６】カルコパイライト構造を有する化合物半導
体膜の形成法は基板への被着を繰り返しおこない所定の
膜厚を得る、あるいは被着分散液のＩｂ族元素、ＩＩＩ
ｂ族元素、ＶＩｂ族元素の組成比を逐次変えることで、
より半導体として性能の安定したカルコパイライト構造
を有する化合物半導体膜を形成することが可能である。
組成の変化で結晶粒径や半導体としてのｐｎ特性を制御
することも可能となる。またＩｎにＩＩＩｂ族元素もし
くはＩＩＩｂ族元素の化合物としてＧａを添加しエナジ
ーギャップの制御をすること、およびＩＩｂ族元素もし
くはＩＩｂ族元素の化合物をドーピング剤として分散液
中に添加することも可能である。The method of forming a compound semiconductor film having a chalcopyrite structure is to repeatedly deposit a substrate on a substrate to obtain a predetermined film thickness, or to obtain an Ib group element, III
By sequentially changing the composition ratio of group b element and group VIb element,
It is possible to form a compound semiconductor film having a chalcopyrite structure with more stable performance as a semiconductor.
It is also possible to control the crystal grain size and the pn characteristics as a semiconductor by changing the composition. It is also possible to control the energy gap by adding Ga as a group IIIb element or a compound of a group IIIb element to In, and to add a group IIb element or a group IIb element compound as a doping agent to the dispersion. .
【００２７】被着分散液中のＶＩｂ族元素の存在割合は
カルコパイライト化合物の定比付近であれば良いが、好
ましくは定比以上、即ちモル比で、ＶＩｂ族元素／（Ｉ
ｂ族元素＋ＩＩＩｂ族元素）＞１ の存在割合でカルコ
パイライト化合物が得られやすい。The proportion of the group VIb element in the applied dispersion may be near the stoichiometric ratio of the chalcopyrite compound, but is preferably higher than the stoichiometric ratio, that is, the molar ratio of the group VIb element / (I
A chalcopyrite compound is easily obtained when the proportion of (group b element + group IIIb element)> 1 is satisfied.
【００２８】本発明で分散液を付着する導電性の基板は
サブストレート型太陽電池の構成においては金属電極薄
膜（Ｍｏ、Ａｕ、Ｐｄ、Ｐｔ、Ｎｉ、Ｔｉ等からの１
種）を表面に有する基板となり、スーパーストレート型
太陽電池の構成では金属酸化物電極薄膜（ＺｎＯ、Ｓｎ
Ｏ2、ＩＴＯ等からの１種）を有する基板となる。また
本発明によるｐタイプのカルコパイライト構造を有する
化合物半導体は従来よりも低温で形成できることから、
スーパーストレート型太陽電池においても変換効率の向
上が期待できる。In the present invention, the conductive substrate to which the dispersion is applied is a metal electrode thin film (Mo, Au, Pd, Pt, Ni, Ti, etc.) in the structure of the substrate type solar cell.
Seed) on the surface, and a metal oxide electrode thin film (ZnO, Sn
O 2, 1 or from ITO or the like) as a substrate having. Since the compound semiconductor having a p-type chalcopyrite structure according to the present invention can be formed at a lower temperature than before,
An improvement in the conversion efficiency can also be expected in super-straight solar cells.
【００２９】[0029]
【実施例】［実施例１］Ｃｕ金属微粉末（平均粒径０．
２μｍ）０．１モル、Ｉｎアセチルアセトナート ０．
１モル、Ｓｅ（平均粒径４０μｍ）０．２モルをトルエ
ン１Ｌに高分子系増粘剤を添加して、被着用の分散液を
調製した。このときＩｎアセチルアセナートはトルエン
に溶解している。バーコート法でガラス基板上に分散液
を塗布し、オーブンにて １１０℃、１０分乾燥後、環状
炉にて窒素ガスの不活性雰囲気中で ３５０℃、１時間
加熱処理をおこなった。得られた膜の膜厚は １０μｍ
以上あったが、ひび割れの発生が認められた。この膜の
Ｘ線回折より結晶構造を分析し図ー１に示すグラフを得
た。グラフの横軸は回折角度、縦軸はＸ線回折強度を示
している。カルコパイライト化合物であるＣｕＩｎＳｅ
2の特徴である回折線（１１２）、（２２０）が現れ、
得られた膜中にＣｕＩｎＳｅ2が含まれていることを同
定した。 ［実施例２］Ｃｕ金属微粉末（平均粒径０．２μｍ）
０．１モル、Ｉｎアセチルアセトナート ０．１モル、
Ｓｅ（平均粒径４０μｍ）０．４モルをトルエン１Ｌに
高分子系増粘剤を添加して、被着用の分散液を調整し
た。デッピング法でガラス基板上に分散液を塗布した。
分散液中に基板を浸積し分散液中から基板を３０ｃｍ／
分の引き上げ速度で引き上げることを １０回繰り返し
た後、オーブンにて1１０℃、１０分乾燥後、環状炉に
て窒素ガスの不活性雰囲気中で３５０℃、１時間加熱処
理をおこなった。得られた膜の膜厚は約１μｍであっ
た。Ｘ線回折よりこの膜の結晶構造を分析し、図ー２に
示すグラフを得た。グラフの横軸は回折角度、縦軸はＸ
線回折強度を示している。カルコパイライト化合物であ
るＣｕＩｎＳｅ2以外の回折線のピークが小さくなり、
得られた膜中でのＣｕＩｎＳｅ2の含有比が実施例１の
膜より大きい結果であった。[Example 1] Cu metal fine powder (average particle diameter of 0.1 mm).
2 μm) 0.1 mol, In acetylacetonate
1 mol of Se and 0.2 mol of Se (average particle diameter: 40 μm) were added to 1 L of toluene with a polymer-based thickener to prepare a dispersion for coating. At this time, In acetylacenate is dissolved in toluene. The dispersion was applied on a glass substrate by a bar coating method, dried at 110 ° C. for 10 minutes in an oven, and then heated at 350 ° C. for 1 hour in an inert atmosphere of nitrogen gas in an annular furnace. The thickness of the obtained film is 10 μm
As described above, cracking was observed. The crystal structure of the film was analyzed by X-ray diffraction, and the graph shown in FIG. 1 was obtained. The horizontal axis of the graph indicates the diffraction angle, and the vertical axis indicates the X-ray diffraction intensity. CuInSe, a chalcopyrite compound
Diffraction lines (112) and (220), which are features of 2 , appear,
It was identified that CuInSe 2 was contained in the obtained film. [Example 2] Cu metal fine powder (average particle size 0.2 µm)
0.1 mol, In acetylacetonate 0.1 mol,
0.4 mol of Se (average particle size: 40 μm) was added to 1 L of toluene with a polymer-based thickener to prepare a dispersion to be applied. The dispersion was applied on a glass substrate by a dipping method.
The substrate is immersed in the dispersion, and the substrate is immersed in the dispersion by 30 cm /
After 10 times of pulling up at a pulling rate of 1 minute, drying was performed in an oven at 110 ° C. for 10 minutes, and then heat treatment was performed in an annular furnace at 350 ° C. for 1 hour in an inert atmosphere of nitrogen gas. The thickness of the obtained film was about 1 μm. The crystal structure of this film was analyzed by X-ray diffraction, and the graph shown in FIG. 2 was obtained. The horizontal axis of the graph is the diffraction angle, and the vertical axis is X
The figure shows the line diffraction intensity. The peak of the diffraction line other than the chalcopyrite compound CuInSe 2 becomes smaller,
The result was that the content ratio of CuInSe 2 in the obtained film was larger than that of the film of Example 1.
【００３０】[0030]
【発明の効果】本発明では、Ｉｂ族元素単体の微粉末、
ＶＩｂ族元素単体の微粉末およびＩＩＩｂ族元素を含む
有機金属塩よりなる分散液、またはＩＩＩｂ族元素単体
の微粉末、ＶＩｂ族元素単体の微粉末およびＩｂ族元素
を含む有機金属塩よりなる分散液を導電性基板上に被着
し、非酸化性雰囲気中で加熱処理をおこなって、一度に
Ｉｂ−ＩＩＩｂ−ＶＩｂ２系のカルコパイライト構造を
有する化合物半導体膜を得ることが可能であることか
ら、簡便な製造方法で、低コストの大面積対応可能な、
且つ製造時の熱履歴を抑制した高品質の太陽電池の光吸
収層を製造することができる。According to the present invention, a fine powder of a simple substance of group Ib is provided,
Dispersion consisting of fine powder of group VIb element alone and organic metal salt containing group IIIb element, or dispersion liquid consisting of fine powder of group IIIb element alone, fine powder of group VIb element alone and organic metal salt containing group Ib element On a conductive substrate, and heat-treated in a non-oxidizing atmosphere to obtain a compound semiconductor film having an Ib-IIIb-VIb2-based chalcopyrite structure at a time. With a simple manufacturing method, it can support low cost and large area,
In addition, it is possible to manufacture a high-quality light absorbing layer of a solar cell in which the heat history during manufacturing is suppressed.
【図面の簡単な説明】[Brief description of the drawings]
【図１】実施例１で得られた膜のＸ線回折測定チャー
ト。FIG. 1 is an X-ray diffraction measurement chart of a film obtained in Example 1.
【図２】実施例２で得られた膜のＸ線回折測定チャー
ト。FIG. 2 is an X-ray diffraction measurement chart of a film obtained in Example 2.
Claims (5)
末、およびＩＩＩｂ族元素の有機金属塩を含む分散液を
導電性の基板に被着する工程と非酸化性雰囲気中で加熱
処理する工程より化合物半導体膜を形成することを特徴
とする化合物半導体膜の製造方法。1. A step of applying a dispersion containing a fine powder of a group Ib element, a fine powder of a group VIb element, and an organic metal salt of a group IIIb element to a conductive substrate, and a heat treatment in a non-oxidizing atmosphere. Forming a compound semiconductor film from the step of forming a compound semiconductor film.
微粉末、およびＩｂ族元素の有機金属塩を含む分散液を
導電性の基板に被着する工程と非酸化性雰囲気中で加熱
処理する工程より化合物半導体膜を形成することを特徴
とする化合物半導体膜の製造方法。2. A step of applying a dispersion containing a fine powder of a group IIIb element, a fine powder of a group VIb element, and an organic metal salt of a group Ib element to a conductive substrate, and performing heat treatment in a non-oxidizing atmosphere. Forming a compound semiconductor film from the step of forming a compound semiconductor film.
金属塩、およびＩＩＩｂ族元素の有機金属塩を含む分散
液を導電性の基板に被着する工程と非酸化性雰囲気中で
加熱処理する工程より化合物半導体膜を形成することを
特徴とする化合物半導体膜の製造方法。3. A step of applying a dispersion containing fine powder of a Group VIb element, an organic metal salt of a Group Ib element, and an organic metal salt of a Group IIIb element to a conductive substrate, and heating in a non-oxidizing atmosphere. A method for producing a compound semiconductor film, comprising forming a compound semiconductor film from the step of treating.
粉末、およびＶＩｂ族元素の微粉末に加えて、Ｉｂ族元
素の有機金属塩あるいはＩＩＩｂ族元素の有機金属塩の
うち１種以上を含む分散液を導電性の基板に被着する工
程と非酸化性雰囲気中で加熱処理する工程より化合物半
導体膜を形成することを特徴とする化合物半導体膜の製
造方法。4. In addition to a fine powder of a Group Ib element, a fine powder of a Group IIIb element, and a fine powder of a Group VIb element, at least one of an organic metal salt of a Group Ib element and an organic metal salt of a Group IIIb element A method for producing a compound semiconductor film, comprising: forming a compound semiconductor film from a step of applying a dispersion containing the compound to a conductive substrate and a step of performing heat treatment in a non-oxidizing atmosphere.
化合物半導体膜の製造方法において、分散液を導電性の
基板に被着後、ＶＩｂ族元素を含む非酸化性雰囲気中で
加熱処理することを特徴とする化合物半導体膜の製造方
法。5. The method for manufacturing a compound semiconductor film according to claim 1, wherein the dispersion liquid is applied to a conductive substrate and then the dispersion liquid is applied to a non-oxidizing atmosphere containing a group VIb element. A method for producing a compound semiconductor film, comprising performing heat treatment.
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|---|---|---|---|
| JP11230480A JP2001053314A (en) | 1999-08-17 | 1999-08-17 | Method for manufacturing compound semiconductor film |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11230480A JP2001053314A (en) | 1999-08-17 | 1999-08-17 | Method for manufacturing compound semiconductor film |
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| WO2012014924A1 (en) * | 2010-07-29 | 2012-02-02 | 京セラ株式会社 | Photoelectric conversion device |
| WO2013038870A1 (en) * | 2011-09-16 | 2013-03-21 | 京セラ株式会社 | Photoelectric conversion device and method for manufacturing photoelectric conversion device |
| JPWO2013038870A1 (en) * | 2011-09-16 | 2015-03-26 | 京セラ株式会社 | Photoelectric conversion device and method for manufacturing photoelectric conversion device |
| KR101299584B1 (en) * | 2011-11-28 | 2013-08-26 | 금호전기주식회사 | Thin-film solar cell and its manufacturing method |
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