JPH0860359A - Production of semiconductor thin film having chalcopyrite structure - Google Patents
Production of semiconductor thin film having chalcopyrite structureInfo
- Publication number
- JPH0860359A JPH0860359A JP6199418A JP19941894A JPH0860359A JP H0860359 A JPH0860359 A JP H0860359A JP 6199418 A JP6199418 A JP 6199418A JP 19941894 A JP19941894 A JP 19941894A JP H0860359 A JPH0860359 A JP H0860359A
- Authority
- JP
- Japan
- Prior art keywords
- substrate
- thin film
- semiconductor thin
- chalcopyrite structure
- structure semiconductor
- 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
Landscapes
- Physical Vapour Deposition (AREA)
- Physical Deposition Of Substances That Are Components Of Semiconductor Devices (AREA)
- Photovoltaic Devices (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、高効率の薄膜太陽電池
の構成とその製造プロセスに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high efficiency thin film solar cell structure and its manufacturing process.
【０００２】[0002]
【従来の技術】太陽電池の吸収層として用いられるI
族、III族、VI族からなるカルコパイライト型化合物半
導体薄膜は光吸収係数が大きく、太陽電池を構成するの
に有利な材料である。2. Description of the Related Art I used as an absorption layer for solar cells
A chalcopyrite type compound semiconductor thin film made of Group III, Group III or Group VI has a large light absorption coefficient and is an advantageous material for forming a solar cell.
【０００３】このカルコパイライト薄膜を作製する場
合、例えばＣｕＩｎＳｅ2を作成する場合は、I族である
Ｃｕ過剰のカルコパイライト薄膜を形成した後、III族
であるＩｎ過剰のカルコパイライト層を前記薄膜上に形
成することによって結晶粒径が大きく、さらにＣｕ2-X
Ｓｅ等の異相化合物を析出させない二重層カルコパイラ
イト薄膜形成方法により作製する。この２層構造のカル
コパイライト薄膜層を形成するとき、基板の熱膨張係数
がカルコパイライト薄膜の熱膨張係数に近い値を持つ基
板を用いることによって基板温度を５００℃以上に設定
できるようになり、結晶粒径が２μｍ以上でしかも下部
電極との密着性に優れたとカルコパイライト薄膜が得ら
れる。In the case of producing this chalcopyrite thin film, for example, in the case of producing CuInSe 2, after forming a group I Cu-excessive chalcopyrite thin film, a group III In-excessive chalcopyrite layer is formed on the thin film. Has a large crystal grain size, and Cu 2-X
It is prepared by a double layer chalcopyrite thin film forming method that does not precipitate a heterophase compound such as Se. When the chalcopyrite thin film layer having the two-layer structure is formed, the substrate temperature can be set to 500 ° C. or higher by using a substrate whose coefficient of thermal expansion is close to that of the chalcopyrite thin film. A chalcopyrite thin film is obtained when the crystal grain size is 2 μm or more and the adhesion to the lower electrode is excellent.
【０００４】[0004]
【発明が解決しようとする課題】上記二重層カルコパイ
ライト薄膜を形成する場合、基板温度が高いほどカルコ
パイライト薄膜の粒径が大きくなり結晶性が良くなるた
め、光を吸収する能力が高まる。しかし、基板を５００
℃以上に加熱するとその熱膨張により基板にかなりの応
力がかかることとなる。実際、急激な熱膨張のため基板
に歪が生じたり、基板あるいは下部電極に亀裂が入る現
象が起こったり、この応力によりカルコパイライト薄膜
が剥離したりする。In the case of forming the above-mentioned double-layer chalcopyrite thin film, the higher the substrate temperature, the larger the grain size of the chalcopyrite thin film and the better the crystallinity, so that the ability to absorb light is enhanced. However, the substrate
When heated to above ℃, the thermal expansion causes a considerable stress on the substrate. In fact, the substrate may be distorted due to the rapid thermal expansion, a crack may occur in the substrate or the lower electrode, and the stress may cause the chalcopyrite thin film to peel off.
【０００５】また、従来は基板裏側からの基板加熱方法
であり、例えばＣｕ（Ｉｎ、Ｇａ）Ｓｅ2等の固溶体を
作製する場合において、基板温度によりＩｎとＧａの膜
厚方向に対する分布の制御は考えられていなかった。The conventional method is to heat the substrate from the back side of the substrate. For example, when a solid solution such as Cu (In, Ga) Se 2 is prepared, the distribution of In and Ga in the film thickness direction can be controlled by the substrate temperature. I wasn't thinking.
【０００６】[0006]
【課題を解決するための手段】上記課題を解決するため
に、本発明は、I族III族VI族元素からなるカルコパイラ
イト構造半導体薄膜を５００℃以上の基板温度で堆積す
る際に、基板表面側から基板を加熱することによって半
導体薄膜を形成する方法をとる。In order to solve the above-mentioned problems, the present invention provides a substrate surface when a chalcopyrite structure semiconductor thin film made of a group I III group VI element is deposited at a substrate temperature of 500 ° C. or higher. A semiconductor thin film is formed by heating the substrate from the side.
【０００７】また、I族III族VI族元素からなるカルコパ
イライト構造半導体薄膜を形成中に直線的あるいは段階
的に基板の加熱温度を変えることにより基板温度の制御
を行いながらカルコパイライト構造半導体薄膜を形成す
る。Further, the chalcopyrite structure semiconductor thin film is formed while controlling the substrate temperature by changing the heating temperature of the substrate linearly or stepwise during formation of the chalcopyrite structure semiconductor thin film composed of the group I group III group VI element. Form.
【０００８】[0008]
【作用】上記の手段により、基板に損傷を与えることな
く、しかも基板と下部電極との密着性を保持したまま結
晶性の優れたカルコパイライト薄膜を得られる。また、
基板表面側からの加熱により基板表面温度の制御性に優
れ、さらにI族、III族、VI族元素間の相互拡散の割合を
制御することが可能であり、太陽光を吸収するのに最適
なバンドギャッププロファイルを設計できる。By the above means, a chalcopyrite thin film having excellent crystallinity can be obtained without damaging the substrate and maintaining the adhesion between the substrate and the lower electrode. Also,
It has excellent controllability of the substrate surface temperature by heating from the substrate surface side, and it is also possible to control the ratio of interdiffusion between group I, group III, and group VI elements, making it ideal for absorbing sunlight. Can design bandgap profiles.
【０００９】[0009]
（実施例１）以下、本発明の第１の実施例について図
１、図２に基づき説明する。(Embodiment 1) A first embodiment of the present invention will be described below with reference to FIGS.
【００１０】図１は、スパッタ装置の真空容器の概略図
である。以下、カルコパイライト薄膜の作製方法につい
て説明する。FIG. 1 is a schematic view of a vacuum container of a sputtering apparatus. Hereinafter, a method for producing the chalcopyrite thin film will be described.
【００１１】基板３には熱膨張係数８０×１０-7／℃の
ソ−ダライムガラスを用いた。このガラス基板３上に、
ＲＦスパッタ法によりＭｏ膜を堆積し、さらに前記Ｍｏ
上にＣｕＩｎＳｅ2薄膜を以下に示すように堆積させ
た。For the substrate 3, soda lime glass having a thermal expansion coefficient of 80 × 10 -7 / ° C. was used. On this glass substrate 3,
A Mo film is deposited by the RF sputtering method, and
A CuInSe 2 thin film was deposited on top as shown below.
【００１２】真空容器１内部にＣｕＩｎＳｅ2の主成分
であるＣｕの蒸着源７とＩｎの蒸着源８とＳｅ９の蒸着
源を用意し、真空度約１０-7torrのもとで、Ｃｕ、Ｉ
ｎ、Ｓｅの蒸着源ルツボの温度をそれぞれ１２２０℃、
８５０℃〜９００℃、１８０℃に熱し、各元素を蒸発さ
せる。また、前記真空容器１は赤外線ヒ−タ１５と赤外
線レ−ザ１６を装備している。ＣｕＩｎＳｅ2薄膜は、
Ｃｕ過剰膜上にＩｎ過剰膜を堆積した２層構造である。
１層目のＣｕ過剰膜の基板温度は５００℃一定とする。
この時基板の加熱は基板裏側からのヒ−タ−２のみの加
熱とする。Inside the vacuum vessel 1, a Cu vapor deposition source 7 which is the main component of CuInSe 2, an In vapor deposition source 8 and an Se 9 vapor deposition source are prepared, and under the vacuum degree of about 10 −7 torr, Cu, I
n, Se vapor deposition source crucible temperature of 1220 ℃,
Each element is evaporated by heating at 850 ° C to 900 ° C and 180 ° C. The vacuum container 1 is equipped with an infrared heater 15 and an infrared laser 16. CuInSe 2 thin film is
It has a two-layer structure in which an In excess film is deposited on a Cu excess film.
The substrate temperature of the Cu excess film of the first layer is kept constant at 500 ° C.
At this time, the substrate is heated by heating only the heater-2 from the back side of the substrate.
【００１３】このＣｕ過剰膜を約２μｍ蒸着する。この
Ｃｕ過剰膜の組成比は約Ｃｕ／Ｉｎ＝１．０〜１．２で
ある。次に２層目のＩｎ過剰膜を作製するために、Ｃｕ
とＳｅの分子線強度はＣｕ過剰膜と同じ値に保持し、Ｉ
ｎの分子線強度が増加するようにＫセル温度を上昇させ
る。この時、同時に基板温度も５２５℃まで上昇させ
る。基板加熱は基板裏側からのヒ−タ−２と赤外線ヒ−
タ１５による輻射の２通りとする。その後Ｉｎ過剰膜を
堆積し、最終的な組成がＣｕ／Ｉｎ＝０．８〜０．９に
なるようＩｎ過剰膜を制御する。This Cu excess film is vapor-deposited to a thickness of about 2 μm. The composition ratio of the Cu excess film is about Cu / In = 1.0 to 1.2. Next, in order to produce a second layer of In-rich film, Cu
The molecular beam intensities of and Se are kept at the same values as those of the Cu excess film,
The K cell temperature is raised so that the molecular beam intensity of n increases. At this time, the substrate temperature is also raised to 525 ° C. at the same time. The board is heated from the backside of the board by a heater-2 and infrared heater.
There are two types of radiation from the data 15. After that, an In excess film is deposited, and the In excess film is controlled so that the final composition is Cu / In = 0.8 to 0.9.
【００１４】また、基板温度の測定は真空容器下部に真
空ガラス窓５を設け、赤外線放射温度計６によって基板
表面温度を測定している。For measuring the substrate temperature, a vacuum glass window 5 is provided in the lower part of the vacuum container, and the substrate surface temperature is measured by an infrared radiation thermometer 6.
【００１５】Ｃｕ過剰膜の上にＩｎ過剰膜を作製する際
の２５℃の基板温度の昇温を、基板裏側のヒ−タから５
℃／ｍｉｎの割合で昇温した場合と、基板表面からヒ−
タの輻射熱により同じく５℃／ｍｉｎの割合で昇温した
場合における基板表面温度の変化を図２に示す。When the In-excess film is formed on the Cu-excess film, the substrate temperature is raised by 25 ° C. from the heater on the backside of the substrate to 5
When the temperature is raised at a rate of
FIG. 2 shows the change in the substrate surface temperature when the temperature is raised at a rate of 5 ° C./min by the radiant heat of the substrate.
【００１６】図２に示されているように、基板裏側から
のヒ−タの加熱による基板温度の昇温は、指数関数的な
昇温過程である。それに対し基板表面側からのヒ−タの
輻射熱による昇温は、一定の割合で昇温する緩やかな昇
温過程である。As shown in FIG. 2, the heating of the substrate temperature by heating the heater from the back side of the substrate is an exponential heating process. On the other hand, the temperature rise by the radiant heat of the heater from the substrate surface side is a gradual temperature rise process in which the temperature rises at a constant rate.
【００１７】また、これらの基板を１００℃以下に冷却
して真空容器内から取り出したところ、基板裏側からヒ
−タで加熱した基板は歪が生じているのに対し、基板表
面側からのヒ−タの輻射熱によって昇温した基板には歪
がみられなかった。これら基板の上に堆積したＣｕＩｎ
Ｓｅ2薄膜と下部電極との密着性を調べるためにメンデ
ィングテ−プによる引き剥し試験を行ったところ、基板
裏側からヒ−タで加熱した基板からはＣｕＩｎＳｅ2薄
膜が少し剥離しているのに対し、基板表面側からのヒ−
タの輻射熱によって昇温した基板からは目立ったような
剥離はなく、密着性にも優れていることがわかった。Further, when these substrates were cooled to 100 ° C. or lower and taken out from the vacuum container, the substrate heated by the heater from the back side of the substrate was distorted, while the substrate from the front side was heated. -No distortion was observed on the substrate heated by the radiant heat of the electrode. CuIn deposited on these substrates
A peeling test using a mending tape was conducted to examine the adhesion between the Se 2 thin film and the lower electrode, but the CuInSe 2 thin film was slightly peeled from the substrate heated with a heater from the backside of the substrate. , From the front side of the board
It was found that there was no noticeable peeling from the substrate whose temperature was raised by the radiant heat of the wafer, and the adhesiveness was excellent.
【００１８】以下に、基板表面側からヒ−タの輻射熱を
使って基板の昇温を行ったときの基板温度に対する、そ
れによって得られたカルコパイライト薄膜を用いて作製
した太陽電池の特性値を示す。太陽電池の構成は、ガラ
スの上にＭｏ、ＣｕＩｎＳｅ 2、ＣｄＳ、ＺｎＯ、ＩＴ
Ｏの順に堆積している。ＣｄＳは化学溶液析出法によ
り、ＺｎＯ、ＩＴＯはＲＦマグネトロンスパッタ装置に
より形成している。Below, the radiant heat of the heater from the substrate surface side
The temperature of the board when the temperature of the board is raised using
Fabrication using the chalcopyrite thin film obtained by this
The characteristic value of the solar cell is shown. The structure of the solar cell is
Mo, CuInSe on top 2, CdS, ZnO, IT
O is deposited in this order. CdS is a chemical solution deposition method.
ZnO and ITO are used in RF magnetron sputtering equipment.
More formed.
【００１９】また、基板の昇温は５００℃までを基板裏
側からのヒ−タによる加熱とし、５００℃以上の昇温は
基板表面側からのヒ−タの輻射熱によるものとした。The temperature of the substrate was raised up to 500 ° C. by heating with a heater from the back side of the substrate, and the temperature of 500 ° C. or higher was radiated by the heater from the front side of the substrate.
【００２０】[0020]
【表１】 [Table 1]
【００２１】（表１）よりわかるよう、１層目と２層目
の基板温度がそれぞれ５２５℃と５５０℃である太陽電
池において最も高い変換効率を得られた。２層目の基板
温度が５７５℃以上ではＣｕＩｎＳｅ2薄膜の剥離によ
り太陽電池を作製できなかった。さらに基板の歪も生じ
ていたが、５５０℃以下の温度では歪は生じていなかっ
た。As can be seen from (Table 1), the highest conversion efficiency was obtained in the solar cells in which the substrate temperatures of the first and second layers were 525 ° C. and 550 ° C., respectively. When the substrate temperature of the second layer was 575 ° C. or higher, the solar cell could not be manufactured due to the peeling of the CuInSe 2 thin film. Further, the substrate was distorted, but the strain was not generated at a temperature of 550 ° C. or lower.
【００２２】また、（表１）より基板温度が高い方が開
放電圧値が高いことがわかる。従って、基板表面側から
の基板加熱より基板が歪むこと無く、しかも結晶性の優
れたＣｕＩｎＳｅ2薄膜を作製できた。Further, it can be seen from Table 1 that the higher the substrate temperature, the higher the open circuit voltage value. Therefore, a CuInSe 2 thin film having excellent crystallinity could be produced without the substrate being distorted by heating the substrate from the surface side.
【００２３】同様な結果はI族元素にＡｇ１０を、III族
元素にＧａ１１あるいはＡｌ１２を、IV族元素にＳ１３
あるいはＴｅ１４をそれぞれ用いた場合においても、あ
るいはそれらの混晶を用いた場合においても得られた。Similar results show that the group I element is Ag10, the group III element is Ga11 or Al12, and the group IV element is S13.
Alternatively, it was obtained when Te14 was used, respectively, or when a mixed crystal thereof was used.
【００２４】さらに、基板表面側からの基板加熱はレ−
ザ１６においても可能である。 （実施例２）次に第２の実施例として、１層目と２層目
にそれぞれＣｕとＧａの合金薄膜とＣｕとＩｎの合金薄
膜を堆積した薄膜を真空容器１内で作製した。それぞれ
の膜厚は１μｍである。この合金薄膜をＳｅ雰囲気中基
板温度４００℃で３０分間熱処理を行った。同時に、基
板表面側からも赤外線ヒ−タを用いて基板温度を上げる
ことも行った。基板温度の昇温は、基板表面側からのヒ
−タの輻射熱により０．５℃／ｍｉｎと１℃／ｍｉｎの
割合で行った。Further, the heating of the substrate from the substrate surface side is delayed.
It is also possible in The 16. (Example 2) Next, as a second example, a thin film in which an alloy thin film of Cu and Ga and an alloy thin film of Cu and In were deposited on the first layer and the second layer, respectively, was prepared in the vacuum container 1. Each film thickness is 1 μm. This alloy thin film was heat-treated in a Se atmosphere at a substrate temperature of 400 ° C. for 30 minutes. At the same time, the substrate temperature was also increased from the substrate surface side using an infrared heater. The substrate temperature was raised at a rate of 0.5 ° C./min and 1 ° C./min by the radiant heat of the heater from the substrate surface side.
【００２５】オ−ジェ電子分光法（ＡＥＳ）による、そ
れぞれの薄膜における深さ方向に対するＧａとＩｎの分
布の様子を図３、４に示す。FIGS. 3 and 4 show the distribution of Ga and In in the depth direction of each thin film by Auger electron spectroscopy (AES).
【００２６】図３、４より、膜の深さ方向に対してＧａ
とＩｎの分布の様子が異なっていることがわかる。基板
表面側からのヒ−タの輻射熱による基板加熱昇温が０．
５℃／ｍｉｎの場合では、膜中深さ方向に対して基板側
にＧａが多く分布しているが、膜の表面側にはＩｎが多
く分布している。From FIGS. 3 and 4, Ga is measured in the depth direction of the film.
It can be seen that the distribution states of In and In are different. The substrate heating temperature rise due to the radiant heat of the heater from the substrate surface side is 0.
In the case of 5 ° C./min, a large amount of Ga is distributed on the substrate side with respect to the depth direction in the film, but a large amount of In is distributed on the surface side of the film.
【００２７】ところが基板加熱昇温が０．５℃／ｍｉｎ
に比べて１℃／ｍｉｎでは、膜中深さ方向に対してＧａ
とＩｎの分布がより均一に分布している。すなわち、基
板温度が高くなればＧａとＩｎの相互拡散の割合が大き
くなる。However, the substrate heating temperature rise is 0.5 ° C./min.
At 1 ° C./min, compared to Ga in the depth direction in the film,
The distributions of In and In are more evenly distributed. That is, the higher the substrate temperature, the greater the ratio of Ga and In interdiffusion.
【００２８】従って、基板表面側からの基板加熱の温度
の変化によってIII族元素間の相互拡散の割合を制御す
ることが可能であり、バンドギャッププロファイルの設
定に有効である。Therefore, it is possible to control the mutual diffusion ratio between the group III elements by changing the temperature of the substrate heating from the substrate surface side, which is effective for setting the band gap profile.
【００２９】このほか、ＣｕＩｎＳｅ2だけでなくＡ
ｇ、Ｇａ、Ａｌ、Ｓ、Ｔｅ等の元素によるカルコパイラ
イト構造半導体薄膜においても形成が可能である。In addition to CuInSe 2 , A
It can also be formed in a chalcopyrite structure semiconductor thin film made of an element such as g, Ga, Al, S or Te.
【００３０】以上、カルコパイライト構造半導体薄膜を
基板上に堆積する場合において、基板裏側から基板加熱
ヒ−タにより基板温度を５００℃以下におさえながら基
板表面側から加熱することにより、基板表面温度を５０
０℃以上にすることによって基板に歪が生じることな
く、結晶性の優れたカルコパイライト構造半導体薄膜を
形成できた。As described above, when the chalcopyrite structure semiconductor thin film is deposited on the substrate, the substrate surface temperature is controlled by heating the substrate surface side from the substrate backside while keeping the substrate temperature at 500 ° C. or less by the substrate heating heater. Fifty
By setting the temperature to 0 ° C. or more, a chalcopyrite structure semiconductor thin film having excellent crystallinity could be formed without distortion of the substrate.
【００３１】また、カルコパイライト構造半導体薄膜を
形成中に基板表面側から加熱温度を変えることにより、
基板温度の制御を行いながらI族元素間およびIII族、IV
族元素間の相互拡散の割合を制御を可能とできる。By changing the heating temperature from the substrate surface side during formation of the chalcopyrite structure semiconductor thin film,
Controlling the substrate temperature while controlling group I elements and groups III and IV
It is possible to control the rate of mutual diffusion between group elements.
【００３２】[0032]
【発明の効果】本発明により、基板の損傷を起こすこと
無く、かつ下部電極との密着性に優れた結晶性の良いカ
ルコパイライト薄膜を作製することができ、さらに太陽
光吸収層のカルコパイライト薄膜によるバンドギャップ
プロファイルの制御を可能にし、これによりカルコパイ
ライト薄膜を用いた太陽電池の高効率化が図れる。According to the present invention, it is possible to produce a chalcopyrite thin film having good crystallinity and excellent adhesion to the lower electrode without causing damage to the substrate, and further, the chalcopyrite thin film of the solar light absorbing layer. It becomes possible to control the bandgap profile by using, and thereby the efficiency of the solar cell using the chalcopyrite thin film can be improved.
【図面の簡単な説明】[Brief description of drawings]
【図１】カルコパイライト薄膜形成装置を示す図FIG. 1 is a view showing a chalcopyrite thin film forming apparatus.
【図２】カルコパイライト薄膜形成時における昇温時間
に対する基板表面温度の変化を示す図FIG. 2 is a diagram showing changes in the substrate surface temperature with respect to the temperature rise time when forming a chalcopyrite thin film.
【図３】基板温度を４００℃から０．５℃／ｍｉｎで昇
温したときのカルコパイライト薄膜形成時における膜中
深さ方向に対するＧａとＩｎの分布図FIG. 3 is a Ga and In distribution diagram in the depth direction of the film during formation of a chalcopyrite thin film when the substrate temperature is increased from 400 ° C. to 0.5 ° C./min.
【図４】基板温度を４００℃から１℃／ｍｉｎで昇温し
たときのカルコパイライト薄膜形成時における膜中深さ
方向に対するＧａとＩｎの分布図FIG. 4 is a Ga and In distribution diagram in the depth direction of the film during formation of a chalcopyrite thin film when the substrate temperature is raised from 400 ° C. at 1 ° C./min.
１ 真空容器 ２ 基板ヒ−タ ３ 基板 ４ 排気口 ５ 真空窓 ６ 放射温度計 ７ Ｃｕ源 ８ Ｉｎ源 ９ Ｓｅ源 １０ Ａｇ源 １１ Ｇａ源 １２ Ａｌ源 １３ Ｓ源 １４ Ｔｅ源 １５ 赤外線ヒ−タ １６ 赤外線レ−ザ １７ 基板裏側から昇温した場合の基板温度の変化 １９ 基板表面側から昇温した場合の基板温度の変化 ２０ 基板昇温０．５℃／ｍｉｎにおけるＧａの膜中深
さ方向に対する分布 ２１ 基板昇温０．５℃／ｍｉｎにおけるＩｎの膜中深
さ方向に対する分布 ２２ 基板昇温１℃／ｍｉｎにおけるＧａの膜中深さ方
向に対する分布 ２３ 基板昇温１℃／ｍｉｎにおけるＩｎの膜中深さ方
向に対する分布1 Vacuum Container 2 Substrate Heater 3 Substrate 4 Exhaust Port 5 Vacuum Window 6 Radiation Thermometer 7 Cu Source 8 In Source 9 Se Source 10 Ag Source 11 Ga Source 12 Al Source 13 S Source 14 Te Source 15 Infrared Heater 16 Infrared laser 17 Change in substrate temperature when the temperature is raised from the back side of the substrate 19 Change in substrate temperature when the temperature is raised from the front side of the substrate 20 Ga relative to the depth direction of Ga at a temperature increase of 0.5 ° C / min Distribution 21 Distribution of In at the substrate temperature rise of 0.5 ° C./min in the depth direction of the film 22 Distribution of Ga at the substrate temperature rise of 1 ° C./min in the depth direction of the film 23 In of In at the substrate temperature rise of 1 ° C./min Distribution in the depth direction in the film
───────────────────────────────────────────────────── フロントページの続き (72)発明者 根上 卓之 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takuyuki Negami 1006 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd.
Claims (12)
に堆積する工程において、基板の表面側から加熱し薄膜
を堆積させることを特徴とするカルコパイライト構造半
導体薄膜の製造方法。1. A method for producing a chalcopyrite structure semiconductor thin film, characterized in that, in the step of depositing a chalcopyrite structure semiconductor thin film on a substrate, the thin film is deposited by heating from the front surface side of the substrate.
る請求項１記載のカルコパイライト構造半導体薄膜の製
造方法。2. The method for producing a chalcopyrite structure semiconductor thin film according to claim 1, wherein the back side of the substrate is heated at the same time.
程時、基板表面側からの加熱温度あるいは加熱時間のう
ち少なくとも１つを変化させることにより、基板温度を
直線的あるいは段階的に加熱することを特徴とする請求
項１または２記載のカルコパイライト構造半導体薄膜の
製造方法。3. The substrate temperature is linearly or stepwise heated by changing at least one of the heating temperature and the heating time from the substrate surface side during the deposition process of the chalcopyrite structure semiconductor thin film. The method for producing a chalcopyrite structure semiconductor thin film according to claim 1 or 2.
ことを特徴とする請求項１〜３のいずれかに記載のカル
コパイライト構造半導体薄膜の製造方法。4. The method for producing a chalcopyrite structure semiconductor thin film according to claim 1, wherein the substrate temperature is maintained at 500 ° C. or higher and heated.
０℃以下に保持し、基板表面側からの加熱により基板温
度を５００℃以上に保持することを特徴とする請求項４
記載のカルコパイライト構造半導体薄膜の製造方法。5. The substrate temperature is controlled to 50 by heating from the back side of the substrate.
5. The substrate temperature is kept at 0 ° C. or lower, and the substrate temperature is kept at 500 ° C. or higher by heating from the substrate surface side.
A method for producing the chalcopyrite structure semiconductor thin film described.
徴とする請求項１記載のカルコパイライト構造半導体薄
膜の製造方法。6. The method for producing a chalcopyrite structure semiconductor thin film according to claim 1, wherein the substrate surface is heated by radiant heat.
１つにより輻射熱を発生させることを特徴とする請求項
６記載のカルコパイライト構造半導体薄膜の製造方法。7. The method for producing a chalcopyrite structure semiconductor thin film according to claim 6, wherein radiant heat is generated by at least one of a heater and a laser beam.
μｍ以下とする請求項７記載のカルコパイライト構造半
導体薄膜の製造方法。8. A laser light having a wavelength of 0.6 μm or more, 20
The method for producing a chalcopyrite structure semiconductor thin film according to claim 7, wherein the thickness is at most μm.
あるI族、III族、VI族元素を同時に蒸着し堆積する工程
を含むことを特徴とする請求項１〜３のいずれかに記載
のカルコパイライト構造半導体薄膜の製造方法。9. The chalcopyrite according to any one of claims 1 to 3, further comprising a step of simultaneously vapor depositing and depositing a group I element, a group III element and a group VI element which are constituent elements of the chalcopyrite structure semiconductor. Method for manufacturing structural semiconductor thin film.
堆積した後に、VI族元素を蒸着して堆積する工程を含む
ことを特徴とする請求項１〜３のいずれかに記載のカル
コパイライト構造半導体薄膜の製造方法。10. The method according to claim 1, further comprising a step of depositing a thin film of a group I element and a group III element on a substrate and then depositing a group VI element by vapor deposition. Method for manufacturing chalcopyrite structure semiconductor thin film.
板上にカルコパイライト構造半導体薄膜を形成する場合
において、基板の熱膨張係数がカルコパイライト構造半
導体薄膜の値から±２０×１０-7／℃の範囲内であるこ
とを特徴とする請求項１〜１０のいずれかに記載のカル
コパイライト構造半導体薄膜の製造方法。11. When a chalcopyrite structure semiconductor thin film is formed on a metal-coated dielectric or metal substrate, the coefficient of thermal expansion of the substrate is ± 20 × 10 −7 / ° C. from the value of the chalcopyrite structure semiconductor thin film. The method for producing a chalcopyrite structure semiconductor thin film according to any one of claims 1 to 10, wherein the method is within the range.
なくとも１つを、III族元素としてＩｎあるいはＧａ、
Ａｌのうち少なくとも１つを、VI族元素としてＳあるい
はＳｅ、Ｔｅのうち少なくとも１つを用いることを特徴
とする請求項１〜１１のいずれかに記載のカルコパイラ
イト構造半導体薄膜の製造方法。12. At least one of Cu or Ag as a group I element, In or Ga as a group III element,
12. The method for producing a chalcopyrite structure semiconductor thin film according to claim 1, wherein at least one of Al is used and at least one of S, Se, and Te is used as a group VI element.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6199418A JPH0860359A (en) | 1994-08-24 | 1994-08-24 | Production of semiconductor thin film having chalcopyrite structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6199418A JPH0860359A (en) | 1994-08-24 | 1994-08-24 | Production of semiconductor thin film having chalcopyrite structure |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0860359A true JPH0860359A (en) | 1996-03-05 |
Family
ID=16407479
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6199418A Pending JPH0860359A (en) | 1994-08-24 | 1994-08-24 | Production of semiconductor thin film having chalcopyrite structure |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0860359A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012002381A1 (en) * | 2010-06-30 | 2012-01-05 | 京セラ株式会社 | Photoelectric conversion device |
-
1994
- 1994-08-24 JP JP6199418A patent/JPH0860359A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012002381A1 (en) * | 2010-06-30 | 2012-01-05 | 京セラ株式会社 | Photoelectric conversion device |
| JPWO2012002381A1 (en) * | 2010-06-30 | 2013-08-29 | 京セラ株式会社 | Photoelectric conversion device |
| JP5328982B2 (en) * | 2010-06-30 | 2013-10-30 | 京セラ株式会社 | Photoelectric conversion device |
| US8653616B2 (en) | 2010-06-30 | 2014-02-18 | Kyocera Corporation | Photoelectric conversion device |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6137048A (en) | Process for fabricating polycrystalline semiconductor thin-film solar cells, and cells produced thereby | |
| EP1424735B1 (en) | Method for forming light-absorbing layer | |
| JP3064701B2 (en) | Method for producing chalcopyrite-type compound thin film | |
| TWI427814B (en) | Method of manufacturing solar cell | |
| US20070093059A1 (en) | Method And Apparatus For Thin Film Solar Cell Manufacturing | |
| JP3897622B2 (en) | Method for producing compound semiconductor thin film | |
| JP4288641B2 (en) | Compound semiconductor deposition system | |
| TWI558830B (en) | Method of making a transparent conductive oxide layer | |
| JPH05262504A (en) | Compound semiconductor, production of its thin film and semiconductor device using the same | |
| US20100065418A1 (en) | Reactive magnetron sputtering for the large-scale deposition of chalcopyrite absorber layers for thin layer solar cells | |
| JP3484259B2 (en) | Precursor for forming semiconductor thin film and method for producing semiconductor thin film | |
| JP3431388B2 (en) | Method for producing chalcopyrite structure semiconductor thin film | |
| JP2003282600A (en) | Method and device for manufacturing light-absorbing layer | |
| Basol et al. | CuInSe2 films and solar cells obtained by selenization of evaporated Cu‐In layers | |
| KR100347106B1 (en) | The manufacturing method of CuInSe2 thin film using vacuum evaporation of binary selenides | |
| JPH06120545A (en) | Manufacture of thin film solar cell | |
| Martı́nez et al. | Comparison between large area dc-magnetron sputtered and e-beam evaporated molybdenum as thin film electrical contacts | |
| JP4056702B2 (en) | Method for producing compound semiconductor thin film | |
| Zweigart et al. | CuInSe 2 film growth using precursors deposited at low temperature | |
| JPH0860359A (en) | Production of semiconductor thin film having chalcopyrite structure | |
| JP2003282908A (en) | Method and device for manufacturing light absorbing layer | |
| JP2002064062A (en) | Film formation method of compound semiconductor | |
| JPH05234890A (en) | Forming method for compound semiconductor thin film layer | |
| JPH05275331A (en) | Manufacture of chalocopyrite thin film and solar cell | |
| JPH05234894A (en) | Method and apparatus for manufacturing chalcopyrite type compound thin film |