JPH0548141A - Manufacture of culnse2 photoelectric transfer element - Google Patents
Manufacture of culnse2 photoelectric transfer elementInfo
- Publication number
- JPH0548141A JPH0548141A JP3230912A JP23091291A JPH0548141A JP H0548141 A JPH0548141 A JP H0548141A JP 3230912 A JP3230912 A JP 3230912A JP 23091291 A JP23091291 A JP 23091291A JP H0548141 A JPH0548141 A JP H0548141A
- Authority
- JP
- Japan
- Prior art keywords
- film
- cuinse
- etching
- photoelectric conversion
- concentration
- 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
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 238000005530 etching Methods 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 20
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 19
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 19
- 229910052794 bromium Inorganic materials 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 12
- 239000004065 semiconductor Substances 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 6
- 238000010030 laminating Methods 0.000 claims description 2
- 239000011521 glass Substances 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 150000003346 selenoethers Chemical class 0.000 abstract 1
- 239000010408 film Substances 0.000 description 37
- 239000012535 impurity Substances 0.000 description 7
- 239000000370 acceptor Substances 0.000 description 6
- 239000010409 thin film Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 3
- MODGUXHMLLXODK-UHFFFAOYSA-N [Br].CO Chemical compound [Br].CO MODGUXHMLLXODK-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000009499 grossing Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000005424 photoluminescence Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052951 chalcopyrite Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
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
Landscapes
- Photovoltaic Devices (AREA)
- Weting (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、薄膜作製が可能で、か
つ広い波長範囲にわたって光吸収係数が大きい直接遷移
半導体であるカルコパイライト型ＣｕＩｎＳｅ2 を用い
た光電変換素子の作製方法に関し、さらに詳しくは、ｐ
ｎ接合を形成する前に、ＣｕＩｎＳｅ2 層の表面処理を
行って該層表面の不純物準位濃度を実質的に減少させる
ことをを特徴とする上記光電変換素子の作製方法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a photoelectric conversion element using chalcopyrite type CuInSe 2 which is a direct transition semiconductor capable of producing a thin film and having a large light absorption coefficient over a wide wavelength range. Is p
The present invention relates to a method for producing a photoelectric conversion element, which comprises subjecting a CuInSe 2 layer to surface treatment before forming an n-junction to substantially reduce the impurity level concentration of the layer surface.
【０００２】[0002]
【従来の技術】従来公知のＣｕＩｎＳｅ2 系光電変換素
子作製方法においても、ｐ形ＣｕＩｎＳｅ2 層にｎ形半
導体層を積層してｐｎ接合する際に、前処理として 2％
の臭素を含む臭素−メタノール溶液でエッチング[Solar
Cells, 16, 529 (1986)] 処理することや、特性の面内
均一化を目的として臭素水溶液でエッチング [米国特許
第 4,909,863号] 処理することなどが行われていた。 2. Description of the Related Art Even in a conventionally known method of manufacturing a CuInSe 2 system photoelectric conversion element, when a n-type semiconductor layer is laminated on a p-type CuInSe 2 layer to form a pn junction, 2% is required as a pretreatment.
Etching with bromine-methanol solution containing bromine [Solar
Cells, 16 , 529 (1986)] and etching with an aqueous solution of bromine [US Pat. No. 4,909,863] for the purpose of homogenizing the properties in-plane.
【０００３】しかしながら、臭素−メタノール溶液での
エッチングは、エッチング速度が大きいためエッチング
量の制御が困難で、ＣｕＩｎＳｅ2 薄膜のエッチングに
は適さないものであった。However, since etching with a bromine-methanol solution has a high etching rate, it is difficult to control the etching amount, and it is not suitable for etching a CuInSe 2 thin film.
【０００４】また、特性の面内均一化を目的とするＣｕ
ＩｎＳｅ2 膜表面の平滑化のために臭素水溶液でエッチ
ングを行う場合には、エッチングを0.1〜1.5 μｍ程度
の厚さで行わなければならないことから、この処理を、
たとえば 0.1μｍ以下という薄い膜を対象として行うこ
とは全く考えられていなかった。Cu for the purpose of homogenizing the properties in-plane
When etching with an aqueous solution of bromine for smoothing the surface of the InSe 2 film, the etching must be performed with a thickness of about 0.1 to 1.5 μm, so this treatment is
For example, it has never been considered to target a thin film of 0.1 μm or less.
【０００５】さらに、 0.1〜1.5 μｍの厚さのエッチン
グを比較的短時間で行うためには、臭素水溶液の臭素濃
度を 0.02 mol/l以上とすることが必要であることか
ら、前記表面平滑化のためのエッチング処理においては
比較的多量の臭素を使用しなければならず安全性・経済
性の点で問題があった。Further, in order to perform etching with a thickness of 0.1 to 1.5 μm in a relatively short time, it is necessary to set the bromine concentration of the bromine aqueous solution to 0.02 mol / l or more. In the etching process for the above, a relatively large amount of bromine had to be used, and there was a problem in terms of safety and economy.
【０００６】[0006]
【発明が解決しようとする課題】上述のように従来の臭
素水溶液によるエッチング法は、十分な膜厚のあるＣｕ
ＩｎＳｅ2 膜を対象としてその表面の平滑化を図ること
を目的として行われたものであるため、たとえば 0.1μ
ｍ以下というような極薄膜には使用できなかった。As described above, in the conventional etching method using an aqueous bromine solution, Cu having a sufficient film thickness is used.
This was done for the purpose of smoothing the surface of the InSe 2 film.
It could not be used for an ultrathin film having a thickness of m or less.
【０００７】これに対し、本発明においては、ＣｕＩｎ
Ｓｅ2 系光電変換素子の作製に際し、 0.1μｍ以下のＣ
ｕＩｎＳｅ2 薄膜に対してエッチング処理を行うもので
あり、しかもこの処理は、従来よりも安全かつ経済的に
実施できるエッチング方法でなければならない。On the other hand, in the present invention, CuIn
When manufacturing a Se 2 -based photoelectric conversion element, C of 0.1 μm or less is used.
The uInSe 2 thin film is subjected to an etching treatment, and this treatment must be a safer and more economical etching method than ever before.
【０００８】[0008]
【課題を解決するための手段】本発明者等は、斯る課題
を解決するため鋭意研究し、ＣｕＩｎＳｅ2 膜のエッチ
ング前後のサンプルに対してフォトルミネセンス測定を
したところ、ＣｕＩｎＳｅ2 膜の表面を極薄くエッチン
グするのみで表面の不純物準位濃度が実質的に減少する
ことを見い出し本発明を提供することができた。The present inventors have SUMMARY OF THE INVENTION The intensive research to solve the斯Ru problem, was the photoluminescence measurement for a sample before and after etching of the CuInSe 2 film, the surface of the CuInSe 2 film It has been found that the concentration of impurity levels on the surface is substantially reduced only by etching very thinly, and the present invention can be provided.
【０００９】すなわち本発明は、ｐ形ＣｕＩｎＳｅ2 膜
上にｎ形半導体膜を積層してｐｎ接合を形成する光電変
換素子の作製に際し、ｎ形半導体膜を積層する前にｐ形
ＣｕＩｎＳｅ2 膜の表面を 100〜500Ａ（オングストロ
ーム）の微小な厚さでエッチング除去することを特徴と
するＣｕＩｎＳｅ2 系光電変換素子の作製方法に関する
ものである。That is, according to the present invention, in the production of a photoelectric conversion element in which an n-type semiconductor film is laminated on a p-type CuInSe 2 film to form a pn junction, the p-type CuInSe 2 film is formed before the n-type semiconductor film is laminated. The present invention relates to a method for producing a CuInSe 2 -based photoelectric conversion element, characterized by etching and removing the surface with a minute thickness of 100 to 500 A (angstrom).
【００１０】なお、本発明方法において使用するエッチ
ング液は、臭素濃度が0.01 mol/l以下の薄い臭素水溶液
であることが特に好ましい。The etching solution used in the method of the present invention is particularly preferably a thin aqueous bromine solution having a bromine concentration of 0.01 mol / l or less.
【００１１】[0011]
【作用】一般に、ｐ形ＣｕＩｎＳｅ2 とＣｄＳやＺｎＯ
のようなｎ形半導体とでｐｎ接合を形成して光電変換素
子を作製する場合、ｐ形ＣｕＩｎＳｅ2 の表面不純物準
位濃度が大きいと、ｐｎ接合界面でも界面準位濃度が大
きくなると考えられている。この場合、界面準位濃度が
大きいと、例えば光エネルギーなどの吸収で発生した電
子と正孔が界面準位を介して再結合してしまう場合が多
くなり、結果的に光起電力の発生が小さく、光電変換素
子の感度が不良となっていた。したがって、ＣｕＩｎＳ
ｅ2 系光電変換素子の感度向上のために、ＣｕＩｎＳｅ
2 の表面不純物準位濃度を減少させることが一つの課題
となっていた。Function: Generally, p-type CuInSe 2 and CdS or ZnO
When a photoelectric conversion element is manufactured by forming a pn junction with an n-type semiconductor like that described above, it is considered that if the surface impurity level concentration of p-type CuInSe 2 is high, the interface level concentration will be high even at the pn junction interface. There is. In this case, if the interface state concentration is high, for example, electrons and holes generated by absorption of light energy or the like are often recombined via the interface states, and as a result, generation of a photovoltaic power is generated. It was small and the sensitivity of the photoelectric conversion element was poor. Therefore, CuInS
In order to improve the sensitivity of the e 2 -based photoelectric conversion element, CuInSe
One of the problems was to reduce the surface impurity level concentration of 2 .
【００１２】本発明者等は、ＣｕＩｎＳｅ2 の表面不純
物準位濃度低減のための方法を種々に検討したところ、
エッチング速度が比較的遅い臭素水溶液によるエッチン
グが有効であることが判明した。The present inventors have studied various methods for reducing the surface impurity level concentration of CuInSe 2 ,
It has been found that etching with an aqueous bromine solution, which has a relatively low etching rate, is effective.
【００１３】そこで、ガラス基板上に作製した厚さ 0.5
μｍのＣｕＩｎＳｅ2 膜を、臭素濃度 0.005 mol/lの臭
素水溶液で約 200Ａエッチングし、エッチング前後にお
けるフォトルミネセンスの変化を調べた。この試験にお
いて、励起光として波長 647mmのＫｒレーザー光を用い
た場合の測定結果を図１に示した。図１からわかるよう
に、エッチングを行うことによって 0.9ｅＶ（波長で約
1.35μｍ）付近のピーク位置が長波長側に移動すること
が認められた。Therefore, the thickness of 0.5 formed on the glass substrate
A CuInSe 2 film having a thickness of μm was etched by about 200 A with an aqueous bromine solution having a bromine concentration of 0.005 mol / l, and the change in photoluminescence before and after the etching was examined. In this test, the measurement result when Kr laser light having a wavelength of 647 mm was used as the excitation light is shown in FIG. As can be seen from Fig. 1, 0.9eV (approx.
It was confirmed that the peak position around 1.35 μm) moved to the long wavelength side.
【００１４】0.9ｅＶ付近のピークは、ドナーとアクセ
プター間の遷移によるルミネセンスと考えられており
［例えば、Solid State Communications, 18, 395 (197
6)参照］、ルミネセンスのエネルギーｈνと各不純物準
位との間には次式が成立する。 式： ｈν＝Ｅｇ−（Ｅｄ＋Ｅａ）＋ｅ2 ／εｒ Ｅｇ：半導体の禁制帯幅 Ｅｄ：伝導帯下端とドナー準位間のエネルギー差 Ｅａ：価電子帯上端とアクセプター準位間のエネルギー
差 ｅ： 電子電荷 ε： 誘電率 ｒ： ドナーとアクセプターの間隔The peak around 0.9 eV is considered to be luminescence due to the transition between the donor and the acceptor [eg Solid State Communications, 18 , 395 (197
6)], the following equation holds between the luminescence energy hν and each impurity level. Formula: hν = Eg− (Ed + Ea) + e 2 / εr Eg: Forbidden band width of semiconductor Ed: Energy difference between bottom of conduction band and donor level Ea: Energy difference between top of valence band and acceptor level e: Electron Charge ε: Dielectric constant r: Distance between donor and acceptor
【００１５】この場合、ドナーやアクセプターが多いと
きは、平均的にｒが短くなりｈνが大きくなるが、ドナ
ーやアクセプターが相対的に少ないときは、平均的にｒ
が長くなりｈνは小さくなる。In this case, when the number of donors and acceptors is large, r is short and hν is large on average, but when the number of donors and acceptors is relatively small, r is average.
Becomes longer and hν becomes smaller.
【００１６】したがって、上記のように、エッチングを
行ったＣｕＩｎＳｅ2 のスペクトルを見た場合、 0.9ｅ
Ｖ付近のピーク位置が長波長側、すなわち低エネルギー
側に移動したということは、ＣｕＩｎＳｅ2 膜の成膜
時、ＣｕＩｎＳｅ2 膜の内部よりも膜表面近傍に多量に
存在していたと考えられるドナーやアクセプターが、エ
ッチングによって除去されたことによるものと推定され
る。Therefore, when looking at the spectrum of the etched CuInSe 2 as described above, 0.9e
Peak position long wavelength side in the vicinity of V, i.e. that has moved to a lower energy side, CuInSe 2 When film deposition of, Ya donor believed to have been present in a large amount on the film surface near than the interior of the CuInSe 2 film It is presumed that the acceptor was removed by etching.
【００１７】すなわち、低濃度の臭素水溶液を使用した
ＣｕＩｎＳｅ2 膜表面の穏やかなエッチングによってＣ
ｕＩｎＳｅ2 膜の表面不純物準位濃度を減少させること
ができたものと考えられる。実際、このようなエッチン
グ処理したＣｕＩｎＳｅ2 膜にＣｄＳ膜を積層して作製
した光電変換素子を用いたところ、処理しない従来品に
比較し光起電力の大幅な向上が確認できた。That is, by gently etching the surface of the CuInSe 2 film using a low concentration aqueous bromine solution, C
It is considered that the surface impurity level concentration of the uInSe 2 film could be reduced. In fact, when a photoelectric conversion element produced by laminating a CdS film on such an etched CuInSe 2 film was used, it was confirmed that the photovoltaic power was significantly improved as compared with the conventional product which was not processed.
【００１８】以下、実施例をもって詳細に説明する。A detailed description will be given below with reference to embodiments.
【００１９】[0019]
【実施例１】膜厚約 0.1μｍのＭｏスパッター膜付きガ
ラス板を基板として、この基板上にＣｕを 600Ａ、Ｉｎ
を 1,400Ａ蒸着で順次積層した。次いで、このＣｕ、Ｉ
ｎ積層膜をＳｅガス雰囲気下で 400℃で加熱処理する気
相セレン化法により、基板上に厚さ 0.5μｍのｐ形Ｃｕ
ＩｎＳｅ2 膜を作製した。Example 1 A glass plate with a Mo sputter film having a film thickness of about 0.1 μm was used as a substrate, and Cu was deposited on the substrate at 600 A and In.
Were sequentially laminated by vapor deposition of 1,400A. Then, this Cu, I
A 0.5 μm thick p-type Cu film was formed on the substrate by the vapor phase selenization method in which the n-layered film was heat-treated at 400 ° C. in a Se gas atmosphere.
An InSe 2 film was prepared.
【００２０】一方、Ｂｒ2 濃度 0.005 mol/l、ＫＢｒ濃
度 150 g/lの水溶液を予め用意し、この溶液中に前記ｐ
形ＣｕＩｎＳｅ2 膜を10秒間浸漬して、ＣｕＩｎＳｅ2
膜表面を 200Ａエッチング除去した。次いで、純水にて
洗浄して乾燥した後、ＣｕＩｎＳｅ2 膜にノンドープＣ
ｄＳを 2,000Ａ、さらにその上にＩｎドープＣｄＳを8,
000Ａそれぞれ蒸着して光電変換素子を作製した。On the other hand, an aqueous solution having a Br 2 concentration of 0.005 mol / l and a KBr concentration of 150 g / l was prepared in advance, and the p
The CuInSe 2 film is dipped for 10 seconds to form CuInSe 2
The film surface was removed by etching at 200 A. Then, after washing with pure water and drying, the CuInSe 2 film is subjected to non-doped C
dS of 2,000 A, and In-doped CdS of 8,
Each 000 A was vapor-deposited to produce a photoelectric conversion element.
【００２１】得られた光電変換素子にハロゲンランプ光
を照射して光起電力を測定したところ、ＣｕＩｎＳｅ2
膜のエッチングを行わずに作製した光電変換素子に比
べ、開放電圧が約３倍、短絡電流が約２倍増加し、結
局、光起電力としては約６倍増加したことが確認され
た。When the obtained photoelectric conversion element was irradiated with halogen lamp light and the photoelectromotive force was measured, CuInSe 2
It was confirmed that the open-circuit voltage increased about 3 times, the short-circuit current increased about 2 times, and the photovoltaic power increased about 6 times as compared with the photoelectric conversion element manufactured without etching the film.
【００２２】[0022]
【比較例１】実施例１と同様な手段で、Ｍｏ膜付きガラ
ス基板上に厚さ 0.5μｍのｐ形ＣｕＩｎＳｅ2 膜を作製
した。Comparative Example 1 By the same means as in Example 1, a 0.5 μm-thick p-type CuInSe 2 film was formed on a glass substrate with a Mo film.
【００２３】一方、Ｂｒ2 濃度 0.02 mol/l 、ＫＢｒ濃
度 150 g/lを含有する水溶液を予め準備し、この液中に
前記ｐ形ＣｕＩｎＳｅ2 膜を10秒間浸漬して、ＣｕＩｎ
Ｓｅ2 膜表面を 0.1μｍ除去した。次いで、純水にて洗
浄して乾燥した後、実施例１に示すようにＣｕＩｎＳｅ
2 膜上にＣｄＳを積層して光電変換素子を作製した。On the other hand, an aqueous solution containing a Br 2 concentration of 0.02 mol / l and a KBr concentration of 150 g / l was prepared in advance, and the p-type CuInSe 2 film was immersed in this solution for 10 seconds to form CuIn
The surface of the Se 2 film was removed by 0.1 μm. Then, after washing with pure water and drying, as shown in Example 1, CuInSe
A photoelectric conversion element was manufactured by stacking CdS on the two films.
【００２４】得られた光電変換素子にハロゲンランプ光
を照射して光起電力を測定したところ、ＣｕＩｎＳｅ2
のエッチングを行わずに作製した光電変換素子と開放電
圧や短絡電流がほとんど同じであり、結局光起電力の向
上は認められなかった。When the obtained photoelectric conversion element was irradiated with halogen lamp light and the photoelectromotive force was measured, CuInSe 2
The open-circuit voltage and the short-circuit current were almost the same as those of the photoelectric conversion element manufactured without etching, and the improvement of the photovoltaic power was not recognized after all.
【００２５】実施例１のエッチングに比べて、光起電力
向上に対する効果が現われなかった原因として、以下の
ことが考えられる。 (1) エッチング速度が速すぎることによるＣｕＩｎＳｅ
2 膜表面のエッチングによる劣化。 (2) エッチング量が多すぎるために、ＣｕＩｎＳｅ2 膜
に部分的に薄いところがある場合、そこのエッチングが
下地のＭｏまで達してしまい、ＣｄＳ積層時にＭｏとＣ
ｄＳが直接接触して短絡する。The reason why the effect of improving the photovoltaic power was not exhibited as compared with the etching of Example 1 is considered as follows. (1) CuInSe due to too fast etching rate
2 Deterioration due to etching of the film surface. (2) When the CuInSe 2 film has a partly thin portion because the etching amount is too large, the etching reaches the underlying Mo, and Mo and C are deposited at the time of CdS lamination.
dS directly contacts and short-circuits.
【００２６】以上の結果から、本発明法においては、エ
ッチング量の制御性および過剰エッチング防止の面か
ら、臭素水溶液の臭素濃度は 0.01 mol/l 以下とし、エ
ッチング量は 100〜500 Ａの厚さの微小量とする必要の
あることが確かめられた。From the above results, in the method of the present invention, the bromine concentration of the aqueous bromine solution is 0.01 mol / l or less and the etching amount is 100 to 500 A in terms of controllability of the etching amount and prevention of excessive etching. It has been confirmed that it is necessary to make a minute amount of.
【００２７】[0027]
【発明の効果】従来、ＣｕＩｎＳｅ2 膜を用いてｐｎ接
合を形成する場合、ＣｕＩｎＳｅ2 膜の前処理として比
較的高濃度の臭素含有液を用いてエッチングを行うこと
があったが、安全性や経済性の点で問題があったほか、
エッチング速度が大きいために薄膜の処理には適さなか
った。しかしながら本発明法は、低濃度の臭素水溶液を
用いてＣｕＩｎＳｅ2 膜の表面を極薄くエッチング除去
するだけであるため、上記の問題を解決でき、良好なＣ
ｕＩｎＳｅ2 系光電変換素子の作製が可能となった。Effect of the Invention Conventionally, when forming a pn junction with the CuInSe 2 film, there was be etched using relatively high concentrations of bromine-containing solution as a pretreatment for CuInSe 2 film, Ya safety There was a problem in terms of economy,
It was not suitable for thin film processing due to its high etching rate. However, since the method of the present invention only removes the surface of the CuInSe 2 film by etching with a very thin aqueous solution of bromine, the above problems can be solved and a good C
It has become possible to manufacture a uInSe 2 system photoelectric conversion element.
【図１】エッチング処理の効果を示すＣｕＩｎＳｅ2 の
フォトルミネセンスのスペクトル図である。FIG. 1 is a photoluminescence spectrum diagram of CuInSe 2 showing the effect of etching treatment.
───────────────────────────────────────────────────── 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 (72)発明者 菊地 英治 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 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kazuto Ito 1-8-2 Marunouchi, Chiyoda-ku, Tokyo Dowa Mining Co., Ltd. (72) Eiji Kikuchi 1-2-8 Marunouchi, Chiyoda-ku, Tokyo Dowa Mining Co., Ltd.
Claims (2)
導体層を積層してｐｎ接合を形成する光電変換素子の作
製において、ｎ形半導体層を積層する前にｐ形ＣｕＩｎ
Ｓｅ2 層表面を 100〜500 Ａ（オングストローム）の極
微小な厚さでエッチング除去することを特徴とするＣｕ
ＩｎＳｅ2 系光電変換素子の作製方法。1. In manufacturing a photoelectric conversion element in which an n-type semiconductor layer is laminated on a p-type CuInSe 2 layer on a substrate to form a pn junction, p-type CuIn is formed before laminating the n-type semiconductor layer.
Cu characterized by etching and removing the surface of the Se 2 layer with an extremely small thickness of 100 to 500 A (angstrom)
A method for manufacturing an InSe 2 photoelectric conversion element.
01 mol/l以下の臭素水溶液を用いることを特徴とする請
求項１記載のＣｕＩｎＳｅ2系光電変換素子の作製方
法。2. The etching solution having a bromine concentration of 0.
The method for producing a CuInSe 2 system photoelectric conversion device according to claim 1, wherein an aqueous solution of bromine of 01 mol / l or less is used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03230912A JP3100692B2 (en) | 1991-08-19 | 1991-08-19 | Method for manufacturing CuInSe2-based photoelectric conversion element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03230912A JP3100692B2 (en) | 1991-08-19 | 1991-08-19 | Method for manufacturing CuInSe2-based photoelectric conversion element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0548141A true JPH0548141A (en) | 1993-02-26 |
| JP3100692B2 JP3100692B2 (en) | 2000-10-16 |
Family
ID=16915234
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03230912A Expired - Fee Related JP3100692B2 (en) | 1991-08-19 | 1991-08-19 | Method for manufacturing CuInSe2-based photoelectric conversion element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3100692B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007052668A1 (en) * | 2005-10-31 | 2007-05-10 | Rohm Co., Ltd. | Method for manufacturing photoelectric converter and photoelectric converter |
| JP2010212692A (en) * | 2001-01-31 | 2010-09-24 | Saint-Gobain Glass France | Transparent substrate equipped with electrode |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4909863A (en) | 1988-07-13 | 1990-03-20 | University Of Delaware | Process for levelling film surfaces and products thereof |
-
1991
- 1991-08-19 JP JP03230912A patent/JP3100692B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010212692A (en) * | 2001-01-31 | 2010-09-24 | Saint-Gobain Glass France | Transparent substrate equipped with electrode |
| US8809668B2 (en) | 2001-01-31 | 2014-08-19 | Saint-Gobain Glass France | Transparent substrate equipped with an electrode |
| WO2007052668A1 (en) * | 2005-10-31 | 2007-05-10 | Rohm Co., Ltd. | Method for manufacturing photoelectric converter and photoelectric converter |
| JP2007123721A (en) * | 2005-10-31 | 2007-05-17 | Rohm Co Ltd | Method for manufacturing photoelectric conversion device and photoelectric conversion device |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3100692B2 (en) | 2000-10-16 |
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