JPH0693514B2 - Method for treating CIS structure including transparent conductive oxide film - Google Patents
Method for treating CIS structure including transparent conductive oxide filmInfo
- Publication number
- JPH0693514B2 JPH0693514B2 JP2009038A JP903890A JPH0693514B2 JP H0693514 B2 JPH0693514 B2 JP H0693514B2 JP 2009038 A JP2009038 A JP 2009038A JP 903890 A JP903890 A JP 903890A JP H0693514 B2 JPH0693514 B2 JP H0693514B2
- Authority
- JP
- Japan
- Prior art keywords
- oxide film
- transparent conductive
- conductive oxide
- cis structure
- present
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims description 29
- 239000001257 hydrogen Substances 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 21
- 239000004065 semiconductor Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 description 8
- 238000000137 annealing Methods 0.000 description 7
- 238000005229 chemical vapour deposition Methods 0.000 description 7
- 238000005566 electron beam evaporation Methods 0.000 description 7
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 239000000758 substrate Substances 0.000 description 5
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 5
- 229910001887 tin oxide Inorganic materials 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 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
Landscapes
- Light Receiving Elements (AREA)
- Photovoltaic Devices (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は各種半導体素子の少なくとも一部に用いられる
CIS（導電体−絶縁物−半導体）構造に関し、特に導電
体（Ｃ）領域として透明導電酸化膜を用いたCIS構造に
おいて、その作製後に特性を改善するか、ないしは作製
時に生じた特性の低下を補うための処理方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial application] The present invention is used for at least a part of various semiconductor devices.
Regarding a CIS (conductor-insulator-semiconductor) structure, particularly in a CIS structure using a transparent conductive oxide film as a conductor (C) region, the characteristics are improved after fabrication, or the degradation of characteristics caused during fabrication is suppressed. The present invention relates to a processing method for supplementing.
［従来の技術］ 上記したようなCIS構造も、それ自体単独で用いられる
ことはむしろ稀であり、各種半導体素子の全体構造の中
の一部の構造部分として用いられるのが普通であるが、
太陽電池に代表されるように、各種の光電変換素子を作
製する場合、当該CIS構造中の導電体（Ｃ）に相当する
領域を、光透過性のある透明導電酸化膜（TCO:Transpar
ent Conductive Oxide）で構成したものは今後さらに利
用されるようになると思われる。[Prior Art] The CIS structure as described above is rarely used by itself, and is usually used as a part of the entire structure of various semiconductor elements.
When manufacturing various types of photoelectric conversion elements as represented by solar cells, a region corresponding to the conductor (C) in the CIS structure is provided with a transparent conductive oxide film (TCO: Transpar
ent Conductive Oxide) will be used more in the future.
これはまた、電子ビーム蒸着法により比較的容易に成膜
でき、かつ低い抵抗率が得られる透明導電酸化膜材料と
して、酸化インジウム錫膜（いわゆるITO）とか酸化錫
膜（SnO2）、あるいはまた酸化亜鉛膜（ZnO）等、多く
の適当な材料が簡単に入手できるという事情も寄与して
いる。This is also a transparent conductive oxide film material that can be formed relatively easily by the electron beam evaporation method and has a low resistivity, such as indium tin oxide film (so-called ITO) or tin oxide film (SnO 2 ), or The fact that many suitable materials such as zinc oxide film (ZnO) are easily available also contributes.
なお、こうした透明導電酸化膜は、電子ビーム蒸着法の
外、スプレー法や化学蒸着法（CVD）によっての作製も
可能である。Note that such a transparent conductive oxide film can be produced by a spray method or a chemical vapor deposition method (CVD) in addition to the electron beam vapor deposition method.
［発明が解決しようとする課題］ しかし、上記のように、半導体基板自体であるか、また
は半導体基板の上に積層された層構造の最上層に位置す
る半導体層等、いずれにしても半導体の上にまずは絶縁
膜を形成し、さらにその上に上記したような材料製の透
明導電酸化膜を作製するにあたり、最後の透明導電酸化
膜の形成に電子ビーム蒸着法を採用すると、高速に加速
される電子ビームや、これに伴って付随的に発生するＸ
線が下地層である絶縁膜に物理的な損傷を与えたり、絶
縁膜と半導体との界面における界面準位密度が増して、
CIS構造として望ましい特性が得られなくなるという欠
点があった。[Problems to be Solved by the Invention] However, as described above, the semiconductor substrate itself, or the semiconductor layer positioned on the uppermost layer of the layer structure laminated on the semiconductor substrate, etc. When an insulating film is first formed on the top, and when a transparent conductive oxide film made of the above-mentioned material is further formed on it, the electron beam evaporation method is adopted for the formation of the final transparent conductive oxide film, which accelerates at high speed. Electron beam and accompanying X
The line physically damages the insulating film which is the underlayer, or the interface state density at the interface between the insulating film and the semiconductor increases,
There is a drawback that the desired characteristics cannot be obtained as a CIS structure.
また、材料として酸化錫を選択し、これによる透明導電
酸化膜の形成にCVDやスプレー法を利用した場合にも、
成膜環境は、温度こそ、一般に400〜600℃前後の比較的
低温とは言え、酸化性雰囲気であるため、CIS構造の電
気的特性は安定し難かった。Also, when tin oxide is selected as the material and CVD or spray method is used to form a transparent conductive oxide film by this,
Although the temperature of the film forming environment is generally a relatively low temperature of about 400 to 600 ° C., the electrical characteristics of the CIS structure were difficult to stabilize because of the oxidizing atmosphere.
そこで従来からも、特性改善、ないしは低下した特性の
回復のため、CIS構造を水素プラズマに曝すという処理
を追加する場合があったが、このようにすると200℃程
度の低温でも透明導電酸化膜の表面が変質し、透明度を
失って曇ってしまうことが多かった。Therefore, in the past, in order to improve the characteristics or to recover the deteriorated characteristics, a process of exposing the CIS structure to hydrogen plasma may be added in some cases, but this makes it possible to form a transparent conductive oxide film at a low temperature of about 200 ° C. The surface often deteriorated, lost transparency and became cloudy.
本発明はこのような従来の実情に鑑み、電子ビーム蒸着
法によるにしろCVDやスプレー法によるにしろ、作製さ
れるCIS構造中の絶縁膜の損傷や当該絶縁膜と半導体層
との界面準位を効果的に低減でき、かつまた従来の水素
プラズマ処理を適用した場合のように透明導電酸化膜を
曇らせることがないか、その程度を大きく低減し得る新
たなる処理方法を提供せんとするものである。In view of such a conventional situation, the present invention, whether by the electron beam evaporation method or the CVD method or the spray method, damages the insulating film in the CIS structure to be produced and the interface state between the insulating film and the semiconductor layer. It is intended to provide a new treatment method capable of effectively reducing the amount of the transparent conductive oxide film that does not cloud the transparent conductive oxide film as in the case where the conventional hydrogen plasma treatment is applied, or can significantly reduce the degree. is there.
［課題を解決するための手段］ 本発明は上記目的を達成するため、半導体の上に絶縁膜
を形成し、さらにその上に透明導電酸化膜を形成して成
るCIS構造の処理方法として、透明導電酸化膜を形成し
た後に、水素雰囲気中で300℃から500℃の温度範囲内に
までの加熱処理を行なうという処理方法を提案する。[Means for Solving the Problems] In order to achieve the above object, the present invention provides a method for treating a CIS structure, which comprises forming an insulating film on a semiconductor and further forming a transparent conductive oxide film on the insulating film. We propose a treatment method in which a conductive oxide film is formed and then heat treatment is performed in a hydrogen atmosphere within a temperature range of 300 ° C to 500 ° C.
［作用］ 透明導電酸化膜を有する作製済みのCIS構造に対し、本
発明に従い、水素雰囲気中、300℃から500℃までの温度
範囲内にて加熱処理を行なうと、透明導電酸化膜を問題
となる程曇らせることもなく、むしろ良好な透明性を保
ちながら、水素が透明導電酸化膜中を通過し、その下の
絶縁膜中にまで侵入し得ることが判明した。[Operation] When a heat treatment is performed on a prepared CIS structure having a transparent conductive oxide film in a hydrogen atmosphere in a temperature range of 300 ° C. to 500 ° C. according to the present invention, the transparent conductive oxide film causes a problem. It has been found that hydrogen can pass through the transparent conductive oxide film and penetrate into the insulating film below the transparent conductive oxide film while maintaining good transparency without causing clouding.
その結果、当該絶縁膜中の欠陥や、この絶縁膜とその下
の半導体との界面に生じていた欠陥が当該水素により埋
められ、未結合シリコンが減少するようになった。As a result, defects in the insulating film and defects generated at the interface between the insulating film and the semiconductor below the insulating film are filled with the hydrogen, and unbonded silicon is reduced.
これは取りも直さず、透明導電酸化膜形成時に生じた欠
陥とか界面準位を低減させることとなり、CIS構造とし
ての特性の向上を生んだし、また、絶縁物中の固定電荷
と導電体の仕事関数の差で決まるフラット・バンド電圧
VFBの調節ないし制御も可能となった。This is irreversible, it reduces defects and interface states generated during the formation of the transparent conductive oxide film, improves the characteristics of the CIS structure, and also fixes the fixed charge in the insulator and the work of the conductor. Flat band voltage determined by the difference between the functions
It is also possible to adjust or control V FB .
そして特に、このような効果は、欠陥発生確率が高いと
考えられる電子ビーム蒸着法の適用後でも顕著であっ
た。And, in particular, such an effect was remarkable even after the application of the electron beam evaporation method, which is considered to have a high probability of generating defects.
ただし、上記した温度範囲を外れると特性改善ないし回
復効果は薄れることが多く、わざわざ一工程を追加する
程の意味はなくなった。However, if the temperature is out of the above range, the effect of improving the characteristics or the recovery is often weakened, and it is meaningless to add one step.
［実施例］ 具体的なCIS構造の作製例とこれに対する本発明の処理
方法につき説明するに、まず、乾燥酸素中、1000℃でシ
リコン基板を熱酸化し、表面部分に80nmのシリコン酸化
膜を形成した後、100％の水素雰囲気中で400℃、30分間
に亙る熱処理を行なった。[Example] To describe a specific example of manufacturing a CIS structure and a treatment method of the present invention for this, first, a silicon substrate was thermally oxidized at 1000 ° C. in dry oxygen to form a silicon oxide film of 80 nm on the surface portion. After the formation, heat treatment was performed at 400 ° C. for 30 minutes in a 100% hydrogen atmosphere.
このようにして処理したシリコン酸化膜上に電子ビーム
蒸着法を援用し、酸化インジウム錫電極を90nmの厚味に
まで蒸着し、本発明による処理対象試料としてのCIS構
造試料を幾つか作製した。On the silicon oxide film treated in this manner, an indium tin oxide electrode was vapor-deposited to a thickness of 90 nm with the aid of an electron beam vapor deposition method, and several CIS structure samples as samples to be treated according to the present invention were produced.
その後、これらCIS構造試料群に対して本発明を適用
し、100％水素雰囲気中で200℃から500℃の温度範囲内
の各温度で30分間に亙る熱処理を行なった。After that, the present invention was applied to these CIS structural sample groups, and heat treatment was performed for 30 minutes at each temperature within a temperature range of 200 ° C. to 500 ° C. in a 100% hydrogen atmosphere.
このように処理したことの効果は界面準位密度Ditの低
減により、良く示すことができるが、周知のように、当
該準位密度DitとCIS構造のいわゆるＣ−Ｖ特性（容量対
電圧特性）とは深い相関があり、Ｃ−Ｖ特性の周波数依
存性に基づき、当該界面準位密度Ditを求めることがで
きるので、理論値にほぼ一致した高周波100KHzにおける
Ｃ−Ｖ特性の曲線と低周波100Hzなおけるそれとの関係
により、被検試料の界面準位密度Ditを求めた。The effect of such treatment can be well shown by reducing the interface state density D it , but as is well known, the state density D it and the so-called CV characteristic (capacitance vs. voltage) of the CIS structure are known. Characteristic), and the interface state density D it can be obtained based on the frequency dependence of the CV characteristic, so that it is a curve of the CV characteristic at a high frequency of 100 KHz, which almost agrees with the theoretical value. The interface state density D it of the test sample was obtained from the relationship with that at a low frequency of 100 Hz.
第１図はバンド・ギヤップ中の界面準位密度の最大値D
itmの水素アニール温度依存性を示している。Fig. 1 shows the maximum value D of the interface state density in the band and gap.
The hydrogen annealing temperature dependence of itm is shown.
本図から明らかなように、水素アニール温度が300℃よ
りも低い試料の界面準位密度Ditmは総体的にほぼ1011個
／cm2であり、あえて水素処理を行なわなかった試料の
それとほぼ同一のレベルにあった。As is clear from this figure, the interface state density D itm of the sample whose hydrogen annealing temperature is lower than 300 ° C. is about 10 11 pieces / cm 2 as a whole, which is almost the same as that of the sample not subjected to the hydrogen treatment. Were on the same level.
これに対し、本発明の趣旨に従い、300℃から500℃の間
の温度範囲にて水素アニール処理を行なった試料では、
界面準位密度Ditmは一桁程度も改善され、1010個／cm2
のレベルとなった。On the other hand, according to the gist of the present invention, in the sample subjected to the hydrogen annealing treatment in the temperature range between 300 ° C and 500 ° C,
The interface state density D itm is improved by an order of magnitude, 10 10 / cm 2
Became the level of.
また、水素アニール温度の上昇に伴ってフラット・バン
ド電圧VFBのシフトが観測された。Also, a shift of the flat band voltage V FB was observed with the increase of the hydrogen annealing temperature.
第２図はこのフラット・バンド電圧VFBの水素アニール
温度依存性を示しているが、250℃を越えた温度でのフ
ラット・バンド電圧VFBの正方向へのシフトは、第１図
にも示した通り、Ｃ−Ｖ特性の形が理論値に近づき、界
面準位密度Ditが減少していることに対応しており、か
つ、本発明により規定される300℃から500℃のアニール
温度範囲内では、当該フラット・バンド電圧VFBを容易
に制御可能なことが分かる。Fig. 2 shows the dependence of the flat band voltage V FB on the hydrogen annealing temperature, but the positive shift of the flat band voltage V FB at temperatures above 250 ° C is also shown in Fig. 1. As shown, the shape of the C-V characteristic approaches the theoretical value, which corresponds to the decrease of the interface state density D it , and the annealing temperature of 300 ° C. to 500 ° C. defined by the present invention. It can be seen that the flat band voltage V FB can be easily controlled within the range.
さらに透明導電酸化膜の曇りの有無を調べるため、先と
同様に電子ビーム蒸着法を援用し、ただしシリコン基板
ではなく石英基板上に酸化インジウム錫を90nmの厚味に
まで蒸着した試料を用意し、波長600nmにおける透過率
の水素アニール温度依存性を測定した。Furthermore, in order to investigate the presence or absence of cloudiness of the transparent conductive oxide film, the electron beam evaporation method was used as in the previous case, except that a sample was prepared by depositing indium tin oxide to a thickness of 90 nm on a quartz substrate instead of a silicon substrate. The hydrogen annealing temperature dependence of the transmittance at a wavelength of 600 nm was measured.
その結果は第３図に示されているが、アニール温度を50
0℃近傍にまで上げてくると透過率の減少が見られ、こ
れはすなわち、これ以上にさらに温度を上げると酸化イ
ンジウム錫膜に曇りが生じ、透明導電酸化膜としての機
能が劣化することを教えている。The result is shown in FIG.
A decrease in transmittance was observed when the temperature was raised to near 0 ° C. This means that if the temperature is further increased, the indium tin oxide film will fog and the function as a transparent conductive oxide film will deteriorate. I'm teaching.
このような実施例から明らかなように、処理自体は簡単
な本発明の処理工程を適用しただけで、界面準位密度は
大きく低減しており、界面特性の向上効果は顕著であ
る。As is clear from these examples, the interface itself is greatly reduced and the effect of improving the interface characteristics is remarkable only by applying the simple process of the present invention to the process itself.
なお、同様の傾向は、上記実施例のように酸化インジウ
ム錫以外、酸化錫、酸化亜鉛にても得られるものであ
る。The same tendency is obtained with tin oxide and zinc oxide other than indium tin oxide as in the above embodiment.
さらに、CVDやスプレー法等、電子ビーム蒸着法よりも
ダメージの少ない方法で透明導電酸化膜を形成した後の
処理方法としても、本発明は全く同様に適用することが
できる。Furthermore, the present invention can be applied in exactly the same way even as a processing method after the transparent conductive oxide film is formed by a method such as a CVD method or a spray method that causes less damage than the electron beam evaporation method.
例えば、四塩化錫（SnCl4）と水蒸気とを原料とし、CVD
により成膜した酸化錫膜に対し、本発明に従って水素雰
囲気中での熱処理を施した所、熱処理温度による界面準
位密度の変化は少なかったが、第４図示のように、300
℃以下の温度ではフラット・バンド電圧VFBの変化が著
しく、かなり問題であったのに、本発明により規定され
る温度範囲下限である300℃以上では安定なフラット・
バンド電圧VFBが得られた。For example, using tin tetrachloride (SnCl 4 ) and steam as raw materials, CVD
When the tin oxide film formed according to the present invention was heat-treated in a hydrogen atmosphere according to the present invention, the interface state density changed little with the heat-treatment temperature, but as shown in FIG.
The change in the flat band voltage V FB was remarkable at a temperature of ℃ or less, which was a serious problem, but a stable flat voltage was obtained at a temperature lower than the lower limit of 300 ℃ specified by the present invention.
The band voltage V FB was obtained.
しかも、本発明の処理方法は、すでに述べた従来の水素
プラズマ法における処理温度200℃に比せば高い温度範
囲にあるにもかかわらず、形成された透明導電酸化膜の
透明度の低下も水素処理時間の調節により、ほとんど問
題とならなかった。Moreover, although the treatment method of the present invention is in a temperature range higher than the treatment temperature of 200 ° C. in the conventional hydrogen plasma method already described, the reduction in the transparency of the formed transparent conductive oxide film is caused by the hydrogen treatment. By adjusting the time, there was almost no problem.
また、上記した実施例ではいずれも水素雰囲気中での実
験であったが、He,Ne,Ar等の不活性ガスを水素の希釈ガ
スとして混入した実験例においてもほぼ同様な望ましい
効果が得られた。Further, in the above-mentioned examples, all were experiments in a hydrogen atmosphere, but in the experimental examples in which an inert gas such as He, Ne, Ar was mixed as a diluting gas of hydrogen, almost the same desirable effect can be obtained. It was
ただし、すでに述べたように、本発明において指定して
いる温度範囲（300℃〜500℃）を外れる温度範囲では、
上記のようなCIS構造の特性改善ないし回復効果が必ず
しも顕著に表れない場合が生じ、処理工程を一つ追加す
る程の効果は認められないことが多かった。本発明にお
ける温度範囲の限定はこのような事実に立脚したもので
ある。However, as described above, in the temperature range outside the temperature range specified in the present invention (300 ° C to 500 ° C),
In some cases, the effect of improving or recovering the characteristics of the CIS structure as described above does not always appear prominently, and the effect of adding one treatment step is often not recognized. The limitation of the temperature range in the present invention is based on such a fact.
［効果］ 以上のように、本発明によると、従来の水素プラズマ処
理のように、場合によっては特性改善のための処理が逆
に透明導電酸化膜に大幅な曇りを生じさせてしまうよう
なおそれもなく、透明導電酸化膜形成時に発生した絶縁
膜の損傷や絶縁膜と半導体界面における界面準位密度を
効果的に低減することができる外、フラット・バンド電
圧の安定化ないしは制御も可能となり、この種のCIS構
造の特性を大いに改善ないし回復することができる。[Effects] As described above, according to the present invention, there is a possibility that the process for improving the characteristics, as in the case of the conventional hydrogen plasma process, may cause the transparent conductive oxide film to be greatly fogged. In addition, it is possible to effectively reduce the damage to the insulating film generated at the time of forming the transparent conductive oxide film and the interface state density at the interface between the insulating film and the semiconductor, and also to stabilize or control the flat band voltage. The properties of this kind of CIS structure can be greatly improved or restored.
第１図は透明導電酸化膜に電子ビーム蒸着法により成膜
した酸化インジウム錫膜を用いて成るCIS構造試料に対
し、本発明に従う処理を施した場合の一例における熱処
理温度対界面準位密度の特性図， 第２図は同じくCIS構造試料に対し、本発明処理を施し
た場合の一例における熱処理温度対フラット・バンド電
圧の特性図， 第３図は本発明に従う処理を施すに際し、透明導電酸化
膜の一例としての酸化インジウム錫膜における曇りの発
生の如何を検討するため、熱処理温度と透過率との関係
を測定した特性図， 第４図は透明導電酸化膜にCVDによって成膜した酸化錫
膜を用いて成るCIS構造試料に対し、本発明に従う処理
を施した場合の一例における熱処理温度対フラット・バ
ンド電圧の特性図，である。FIG. 1 shows the heat treatment temperature vs. interface state density in an example of the case where the treatment according to the present invention is applied to a CIS structure sample composed of an indium tin oxide film formed by an electron beam evaporation method on a transparent conductive oxide film. Fig. 2 is a characteristic diagram of heat treatment temperature vs. flat band voltage in one example when the treatment of the present invention is applied to the CIS structure sample, and Fig. 3 is a transparent conductive oxidation during the treatment according to the present invention. In order to examine the occurrence of fogging in an indium tin oxide film as an example of the film, a characteristic diagram was obtained by measuring the relationship between the heat treatment temperature and the transmittance. Fig. 4 shows the tin oxide film formed by CVD on the transparent conductive oxide film. FIG. 4 is a characteristic diagram of a heat treatment temperature vs. flat band voltage in an example of a case where a treatment according to the present invention is applied to a CIS structure sample formed by using a film.
Claims (1)
上に透明導電酸化膜を形成して成るCIS構造の処理方法
であって： 上記透明導電酸化膜を形成した後、水素雰囲気中、また
は不活性ガス中に水素を含む雰囲気中、300℃から500℃
の温度範囲内での加熱処理を行なうことを特徴とする透
明導電酸化膜を含むCIS構造の処理方法。1. A method for treating a CIS structure comprising forming an insulating film on a semiconductor and further forming a transparent conductive oxide film on the insulating film, comprising: forming a transparent conductive oxide film in a hydrogen atmosphere. , Or in an atmosphere containing hydrogen in an inert gas, 300 ° C to 500 ° C
A method for treating a CIS structure including a transparent conductive oxide film, which comprises performing heat treatment within a temperature range of 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009038A JPH0693514B2 (en) | 1990-01-18 | 1990-01-18 | Method for treating CIS structure including transparent conductive oxide film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009038A JPH0693514B2 (en) | 1990-01-18 | 1990-01-18 | Method for treating CIS structure including transparent conductive oxide film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03212976A JPH03212976A (en) | 1991-09-18 |
| JPH0693514B2 true JPH0693514B2 (en) | 1994-11-16 |
Family
ID=11709482
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2009038A Expired - Lifetime JPH0693514B2 (en) | 1990-01-18 | 1990-01-18 | Method for treating CIS structure including transparent conductive oxide film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0693514B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3202362B2 (en) * | 1992-07-21 | 2001-08-27 | 株式会社半導体エネルギー研究所 | Method for manufacturing semiconductor device |
| US5808315A (en) * | 1992-07-21 | 1998-09-15 | Semiconductor Energy Laboratory Co., Ltd. | Thin film transistor having transparent conductive film |
| JP3587537B2 (en) | 1992-12-09 | 2004-11-10 | 株式会社半導体エネルギー研究所 | Semiconductor device |
| US5840620A (en) * | 1994-06-15 | 1998-11-24 | Seager; Carleton H. | Method for restoring the resistance of indium oxide semiconductors after heating while in sealed structures |
| WO1998029902A1 (en) * | 1996-12-27 | 1998-07-09 | Radiant Technologies, Inc. | Method for restoring the resistance of indium oxide semiconductors after heating while in sealed structures |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5623784A (en) * | 1979-08-05 | 1981-03-06 | Shunpei Yamazaki | Manufacture of semiconductor device |
| JPS60163429A (en) * | 1984-02-03 | 1985-08-26 | Sumitomo Electric Ind Ltd | Manufacture of amorphous silicon solar cell |
-
1990
- 1990-01-18 JP JP2009038A patent/JPH0693514B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03212976A (en) | 1991-09-18 |
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