本発明は、非晶質酸化物に関する。また、該非晶質酸化物を用いた電界効果型トランジスタに関する。 The present invention relates to an amorphous oxide. The present invention also relates to a field effect transistor using the amorphous oxide.
近年、液晶やエレクトロルミネッセンス（ＥｌｅｃｔｒｏＬｕｍｉｎｅｓｃｅｎｃｅ：ＥＬ）技術等の進歩により、平面薄型画像表示装置（Ｆｌａｔ Ｐａｎｅｌ Ｄｉｓｐｌａｙ：ＦＰＤ）が実用化されている。 2. Description of the Related Art In recent years, flat and thin image display devices (Flat Panel Displays: FPD) have been put into practical use due to advances in liquid crystal and electroluminescence (EL) technologies.
これらＦＰＤは、ガラス基板上に設けた非晶質シリコン薄膜や多結晶シリコン薄膜を活性層に用いる電界効果型薄膜トランジスタ（Ｔｈｉｎ Ｆｉｌｍ Ｔｒａｎｓｉｓｔｏｒ：ＴＦＴ）のアクティブマトリクス回路により駆動されている。 These FPDs are driven by an active matrix circuit of a field effect thin film transistor (TFT) using an amorphous silicon thin film or a polycrystalline silicon thin film provided on a glass substrate as an active layer.
一方、これらＦＰＤのより一層の薄型化、軽量化、耐破損性の向上を求めて、ガラス基板の替わりに軽量で可撓性のある樹脂基板を用いる試みも行われている。 On the other hand, in order to further reduce the thickness, weight, and breakage resistance of these FPDs, an attempt has been made to use a lightweight and flexible resin substrate instead of a glass substrate.
しかし、上述のシリコン薄膜を用いるトランジスタの製造は、比較的高温の熱工程を要し、一般的に耐熱性の低い樹脂基板上に直接形成することは困難である。 However, the manufacture of the transistor using the above-described silicon thin film requires a relatively high temperature thermal process and is generally difficult to form directly on a resin substrate having low heat resistance.
そこで、低温での成膜が可能な、たとえばＺｎＯを材料とした酸化物半導体薄膜を用いるＴＦＴの開発が活発に行われている（特許文献１）。 In view of this, TFTs that can be formed at a low temperature and that use an oxide semiconductor thin film made of, for example, ZnO have been actively developed (Patent Document 1).
一方、従来の酸化物半導体薄膜を用いたTFTは、シリコンを用いたTFTに並ぶだけの充分な特性が得られていなかった。
本発明の目的は、TFTなど半導体デバイスの活性層に用いられて好適な半導体となる非晶質酸化物及び電界効果型トランジスタを提供することにある。 An object of the present invention is to provide an amorphous oxide and a field effect transistor that can be used in an active layer of a semiconductor device such as a TFT and become a suitable semiconductor.
本発明の第１の骨子は、
非晶質酸化物であって、
前記非晶質酸化物は、微結晶を含み、且つ
電子キャリア濃度が１０１８／ｃｍ３未満である、
ことを特徴とする。The first outline of the present invention is:
An amorphous oxide,
The amorphous oxide includes microcrystals and has an electron carrier concentration of less than 1018 / cm3 .
It is characterized by that.
本発明の第２の骨子は、非晶質酸化物であって、
前記非晶質酸化物は、微結晶を含み、且つ
電子キャリア濃度が増加すると共に、電子移動度が増加する傾向を示す、
ことを特徴とする。The second gist of the present invention is an amorphous oxide,
The amorphous oxide contains microcrystals and has a tendency to increase electron mobility as the electron carrier concentration increases.
It is characterized by that.
本発明の第３の骨子は、電界効果型トランジスタであって、
微結晶を含む非晶質酸化物を有する活性層と、
前記活性層に対してゲート絶縁膜を介して設けられたゲート電極と、
を具備することを特徴とする。The third essence of the present invention is a field effect transistor,
An active layer having an amorphous oxide containing microcrystals;
A gate electrode provided on the active layer via a gate insulating film;
It is characterized by comprising.
本発明の第４の骨子は、非晶質酸化物であって、
前記非晶質酸化物は層厚方向に組成が変化しており、且つ、
前記非晶質酸化物は、
電子キャリア濃度が１０１８／ｃｍ３未満である、
ことを特徴とする。The fourth aspect of the present invention is an amorphous oxide,
The amorphous oxide has a composition changing in the layer thickness direction, and
The amorphous oxide is
The electron carrier concentration is less than 1018 / cm3 ;
It is characterized by that.
本発明の第５の骨子は、電界効果型トランジスタであって、
層厚方向に組成が変化している非晶質酸化物を含む活性層と、
前記活性層に対してゲート絶縁膜を介して設けられたゲート電極と、
を具備し、
前記活性層は、第１の領域と該第１の領域よりも前記ゲート絶縁膜に近い第２の領域とを含み、
前記第２の領域の酸素濃度が、前記第１の領域の酸素濃度より高いことを特徴とする。The fifth essence of the present invention is a field effect transistor,
An active layer containing an amorphous oxide whose composition changes in the layer thickness direction;
A gate electrode provided on the active layer via a gate insulating film;
Comprising
The active layer includes a first region and a second region closer to the gate insulating film than the first region,
The oxygen concentration in the second region is higher than the oxygen concentration in the first region.
本発明の第６の骨子は、電界効果型トランジスタであって、
ＩｎあるいはＺｎの少なくとも一方を有する非晶質酸化物を含む活性層と、
前記活性層に対してゲート絶縁膜を介して設けられたゲート電極と、
を具備し、
前記活性層は、第１の領域と該第１の領域よりも前記ゲート絶縁膜に近い第２の領域とを含み、
前記第２の領域のＩｎ濃度あるいはＺｎ濃度が、前記第１の領域のＩｎ濃度あるいはＺｎ濃度より高いことを特徴とする。The sixth aspect of the present invention is a field effect transistor,
An active layer containing an amorphous oxide having at least one of In or Zn;
A gate electrode provided on the active layer via a gate insulating film;
Comprising
The active layer includes a first region and a second region closer to the gate insulating film than the first region,
The In concentration or Zn concentration in the second region is higher than the In concentration or Zn concentration in the first region.
本発明の第７の骨子は、
非晶質酸化物であって、
前記非晶質酸化物は膜厚方向に組成が変化しており、且つ、
前記非晶質酸化物は、
電子キャリア濃度が増加すると共に、電子移動度が増加する傾向を示す、
ことを特徴とする。The seventh aspect of the present invention is:
An amorphous oxide,
The amorphous oxide has a composition changing in the film thickness direction, and
The amorphous oxide is
As the electron carrier concentration increases, the electron mobility tends to increase.
It is characterized by that.
本発明の第８の骨子は、
電界効果型トランジスタであって、
Ｉｎ及びＺｎを有する非晶質酸化物を含む活性層と、
前記活性層に対してゲート絶縁膜を介して設けられたゲート電極と、
を具備し、
前記活性層は、第１の領域と該第１の領域よりも前記ゲート絶縁膜に近い第２の領域とを含み、
前記第２の領域のＩｎ濃度が、前記第１の領域のＩｎ濃度より高いか、あるいは前記第２の領域のＺｎ濃度が、前記第１の領域のＺｎ濃度より高いことを特徴とする。The eighth aspect of the present invention is:
A field effect transistor,
An active layer comprising an amorphous oxide comprising In and Zn;
A gate electrode provided on the active layer via a gate insulating film;
Comprising
The active layer includes a first region and a second region closer to the gate insulating film than the first region,
The In concentration of the second region is higher than the In concentration of the first region, or the Zn concentration of the second region is higher than the Zn concentration of the first region.
本発明の第９の骨子は、
非晶質酸化物であって、
該非晶質酸化物の電子キャリア濃度が１０１８／ｃｍ３未満であり、且つ
Li、Na、Mn、Ni、Pd、Cu、Cｄ、C、N、P、Ti、Zr、V、Ru、Ge、Sn、Fから選ばれる１種または複数種の元素を含むことを特徴とする。The ninth aspect of the present invention is:
An amorphous oxide,
The amorphous oxide has an electron carrier concentration of less than 1018 / cm3 , and
It contains one or more elements selected from Li, Na, Mn, Ni, Pd, Cu, Cd, C, N, P, Ti, Zr, V, Ru, Ge, Sn, and F. .
本発明の第１０の骨子は、
非晶質酸化物であって、
前記非晶質酸化物は、
電子キャリア濃度が増加すると共に、電子移動度が増加する傾向を示し、且つ
Li、Na、Mn、Ni、Pd、Cu、Cｄ、C、N、P、Ti、Zr、V、Ru、Ge、Sn、Fから選ばれる少なくとも１種の元素を含むことを特徴とする。The tenth aspect of the present invention is:
An amorphous oxide,
The amorphous oxide is
As the electron carrier concentration increases, the electron mobility tends to increase, and
It contains at least one element selected from Li, Na, Mn, Ni, Pd, Cu, Cd, C, N, P, Ti, Zr, V, Ru, Ge, Sn, and F.
本発明の第１１の骨子は、
電界効果型トランジスタであって、
Li、Na、Mn、Ni、Pd、Cu、Cｄ、C、N、P、Ti、Zr、V、Ru、Ge、Sn、Fから選ばれる少なくとも１種の元素を含む非晶質酸化物を有する活性層と、
前記活性層に対してゲート絶縁膜を介して設けられたゲート電極と、
を具備することを特徴とする。The eleventh aspect of the present invention is:
A field effect transistor,
It has an amorphous oxide containing at least one element selected from Li, Na, Mn, Ni, Pd, Cu, Cd, C, N, P, Ti, Zr, V, Ru, Ge, Sn, and F An active layer,
A gate electrode provided on the active layer via a gate insulating film;
It is characterized by comprising.
本発明においては、前記非晶質酸化物が、Ｉｎ、Ｚｎ、及びＳｎの少なくとも一つを含有する酸化物であることが好ましい。 In the present invention, the amorphous oxide is preferably an oxide containing at least one of In, Zn, and Sn.
又、本発明においては、前記非晶質酸化物が、Ｉｎ、Ｇａ、及びＺｎを含有する酸化物であることが好ましいものである。 In the present invention, it is preferable that the amorphous oxide is an oxide containing In, Ga, and Zn.
また、本発明においては、
前記非晶質酸化物が、ＩｎとＺｎとＳｎを含む酸化物、ＩｎとＺｎを含む酸化物、ＩｎとＳｎを含む酸化物、またはＩｎを含む酸化物のいずれかであることが好ましいのものである。In the present invention,
The amorphous oxide is preferably an oxide containing In, Zn, and Sn, an oxide containing In and Zn, an oxide containing In and Sn, or an oxide containing In It is.
ところで、本発明者が酸化物半導体を検討したところ、ZｎOは、一般に安定なアモルファス相を形成することができないことが判った。そして、殆どのZnOは多結晶相を呈するために、多結晶粒子間の界面でキャリアは散乱され、結果として電子移動度を大きくすることができないようである。 By the way, when the present inventor examined an oxide semiconductor, it was found that ZnO cannot generally form a stable amorphous phase. Since most ZnO exhibits a polycrystalline phase, carriers are scattered at the interface between the polycrystalline particles, and as a result, it seems that the electron mobility cannot be increased.
また、ＺｎＯには、酸素欠陥が入りやすく、キャリア電子が多数発生してしまうため、電気伝導度を小さくすることが難しい。このために、トランジスタのゲート電圧が無印加時でも、ソース端子とドレイン端子間に大きな電流が流れてしまい、ＴＦＴのノーマリーオフ動作を実現できないことが判った。また、トランジスタのオン・オフ比を大きくすることも難しいようである。 In addition, oxygen defects are easily introduced into ZnO, and a large number of carrier electrons are generated. Therefore, it is difficult to reduce the electrical conductivity. For this reason, it was found that even when the gate voltage of the transistor is not applied, a large current flows between the source terminal and the drain terminal, and the normally-off operation of the TFT cannot be realized. It also seems difficult to increase the on / off ratio of the transistor.
また、本発明者は、特開２０００−０４４２３６号公報に記載されている非晶質酸化物膜ZnxMyInzO(x+3y/2+3z/2)（式中、MはＡｌ及びＧａのうち少なくとも一つの元素である。）について検討した。この材料は、電子キャリア濃度が、１０１８／ｃｍ３以上であり、単なる透明電極としては好適な材料である。Further, the present inventor has amorphous oxide filmZn x M y In z O ( x + 3y / 2 + 3z / 2) ( in the formula as described in JP 2000-044236, M is Al And at least one element of Ga). This material has an electron carrier concentration of 1018 / cm3 or more, and is a suitable material as a simple transparent electrode.
しかし、電子キャリア濃度が１０１８／ｃｍ３以上の酸化物をTFTのチャネル層に用いた場合、オン・オフ比が十分にとれず、ノーマリーオフ型のＴＦＴにはふさわしくないことが分かった。However, it has been found that when an oxide having an electron carrier concentration of 1018 / cm3 or more is used for the TFT channel layer, the on / off ratio is not sufficient, which is not suitable for a normally-off type TFT.
つまり、従来の非晶質酸化物膜では、電子キャリア濃度が１０１８／ｃｍ３未満の膜を得ることはできていなかった。That is, in the conventional amorphous oxide film, a film having an electron carrier concentration of less than 1018 / cm3 could not be obtained.
本発明者は、電界効果型トランジスタの活性層として、電子キャリア濃度が１０１８／ｃｍ３未満の非晶質酸化物を用いたTFTを作製したところ、所望の特性のTFTが得られ、トランジスタなどの半導体デバイスに適用できることを発見した。The present inventor manufactured a TFT using an amorphous oxide having an electron carrier concentration of less than 1018 / cm3 as an active layer of a field effect transistor. As a result, a TFT having desired characteristics was obtained. Discovered that it can be applied to semiconductor devices.
本発明者らは、ＩｎＧａＯ３（ＺｎＯ）ｍ、及びこの材料の成膜条件に関する研究開発を精力的に進めた結果、成膜時の酸素雰囲気の条件を制御することで、電子キャリア濃度を１０１８／ｃｍ３未満にできることを見出した。As a result of intensive research and development on InGaO3 (ZnO)m and film formation conditions of this material, the present inventors have controlled the oxygen atmosphere conditions during film formation to reduce the electron carrier concentration to 10 It has been found that it can be less than18 / cm3 .
なお、上述したとおり、非晶質酸化物をＴＦＴのチャネルとなる活性層として使用する場合に主眼をおいて説明したが、本発明は、このような活性層に使用する場合に限定されるものではない。 Note that, as described above, the description has been given mainly when the amorphous oxide is used as an active layer serving as a channel of the TFT. However, the present invention is limited to the case where the amorphous oxide is used for such an active layer. is not.
本発明によれば、例えばＴＦＴのチャネル層に好適に用いられる非晶質酸化物を提供できる。また、優れた特性の電界効果型トランジスタを提供できる。 According to the present invention, for example, it is possible to provide an amorphous oxide that is suitably used for a channel layer of a TFT. In addition, a field effect transistor having excellent characteristics can be provided.
以下、本発明の実施の形態について図面を用いて詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
以下、第１から第３の実施形態において、上記第１から第３の本発明を説明する。 The first to third aspects of the present invention will be described below in the first to third embodiments.
その後、本発明に適用できる非晶質酸化物材料について詳述する。
なお、以下の実施形態においては、Ｉｎ−Ｇａ−Ｚｎ−Ｏ系の酸化物に関して主として説明するが、本発明はこれらの組成の材料に限定されるものではない。
（第１の実施形態：微結晶を含有する非晶質酸化物）
本実施形態に係る発明は、非晶質酸化物に関し、
該非晶質酸化物は微結晶を含むことを特徴とする。
ここで、非晶質酸化物内に微結晶が含有されているか否かは、例えば成膜された非晶質酸化物の膜の断面ＴＥＭ（透過型電子顕微鏡）写真などから判断される。
上記非晶質酸化物膜とは例えば、具体的には、In-Ga-Zn-Oを含み構成され、結晶状態における組成がInGaO3(ZnO)m (mは６未満の自然数)で表される。Thereafter, the amorphous oxide material applicable to the present invention will be described in detail.
Note that in the following embodiments, an In—Ga—Zn—O-based oxide will be mainly described; however, the present invention is not limited to materials having these compositions.
(First Embodiment: Amorphous oxide containing microcrystals)
The invention according to this embodiment relates to an amorphous oxide,
The amorphous oxide is characterized by containing microcrystals.
Here, whether or not microcrystals are contained in the amorphous oxide is determined from, for example, a cross-sectional TEM (transmission electron microscope) photograph of the formed amorphous oxide film.
For example, the amorphous oxide film specifically includes In—Ga—Zn—O, and the composition in the crystalline state is represented by InGaO3 (ZnO)m (m is a natural number less than 6). The
ここでいう、非晶質酸化物とは、その電子キャリア濃度が１０１８／ｃｍ３未満である酸化物であるか、電子キャリア濃度が増加すると共に、電子移動度が増加する傾向を示す酸化物などである。どのような用途のＴＦＴに用いるかにもよるが、前記非晶質酸化物を用いてノーマリーオフ型のＴＦＴを構成することは好ましい。As used herein, an amorphous oxide is an oxide having an electron carrier concentration of less than 1018 / cm3 , or an oxide that tends to increase electron mobility as the electron carrier concentration increases. Etc. Depending on the type of TFT used, it is preferable to form a normally-off type TFT using the amorphous oxide.
または、In-Ga-Zn-Ｍｇ-Oを含み構成され、結晶状態の組成がInGaO3(Zn1-xMｇxO)m(mは６未満の自然数、0<x≦1)で表される。Alternatively, it is composed of In—Ga—Zn—Mg—O, and the composition of the crystalline state is represented by InGaO3 (Zn1−x Mg× O)m (m is a natural number of less than 6, 0 <x ≦ 1). The
なお、これら非晶質酸化物の膜において、電子移動度が１ｃｍ２／（Ｖ・秒）超にすることも好ましい形態である。Note that in these amorphous oxide films, it is also preferable that the electron mobility exceeds 1 cm2 / (V · sec).
上記膜をチャネル層に用いれば、トランジスターオフ時のゲート電流が０．１マイクロアンペア未満のノーマリーオフで、オン・オフ比が１０３超のトランジスタ特性を持ち、かつ可視光に透明で、フレキシブルなＴＦＴを作成することができることを見出した。When the above film is used for the channel layer, the transistor current is normally off with a gate current of less than 0.1 microamperes when the transistor is off, the transistor has an on / off ratio of more than 103 , transparent to visible light, and flexible. It was found that a simple TFT can be produced.
なお、上記透明膜は、伝導電子数の増加と共に、電子移動度が大きくなることを特徴とする。透明膜を形成する基板としては、ガラス基板、プラスチック基板又はプラスチックフィルムなどを用いることができる。 The transparent film is characterized in that the electron mobility increases as the number of conduction electrons increases. As the substrate on which the transparent film is formed, a glass substrate, a plastic substrate, a plastic film, or the like can be used.
上記透明酸化物膜をチャネル層に利用する際には、Ａｌ２Ｏ３、Ｙ２Ｏ３、又はＨｆＯ２の1種、又はそれらの化合物を少なくとも二種以上含む混晶化合物をゲート絶縁膜を用いトランジスタを形成することも好ましい形態である。When the transparent oxide film is used for a channel layer, a gate insulating film containing a mixed crystal compound containing at least one of Al2 O3 , Y2 O3 , or HfO2 or at least two of these compounds is used. It is also a preferable form to use a transistor.
また、電気抵抗を高めるための不純物イオンを意図的に添加せず、酸素ガスを含む雰囲気中および、光照射下で成膜することも好ましい形態である。 In addition, it is also preferable to form a film in an atmosphere containing oxygen gas and under light irradiation without intentionally adding impurity ions for increasing electric resistance.
本発明者らは、この半絶縁性酸化物アモルファス薄膜は、伝導電子数の増加と共に、電子移動度が大きくなるという特異な特性を見出した。そして、その膜を用いてＴＦＴを作成し、オン・オフ比、ピンチオフ状態での飽和電流、スイッチ速度などのトランジスタ特性が更に向上することを見出した。 The present inventors have found that the semi-insulating oxide amorphous thin film has a unique characteristic that the electron mobility increases as the number of conduction electrons increases. Then, a TFT was formed using the film, and it was found that transistor characteristics such as an on / off ratio, a saturation current in a pinch-off state, and a switch speed were further improved.
透明半絶縁性アモルファス酸化物薄膜を膜トランジスタのチャネル層として用いると、電子移動度が１ｃｍ２／（Ｖ・秒）超、好ましくは５ｃｍ２／（Ｖ・秒）超、かつ電子キャリア濃度が１０１８／ｃｍ３未満、好ましくは、１０１６／ｃｍ３未満のときは、オフ時（ゲート電圧無印加時）のドレイン・ソース端子間の電流を、１０マイクロアンペア未満、好ましくは０．１マイクロアンペア未満にすることができる。また、該薄膜を用いれば、電子移動度が１ｃｍ２／（Ｖ・秒）超、好ましくは５ｃｍ２／（Ｖ・秒）超の時は、ピンチオフ後の飽和電流を１０マイクロアンペア超にでき、オン・オフ比を１０３超とすることができる。When a transparent semi-insulating amorphous oxide thin film is used as a channel layer of a film transistor, the electron mobility is more than 1 cm2 / (V · sec), preferably more than 5 cm2 / (V · sec) and the electron carrier concentration is 10When it is less than18 / cm3 , preferably less than 1016 / cm3 , the current between the drain and source terminals when off (when no gate voltage is applied) is less than 10 microamperes, preferably 0.1 microamperes. Can be less than. When the thin film is used, when the electron mobility is more than 1 cm2 / (V · sec), preferably more than 5 cm2 / (V · sec), the saturation current after pinch-off can be more than 10 microamperes, The on / off ratio can be greater than 103 .
ＴＦＴでは、ピンチオフ状態では、ゲート端子に高電圧が印加され、チャネル中には高密度の電子が存在している。したがって、本発明によれば、電子移動度が増加した分だけ、より飽和電流値を大きくすることができる。この結果、オン・オフ比の増大、飽和電流の増大、スイッチング速度の増大など、ほとんど全てのトランジスタ特性が向上する。なお、通常の化合物中では、電子数が増大すると、電子間の衝突により、電子移動度は減少する。 In the TFT, in a pinch-off state, a high voltage is applied to the gate terminal, and high-density electrons exist in the channel. Therefore, according to the present invention, the saturation current value can be further increased by the amount of increase in electron mobility. As a result, almost all transistor characteristics such as an increase in on / off ratio, an increase in saturation current, and an increase in switching speed are improved. In a normal compound, when the number of electrons increases, electron mobility decreases due to collisions between electrons.
なお、上記ＴＦＴの構造は、半導体チャネル層の上にゲート絶縁膜とゲート端子とを順に形成するスタガ（トップゲート）構造のものに用いることができる。また、ゲート端子の上にゲート絶縁膜と半導体チャネル層を順に形成する逆スタガ（ボトムゲート）構造のものに用いることができる。 The TFT structure can be used for a staggered (top gate) structure in which a gate insulating film and a gate terminal are sequentially formed on a semiconductor channel layer. Further, it can be used for an inverted stagger (bottom gate) structure in which a gate insulating film and a semiconductor channel layer are formed in order on a gate terminal.
（膜組成について）
結晶状態における組成がInGaO3(ZnO)m(mは６未満の自然数)で表される透明アモルファス酸化物薄膜は、ｍの値が６未満の場合は、８００℃以上の高温までアモルファス状態が安定に保たれるが、ｍの値が大きくなるにつれ結晶化しやすくなる。すなわち、InGaO3に対するZnOの比が増大して、ＺｎＯ組成に近づくにつれ、結晶化しやすくなる。(About film composition)
A transparent amorphous oxide thin film whose composition in the crystalline state is represented by InGaO3 (ZnO)m (m is a natural number less than 6) is stable in amorphous state up to a high temperature of 800 ° C. or higher when the value of m is less than 6. However, it becomes easier to crystallize as the value of m increases. That is, as the ratio of ZnO to InGaO3 increases and approaches the ZnO composition, it becomes easier to crystallize.
したがって、アモルファスＴＦＴのチャネル層としては、ｍの値が６未満であることが好ましい。但し、成膜時光照射下では、ｍの値が小さくても、微結晶が形成できることもわかった。 Therefore, the value of m is preferably less than 6 for the channel layer of the amorphous TFT. However, it was also found that microcrystals can be formed under light irradiation during film formation even if the value of m is small.
成膜方法は、InGaO3(ZnO)m組成を有する多結晶焼結体をターゲットとして、気相成膜法を用いるのが良い。気相成膜法の中でも、スパッタ法、パルスレーザー蒸着法が適している。さらに、量産性の観点から、スパッタ法が最も適している。As a film forming method, a vapor phase film forming method is preferably used with a polycrystalline sintered body having an InGaO3 (ZnO)m composition as a target. Of the vapor deposition methods, sputtering and pulsed laser deposition are suitable. Furthermore, the sputtering method is most suitable from the viewpoint of mass productivity.
しかしながら、通常の条件で該アモルファス膜を作製すると、主として酸素欠損が生じ、これまで、電子キャリア濃度を１０１８／ｃｍ３未満、電気伝導度にして、１０Ｓ／ｃｍ以下にすることができなかった。However, when the amorphous film is produced under normal conditions, oxygen vacancies mainly occur, and until now, the electron carrier concentration has been less than 1018 / cm3 and the electric conductivity has not been able to be 10 S / cm or less. .
そうした薄膜を用いた場合、ノーマリーオフのトランジスタを構成することができない。 When such a thin film is used, a normally-off transistor cannot be formed.
図７に示す装置を用いて、パルスレーザー蒸着法で作成したIn-Ga-Zn-Oから構成され、結晶状態における組成がInGaO3(ZnO)m(mは６未満の自然数)で表される透明アモルファス酸化物薄膜を、電子キャリア濃度を１０１８／ｃｍ３未満に低下させることができる。例えば酸素分圧を3.2Ｐａ超の高い雰囲気中で、成膜することにより、電子キャリア濃度を１０１８／ｃｍ３未満に低下させることができる。It is composed of In-Ga-Zn-O prepared by pulse laser deposition using the apparatus shown in FIG. 7, and the composition in the crystalline state is represented by InGaO3 (ZnO)m (m is a natural number less than 6). The transparent amorphous oxide thin film can reduce the electron carrier concentration to less than 1018 / cm3 . For example, the electron carrier concentration can be reduced to less than 1018 / cm3 by forming a film in an atmosphere having a high oxygen partial pressure of more than 3.2 Pa.
この場合、基板の温度は意図的に加温しない状態で、ほぼ室温に維持されている。プラスチックフィルムを基板として使用できるために、基板温度は100℃未満に保つことが好ましい。 In this case, the temperature of the substrate is maintained at substantially room temperature without intentionally heating. Since a plastic film can be used as a substrate, the substrate temperature is preferably kept below 100 ° C.
本実施形態に係る発明は、光照射下におけるパルスレーザー蒸着法で作製したIn-Ga-Zn-Oから構成される。 The invention according to this embodiment is composed of In-Ga-Zn-O produced by a pulse laser deposition method under light irradiation.
具体的には、結晶状態における組成InGaO3(ZnO)m(mは６未満の自然数)で表される微結晶を含む透明アモルファス酸化物薄膜であり、これを用いれば、ノーマリーオフのトランジスタを構成することができる。Specifically, it is a transparent amorphous oxide thin film containing microcrystals represented by the composition InGaO3 (ZnO)m (m is a natural number less than 6) in the crystalline state. Can be configured.
また、該薄膜の電子移動度は、１ｃｍ２／Ｖ・秒超が得られ、オン・オフ比を１０３超に大きくすることができる。Further, the electron mobility of the thin film can be more than 1 cm2 / V · second, and the on / off ratio can be increased to more than 103 .
また、本発明は、光照射下でアルゴンガスを用いたスパッタ蒸着法で作成したIn-Ga-Zn-Oから構成される。 Further, the present invention is composed of In—Ga—Zn—O prepared by a sputter deposition method using argon gas under light irradiation.
例えば、本発明に係る非晶質酸化物は、図８に記載の装置を用いて得ることができる。この場合、本発明に係る非晶質酸化物は、結晶状態における組成がInGaO3(ZnO)m(mは６未満の自然数)で表される微結晶を含む透明アモルファス酸化物薄膜を、酸素分圧を1×１０-２Ｐａ超の高い雰囲気中で、成膜することにより得られる。For example, the amorphous oxide according to the present invention can be obtained using the apparatus shown in FIG. In this case, the amorphous oxide according to the present invention is obtained by converting a transparent amorphous oxide thin film containing a microcrystal whose composition in the crystalline state is represented by InGaO3 (ZnO)m (m is a natural number of less than 6) to an oxygen content. It can be obtained by forming a film in an atmosphere having a high pressure exceeding 1 × 10−2 Pa.
この場合、基板の温度は意図的に加温しない状態で、ほぼ室温に維持されている。プラスチックフィルムを基板として使用できるために、基板温度は100℃未満に保つことが好ましい。酸素分圧をさらに大きくすることにより、電子キャリア数を低下させることができる。 In this case, the temperature of the substrate is maintained at substantially room temperature without intentionally heating. Since a plastic film can be used as a substrate, the substrate temperature is preferably kept below 100 ° C. By further increasing the oxygen partial pressure, the number of electron carriers can be reduced.
即ち、本発明は、光照射下でスパッタ蒸着法で作製したIn-Ga-Zn-Oから構成される。
結晶状態における組成InGaO3(ZnO)m(mは６未満の自然数)で表される微結晶を含む透明アモルファス酸化物薄膜を用い、ノーマリーオフで、かつオン・オフ比を１０３超のトランジスタを構成することができる。That is, the present invention is composed of In—Ga—Zn—O produced by sputtering deposition under light irradiation.
A transistor having a transparent amorphous oxide thin film containing a microcrystal represented by a composition InGaO3 (ZnO)m (m is a natural number less than 6) in a crystalline state, normally off, and having an on / off ratio of more than 103 Can be configured.
光照射下でのパルスレーザー蒸着法およびスパッタ法で作成された薄膜では、伝導電子数の増加と共に、電子移動度が増加する。 In a thin film prepared by pulse laser deposition and sputtering under light irradiation, the electron mobility increases as the number of conduction electrons increases.
同様に、ターゲットとして、多結晶InGaO3(Zn1-xＭｇｘO)m(mは６未満の自然数、0<x≦1)を用いれば、１Ｐａ未満の酸素分圧下でも、高抵抗アモルファスInGaO3(Zn1-xＭｇｘO)m膜を得ることができる。Similarly, if polycrystalline InGaO3 (Zn1-x Mgx O)m (m is a natural number less than 6 and 0 <x ≦ 1) is used as a target, a high-resistance amorphous InGaO even under an oxygen partial pressure of less than 1 Pa.3 (Zn1-x Mgx O)m film can be obtained.
上記のとおり、酸素分圧を制御することにより、酸素欠陥を低減でき、その結果、特定の不純物イオンを添加することなしに、電子キャリア濃度を減少できる。本発明に係る非晶質酸化物は、図１から図５を用いて作製される薄膜の製造時に、光照射を行うことにより得られる。 As described above, by controlling the oxygen partial pressure, oxygen defects can be reduced, and as a result, the electron carrier concentration can be decreased without adding specific impurity ions. The amorphous oxide according to the present invention can be obtained by irradiating with light during the production of a thin film produced using FIGS.
酸素分圧等の条件は、図７や８に記載の装置を用いた場合は、およそ後述する範囲の分圧で製造可能である。 Conditions such as oxygen partial pressure can be produced with a partial pressure in the range described later when the apparatus shown in FIGS. 7 and 8 is used.
また、微結晶を含むアモルファス状態では、微結晶粒界界面をアモルファス構造で覆うため、酸化亜鉛等の多結晶状態とは異なり、電子や正孔の移動をトラップしてしまうような本質的に粒子界面が存在しない。そのために、高電子移動度のアモルファス薄膜を得ることができる。さらに、特定の不純物を添加せずに伝導電子数を減少できるので、不純物による散乱がなく、電子移動度を高く保つことができる。 In addition, in the amorphous state including microcrystals, the interface between the microcrystalline grain boundaries is covered with an amorphous structure, so unlike the polycrystalline state such as zinc oxide, essentially particles that trap the movement of electrons and holes. There is no interface. Therefore, an amorphous thin film with high electron mobility can be obtained. Furthermore, since the number of conduction electrons can be reduced without adding specific impurities, there is no scattering due to impurities, and electron mobility can be kept high.
本発明に用いられる微結晶としてはInGaO3(ZnO)m(mは６未満の自然数)で表される組成比の微結晶に限定されることはない。The microcrystal used in the present invention is not limited to a microcrystal having a composition ratio represented by InGaO3 (ZnO)m (m is a natural number of less than 6).
上記した透明膜を用いた薄膜トランジスタにおいて、Ａｌ２Ｏ３、Ｙ２Ｏ３、ＨｆＯ２、又はそれらの化合物を少なくとも二つ以上含む混晶化合物をゲート絶縁膜とすることが好ましい。ゲート絶縁薄膜とチャネル層薄膜との界面に欠陥が存在すると、電子移動度の低下及びトランジスタ特性にヒステリシスが生じる。また、ゲート絶縁膜の種類により、リーク電流が大きく異なる。このために、チャネル層に適合したゲート絶縁膜を選定する必要がある。Ａｌ２Ｏ３膜を用いれば、リーク電流を低減できる。また、Ｙ２Ｏ３膜を用いればヒステリシスを小さくできる。さらに、高誘電率のＨｆＯ２膜を用いれば、電子移動度を大きくすることができる。また、これらの膜の混晶を用いて、リーク電流、ヒステリシスが小さく、電子移動度の大きなＴＦＴを形成できる。また、ゲート絶縁膜形成プロセス及びチャネル層形成プロセスは、室温で行うことができるので、ＴＦＴ構造として、スタガ構造及び逆スタガ構造いずれをも形成することができる。In the thin film transistor using the transparent film described above, it is preferable that a mixed crystal compound containing at least two of Al2 O3 , Y2 O3 , HfO2 , or a compound thereof is used as the gate insulating film. If there is a defect at the interface between the gate insulating thin film and the channel layer thin film, the electron mobility is lowered and the transistor characteristics are hysteresis. Further, the leakage current varies greatly depending on the type of the gate insulating film. For this purpose, it is necessary to select a gate insulating film suitable for the channel layer. If an Al2 O3 film is used, leakage current can be reduced. Further, the hysteresis can be reduced by using a Y2 O3 film. Further, if a high dielectric constant HfO2 film is used, the electron mobility can be increased. Further, by using mixed crystals of these films, a TFT with small leakage current and hysteresis and high electron mobility can be formed. In addition, since the gate insulating film formation process and the channel layer formation process can be performed at room temperature, both a staggered structure and an inverted staggered structure can be formed as the TFT structure.
薄膜トランジスタ（Thin Film Transistor, ＴＦＴ）は、ゲート端子、ソース端子、及び、ドレイン端子を備えた３端子素子である。そしてＴＦＴは、セラミックス、ガラス、又はプラスチックなどの絶縁基板上に成膜した半導体薄膜を、電子又はホールが移動するチャネル層として用いたものである。また、ＴＦＴは、ゲート端子に電圧を印加して、チャンネル層に流れる電流を制御し、ソース端子とドレイン端子間の電流をスイッチングする機能を有するアクテイブ素子である。 A thin film transistor (TFT) is a three-terminal element including a gate terminal, a source terminal, and a drain terminal. The TFT uses a semiconductor thin film formed on an insulating substrate such as ceramic, glass, or plastic as a channel layer through which electrons or holes move. A TFT is an active element having a function of switching a current between a source terminal and a drain terminal by applying a voltage to a gate terminal to control a current flowing in a channel layer.
なお、非晶質酸化物に含まれる微結晶は、上述のように光照射（具体的には、例えば、ハロゲンランプを用いた光照射や紫外線照射である。）により、形成してもよいが、勿論、光照射によらない他の方法でもよい。
（第２の実施形態：非晶質酸化物の組成分布）
本実施形態に係る非晶質酸化物は、
その膜厚方向で組成が変化していることを特徴とする。Note that microcrystals included in the amorphous oxide may be formed by light irradiation as described above (specifically, for example, light irradiation using a halogen lamp or ultraviolet irradiation). Of course, other methods that do not rely on light irradiation may be used.
(Second Embodiment: Composition Distribution of Amorphous Oxide)
The amorphous oxide according to this embodiment is
The composition changes in the film thickness direction.
ここで、膜厚方向に組成が変化しているとは、酸化物に含有される酸素量が膜厚方向で変化していたり、酸化物を構成する元素が途中で変化していたり（即ち、組成が変わっていたり）、酸化物を構成する元素の含有量が変化していることを意味する。 Here, the composition changes in the film thickness direction means that the amount of oxygen contained in the oxide changes in the film thickness direction, or the elements constituting the oxide change in the middle (that is, It means that the content of the elements constituting the oxide has changed.
従って、前記非晶質酸化物を電界効果型トランジスタの活性層（チャネル層ともいう）に用いる場合には、例えば以下の構成が好ましい。 Therefore, when the amorphous oxide is used for an active layer (also referred to as a channel layer) of a field effect transistor, for example, the following configuration is preferable.
具体的には、前記非晶質酸化物を含む活性層と、該活性層と界面を構成するゲート絶縁膜とを備えるトランジスタにおいて、
該非晶質酸化物に含まれる酸素濃度は、該界面側の領域の方が、該界面より離れた領域よりも高くなるように構成するのである。Specifically, in a transistor comprising an active layer containing the amorphous oxide and a gate insulating film that forms an interface with the active layer,
The oxygen concentration contained in the amorphous oxide is configured such that the region on the interface side is higher than the region far from the interface.
この場合、前記非晶質酸化物層における、前記界面付近の電気抵抗が高くなり、トランジスタのいわゆるチャネルは、前記界面から非晶質酸化物の内部に形成される。前記界面があれているような場合は、かかる構成はリーク電流を減らすという観点から好ましい。 In this case, the electrical resistance in the vicinity of the interface in the amorphous oxide layer is increased, and a so-called channel of the transistor is formed in the amorphous oxide from the interface. When the interface is present, such a configuration is preferable from the viewpoint of reducing leakage current.
すなわち、トランジスタの活性層として上記非晶質酸化物を用いる場合に、該活性層は第１の領域と、該第１の領域よりもゲート絶縁膜側に近い第２の領域を含む構成にして、第２の領域の酸素濃度が、第１の領域のそれよりも高くなるようにするのがよい。 That is, when the amorphous oxide is used as an active layer of a transistor, the active layer includes a first region and a second region closer to the gate insulating film side than the first region. The oxygen concentration of the second region is preferably higher than that of the first region.
なお、２つの領域の境界は明確である必要は無く、勾配やステップ状に、組成比が変化していてもよい。 The boundary between the two regions does not need to be clear, and the composition ratio may change in a gradient or step shape.
特に、該非晶質酸化物の電子キャリア濃度が１０１８／ｃｍ３未満であるのがよい。In particular, the electron carrier concentration of the amorphous oxide is preferably less than 1018 / cm3 .
なお、基板上に成膜されている場合の膜厚方向とは、基板の面内方向ではない方向（例えば、基板の面内方向に垂直な方向）である。
また、ＩｎあるいはＺｎの少なくとも一方を有する非晶質酸化物を含む活性層と、該活性層と界面を構成するゲート絶縁膜とを備えるトランジスタにおいて、該非晶質酸化物に含まれるＩｎあるいはＺｎ濃度は、該界面側の領域の方が、該界面より離れた領域よりも高くなるように構成することも好ましい形態である。この場合、電界効果移動度を高めることができる。Note that the film thickness direction when the film is formed on the substrate is a direction that is not the in-plane direction of the substrate (for example, a direction perpendicular to the in-plane direction of the substrate).
Further, in a transistor including an active layer containing an amorphous oxide having at least one of In or Zn and a gate insulating film that forms an interface with the active layer, the concentration of In or Zn contained in the amorphous oxide It is also a preferred form that the region on the interface side is configured to be higher than the region distant from the interface. In this case, field effect mobility can be increased.
即ち、トランジスタの活性層として上記非晶質酸化物を用いる場合、活性層は第１の領域と、第１の領域よりもゲート絶縁膜側に近い第２の領域を含む構成にし、第２の領域のＩｎ又はＺｎ濃度の少なくとも一方が、第１の領域のそれぞれの濃度よりも高くなるようにするのがよい。 That is, when the above amorphous oxide is used as an active layer of a transistor, the active layer includes a first region and a second region closer to the gate insulating film side than the first region. It is preferable that at least one of the In and Zn concentrations in the region is higher than the respective concentrations in the first region.
勿論、第２の領域のＩｎ濃度を、第１の領域のＩｎ濃度より高くしたり、または第２の領域のＺｎの濃度を、第１の領域のＺｎ濃度より高くすることも好ましい。更に、第２の領域のＩｎ濃度を、第１の領域のＩｎ濃度より高くし、且つ第２の領域のＺｎの濃度を、第１の領域のＺｎ濃度より高くすることも好ましい。 Of course, it is also preferable to make the In concentration of the second region higher than the In concentration of the first region, or to make the Zn concentration of the second region higher than the Zn concentration of the first region. Furthermore, it is also preferable that the In concentration of the second region is higher than the In concentration of the first region, and the Zn concentration of the second region is higher than the Zn concentration of the first region.
第２の本発明に係る酸化物膜とは具体的には、In-Ga-Zn-Oを含み構成され、膜厚方向で組成が分布し、結晶状態における組成がInGaO3(ZnO)m(mは６未満の自然数)で表され、電子キャリア濃度が１０１８／ｃｍ３未満であることを特徴とする。Specifically, the oxide film according to the second aspect of the present invention includes In—Ga—Zn—O, the composition is distributed in the film thickness direction, and the composition in the crystalline state is InGaO3 (ZnO)m ( m is a natural number less than 6), and the electron carrier concentration is less than 1018 / cm3 .
または、In-Ga-Zn-Ｍｇ-Oを含み構成され、膜厚方向で組成が分布し、結晶状態の組成がInGaO3(Zn1-xMｇxO)m(mは６未満の自然数、0<x≦1)で表され、電子キャリア濃度が１０１８／ｃｍ３未満であることを特徴とする透明アモルファス酸化物膜である。Alternatively, it is configured to include In—Ga—Zn—Mg—O, the composition is distributed in the film thickness direction, and the composition in the crystalline state is InGaO3 (Zn1−x Mg× O)m (m is a natural number less than 6, A transparent amorphous oxide film represented by 0 <x ≦ 1) and having an electron carrier concentration of less than 1018 / cm3 .
なお、これらの膜において、電子移動度が１ｃｍ２／（Ｖ・秒）超にすることも好ましい形態である。In these films, it is also a preferable mode that the electron mobility exceeds 1 cm2 / (V · sec).
上記膜をチャネル層に用いれば、トランジスターオフ時のゲート電流が０．１マイクロアンペア未満のノーマリーオフで、オン・オフ比が１０４超のトランジスタ特性を持ち、かつ可視光に透明で、フレキシブルなＴＦＴを作成することができる。When the above film is used for the channel layer, the transistor current is normally off with a gate current of less than 0.1 microamperes when the transistor is turned off, the transistor has an on / off ratio of more than 104 , transparent to visible light, and flexible. TFT can be made.
なお、上記透明膜は、伝導電子数の増加と共に、電子移動度が大きくなることを特徴とする。 The transparent film is characterized in that the electron mobility increases as the number of conduction electrons increases.
透明膜を形成する基板としては、ガラス基板、プラスチック基板又はプラスチックフィルムなどを用いることができる。 As the substrate on which the transparent film is formed, a glass substrate, a plastic substrate, a plastic film, or the like can be used.
上記透明酸化物膜をチャネル層に利用する際には、Ａｌ２Ｏ３、Ｙ２Ｏ３、又はＨｆＯ２の1種、又はそれらの化合物を少なくとも二種以上含む混晶化合物をゲート絶縁膜を用いトランジスタを形成することも好ましい形態である。When the transparent oxide film is used for a channel layer, a gate insulating film containing a mixed crystal compound containing at least one of Al2 O3 , Y2 O3 , or HfO2 or at least two of these compounds is used. It is also a preferable form to use a transistor.
また、電気抵抗を高めるための不純物イオンを意図的に添加せず、酸素ガスを含む雰囲気中で、成膜することも好ましい形態である。 In addition, it is also a preferable mode to form a film in an atmosphere containing oxygen gas without intentionally adding impurity ions for increasing electric resistance.
本発明者らは、この半絶縁性酸化物アモルファス薄膜は、伝導電子数の増加と共に、電子移動度が大きくなるという特異な特性を見出した。そして、その膜を用いてＴＦＴを作成し、オン・オフ比、ピンチオフ状態での飽和電流、スイッチ速度などのトランジスタ特性が更に向上することを見出した。 The present inventors have found that the semi-insulating oxide amorphous thin film has a unique characteristic that the electron mobility increases as the number of conduction electrons increases. Then, a TFT was formed using the film, and it was found that transistor characteristics such as an on / off ratio, a saturation current in a pinch-off state, and a switch speed were further improved.
透明半絶縁性アモルファス酸化物薄膜を膜トランジスタのチャネル層として用いると、電子移動度が１ｃｍ２／（Ｖ・秒）超、好ましくは５ｃｍ２／（Ｖ・秒）超、かつ電子キャリア濃度が１０１８／ｃｍ３未満、好ましくは、１０１６／ｃｍ３未満のときは、オフ時（ゲート電圧無印加時）のドレイン・ソース端子間の電流を、１０マイクロアンペア未満、好ましくは０．１マイクロアンペア未満にすることができる。また、該薄膜を用いれば、電子移動度が１ｃｍ２／（Ｖ・秒）超、好ましくは５ｃｍ２／（Ｖ・秒）超の時は、ピンチオフ後の飽和電流を１０マイクロアンペア超にでき、オン・オフ比を１０４超とすることができる。When a transparent semi-insulating amorphous oxide thin film is used as a channel layer of a film transistor, the electron mobility is more than 1 cm2 / (V · sec), preferably more than 5 cm2 / (V · sec) and the electron carrier concentration is 10When it is less than18 / cm3 , preferably less than 1016 / cm3 , the current between the drain and source terminals when off (when no gate voltage is applied) is less than 10 microamperes, preferably 0.1 microamperes. Can be less than. When the thin film is used, when the electron mobility is more than 1 cm2 / (V · sec), preferably more than 5 cm2 / (V · sec), the saturation current after pinch-off can be more than 10 microamperes, The on / off ratio can be greater than 104 .
ＴＦＴでは、ピンチオフ状態では、ゲート端子に高電圧が印加され、チャネル中には高密度の電子が存在している。したがって、本発明によれば、電子移動度が増加した分だけ、より飽和電流値を大きくすることができる。この結果、オン・オフ比の増大、飽和電流の増大、スイッチング速度の増大など、ほとんど全てのトランジスタ特性が向上する。なお、通常の化合物中では、電子数が増大すると、電子間の衝突により、電子移動度は減少する。 In the TFT, in a pinch-off state, a high voltage is applied to the gate terminal, and high-density electrons exist in the channel. Therefore, according to the present invention, the saturation current value can be further increased by the amount of increase in electron mobility. As a result, almost all transistor characteristics such as an increase in on / off ratio, an increase in saturation current, and an increase in switching speed are improved. In a normal compound, when the number of electrons increases, electron mobility decreases due to collisions between electrons.
なお、上記ＴＦＴの構造としては、半導体チャネル層の上にゲート絶縁膜とゲート端子とを順に形成するスタガ（トップゲート）構造のものに用いることができる。また、ゲート端子の上にゲート絶縁膜と半導体チャネル層を順に形成する逆スタガ（ボトムゲート）構造のものに用いることができる。 The TFT structure can be a staggered (top gate) structure in which a gate insulating film and a gate terminal are sequentially formed on a semiconductor channel layer. Further, it can be used for an inverted stagger (bottom gate) structure in which a gate insulating film and a semiconductor channel layer are formed in order on a gate terminal.
（膜組成について）
結晶状態における組成がInGaO3(ZnO)m(mは６未満の自然数)で表される透明アモルファス酸化物薄膜は、ｍの値が６未満の場合は、８００℃以上の高温までアモルファス状態が安定に保たれるが、ｍの値が大きくなるにつれ結晶化しやすくなる。すなわち、InGaO3に対するZnOの比が増大して、ＺｎＯ組成に近づくにつれ、結晶化しやすくなる。(About film composition)
A transparent amorphous oxide thin film whose composition in the crystalline state is represented by InGaO3 (ZnO)m (m is a natural number less than 6) is stable in amorphous state up to a high temperature of 800 ° C. or higher when the value of m is less than 6. However, it becomes easier to crystallize as the value of m increases. That is, as the ratio of ZnO to InGaO3 increases and approaches the ZnO composition, it becomes easier to crystallize.
したがって、アモルファスＴＦＴのチャネル層としては、ｍの値が６未満であることが好ましい。 Therefore, the value of m is preferably less than 6 for the channel layer of the amorphous TFT.
上記した透明膜を用いた薄膜トランジスタにおいて、Ａｌ２Ｏ３、Ｙ２Ｏ３、ＨｆＯ２、又はそれらの化合物を少なくとも二つ以上含む混晶化合物をゲート絶縁膜とすることが好ましい。ゲート絶縁薄膜とチャネル層薄膜との界面に欠陥が存在すると、電子移動度の低下及びトランジスタ特性にヒステリシスが生じる。また、ゲート絶縁膜の種類により、リーク電流が大きく異なる。このために、チャネル層に適合したゲート絶縁膜を選定する必要がある。Ａｌ２Ｏ３膜を用いれば、リーク電流を低減できる。また、Ｙ２Ｏ３膜を用いればヒステリシスを小さくできる。さらに、高誘電率のＨｆＯ２膜を用いれば、電子移動度を大きくすることができる。また、これらの膜の混晶を用いて、リーク電流、ヒステリシスが小さく、電子移動度の大きなＴＦＴを形成できる。また、ゲート絶縁膜形成プロセス及びチャネル層形成プロセスは、室温で行うことができるので、ＴＦＴ構造として、スタガ構造及び逆スタガ構造いずれをも形成することができる。In the thin film transistor using the transparent film described above, it is preferable that a mixed crystal compound containing at least two of Al2 O3 , Y2 O3 , HfO2 , or a compound thereof is used as the gate insulating film. If there is a defect at the interface between the gate insulating thin film and the channel layer thin film, the electron mobility is lowered and the transistor characteristics are hysteresis. Further, the leakage current varies greatly depending on the type of the gate insulating film. For this purpose, it is necessary to select a gate insulating film suitable for the channel layer. If an Al2 O3 film is used, leakage current can be reduced. Further, the hysteresis can be reduced by using a Y2 O3 film. Further, if a high dielectric constant HfO2 film is used, the electron mobility can be increased. Further, by using mixed crystals of these films, a TFT with small leakage current and hysteresis and high electron mobility can be formed. In addition, since the gate insulating film formation process and the channel layer formation process can be performed at room temperature, both a staggered structure and an inverted staggered structure can be formed as the TFT structure.
薄膜トランジスタ（Thin Film Transistor, ＴＦＴ）は、ゲート端子、ソース端子、及び、ドレイン端子を備えた３端子素子である。またＴＦＴは、セラミックス、ガラス、又はプラスチックなどの絶縁基板上に成膜した半導体薄膜を、電子又はホールが移動するチャネル層として用いたものである。さらにＴＦＴは、ゲート端子に電圧を印加して、チャンネル層に流れる電流を制御し、ソース端子とドレイン端子間の電流をスイッチングする機能を有するアクテイブ素子である。 A thin film transistor (TFT) is a three-terminal element including a gate terminal, a source terminal, and a drain terminal. A TFT uses a semiconductor thin film formed on an insulating substrate such as ceramics, glass, or plastic as a channel layer through which electrons or holes move. Furthermore, a TFT is an active element having a function of switching a current between a source terminal and a drain terminal by applying a voltage to a gate terminal to control a current flowing in a channel layer.
このように第２の本発明は、上記透明膜を用いてＦＥＴを作製する際に、ＦＥＴの活性層である上記透明膜の膜厚方向の組成に改良を行っている。 As described above, according to the second aspect of the present invention, when the FET is manufactured using the transparent film, the composition in the film thickness direction of the transparent film which is the active layer of the FET is improved.
具体的には、パルスレーザー堆積法においては、酸素分圧を膜厚方向で変化させたり、あるいは、パルスレーザーの発振パワーを変化させたり、発振周波数を変化させたり、あるいは、ターゲット−基板間の距離を膜厚方向で変化させ、膜厚方向の組成変化を行う。また、スパッタ蒸着法で作成する場合は、In2O3あるいはZnOのターゲットを追加スパッタする形で、膜厚方向の組成変化を行う。Specifically, in the pulse laser deposition method, the oxygen partial pressure is changed in the film thickness direction, the oscillation power of the pulse laser is changed, the oscillation frequency is changed, or the target-substrate is changed. The composition is changed in the film thickness direction by changing the distance in the film thickness direction. When the sputtering deposition method is used, the composition change in the film thickness direction is performed by additionally sputtering an In2 O3 or ZnO target.
例えば、酸素雰囲気下で成膜する際には、ターゲット間と基板間の距離が離れるに従い、同膜中に含まれる酸素量は多くなる。また、成膜中に、例えばＺｎＯのターゲットを追加すれば、追加して後に成膜される膜中にはＺｎの量が多くなる。
（第３の実施形態：添加物を含有する非晶質酸化物）
本実施形態に係る非晶質酸化物は、
添加物として、Li、Na、Mn、Ni、Pd、Cu、Cｄ、C、N、P、Ti、Zr、V、Ru、Ge、Sn、Fから選ばれる１種または複数種の元素を含むことを特徴とする。For example, when a film is formed in an oxygen atmosphere, the amount of oxygen contained in the film increases as the distance between the target and the substrate increases. Further, if, for example, a ZnO target is added during film formation, the amount of Zn increases in the film that is additionally formed later.
(Third Embodiment: Amorphous Oxide Containing Additive)
The amorphous oxide according to this embodiment is
As an additive, one or more elements selected from Li, Na, Mn, Ni, Pd, Cu, Cd, C, N, P, Ti, Zr, V, Ru, Ge, Sn, and F are included. It is characterized by.
このような非晶質酸化物への添加物の導入は、成膜装置中のガスに含ませたり、成膜装置内に含ませたり、装置内で使用するターゲット材に含ませることにより実現される。勿論、このような添加物を含んでいない非晶質酸化物からなる膜を作製後、後述する実施例のように後から当該膜に前記添加物を導入してもよい。 Such introduction of the additive into the amorphous oxide is realized by including it in the gas in the film forming apparatus, in the film forming apparatus, or in the target material used in the apparatus. The Of course, after a film made of an amorphous oxide not containing such an additive is produced, the additive may be introduced into the film later as in an example described later.
なお、該非晶質酸化物の電子キャリア濃度が１０１８／ｃｍ３未満であるのが好ましい。Note that the electron carrier concentration of the amorphous oxide is preferably less than 1018 / cm3 .
具体的に本発明に係る非晶質酸化物は、In-Ga-Zn-Oを含み構成され、結晶状態における組成がInGaO3(ZnO)m (mは６未満の自然数)で表される透明アモルファス酸化物である。また、本発明に係る非晶質酸化物はIn-Ga-Zn-Mg-Oを含み構成され、結晶状態の組成がInGaO3(Zn1-xMgxO)m(mは６未満の自然数、0<x≦1)で表される酸化物である。これらの酸化物に、さらにLi、Na、Mn、Ni、Pd、Cu、Cｄ、C、N、Pなどから選ばれる1種または複数種の元素を不純物として含ませる。これにより、電子キャリア濃度を減少させることができる。Specifically, the amorphous oxide according to the present invention includes In—Ga—Zn—O, and has a transparent composition represented by InGaO3 (ZnO)m (m is a natural number of less than 6) in the crystalline state. Amorphous oxide. The amorphous oxide according to the present invention includes In—Ga—Zn—Mg—O, and the composition of the crystalline state is InGaO3 (Zn1-x Mgx O)m (m is a natural number less than 6). , 0 <x ≦ 1). These oxides further contain one or more elements selected from Li, Na, Mn, Ni, Pd, Cu, Cd, C, N, P and the like as impurities. Thereby, the electron carrier concentration can be reduced.
また、電子キャリア濃度を大幅に減少させた場合でも、電子キャリア移動度の低減を抑制でき、電子キャリア濃度の制御が容易になる。従って、上記の透明アモルファス酸化物膜をチャネル層に使用すれば、大面積でも、特性の均一性が高いＴＦＴパネルが得易い。 In addition, even when the electron carrier concentration is significantly reduced, the reduction of the electron carrier mobility can be suppressed, and the control of the electron carrier concentration becomes easy. Therefore, if the transparent amorphous oxide film is used for the channel layer, it is easy to obtain a TFT panel having high uniformity of characteristics even in a large area.
また、Li、Na、Mn、Ni、Pd、Cu、Cｄ、C、N、Pを不純物（添加物）として使用する場合、これらの不純物は、In、Ga、Zn、Oの何れかのサイトを置換してアクセプターとして機能し電子キャリア密度を減少させる可能性がある。ただし、メカニズムの詳細は不明である。 In addition, when Li, Na, Mn, Ni, Pd, Cu, Cd, C, N, and P are used as impurities (additives), these impurities are in any one of In, Ga, Zn, and O sites. Substitution may function as an acceptor and reduce the electron carrier density. However, details of the mechanism are unknown.
通常の酸化物半導体では、酸素濃度を適切に制御できないために、多量の酸素欠陥が生じる。また、多結晶であるために粒界に生じる欠陥のため、不純物を導入しても電子キャリア密度が上手く制御できない事が多い。 In a normal oxide semiconductor, a large amount of oxygen defects are generated because the oxygen concentration cannot be appropriately controlled. In addition, since it is a polycrystal, defects generated at grain boundaries often prevent the electron carrier density from being well controlled even if impurities are introduced.
その点、本発明の透明アモルファス酸化物膜は、酸素欠陥が少なく、またアモルファスであり粒界が存在しないため、アクセプターの効果が明瞭に現れると思われる。 In that respect, the transparent amorphous oxide film of the present invention has few oxygen vacancies, is amorphous and does not have a grain boundary, and therefore, the acceptor effect appears clearly.
電子キャリア密度を低下させる目的で、酸素分圧を高めて薄膜を形成すると、原子の結合の骨格が変化して伝導帯のテイル準位が増加し、この準位に電子がトラップされ実効的な電子キャリア移動度を低下させる恐れがある。 When a thin film is formed by increasing the oxygen partial pressure for the purpose of reducing the electron carrier density, the skeleton of the atomic bond changes and the tail level of the conduction band increases, and electrons are trapped at this level and effective. There is a risk of reducing the electron carrier mobility.
しかし、Li、Na、Mn、Ni、Pd、Cu、Cｄ、C、N、Pを併用することで、酸素分圧を適正な範囲に保ちつつキャリア密度を制御できるので、電子キャリア移動度への影響を少なく出来ると思われる。 However, by using Li, Na, Mn, Ni, Pd, Cu, Cd, C, N, and P together, the carrier density can be controlled while maintaining the oxygen partial pressure in an appropriate range, so that the electron carrier mobility can be controlled. It seems that the influence can be reduced.
そのため酸素分圧の調整だけで電子キャリア濃度と電子キャリア移動度を制御する場合より、大面積の基板の場合でも酸化膜の特性の面内均一性を高め易くなる。 Therefore, it is easier to improve the in-plane uniformity of the characteristics of the oxide film even in the case of a large-area substrate than when the electron carrier concentration and the electron carrier mobility are controlled only by adjusting the oxygen partial pressure.
添加物としては、後述のTi、Zr、V、Ru、Ge、Sn、Fでもよい。 As additives, Ti, Zr, V, Ru, Ge, Sn, and F described later may be used.
なお、所望の効果を得るために必要となる不純物の濃度は、Si等の結晶に比べると高く、概ね０.１〜３atomic％程度である。 Note that the concentration of impurities necessary for obtaining a desired effect is higher than that of a crystal such as Si, and is about 0.1 to 3 atomic%.
これは膜がアモルファスなため不純物原子が価電子制御に効果的なサイトに入る確率が結晶に比べ低いためと思われる。 This is probably because the film is amorphous and the probability that impurity atoms enter the site effective for valence electron control is lower than that of crystals.
不純物を導入する方法としては、使用するターゲットに所望の不純物を含有させるのが最も一般的であるが、CやNやPの場合には、酸素とともにCH４やNOやPH３等のガスを雰囲気に含ませて膜に導入する事ができる。不純物が金属元素の場合は、透明アモルファス酸化物膜を形成後、当該金属のイオンを含む溶液やペーストに接触させて導入する事ができる。またガラス等耐熱性の高い基板を使用する場合には、これらの元素を基板に含ませ、膜の形成中、または形成後、基板を加熱して透明アモルファス酸化物膜に拡散させる事もできる。例えばソーダガラスは１０−２０atomic％のNaを含むので、Na源として用いる事ができる。The most common method for introducing impurities is to contain the desired impurities in the target to be used. In the case of C, N, or P, a gas such as CH4 , NO, or PH3 is used together with oxygen. It can be introduced into the film in an atmosphere. When the impurity is a metal element, the transparent amorphous oxide film can be formed and then brought into contact with a solution or paste containing metal ions. In the case of using a substrate having high heat resistance such as glass, these elements can be included in the substrate, and the substrate can be heated and diffused into the transparent amorphous oxide film during or after the formation of the film. For example, soda glass contains 10-20 atomic% Na and can be used as a Na source.
図５には典型的なＴＦＴの素子構造を示すが、ここで電子キャリア密度を減少させる事が効果的なのは、チャネル層２のうちドレイン電極５とソース電極６とに挟まれた部分である。それに対し、チャネル層２のうちうちドレイン電極５とソース電極６に接触する部分は、むしろ電子キャリア密度が高い方が電極との電気的コンタクトを良好に保てるので好都合である。即ちこの部分では不純物濃度が低い方が好ましい。この様な構成は、ドレイン電極５とソース電極６を形成後、ゲート絶縁膜３を形成する前に、チャネル層２を不純物を含む溶液に接触させ、ドレイン電極５とソース電極６をマスクとして不純物を拡散する方法によって実現できる。 FIG. 5 shows a typical TFT element structure, and it is effective to reduce the electron carrier density here in a portion of the channel layer 2 sandwiched between the drain electrode 5 and the source electrode 6. On the other hand, in the portion of the channel layer 2 that contacts the drain electrode 5 and the source electrode 6, the higher the electron carrier density, the better the electrical contact with the electrode, which is advantageous. That is, it is preferable that the impurity concentration is lower in this portion. In such a configuration, after the drain electrode 5 and the source electrode 6 are formed, before the gate insulating film 3 is formed, the channel layer 2 is brought into contact with a solution containing impurities, and the drain electrode 5 and the source electrode 6 are used as impurities as a mask. Can be realized by a method of diffusing.
また、図５のチャネル層２の中で、特に基板に接触する部分はゲート電極４による電子キャリア密度の制御が及び難いので、この部分の電子キャリア密度は予め低く抑えるとオンオフ比を高くするのに役立つ。そこで、前記不純物の濃度は、基板との界面で特に高めると効果的である。この様な構成は、チャネル層を形成する途中で、雰囲気に導入するCH4やNOやPH3等のガスの濃度を過剰なレベルからスタートし次第に低下させる方法や、あるいは基板に含まれるNaを適正な温度で拡散させる方法でも実現できる。Further, in the channel layer 2 of FIG. 5, it is difficult to control the electron carrier density by the gate electrode 4 particularly in the portion in contact with the substrate. Therefore, if the electron carrier density in this portion is kept low beforehand, the on / off ratio is increased. To help. Therefore, it is effective to increase the concentration of the impurities particularly at the interface with the substrate. In such a configuration, the channel layer is formed while the concentration of gases such as CH4 , NO, and PH3 introduced into the atmosphere is started from an excessive level and gradually decreased, or the Na contained in the substrate is reduced. It can also be realized by a method of diffusing at an appropriate temperature.
また、添加物として、非晶質酸化物に、Ti、Zr、V、Ru、Ge、Sn、Fから選ばれる1種または複数種を不純物として含ませることもできる。 As an additive, the amorphous oxide may contain one or more selected from Ti, Zr, V, Ru, Ge, Sn, and F as impurities.
これにより、電子キャリア濃度が１０１８／ｃｍ３未満で、同時に電子移動度を１ｃｍ２／（Ｖ・秒）以上に、さらに５ｃｍ２／（Ｖ・秒）以上に増加させ得る効果が期待される。Thereby, the electron carrier concentration is less than 1018 / cm3 , and at the same time, the effect of increasing the electron mobility to 1 cm2 / (V · second) or more and further to 5 cm2 / (V · second) or more is expected .
電界効果移動度が増加した場合でも、これに伴って電子キャリア濃度が増加する事が少ない。 Even when the field effect mobility is increased, the electron carrier concentration is rarely increased.
そのため上記の透明アモルファス酸化物膜をチャネル層に使用すれば、オン・オフ比が高く、ピンチオフ時の飽和電流が大きく、しかもスイッチ速度の速いＴＦＴを得る事ができる。 Therefore, if the transparent amorphous oxide film is used for the channel layer, a TFT having a high on / off ratio, a large saturation current at the time of pinch-off, and a high switching speed can be obtained.
また酸素分圧の調整だけで電子キャリア濃度と電子キャリア移動度を制御する場合より、電子キャリア密度への影響が少なく、大面積の基板を用いた場合でも、酸化膜特性の面内均一性を高め易い。 In addition, even if the electron carrier density and electron carrier mobility are controlled only by adjusting the oxygen partial pressure, the influence on the electron carrier density is less, and even in the case of using a large area substrate, the in-plane uniformity of the oxide film characteristics is improved. Easy to increase.
そのメカニズムの詳細は不明であるが、酸素分圧を高くして形成した酸化物は、伝導帯の下のテイル準位密度が高くなり、移動度が低下する可能性がある。 Although the details of the mechanism are unknown, an oxide formed with a high oxygen partial pressure has a high tail level density below the conduction band, which may reduce mobility.
Ti、Zr、V、Ru、Ge、Sn、Fを導入する事により、原子結合の骨格に作用し、テイル準位を減少させるため、電子キャリア密度を保ちつつ電子キャリア移動度が高められると推察される。 It is assumed that by introducing Ti, Zr, V, Ru, Ge, Sn, and F, the electron carrier mobility is increased while maintaining the electron carrier density because it acts on the skeleton of the atomic bond and reduces the tail level. Is done.
これらの一連の不純物は、０.１〜３atomic％程度、あるいは０.０１〜１atomic％、の範囲で使用するのが好適である。 These series of impurities are preferably used in the range of about 0.1 to 3 atomic%, or 0.01 to 1 atomic%.
Atomic％とは、酸化物中において含まれる各構成元素の原子数の割合である。なお、酸素量を計測し難い場合は、前述の範囲は、酸素を除いた、各構成元素の原子数の割合であるとすることもできる。 Atomic% is the ratio of the number of atoms of each constituent element contained in the oxide. In addition, when it is difficult to measure the amount of oxygen, the above-described range may be the ratio of the number of atoms of each constituent element excluding oxygen.
上記不純物の導入方法としては、所望の不純物を使用するターゲットに含有させるのが最も一般的であるが、Fの場合には、酸素とともにSF6、SiF4、ClF3等のガスを雰囲気に含ませて膜に導入する事ができる。不純物が金属元素の場合は、透明アモルファス酸化物膜を形成後、当該金属のイオンを含む溶液やペーストに接触させて導入する事ができる。As a method for introducing the impurity, it is most common to include a target in a target using a desired impurity. In the case of F, a gas such as SF6 , SiF4 , or ClF3 is contained in the atmosphere together with oxygen. It can be introduced into the membrane. When the impurity is a metal element, the transparent amorphous oxide film can be formed and then brought into contact with a solution or paste containing metal ions.
図５に示す典型的なＴＦＴの素子構造において、特に高い移動度が求められるのはゲート絶縁膜３に接触する部分である。そこで、本発明の不純物の濃度は、特にゲート絶縁膜３との界面で高めると効果的である。この様な構成は、チャネル層を形成する際に、雰囲気に導入するSF6、SiF4、ClF3等のガスを過少なレベルからスタートし、次第に増加させる方法で実現できる。In the typical TFT device structure shown in FIG. 5, a portion that is particularly in contact with the gate insulating film 3 is required to have high mobility. Therefore, it is effective to increase the impurity concentration of the present invention particularly at the interface with the gate insulating film 3. Such a configuration can be realized by a method of starting a gas such as SF6 , SiF4 , and ClF3 introduced into the atmosphere when the channel layer is formed from a low level and gradually increasing the gas.
なお本発明においては、前提として、酸素量（酸素欠損量）を制御して原子の結合を適切な構造に出来ていることが重要である。 In the present invention, as a premise, it is important to control the amount of oxygen (the amount of oxygen vacancies) so that atomic bonds have an appropriate structure.
上記記載においては、透明酸化物膜の酸素量の制御を、成膜時に酸素を所定濃度含む雰囲気中で行うことで制御しているが、成膜後、当該酸化物膜を酸素を含む雰囲気中で後処理して酸素欠損量を制御（低減あるいは増加）することも好ましいものである。 In the above description, the oxygen amount of the transparent oxide film is controlled by performing it in an atmosphere containing oxygen at a predetermined concentration during film formation. However, after the film formation, the oxide film is placed in an atmosphere containing oxygen. It is also preferable to control (reduce or increase) the amount of oxygen deficiency by post-treatment.
効果的に酸素欠損量を制御するには、酸素を含む雰囲気中の温度を０℃以上３００℃以下、好ましくは、２５℃以上、２５０℃以下、更に好ましくは１００℃以上２００℃以下で行うのがよい。 In order to effectively control the oxygen deficiency, the temperature in the atmosphere containing oxygen is 0 ° C. or higher and 300 ° C. or lower, preferably 25 ° C. or higher and 250 ° C. or lower, more preferably 100 ° C. or higher and 200 ° C. or lower. Is good.
勿論、成膜時にも酸素を含む雰囲気中で行い、且つ成膜後の後処理でも酸素を含む雰囲気中で後処理してもよい。また、所定の電子キャリア濃度（１０１８／ｃｍ３未満）を得られるのであれば、成膜時には、酸素分圧制御は行わないで、成膜後の後処理を酸素を含む雰囲気中で行ってもよい。Needless to say, the film formation may be performed in an atmosphere containing oxygen, and the post-treatment after the film formation may be performed in the atmosphere containing oxygen. If a predetermined electron carrier concentration (less than 1018 / cm3 ) can be obtained, oxygen partial pressure control is not performed during film formation, and post-treatment after film formation is performed in an atmosphere containing oxygen. Also good.
なお、本発明における電子キャリア濃度の下限としては、得られる酸化物膜をどのような素子や回路あるいは装置に用いるかにもよるが、例えば１０１４／ｃｍ３以上である。Note that the lower limit of the electron carrier concentration in the present invention is, for example, 1014 / cm3 or more, although it depends on what kind of element, circuit or device the oxide film obtained is used for.
以下は、前述の第１から第３の実施形態に適用できる非晶質酸化物について詳述する。以下に示す非晶質酸化物、あるいはその製造方法に、第１の実施形態に係る発明では、製造条件として例えば光照射という条件を付加する。第２の実施形態では、膜組成が変化するよう、実施例に記載したような工夫をする。第３の実施形態に係る発明では、下記に示す製造条件に更に、不純物添加用のガスやターゲット材を用いたり、下記で示される非晶質酸化物に事後的に不純物を所定の方法で添加することになる。
（非晶質酸化物）
本発明に係る非晶質酸化物の電子キャリア濃度は、室温で測定する場合の値である。室温とは、例えば２５℃であり、具体的には０℃から４０℃程度の範囲から適宜選択されるある温度である。なお、本発明に係るアモルファス酸化物の電子キャリア濃度は、０℃から４０℃の範囲全てにおいて、１０１８／ｃｍ３未満を充足する必要はない。例えば、２５℃において、キャリア電子密度１０１８／ｃｍ３未満が実現されていればよい。また、電子キャリア濃度を更に下げ、１０１７／ｃｍ３以下、より好ましくは１０１６／ｃｍ３以下にするとノーマリオフのＴＦＴが歩留まり良く得られる。Hereinafter, the amorphous oxide applicable to the first to third embodiments will be described in detail. In the invention according to the first embodiment, a condition of light irradiation, for example, is added to the amorphous oxide shown below or the manufacturing method thereof. In the second embodiment, the device as described in the examples is devised so that the film composition changes. In the invention according to the third embodiment, in addition to the manufacturing conditions shown below, an impurity addition gas or target material is used, or impurities are added to the amorphous oxide shown below by a predetermined method. Will do.
(Amorphous oxide)
The electron carrier concentration of the amorphous oxide according to the present invention is a value when measured at room temperature. The room temperature is, for example, 25 ° C., specifically, a certain temperature appropriately selected from the range of about 0 ° C. to 40 ° C. Note that the electron carrier concentration of the amorphous oxide according to the present invention does not need to satisfy less than 1018 / cm3 in the entire range of 0 ° C. to 40 ° C. For example, a carrier electron density of less than 1018 / cm3 may be realized at 25 ° C. Further, when the electron carrier concentration is further reduced to 1017 / cm3 or less, more preferably 1016 / cm3 or less, a normally-off TFT can be obtained with a high yield.
なお、１０１８／ｃｍ３未満とは、好ましくは１×１０１８／ｃｍ３未満であり、より好適には、１．０×１０１８／ｃｍ３未満である。The term “less than 1018 / cm3” is preferably less than 1 × 1018 / cm3 , and more preferably less than 1.0 × 1018 / cm3 .
電子キャリア濃度の測定は、ホール効果測定により求めることが出来る。 The electron carrier concentration can be measured by Hall effect measurement.
なお、本発明において、アモルファス酸化物とは、Ｘ線回折スペクトルにおいて、ハローパターンが観測され、特定の回折線を示さない酸化物をいう。 In the present invention, an amorphous oxide refers to an oxide that exhibits a halo pattern in an X-ray diffraction spectrum and does not exhibit a specific diffraction line.
本発明のアモルファス酸化物における、電子キャリア濃度の下限値は、ＴＦＴのチャネル層として適用できれば特に限定されるものではない。下限値は、例えば、１０１２／ｃｍ３である。The lower limit of the electron carrier concentration in the amorphous oxide of the present invention is not particularly limited as long as it can be applied as a TFT channel layer. The lower limit is, for example, 1012 / cm3 .
従って、本発明においては、後述する各実施例のようにアモルファス酸化物の材料、組成比、製造条件などを制御して、例えば、電子キャリア濃度を、１０１２／ｃｍ３以上１０１８／ｃｍ３未満とする。より好ましくは１０１３／ｃｍ３以上１０１７／ｃｍ３以下、更には１０１５／ｃｍ３以上１０１６／ｃｍ３以下の範囲にすることが好ましいものである。Therefore, in the present invention, the material, composition ratio, production conditions, etc. of the amorphous oxide are controlled as in the examples described later, for example, the electron carrier concentration is 1012 / cm3 or more and 1018 / cm3. Less than. More preferably, it is in the range of 1013 / cm3 or more and 1017 / cm3 or less, and more preferably 1015 / cm3 or more and 1016 / cm3 or less.
前記非晶質酸化物としては、ＩｎＺｎＧａ酸化物のほかにも、Ｉｎ酸化物、ＩｎｘＺｎ１−ｘ酸化物（0.2≦ｘ≦1）、ＩｎｘＳｎ１−ｘ酸化物（0.8≦ｘ≦1）、あるいはＩｎｘ（Ｚｎ、Ｓｎ）１−ｘ酸化物（0.15≦ｘ≦1）から適宜選択できる。As the amorphous oxide, in addition to InZnGa oxide, In oxide, Inx Zn1-x oxide (0.2 ≦ x ≦ 1), Inx Sn1-x oxide (0.8 ≦ x ≦ 1) or Inx (Zn, Sn)1-x oxide (0.15 ≦ x ≦ 1).
なお、Ｉｎｘ（Ｚｎ、Ｓｎ）１−ｘ酸化物は、Ｉｎｘ（ＺｎｙＳｎ１−ｙ）１−ｘ酸化物と記載することができ、ｙの範囲は１から０である。Note that an Inx (Zn, Sn)1-x oxide can be described as an Inx (Zny Sn1-y )1-x oxide, and the range of y is 1 to 0.
なお、ＺｎとＳｎを含まないＩｎ酸化物の場合は、Ｉｎの一部をＧａに置換することもできる。即ち、ＩｎｘＧａ１−ｘ酸化物（０≦ｘ≦1）の場合である。Note that in the case of an In oxide containing no Zn and Sn, part of In can be substituted with Ga. That is, it is the case of Inx Ga1-x oxide (0 ≦ x ≦ 1).
以下に、本発明者らが作製することに成功した電子キャリア濃度が１０１８／ｃｍ３未満の非晶質酸化物について詳述する。Hereinafter, an amorphous oxide having an electron carrier concentration of less than 1018 / cm3 successfully produced by the present inventors will be described in detail.
上記酸化物とは、In-Ga-Zn-Oを含み構成され、結晶状態における組成がInGaO3(ZnO)m (mは６未満の自然数)で表され、電子キャリア濃度が１０１８／ｃｍ３未満であることを特徴とする。The oxide includes In—Ga—Zn—O, the composition in the crystalline state is represented by InGaO3 (ZnO)m (m is a natural number less than 6), and the electron carrier concentration is 1018 / cm3. It is characterized by being less than.
また上記酸化物は、In-Ga-Zn-Ｍｇ-Oを含み構成され、結晶状態の組成がInGaO3(Zn1-xMｇxO)m(mは６未満の自然数、0<x≦1)で表され、電子キャリア濃度が１０１８／ｃｍ３未満であることを特徴とする。The oxide includes In—Ga—Zn—Mg—O, and the composition of the crystalline state is InGaO3 (Zn1−x Mg× O)m (m is a natural number less than 6, 0 <x ≦ 1 The electron carrier concentration is less than 1018 / cm3 .
なお、これらの酸化物で構成される膜において、電子移動度が１ｃｍ２／（Ｖ・秒）超になるように設計することも好ましい。Note that it is also preferable to design a film formed using these oxides so that the electron mobility exceeds 1 cm2 / (V · sec).
上記膜をチャネル層に用いれば、トランジスターオフ時のゲート電流が０．１マイクロアンペヤ未満のノーマリーオフで、オン・オフ比が１０３超のトランジスタ特性を実現できる。そして、可視光に対して、透明あるいは透光性を有し、フレキシブルなＴＦＴが実現される。When the above film is used for a channel layer, transistor characteristics with a normally-off gate current of less than 0.1 microampere and an on / off ratio of more than 103 can be realized. In addition, a flexible TFT having transparency or translucency with respect to visible light is realized.
なお、上記膜は、伝導電子数の増加と共に、電子移動度が大きくなることを特徴とする。透明膜を形成する基板としては、ガラス基板、樹脂製プラスチック基板又はプラスチックフィルムなどを用いることができる。 The film is characterized in that the electron mobility increases as the number of conduction electrons increases. As the substrate on which the transparent film is formed, a glass substrate, a resin plastic substrate, a plastic film, or the like can be used.
上記非晶質酸化物膜をチャネル層に利用する際には、Ａｌ２Ｏ３、Ｙ２Ｏ３、又はＨｆＯ２の1種、又はそれらの化合物を少なくとも二種以上含む混晶化合物をゲート絶縁膜に利用できる。When the amorphous oxide film is used as a channel layer, a gate insulating layer of a mixed crystal compound containing at least one of Al2 O3 , Y2 O3 , or HfO2 or a compound thereof is used. Available for membranes.
また、非晶質酸化物中に、電気抵抗を高めるための不純物イオンを意図的に添加せず、酸素ガスを含む雰囲気中で、成膜することも好ましい形態である。 In addition, it is also preferable to form a film in an atmosphere containing oxygen gas without intentionally adding impurity ions for increasing electric resistance to the amorphous oxide.
本発明者らは、この半絶縁性酸化物アモルファス薄膜は、伝導電子数の増加と共に、電子移動度が大きくなるという特異な特性を見出した。そして、その膜を用いてＴＦＴを作成し、オン・オフ比、ピンチオフ状態での飽和電流、スイッチ速度などのトランジスタ特性が更に向上することを見出した。即ち、非晶質酸化物を利用して、ノーマリーオフ型のTFTを実現できることを見出した。 The present inventors have found that the semi-insulating oxide amorphous thin film has a unique characteristic that the electron mobility increases as the number of conduction electrons increases. Then, a TFT was formed using the film, and it was found that transistor characteristics such as an on / off ratio, a saturation current in a pinch-off state, and a switch speed were further improved. That is, it has been found that a normally-off type TFT can be realized by using an amorphous oxide.
非晶質酸化物薄膜を膜トランジスタのチャネル層として用いると、電子移動度が１ｃｍ２／（Ｖ・秒）超、好ましくは５ｃｍ２／（Ｖ・秒）超にすることができる。When an amorphous oxide thin film is used as the channel layer of the film transistor, the electron mobility can exceed 1 cm2 / (V · sec), preferably 5 cm2 / (V · sec).
電子キャリア濃度が、１０１８／ｃｍ３未満、好ましくは、１０１６／ｃｍ３未満のときは、オフ時（ゲート電圧無印加時）のドレイン・ソース端子間の電流を、１０マイクロアンペヤ未満、好ましくは０．１マイクロアンペア未満にすることができる。When the electron carrier concentration is less than 1018 / cm3 , preferably less than 1016 / cm3 , the current between the drain and source terminals when off (when no gate voltage is applied) is less than 10 microamperes, Preferably it can be less than 0.1 microamperes.
また、該膜を用いれば、電子移動度が１ｃｍ２／（Ｖ・秒）超、好ましくは５ｃｍ２／（Ｖ・秒）超の時は、ピンチオフ後の飽和電流を１０マイクロアンペア超にでき、オン・オフ比を１０３超とすることができる。When the film is used, when the electron mobility is more than 1 cm2 / (V · sec), preferably more than 5 cm2 / (V · sec), the saturation current after pinch-off can be more than 10 microamperes, The on / off ratio can be greater than 103 .
ＴＦＴでは、ピンチオフ状態では、ゲート端子に高電圧が印加され、チャネル中には高密度の電子が存在している。 In the TFT, in a pinch-off state, a high voltage is applied to the gate terminal, and high-density electrons exist in the channel.
したがって、本発明によれば、電子移動度が増加した分だけ、より飽和電流値を大きくすることができる。この結果、オン・オフ比の増大、飽和電流の増大、スイッチング速度の増大など、トランジスタ特性の向上が期待できる。 Therefore, according to the present invention, the saturation current value can be further increased by the amount of increase in electron mobility. As a result, improvements in transistor characteristics such as an increase in on / off ratio, an increase in saturation current, and an increase in switching speed can be expected.
なお、通常の化合物中では、電子数が増大すると、電子間の衝突により、電子移動度は減少する。 In a normal compound, when the number of electrons increases, electron mobility decreases due to collisions between electrons.
なお、上記ＴＦＴの構造としては、半導体チャネル層の上にゲート絶縁膜とゲート端子を順に形成するスタガ（トップゲート）構造や、ゲート端子の上にゲート絶縁膜と半導体チャネル層を順に形成する逆スタガ（ボトムゲート）構造を用いることができる。 The TFT structure includes a stagger (top gate) structure in which a gate insulating film and a gate terminal are sequentially formed on a semiconductor channel layer, or a reverse structure in which a gate insulating film and a semiconductor channel layer are sequentially formed on a gate terminal. A staggered (bottom gate) structure can be used.
（第1の成膜法：PLD法）
結晶状態における組成がInGaO3(ZnO)m(mは６未満の自然数)で表される非晶質酸化物薄膜は、ｍの値が６未満の場合は、８００℃以上の高温まで、非晶質状態が安定に保たれるが、ｍの値が大きくなるにつれ、結晶化しやすくなる。すなわち、InGaO3に対するZnOの比が増大して、ＺｎＯ組成に近づくにつれ、結晶化しやすくなる。(First film formation method: PLD method)
An amorphous oxide thin film whose composition in the crystalline state is represented by InGaO3 (ZnO)m (m is a natural number less than 6) is amorphous up to a high temperature of 800 ° C. or higher when the value of m is less than 6. Although the quality state is kept stable, it becomes easier to crystallize as the value of m increases. That is, as the ratio of ZnO to InGaO3 increases and approaches the ZnO composition, it becomes easier to crystallize.
したがって、非晶質ＴＦＴのチャネル層としては、ｍの値が６未満であることが好ましい。 Therefore, the value of m is preferably less than 6 for the channel layer of the amorphous TFT.
成膜方法は、InGaO3(ZnO)m組成を有する多結晶焼結体をターゲットとして、気相成膜法を用いるのが良い。気相成膜法の中でも、スパッタ法、パルスレーザー蒸着法が適している。さらに、量産性の観点から、スパッタ法が最も適している。As a film forming method, a vapor phase film forming method is preferably used with a polycrystalline sintered body having an InGaO3 (ZnO)m composition as a target. Of the vapor deposition methods, sputtering and pulsed laser deposition are suitable. Furthermore, the sputtering method is most suitable from the viewpoint of mass productivity.
しかしながら、通常の条件で該非晶質膜を作成すると、主として酸素欠損が生じ、これまで、電子キャリア濃度を１０１８／ｃｍ３未満、電気伝導度にして、１０Ｓ／ｃｍ以下にすることができなかった。そうした膜を用いた場合、ノーマリーオフのトランジスタを構成することができない。However, when the amorphous film is formed under normal conditions, oxygen vacancies mainly occur, and until now, the electron carrier concentration has been less than 1018 / cm3 and the electric conductivity has not been reduced to 10 S / cm or less. It was. When such a film is used, a normally-off transistor cannot be formed.
本発明者らは、図７で示される装置により、パルスレーザー蒸着法で作製したIn-Ga-Zn-Oを作製した。 The present inventors produced In—Ga—Zn—O produced by a pulse laser deposition method using the apparatus shown in FIG.
図７に示すようなＰＬＤ成膜装置を用いて、成膜を行った。 Film formation was performed using a PLD film formation apparatus as shown in FIG.
同図において、７０１はＲＰ（ロータリーポンプ）、７０２はＴＭＰ（ターボ分子ポンプ）、７０３は準備室、７０４はＲＨＥＥＤ用電子銃、７０５は基板を回転、上下移動するための基板保持手段、７０６はレーザー入射窓である。また、７０７は基板、７０８はターゲット、７０９はラジカル源、７１０はガス導入口、７１１はターゲットを回転、上下移動するためのターゲット保持手段である。また、７１２はバイパスライン、７１３はメインライン、７１４はＴＭＰ（ターボ分子ポンプ）、７１５はＲＰ（ロータリーポンプ）、７１６はチタンゲッターポンプ、７１７はシャッターである。また、図中７１８はＩＧ（イオン真空計）、７１９はＰＧ（ピラニ真空計）、７２０はＢＧ（バラトロン真空計）、７２１は成長室（チャンバー）である。 In the figure, 701 is RP (rotary pump), 702 is TMP (turbo molecular pump), 703 is a preparation chamber, 704 is an electron gun for RHEED, 705 is a substrate holding means for rotating and moving the substrate up and down, and 706 is This is a laser incident window. 707 is a substrate, 708 is a target, 709 is a radical source, 710 is a gas inlet, and 711 is a target holding means for rotating and moving the target up and down. Reference numeral 712 denotes a bypass line, 713 denotes a main line, 714 denotes a TMP (turbo molecular pump), 715 denotes an RP (rotary pump), 716 denotes a titanium getter pump, and 717 denotes a shutter. In the figure, 718 is an IG (ion vacuum gauge), 719 is a PG (Pirani vacuum gauge), 720 is a BG (Baratron vacuum gauge), and 721 is a growth chamber (chamber).
KrFエキシマレーザーを用いたパルスレーザー蒸着法により、SiO2ガラス基板（コーニング社製1737）上にIn-Ga-Zn-O系アモルファス酸化物半導体薄膜を堆積させた。堆積前の処理として、基板の超音波による脱脂洗浄を、アセトン, エタノール, 超純水を用いて、各5分間行った後、空気中100℃で乾燥させた。An In-Ga-Zn-O amorphous oxide semiconductor thin film was deposited on a SiO2 glass substrate (Corning 1737) by pulsed laser deposition using a KrF excimer laser. As a pre-deposition treatment, the substrate was degreased and cleaned with ultrasonic waves for 5 minutes each using acetone, ethanol, and ultrapure water, and then dried at 100 ° C. in air.
前記多結晶ターゲットには、InGaO3(ZnO)４焼結体ターゲット（サイズ 20mmΦ5mmt）を用いた。これは、出発原料として、In2O3：Ga2O3：ZnO（各4N試薬）を湿式混合した後(溶媒：エタノール)、仮焼（1000 ℃： 2h）、乾式粉砕、本焼結（1550 ℃： 2h）を経て得られるものである。こうして作製したターゲットの電気伝導度は、90 (S/cm)であった。As the polycrystalline target, an InGaO3 (ZnO)4 sintered body target (size 20 mmΦ5 mmt) was used. This is because, as a starting material, In2 O3 : Ga2 O3 : ZnO (each 4N reagent) is wet-mixed (solvent: ethanol), calcined (1000 ° C .: 2 h), dry pulverized, main sintered ( 1550 ° C: 2 hours). The electric conductivity of the target thus prepared was 90 (S / cm).
成長室の到達真空を2×10-6 (Pa)にして、成長中の酸素分圧を6.5 (Pa)に制御して成膜を行った。The film was formed while the ultimate vacuum in the growth chamber was 2 × 10−6 (Pa) and the oxygen partial pressure during growth was controlled to 6.5 (Pa).
チャンバー７２１内酸素分圧は６．５Pa、基板温度は25℃である。 The partial pressure of oxygen in the chamber 721 is 6.5 Pa, and the substrate temperature is 25 ° C.
なお、ターゲット７０８と被成膜基板７０７間の距離は、30 (mm)であり、入射窓７１６から入射されるＫｒＦエキシマレーザーのパワーは、１.5-3 (mJ/cm２/pulse)の範囲である。また、パルス幅は、20 (nsec)、繰り返し周波数は10 (Hz)、そして照射スポット径は、1 × 1 (mm角)とした。The distance between the target 708 and the film formation substrate 707 is 30 (mm), and the power of the KrF excimer laser incident from the incident window 716 is 1.5-3 (mJ / cm2 / pulse). It is a range. The pulse width was 20 (nsec), the repetition frequency was 10 (Hz), and the irradiation spot diameter was 1 × 1 (mm square).
こうして、成膜レート7 (nm/min)で成膜を行った。 Thus, film formation was performed at a film formation rate of 7 (nm / min).
得られた薄膜について、薄膜のすれすれ入射Ｘ線回折（薄膜法、入射角 0.5度）を行ったところ、明瞭な回折ピークは認めらなかったことから、作製したIn-Ga-Zn-O系薄膜はアモルファスであるといえる。 The thin film obtained was subjected to grazing incidence X-ray diffraction (thin film method, incident angle 0.5 degree) of the thin film, and no clear diffraction peak was observed. Thus, the produced In-Ga-Zn-O thin film Can be said to be amorphous.
さらに、Ｘ線反射率測定を行い、パターンの解析を行った結果、薄膜の平均二乗粗さ（Rrms）は約0.5 nmであり、膜厚は約120 nmであることが分かった。蛍光Ｘ線（XRF）分析の結果、薄膜の金属組成比はIn : Ga : Zn = 0.98 : 1.02 : 4であった。 Furthermore, as a result of measuring the X-ray reflectivity and analyzing the pattern, it was found that the mean square roughness (Rrms) of the thin film was about 0.5 nm and the film thickness was about 120 nm. As a result of X-ray fluorescence (XRF) analysis, the metal composition ratio of the thin film was In: Ga: Zn = 0.98: 1.02: 4.
電気伝導度は、約10-２ S/cm未満であった。電子キャリア濃度は約101６/cm3以下、電子移動度は約５cm2／（Ｖ・秒）と推定される。The electrical conductivity was less than about10-2 S / cm. The electron carrier concentration is estimated to be about 1016 / cm3 or less, and the electron mobility is estimated to be about 5 cm2 / (V · sec).
光吸収スペクトルの解析から、作製したアモルファス薄膜の禁制帯エネルギー幅は、約3 eVと求まった。以上のことから、作製したIn-Ga-Zn-O系薄膜は、結晶のInGaO3(ZnO)４の組成に近いアモルファス相を呈しており、酸素欠損が少なく、電気伝導度が小さな透明な平坦薄膜であることが分かった。From the analysis of the light absorption spectrum, the energy band gap of the fabricated amorphous thin film was found to be about 3 eV. From the above, the fabricated In-Ga-Zn-O-based thin film exhibits an amorphous phase close to the composition of crystalline InGaO3 (ZnO)4 , has a small oxygen deficiency, and has a low electrical conductivity and is a transparent flat surface. It turned out to be a thin film.
具体的に図１を用いて説明する。同図は、In-Ga-Zn-Oから構成され、結晶状態を仮定した時の組成がInGaO3(ZnO)m(mは６未満の数)で表される透明アモルファス酸化物薄膜を本実施例と同じ条件下で作成する場合の特性図である。この特性図は、酸素分圧を変化させた場合に、成膜された酸化物の電子キャリア濃度の変化を示したものである。This will be specifically described with reference to FIG. This figure shows a transparent amorphous oxide thin film composed of In-Ga-Zn-O and having a composition expressed by InGaO3 (ZnO)m (m is a number less than 6) assuming a crystalline state. It is a characteristic view in the case of creating under the same conditions as the example. This characteristic diagram shows the change in the electron carrier concentration of the deposited oxide when the oxygen partial pressure is changed.
本実施例と同じ条件下で酸素分圧を４．５Ｐａ超の高い雰囲気中で、成膜することにより、図１に示すように、電子キャリア濃度を１０１８／ｃｍ３未満に低下させることができた。この場合、基板の温度は意図的に加温しない状態で、ほぼ室温に維持されている。フレキシブルなプラスチックフィルムを基板として使用するには、基板温度は100℃未満に保つことが好ましい。By forming a film in an atmosphere where the oxygen partial pressure is higher than 4.5 Pa under the same conditions as in this example, the electron carrier concentration can be reduced to less than 1018 / cm3 as shown in FIG. did it. In this case, the temperature of the substrate is maintained at substantially room temperature without intentionally heating. In order to use a flexible plastic film as a substrate, the substrate temperature is preferably kept below 100 ° C.
酸素分圧をさらに大きくすると、電子キャリア濃度をさらに低下させることができる。例えば、図１に示す様に、基板温度２５℃、酸素分圧５Ｐａで成膜したInGaO3(ZnO)４薄膜では、さらに、電子キャリア数を１０１６／ｃｍ３に低下させることができた。If the oxygen partial pressure is further increased, the electron carrier concentration can be further reduced. For example, as shown in FIG. 1, in the InGaO3 (ZnO)4 thin film formed at a substrate temperature of 25 ° C. and an oxygen partial pressure of 5 Pa, the number of electron carriers could be further reduced to 1016 / cm3 .
得られた薄膜は、図２に示す様に、電子移動度が１ｃｍ２／（Ｖ・秒）超であった。しかし、本実施例のパルスレーザー蒸着法では、酸素分圧を６．５Ｐａ以上にすると、堆積した膜の表面が凸凹となり、ＴＦＴのチャネル層として用いることが困難となる。The obtained thin film had an electron mobility of more than 1 cm2 / (V · sec) as shown in FIG. However, in the pulse laser vapor deposition method of the present embodiment, when the oxygen partial pressure is set to 6.5 Pa or more, the surface of the deposited film becomes uneven, making it difficult to use it as a TFT channel layer.
従って、酸素分圧４．５Ｐａ超、望ましくは5Ｐａ超、６．５Ｐａ未満の雰囲気で、パルスレーザー蒸着法で、結晶状態における組成InGaO3(ZnO)m(mは６未満の数)で表される透明アモルファス酸化物薄膜を作製する。この透明アモルファス酸化物薄膜を用いれば、ノーマリーオフのトランジスタを構成することができる。Therefore, it is expressed by the composition InGaO3 (ZnO)m (m is a number of less than 6) in a crystalline state by pulse laser deposition in an atmosphere having an oxygen partial pressure of more than 4.5 Pa, desirably more than 5 Pa and less than 6.5 Pa. A transparent amorphous oxide thin film is prepared. If this transparent amorphous oxide thin film is used, a normally-off transistor can be formed.
また、該薄膜の電子移動度は、１ｃｍ２／Ｖ・秒超が得られ、オン・オフ比を１０３超に大きくすることができた。Further, the electron mobility of the thin film was obtained to exceed 1 cm2 / V · second, and the on / off ratio could be increased to more than 103 .
以上、説明したように、本実施例に示した条件下でＰＬＤ法によりＩｎＧａＺｎ酸化物の成膜を行う場合は、酸素分圧を４．５Ｐａ以上６．５Ｐａ未満になるように制御することが望ましい。 As described above, when an InGaZn oxide film is formed by the PLD method under the conditions shown in this embodiment, the oxygen partial pressure can be controlled to be 4.5 Pa or more and less than 6.5 Pa. desirable.
なお、電子キャリア濃度を１０１８／ｃｍ３未満を実現するためには、酸素分圧の条件、成膜装置の構成や、成膜する材料や組成などに依存する。Note that, in order to realize the electron carrier concentration of less than 1018 / cm3 , the electron carrier concentration depends on the oxygen partial pressure conditions, the configuration of the film formation apparatus, the material and composition of the film formation, and the like.
次に、上記装置における酸素分圧６．５Ｐａの条件で、アモルファス酸化物を作製し、図５に示すトップゲート型MISFET素子を作製した。具体的には、まず、ガラス基板（１）上に上記のアモルファスIn-Ga-Zn-O薄膜の作製法により、チャンネル層（２）として用いる厚さ120nmの半絶縁性アモルファスInGaO3(ZnO)４膜を形成した。Next, an amorphous oxide was produced under the condition of an oxygen partial pressure of 6.5 Pa in the above apparatus, and a top gate type MISFET element shown in FIG. 5 was produced. Specifically, first, a semi-insulating amorphous InGaO3 (ZnO) having a thickness of 120 nm used as a channel layer (2) is formed on the glass substrate (1) by the above-described method for producing an amorphous In—Ga—Zn—O thin film.Four films were formed.
さらにその上に、チャンバー内酸素分圧を1Pa未満にして、パルスレーザー堆積法により電気伝導度の大きなInGaO3(ZnO)４及び金膜をそれぞれ30nm積層した。そして、フォトリソグラフィー法とリフトオフ法により、ドレイン端子（５）及びソース端子（６）を形成した。最後にゲート絶縁膜（３）として用いるY2O3膜を電子ビーム蒸着法により成膜し（厚み：90nm、比誘電率：約15、リーク電流密度：0.5 MV/cm印加時に10-3 A/cm2）、その上に金を成膜した。そして、フォトリソグラフィー法とリフトオフ法により、ゲート端子（４）を形成した。Further, an InGaO3 (ZnO)4 film and a gold film having a large electric conductivity were stacked in a thickness of 30 nm by a pulse laser deposition method with an oxygen partial pressure in the chamber of less than 1 Pa. And the drain terminal (5) and the source terminal (6) were formed by the photolithographic method and the lift-off method. Finally, a Y2 O3 film used as the gate insulating film (3) is formed by electron beam evaporation (thickness: 90 nm, relative dielectric constant: about 15, leakage current density: 10-3 A when 0.5 MV / cm is applied) / cm2 ), and a gold film was formed thereon. And the gate terminal (4) was formed by the photolithographic method and the lift-off method.
MISFET素子の特性評価
図６に、室温下で測定したMISFET素子の電流−電圧特性を示す。ドレイン電圧VDSの増加に伴い、ドレイン電流IDSが増加したことからチャネルがn型半導体であることが分かる。これは、アモルファスIn-Ga-Zn-O系半導体がn型であるという事実と矛盾しない。IDSはVDS= 6 V程度で飽和（ピンチオフ）する典型的な半導体トランジスタの挙動を示した。利得特性を調べたところ、VDS = 4 V印加時におけるゲート電圧VGSの閾値は約-0.5 Vであった。また、VG=10 V時には、IDS=1.0 × 10-5Aの電流が流れた。これはゲートバイアスにより絶縁体のIn-Ga-Zn-O系アモルファス半導体薄膜内にキャリアを誘起できたことに対応する。FIG. 6 shows the current-voltage characteristics of the MISFET element measured at room temperature. As the drain voltage VDS increases, the drain current IDS increases, which indicates that the channel is an n-type semiconductor. This is consistent with the fact that amorphous In-Ga-Zn-O based semiconductors are n-type. IDS shows the behavior of a typical semiconductor transistor that saturates (pinch off) at about VDS = 6 V. When the gain characteristic was examined, the threshold value of the gate voltage VGS when VDS = 4 V was applied was about −0.5 V. When VG = 10 V, a current of IDS = 1.0 × 10−5 A flowed. This corresponds to the fact that carriers can be induced in the In-Ga-Zn-O amorphous semiconductor thin film of the insulator by the gate bias.
トランジスタのオン・オフ比は、１０３超であった。また、出力特性から電界効果移動度を算出したところ、飽和領域において約7cm2(Vs)-1の電界効果移動度が得られた。作製した素子に可視光を照射して同様の測定を行なったが、トランジスタ特性の変化は認められなかった。The on / off ratio of the transistor was more than 103 . When the field effect mobility was calculated from the output characteristics, a field effect mobility of about 7 cm2 (Vs)−1 was obtained in the saturation region. A similar measurement was performed by irradiating the fabricated device with visible light, but no change in transistor characteristics was observed.
本実施例によれば、電子キャリア濃度が小さく、したがって、電気抵抗が高く、かつ電子移動度が大きいチャネル層を有する薄膜トランジスタを実現できる。 According to this embodiment, it is possible to realize a thin film transistor having a channel layer having a low electron carrier concentration, a high electrical resistance, and a high electron mobility.
なお、上記したアモルファス酸化物は、電子キャリア濃度の増加と共に、電子移動度が増加し、さらに縮退伝導を示すという優れた特性を備えていた。 The above-described amorphous oxide had excellent characteristics that the electron mobility increased with an increase in the electron carrier concentration and further exhibited degenerate conduction.
本実施例では、ガラス基板上に薄膜トランジスタを作製したが、成膜自体が室温で行えるので、プラスチック板やフィルムなどの基板が使用可能である。 In this embodiment, a thin film transistor is formed on a glass substrate. However, since the film formation itself can be performed at room temperature, a substrate such as a plastic plate or a film can be used.
また、本実施例で得られたアモルファス酸化物は、可視光の光吸収が殆どなく、透明なフレキシブルＴＦＴを実現できる。
（第２の成膜法：スパッタ法（SP法））
雰囲気ガスとしてアルゴンガスを用いた高周波ＳＰ法により、成膜する場合について説明する。Further, the amorphous oxide obtained in this example hardly absorbs visible light and can realize a transparent flexible TFT.
(Second film formation method: sputtering method (SP method))
A case where a film is formed by a high-frequency SP method using argon gas as an atmosphere gas will be described.
ＳＰ法は、図８に示す装置を用いて行った。同図において、８０７は被成膜基板、８０８はターゲット、８０５は冷却機構付き基板保持手段、８１４は、ターボ分子ポンプ、８１５はロータリーポンプ、８１７はシャッターである。また、８１８はイオン真空計、８１９はピラニ真空計、８２１は成長室（チャンバー）、８３０はゲートバルブである。 The SP method was performed using the apparatus shown in FIG. In the figure, reference numeral 807 denotes a film formation substrate, 808 denotes a target, 805 denotes a substrate holding means with a cooling mechanism, 814 denotes a turbo molecular pump, 815 denotes a rotary pump, and 817 denotes a shutter. Reference numeral 818 denotes an ion vacuum gauge, 819 denotes a Pirani vacuum gauge, 821 denotes a growth chamber (chamber), and 830 denotes a gate valve.
被成膜基板８０７としては、SiO2ガラス基板（コーニング社製1737）を用意した。成膜前処理として、この基板の超音波脱脂洗浄を、アセトン、エタノール、超純水により各5分ずつ行った後、空気中１００℃で乾燥させた。As the film formation substrate 807, a SiO2 glass substrate (1737 manufactured by Corning) was prepared. As pre-deposition treatment, the substrate was subjected to ultrasonic degreasing and cleaning with acetone, ethanol, and ultrapure water for 5 minutes each and then dried at 100 ° C. in air.
ターゲット材料としては、ＩｎＧａＯ３（ＺｎＯ）４組成を有する多結晶焼結体（サイズ 20mmΦ5mmt）を用いた。As a target material, a polycrystalline sintered body (size 20 mmΦ5 mmt) having an InGaO3 (ZnO)4 composition was used.
この焼結体は、出発原料として、In2O3：Ga2O3：ZnO（各4N試薬）を湿式混合(溶媒：エタノール)し、仮焼（1000 ℃： 2h）、乾式粉砕、本焼結（1550 ℃： 2h）を経て作製した。このターゲット８０８の電気伝導度は90 (S/cm)であり、半絶縁体状態であった。In this sintered body, as a starting material, In2 O3 : Ga2 O3 : ZnO (each 4N reagent) is wet-mixed (solvent: ethanol), calcined (1000 ° C .: 2 h), dry pulverized, main-fired It was produced after crystallization (1550 ° C: 2h). The electric conductivity of the target 808 was 90 (S / cm) and was in a semi-insulating state.
成長室８２１内の到達真空は、１×10-４(Ｐａ)であり、成長中の酸素ガスとアルゴンガスの全圧は、４〜０．１×１０−１（Pa）の範囲での一定の値とした。そして、アルゴンガスと酸素との分圧比を変えて、酸素分圧を１０−３〜２×１０−１（Pa）の範囲で変化させた。The ultimate vacuum in the growth chamber 821 is 1 × 10−4 (Pa), and the total pressure of oxygen gas and argon gas during growth is constant in the range of 4 to 0.1 × 10−1 (Pa). The value of And the partial pressure ratio of argon gas and oxygen was changed, and the oxygen partial pressure was changed in the range of 10 <-3 > -2 * 10 <-1> (Pa).
また、基板温度は、室温とし、ターゲット８０８と被成膜基板８０７間の距離は、30 (mm)であった。 The substrate temperature was room temperature, and the distance between the target 808 and the deposition target substrate 807 was 30 (mm).
投入電力は、RF180 Wであり、成膜レートは、10 (nm/min)で行った。 The input power was RF 180 W, and the film formation rate was 10 (nm / min).
得られた膜に関し、膜面にすれすれ入射Ｘ線回折（薄膜法、入射角 0.5度）を行ったところ、明瞭な回折ピークは検出されず、作製したＩｎ−Ｚｎ−Ｇａ−Ｏ系膜はアモルファス膜であることが示された。 With respect to the obtained film, grazing incidence X-ray diffraction (thin film method, incident angle 0.5 degree) was performed on the film surface, but no clear diffraction peak was detected, and the produced In—Zn—Ga—O-based film was amorphous. It was shown to be a membrane.
さらに、Ｘ線反射率測定を行い、パターンの解析を行った結果、薄膜の平均二乗粗さ（Rrms）は約０．５nmであり、膜厚は約１２０nmであることが分かった。蛍光Ｘ線（XRF）分析の結果、薄膜の金属組成比はIn : Ga : Zn = 0.98 : 1.02 : 4であった。 Furthermore, as a result of measuring the X-ray reflectivity and analyzing the pattern, it was found that the mean square roughness (Rrms) of the thin film was about 0.5 nm and the film thickness was about 120 nm. As a result of X-ray fluorescence (XRF) analysis, the metal composition ratio of the thin film was In: Ga: Zn = 0.98: 1.02: 4.
成膜時の雰囲気の酸素分圧を変化させ、得られたアモルファス酸化物膜の電気伝導度を測定した。その結果を図３に示す。 The oxygen partial pressure of the atmosphere during film formation was changed, and the electrical conductivity of the obtained amorphous oxide film was measured. The result is shown in FIG.
図３に示すように、酸素分圧を３×１０-２Ｐａ超の高い雰囲気中で、成膜することにより、電気伝導度を１０Ｓ／ｃｍ未満に低下させることができた。As shown in FIG. 3, the electrical conductivity could be reduced to less than 10 S / cm by forming a film in an atmosphere having a high oxygen partial pressure exceeding 3 × 10−2 Pa.
酸素分圧をさらに大きくすることにより、電子キャリア数を低下させることができた。 By further increasing the oxygen partial pressure, the number of electron carriers could be reduced.
例えば、図３に示す様に、基板温度２５℃、酸素分圧１０-１Ｐａで成膜したInGaO3(ZnO)４薄膜では、さらに、電気伝導度を約１０-１０Ｓ／ｃｍに低下させることができた。また、酸素分圧１０-１Ｐａ超で成膜したInGaO3(ZnO)４薄膜は、電気抵抗が高すぎて電気伝導度は測定できなかった。この場合、電子移動度は測定できなかったが、電子キャリア濃度が大きな膜での値から外挿して、電子移動度は、約１ｃｍ２／Ｖ・秒と推定された。For example, as shown in FIG. 3, in an InGaO3 (ZnO)4 thin film formed at a substrate temperature of 25 ° C. and an oxygen partial pressure of 10−1 Pa, the electrical conductivity is further reduced to about 10−10 S / cm. I was able to. In addition, the InGaO3 (ZnO)4 thin film formed at an oxygen partial pressure exceeding 10−1 Pa had an electrical resistance that was too high to measure the electrical conductivity. In this case, although the electron mobility could not be measured, the electron mobility was estimated to be about 1 cm2 / V · second by extrapolating from the value in the film having a high electron carrier concentration.
すなわち、酸素分圧３×１０-２Ｐａ超、望ましくは5×１０-１Ｐａ超のアルゴンガス雰囲気で、スパッタ蒸着法で作製したIn-Ga-Zn-Oから構成され、結晶状態における組成InGaO3(ZnO)m(mは６未満の自然数)で表される透明アモルファス酸化物薄膜を作製した。この透明アモルファス酸化物薄膜を用い、ノーマリーオフで、かつオン・オフ比を１０３超のトランジスタを構成することができた。That is, it is composed of In—Ga—Zn—O produced by sputter deposition in an argon gas atmosphere with an oxygen partial pressure of over 3 × 10−2 Pa, preferably over 5 × 10−1 Pa, and the composition InGaO in the crystalline state. A transparent amorphous oxide thin film represented by3 (ZnO)m (m is a natural number of less than 6) was prepared. Using this transparent amorphous oxide thin film, a transistor having a normally-off and an on / off ratio exceeding 103 could be constructed.
本実施例で示した装置、材料を用いる場合は、スパッタによる成膜の際の酸素分圧としては、例えば、３×１０-２Ｐａ以上、５×１０-１Ｐａ以下の範囲である。なお、パルスレーザー蒸着法およびスパッタ法で作成された薄膜では、図２に示す様に、伝導電子数の増加と共に、電子移動度が増加する。In the case of using the apparatus and materials shown in this embodiment, the oxygen partial pressure during film formation by sputtering is, for example, in the range of 3 × 10−2 Pa to 5 × 10−1 Pa. In the thin film formed by the pulse laser deposition method and the sputtering method, as shown in FIG. 2, the electron mobility increases as the number of conduction electrons increases.
上記のとおり、酸素分圧を制御することにより、酸素欠陥を低減でき、その結果、電子キャリア濃度を減少できる。また、アモルファス状態では、多結晶状態とは異なり、本質的に粒子界面が存在しないために、高電子移動度のアモルファス薄膜を得ることができる。 As described above, by controlling the oxygen partial pressure, oxygen defects can be reduced, and as a result, the electron carrier concentration can be reduced. In the amorphous state, unlike the polycrystalline state, there is essentially no particle interface, so that an amorphous thin film with high electron mobility can be obtained.
なお、ガラス基板の代わりに厚さ２００μｍのポリエチレン・テレフタレート（ＰＥＴ）フィルムを用いた場合にも、得られたＩｎＧａＯ３（ＺｎＯ）４アモルファス酸化物膜は、同様の特性を示した。Even when a polyethylene terephthalate (PET) film having a thickness of 200 μm was used instead of the glass substrate, the obtained InGaO3 (ZnO)4 amorphous oxide film showed similar characteristics.
なお、ターゲットとして、多結晶InGaO3(Zn1-xＭｇｘO)m(mは６未満の自然数、0<x≦1)を用いれば、１Ｐａ未満の酸素分圧下でも、高抵抗非晶質InGaO3(Zn1-xＭｇｘO)m膜を得ることができる。If polycrystalline InGaO3 (Zn1-x Mgx O)m (m is a natural number less than 6 and 0 <x ≦ 1) is used as a target, a high-resistance amorphous material even under an oxygen partial pressure of less than 1 Pa. An InGaO3 (Zn1-x Mgx O)m film can be obtained.
例えば、Ｚｎを８０at％のＭｇで置換したターゲットを使用した場合、酸素分圧０．８Ｐａの雰囲気で、パルスレーザー堆積法で得られた膜の電子キャリア濃度を１０１６／ｃｍ３未満とすることができる（電気抵抗値は、約１０-２Ｓ／ｃｍである。）。For example, when a target in which Zn is replaced with 80 at% Mg is used, the electron carrier concentration of the film obtained by the pulse laser deposition method is less than 1016 / cm3 in an atmosphere with an oxygen partial pressure of 0.8 Pa. (The electric resistance value is about 10−2 S / cm).
こうした膜の電子移動度は、Ｍｇ無添加膜に比べて低下するが、その程度は少なく、室温での電子移動度は約５ｃｍ２／（Ｖ・秒）で、アモルファスシリコンに比べて、１桁程度大きな値を示す。同じ条件で成膜した場合、Ｍｇ含有量の増加に対して、電気伝導度と電子移動度は、共に低下するので、Ｍｇの含有量は、好ましくは、２０％超、８５％未満（ｘにして、０．２＜ｘ＜０．８５）である。The electron mobility of such a film is lower than that of the Mg-free film, but the degree is small, and the electron mobility at room temperature is about 5 cm2 / (V · sec), which is one digit that of amorphous silicon. A large value is shown. When the film is formed under the same conditions, both the electrical conductivity and the electron mobility decrease as the Mg content increases, so the Mg content is preferably more than 20% and less than 85% (x). 0.2 <x <0.85).
上記した非晶質酸化物膜を用いた薄膜トランジスタにおいて、Ａｌ２Ｏ３，Ｙ２Ｏ３、ＨｆＯ２、又はそれらの化合物を少なくとも二つ以上含む混晶化合物をゲート絶縁膜とすることが好ましい。In the thin film transistor using the above-described amorphous oxide film, a gate insulating film is preferably formed using a mixed crystal compound containing at least two of Al2 O3 , Y2 O3 , HfO2 , or a compound thereof.
ゲート絶縁薄膜とチャネル層薄膜との界面に欠陥が存在すると、電子移動度の低下及びトランジスタ特性にヒステリシスが生じる。また、ゲート絶縁膜の種類により、リーク電流が大きく異なる。このために、チャネル層に適合したゲート絶縁膜を選定する必要がある。Ａｌ２Ｏ３膜を用いれば、リーク電流を低減できる。また、Ｙ２Ｏ３膜を用いればヒステリシスを小さくできる。さらに、高誘電率のＨｆＯ２膜を用いれば、電子移動度を大きくすることができる。また、これらの膜の混晶を用いて、リーク電流、ヒステリシスが小さく、電子移動度の大きなＴＦＴを形成できる。また、ゲート絶縁膜形成プロセス及びチャネル層形成プロセスは、室温で行うことができるので、ＴＦＴ構造として、スタガ構造及び逆スタガ構造いずれをも形成することができる。If there is a defect at the interface between the gate insulating thin film and the channel layer thin film, the electron mobility is lowered and the transistor characteristics are hysteresis. Further, the leakage current varies greatly depending on the type of the gate insulating film. For this purpose, it is necessary to select a gate insulating film suitable for the channel layer. If an Al2 O3 film is used, leakage current can be reduced. Further, the hysteresis can be reduced by using a Y2 O3 film. Further, if a high dielectric constant HfO2 film is used, the electron mobility can be increased. Further, by using mixed crystals of these films, a TFT with small leakage current and hysteresis and high electron mobility can be formed. In addition, since the gate insulating film formation process and the channel layer formation process can be performed at room temperature, both a staggered structure and an inverted staggered structure can be formed as the TFT structure.
このように形成したＴＦＴは、ゲート端子、ソース端子、及び、ドレイン端子を備えた３端子素子である。またこのＴＦＴは、セラミックス、ガラス、又はプラスチックなどの絶縁基板上に成膜した半導体薄膜を、電子又はホールが移動するチャネル層として用いたものである。さらにこのＴＦＴは、ゲート端子に電圧を印加して、チャンネル層に流れる電流を制御し、ソース端子とドレイン端子間の電流をスイッチングする機能を有するアクテイブ素子である。 The TFT thus formed is a three-terminal element having a gate terminal, a source terminal, and a drain terminal. In this TFT, a semiconductor thin film formed on an insulating substrate such as ceramics, glass, or plastic is used as a channel layer through which electrons or holes move. Further, this TFT is an active element having a function of switching a current between the source terminal and the drain terminal by applying a voltage to the gate terminal to control a current flowing in the channel layer.
なお、酸素欠損量を制御して所望の電子キャリア濃度を達成できていることが本発明においては重要である。 It is important in the present invention that the desired electron carrier concentration can be achieved by controlling the oxygen deficiency.
上記記載においては、非晶質酸化物膜の酸素量（酸素欠損量）の制御を、成膜時に酸素を所定濃度含む雰囲気中で行うことで制御している。しかし、成膜後、当該酸化物膜を酸素を含む雰囲気中で後処理して酸素欠損量を制御（低減あるいは増加）することも好ましいものである。 In the above description, the amount of oxygen (oxygen deficiency) in the amorphous oxide film is controlled by performing it in an atmosphere containing oxygen at a predetermined concentration during film formation. However, it is also preferable to control (reduce or increase) the amount of oxygen vacancies after film formation by post-processing the oxide film in an atmosphere containing oxygen.
効果的に酸素欠損量を制御するには、酸素を含む雰囲気中の温度を０℃以上３００℃以下、好ましくは、２５℃以上、２５０℃以下、更に好ましくは１００℃以上２００℃以下で行うのがよい。 In order to effectively control the oxygen deficiency, the temperature in the atmosphere containing oxygen is 0 ° C. or higher and 300 ° C. or lower, preferably 25 ° C. or higher and 250 ° C. or lower, more preferably 100 ° C. or higher and 200 ° C. or lower. Is good.
勿論、成膜時にも酸素を含む雰囲気中で行い、且つ成膜後の後処理でも酸素を含む雰囲気中で後処理してもよい。また、所定の電子キャリア濃度（１０１８／ｃｍ３未満）を得られるのであれば、成膜時には、酸素分圧制御は行わないで、成膜後の後処理を酸素を含む雰囲気中で行ってもよい。Needless to say, the film formation may be performed in an atmosphere containing oxygen, and the post-treatment after the film formation may be performed in the atmosphere containing oxygen. If a predetermined electron carrier concentration (less than 1018 / cm3 ) can be obtained, oxygen partial pressure control is not performed during film formation, and post-treatment after film formation is performed in an atmosphere containing oxygen. Also good.
なお、本発明における電子キャリア濃度の下限としては、得られる酸化物膜をどのような素子や回路あるいは装置に用いるかにもよるが、例えば１０１４／ｃｍ３以上である。
（材料系の拡大）
さらに、組成系を拡大して研究を進めた結果、Zn,In及びSnのうち、少なくとも１種類の元素の酸化物からなるアモルファス酸化物で、電子キャリア濃度が小さく、かつ電子移動度が大きいアモルファス酸化物膜を作製できることを見出した。Note that the lower limit of the electron carrier concentration in the present invention is, for example, 1014 / cm3 or more, although it depends on what kind of element, circuit or device the oxide film obtained is used for.
(Expansion of materials)
Furthermore, as a result of expanding the composition system and researching it, an amorphous oxide composed of an oxide of at least one of Zn, In and Sn, an amorphous material with a low electron carrier concentration and a high electron mobility. It has been found that an oxide film can be produced.
また、このアモルファス酸化物膜は、伝導電子数の増加と共に、電子移動度が大きくなるという特異な特性を有することを見出した。 Further, the present inventors have found that this amorphous oxide film has a unique characteristic that the electron mobility increases as the number of conduction electrons increases.
その膜を用いてＴＦＴを作成し、オン・オフ比、ピンチオフ状態での飽和電流、スイッチ速度などのトランジスタ特性に優れたノーマリーオフ型のＴＦＴを作成できる。 A TFT is formed using the film, and a normally-off type TFT excellent in transistor characteristics such as an on / off ratio, a saturation current in a pinch-off state, and a switch speed can be formed.
本発明には、以下（ａ）から（ｈ）の特徴を有する酸化物を用いることができる。
（ａ） 室温での電子キャリア濃度が、１０１８／ｃｍ３未満のアモルファス酸化物。
（ｂ） 電子キャリア濃度が増加すると共に、電子移動度が増加することを特徴とするアモルファス酸化物。In the present invention, an oxide having the following characteristics (a) to (h) can be used.
(A) An amorphous oxide having an electron carrier concentration at room temperature of less than 1018 / cm3 .
(B) An amorphous oxide characterized by an increase in electron carrier concentration and an increase in electron mobility.
なおここで、室温とは０℃から４０℃程度の温度をいう。アモルファスとは、X線回折スペクトルにおいて、ハローパターンのみが観測され、特定の回折線を示さない化合物をいう。また、ここでの電子移動度は、ホール効果測定で得られる電子移動度をいう。
（ｃ） 室温での電子移動度が、０．１ｃｍ２／V・秒超であることを特徴とする上記（ａ）又は（ｂ）に記載されるアモルファス酸化物。
（ｄ） 縮退伝導を示す上記（ｂ）から（ｃ）のいずれかに記載されるアモルファス酸化物である。なお、ここでの縮退伝導とは、電気抵抗の温度依存性における熱活性化エネルギーが、３０ｍｅV以下の状態をいう。
（ｅ） Zn, In及びSnのうち、少なくとも１種類の元素を構成成分として含む上記（ａ）から（ｄ）のいずれかに記載されるアモルファス酸化物。
（ｆ） 上記（ｅ）に記載のアモルファス酸化物に、Ｚｎより原子番号の小さい２族元素Ｍ２（Ｍ２は、Ｍｇ，Ｃａ）、Ｉｎより原子番号の小さい３属元素Ｍ３（Ｍ３は、Ｂ，Ａｌ、Ｇａ、Ｙ），Ｓｎより小さい原子番号の小さい４属元素Ｍ４（Ｍ４は、Ｓｉ，Ｇｅ，Ｚｒ）、５属元素Ｍ５（Ｍ５は、Ｖ，Ｎｂ，Ｔａ）およびＬｕ、Ｗのうち、少なくとも１種類の元素を含むアモルファス酸化物膜。
（ｇ） 結晶状態における組成がＩｎ１−ｘＭ３ｘＯ3(Ｚｎ１−ｙＭ２ｙＯ)m（０≦ｘ、ｙ≦１、mは０又は６未満の自然数）である化合物単体又はｍの異なる化合物の混合体である(a)から（ｆ）のいずれかに記載のアモルファス酸化物膜。Ｍ３たとえば、Ｇａであり、Ｍ２は例えば、Ｍｇである。
(ｈ) ガラス基板、金属基板、プラスチック基板又はプラスチックフィルム上に設けた上記(a)から（g）記載のアモルファス酸化物膜。Here, room temperature refers to a temperature of about 0 ° C. to 40 ° C. Amorphous refers to a compound in which only a halo pattern is observed in an X-ray diffraction spectrum and does not show a specific diffraction line. Moreover, the electron mobility here means the electron mobility obtained by Hall effect measurement.
(C) The amorphous oxide described in the above (a) or (b), wherein the electron mobility at room temperature is more than 0.1 cm2 / V · sec.
(D) The amorphous oxide described in any one of (b) to (c) above showing degenerate conduction. Here, degenerate conduction refers to a state in which the thermal activation energy in the temperature dependence of electrical resistance is 30 meV or less.
(E) The amorphous oxide described in any one of (a) to (d) above, which contains at least one element of Zn, In, and Sn as a constituent component.
(F) To the amorphous oxide described in (e) above, the Group 2 element M2 having an atomic number smaller than Zn (M2 is Mg, Ca), the Group 3 element M3 having an atomic number smaller than In (M3 is B, Among Al, Ga, Y), Sn group 4 element M4 (M4 is Si, Ge, Zr), group 5 element M5 (M5 is V, Nb, Ta) and Lu, W An amorphous oxide film containing at least one element.
(G) the crystal composition in a state thatIn 1-x M3 x O 3 (Zn 1-y M2 y O) m (0 ≦ x, y ≦ 1, m is 0 or less than 6 natural number) is a compound alone or m The amorphous oxide film according to any one of (a) to (f), which is a mixture of different compounds. M3 is, for example, Ga, and M2 is, for example, Mg.
(h) The amorphous oxide film according to the above (a) to (g) provided on a glass substrate, metal substrate, plastic substrate or plastic film.
また、本発明は、（１０）上記記載のアモルファス酸化物、又はアモルファス酸化物膜をチャネル層に用いた電界効果型トランジスタである。 The present invention is (10) a field effect transistor using the amorphous oxide or the amorphous oxide film described above as a channel layer.
なお、電子キャリア濃度が１０１８／ｃｍ３未満、１０１５／ｃｍ３超のアモルファス酸化物膜をチャネル層に用い、ソース端子、ドレイン端子及びゲート絶縁膜を介してゲート端子を配した電界効果型トランジスタを構成する。ソース・ドレイン端子間に５V程度の電圧を印加したとき、ゲート電圧を印加しないときのソース・ドレイン端子間の電流を約１０−７アンペヤにすることができる。Note that a field effect type in which an amorphous oxide film having an electron carrier concentration of less than 1018 / cm3 and more than 1015 / cm3 is used for a channel layer, and a gate terminal is arranged via a source terminal, a drain terminal, and a gate insulating film. A transistor is formed. When a voltage of about 5 V is applied between the source and drain terminals, the current between the source and drain terminals when no gate voltage is applied can be about 10−7 ampere.
酸化物結晶の電子移動度は、金属イオンのｓ軌道の重なりが大きくなるほど、大きくなり、原子番号の大きなＺｎ，Ｉｎ，Ｓｎの酸化物結晶は、０．１から２００ｃｍ２／（Ｖ・秒）の大きな電子移動度を持つ。The electron mobility of the oxide crystal increases as the s orbital overlap of the metal ions increases, and the oxide crystal of Zn, In, Sn having a large atomic number has a value of 0.1 to 200 cm2 / (V · sec). It has a large electron mobility.
さらに、酸化物では、酸素と金属イオンとがイオン結合している。 Further, in the oxide, oxygen and metal ions are ionically bonded.
そのため、化学結合の方向性がなく、構造がランダムで、結合の方向が不均一なアモルファス状態でも、電子移動度は、結晶状態の電子移動度に比較して、同程度の大きさを有することが可能となる。 Therefore, even in the amorphous state where there is no chemical bond directionality, the structure is random, and the bond direction is non-uniform, the electron mobility should be comparable to the electron mobility in the crystalline state. Is possible.
一方で、Ｚｎ，Ｉｎ，Ｓｎを原子番号の小さな元素で置換することにより、電子移動度は小さくなる、こうした結果により、本発明のよるアモルファス酸化物の電子移動度は、約０．０１ｃｍ２／（Ｖ・秒）から２０ｃｍ２／（Ｖ・秒）である。On the other hand, by substituting Zn, In, and Sn with an element having a small atomic number, the electron mobility is reduced. As a result, the electron mobility of the amorphous oxide according to the present invention is about 0.01 cm2 / (V · second) to 20 cm2 / (V · second).
上記酸化物を用いてトランジスタのチャネル層を作製する場合、トランジスタにおいて、Ａｌ２Ｏ３、Ｙ２Ｏ３、ＨｆＯ２、又はそれらの化合物を少なくとも二つ以上含む混晶化合物をゲート絶縁膜とすることが好ましい。In the case where a channel layer of a transistor is formed using the above oxide, in the transistor, a mixed crystal compound containing at least two of Al2 O3 , Y2 O3 , HfO2 , or a compound thereof is used as a gate insulating film. It is preferable.
ゲート絶縁薄膜とチャネル層薄膜との界面に欠陥が存在すると、電子移動度の低下及びトランジスタ特性にヒステリシスが生じる。また、ゲート絶縁膜の種類により、リーク電流が大きく異なる。このために、チャネル層に適合したゲート絶縁膜を選定する必要がある。Ａｌ２Ｏ３膜を用いれば、リーク電流を低減できる。また、Ｙ２Ｏ３膜を用いればヒステリシスを小さくできる。さらに、高誘電率のＨｆＯ２膜を用いれば、電界効果移動度を大きくすることができる。また、これらの化合物の混晶からなる膜を用いて、リーク電流、ヒステリシスが小さく、電界効果移動度の大きなＴＦＴを形成できる。また、ゲート絶縁膜形成プロセス及びチャネル層形成プロセスは、室温で行うことができるので、ＴＦＴ構造として、スタガ構造及び逆スタガ構造いずれをも形成することができる。If there is a defect at the interface between the gate insulating thin film and the channel layer thin film, the electron mobility is lowered and the transistor characteristics are hysteresis. Further, the leakage current varies greatly depending on the type of the gate insulating film. For this purpose, it is necessary to select a gate insulating film suitable for the channel layer. If an Al2 O3 film is used, leakage current can be reduced. Further, the hysteresis can be reduced by using a Y2 O3 film. Furthermore, if a high dielectric constant HfO2 film is used, the field effect mobility can be increased. In addition, by using a film made of a mixed crystal of these compounds, a TFT with small leakage current and hysteresis and high field effect mobility can be formed. In addition, since the gate insulating film formation process and the channel layer formation process can be performed at room temperature, both a staggered structure and an inverted staggered structure can be formed as the TFT structure.
Ｉｎ２Ｏ３酸化物膜は、気相法により成膜でき、成膜中の雰囲気に水分を、０．１Ｐａ程度添加することにより、アモルファス膜が得られる。The In2 O3 oxide film can be formed by a vapor phase method, and an amorphous film can be obtained by adding about 0.1 Pa of moisture to the atmosphere during film formation.
また、ＺｎＯ及びＳｎＯ２は、アモルファス膜を得ることは難しいが、Ｉｎ２Ｏ３を、ＺｎＯの場合には２０原子量％程度、ＳｎＯ２の場合には、９０原子量％程度添加することによりアモルファス膜を得ることができる。特に、Ｓｎ−Ｉｎ―Ｏ系アモルファス膜を得るためには、雰囲気中に窒素ガスを０．１Ｐａ程度導入すればよい。In addition, although it is difficult to obtain an amorphous film of ZnO and SnO2 , an amorphous film can be obtained by adding In2 O3 to about 20 atomic% in the case of ZnO and about 90 atomic% in the case of SnO2. Can be obtained. In particular, in order to obtain a Sn—In—O-based amorphous film, nitrogen gas may be introduced into the atmosphere at about 0.1 Pa.
上記のアモルファス膜に、Ｚｎより原子番号の小さい２族元素Ｍ２（Ｍ２は、Ｍｇ，Ｃａ）、Ｉｎより原子番号の小さい３属元素Ｍ３（Ｍ３は、Ｂ，Ａｌ、Ｇａ、Ｙ），Ｓｎより小さい原子番号の小さい４属元素Ｍ４（Ｍ４は、Ｓｉ，Ｇｅ，Ｚｒ）、５属元素Ｍ５（Ｍ５は、Ｖ，Ｎｂ，Ｔａ）およびＬｕ、Ｗのうち、少なくとも１種類の複合酸化物を構成する元素を添加できる。 From the group II element M2 (M2 is Mg, Ca) having an atomic number smaller than Zn and the group 3 element M3 (M3 is B, Al, Ga, Y), Sn having an atomic number smaller than In Consists of at least one complex oxide of group 4 element M4 having a small atomic number (M4 is Si, Ge, Zr), group 5 element M5 (M5 is V, Nb, Ta) and Lu, W Can be added.
それにより、室温での、アモルファス膜をより安定化させることができる。また、アモルファス膜が得られる組成範囲を広げることができる。 Thereby, the amorphous film at room temperature can be further stabilized. Moreover, the composition range in which an amorphous film is obtained can be expanded.
特に、共有結合性の強い、Ｂ，Ｓｉ，Ｇｅの添加は、アモルファス相安定化に有効であるし、イオン半径の差の大きいイオンから構成される複合酸化物は、アモルファス相が安定化する。 In particular, the addition of B, Si, and Ge, which has strong covalent bonding, is effective for stabilizing the amorphous phase, and the complex phase composed of ions having a large difference in ionic radius stabilizes the amorphous phase.
たとえば、Ｉｎ−Ｚｎ−Ｏ系では、Inが約２０原子％超の組成範囲でないと、室温で安定なアモルファス膜は得難いが、ＭｇをＩｎと当量添加することにより、Ｉｎが約１５原子量％超の組成範囲で、安定なアモルファス膜を得ることができる。 For example, in the case of the In—Zn—O system, it is difficult to obtain an amorphous film that is stable at room temperature unless In is in a composition range of more than about 20 atomic%. With this composition range, a stable amorphous film can be obtained.
気相法による成膜において、雰囲気を制御することにより、電子キャリア濃度が、１０１８／ｃｍ３未満、１０１５／ｃｍ３超のアモルファス酸化膜を得ることができる。In film formation by a vapor phase method, an amorphous oxide film having an electron carrier concentration of less than 1018 / cm3 and more than 1015 / cm3 can be obtained by controlling the atmosphere.
アモルファス酸化物の成膜方法としては、パルスレーザー蒸着法（ＰＬＤ法）、スパッタ法（ＳＰ法）及び電子ビーム蒸着法などの気相法を用いるのがよい。気相法の中でも、材料系の組成を制御しやすい点では、ＰＬＤ法が、量産性の点からは、ＳＰ法が適している。しかし、成膜法は、これらの方法に限られるのものではない。
（ＰＬＤ法によるＩｎ−Ｚｎ−Ｇａ−Ｏ系アモルファス酸化膜の成膜）
KrFエキシマレーザーを用いたＰＬＤ法により、ガラス基板（コーニング社製1737）上にＩｎ−Ｚｎ―Ｇａ―Ｏ系アモルファス酸化物膜を堆積させた。このとき、ＩｎＧａＯ３（ＺｎＯ）及びＩｎＧａＯ３（ＺｎＯ）４組成を有する多結晶焼結体をそれぞれターゲットとした。As a film formation method of the amorphous oxide, it is preferable to use a vapor phase method such as a pulse laser deposition method (PLD method), a sputtering method (SP method), or an electron beam evaporation method. Among the gas phase methods, the PLD method is suitable from the viewpoint of easily controlling the composition of the material system, and the SP method is suitable from the viewpoint of mass productivity. However, the film forming method is not limited to these methods.
(Formation of In-Zn-Ga-O-based amorphous oxide film by PLD method)
An In—Zn—Ga—O amorphous oxide film was deposited on a glass substrate (1737 manufactured by Corning) by a PLD method using a KrF excimer laser. At this time, polycrystalline sintered bodies having InGaO3 (ZnO) and InGaO3 (ZnO)4 compositions were used as targets, respectively.
成膜装置は、既述の図９に記載されている装置を用い、成膜条件は、当該装置を用いた場合と同様とした。 As the film forming apparatus, the apparatus described in FIG. 9 described above was used, and the film forming conditions were the same as in the case of using the apparatus.
基板温度は25℃である。得られた膜に関し、膜面にすれすれ入射Ｘ線回折（薄膜法、入射角 0.5度）を行ったところ、明瞭な回折ピークは検出されず、２種類のターゲットから作製したＩｎ−Ｚｎ−Ｇａ−Ｏ系膜は、いずれもアモルファス膜であることが示された。 The substrate temperature is 25 ° C. With respect to the obtained film, grazing incidence X-ray diffraction (thin film method, incident angle 0.5 degree) was performed on the film surface, and no clear diffraction peak was detected. In—Zn—Ga— produced from two types of targets All of the O-based films were shown to be amorphous films.
さらに、ガラス基板上のＩｎ−Ｚｎ―Ｇａ―Ｏ系アモルファス酸化物膜のＸ線反射率測定を行い、パターンの解析を行った結果、薄膜の平均二乗粗さ（Rrms）は約0.5 nmであり、膜厚は約120 nmであることが分かった。 Furthermore, the X-ray reflectivity measurement of the In—Zn—Ga—O-based amorphous oxide film on the glass substrate was performed and the pattern was analyzed. As a result, the mean square roughness (Rrms) of the thin film was about 0.5 nm. The film thickness was found to be about 120 nm.
蛍光Ｘ線（XRF）分析の結果、ＩｎＧａＯ３（ＺｎＯ）組成を有する多結晶焼結体をターゲットとして得られた膜の金属組成比はIn : Ga : Zn = １．１ : １．１ : ０．９であった。また、ＩｎＧａＯ（ＺｎＯ）４組成を有する多結晶焼結体をターゲットとして得られた膜の金属組成比は、In : Ga : Zn = 0.98 : 1.02 : 4であった。As a result of X-ray fluorescence (XRF) analysis, the metal composition ratio of a film obtained using a polycrystalline sintered body having an InGaO3 (ZnO) composition as a target was In: Ga: Zn = 1.1: 1.1: 0. .9. The metal composition ratio of the film obtained using the polycrystalline sintered body having the InGaO (ZnO)4 composition as a target was In: Ga: Zn = 0.98: 1.02: 4.
成膜時の雰囲気の酸素分圧を変化させ、ＩｎＧａＯ３（ＺｎＯ）４組成を有する多結晶焼結体をターゲットとして得られたアモルファス酸化膜の電子キャリア濃度を測定した。その結果を図１に示す。酸素分圧が４．２Ｐａ超の雰囲気中で成膜することにより、電子キャリア濃度を１０１８／ｃｍ３未満に低下させることができた。この場合、基板の温度は意図的に加温しない状態でほぼ室温に維持されている。また、酸素分圧が６．５Ｐａ未満の時は、得られたアモルファス酸化物膜の表面は平坦であった。The oxygen partial pressure of the atmosphere during film formation was changed, and the electron carrier concentration of the amorphous oxide film obtained using a polycrystalline sintered body having an InGaO3 (ZnO)4 composition as a target was measured. The result is shown in FIG. By forming a film in an atmosphere having an oxygen partial pressure of over 4.2 Pa, the electron carrier concentration could be lowered to less than 1018 / cm3 . In this case, the temperature of the substrate is maintained at substantially room temperature without intentionally heating. When the oxygen partial pressure was less than 6.5 Pa, the surface of the obtained amorphous oxide film was flat.
酸素分圧が５Ｐａの時、ＩｎＧａＯ３（ＺｎＯ）４組成を有する多結晶焼結体をターゲットとして得られたアモルファス酸化膜の電子キャリア濃度は１０１６／ｃｍ３、電気伝導度は、１０−２Ｓ／ｃｍであった。また、電子移動度は、約５ｃｍ２／Ｖ・秒と推測された。光吸収スペクトルの解析から、作製したアモルファス酸化物膜の禁制帯エネルギー幅は、約3 eVと求まった。When the oxygen partial pressure is 5 Pa, the electron carrier concentration of an amorphous oxide film obtained using a polycrystalline sintered body having an InGaO3 (ZnO)4 composition as a target is 1016 / cm3 , and the electric conductivity is 10−2. S / cm. The electron mobility was estimated to be about 5 cm2 / V · sec. From the analysis of the light absorption spectrum, the band gap energy width of the fabricated amorphous oxide film was found to be about 3 eV.
酸素分圧をさらに大きくすると、電子キャリア濃度をさらに低下させることができた。図１に示す様に、基板温度２５℃、酸素分圧６Ｐａで成膜したＩｎ−Ｚｎ−Ｇａ−Ｏ系アモルファス酸化物膜では、電子キャリア濃度を８×１０１５／ｃｍ３（電気伝導：約８×１０-３Ｓ／ｃｍ）に低下させることができた。得られた膜は、電子移動度が１ｃｍ２／（Ｖ・秒）超と推測された。しかし、ＰＬＤ法では、酸素分圧を６．５Ｐａ以上にすると、堆積した膜の表面が凸凹となり、ＴＦＴのチャネル層として用いることが困難となった。Increasing the oxygen partial pressure further reduced the electron carrier concentration. As shown in FIG. 1, an In—Zn—Ga—O-based amorphous oxide film formed at a substrate temperature of 25 ° C. and an oxygen partial pressure of 6 Pa has an electron carrier concentration of 8 × 1015 / cm3 (electric conduction: about 8 × 10−3 S / cm). The obtained film was estimated to have an electron mobility exceeding 1 cm2 / (V · sec). However, in the PLD method, when the oxygen partial pressure is set to 6.5 Pa or more, the surface of the deposited film becomes uneven, making it difficult to use as a TFT channel layer.
ＩｎＧａＯ３（ＺｎＯ）４組成を有する多結晶焼結体をターゲットとし、異なる酸素分圧で成膜したＩｎ−Ｚｎ−Ｇａ−Ｏ系アモルファス酸化物膜に関して、電子キャリア濃度と電子移動度の関係を調べた。その結果を図２に示す。電子キャリア濃度が、１０１６／ｃｍ３から１０２０／ｃｍ３に増加すると、電子移動度は、約３ｃｍ２／（Ｖ・秒）から約１１ｃｍ２／（Ｖ・秒）に増加することが示された。また、ＩｎＧａＯ３（ＺｎＯ）組成を有する多結晶焼結体をターゲットとして得られたアモルファス酸化膜に関しても、同様の傾向が見られた。Regarding the In—Zn—Ga—O amorphous oxide film formed with different oxygen partial pressures, targeting a polycrystalline sintered body having an InGaO3 (ZnO)4 composition, the relationship between the electron carrier concentration and the electron mobility is as follows. Examined. The result is shown in FIG. It is shown that as the electron carrier concentration increases from 1016 / cm3 to 1020 / cm3 , the electron mobility increases from about 3 cm2 / (V · sec) to about 11 cm2 / (V · sec). It was done. Further, with regard InGaO 3(ZnO) amorphous oxide film obtained as a target, a polycrystalline sintered body having a composition, similar trend was observed.
ガラス基板の代わりに厚さ２００μｍのポリエチレン・テレフタレート（ＰＥＴ）フィルムを用いた場合にも、得られたＩｎ−Ｚｎ−Ｇａ−Ｏ系アモルファス酸化物膜は、同様の特性を示した。
（ＰＬＤ法によるＩｎ−Ｚｎ−Ｇａ−Ｍｇ−Ｏ系アモルファス酸化物膜の成膜）
ターゲットとして多結晶ＩｎＧａＯ３ (Ｚｎ1-xＭｇｘＯ)４(0<x≦1)を用い、ＰＬＤ法により、ガラス基板上にＩｎＧａＯ３(Ｚｎ1-xＭｇｘＯ)４(0<x≦1)膜を成膜した。成膜装置は、図７に記載の装置を用いた。Even when a polyethylene terephthalate (PET) film having a thickness of 200 μm was used instead of the glass substrate, the obtained In—Zn—Ga—O-based amorphous oxide film exhibited similar characteristics.
(Formation of In-Zn-Ga-Mg-O-based amorphous oxide film by PLD method)
Polycrystalline InGaO3 (Zn1-x Mgx O)4 (0 <x ≦ 1) was used as a target, and InGaO3 (Zn1-x Mgx O)4 (0 <x ≦ 1) A film was formed. As the film forming apparatus, the apparatus shown in FIG. 7 was used.
被成膜基板としては、SiO2ガラス基板（コーニング社製1737）を用意した。その基板に前処理として、超音波脱脂洗浄を、アセトン、エタノール、超純水により各5分間ずつ行った後、空気中１００℃で.乾燥させた。ターゲットとしては、InGa(Zn1-xMgxO)4(x=1-0)焼結体（サイズ 20mmΦ5mmt）を用いた。As a film formation substrate, a SiO2 glass substrate (1737 manufactured by Corning) was prepared. As a pretreatment, the substrate was subjected to ultrasonic degreasing and washing with acetone, ethanol, and ultrapure water for 5 minutes each and then dried at 100 ° C. in air. As a target, an InGa (Zn1-x Mgx O)4 (x = 1-0) sintered body (size 20 mmΦ5 mmt) was used.
ターゲットは、出発原料In2O3：Ga2O3:ZnO:MgO（各4N試薬）を、湿式混合(溶媒：エタノール)、仮焼（1000 ℃： 2h）、乾式粉砕、本焼結（1550 ℃： 2h）を経て作製した。The target is starting material In2 O3 : Ga2 O3 : ZnO: MgO (each 4N reagent), wet mixing (solvent: ethanol), calcining (1000 ° C: 2h), dry grinding, main sintering (1550 (C: 2h).
成長室到達真空は、2×10-6(Pa)であり、成長中の酸素分圧は、0.8 (Pa)とした。基板温度は、室温（２５℃）で行い、ターゲットと被成膜基板間の距離は、30 (mm)であった。The growth chamber reaching vacuum was 2 × 10−6 (Pa), and the oxygen partial pressure during growth was 0.8 (Pa). The substrate temperature was room temperature (25 ° C.), and the distance between the target and the deposition target substrate was 30 (mm).
なお、ＫｒＦエキシマレーザーのパワーは、１.5 (mJ/cm２/pulse)、パルス幅は、20 (nsec)、繰り返し周波数は、10 (Hz) 、照射スポット径は、1 × 1 (mm角)とした。成膜レートは、7 (nm/min)であった。The power of the KrF excimer laser is 1.5 (mJ / cm2 / pulse), the pulse width is 20 (nsec), the repetition frequency is 10 (Hz), and the irradiation spot diameter is 1 × 1 (mm square) ). The film formation rate was 7 (nm / min).
雰囲気は酸素分圧０．８Ｐａで、基板温度は25℃である。得られた膜に関し、膜面にすれすれ入射Ｘ線回折（薄膜法、入射角 0.5度）を行ったところ、明瞭な回折ピークは検出されず、作製したＩｎ−Ｚｎ−Ｇａ−Ｍｇ−Ｏ系膜はアモルファス膜であることが示された。得られた膜の表面は平坦であった。 The atmosphere is an oxygen partial pressure of 0.8 Pa, and the substrate temperature is 25 ° C. With respect to the obtained film, grazing incidence X-ray diffraction (thin film method, incident angle 0.5 degree) was performed on the film surface, but no clear diffraction peak was detected, and the produced In—Zn—Ga—Mg—O-based film Was shown to be an amorphous film. The surface of the obtained film was flat.
異なるｘ値のターゲットを用いて、酸素分圧０．８Ｐａの雰囲気中で成膜したＩｎ−Ｚｎ−Ｇａ−Ｍｇ−Ｏ系アモルファス酸化物膜の電気伝導度、電子キャリア濃度及び電子移動度のｘ値依存性を調べた。
その結果を、図４に示す。ｘ値が０．４超のとき、酸素分圧０．８Ｐａの雰囲気中で、ＰＬＤ法により成膜したアモルファス酸化物膜では、電子キャリア濃度を１０１８／ｃｍ３未満にできることが示された。また、ｘ値が０．４超のアモルファス酸化物膜では、電子移動度は、１ｃｍ２／Ｖ・秒超であった。The electric conductivity, electron carrier concentration, and electron mobility x of an In—Zn—Ga—Mg—O-based amorphous oxide film formed in an atmosphere having an oxygen partial pressure of 0.8 Pa using targets with different x values. The value dependency was examined.
The result is shown in FIG. It was shown that when the x value exceeds 0.4, the electron carrier concentration can be made less than 1018 / cm3 in the amorphous oxide film formed by the PLD method in an atmosphere having an oxygen partial pressure of 0.8 Pa. Further, in the amorphous oxide film having an x value exceeding 0.4, the electron mobility was more than 1 cm2 / V · second.
図４に示すように、Ｚｎを８０原子％のＭｇで置換したターゲットを使用した場合、酸素分圧０．８Ｐａの雰囲気で、パルスレーザー堆積法で得られた膜の電子キャリア濃度を１０１６／ｃｍ３未満とすることができる（電気抵抗値は、約１０-２Ｓ／ｃｍである。）。こうした膜の電子移動度は、Ｍｇ無添加膜に比べて低下するが、その程度は少なく、室温での電子移動度は約５ｃｍ２／（Ｖ・秒）で、アモルファスシリコンに比べて、１桁程度大きな値を示す。同じ条件で成膜した場合、Ｍｇ含有量の増加に対して、電気伝導度と電子移動度は、共に低下するので、Ｍｇの含有量は、好ましくは、２０原子％超、８５原子％未満（ｘにして、０．２＜ｘ＜０．８５）、より好適には０.５＜ｘ＜０．８５である。As shown in FIG. 4, when a target in which Zn is replaced with 80 atomic% Mg is used, the electron carrier concentration of the film obtained by the pulse laser deposition method is 1016 / in an atmosphere with an oxygen partial pressure of 0.8 Pa. It can be less than cm3 (the electrical resistance is about 10−2 S / cm). The electron mobility of such a film is lower than that of the Mg-free film, but the degree is small, and the electron mobility at room temperature is about 5 cm2 / (V · sec), which is one digit that of amorphous silicon. A large value is shown. When the film is formed under the same conditions, both the electrical conductivity and the electron mobility decrease with an increase in the Mg content. Therefore, the Mg content is preferably more than 20 atomic% and less than 85 atomic% ( x is 0.2 <x <0.85), and more preferably 0.5 <x <0.85.
ガラス基板の代わりに厚さ２００μｍのポリエチレン・テレフタレート（ＰＥＴ）フィルムを用いた場合にも、得られたＩｎＧａＯ３ (Ｚｎ1-xＭｇｘＯ)４(0<x≦1)アモルファス酸化物膜は、同様の特性を示した。
（ＰＬＤ法によるＩｎ２Ｏ３アモルファス酸化物膜の成膜）
KrFエキシマレーザーを用いたＰＬＤ法により、Ｉｎ２Ｏ３多結晶焼結体をターゲットとして、厚さ２００μｍのＰＥＴフィルム上にＩｎ２Ｏ３膜を成膜した。Even when a polyethylene terephthalate (PET) film having a thickness of 200 μm is used instead of the glass substrate, the obtained InGaO3 (Zn1-x Mgx O)4 (0 <x ≦ 1) amorphous oxide film is Showed similar characteristics.
(In2 O3 amorphous oxide film deposition by PLD method)
An In2 O3 film was formed on a 200 μm thick PET film by using a PLD method using a KrF excimer laser and targeting an In2 O3 polycrystalline sintered body.
装置は、図７に示した装置を用いた。被成膜基板として、SiO2ガラス基板（コーニング社製1737）を用意した。The apparatus shown in FIG. 7 was used. A SiO2 glass substrate (1737 manufactured by Corning) was prepared as a film formation substrate.
この基板の前処理として、超音波脱脂洗浄を、アセトン、エタノール、超純水で各5分間ずつ行った後、空気中１００℃で乾燥させた。 As a pretreatment of this substrate, ultrasonic degreasing was performed for 5 minutes each with acetone, ethanol, and ultrapure water, and then dried at 100 ° C. in air.
ターゲットとしては、In2O3焼結体（サイズ 20mmΦ5mmt）を用いた。これは、出発原料In2O3（4N試薬）を仮焼（1000 ℃： 2h）、乾式粉砕、本焼結（1550 ℃： 2h）を経て準備した。As a target, an In2 O3 sintered body (size 20 mmΦ5 mmt) was used. This was prepared by calcining the starting material In2 O3 (4N reagent) through calcining (1000 ° C .: 2 h), dry grinding and main sintering (1550 ° C .: 2 h).
成長室到達真空は、2×10-6(Pa)、成長中の酸素分圧は、５ (Pa)、基板温度は室温とした。The growth chamber reaching vacuum was 2 × 10−6 (Pa), the oxygen partial pressure during growth was 5 (Pa), and the substrate temperature was room temperature.
酸素分圧は５Ｐａ、水蒸気分圧は０．１Ｐａとし、さらに、酸素ラジカル発生装置に２００Ｗを印加して、酸素ラジカルを発生させた。 The oxygen partial pressure was 5 Pa, the water vapor partial pressure was 0.1 Pa, and 200 W was applied to the oxygen radical generator to generate oxygen radicals.
ターゲットと被成膜基板間の距離は、40 (mm)、ＫｒＦエキシマレーザーのパワーは0.5 (mJ/cm２/pulse)、パルス幅は、20 (nsec)、繰り返し周波数は、10 (Hz) 、照射スポット径は1 × 1 (mm角)であった。成膜レートは、3 (nm/min)であった。The distance between the target and the deposition substrate is 40 (mm), the power of the KrF excimer laser is 0.5 (mJ / cm2 / pulse), the pulse width is 20 (nsec), the repetition frequency is 10 (Hz), The irradiation spot diameter was 1 × 1 (mm square). The film formation rate was 3 (nm / min).
得られた膜に関し、膜面にすれすれ入射Ｘ線回折（薄膜法、入射角 0.5度）を行ったところ、明瞭な回折ピークは検出されず、作製したＩｎ−Ｏ系膜はアモルファス膜であることが示された。膜厚は、８０ｎｍであった。 Regarding the obtained film, grazing incidence X-ray diffraction (thin film method, incident angle 0.5 degree) was performed on the film surface, and no clear diffraction peak was detected, and the produced In-O film was an amorphous film. It has been shown. The film thickness was 80 nm.
得られたＩｎ−Ｏ系アモルファス酸化物膜の電子キャリア濃度は５×１０１７／ｃｍ３で、電子移動度は、約７ｃｍ２／Ｖ・秒であった。
（ＰＬＤ法によるＩｎ−Ｓｎ−Ｏ系アモルファス酸化物膜の成膜）
KrFエキシマレーザーを用いたＰＬＤ法により、（Ｉｎ０．９Ｓｎ０．１）Ｏ３．１多結晶焼結体をターゲットとして、厚さ２００μｍのＰＥＴフィルム上にＩｎ−Ｓｎ−Ｏ系酸化物膜を成膜した。
具体的には、
被成膜基板として、SiO2ガラス基板（コーニング社製1737）を用意した。
基板前処理として、超音波脱脂洗浄をアセトン、エタノール、超純水を用いて各5分間ずつ行った。 その後、空気中１００℃で乾燥させた。
ターゲットは、In2O3-SnO2焼結体（サイズ 20mmΦ5mmt）を準備した。これは、出発原料として、In2O3-SnO2（4N試薬）を湿式混合(溶媒：エタノール)、仮焼（1000 ℃： 2h）、乾式粉砕、本焼結（1550 ℃： 2h）を経て得られる。The obtained In—O amorphous oxide film had an electron carrier concentration of 5 × 1017 / cm3 and an electron mobility of about 7 cm2 / V · sec.
(Formation of In-Sn-O amorphous oxide film by PLD method)
By using a PLD method using a KrF excimer laser, an In-Sn-O-based oxide film is formed on a PET film having a thickness of 200 [mu] m with a (In<0.9 >Sn0.1 )O3.1 polycrystalline sintered body as a target. Was deposited.
In particular,
A SiO2 glass substrate (1737 manufactured by Corning) was prepared as a film formation substrate.
As the substrate pretreatment, ultrasonic degreasing was performed for 5 minutes each using acetone, ethanol, and ultrapure water. Then, it was dried in air at 100 ° C.
As a target, an In2 O3 —SnO2 sintered body (size 20 mmΦ5 mmt) was prepared. As a starting material, In2 O3 -SnO2 (4N reagent) is wet mixed (solvent: ethanol), calcined (1000 ° C: 2h), dry pulverized, and finally sintered (1550 ° C: 2h). can get.
基板温度は室温である。酸素分圧は５（Ｐａ）、窒素分圧は、０．１（Ｐａ）とし、さらに、酸素ラジカル発生装置に２００Ｗを印加して、酸素ラジカルを発生させた。 The substrate temperature is room temperature. The oxygen partial pressure was 5 (Pa), the nitrogen partial pressure was 0.1 (Pa), and 200 W was applied to the oxygen radical generator to generate oxygen radicals.
ターゲットと被成膜基板間の距離は、30 (mm)とし、ＫｒＦエキシマレーザーのパワーは、1.5 (mJ/cm２/pulse)、パルス幅は、20 (nsec)であった。また、繰り返し周波数は、10 (Hz) 、照射スポット径は、1 × 1 (mm角)であった。成膜レートは、6 (nm/min)であった。The distance between the target and the deposition substrate was 30 (mm), the power of the KrF excimer laser was 1.5 (mJ / cm2 / pulse), and the pulse width was 20 (nsec). The repetition frequency was 10 (Hz), and the irradiation spot diameter was 1 × 1 (mm square). The film formation rate was 6 (nm / min).
得られた膜に関し、膜面にすれすれ入射Ｘ線回折（薄膜法、入射角 0.5度）を行ったところ、明瞭な回折ピークは検出されず、作製したＩｎ−Ｓｎ−Ｏ系膜はアモルファス膜であることが示された。 With respect to the obtained film, grazing incidence X-ray diffraction (thin film method, incident angle 0.5 degree) was performed on the film surface, but no clear diffraction peak was detected, and the produced In—Sn—O film was an amorphous film. It was shown that there is.
得られたＩｎ−Ｓｎ−Ｏアモルファス酸化物膜の電子キャリア濃度は、８×１０１７／ｃｍ３で、電子移動度は、約５ｃｍ２／Ｖ・秒であった。膜厚は、１００ｎｍであった。
（ＰＬＤ法によるＩｎ−Ｇａ−Ｏ系アモルファス酸化物膜の成膜）
被成膜基板として、SiO2ガラス基板（コーニング社製1737）を用意した。The obtained In—Sn—O amorphous oxide film had an electron carrier concentration of 8 × 1017 / cm3 and an electron mobility of about 5 cm 2 / V · sec. The film thickness was 100 nm.
(Formation of In-Ga-O amorphous oxide film by PLD method)
A SiO2 glass substrate (1737 manufactured by Corning) was prepared as a film formation substrate.
基板の前処理として、超音波脱脂洗浄をアセトン、エタノール、超純水を用いて、各5分間行った後、空気中１００℃で乾燥させた。 As a pretreatment of the substrate, ultrasonic degreasing cleaning was performed for 5 minutes each using acetone, ethanol, and ultrapure water, and then dried at 100 ° C. in air.
ターゲットとして、(In2O3)1-x-(Ga2O3)x(X = 0-1)焼結体（サイズ 20mmΦ5mmt）を用意した。なお、例えばｘ＝０．１の場合は、ターゲットは、（Ｉｎ０．９Ｇａ０．１）２Ｏ３多結晶焼結体ということになる。As a target, an (In2 O3 )1-x- (Ga2 O3 )x (X = 0-1) sintered body (size 20 mmΦ5 mmt) was prepared. For example, when x = 0.1, the target is an (In0.9 Ga0.1 )2 O3 polycrystalline sintered body.
これは、出発原料：In2O3- Ga2O2（4N試薬）を、湿式混合(溶媒：エタノール)、仮焼（1000 ℃： 2h）、乾式粉砕、本焼結（1550 ℃： 2h）を経て得られる。This consists of starting material: In2 O3 -Ga2 O2 (4N reagent), wet mixing (solvent: ethanol), calcining (1000 ° C: 2h), dry grinding, main sintering (1550 ° C: 2h) It is obtained through
成長室到達真空は、2×10-6(Pa)であり、成長中の酸素分圧は、1 (Pa)とした。The growth chamber reaching vacuum was 2 × 10−6 (Pa), and the oxygen partial pressure during growth was 1 (Pa).
基板温度は、室温で行い、ターゲットと被成膜基板間の距離は、30 (mm)、ＫｒＦエキシマレーザーのパワーは、1.5 (mJ/cm２/pulse)であった。また、パルス幅は、20 (nsec)、繰り返し周波数は、10 (Hz)、照射スポット径は、1 × 1 (mm角)であった。成膜レートは、6 (nm/min)であった。The substrate temperature was room temperature, the distance between the target and the deposition target substrate was 30 (mm), and the power of the KrF excimer laser was 1.5 (mJ / cm2 / pulse). The pulse width was 20 (nsec), the repetition frequency was 10 (Hz), and the irradiation spot diameter was 1 × 1 (mm square). The film formation rate was 6 (nm / min).
基板温度は25℃である。酸素分圧は１Ｐａであった。得られた膜に関し、膜面にすれすれ入射Ｘ線回折（薄膜法、入射角 0.5度）を行ったところ、明瞭な回折ピークは検出されず、作製したＩｎ−Ｇａ−Ｏ系膜はアモルファス膜であることが示された。膜厚は、１２０ｎｍであった。 The substrate temperature is 25 ° C. The oxygen partial pressure was 1 Pa. Regarding the obtained film, grazing incidence X-ray diffraction (thin film method, incident angle 0.5 degree) was performed on the film surface, but no clear diffraction peak was detected, and the produced In—Ga—O film was an amorphous film. It was shown that there is. The film thickness was 120 nm.
得られたＩｎ−Ｇａ−Ｏアモルファス酸化物膜の電子キャリア濃度は、８×１０１６／ｃｍ３で、電子移動度は、約１ｃｍ２／Ｖ・秒であった。
（Ｉｎ−Ｚｎ−Ｇａ−Ｏ系アモルファス酸化物膜を用いたＴＦＴ素子の作製（ガラス基板））
ＴＦＴ素子の作製
図５に示すトップゲート型ＴＦＴ素子を作製した。The obtained In—Ga—O amorphous oxide film had an electron carrier concentration of 8 × 1016 / cm3 and an electron mobility of about 1 cm 2 / V · sec.
(Production of TFT element using In—Zn—Ga—O amorphous oxide film (glass substrate))
Fabrication of TFT Element A top gate TFT element shown in FIG. 5 was fabricated.
まず、ガラス基板（１）上に、ＩｎＧａＯ３（ＺｎＯ）４組成を有する多結晶焼結体をターゲットとし、酸素分圧５Ｐａの条件で、前述したPLD装置を用いて、In-Ga-Zn-O系アモルファス酸化物膜を作製した。チャンネル層（２）として用いる厚さ120nmのIn-Ga-Zn-O系アモルファス膜を形成した。First, on a glass substrate (1), a polycrystalline sintered body having an InGaO3 (ZnO)4 composition is used as a target, and the above-described PLD apparatus is used under the condition of an oxygen partial pressure of 5 Pa. An O-based amorphous oxide film was prepared. An In-Ga-Zn-O-based amorphous film having a thickness of 120 nm used as the channel layer (2) was formed.
さらにその上に、チャンバー内の酸素分圧を1Pa未満にして、ＰＬＤ法により電気伝導度の大きなIn-Ga-Zn-O系アモルファス膜及び金膜をそれぞれ30nm積層した。そして、フォトリソグラフィー法とリフトオフ法により、ドレイン端子（５）及びソース端子（６）を形成した。 Further, an In—Ga—Zn—O-based amorphous film and a gold film having a high electric conductivity were stacked by 30 nm by the PLD method with an oxygen partial pressure in the chamber of less than 1 Pa. And the drain terminal (5) and the source terminal (6) were formed by the photolithographic method and the lift-off method.
最後にゲート絶縁膜（３）として用いるY2O3膜を電子ビーム蒸着法により成膜し（厚み：90nm、比誘電率：約15、リーク電流密度：0.5 MV/cm印加時に10-3 A/cm2）、その上に金を成膜した。そして、フォトリソグラフィー法とリフトオフ法により、ゲート端子（４）を形成した。チャネル長は、５０μｍで、チャネル幅は、２００μｍであった。Finally, a Y2 O3 film used as the gate insulating film (3) is formed by electron beam evaporation (thickness: 90 nm, relative dielectric constant: about 15, leakage current density: 10-3 A when 0.5 MV / cm is applied) / cm2 ), and a gold film was formed thereon. And the gate terminal (4) was formed by the photolithographic method and the lift-off method. The channel length was 50 μm and the channel width was 200 μm.
ＴＦＴ素子の特性評価
図６に、室温下で測定したＴＦＴ素子の電流−電圧特性を示す。ドレイン電圧VDSの増加に伴い、ドレイン電流IDSが増加したことからチャネルがn型伝導であることが分かる。FIG. 6 shows the current-voltage characteristics of the TFT element measured at room temperature. As the drain voltage VDS increases, the drain current IDS increases, indicating that the channel is n-type conductive.
これは、アモルファスIn-Ga-Zn-O系アモルファス酸化物膜がn型伝導体であるという事実と矛盾しない。IDSはVDS= 6 V程度で飽和（ピンチオフ）する典型的な半導体トランジスタの挙動を示した。利得特性を調べたところ、VDS = 4 V印加時におけるゲート電圧VGSの閾値は約-0.5 Vであった。This is consistent with the fact that the amorphous In—Ga—Zn—O amorphous oxide film is an n-type conductor. IDS shows the behavior of a typical semiconductor transistor that saturates (pinch off) at about VDS = 6 V. When the gain characteristic was examined, the threshold value of the gate voltage VGS when VDS = 4 V was applied was about −0.5 V.
また、VG=10 V時には、IDS=1.0 × 10-5Aの電流が流れた。これはゲートバイアスにより絶縁体のIn-Ga-Zn-O系アモルファス酸化物膜内にキャリアを誘起できたことに対応する。When VG = 10 V, a current of IDS = 1.0 × 10−5 A flowed. This corresponds to the fact that carriers can be induced in the insulator In-Ga-Zn-O amorphous oxide film by the gate bias.
トランジスタのオン・オフ比は、１０３超であった。また、出力特性から電界効果移動度を算出したところ、飽和領域において約7cm2(Vs)-1の電界効果移動度が得られた。作製した素子に可視光を照射して同様の測定を行なったが、トランジスタ特性の変化は認められなかった。The on / off ratio of the transistor was more than 103 . When the field effect mobility was calculated from the output characteristics, a field effect mobility of about 7 cm2 (Vs)−1 was obtained in the saturation region. A similar measurement was performed by irradiating the fabricated device with visible light, but no change in transistor characteristics was observed.
なお、アモルファス酸化物の電子キャリア濃度を１０１８／ｃｍ３未満にすることでＴＦＴのチャネル層として適用できる。この電子キャリア濃度としては、１０１７／ｃｍ３以下がより好ましく、１０１６／ｃｍ３以下にすると更に好ましかった。
（Ｉｎ−Ｚｎ−Ｇａ−Ｏ系アモルファス酸化物膜を用いたＴＦＴ素子の作製（アモルファス基板））
図５に示すトップゲート型ＴＦＴ素子を作製した。まず、ポリエチレン・テレフタレート（ＰＥＴ）フィルム（１）上に、PLD法により、酸素分圧５Ｐａの雰囲気で、チャンネル層（２）として用いる厚さ120nmのＩｎ−Ｚｎ−Ｇａ−Ｏ系アモルファス酸化物膜を形成した。このとき、ＩｎＧａＯ３（ＺｎＯ）組成を有する多結晶焼結体をターゲットとした。In addition, it can apply as a channel layer of TFT by making the electron carrier density | concentration of an amorphous oxide less than 10 <18 > / cm <3 >. The electron carrier concentration is more preferably 1017 / cm3 or less, and even more preferably 1016 / cm3 or less.
(Production of TFT element using In-Zn-Ga-O-based amorphous oxide film (amorphous substrate))
The top gate type TFT element shown in FIG. 5 was produced. First, an In—Zn—Ga—O-based amorphous oxide film having a thickness of 120 nm used as a channel layer (2) on an polyethylene terephthalate (PET) film (1) by an PLD method in an atmosphere having an oxygen partial pressure of 5 Pa. Formed. At this time, a polycrystalline sintered body having an InGaO3 (ZnO) composition was used as a target.
さらにその上に、チャンバー内酸素分圧を1Pa未満にして、ＰＬＤ法により電気伝導度の大きなＩｎ−Ｚｎ−Ｇａ−Ｏ系アモルファス酸化物膜及び金膜をそれぞれ30nm積層した。そして、フォトリソグラフィー法とリフトオフ法により、ドレイン端子（５）及びソース端子（６）を形成した。最後にゲート絶縁膜（３）を電子ビーム蒸着法により成膜して、その上に金を成膜し、フォトリソグラフィー法とリフトオフ法により、ゲート端子（４）を形成した。チャネル長は、５０μｍで、チャネル幅は、２００μｍであった。ゲート絶縁膜として、Ｙ２Ｏ３（厚さ：１４０ｎｍ），Ａｌ２Ｏ３（厚さ：１３０μｍ）及びＨｆＯ２（厚さ：１４０μｍ）を用いた３種類の上記の構造を有するＴＦＴを作成した。Further, an In—Zn—Ga—O-based amorphous oxide film and a gold film having a high electric conductivity were stacked by 30 nm by a PLD method with an oxygen partial pressure in the chamber of less than 1 Pa. And the drain terminal (5) and the source terminal (6) were formed by the photolithographic method and the lift-off method. Finally, a gate insulating film (3) was formed by an electron beam evaporation method, gold was formed thereon, and a gate terminal (4) was formed by a photolithography method and a lift-off method. The channel length was 50 μm and the channel width was 200 μm. Three types of TFTs having the above-described structures using Y2 O3 (thickness: 140 nm), Al2 O3 (thickness: 130 μm) and HfO2 (thickness: 140 μm) as gate insulating films were prepared. .
ＴＦＴ素子の特性評価
ＰＥＴフィルム上に形成したＴＦＴの室温下で測定した電流−電圧特性は、図６と同様であった。すなわち、ドレイン電圧VDSの増加に伴い、ドレイン電流IDSが増加したことから、チャネルがn型伝導であることが分かる。これは、アモルファスＩｎ−Ｇａ−Ｚｎ−Ｏ系アモルファス酸化物膜がn型伝導体であるという事実と矛盾しない。IDSはVDS= 6 V程度で飽和（ピンチオフ）する典型的なトランジスタの挙動を示した。また、Ｖｇ＝０のときには、Ｉｄｓ＝１０−８Ａ，Ｖｇ=10 V時には、IDS=２.０ × 10-5Aの電流が流れた。これはゲートバイアスにより絶縁体のIn-Ga-Zn-O系アモルファス酸化物膜内に電子キャリアを誘起できたことに対応する。Characteristic Evaluation of TFT Element The current-voltage characteristic measured at room temperature of the TFT formed on the PET film was the same as that shown in FIG. That is, as the drain voltage VDS increases, the drain current IDS increases, indicating that the channel has n-type conduction. This is consistent with the fact that the amorphous In—Ga—Zn—O-based amorphous oxide film is an n-type conductor. IDS shows the behavior of a typical transistor that saturates (pinch off) at around VDS = 6 V. Further, when Vg = 0, a current of IDS = 2.0 × 10−5 A flowed when Ids = 10−8 A and Vg = 10 V. This corresponds to the fact that electron carriers can be induced in the In-Ga-Zn-O amorphous oxide film of the insulator by the gate bias.
トランジスタのオン・オフ比は、１０３超であった。また、出力特性から電界効果移動度を算出したところ、飽和領域において約7cm2(Vs)-1の電界効果移動度が得られた。The on / off ratio of the transistor was more than 103 . When the field effect mobility was calculated from the output characteristics, a field effect mobility of about 7 cm2 (Vs)−1 was obtained in the saturation region.
ＰＥＴフィルム上に作成した素子を、曲率半径３０ｍｍで屈曲させ、同様のトランジスタ特性の測定を行ったが、トランジスタ特性に変化は認められなかった。また、可視光を照射して同様の測定を行なったが、トランジスタ特性の変化は認められなかった。 The device prepared on the PET film was bent with a curvature radius of 30 mm, and the same transistor characteristics were measured, but no change was observed in the transistor characteristics. Further, the same measurement was performed by irradiating visible light, but no change in transistor characteristics was observed.
ゲート絶縁膜としてＡｌ２Ｏ３膜を用いたＴＦＴでも、図６に示したものと類似のトランジスタ特性を示したが、Ｖｇ＝０のときには、Ｉｄｓ＝１０−８Ａ，Ｖｇ=10 V時には、IDS=５.0 × 10-６Aの電流が流れた。トランジスタのオン・オフ比は、１０２超であった。また、出力特性から電界効果移動度を算出したところ、飽和領域において約２cm2(Vs)-1の電界効果移動度が得られた。The TFT using the Al2 O3 film as the gate insulating film also showed transistor characteristics similar to those shown in FIG. 6, but when Vg = 0, Ids = 10−8 A, Vg = 10 V Occasionally, a current of IDS = 5.0 × 10−6 A flowed. On-off ratio of the transistor was 10 greater than2. When the field effect mobility was calculated from the output characteristics, a field effect mobility of about 2 cm2 (Vs)−1 was obtained in the saturation region.
ゲート絶縁膜としてＨｆＯ２膜を用いたＴＦＴでも、図６に示したものと類似のトランジスタ特性を示したが、Ｖｇ＝０のときには、Ｉｄｓ＝１０−８Ａ，Ｖｇ=10 V時には、IDS=１.0 × 10-６Aの電流が流れた。トランジスタのオン・オフ比は、１０２超であった。また、出力特性から電界効果移動度を算出したところ、飽和領域において約１０cm2(Vs)-1の電界効果移動度が得られた。
（ＰＬＤ法によるＩｎ２Ｏ３アモルファス酸化物膜を用いたＴＦＴ素子の作成）
図５に示すトップゲート型ＴＦＴ素子を作製した。まず、ポリエチレン・テレフタレート（ＰＥＴ）フィルム（１）上に、PLD法により、チャンネル層（２）として用いる厚さ８０nmのＩｎ２Ｏ３アモルファス酸化物膜を形成した。The TFT using the HfO2 film as the gate insulating film also showed similar transistor characteristics to those shown in FIG. 6, but when Vg = 0, Ids = 10−8 A, and Vg = 10 V, A current of IDS = 1.0 × 10−6 A flowed. On-off ratio of the transistor was 10 greater than2. Further, when the field effect mobility was calculated from the output characteristics, a field effect mobility of about 10 cm2 (Vs)−1 was obtained in the saturation region.
(Creation of TFT element using In2 O3 amorphous oxide film by PLD method)
The top gate type TFT element shown in FIG. 5 was produced. First, an 80 nm thick In2 O3 amorphous oxide film used as a channel layer (2) was formed on a polyethylene terephthalate (PET) film (1) by a PLD method.
さらにその上に、チャンバー内酸素分圧を1Pa未満にして、さらに酸素ラジカル発生装置への印加電圧をゼロにして、ＰＬＤ法により、電気伝導度の大きなＩｎ２Ｏ３アモルファス酸化物膜及び金膜をそれぞれ30nm積層した。そして、フォトリソグラフィー法とリフトオフ法により、ドレイン端子（５）及びソース端子（６）を形成した。最後にゲート絶縁膜（３）として用いるY2O3膜を電子ビーム蒸着法により成膜して、その上に金を成膜して、フォトリソグラフィー法とリフトオフ法により、ゲート端子（４）を形成した。Further, an In2 O3 amorphous oxide film and a gold film having a high electric conductivity are formed by PLD method by setting the oxygen partial pressure in the chamber to less than 1 Pa and further applying zero voltage to the oxygen radical generator. Each was laminated with 30 nm. And the drain terminal (5) and the source terminal (6) were formed by the photolithographic method and the lift-off method. Finally, a Y2 O3 film used as a gate insulating film (3) is formed by an electron beam evaporation method, gold is formed thereon, and a gate terminal (4) is formed by a photolithography method and a lift-off method. Formed.
ＴＦＴ素子の特性評価
ＰＥＴフィルム上に形成したＴＦＴの室温下で測定した電流−電圧特性を測定した。ドレイン電圧VDSの増加に伴い、ドレイン電流IDSが増加したことからチャネルがn型半導体であることが分かる。これは、In -O系アモルファス酸化物膜がn型伝導体であるという事実と矛盾しない。IDSはVDS= ５ V程度で飽和（ピンチオフ）する典型的なトランジスタの挙動を示した。また、Ｖｇ＝０Ｖ時には、２×１０−８Ａ、VG=10 V時には、IDS=２.0 ×10-６Aの電流が流れた。これはゲートバイアスにより絶縁体のIn-O系アモルファス酸化物膜内に電子キャリアを誘起できたことに対応する。Characteristic Evaluation of TFT Element A current-voltage characteristic measured at room temperature of a TFT formed on a PET film was measured. As the drain voltage VDS increases, the drain current IDS increases, which indicates that the channel is an n-type semiconductor. This is consistent with the fact that the In—O amorphous oxide film is an n-type conductor. IDS shows the behavior of a typical transistor that saturates (pinch off) at about VDS = 5 V. In addition, when Vg = 0V, a current of 2 × 10−8 A flows, and when VG = 10 V, a current of IDS = 2.0 × 10−6 A flows. This corresponds to the fact that electron carriers can be induced in the In-O amorphous oxide film of the insulator by the gate bias.
トランジスタのオン・オフ比は、約１０２であった。また、出力特性から電界効果移動度を算出したところ、飽和領域において約１０cm2(Vs)-1の電界効果移動度が得られた。ガラス基板上に作成したＴＦＴ素子も同様の特性を示した。On-off ratio of the transistor was about 102. Further, when the field effect mobility was calculated from the output characteristics, a field effect mobility of about 10 cm2 (Vs)−1 was obtained in the saturation region. The TFT element formed on the glass substrate also showed similar characteristics.
ＰＥＴフィルム上に作成した素子を、曲率半径３０ｍｍで曲げ、同様のトランジスタ特性の測定を行ったが、トランジスタ特性に変化は認められなかった。
（ＰＬＤ法によるＩｎ−Ｓｎ−Ｏ系アモルファス酸化物膜を用いたＴＦＴ素子の作成）
図５に示すトップゲート型ＴＦＴ素子を作製した。まず、ポリエチレン・テレフタレート（ＰＥＴ）フィルム（１）上に、PLD法により、チャンネル層（２）として用いる厚さ１００nmのＩｎ−Ｓｎ−Ｏ系アモルファス酸化物膜を形成した。さらにその上に、チャンバー内酸素分圧を1Pa未満にして、さらに酸素ラジカル発生装置への印加電圧をゼロにして、ＰＬＤ法により、電気伝導度の大きなＩｎ−Ｓｎ−Ｏ系アモルファス酸化物膜及び金膜をそれぞれ30nm積層した。そして、フォトリソグラフィー法とリフトオフ法により、ドレイン端子（５）及びソース端子（６）を形成した。最後にゲート絶縁膜（３）として用いるY2O3膜を電子ビーム蒸着法により成膜し、その上に金を成膜して、フォトリソグラフィー法とリフトオフ法により、ゲート端子（４）を形成した。The device prepared on the PET film was bent with a radius of curvature of 30 mm and the same transistor characteristics were measured, but no change was observed in the transistor characteristics.
(Preparation of TFT element using In-Sn-O amorphous oxide film by PLD method)
The top gate type TFT element shown in FIG. 5 was produced. First, an In—Sn—O-based amorphous oxide film having a thickness of 100 nm used as a channel layer (2) was formed on a polyethylene terephthalate (PET) film (1) by a PLD method. Further, an In-Sn-O amorphous oxide film having a high electrical conductivity and a PLD method are used by setting the partial pressure of oxygen in the chamber to less than 1 Pa, further reducing the voltage applied to the oxygen radical generator to zero. Each gold film was laminated to 30 nm. And the drain terminal (5) and the source terminal (6) were formed by the photolithographic method and the lift-off method. Finally, a Y2 O3 film used as a gate insulating film (3) is formed by an electron beam evaporation method, gold is formed thereon, and a gate terminal (4) is formed by a photolithography method and a lift-off method. did.
ＴＦＴ素子の特性評価
ＰＥＴフィルム上に形成したＴＦＴの室温下で測定した電流−電圧特性を測定した。ドレイン電圧VDSの増加に伴い、ドレイン電流IDSが増加したことからチャネルがn型半導体であることが分かる。これは、In -Ｓｎ−O系アモルファス酸化物膜がn型伝導体であるという事実と矛盾しない。IDSはVDS= ６ V程度で飽和（ピンチオフ）する典型的なトランジスタの挙動を示した。また、Ｖｇ＝０Ｖ時には、５×１０−８Ａ、VG=10 V時には、IDS=５.0 × 10-５Aの電流が流れた。これはゲートバイアスにより絶縁体のIn-Ｓｎ-O系アモルファス酸化物膜内に電子キャリアを誘起できたことに対応する。Characteristic Evaluation of TFT Element A current-voltage characteristic measured at room temperature of a TFT formed on a PET film was measured. As the drain voltage VDS increases, the drain current IDS increases, which indicates that the channel is an n-type semiconductor. This is consistent with the fact that the In—Sn—O-based amorphous oxide film is an n-type conductor. IDS shows the behavior of a typical transistor that saturates (pinch off) at about VDS = 6 V. Further, when Vg = 0V, a current of 5 × 10−8 A flows, and when VG = 10 V, a current of IDS = 5.0 × 10−5 A flows. This corresponds to the fact that electron carriers could be induced in the insulator In—Sn—O amorphous oxide film by the gate bias.
トランジスタのオン・オフ比は、約１０３であった。また、出力特性から電界効果移動度を算出したところ、飽和領域において約５cm2(Vs)-1の電界効果移動度が得られた。ガラス基板上に作成したＴＦＴ素子も同様の特性を示した。The on / off ratio of the transistor was about 103 . Further, when the field effect mobility was calculated from the output characteristics, a field effect mobility of about 5 cm2 (Vs)−1 was obtained in the saturation region. The TFT element formed on the glass substrate also showed similar characteristics.
ＰＥＴフィルム上に作成した素子を、曲率半径３０ｍｍで曲げ、同様のトランジスタ特性の測定を行ったが、トランジスタ特性に変化は認められなかった。
（ＰＬＤ法によるＩｎ−Ｇａ−Ｏ系アモルファス酸化物膜を用いたＴＦＴ素子の作成）
図５に示すトップゲート型ＴＦＴ素子を作製した。まず、ポリエチレン・テレフタレート（ＰＥＴ）フィルム（１）上に、実施例６に示した成膜法により、チャンネル層（２）として用いる厚さ120nmのＩｎ−Ｇａ−Ｏ系アモルファス酸化物膜を形成した。さらにその上に、チャンバー内の酸素分圧を1Pa未満にして、さらに酸素ラジカル発生装置への印加電圧をゼロにして、ＰＬＤ法により、電気伝導度の大きなＩｎ−Ｇａ−Ｏ系アモルファス酸化物膜及び金膜をそれぞれ30nm積層した。そして、フォトリソグラフィー法とリフトオフ法により、ドレイン端子（５）及びソース端子（６）を形成した。最後にゲート絶縁膜（３）として用いるY2O3膜を電子ビーム蒸着法により成膜し、その上に金を成膜して、フォトリソグラフィー法とリフトオフ法により、ゲート端子（４）を形成した。The device prepared on the PET film was bent with a radius of curvature of 30 mm and the same transistor characteristics were measured, but no change was observed in the transistor characteristics.
(Preparation of TFT element using In-Ga-O amorphous oxide film by PLD method)
The top gate type TFT element shown in FIG. 5 was produced. First, an In—Ga—O-based amorphous oxide film having a thickness of 120 nm used as the channel layer (2) was formed on the polyethylene terephthalate (PET) film (1) by the film forming method shown in Example 6. . Further, an In—Ga—O amorphous oxide film having a high electrical conductivity is formed by the PLD method by setting the oxygen partial pressure in the chamber to less than 1 Pa and further applying zero voltage to the oxygen radical generator. And 30 nm thick gold films. And the drain terminal (5) and the source terminal (6) were formed by the photolithographic method and the lift-off method. Finally, a Y2 O3 film used as a gate insulating film (3) is formed by an electron beam evaporation method, gold is formed thereon, and a gate terminal (4) is formed by a photolithography method and a lift-off method. did.
ＴＦＴ素子の特性評価
ＰＥＴフィルム上に形成したＴＦＴの室温下で測定した電流−電圧特性を測定した。ドレイン電圧VDSの増加に伴い、ドレイン電流IDSが増加したことからチャネルがn型半導体であることが分かる。これは、In −Ｇａ−O系アモルファス酸化物膜がn型伝導体であるという事実と矛盾しない。IDSはVDS= ６ V程度で飽和（ピンチオフ）する典型的なトランジスタの挙動を示した。また、Ｖｇ＝０Ｖ時には、１×１０−８Ａ、VG=10 V時には、IDS=１.0 × 10-６Aの電流が流れた。これはゲートバイアスにより絶縁体のIn-Ga-O系アモルファス酸化物膜内に電子キャリアを誘起できたことに対応する。Characteristic Evaluation of TFT Element A current-voltage characteristic measured at room temperature of a TFT formed on a PET film was measured. As the drain voltage VDS increases, the drain current IDS increases, which indicates that the channel is an n-type semiconductor. This is consistent with the fact that the In—Ga—O amorphous oxide film is an n-type conductor. IDS shows the behavior of a typical transistor that saturates (pinch off) at about VDS = 6 V. Further, when Vg = 0V, a current of 1 × 10−8 A flows, and when VG = 10 V, a current of IDS = 1.0 × 10−6 A flows. This corresponds to the fact that electron carriers could be induced in the insulator In-Ga-O amorphous oxide film by the gate bias.
トランジスタのオン・オフ比は、約１０２であった。また、出力特性から電界効果移動度を算出したところ、飽和領域において約０．８cm2(Vs)-1の電界効果移動度が得られた。ガラス基板上に作成したＴＦＴ素子も同様の特性を示した。On-off ratio of the transistor was about 102. Further, when the field effect mobility was calculated from the output characteristics, a field effect mobility of about 0.8 cm2 (Vs)−1 was obtained in the saturation region. The TFT element formed on the glass substrate also showed similar characteristics.
ＰＥＴフィルム上に作成した素子を、曲率半径３０ｍｍで曲げ、同様のトランジスタ特性の測定を行ったが、トランジスタ特性に変化は認められなかった。 The device prepared on the PET film was bent with a radius of curvature of 30 mm and the same transistor characteristics were measured, but no change was observed in the transistor characteristics.
なお、アモルファス酸化物の電子キャリア濃度を１０１８／ｃｍ３未満にすることでＴＦＴのチャネル層として適用できる。この電子キャリア濃度としては、１０１７／ｃｍ３以下がより好ましく、１０１６／ｃｍ３以下にすると更に好ましかった。In addition, it can apply as a channel layer of TFT by making the electron carrier density | concentration of an amorphous oxide less than 10 <18 > / cm <3 >. The electron carrier concentration is more preferably 1017 / cm3 or less, and even more preferably 1016 / cm3 or less.
以下、本発明の実施例について説明する。 Examples of the present invention will be described below.
（実施例１：微結晶を含むアモルファスIn-Ga-Zn-O薄膜の作製）
図７に記載の装置を用いて行う。(Example 1: Preparation of amorphous In-Ga-Zn-O thin film containing microcrystals)
This is performed using the apparatus shown in FIG.
KrFエキシマレーザーを用いたパルスレーザー蒸着法により、InGaO3(ZnO)４組成を有する多結晶焼結体をターゲットとして用いる。A polycrystalline sintered body having an InGaO3 (ZnO)4 composition is used as a target by pulsed laser deposition using a KrF excimer laser.
ガラス基板（コーニング社製1737）上に、微結晶を含むIn-Ga-Zn-O系アモルファス酸化物半導体薄膜を堆積させる。 An In-Ga-Zn-O-based amorphous oxide semiconductor thin film containing microcrystals is deposited on a glass substrate (Corning 1737).
成膜時には光照射のために、20ｍＷ/ｃｍ2のハロゲンランプを基板面に照射する。During film formation, the substrate surface is irradiated with a halogen lamp of 20 mW / cm2 for light irradiation.
なお、微結晶の存在の確認は、断面ＴＥＭ（透過型電子顕微鏡）観察により確認される。 In addition, confirmation of presence of a microcrystal is confirmed by cross-sectional TEM (transmission electron microscope) observation.
（MISFET素子の作製）
図５に示すトップゲート型MISFET素子を作製する。(Preparation of MISFET element)
The top gate type MISFET element shown in FIG. 5 is manufactured.
まず、ガラス基板（１）上に上記の微結晶を含むアモルファスIn-Ga-Zn-O薄膜の作製法により、チャンネル層（２）として用いる厚さ30nmの微結晶を含む半絶縁性アモルファスInGaO3(ZnO)４膜を形成する。First, the semi-insulating amorphous InGaO3 containing microcrystals with a thickness of 30 nm used as the channel layer (2) is prepared by the above-described method for producing an amorphous In—Ga—Zn—O thin film containing microcrystals on the glass substrate (1). A (ZnO)4 film is formed.
さらにその上に、チャンバー内酸素分圧を1Pa未満にして、パルスレーザー堆積法により電気伝導度の大きなInGaO3(ZnO)４及び金膜をそれぞれ30nm積層した。そして、フォトリソグラフィー法とリフトオフ法により、ドレイン端子（５）及びソース端子（６）を形成する。Further, an InGaO3 (ZnO)4 film and a gold film having a large electric conductivity were stacked in a thickness of 30 nm by a pulse laser deposition method with an oxygen partial pressure in the chamber of less than 1 Pa. Then, the drain terminal (5) and the source terminal (6) are formed by a photolithography method and a lift-off method.
最後にゲート絶縁膜（３）として用いるY2O3膜を電子ビーム蒸着法により成膜する（厚み：110nm、比誘電率：約15、リーク電流密度：0.5 MV/cm印加時に10-3 A/cm2）。そして、その上に金を成膜し、フォトリソグラフィー法とリフトオフ法により、ゲート端子（４）を形成する。Finally, a Y2 O3 film used as a gate insulating film (3) is formed by electron beam evaporation (thickness: 110 nm, relative dielectric constant: about 15, leakage current density: 10-3 A when 0.5 MV / cm is applied) / cm2 ). And gold | metal | money is formed on it and a gate terminal (4) is formed by the photolithographic method and the lift-off method.
こうして、電界効果型トランジスタが形成される。 Thus, a field effect transistor is formed.
トランジスタのオン・オフ比は、１０4超である。また、出力特性から電界効果移動度を算出したところ、飽和領域において約7.5cm2(Vs)-1の電界効果移動度が得られた。作製した素子に可視光を照射して同様の測定を行なったが、トランジスタ特性の変化は認められない。The on / off ratio of the transistor is greater than 104 . Further, when the field effect mobility was calculated from the output characteristics, a field effect mobility of about 7.5 cm2 (Vs)−1 was obtained in the saturation region. A similar measurement was performed by irradiating the fabricated device with visible light, but no change in transistor characteristics was observed.
さらに上記微結晶を含むIn-Ga-Zn-Oなどの薄膜作製の実施例において、基板に光照射する際に、0.3ｍＷ/ｃｍ2〜100ｍＷ/ｃｍ2の範囲において、より効果的であった。このようにすると、トランジスタのオン・オフ比を大きくでき、また、電界効果移動度も大きな値が得られると言う面でより好ましいものとなる。In yet an embodiment of the thin film preparation, such as In-Ga-Zn-O containing the microcrystals, when the light irradiation to the substrate, in the range of0.3mW / cm 2 ~100mW / cm 2 , was more effective . This is more preferable in that the ON / OFF ratio of the transistor can be increased and the field effect mobility can be increased.
なお、非晶質酸化物膜中における微結晶の量にもよるが、同膜中に微結晶が存在することの確認は、Ｘ線回折による測定により、特定のピークが観測されることによっても確認できる。
（実施例２：膜厚方向で組成分布を有するアモルファスIn-Ga-Zn-O薄膜の作製）
KrFエキシマレーザーを用いたパルスレーザー蒸着法により、ガラス基板（コーニング社製1737）上に膜厚方向で組成分布を有するIn-Ga-Zn-O系アモルファス酸化物半導体薄膜を堆積する。このとき、InGaO3(ZnO)４組成を有する多結晶焼結体をターゲットとした。Although it depends on the amount of microcrystals in the amorphous oxide film, the presence of microcrystals in the film can be confirmed by observing a specific peak by measurement by X-ray diffraction. I can confirm.
(Example 2: Preparation of amorphous In-Ga-Zn-O thin film having a composition distribution in the film thickness direction)
An In-Ga-Zn-O-based amorphous oxide semiconductor thin film having a composition distribution in the film thickness direction is deposited on a glass substrate (Corning 1737) by a pulsed laser deposition method using a KrF excimer laser. At this time, a polycrystalline sintered body having an InGaO3 (ZnO)4 composition was used as a target.
チャンバー内酸素分圧を所定の範囲に設定し、ターゲット-基板間距離を５ｍｍ遠ざける方向へ変化させながら堆積する。両者の距離が長くなるにつれて、成膜される膜中に取り込まれる酸素量は多くなる。基板温度は25℃である。 The deposition is performed while the oxygen partial pressure in the chamber is set within a predetermined range and the distance between the target and the substrate is changed by 5 mm. As the distance between the two becomes longer, the amount of oxygen taken into the film to be formed increases. The substrate temperature is 25 ° C.
なお、上記膜厚方向で組成分布を有する薄膜作製の実施例において、膜厚方向で組成分布を有する際に、酸素分圧を膜厚方向で変化させてもよい。または、パルスレーザーの発振パワーを変化させたり、発振周波数を変化させたりしても、膜厚方向で組成変化させることができる。 Note that, in the example of manufacturing a thin film having a composition distribution in the film thickness direction, the oxygen partial pressure may be changed in the film thickness direction when the composition distribution is present in the film thickness direction. Alternatively, the composition can be changed in the film thickness direction even when the oscillation power of the pulse laser is changed or the oscillation frequency is changed.
このようにすると、リーク電流が減ったり、トランジスタのオン・オフ比を大きくできたり、あるいは、電界効果移動度を大きくすることができる。
（実施例３：膜厚方向で組成分布を有するアモルファスIn-Ga-Zn-O薄膜の作製）
アルゴンガスを用いたスパッタ蒸着法を用いる。In this way, the leakage current can be reduced, the on / off ratio of the transistor can be increased, or the field effect mobility can be increased.
(Example 3: Preparation of amorphous In-Ga-Zn-O thin film having a composition distribution in the film thickness direction)
A sputter deposition method using argon gas is used.
ターゲットとして、１）InGaO3(ZnO)４組成を有する多結晶焼結体と、２）酸化亜鉛の焼結体を用意する。As targets, 1) a polycrystalline sintered body having an InGaO3 (ZnO)4 composition and 2) a sintered body of zinc oxide are prepared.
そして、膜厚方向で組成分布を有するアモルファスIn-Ga-Zn-O薄膜をガラス基板（コーニング社製1737）上に作製する。 Then, an amorphous In—Ga—Zn—O thin film having a composition distribution in the film thickness direction is formed on a glass substrate (Corning 1737).
酸素分圧を所定の値にした、雰囲気中で、始めに、ターゲット１）を用いてスパッタ法による成膜を行う。 First, film formation by sputtering is performed using the target 1) in an atmosphere in which the oxygen partial pressure is set to a predetermined value.
次いで、ターゲット１）と２）を同時に用いて、スパッタ法による成膜を行う。こうして、膜厚方向で、組成分布を有するアモルファスIn-Ga-Zn-O薄膜が作製できる。基板温度は25℃である。 Next, a film is formed by sputtering using the targets 1) and 2) simultaneously. Thus, an amorphous In—Ga—Zn—O thin film having a composition distribution in the film thickness direction can be manufactured. The substrate temperature is 25 ° C.
なお、上記膜厚方向で組成分布を有するIn-Ga-Zn-Oなどの薄膜作製は以下のように行うこともできる。 Note that a thin film such as In—Ga—Zn—O having a composition distribution in the film thickness direction can also be manufactured as follows.
例えば、膜厚方向で組成分布を有する際に、In2O3ターゲットを同時または、別々にスパッタしたり、あるいは、酸素分圧を膜厚方向で変化させたり、あるいは、スパッタの投入電力を各ターゲットごと膜厚方向で変化させるのである。For example, when the composition distribution is in the film thickness direction, the In2 O3 target is sputtered simultaneously or separately, or the oxygen partial pressure is changed in the film thickness direction, or the sputtering input power is Each target is changed in the film thickness direction.
特にゲート絶縁膜近傍では、In２O3あるいはZnO組成の多い方が、電界効果移動度が大きくなることが期待される。
（実施例４：アモルファスIn-Ga-Zn-O(N)薄膜の作製）
非晶質酸化物に添加物として窒素（Ｎ）を含む酸化物の製法について説明する。Particularly in the vicinity of the gate insulating film, the field effect mobility is expected to increase as the In2 O3 or ZnO composition increases.
(Example 4: Preparation of amorphous In-Ga-Zn-O (N) thin film)
A method for manufacturing an oxide containing nitrogen (N) as an additive in an amorphous oxide will be described.
次にKrFエキシマレーザーを用いたパルスレーザー蒸着法により、同じガラス基板上に、窒素を不純物として含むIn-Ga-Zn-O系アモルファス酸化物半導体（In-Ga-Zn-O(N)と略記する）薄膜を堆積させる。このとき、InGaO3(ZnO)４多結晶焼結体をターゲットとした。Next, an In-Ga-Zn-O amorphous oxide semiconductor containing nitrogen as an impurity (In-Ga-Zn-O (N) is abbreviated on the same glass substrate by pulsed laser deposition using a KrF excimer laser. Deposit a thin film. At this time, an InGaO3 (ZnO)4 polycrystalline sintered body was used as a target.
具体的には、チャンバー内酸素分圧を例えば4 Pa、窒素分圧を1Paとする。
基板温度は25℃である。Specifically, the oxygen partial pressure in the chamber is 4 Pa, for example, and the nitrogen partial pressure is 1 Pa.
The substrate temperature is 25 ° C.
また２次イオン質量分析（SIMS）分析した場合に、薄膜の酸素と窒素の組成比が50：1程度であるのがよい。
（実施例５：アモルファスIn-Ga-Zn-O(Ti)薄膜の作製）
KrFエキシマレーザーを用いたパルスレーザー蒸着法により、InGaO3(ZnO)４組成を有する多結晶焼結体をターゲットとして、ガラス基板（コーニング社製1737）上に、In-Ga-Zn-O系アモルファス酸化物半導体薄膜を堆積させる。In addition, when the secondary ion mass spectrometry (SIMS) analysis is performed, the composition ratio of oxygen and nitrogen in the thin film is preferably about 50: 1.
(Example 5: Preparation of amorphous In-Ga-Zn-O (Ti) thin film)
An In-Ga-Zn-O amorphous material is formed on a glass substrate (Corning 1737) using a polycrystalline sintered body having an InGaO3 (ZnO)4 composition as a target by pulsed laser deposition using a KrF excimer laser. An oxide semiconductor thin film is deposited.
得られるIn-Ga-Zn-O系薄膜を、８０℃に保温した３塩化チタンの水溶液に浸漬する。 The obtained In—Ga—Zn—O-based thin film is immersed in an aqueous solution of titanium trichloride kept at 80 ° C.
その後引き上げて、空気中で３００℃でアニールする。 Thereafter, it is pulled up and annealed at 300 ° C. in air.
こうして、非晶質酸化物に添加物としてＴｉの導入が可能となる。 Thus, Ti can be introduced into the amorphous oxide as an additive.
なお、SIMSで、薄膜の表面からTiの濃度を分析した場合に、最表面で０.５％程度含有し、表面から離れるに従い、Ｔｉの濃度が低下するのがよい。 In addition, when the concentration of Ti is analyzed from the surface of the thin film by SIMS, it is preferable that the content of Ti is about 0.5% at the outermost surface, and the concentration of Ti decreases as the distance from the surface increases.
本発明に係る非晶質酸化物は、当該膜をチャネル層に用いたトランジスタはＬＣＤや有機ＥＬディスプレイのスイッチング素子として適用できる。また、プラスチックフィルムをはじめとするフレキシブル素材に半導体の薄膜を形成し、フレキシブル・ディスプレイなどのパネルをはじめ、ＩＣカードやＩＤタグなどに幅広く応用できる。 The amorphous oxide according to the present invention can be applied to a transistor using the film as a channel layer as a switching element of an LCD or an organic EL display. Moreover, a thin film of a semiconductor is formed on a flexible material such as a plastic film, and can be widely applied to panels such as flexible displays, IC cards and ID tags.
１ 基板
２ チャネル層
３ ゲート絶縁膜
４ ゲート電極（ゲート端子）
５ ドレイン電極（ドレイン端子）
６ ソース電極（ソース端子）1 Substrate 2 Channel layer 3 Gate insulating film 4 Gate electrode (gate terminal)
5 Drain electrode (drain terminal)
6 Source electrode (source terminal)
| Application Number | Priority Date | Filing Date | Title |
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| JP2005325366AJP5138163B2 (en) | 2004-11-10 | 2005-11-09 | Field effect transistor |
| Application Number | Priority Date | Filing Date | Title |
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| JP2004326687 | 2004-11-10 | ||
| JP2004326687 | 2004-11-10 | ||
| JP2005325366AJP5138163B2 (en) | 2004-11-10 | 2005-11-09 | Field effect transistor |
| Application Number | Title | Priority Date | Filing Date |
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| JP2011156724ADivisionJP2011256108A (en) | 2004-11-10 | 2011-07-15 | Amorphous oxide and field effect transistor |
| JP2011156723ADivisionJP5337849B2 (en) | 2004-11-10 | 2011-07-15 | Amorphous oxide and field effect transistor |
| JP2012148444ADivisionJP5589030B2 (en) | 2004-11-10 | 2012-07-02 | Amorphous oxide and field effect transistor |
| Publication Number | Publication Date |
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| JP2006165529Atrue JP2006165529A (en) | 2006-06-22 |
| JP2006165529A5 JP2006165529A5 (en) | 2008-02-07 |
| JP5138163B2 JP5138163B2 (en) | 2013-02-06 |
| Application Number | Title | Priority Date | Filing Date |
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| JP2005325366AActiveJP5138163B2 (en) | 2004-11-10 | 2005-11-09 | Field effect transistor |
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