JP2014194076A - スパッタリングターゲットの製造方法、酸化物膜の成膜方法、及びトランジスタ - Google Patents
スパッタリングターゲットの製造方法、酸化物膜の成膜方法、及びトランジスタ Download PDFInfo
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- JP2014194076A JP2014194076A JP2014029808A JP2014029808A JP2014194076A JP 2014194076 A JP2014194076 A JP 2014194076A JP 2014029808 A JP2014029808 A JP 2014029808A JP 2014029808 A JP2014029808 A JP 2014029808A JP 2014194076 A JP2014194076 A JP 2014194076A
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- oxide semiconductor
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Abstract
【解決手段】、酸化インジウム、酸化金属(該金属は、アルミニウム、チタン、ガリウム、イットリウム、ジルコニウム、ランタン、セシウム、ネオジム、またはハフニウム)、及び酸化亜鉛を混合し焼成した後粉砕して、多結晶In−M−Zn酸化物(Mは、アルミニウム、チタン、ガリウム、イットリウム、ジルコニウム、ランタン、セシウム、ネオジム、またはハフニウム)粉体を形成し、多結晶In−M−Zn酸化物粉体と、酸化亜鉛粉体とを混合して混合物を形成し、混合物を成形して成形体を形成し、成形体を焼成するスパッタリングターゲットの製造方法である。
【選択図】図1
Description
本実施の形態では、スパッタリングターゲットの製造方法について説明する。
はじめに、InMO3(ZnO)m(MはAl、Ti、Ga、Y、Zr、La、Cs、Nd、またはHf、mは自然数)で表されるホモロガス化合物について説明する。InMO3(ZnO)mで表されるホモロガス化合物の結晶構造は、LuO2 −層と(FeZnm)Om+1 1+層とが規則的に交互に積み重ねられた層状構造であるLuFeO3(ZnO)mと同じ構造を有し、mが奇数のときは、R−3mの空間群を有し、mが偶数のときは、P63/mmcの空間群を有する。なお、InMO3(ZnO)m(m=1)の場合、YbFe2O4型ともいう。このような結晶構造をホモロガス構造とよぶ。なお、本明細書中では、結晶構造は六方晶表示を基本とする。
次に、CAAC−OS(C Axis Aligned Crystalline Oxide Semiconductor)について説明する。なお、ここでは、CAAC−OSの結晶構造についてのみ説明し、CAAC−OSの詳細については、実施の形態2で説明する。
次に、ホモロガス構造を有するIn−Ga−Zn酸化物膜を成膜することが可能なスパッタリングターゲットの製造方法について、図2を用いて説明する。また、ホモロガス構造を有するCAAC−OS膜を成膜することが可能なスパッタリングターゲットの製造方法について、図2を用いて説明する。
ここでは、InGaO3(ZnO)mで表されるホモロガス化合物を成膜することが可能なスパッタリングターゲットの製造方法について、図3を用いて説明する。また、InGaO3(ZnO)mで表されるホモロガス化合物であって、且つCAAC−OS膜を成膜することが可能なスパッタリングターゲットの製造方法について、図3を用いて説明する。
本実施の形態では、実施の形態1で製造されたスパッタリングターゲットを用いた酸化物膜の成膜方法について、図4乃至図18を用いて説明する。ここでは、In−M−Zn酸化物(MはAl、Ti、Ga、Y、Zr、La、Cs、Nd、またはHf)の代表例としてIn−Ga−Zn酸化物を用いて説明する。
図4(A)に示すように、成膜装置の成膜室11内に、基板ステージ12と、実施の形態1で作製されたスパッタリングターゲット13が対向して設けられている。基板ステージ12上には、基板121が設置されている。
ここで、図4(B)に示す酸化亜鉛膜125の結晶成長機構について、図11乃至図13を用いて説明する。
次に、図4乃至図9と異なる成膜方法について、図14乃至図16を用いて説明する。図14乃至図16に示す成膜方法は、成膜温度が図4乃至図9に示す成膜方法より高い。酸化亜鉛は、減圧雰囲気において、600℃以上で蒸発しやすい。このため、図4乃至図9に示す成膜方法と、図14乃至図16に示す成膜方法とを用いて形成された酸化物膜の結晶構造が異なる。
次に、図4乃至図9と異なる成膜方法について、図17及び図18を用いて説明する。図17及び図18に示す成膜方法は、成膜温度が図4乃至図9に示す成膜方法より低い。
本実施の形態においては、結晶性の高い酸化物膜を成膜するための成膜装置について、図19及び図20を用いて説明する。
本実施の形態では、本発明の一態様である半導体装置及びその作製方法について図面を参照して説明する。
本実施の形態に示すトランジスタ250において、必要に応じて、基板211及びゲート電極215の間に下地絶縁膜を設けることができる。下地絶縁膜の材料としては、酸化シリコン、酸化窒化シリコン、窒化シリコン、窒化酸化シリコン、酸化ガリウム、酸化ハフニウム、酸化イットリウム、酸化アルミニウム、酸化窒化アルミニウム等がある。なお、下地絶縁膜の材料として、窒化シリコン、酸化ガリウム、酸化ハフニウム、酸化イットリウム、酸化アルミニウム等を用いることで、基板211から不純物、代表的にはアルカリ金属、水、水素等の酸化物半導体膜218への拡散を抑制することができる。
本実施の形態に示すトランジスタ250において、必要に応じて、ゲート絶縁膜217を積層構造とすることができる。
本実施の形態に示すトランジスタ250に設けられる一対の電極221、222として、タングステン、チタン、アルミニウム、銅、モリブデン、クロム、またはタンタル単体若しくは合金等の酸素と結合しやすい導電材料を用いることが好ましい。この結果、酸化物半導体膜218に含まれる酸素と一対の電極221、222に含まれる導電材料とが結合し、酸化物半導体膜218において、酸素欠損領域が形成される。また、酸化物半導体膜218に一対の電極221、222を形成する導電材料の構成元素の一部が混入する場合もある。これらの結果、図24に示すように、酸化物半導体膜218において、一対の電極221,222と接する領域近傍に、低抵抗領域220a、220bが形成される。低抵抗領域220a、220bは、一対の電極221、222に接し、且つゲート絶縁膜217と、一対の電極221、222の間に形成される。低抵抗領域220a、220bは、導電性が高いため、酸化物半導体膜218と一対の電極221、222との接触抵抗を低減することが可能であり、トランジスタのオン電流を増大させることが可能である。
本実施の形態に示すトランジスタ250の作製方法において、一対の電極221、222を形成した後、酸化物半導体膜218を酸素雰囲気で発生させたプラズマに曝し、酸化物半導体膜218に酸素を供給することができる。酸化雰囲気としては、酸素、オゾン、一酸化二窒素、二酸化窒素等の雰囲気がある。さらに、当該プラズマ処理において、基板211側にバイアスを印加しない状態で発生したプラズマに酸化物半導体膜218を曝すことが好ましい。この結果、酸化物半導体膜218にダメージを与えず、且つ酸素を供給することが可能であり、酸化物半導体膜218に含まれる酸素欠損量を低減することができる。また、エッチング処理により酸化物半導体膜218の表面に残存する不純物、例えば、フッ素、塩素等のハロゲン等を除去することができる。
本実施の形態では、実施の形態4と比較して、酸化物半導体膜の欠陥量をさらに低減することが可能なトランジスタを有する半導体装置について図面を参照して説明する。本実施の形態で説明するトランジスタは、実施の形態4と比較して、酸化物半導体膜、及び酸化物半導体膜に接する酸化物を有する多層膜を有する点が異なる。
本実施の形態では、実施の形態4及び実施の形態5と異なる構造のトランジスタについて、図26を用いて説明する。本実施の形態に示すトランジスタ280は、酸化物半導体膜を介して対向する複数のゲート電極を有することを特徴とする。
本実施の形態では、実施の形態4乃至実施の形態6と異なる構造のトランジスタについて、図27を用いて説明する。
本実施の形態では、実施の形態4乃至実施の形態7と異なる構造のトランジスタについて、図28を用いて説明する。
本実施の形態では、トップゲート構造のトランジスタおよびその作製方法について説明する。
上記実施の形態で開示された金属膜、酸化物半導体膜、無機絶縁膜など様々な膜はスパッタ法やプラズマCVD(Chemical Vapor Deposition)法により形成することができるが、他の方法、例えば、熱CVD法により形成してもよい。熱CVD法の例としてMOCVD(Metal Organic Chemical Vapor Deposition)法やALD(Atomic Layer Deposition)法を使っても良い。
はじめに、試料の作製方法について説明する。
次に、試料1乃至試料10において、In−Ga−Zn酸化物膜及び試料1乃至試料10の成膜に用いたスパッタリングターゲットに含まれる金属元素の原子数比をX線光電子分光法(X−ray Photoelectron Spectroscopy:)分析によって定量化した。次に、Inに対するGaの原子数比、及びInに対するZnの原子数比をそれぞれ、図32に示す。なお、図32において、( )内は、成膜に用いたスパッタリングターゲットに含まれるIn:Ga:Znの原子数比を示す。
次に、試料1乃至試料10に含まれるIn−Ga−Zn酸化物膜の結晶構造について、X線回折(X−ray Diffraction:XRD)測定を行った。なお、試料1乃至試料10において、In−Ga−Zn酸化物膜を成膜するためのスパッタリングガスとして、流量比が酸素:アルゴン=1:2の混合ガス、または酸素のみの2条件を用いて試料を作製した。
次に、試料2及び試料3の断面の原子配列を、透過型電子顕微鏡(Transmission Electron Microscope:TEM)を用いて観察して得られた断面観察像(明視野像)を図37に示す。ここでは、加速電圧300kVとし、倍率を800万倍として、各試料におけるIn−Ga−Zn酸化物膜の表面近傍を観察した。また、図37において、( )内はスパッタリングターゲットに含まれるIn、Ga、Znの組成を表す。
次に、試料2及び試料3断面の原子配列を高角散乱環状暗視野走査透過電子顕微鏡法(HAADF−STEM:High−Angle Annular Dark Field Scanning Transmission Electron Microscopy)を用いて観察して得られた断面観察像を図38に示す。ここでは、加速電圧200kVとし、倍率を800万倍として、各試料におけるIn−Ga−Zn酸化物膜を観察した。
次に、実施例1で作製した試料1乃至試料4、試料6、試料7、及び試料10に形成されるIn−Ga−Zn酸化物膜の伝電帯下端Ecと価電子帯上端Evとのエネルギー差、即ちエネルギーギャップEgを分光エリプソメータを用いて測定した。また、紫外線光電子分光分析(UPS:Ultraviolet Photoelectron Spectroscopy)を行って、真空準位Evacと価電子帯上端Evとのエネルギー差、即ちイオン化ポテンシャルIpを測定した。次に、イオン化ポテンシャルIpとエネルギーギャップEgとの差を算出することで、真空準位Evacと伝電帯下端Ecとのエネルギー差、即ち電子親和力χを算出した。この結果、得られたバンドダイヤグラムを図39に示す。
次に、試料11乃至試料13の断面の原子配列を、透過型電子顕微鏡(Transmission Electron Microscope:TEM)を用いて観察して得られた断面観察像(明視野像)を図41乃至図43に示す。ここでは、加速電圧300kVとし、倍率を200万倍、400万倍として、各試料におけるIn−Ga−Zn酸化物膜を観察した。
Claims (7)
- 酸化インジウム、酸化金属(前記金属は、アルミニウム、チタン、ガリウム、イットリウム、ジルコニウム、ランタン、セシウム、ネオジム、またはハフニウム)、及び酸化亜鉛を混合し焼成した後粉砕して、多結晶In−M−Zn酸化物(前記Mは、アルミニウム、チタン、ガリウム、イットリウム、ジルコニウム、ランタン、セシウム、ネオジム、またはハフニウム)粉体を形成し、
前記多結晶In−M−Zn酸化物粉体と、酸化亜鉛粉体とを混合して混合物を形成し、
前記混合物を成形して成形体を形成し、
前記成形体を焼成することを特徴とするスパッタリングターゲットの製造方法。 - 請求項1において、前記スパッタリングターゲットに含まれる前記M(Mは、アルミニウム、チタン、ガリウム、イットリウム、ジルコニウム、ランタン、セシウム、ネオジム、またはハフニウム)より、前記スパッタリングターゲットに含まれる前記亜鉛の組成の方が大きいことを特徴とするスパッタリングターゲットの製造方法。
- 請求項1または請求項2において、前記多結晶In−M−Zn酸化物粉体はホモロガス化合物であることを特徴とするスパッタリングターゲットの製造方法。
- インジウム、M(Mは、アルミニウム、チタン、ガリウム、イットリウム、ジルコニウム、ランタン、セシウム、ネオジム、またはハフニウム)、及び亜鉛を有し、前記Mより前記亜鉛の組成が大きいスパッタリングターゲットを用いたスパッタリング法により、In−M−Zn酸化物(Mは、アルミニウム、チタン、ガリウム、イットリウム、ジルコニウム、ランタン、セシウム、ネオジム、またはハフニウム)を成膜することを特徴とする酸化物膜の成膜方法。
- 請求項4において、前記In−M−Zn酸化物(Mは、アルミニウム、チタン、ガリウム、イットリウム、ジルコニウム、ランタン、セシウム、ネオジム、またはハフニウム)は、ホモロガス構造を有することを特徴とする酸化物膜の成膜方法。
- 請求項4または請求項5において、前記In−M−Zn酸化物(Mは、アルミニウム、チタン、ガリウム、イットリウム、ジルコニウム、ランタン、セシウム、ネオジム、またはハフニウム)は、前記Mの組成に対する前記Znの組成の比が0.5より大きいことを特徴とする酸化物膜の成膜方法。
- 請求項4乃至請求項6のいずれか一項に記載の酸化物を用いて形成したトランジスタ。
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US20230260785A1 (en) | 2023-08-17 |
US11139166B2 (en) | 2021-10-05 |
JP6377803B2 (ja) | 2018-08-22 |
JP2022123009A (ja) | 2022-08-23 |
US20140241978A1 (en) | 2014-08-28 |
US20200144059A1 (en) | 2020-05-07 |
US20160160342A1 (en) | 2016-06-09 |
US20170178904A1 (en) | 2017-06-22 |
US20220020586A1 (en) | 2022-01-20 |
JP2017145510A (ja) | 2017-08-24 |
JP7089001B2 (ja) | 2022-06-21 |
US11967505B2 (en) | 2024-04-23 |
JP2021036595A (ja) | 2021-03-04 |
JP6141777B2 (ja) | 2017-06-07 |
US10522347B2 (en) | 2019-12-31 |
US11637015B2 (en) | 2023-04-25 |
JP2018195842A (ja) | 2018-12-06 |
US9267199B2 (en) | 2016-02-23 |
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