JP2012517101A - 導電材料の誘電体層上へのプラズマ増強原子層堆積 - Google Patents
導電材料の誘電体層上へのプラズマ増強原子層堆積 Download PDFInfo
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- JP2012517101A JP2012517101A JP2011548001A JP2011548001A JP2012517101A JP 2012517101 A JP2012517101 A JP 2012517101A JP 2011548001 A JP2011548001 A JP 2011548001A JP 2011548001 A JP2011548001 A JP 2011548001A JP 2012517101 A JP2012517101 A JP 2012517101A
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- C—CHEMISTRY; METALLURGY
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- H01L29/40—Electrodes ; Multistep manufacturing processes therefor
- H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
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- H01L29/517—Insulating materials associated therewith the insulating material comprising a metallic compound, e.g. metal oxide, metal silicate
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- H—ELECTRICITY
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Abstract
【選択図】図1
Description
本出願は、2009年2月2日に出願された米国特許仮出願第61/149,140号の利益を主張し、当該特許はその全体の内容が本明細書において参照によって組み込まれ、本出願の一部と考慮されるべきである。本出願は、2001年3月6日に出願され、2003年3月18日に発行された米国特許第6,534,395号、2001年8月31日に出願され、2003年9月2日に発行された米国特許第6,613,695号、2001年8月31日に出願され、2003年12月9日に発行された米国特許第6,660,660号、2003年5月5日に出願され、2005年2月22日に発行された米国特許第6,858,524号、および2003年5月5日に出願され、2006年5月16日に発行された米国特許第7,045,406号に関する。上記の出願のすべての全体の内容は、参照によって本明細書に組み込まれ、本明細書の一部として考慮されるべきである。
Ar等の不活性ガスによる反応物質の分離は、反応物質間の気相反応を防止し、表面反応を自己飽和することを可能にする。反応は自己飽和するため、基板の厳しい温度制御および正確な前駆体の投与量の制御は必要ない。しかし、基板の温度は、入射ガス種が単層へ凝縮しない、または表面上で分解しないような温度が好ましい。過剰の化学物質および反応副産物を、もしあれば、次の反応化学パルスを室へ導入する前に、反応空間から除去する。不必要なガス状分子を、不活性な一掃するガスを活用して反応空間から効率よく排出することができる。一掃するガスは、過剰な分子を室外へ方向付ける。吸引ポンプを、一掃を援助するために使用することができる。
TiNプラズマバリア層を、PEALDによってTiN導電層の堆積前に、Al2O3誘電体層上にプラズマバリア層として堆積した。
チタン窒化物(TiN)バリア層を、ALDタイププロセスによって、基板上にアルミニウム酸化物(Al2O3)誘電体物質を堆積した。プロセスのステップの順序は、約375℃の反応温度で基板を含有する反応空間へ金属化合物(TiCl4)、窒素源化合物(NH3)、およびパージガス(Ar)を交互かつ順次にパルスすることを含んだ。ガスパルスおよびパージの順序は以下の通りである。
(1)TiCl4パルス、
(2)Arパージ、
(3)NH3パルス、および
(4)Arパージ。
TiN導電層を、その後、同じ反応室においてプラズマ増強ALDタイプのプロセスによって、TiNバリア層上に、直接堆積した。金属化合物(TiCl4)、水素−窒素(NH*)プラズマ、およびパージガス(Ar)を、約375℃の反応温度で基板を含有する反応空間へ交互かつ順次にパルスした。ガスパルスおよびパージの順序は、以下の通りである。
(1)TiCl4パルス、
(2)Arパージ、
(3)NH*パルス、および
(4)Arパージ。
TaCNプラズマバリア層を、PEALDによってTaCN導電層の堆積前に、熱ALDによってAl2O3誘電体層上にプラズマバリア層として堆積した。
非晶質TaCN層を、ALDタイプのプロセスによって基板上の非晶質アルミニウム酸化物(Al2O3)誘電体物質上にプラズマバリア層として堆積した。プロセスのステップの順序は、約300℃の反応温度、約1.5トルの反応圧力、および約275Wの電力で基板を含有する反応空間へタンタル化合物(TBTDET)、窒素源化合物(NH3)、およびパージガス(Ar)を交互かつ順次にパルスすることを含んだ。ガスパルスおよびパージの順序は以下の通りである。
(1)TBTDETパルス、
(2)Arパージ、
(3)NH3パルス、および
(4)Arパージ。
TaCN導電層を、その後、同じ反応室においてプラズマ増強ALDタイプのプロセスによってプラズマバリア層上に直接堆積した。TBTDET、水素(H*)プラズマ、およびパージガス(Ar)を、約375℃の反応温度で基板を含有する反応空間へ交互かつ順次に提供した。ガスパルスおよびパージの順番は、以下の通りである。
(1)TBTDETパルス、
(2)Arパージ、
(3)H*パルス、および
(4)Arパージ。
TaCNプラズマバリア層を、PEALDによってTaC導電層の堆積前に、熱ALDによってAl2O3誘電体層上にプラズマバリア層として堆積した。
非晶質TaCN層を、ALDタイプのプロセスによって基板上のガンマ相アルミニウム酸化物(Al2O3)誘電体物質上に、プラズマバリア層として堆積した。プロセスのステップの順序は、約300℃の反応温度、約1.5トルの反応圧力、および約275Wの電力で基板を含有する反応空間へタンタル化合物(TBTDET)、窒素源化合物(NH3)、およびパージガス(Ar)を交互かつ順次にパルスすることを含んだ。ガスパルスおよびパージの順序は以下の通りである。
(1)TBTDETパルス、
(2)Arパージ、
(3)NH3パルス、および
(4)Arパージ。
TaC導電層を、その後、同じ反応室においてプラズマ増強ALDタイプのプロセスによってプラズマバリア層上に直接堆積した。TBTDET、水素(H*)プラズマ、およびパージガス(Ar)を、約375℃の反応温度で基板を含有する反応空間へ交互かつ順次に提供した。ガスパルスおよびパージの順番は、以下の通りである。
(1)TBTDETパルス、
(2)Arパージ、
(3)H*パルス、および
(4)Arパージ。
Claims (41)
- 集積回路を形成するための方法であって、
原子層堆積(ALD)プロセスによって基板上の金属酸化物誘電体層上に直接プラズマバリアを堆積することであって、前記ALDプロセスは、前記基板を金属反応物質および非プラズマ反応物質と交互かつ順次に接触させることを含む、プラズマバリアを堆積することと、
プラズマ増強原子層堆積(PEALD)プロセスによって前記プラズマバリア上に直接導電層を堆積することであって、前記PEALDプロセスは前記基板を前記金属反応物質およびプラズマ反応物質と交互かつ順次に接触させることを含む、導電層を堆積することと、を含む、方法。 - 前記金属酸化物誘電体層はAl2O3を含む、請求項1に記載の方法。
- 前記プラズマバリアは、約0.5nm〜約5nmの厚みで堆積される、請求項1に記載の方法。
- 前記プラズマバリアは、前記導電層の堆積の前に非晶質金属窒化物を含む、請求項1に記載の方法。
- 前記非晶質金属窒化物のプラズマバリアの一部は、前記PEALDプロセスの間に結晶相へ変換される、請求項4に記載の方法。
- 前記金属反応物質は、Ti、Zr、Hf、V、Nb、Ta、Cr、Mo、W、Mn、Re、Fe、Co、およびNiからなる群から選択される金属を含む、請求項1に記載の方法。
- 前記金属反応物質はハロゲン化金属を含む、請求項6に記載の方法。
- 前記金属反応物質はTiCl4を含む、請求項7に記載の方法。
- 前記金属反応物質は有機金属前駆体を含む、請求項6に記載の方法。
- 前記非プラズマ反応物質は、アンモニア(NH3)およびその塩、アジ化水素(HN3)およびそのアルキル誘導体、ヒドラジン(N2H4)およびヒドラジンの塩、ヒドラジンのアルキル誘導体、1級、2級、および3級アミン、tert−ブチルアミド、CH3N3、塩酸ヒドラジン、ジメチルヒドラジン、ヒドロキシルアミン塩酸塩、メチルアミン、ジエチルアミン、およびトリエチルアミンからなる群から選択される、請求項1に記載の方法。
- 前記プラズマ反応物質は、水素または水素−窒素プラズマである、請求項1に記載の方法。
- 前記水素−窒素プラズマは、NH*、NH2 *、NH3 *、およびN*+H*からなる群から選択される、請求項11に記載の方法。
- 前記プラズマバリアは、非晶質のTaCNである、請求項1に記載の方法。
- 前記非晶質のTaCNの少なくとも一部は、前記PEALDプロセスの間に結晶性TaCNへ変換される、請求項13に記載の方法。
- 前記プラズマバリアはTiNを含む、請求項1に記載の方法。
- ゲート電極を形成する方法であって、
非プラズマ原子層堆積(ALD)プロセスによって、反応空間の基板上の誘電体層上に直接、約1〜5nmの厚みでプラズマバリア層を堆積することと、
プラズマ増強原子層堆積(PEALD)プロセスによって、前記プラズマバリア層上に直接導電材料を堆積することと、を含む、方法。 - 前記非プラズマALDプロセスは、
前記基板を第1の金属反応物質の蒸気相パルスと接触させることと、
前記反応空間から過剰の第1の金属反応物質を除去することと、
前記基板を非プラズマの第2の反応物質と接触させることと、
前記反応空間から過剰の第2の反応物質を除去することと、を含む請求項16に記載の方法。 - 前記PEALDプロセスは、
前記基板を第3の金属反応物質と接触させることと、
前記反応空間から過剰の第3の金属反応物質を除去することと、
前記基板を第4のプラズマ反応物質と接触させることと、
前記反応空間から過剰の第4の反応物質を除去することと、を含む、請求項17に記載の方法。 - 前記第1の金属反応物質および前記第3の金属反応物質は、同一である、請求項18に記載の方法。
- 前記プラズマはイン・サイチュで生成される、請求項18に記載の方法。
- 前記プラズマは遠隔で生成される、請求項18に記載の方法。
- 前記非プラズマALDプロセスおよび前記PEALDプロセスは、同じ反応空間で行われる、請求項16に記載の方法。
- 前記誘電体層は金属酸化物を含む、請求項16に記載の方法。
- 金属酸化物誘電体層上にTaCN層を含む集積回路素子を形成する方法であって、
非プラズマ原子層堆積(ALD)プロセスによって、基板上の金属酸化物誘電体層に直接非晶質TaCN層を堆積することと、
プラズマ増強ALDプロセスによって前記非晶質TaCN層上に直接TaNC層を堆積することと、を含む、方法。 - 前記非プラズマALDプロセスおよび前記PEALDプロセスにおいて、同じ金属反応物質が使用される、請求項24に記載の方法。
- 前記金属反応物質はTBTDETである、請求項25に記載の方法。
- 前記非プラズマALDプロセスは、前記基板をTBTDETおよびNH3と交互かつ順次に接触させることを含む、請求項24に記載の方法。
- 前記PEALDプロセスは、前記基板をTBTDETおよび水素プラズマ(H*)と交互かつ順次に接触させることを含む、請求項24に記載の方法。
- 誘電体層と、
第1の金属を含む前記誘電体層上のプラズマバリアであって、約0.25nm〜約1.75nmの厚みである、プラズマバリアと、
第2の金属を含む前記プラズマバリア上の導電層と、を含む、集積回路素子。 - 第1および第2の金属は同一である、請求項29に記載の集積回路素子。
- 前記プラズマバリアは、約0.125nm〜約0.875nmの厚みである、請求項29に記載の集積回路素子。
- 前記プラズマバリアは、約0.05nm〜約0.35nmの厚みである、請求項31に記載の集積回路素子。
- 前記プラズマバリアは非晶質であり、前記導電層は結晶性である、請求項29に記載の集積回路素子。
- 前記第1の金属は第1の構造を有し、前記第2の金属は第2の構造を有し、前記第1の構造および前記第2の構造は、実質的に一致する、請求項29に記載の集積回路素子。
- 前記誘電体層は、Ta2O5、TiO2、HfO2、ZrO2、Al2O3、La2O3、HfSiOx、HfZrOx、HfAlOx、およびLnAlOxからなる群から選択される、請求項29に記載の集積回路素子。
- 前記誘電体層はAl2O3である、請求項35に記載の集積回路素子。
- 前記プラズマバリアは、元素金属、導電性金属窒化物、金属炭化物−窒化物、金属炭化物、金属窒化シリコン、または金属炭化シリコンを含む、請求項29に記載の集積回路素子。
- 前記プラズマバリアは、Ti、Zr、Hf、V、Nb、Ta、Cr、Mo、W、Mn、Re、Fe、Co、Ni、Pd、Pt、Rh、Ir、Ru、およびOsからなる群のうち少なくとも1つを含む、請求項29に記載の集積回路素子。
- 前記プラズマバリアはTaCNを含む、請求項38に記載の集積回路素子。
- 前記導電層はTaCNおよびTiNからなる群から選択される、請求項29に記載の集積回路素子。
- 前記導電層はTaCNを含む、請求項40に記載の集積回路素子。
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US20140008803A1 (en) | 2014-01-09 |
US8557702B2 (en) | 2013-10-15 |
WO2010088015A3 (en) | 2010-10-21 |
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TW201601216A (zh) | 2016-01-01 |
KR101648062B1 (ko) | 2016-08-12 |
US9466574B2 (en) | 2016-10-11 |
US20100193955A1 (en) | 2010-08-05 |
TWI578398B (zh) | 2017-04-11 |
KR20150130564A (ko) | 2015-11-23 |
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WO2010088015A2 (en) | 2010-08-05 |
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