JP7050468B2 - 酸化物薄膜の堆積 - Google Patents
酸化物薄膜の堆積 Download PDFInfo
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- JP7050468B2 JP7050468B2 JP2017222532A JP2017222532A JP7050468B2 JP 7050468 B2 JP7050468 B2 JP 7050468B2 JP 2017222532 A JP2017222532 A JP 2017222532A JP 2017222532 A JP2017222532 A JP 2017222532A JP 7050468 B2 JP7050468 B2 JP 7050468B2
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
- H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
- H01L21/28512—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table
- H01L21/2855—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table by physical means, e.g. sputtering, evaporation
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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Description
集積回路は、現在、様々な材料の層が半導体基材上の所定の配置で順次構築される精巧なプロセスによって製造されている。
選択性は、[(第1の表面上の堆積)-(第2の表面上の堆積)]/(第1の表面上の堆積)によって計算される百分率として与えられ得る。堆積は、様々な方法のいずれかで測定され得る。いくつかの実施形態では、堆積は、堆積した材料の測定された厚さとして与えられてもよい。いくつかの実施形態では、堆積は、堆積した材料の測定量として与えられてもよい。
原子層堆積(ALD)タイプのプロセスは、前駆体化学物質又は反応物質の制御された自己制御表面反応に基づいている。気相反応は、基材を前駆体と交互に順次接触させることによって回避される。気相反応物質は、例えば、過剰な反応物質及び/又は反応物質副生成物を反応物質パルス間に対象の基材の表面から除去することにより、基材の表面上で互いに分離される。いくつかの実施形態では、1つ又は複数の基材の表面は、2つ以上の気相前駆体又は反応物質と交互に順次接触する。基材の表面を気相反応物質と接触させることは、反応物質蒸気が限られた時間、基材の表面と接触することを意味する。換言すれば、基材の表面が各気相の反応物質に限られた時間曝されると理解され得る。
工程120において、基材を第1の気相前駆体と接触させることと、
工程130において、任意の過剰な第1の前駆体及び反応副生成物がある場合には、これらを基材から除去することと、
工程140において、基材を分子状酸素(O2)を含む第2の気相前駆体と接触させるために、基材の表面に分子状酸素(O2)を供給することと、
工程150において、分子状酸素及び/又は任意の気体副生成物を含む任意の過剰の第2の前駆体を基材から除去することと、
工程170において、基材上に所望の厚さの酸化物材料が形成されるまで、工程160で接触させる工程及び除去する工程を任意に繰り返すことと、を含む少なくとも1つのサイクルを含む周期的熱蒸着堆積プロセス100により基材上に選択的に堆積される。
基材を第1の気相前駆体と接触させることと、
基材を第1の気相前駆体と接触させた後、基材をパージガス又は真空に曝すことと、
基材を分子状酸素(O2)を含む第2の気相前駆体と接触させるために、基材の表面に分子状酸素(O2)を供給することと、
基材を分子状酸素と接触させた後、基材をパージガス又は真空に曝すことと、
基材上に所望の厚さの酸化物材料が形成されるまで、接触させる工程及び除去する工程を任意に繰り返すことと、を含む。
工程220において、基材をマグネシウムを含む第1の気相前駆体と接触させることと、
工程230において、任意の過剰な、マグネシウムを含む第1の気相前駆体及び反応副生成物がある場合には、これらを表面から除去することと、
工程240において、基材を分子状酸素を含む第2の気相前駆体と接触させるために、基材の表面に分子状酸素(O2)を供給することと、
工程250において、分子状酸素及び/又は任意の気体副生成物を含む任意の過剰の第2の前駆体を表面から除去することと、
工程270において、基材の表面上に所望の厚さの酸化マグネシウム薄膜が形成されるまで、工程260で接触させる工程及び除去する工程を任意に繰り返すことと、を含む少なくとも1サイクルを含む周期的堆積プロセス200により、基材の表面上に堆積される。
工程320において、基材をランタンを含む第1の気相前駆体と接触させることと、
工程330において、任意の過剰な第1の前駆体及び反応副生成物がある場合には、これらを基材から除去することと、
工程340において、基材を分子状酸素を含む第2の気相前駆体と接触させるために、基材の表面に分子状酸素(O2)を供給することと、
工程350において、分子状酸素及び任意の気体副生成物を含む任意の過剰の第2の前駆体を基材から除去することと、
工程370において、基材の第1の表面上に所望の厚さの酸化物材料が形成されるまで、工程360で接触させる工程及び除去する工程を任意に繰り返すことと、を含む少なくとも1サイクルを含むADLタイプの堆積プロセス300により、基材上に選択的に堆積される。
工程420において、基材をハフニウムを含む第1の気相前駆体と接触させることと、
工程430において、任意の過剰な第1の前駆体及び反応副生成物がある場合には、これらを基材から除去することと、
工程440において、基材を分子状酸素を含む第2の気相前駆体と接触させるために、基材の表面に分子状酸素(O2)を供給することと、
工程450において、分子状酸素及び任意の気体副生成物を含む任意の過剰の第2の前駆体を基材から除去することと、
工程470において、基材の第1の表面上に所望の厚さの酸化物材料が形成されるまで、工程460で接触させる工程及び除去する工程を任意に繰り返すことと、を含む少なくとも1サイクルを含むADLタイプの堆積プロセス400により、基材上に選択的に堆積される。
いくつかの異なる第1の前駆体を、本明細書に記載の選択的堆積プロセスで使用し得る。いくつかの実施形態では、第1の前駆体は金属を含み得る。いくつかの実施形態では、第1の前駆体は、少なくとも1つのアルキル配位子、例えばC1-C4アルキル配位子等、を含み得る。いくつかの実施形態では、第1の前駆体は、有機金属化合物又は金属有機化合物を含み得る。いくつかの実施形態では、第1の前駆体は、少なくとも1つのシクロペンタジエニル(Cp)配位子を含み得る。いくつかの実施形態では、第1の前駆体は、ホルムアミジネート又はアミジネート化合物を含み得る。いくつかの実施形態では、第1の前駆体はβ-ジケトネート化合物を含み得る。いくつかの実施形態では、第1の前駆体は、ジアルキルアミノ化合物等のアルキルアミノ化合物を含み得る。いくつかの実施形態では、第1の前駆体は、-NMe2、-NEt2又は-NEtMe等のアルキルアミノ配位子を含み得る。
MgL2 (I)
(式中、Mgはマグネシウム、及び各Lは炭化水素基であるように互いに独立して選択され得る)を有する。
Mg(R1R2R3R4R5Cp)2 (II)
(式中、R1基のそれぞれ、R2基のそれぞれ、R3基のそれぞれ、R4基のそれぞれ、及びR5基のそれぞれは、水素、又は置換若しくは非置換のアルキル基であるように互いに独立して選択され得る)を有する。
(Cp)xLa (III);
(Cp)xLyLa (IV);
(Cp)xWnLa (V);
(CP)xLyWnLa (VI);
Laはランタン、Cpはシクロペンタジエニル又はシクロオクタジエニル基であり、化学式I~IVのCp基は互いに同じであっても他のものと異なっていてもよい。xはCp配位子の数を示し、1からLaの酸化状態までの整数である。シクロオクタジエンは、通常、Codと短縮されるが、ここでは、シクロペンタジエニル及びシクロオクタジエニルの両方に対して単一の一般的な略語Cpを使用することにより表記を簡略化することとする。
Lyはその1つ又は複数の原子から金属に結合する中性付加物配位子であり、yは結合配位子の数を表す。
WはCpではない1価の他の配位子であり、nは配位子の数を示す。いくつかの実施形態では、Wはアミジネート又はホルムアミジネートである。いくつかの実施形態では、Wはβ-ジケトネート又はその対応する硫黄若しくは窒素化合物、ハロゲン化物、アミド、アルコキシド、カルボキシレート又はシッフ塩基である。
(i)炭化水素、
(ii)酸素を含有する炭化水素、
(iii)窒素を含有する炭化水素、
(iv)硫黄を含有する炭化水素、
(v)リンを含有する炭化水素、
(vi)ヒ素を含有する炭化水素、
(vii)セレンを含有する炭化水素、及び/又は
(viii)テルルを含有する炭化水素、である。
(a)アミン又はポリアミン、
(b)ビピリジン、
(c)化学図式:
(d)エーテル又はチオエーテル、である。
Cp’RmHa-m (VII)
(式中、aが8である場合mは0~8の整数であり、aが5である場合、mは0~5の整数であり、
Cp’は、縮合した又は単離したシクロペンタジエニル若しくはシクロオクタジエニルであり、
Rは、互いに独立して選択された1~6個の炭素原子を含む炭化水素フラグメント、例えばC1-C6炭化水素である)を有する。
(R1R2R3R4R5Cp)x-MR0 z-(R6)y (VIII)
(式中、Mは、Mg、Sr、Ba、Sc、Y、及びランタニドからなる群から選択される金属であり、
ここで、R0基のそれぞれ、R1基のそれぞれ、R2基のそれぞれ、R3基のそれぞれ、R4基のそれぞれ、及びR5基のそれぞれは、互いに独立して、
i. 水素、
ii. 互いに独立して置換又は非置換の、直鎖及び分枝鎖C1-C6アルキル、アルケニル並びにアルキニル基、
iii. アリール、フェニル、シクロペンタジエニル、アルキルアリール、及びハロゲン化炭素環式基等の炭素環式基、及び
iv. 複素環式基、から選択されることができ、
ここで、R6は、互いに独立して、
i. 水素、
ii. 互いに独立して置換又は非置換の、直鎖及び分枝鎖C1-C6アルキル、アルケニル並びにアルキニル基、
iii. アリール、フェニル、シクロペンタジエニル、アルキルアリール、ハロゲン化炭素環基等の炭素環式基、
iv. 複素環式基、及び、
v. NR1R2、から選択され、並びに、
ここで、x≧1、y≧1、及びz≧0である)、により記載され得る。
(R1R2R3R4R5Cp)x-MR0 z-(NR1R2)y (IX)
(式中、Mは、Mg、Sr、Ba、Sc、Y、又はランタニドからなる群から選択される金属であり、
ここで、R0基のそれぞれ、R1基のそれぞれ、R2基のそれぞれ、R3基のそれぞれ、R4基のそれぞれ、及びR5基のそれぞれは、互いに独立して、
i. 水素、
ii. 互いに独立して置換又は非置換の、直鎖及び分枝鎖C1-C6アルキル、アルケニル並びにアルキニル基、
iii. アリール、フェニル、シクロペンタジエニル、アルキルアリール、及びハロゲン化炭素環式基等の炭素環式基、及び
iv. 複素環式基、から選択され、並びに、
ここで、x≧1、y≧1、及びz≧0である)、により記載されるように、窒素を介して金属と結合する少なくとも1つの配位子を含む。
Rは、互いに独立して置換若しくは非置換の、任意の直鎖及び分枝鎖C1-C6アルキル、アルケニル又はアルキニル基であり、Rは、2つの架橋窒素原子にアルキル、アルケニル及びアルキニル基の任意の位置に結合し得る。
ここで、R0基のそれぞれ、R1基のそれぞれ、R2基のそれぞれ、R3基のそれぞれ、R4基のそれぞれ、及びR5基のそれぞれは、互いに独立して、
i. 水素、
ii. 互いに独立して置換又は非置換の、直鎖及び分枝鎖C1-C6アルキル、アルケニル並びにアルキニル基、
iii. アリール、フェニル、シクロペンタジエニル、アルキルアリール、及びハロゲン化炭素環式基等の炭素環式基、及び
iv. 複素環式基、から選択され、並びに、
ここで、x≧1、y≧1、及びz≧0である)、により表される。
ここで、R0基のそれぞれ、R1基のそれぞれ、R2基のそれぞれ、R3基のそれぞれ、R4基のそれぞれ、及びR5基のそれぞれは、互いに独立して、
i. 水素、
ii. 互いに独立して置換又は非置換の、直鎖及び分枝鎖C1-C6アルキル、アルケニル並びにアルキニル基、
iii. アリール、フェニル、シクロペンタジエニル、アルキルアリール、及びハロゲン化炭素環式基等の炭素環式基、及び
iv. 複素環式基、から選択され、並びに、
ここで、x≧1、y≧1、及びz≧0である)、により表される。
ここで、R0基のそれぞれ、R1基のそれぞれ、R2基のそれぞれ、R3基のそれぞれ、R4基のそれぞれ、及びR5基のそれぞれは、互いに独立して、
i. 水素、
ii. 互いに独立して置換又は非置換の、直鎖及び分枝鎖C1-C6アルキル、アルケニル並びにアルキニル基、
iii. アリール、フェニル、シクロペンタジエニル、アルキルアリール、及びハロゲン化炭素環式基等の炭素環式基、及び
iv. 複素環式基、から選択され、並びに、
ここで、x≧1、y≧1、及びz≧0である)、により表される。
i. 水素、
ii. 互いに独立して置換又は非置換の、直鎖及び分枝鎖C1-C6アルキル、アルケニル並びにアルキニル基、
iii. アリール、フェニル、シクロペンタジエニル、及びアルキルアリール等の炭素環式基、並びに、
iv. 複素環式基、から選択され得る。
第2の配位子
マグネシウムを含む第1の前駆体としてビス(シクロペンタジエニル)マグネシウム(Mg(Cp)2)、及び第2の前駆体として分子状酸素(O2)を用いて、いくつかの実施形態によるALDタイプのプロセスにより、酸化マグネシウム(MgO)薄膜を堆積が行われた。堆積温度は約250℃であり、各サンプル毎に堆積サイクル数を変えた。
酸化マグネシウム(MgO)の堆積は2つの試験基材片、自然酸化シリコン表面を有する参照シリコン試験基材片、及び2つのSAMシリコン試験基材片上で行われ、各基材は、自然酸化シリコン表面の一部の上に形成されたSAM層を含む表面を有していた。
酸化ハフニウム(HfO2)の堆積は、自然酸化シリコン表面を有する第1のシリコン試験基材片上と、自然酸化シリコン表面の一部の上に形成されたSAM層を含む表面を有する第2のシリコン試験基材片上で行われた。試験基材片は、いくつかの実施形態による、及び本明細書に記載の、第1前駆体としてTEMAH及び第2の前駆体としてO2を含むALDハフニウム酸化物堆積プロセスで処理された。堆積温度は285℃であった。
Claims (19)
- 第2の表面に対して基材の第1の表面上に選択的に薄膜を堆積する方法であって、前記方法は、
前記基材を第1の気相前駆体と接触させることと、
前記基材を前記第1の気相前駆体と接触させた後、前記基材をパージガス又は真空に曝すことと、
前記基材をパージガス又は真空に曝した後、前記基材を分子状酸素(O2)を含む第2の気相前駆体と接触させることと、ここで、前記第2の気相前駆体は、酸素を含む追加の化合物を含まない、を含み、
前記薄膜は絶縁金属酸化物を含み、また、
前記第2の表面は有機種を含む、方法。 - 前記第1の表面は、前記第2の表面とは実質的に異なる材料である、請求項1に記載の方法。
- 前記基材を分子状酸素を含む前記第2の気相前駆体と接触させた後、前記基材をパージガス又は真空に曝すことを更に含む、請求項1に記載の方法。
- 前記第2の表面は、自己組織化単分子膜(SAM)を含む、請求項1に記載の方法。
- 前記第2の表面上に堆積された前記薄膜の厚さ又は量は、前記基材の前記第1の表面上に選択的に堆積された前記薄膜の厚さ又は量の約50%未満である、請求項1に記載の方法。
- 前記第1の気相前駆体は有機金属化合物を含む、請求項1に記載の方法。
- 前記第1の気相前駆体は、マグネシウム、ランタン、ハフニウム、ジルコニウム、アルミニウム、イットリウム、スカンジウム、ランタニド、又は遷移金属を含む、請求項6に記載の方法。
- 前記第1の気相前駆体は、ビス(シクロペンタジエニル)マグネシウム(Mg(Cp)2)を含む、請求項7に記載の方法。
- 前記第1の気相前駆体は、ランタンホルムアミジネート(La(FAMD)3)を含む、請求項7に記載の方法。
- 前記第1の気相前駆体は、テトラメチルエチルアルキルアミドハフニウム(TEMAH)を含む、請求項7に記載の方法。
- 前記基材を分子状酸素を含む前記第2の気相前駆体と接触させることは、前記第2の表面を分解も酸化もさせない、請求項1に記載の方法。
- 前記薄膜は、100℃~500℃の温度で堆積される、請求項1に記載の方法。
- 基材の表面上に酸化マグネシウム、酸化ランタン、又は酸化ハフニウム薄膜を選択的に堆積させる方法であって、前記方法は、
前記基材をマグネシウム、ランタン、又はハフニウムを含む第1の気相前駆体と接触させることと、
前記基材をマグネシウム、ランタン、又はハフニウムを含む前記第1の気相前駆体と接触させた後、前記基材をパージガス又は真空に曝すことと、
前記基材をパージガス又は真空に曝した後、前記基材を分子状酸素(O2)を含む第2の気相前駆体と接触させることと、ここで、分子状酸素を含む前記第2の気相前駆体は、酸素を含む他の化合物を全く含まない、
ここで、前記基材は、第1の表面及び第2の実質的に異なる表面とを含み、酸化マグネシウム、酸化ランタン、又は酸化ハフニウムが、前記第2の実質的に異なる表面に対して前記基材の前記第1の表面上に選択的に堆積される、
を含む、方法。 - 前記基材を前記第2の気相前駆体と接触させた後、前記基材をパージガス又は真空に曝すことを更に含む、請求項13に記載の方法。
- 前記基材の前記第2の表面は、有機種を有する、請求項に13記載の方法。
- マグネシウム、ランタン、又はハフニウムを含む前記第1の気相前駆体は、少なくとも1つのシクロペンタジエニル(Cp)配位子を含む、請求項13に記載の方法。
- 前記酸化マグネシウム、酸化ランタン、又は酸化ハフニウム薄膜は、前記基材の第2の表面に対して前記基材の第1の表面上に選択的に堆積され、前記第2の表面は有機材料を含む、請求項13に記載の方法。
- 前記第2の表面は、自己組織化単分子膜(SAM)を含む、請求項13に記載の方法。
- 前記第2の表面は、ポリマーを含む、請求項13に記載の方法。
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