JP2000054134A - 原子層蒸着法を用いた薄膜製造方法 - Google Patents
原子層蒸着法を用いた薄膜製造方法Info
- Publication number
- JP2000054134A JP2000054134A JP11034413A JP3441399A JP2000054134A JP 2000054134 A JP2000054134 A JP 2000054134A JP 11034413 A JP11034413 A JP 11034413A JP 3441399 A JP3441399 A JP 3441399A JP 2000054134 A JP2000054134 A JP 2000054134A
- Authority
- JP
- Japan
- Prior art keywords
- reactant
- thin film
- substrate
- chamber
- producing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000010409 thin film Substances 0.000 title claims abstract description 71
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 45
- 238000007740 vapor deposition Methods 0.000 title abstract 2
- 239000000376 reactant Substances 0.000 claims abstract description 180
- 239000000758 substrate Substances 0.000 claims abstract description 57
- 239000000126 substance Substances 0.000 claims abstract description 23
- 239000007787 solid Substances 0.000 claims abstract description 18
- 238000006467 substitution reaction Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 71
- 239000010408 film Substances 0.000 claims description 39
- 238000002347 injection Methods 0.000 claims description 27
- 239000007924 injection Substances 0.000 claims description 27
- 239000002131 composite material Substances 0.000 claims description 12
- 150000004767 nitrides Chemical class 0.000 claims description 11
- 238000010926 purge Methods 0.000 claims description 10
- 239000003446 ligand Substances 0.000 claims description 7
- 238000005086 pumping Methods 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 102100032047 Alsin Human genes 0.000 claims description 3
- 101710187109 Alsin Proteins 0.000 claims description 3
- 229910004200 TaSiN Inorganic materials 0.000 claims description 3
- 229910008807 WSiN Inorganic materials 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910002367 SrTiO Inorganic materials 0.000 claims description 2
- 229910008482 TiSiN Inorganic materials 0.000 claims description 2
- -1 YaThreeNFive Chemical compound 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims description 2
- QRXWMOHMRWLFEY-UHFFFAOYSA-N isoniazide Chemical compound NNC(=O)C1=CC=NC=C1 QRXWMOHMRWLFEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910004121 SrRuO Inorganic materials 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 239000007789 gas Substances 0.000 description 23
- 238000000231 atomic layer deposition Methods 0.000 description 20
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000010410 layer Substances 0.000 description 9
- 239000011261 inert gas Substances 0.000 description 6
- 239000002356 single layer Substances 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 241001676573 Minium Species 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000011549 displacement method Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910008484 TiSi Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 238000003681 chemical substitution reactions by method Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
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- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
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- H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
- H01L21/0228—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
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- 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
- 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—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 method of coating
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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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
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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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—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 method of coating
- C23C16/455—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 method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45561—Gas plumbing upstream of the reaction chamber
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Abstract
論的な薄膜を得ることができる薄膜製造方法。 【解決手段】基板がローディングされたチャンバに第1
反応物を注入して基板上に第1反応物を化学吸着させ、
チャンバをパージしたりポンピングして(Pして)、化
学吸着された第1反応物上に物理吸着された第1反応物
を取り除き、チャンバに再び第1反応物を注入して基板
上に第1反応物を稠密するように化学吸着させ、Pして
稠密するように化学吸着された第1反応物上に物理吸着
された第1反応物を取り除き、チャンバに第2反応物を
注入して基板の表面に化学吸着させ、Pして稠密するよ
うに化学吸着された第1反応物及び第2反応物上に物理
吸着された第2反応物を取り除き、チャンバに再び第2
反応物を注入して基板上に第2反応物を稠密するように
吸着させて化学置換によって原子単位厚さに固体薄膜を
形成する方法。
Description
り、特に原子層蒸着法(Atomic Layer Deposition:以
下、"ALD法"と称する)による薄膜製造方法に関する。 【0002】 【従来の技術および発明が解決しようとする課題】一般
的に、薄膜は半導体素子の誘電体(dielectric)、液晶
表示素子の透明な導電体(transparent conductor)及
び電子発光薄膜表示素子の保護層等で多様に使われる。
前記薄膜は蒸気法、化学気相蒸着法、ALD法等によっ
て形成される。 【0003】この中から、前記ALD法は表面調節工程
であり2次元的な層間(layer by layer)蒸着を用い
る。このようなALD法は吸着が常に表面運動領域でな
されるので非常に優秀な段差被覆性を有する。また、熱
分解ではない各反応物の周期的供給を通した化学置換で
反応物を分解するので膜密度が高くて優秀な化学量論的
な膜を得ることができる。また、工程中発生する化学置
換による副産物は全て気体であるから除去が容易でチャ
ンバの洗浄が容易であり、温度のみ工程変数であるから
工程調節と維持が容易である。 【0004】しかし、従来のALD法は基板表面に反応
物を十分に吸着させられなくて薄膜内にピンホールなど
の欠陥が発生して薄膜の物理的特性、例えば膜密度が落
ちる問題点がある。また、従来のALD法は化学配位子
などが完全に取り除かれなくて優秀な化学量論的な薄膜
を得られない問題点がある。 【0005】 【発明が解決しようとする課題】本発明は前記のような
問題点に鑑みてなされたものであり、本発明の目的は、
原子層蒸着法で膜密度が高くて、優秀な化学量論的な薄
膜を得ることができる薄膜製造方法を提供することにあ
る。 【0006】 【課題を解決するための手段】前記のような目的を達成
するための本発明による薄膜製造方法は、基板がローデ
ィングされたチャンバに第1反応物を注入して前記基板
上に前記第1反応物を化学吸着させる段階を含む。続い
て、前記化学吸着された第1反応物上に物理吸着された
第1反応物を取り除く。次に、前記チャンバに再び前記
第1反応物を注入して前記基板上に稠密するように化学
吸着させた後、前記稠密するように化学吸着された第1
反応物上に物理吸着された第1反応物を取り除く。続い
て、前記チャンバに第2反応物を注入して前記基板の表
面に化学吸着させた後、前記稠密するように化学吸着さ
れた第1反応物と第2反応物上に物理吸着された第2反
応物を取り除く。次に、前記チャンバに再び前記第2反
応物を注入して前記基板上に前記第2反応物を稠密する
ように吸着させて化学置換によって固体薄膜を形成す
る。 【0007】本発明の薄膜製造方法は前記第2反応物を
稠密するように吸着させた後、物理吸着された第2反応
物と前記化学置換時生成される残留物を取り除くことも
できる。ここに、前記した物理吸着された反応物を取り
除くには、チャンバを不活性ガス等でパージしたりまた
は減圧にポンピングすることにより達成することができ
る。そして、前記第1反応物注入から物理吸着された第
1反応物の除去を順次的に2回以上反復して実施でき
る。また、前記第2反応物注入から物理吸着された第2
反応物及び残留物の除去を順次的に2回以上反復して実
施することもできる。前記基板は(100)のシリコン
基板で構成できる。前記第1反応物及び第2反応物は各
々前記固体薄膜を構成する元素と化学配位子で構成され
る。 【0008】前記固体薄膜は単原子、単原子酸化物、複
合酸化物、単原子窒化物または複合窒化物である。 【0009】前記単原子の例としてはMo、Al、C
u、Ti、Ta、Pt、Ru、Rh、Ir、W又はAg
を挙げることができる。前記単原子酸化物の例としては
Al2O3、TiO2、Ta2O5、ZrO2、HfO2、N
b2O5、CeO2、Y2O3、SiO2、In2O3、RuO
2又はIrO2を挙げることができる。 【0010】前記複合酸化物の例としてはSrTi
O3、PbTiO3、SrRuO3、CaRuO3、(B
a、Sr)TiO3、Pb(Zr、Ti)O3、(Pb、
La)(Zr、Ti)O3、(Sr、Ca)RuO3、S
nがドーピングされたIn2 O3、Feがドーピングさ
れたIn2O3又はZrがドーピングされたIn2O3を挙
げることができる。前記単原子窒化物の例としてはSi
N、NbN、ZrN、TiN、TaN、Ya3N5、Al
N、GaN、WN又はBNを挙げることができる。前記
複合窒化物の例としてはWBN、WSiN、TiSi
N、TaSiN、AlSiN又はAlTiNを挙げるこ
とができる。 【0011】このように本発明は第1反応物及び第2反
応物を稠密するように吸着させて不純物を、例えば減圧
にポンピングまたは不活性ガス等のパージによって完全
に取り除くので膜密度が高くて優秀な化学量論的な薄膜
を得ることができる。 【0012】 【発明の実施の形態】以下、添付した図面を参照して本
発明の望ましい実施例を詳しく説明する。 【0013】図1乃至図8は本発明による原子層蒸着法
を用いた薄膜を製造する過程を説明するために示した図
面である。図1乃至図8で、蒸着しようとする薄膜をA
とBでなされる2成分化合物とする時、第1反応物をA
Rn(g)として第2反応物をBPn(g)という。こ
こで、Rnはn個のRという基で形成された化学配位子
であり、Pnはn個のPという基で形成された化学配位
子である。gはガス状態であることを示す。 【0014】図1を参照すると、ARn(g)という第
1反応物を基板1がローディングされたチャンバ(図示
せず)に注入して基板1、例えば(100)のシリコン
基板の表面に第1反応物を化学吸着及び物理吸着させ
る。前記第1反応物は基板の表面に吸着されたことは化
学吸着されていることであり、前記化学吸着された第1
反応物上に吸着されたことは物理吸着されていることで
ある。ところが、ARn(g)という第1反応物は一度
注入されたので化学吸着を起こすことができる空間が物
理吸着されたARnによって遮られてあって基板上に空
き空間3が形成されている。 【0015】図2を参照すると、前記化学吸着及び物理
吸着された第1反応物が形成されたチャンバを不活性ガ
ス等でパージしたり減圧にポンピングして物理吸着され
た第1反応物をすべて取り除く。このようになると、基
板1の表面には化学吸着されている第1反応物が形成さ
れる。前記化学吸着された第1反応物は固体状態のAR
n(s)であり、基板1の表面は露出されている部分が
多くある。ここで、sは固体状態を示す。 【0016】図3を参照すると、固体状態のARn
(s)が形成された基板1を含むチャンバに再びARn
(g)という第1反応物を注入して前記基板1の表面に
第1反応物を稠密するように化学吸着及び物理吸着させ
る。このようになると、図1で示された空き空間3に第
1反応物が化学吸着及び物理吸着される。ここでも図1
と同じく基板1の表面には第1反応物が化学吸着され、
化学吸着された第1反応物上に物理吸着された第1反応
物が形成される。 【0017】図4を参照すると、前記化学吸着された第
1反応物が形成された基板1を含むチャンバを減圧にポ
ンピングしたり不活性ガス等をパージして物理吸着され
た第1反応物をすべて取り除く。このように第1反応物
の注入及び物理吸着された第1反応物の除去過程を二回
経るようになると、基板1の表面には稠密するように化
学吸着されている第1反応物、すなわち固体状態のAR
n(s)のみ残っているようになって化学配位子などの
不純物が完全に取り除かれる。ここで、sは固体状態を
示す。本実施例で、前記図1乃至図4の過程を2回以上
反復することもある。 【0018】図5を参照すると、稠密するように化学吸
着された第1反応物が形成された基板1を含むチャンバ
にBPn(g)という第2反応物を注入して化学吸着及
び物理吸着させる。前記基板の表面に吸着されている第
2反応物は化学吸着されていることであり、前記化学吸
着された第2反応物上に吸着された第2反応物は物理吸
着されているものである。このようになると、前記化学
吸着された第1反応物と第2反応物は化学置換方法によ
ってA及びB原子でなされた原子層単位の稠密しない単
一層を形成するようになる。この時、化学配位子である
RnとPnは蒸気圧が高い状態で取り除かれる。ところ
が、図5の第2反応物は図1の第1反応物と同じく基板
の表面に稠密するように化学吸着されないため、前記第
2反応物は第1反応物と十分に化学置換されなくて単一
層内に不純物が発生したり化学量論的な組成比が合わな
くなる。 【0019】図6を参照すると、前記稠密しない単一層
及び物理吸着された第2反応物が形成された基板を含む
チャンバを減圧にポンピングしたり不活性ガス等をパー
ジして物理吸着された第2反応物を取り除く。このよう
になると、基板の表面には化学吸着されている固体状態
の単一層が形成される。ところが、図6の固体状態の単
一層はARnBPn(s)形態になってRnPn(s)
の不純物が残っているため化学量論的な組成比が合わな
くて膜密度が低下される。ここで、sは固体状態を示
す。 【0020】図7を参照すると、前述した化学量論的な
組成比と膜密度を向上させるために、固体状態の稠密し
ない単一層が形成された基板を含むチャンバに再びBP
n(g)という第2反応物を注入して前記基板の表面に
第2反応物を化学吸着及び物理吸着させる。前記基板の
表面に吸着されている第2反応物は化学吸着されている
ことであり、前記化学吸着された第2反応物上に吸着さ
れた第2反応物は物理吸着されていることである。この
ようになると、前記化学吸着された第1反応物と第2反
応物は化学置換方法によってA及びB原子でなされた、
原子層単位の厚さを有する稠密した単一層を形成するよ
うになる。この時、化学配位子であるRnとPnは蒸気
圧が高い気体状態で取り除かれる。 【0021】ところが、図7の第2反応物は図5で稠密
するように化学吸着されない基板の表面に化学吸着され
るために、前記第2反応物は稠密した第1反応物と十分
に化学置換されて単一層内に不純物を減少させ化学量論
的な組成比も合うようになる。 【0022】図8を参照すると、前記稠密した単一層と
物理吸着された第2反応物が形成された基板を含むチャ
ンバを不活性ガス等でパージしたり減圧にポンピングし
て物理吸着された第2反応物をすべて取り除く。このよ
うになると、基板の表面には稠密するように化学吸着さ
れている固体状態の稠密した単一層、すなわちAB
(s)のみ残るようになる。ここで、sは固体状態を示
す。本実施例で、前記図5乃至図8の過程を2回以上反
復することもできる。 【0023】一方、図8では基板の表面上にAとBが形
成されてAB(s)という化合物が形成されている。し
かし、本発明の原子層蒸着法を適用すると図9の9aの
ように基板の表面にAが形成され、A上にBが形成され
てAB(s)という化合物が形成されたり、図9の9b
のように基板の表面にA及びBが形成されて前記A及び
B上に各々B及びAが形成されて全体的にAB(s)と
いう化合物が形成されることができる。 【0024】ここで、本発明の薄膜製造方法を用いて薄
膜を形成する過程を説明する。 【0025】図10は本発明の薄膜製造方法に利用され
た薄膜製造装置を説明するために示した概略図であり、
図11は本発明の薄膜製造方法を説明するために示した
流れ図である。 【0026】まず、チャンバ30に基板1、例えば(1
00)のシリコン基板をローディングさせた後、ヒータ
ー5を用いて前記基板を150乃至375℃、望ましく
は300℃の温度に維持する(ステップ100)。この
時、前記基板を300℃に維持するためにはヒーター5
の温度は約450℃に維持する。 【0027】続いて、前記チャンバ30を150乃至3
75℃の工程温度に維持した状態で第1バブラ12中に
ある第1反応物11、例えばトリメチルアルミニウム
(Al(CH3)3:TMA)を前記チャンバ30に1m
秒乃至10秒間、望ましくは0.5秒間注入する(ステ
ップ105)。 【0028】ここで、前記第1反応物11の注入はバブ
リング方式を用いるが、ガスソース19のアルゴンガス
100sccmをキャリアガスとして20乃至22℃に
維持された第1バブラ12に注入して前記液体状態の第
1反応物11をガス形態に変更させた後、バルブ9を選
択的に作動させて第1ガスライン13及びシャワーヘッ
ド15を通して注入する。そして、前記第1反応物11
の注入時前記第1反応物11の流速の向上及び稀釈のた
めに前記ガスソース19の窒素ガスを第2ガスライン1
8及びシャワーヘッド15を通して400sccm注入
する。結果的に、第1反応物11の注入時チャンバ30
に提供されるガスの量は500sccmであり、この時
チャンバの圧力は1乃至2Torrに維持する。このよ
うになると、基板1の表面に原子大きさ程度で第1反応
物11が化学吸着され、前記化学吸着された第1反応物
11上に物理吸着第1反応物11が形成される。 【0029】次に、前記150乃至375℃の工程温度
と1乃至2Torrの工程圧力を維持した状態で、チャ
ンバ30に選択的にバルブ9を作動させて第1ガスライ
ン13または第2ガスライン18を用いてガスソース1
9の窒素ガス400sccmを0.1乃至10秒間、望
ましくは1秒間パージして物理吸着された第1反応物を
取り除く(ステップ110)。本実施例では前記物理吸
着された第1反応物をパージして除去したが、パージし
なくて前記チャンバを真空状態にポンピングして物理吸
着された第1反応物を取り除くこともできる。 【0030】次に、前記物理吸着された第1反応物が取
り除かれたチャンバ30にステップ105のように第1
反応物11を再び注入する(ステップ115)。この
時、前記ステップ115の第1反応物の注入時間はステ
ップ105の第1反応物の注入時間より同じであったり
短くする。続いて、前記チャンバ30にステップ110
のように物理吸着された第1反応物を取り除く(ステッ
プ120)。この時、前記ステップ120の物理吸着さ
れた第1反応物の除去時間はステップ110の第1反応
物の除去時間より同じであったり短くする。このように
第1反応物の注入、第1パージ過程を再び反復的に実施
すると、基板上に稠密するように化学吸着された第1反
応物が形成される。本実施例では前記第1反応物の注入
及び物理吸着された第1反応物除去過程を順次的に各々
2回実施したが、さらに実施することもある。 【0031】次に、稠密するように化学吸着された第1
反応物が形成された基板が含まれたチャンバに前記15
0乃至375℃の工程温度と1乃至2Torrの工程圧
力を維持した状態で、第2バブラ14中にある第2反応
物17、例えば純水をバルブ10を選択的に作動させて
ガスライン16及びシャワーヘッド15を通して1m秒
乃至10秒間、望ましくは0.5秒間注入する(ステッ
プ125)。 【0032】ここで、前記第2反応物17の注入方法は
第1反応物の注入と同一にバブリング方式を用いる。す
なわち、ガスソース19のアルゴンガス100sccm
をキャリアガスとして20乃至22℃に維持された第2
バブラ14に注入して前記液体状態の第2反応物17を
ガス形態に変更させた後、第3ガスライン16及びシャ
ワーヘッド15を通して注入する。そして、前記第2反
応物17の注入時前記第2反応物17の流速の向上及び
稀釈のために、前記ガスソース19の窒素ガスを第2ガ
スライン18及びシャワーヘッド15を通して400s
ccm注入する。結果的に、第2反応物17の注入時チ
ャンバ30に提供されるガスの量は500sccmであ
り、この時チャンバ30の圧力は1乃至2Torrに維
持する。このようになると、稠密するように化学吸着さ
れた第1反応物が形成された基板1上に第2反応物が化
学吸着され、前記化学吸着された第2反応物と第1反応
物上に第2反応物が物理吸着される。そして、前記稠密
するように化学吸着された第1反応物と稠密するように
化学吸着されない第2反応物は化学置換方法によって原
子層単位の稠密しないアルミニウム酸化膜を形成させ
る。 【0033】次に、前記150乃至375℃の工程温度
と1乃至2Torrの工程圧力を維持した状態で稠密し
ない原子層単位のアルミニウム酸化膜が形成された基板
を含むチャンバ30に選択的にバルブ10を作動させて
第2ガスライン18または第3ガスライン16を用いて
ガスソース19の窒素ガス400sccmを0.1乃至
10秒間、望ましくは1秒間パージして物理吸着された
第2反応物を取り除く(ステップ130)。本実施例で
は前記物理吸着された第2反応物をパージして除去した
が、パージしなくて前記チャンバを真空状態にポンピン
グして物理吸着された第2反応物を取り除くこともあ
る。 【0034】次に、前記物理吸着された第2反応物が取
り除かれたチャンバ30にステップ125のように第2
反応物11を再び注入する(ステップ135)。この
時、前記ステップ135の第2反応物の注入時間はステ
ップ125の第2反応物の注入時間より同じであったり
短くする。続いて、前記チャンバ30に段階130のよ
うに物理吸着された第2反応物を取り除く(ステップ1
40)。このように第2反応物の注入、物理吸着された
第2反応物の除去過程を再び反復的に実施すると、基板
上に稠密するように化学吸着された第2反応物が形成さ
れる。結果的に、前記稠密するように化学吸着された第
1反応物と稠密するように化学吸着された第2反応物は
化学置換方法によって原子層単位の稠密したアルミニウ
ム酸化膜を形成するようになる。本実施例では前記第2
反応物の注入及び物理吸着された第2反応物除去過程を
順次的に各々2回実施したが、さらに実施することもあ
る。 【0035】以後に、前記したような原子層大きさの薄
膜を形成する段階、すなわち第1反応物注入段階(ステ
ップ105)から物理吸着された第2反応物除去段階
(ステップ140)までを周期的に反復遂行して適正厚
さ、例えば10Å乃至1000Å程度の薄膜が形成され
たのかを確認する(ステップ145)。適正厚さになる
と前記サイクルを反復しなくてチャンバの工程温度と工
程圧力を常温及び常圧に維持することによって薄膜製造
過程を完了する(ステップ150)。 【0036】前記図11で、第1反応物及び第2反応物
を各々トリメチルアルミニウム(Al(CH3)3:TM
A)及び純水を用いてアルミニウム酸化膜(Al2O3)
を形成したが、第1反応物と第2反応物を各々TiCl
4とNH3を用いればTiN膜を形成することができる。
そして、第1反応物及び第2反応物としてMoCl5と
H2を用いればMo膜を形成することができる。 【0037】さらに、本発明の薄膜製造方法によると前
記アルミニウム酸化膜、TiN膜、Mo膜以外の、単原
子の固体薄膜、単原子酸化物、複合酸化物、単原子窒化
物または複合窒化物を形成することができる。前記単原
子の固体薄膜の例としてはAl、Cu、Ti、Ta、P
t、Ru、Rh、Ir、WまたはAgを挙げることがで
き、単原子酸化物の例としてはAl2O3、TiO2、T
a2O5、ZrO2、HfO2、Nb2O5、CeO2、Y2O
3、SiO2、In2O3、RuO2又はIrO2等を挙げる
ことができ、複合酸化物の例としてはSrTiO3、P
bTiO3、SrRuO3、CaRuO3、(Ba、S
r)TiO3、Pb(Zr、Ti)O3、(Pb、La)
(Zr、Ti)O3、(Sr、Ca)RuO3、Snがド
ーピングされたIn2O3、FeがドーピングされたIn
2O3又はZrがドーピングされたIn 2O3を挙げること
ができる。また、前記単原子窒化物の例としてはSi
N、NbN、ZrN、TiN、TaN、Ya3N5、Al
N、GaN、WN又はBNを挙げることができ、前記複
合窒化物の例としてはWBN、WSiN、TiSiN、
TaSiN、AlSiN又はAlTiNを挙げることが
できる。 【0038】以上のように本発明の薄膜製造方法は工程
温度と工程圧力を一定に維持した状態で、第1反応物注
入、物理吸着された第1反応物の除去を反復的に遂行し
た後、第2反応物注入及び物理吸着された第2反応物の
除去を反復的に遂行する。このようになると、基板上に
第1反応物が稠密するように蒸着された状態で稠密する
ように蒸着される第2反応物と化学置換によって反応す
るので、薄膜の膜密度が高くて優秀な化学量論的な薄膜
を得ることができる。 【0039】図12は本発明による薄膜製造方法によっ
て製造されたアルミニウム酸化膜のサイクル当厚さを示
したグラフである。 【0040】具体的に、X軸はサイクル数を示す。ここ
で、一つのサイクルは図11に説明されたように第1反
応物注入、物理吸着された第1反応物の除去、第1反応
物注入、物理吸着された第1反応物除去、第2反応物注
入及び物理吸着された第2反応物の除去、第2反応物注
入、物理吸着された第2反応物を取り除く段階を示す。
また、Y軸はアルミニウム酸化膜の厚さを示す。図12
に示されたように本発明の薄膜製造方法によると、アル
ミニウム酸化膜がサイクル当1.1Åの厚さに成長さ
れ、これは理論値と類似な値を示す。 【0041】図13は本発明による薄膜製造方法によっ
て製造されたアルミニウム酸化膜の基板内均一度を説明
するために示したグラフである。 【0042】具体的に、X軸は8インチ基板の中央点、
前記中央点を中心に1.75インチの半径を有する円で
90度間隔で4点、前記中央点を中心に3.5インチの
半径を有する円で90度間隔で4点を合せて総9点の測
定位置を示す。Y軸はアルミニウム酸化膜の厚さを示
す。図13に示されたように8インチ基板内で均一度が
非常に優秀なことが分かる。 【0043】図14及び図15は各々本発明及び従来方
法によって製造されたアルミニウム酸化膜の波長による
屈折率を示したグラフである。X軸は400乃至800
nmの波長を示し、Y軸は屈折率を示す。 【0044】具体的に、本発明によって製造されたアル
ミニウム酸化膜の屈折率は波長400乃至800nmの
範囲で約1.67乃至1.73を示し、本発明では、波
長400乃至800nmの範囲で約1.67乃至1.7
3であることが好ましく、より好ましくは約1.689
乃至1.710である。特に、図14及び図15に示さ
れたように本発明によって製造されたアルミニウム酸化
膜の屈折率が500nm波長で1.698であり、従来
方法アルミニウム酸化膜の屈折率1.649より大きく
て膜密度が高いことがわかる。また、本発明によって製
造されたアルミニウム酸化膜の屈折率は一般的な方法に
よって製造されたアルミニウム酸化膜を850℃で30
分間アニーリングした後に測定した屈折率と類似し、本
発明のアルミニウム酸化膜はアニーリング工程が不要に
なる。 【0045】 【発明の効果】前述したように本発明の薄膜製造方法に
よると、原子層蒸着法を用いるため段差被覆性と均一度
が優秀な薄膜を得ることができる。また、本発明の薄膜
製造方法によると、工程温度と工程圧力を一定に維持し
た状態でそれぞれの反応物を注入した後、パージまたは
ポンピングして不純物を完全に取り除く過程を反復的に
遂行することにより、基板上に反応物を稠密するように
化学吸着させることができる。このようになると、膜密
度が高く、優秀な化学量論的な薄膜を得ることができ
る。 【0046】以上、実施例を通して本発明を具体的に説
明したが、本発明はこれに限らず、本発明の技術的思想
内で当分野で通常の知識でその変形や改良が可能であ
る。
する過程を説明するために示した図面である。 【図2】本発明による原子層蒸着法を用いた薄膜を製造
する過程を説明するために示した図面である。 【図3】本発明による原子層蒸着法を用いた薄膜を製造
する過程を説明するために示した図面である。 【図4】本発明による原子層蒸着法を用いた薄膜を製造
する過程を説明するために示した図面である。 【図5】本発明による原子層蒸着法を用いた薄膜を製造
する過程を説明するために示した図面である。 【図6】本発明による原子層蒸着法を用いた薄膜を製造
する過程を説明するために示した図面である。 【図7】本発明による原子層蒸着法を用いた薄膜を製造
する過程を説明するために示した図面である。 【図8】本発明による原子層蒸着法を用いた薄膜を製造
する過程を説明するために示した図面である。 【図9】図9において9a及び9bは、本発明による原
子層蒸着法を用いて薄膜を製造した時、図8と異なるよ
うに形成された例を示した図面である。 【図10】本発明の薄膜製造方法に利用された薄膜製造
装置を説明するために示した概略図である。 【図11】本発明の薄膜製造方法を説明するために示し
た流れ図である。 【図12】本発明による薄膜製造方法によって製造され
たアルミニウム酸化膜のサイクル当厚さを示したグラフ
である。 【図13】本発明による薄膜製造方法によって製造され
たアルミニウム酸化膜の基板内均一度を説明するために
示したグラフである。 【図14】本発明によって製造されたアルミニウム酸化
膜の波長による屈折率を示したグラフである。 【図15】従来方法によって製造されたアルミニウム酸
化膜の波長による屈折率を示したグラフである。 【符号の説明】 1 基板 5 ヒーター 9 バルブ 12、14 バブラ 19 ガスソース 30 チャンバ
Claims (1)
- 【特許請求の範囲】 【請求項1】 (A)基板がローディングされたチャン
バに第1反応物を注入して前記基板上に前記第1反応物
を化学吸着させる段階と、 (B)前記化学吸着された第1反応物上に物理吸着され
た第1反応物を取り除く段階と、 (C)前記チャンバに再び前記第1反応物を注入して前
記基板上に稠密するように化学吸着させる段階と、 (D)前記稠密するように化学吸着された第1反応物上
に物理吸着された第1反応物を取り除く段階と、 (E)前記チャンバに第2反応物を注入して前記基板の
表面に化学吸着させる段階と、 (F)前記稠密するように化学吸着された第1反応物と
第2反応物上に物理吸着された第2反応物を取り除く段
階と、 (G)前記チャンバに再び前記第2反応物を注入して前
記基板上に前記第2反応物を稠密するように吸着させて
化学置換によって固体薄膜を形成することを特徴とする
薄膜製造方法。 【請求項2】 前記(G)段階後、 (H)物理吸着された第2反応物と前記(G)段階の化
学置換時生成される残留物を取り除く段階をさらに含ん
でなされることを特徴とする請求項1に記載の薄膜製造
方法。 【請求項3】 前記(B)、(D)および(F)におけ
る取り除く段階が、前記チャンバのパージまたはポンピ
ングによることを特徴とする請求項1記載の薄膜膜製造
方法。 【請求項4 】 前記取り除く段階が、前記チャンバの
パージまたはポンピングによることを特徴とする請求項
2記載の得る膜製造方法。 【請求項5】 前記(E)、(F)、(G)及び(H)
段階の第2反応物注入及び物理吸着された第2反応物及
び残留物の除去を順次的に2回以上反復して実施するこ
とを特徴とする請求項2または4に記載の薄膜製造方
法。 【請求項6】 前記(A)、(B)、(C)、(D)段
階の第1反応物注入及び物理吸着された第1反応物の除
去を順次的に2回以上反復して実施することを特徴とす
る請求項1に記載の薄膜製造方法。 【請求項7】 前記(C)段階の第1反応物の注入時間
は(A)段階の第1反応物の注入時間と同じであったり
短いことを特徴とする請求項1に記載の薄膜製造方法。 【請求項8】 前記(G)段階の第2反応物の注入時間
は(E)段階の第2反応物の注入時間と同じであったり
短いことを特徴とする請求項1に記載の薄膜製造方法。 【請求項9】 前記基板は(100)のシリコン基板で
あることを特徴とする請求項1に記載の薄膜製造方法。 【請求項10】 前記第1反応物及び第2反応物は各々
前記固体薄膜を構成する元素と化学配位子で構成されて
いることを特徴とする請求項1に記載の薄膜製造方法。 【請求項11】 前記固体薄膜は単原子、単原子酸化
物、複合酸化物、単原子窒化物及び複合窒化物でなされ
た一群から選択されたいずれか一つで形成されることを
特徴とする請求項1に記載の薄膜製造方法。 【請求項12】 前記単原子はMo、Al、Cu、T
i、Ta、Pt、Ru、Rh、Ir、W及びAgでなさ
れた一群から選択されたいずれか一つであることを特徴
とする請求項11に記載の薄膜製造方法。 【請求項13】 前記単原子酸化物はAl2O3、TiO
2、Ta2O5、ZrO2、HfO2、Nb2O5、CeO2、
Y2O3、SiO2、In2O3、RuO2及びIrO2でな
された一群から選択されたいずれか一つであることを特
徴とする請求項11に記載の薄膜製造方法。 【請求項14】 前記Al2O3でなされた膜の屈折率は
400乃至800nmの波長範囲で1.67乃至1.7
3であることを特徴とする請求項13に記載の薄膜製造
方法。 【請求項15】 前記複合酸化物はSrTiO3、Pb
TiO3、SrRuO 3、CaRuO3、(Ba、Sr)
TiO3、Pb(Zr、Ti)O3、(Pb、La)(Z
r、Ti)O3、(Sr、Ca)RuO3、Snがドーピ
ングされたIn 2O3、FeがドーピングされたIn2O3
及びZrがドーピングされたIn2O3でなされた一群か
ら選択されたいずれか一つであることを特徴とする請求
項11に記載の薄膜製造方法。 【請求項16】 前記単原子窒化物はSiN、NbN、
ZrN、TiN、TaN、Ya3N5、AlN、GaN、
WN及びBNでなされた一群から選択されたいずれか一
つであることを特徴とする請求項11に記載の薄膜製造
方法。 【請求項17】 前記複合窒化物はWBN、WSiN、
TiSiN、TaSiN、AlSiN及びAlTiNで
なされた一群から選択されたいずれか一つであることを
特徴とする請求項11に記載の薄膜製造方法。
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US (1) | US6270572B1 (ja) |
JP (1) | JP4057184B2 (ja) |
KR (1) | KR100275738B1 (ja) |
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- 1998-11-25 TW TW087119573A patent/TW432119B/zh not_active IP Right Cessation
- 1998-12-04 GB GB9826781A patent/GB2340508B/en not_active Expired - Fee Related
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Also Published As
Publication number | Publication date |
---|---|
GB9826781D0 (en) | 1999-01-27 |
KR100275738B1 (ko) | 2000-12-15 |
GB2340508B (en) | 2003-03-12 |
JP4057184B2 (ja) | 2008-03-05 |
DE19853598B4 (de) | 2013-04-18 |
CN1200135C (zh) | 2005-05-04 |
CN1244598A (zh) | 2000-02-16 |
GB2340508A (en) | 2000-02-23 |
DE19853598A1 (de) | 2000-02-10 |
KR20000013329A (ko) | 2000-03-06 |
US6270572B1 (en) | 2001-08-07 |
TW432119B (en) | 2001-05-01 |
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