JP2006131606A - Tert-amylimido-tris(dimethylamido)-niobium, method for producing the same, raw material solution for ald using the same and method for forming niobium nitride film or niobium oxide film by using the same - Google Patents
Tert-amylimido-tris(dimethylamido)-niobium, method for producing the same, raw material solution for ald using the same and method for forming niobium nitride film or niobium oxide film by using the same Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 36
- 229910000484 niobium oxide Inorganic materials 0.000 title claims abstract description 18
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000002994 raw material Substances 0.000 title claims abstract description 18
- CFJRGWXELQQLSA-UHFFFAOYSA-N azanylidyneniobium Chemical compound [Nb]#N CFJRGWXELQQLSA-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 239000000243 solution Substances 0.000 title claims abstract description 11
- 239000010955 niobium Substances 0.000 title abstract description 55
- 238000004519 manufacturing process Methods 0.000 title abstract description 10
- 229910052758 niobium Inorganic materials 0.000 title abstract description 5
- 239000007983 Tris buffer Substances 0.000 title abstract 2
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- MVIBAPPKIMZVTF-UHFFFAOYSA-N dimethylazanide;niobium(3+) Chemical compound [Nb+3].C[N-]C.C[N-]C.C[N-]C MVIBAPPKIMZVTF-UHFFFAOYSA-N 0.000 claims description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 8
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 claims description 7
- DCDGRPWOFIJPJR-UHFFFAOYSA-N lithium;2-methylbutan-2-ylazanide Chemical compound [Li+].CCC(C)(C)[NH-] DCDGRPWOFIJPJR-UHFFFAOYSA-N 0.000 claims description 6
- YDGSUPBDGKOGQT-UHFFFAOYSA-N lithium;dimethylazanide Chemical compound [Li+].C[N-]C YDGSUPBDGKOGQT-UHFFFAOYSA-N 0.000 claims description 6
- 239000006227 byproduct Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 abstract description 22
- 230000008018 melting Effects 0.000 abstract description 9
- 238000002844 melting Methods 0.000 abstract description 9
- 239000007789 gas Substances 0.000 abstract description 7
- 239000000047 product Substances 0.000 abstract description 3
- 239000000706 filtrate Substances 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 238000005292 vacuum distillation Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 34
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 33
- 239000007788 liquid Substances 0.000 description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000010409 thin film Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000005587 bubbling Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 238000002451 electron ionisation mass spectrometry Methods 0.000 description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000006557 surface reaction Methods 0.000 description 2
- 239000006200 vaporizer Substances 0.000 description 2
- 235000020338 yellow tea Nutrition 0.000 description 2
- GELMWIVBBPAMIO-UHFFFAOYSA-N 2-methylbutan-2-amine Chemical compound CCC(C)(C)N GELMWIVBBPAMIO-UHFFFAOYSA-N 0.000 description 1
- WYDFSSCXUGNICP-CDLQDMDJSA-N C[C@@H]([C@H]1CC[C@H]2[C@@H]3[C@@H]4O[C@@H]4[C@@]4(O)CC=CC(=O)[C@]4(C)[C@H]3CC[C@]12C)[C@H]1C[C@]2(C)O[C@]2(C)C(O)O1 Chemical compound C[C@@H]([C@H]1CC[C@H]2[C@@H]3[C@@H]4O[C@@H]4[C@@]4(O)CC=CC(=O)[C@]4(C)[C@H]3CC[C@]12C)[C@H]1C[C@]2(C)O[C@]2(C)C(O)O1 WYDFSSCXUGNICP-CDLQDMDJSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000000160 carbon, hydrogen and nitrogen elemental analysis Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001793 charged compounds Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000000752 ionisation method Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- AHNJTQYTRPXLLG-UHFFFAOYSA-N lithium;diethylazanide Chemical compound [Li+].CC[N-]CC AHNJTQYTRPXLLG-UHFFFAOYSA-N 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- 150000002822 niobium compounds Chemical class 0.000 description 1
- ZTILUDNICMILKJ-UHFFFAOYSA-N niobium(v) ethoxide Chemical compound CCO[Nb](OCC)(OCC)(OCC)OCC ZTILUDNICMILKJ-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- -1 peptane Chemical compound 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- HSXKFDGTKKAEHL-UHFFFAOYSA-N tantalum(v) ethoxide Chemical compound [Ta+5].CC[O-].CC[O-].CC[O-].CC[O-].CC[O-] HSXKFDGTKKAEHL-UHFFFAOYSA-N 0.000 description 1
- 235000013618 yogurt Nutrition 0.000 description 1
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Abstract
Description
本発明は、超電導膜やキャパシタ用高誘電率材料に適した窒化ニオブ膜もしくは酸化ニオブ膜をＡＬＤ法にて形成するのに好適なニオブ化合物、その製造方法およびこれを用いた窒化ニオブ膜もしくは酸化ニオブ膜の形成方法に関する。 The present invention relates to a niobium compound suitable for forming a niobium nitride film or a niobium oxide film suitable for a superconducting film or a high dielectric constant material for a capacitor by an ALD method, a manufacturing method thereof, a niobium nitride film or an oxide using the same. The present invention relates to a method for forming a niobium film.
ニオブ元素を有する薄膜材料は、その特性により様々な用途に用いられている。例えば窒化ニオブ膜は超電導材料でありＳＩＳミキサー素子の電極材として検討されている。酸化ニオブ膜は誘電率が高く、キャパシタ用の高誘電率材料として検討されている。さらには光学素子としても検討されている。
これらの薄膜の成膜方法としてはスパッタリング法や塗布法、ＭＯＣＶＤ法が挙げられるが、加工寸法が微細になるにつれ薄膜化が要求されており、これらの方法はさらなる薄膜化に応えられるものではない。Thin film materials containing niobium elements are used in various applications due to their characteristics. For example, a niobium nitride film is a superconducting material and has been studied as an electrode material for SIS mixer elements. A niobium oxide film has a high dielectric constant, and has been studied as a high dielectric constant material for capacitors. Furthermore, it is also examined as an optical element.
As a method for forming these thin films, a sputtering method, a coating method, and an MOCVD method can be mentioned. However, as processing dimensions become finer, thinning is required, and these methods cannot be used for further thinning. .
この薄膜化に応える手段として、原子及び分子レベルの膜厚を制御できるＡＬＤ法が有望視されている。ＡＬＤ法は、各原料ガスを同時ではなく交互に供給することで、ＭＯＣＶＤの素過程である各原料ガスの表面吸着と表面反応を単分子層レベルで制御して、原子層あるいは分子層を一層毎に成長させる方法である。
ＡＬＤ法用の原料として特に求められることは、蒸気圧が高く、酸素供給源や窒素供給源と反応しやすいことが挙げられる。As a means for responding to this thinning, the ALD method capable of controlling the film thickness at the atomic and molecular level is promising. In the ALD method, by supplying each source gas alternately instead of simultaneously, the surface adsorption and surface reaction of each source gas, which is an elementary process of MOCVD, are controlled at the monomolecular layer level, so that one atomic layer or one molecular layer is formed. It is a method of growing every time.
What is particularly required as a raw material for the ALD method is that it has a high vapor pressure and easily reacts with an oxygen supply source or a nitrogen supply source.
酸化ニオブもしくは窒化ニオブ薄膜用ＡＬＤ材料としては、塩化物、金属アルコキシド、金属アミドが挙げられる。酸素供給源としては、Ｈ２ＯやＨ２Ｏ２、Ｏ３等が挙げられる。また窒素供給源としては、ＮＨ３やＮＯ２等が挙げられる。Examples of ALD materials for niobium oxide or niobium nitride thin films include chlorides, metal alkoxides, and metal amides. Examples of the oxygen supply source include H 2 O, H 2 O 2 , and O 3 . As the nitrogen source, NH 3 and NO 2, and the like.
しかし塩化ニオブＮｂＣｌ５は固体であり、蒸気圧が低く、また膜中に塩素が含まれるという問題がある。However, niobium chloride NbCl 5 has a problem that it is a solid, has a low vapor pressure, and contains chlorine in the film.
ペンタエトキシニオブＮｂ（ＯＣ２Ｈ５）５は蒸気圧が低く、０．１Ｔｏｒｒ／１３３℃である。
非特許文献１では、Ｎｂ（ＯＣ２Ｈ５）５ならびにＮｂ（ＯＣ２Ｈ５）５の類似化合物であるペンタエトキシタンタルＴａ（ＯＣ２Ｈ５）５および水を用い、ＡＬＤ法にて酸化ニオブ膜と酸化タンタル膜を形成している。しかしＮｂ（ＯＣ２Ｈ５）５ならびにＴａ（ＯＣ２Ｈ５）５は、ともに熱により自己反応が起こり、連鎖的に膜が堆積されることが明らかになっており、制御性に問題がある。
In Non-patent Document 1, Nb (OC 2 H 5 ) 5 and pentaethoxytantalum Ta (OC 2 H 5 ) 5 , which is a similar compound of Nb (OC 2 H 5 ) 5 , and water are used, and niobium oxide is oxidized by ALD. A film and a tantalum oxide film are formed. However, Nb (OC 2 H 5 ) 5 and Ta (OC 2 H 5 ) 5 both have self-reactions caused by heat, and it is clear that films are deposited in a chain, and there is a problem in controllability. .
また、金属アルコキシドは分子中に酸素を含むため、膜中の酸素量の厳密な制御が難しい。特に窒化膜を形成する場合には、酸素を除くことが必要であるため適さない。従って金属アルコキシドは、各原料ガスの表面吸着と表面反応を単分子層レベルでの制御と、膜中の元素量の厳密な制御が求められるＡＬＤ法に好適な原料であるとは言い難い。 In addition, since metal alkoxide contains oxygen in the molecule, it is difficult to strictly control the amount of oxygen in the film. In particular, when a nitride film is formed, it is not suitable because it is necessary to remove oxygen. Therefore, it is difficult to say that metal alkoxide is a suitable raw material for the ALD method that requires control of the surface adsorption and surface reaction of each raw material gas at the monomolecular layer level and strict control of the amount of elements in the film.
金属アミドとしては、非特許文献２にＮｂ（ＮｔＣ４Ｈ９）［Ｎ（Ｃ２Ｈ５）２］３（以下、Ｎｂ（ＮｔＢｕ）（ＮＥｔ２）３と表す）、Ｎｂ（ＮｉＣ３Ｈ７）［Ｎ（Ｃ２Ｈ５）２］３（以下、Ｎｂ（ＮｉＰｒ）（ＮＥｔ２）３と表す）、Ｎｂ（ＮｎＣ３Ｈ７）［Ｎ（Ｃ２Ｈ５）２］３（以下、Ｎｂ（ＮｎＰｒ）（ＮＥｔ２）３と表す）がＭＯＣＶＤ法用原料として報告されている。しかしその製法は、臭気が強いピリジンを用いたり、自然発火性で活性が高いリチウムジエチルアミドを取り出し、それを徐々に添加しなければならないなど、安全性、生産性に問題がある。
そこで、量産性に優れステップカバレジ能力の高いＡＬＤ法用の窒化ニオブ薄膜もしくは酸化ニオブ薄膜形成材料、ならびに安全性および生産性が高い製法が必要となった。 Therefore, a niobium nitride thin film or a niobium oxide thin film forming material for ALD method having excellent mass productivity and high step coverage ability, and a manufacturing method with high safety and productivity are required.
本発明者らは特許文献１にて、Ｎｂ（ＮｔＢｕ）（ＮＥｔ２）３の類似化合物であるＴａ（ＮｔＣ５Ｈ１１）［Ｎ（ＣＨ３）２］３（以下、Ｔａ（ＮｔＡｍ）（ＮＭｅ２）３と表す）が、窒化タンタル膜をＭＯＣＶＤ法で成膜するのに好適な化合物であることを見出し、安全性、生産性が高い製法を発明した。
一般に量産用ＡＬＤの原料化合物が持つべき供給時の好ましい性質としては、純品で高い蒸気圧を持ち、供給時に熱的に安定で、室温付近、少なくとも使用ソース温度で液体であることが挙げられる。これらの観点から非特許文献２のＮｂ（ＮｔＢｕ）（ＮＥｔ２）３を見ると、分子量が大きいため蒸気圧が高くないという欠点がある。In general, preferable properties at the time of supply of a raw material compound for ALD for mass production include a pure product having high vapor pressure, being thermally stable at the time of supply, and being liquid at around room temperature, at least at the source temperature used. . From these points of view, Nb (NtBu) (NEt 2 ) 3 of Non-Patent
本発明はＮｂ（ＮｔＢｕ）（ＮＥｔ２）３よりも高い蒸気圧を持ち、かつ５０℃以下の融点である、新規な化合物を提供することである。また安全性、生産性が高い製造方法を提供することである。さらには、それを用いてＡＬＤ法で窒化ニオブ薄膜もしくは酸化ニオブ薄膜を形成する方法を提供することである。The present invention is to provide a novel compound having a vapor pressure higher than that of Nb (NtBu) (NEt 2 ) 3 and having a melting point of 50 ° C. or lower. Moreover, it is providing the manufacturing method with high safety | security and productivity. Furthermore, it is to provide a method of forming a niobium nitride thin film or a niobium oxide thin film by using the ALD method.
本発明は、新規化合物であるターシャリーアミルイミドトリス（ジメチルアミド）ニオブである。 The present invention is a novel compound, tertiary amylimide tris (dimethylamide) niobium.
本発明は、五塩化ニオブ１モルとリチウムジメチルアミド４モル、リチウムターシャリーアミルアミド１モルを有機溶媒中で反応させ、次いで副生塩化リチウムを濾過分離し、溶媒を留去し、次いで真空下で蒸留することよりなるターシャリーアミルイミドトリス（ジメチルアミド）ニオブの製造方法である。 In the present invention, 1 mol of niobium pentachloride, 4 mol of lithium dimethylamide and 1 mol of lithium tertiary amylamide are reacted in an organic solvent, then by-product lithium chloride is separated by filtration, the solvent is distilled off, and Is a method for producing tertiary amylimidotris (dimethylamido) niobium, which comprises distilling with bismuth.
本発明は、ターシャリーアミルイミドトリス（ジメチルアミド）ニオブに１０ｗｔ％以上の有機溶媒を添加してなるＡＬＤ用原料溶液である。 The present invention is an ALD raw material solution obtained by adding 10 wt% or more of an organic solvent to tertiary amylimide tris (dimethylamide) niobium.
本発明は、ターシャリーアミルイミドトリス（ジメチルアミド）ニオブを原料として用いることを特徴とするＡＬＤ法による窒化ニオブ膜もしくは酸化ニオブ膜の形成方法である。 The present invention is a method for forming a niobium nitride film or a niobium oxide film by an ALD method characterized by using tertiary amylimide tris (dimethylamide) niobium as a raw material.
本発明のＮｂ（ＮｔＡｍ）（ＮＭｅ２）３は、公知のＮｂ（ＮｔＢｕ）（ＭＥｔ２）３と比較して、同じ温度で約１０倍の高い蒸気圧を有する新規化合物である。
そのため、ＡＬＤ法において容易に蒸気を供給することができる。本化合物は再結晶と蒸留により容易に高純度化できるので、半導体装置用ＡＬＤ原料として好ましい。また本化合物は融点が４７℃なので、わずかな加熱により液体化できるので、液体マスフローコントローラーにより定量安定供給ができる。
このＮｂ（ＮｔＡｍ）（ＮＭｅ２）３と水によるＡＬＤ法により、良質な酸化ニオブ膜あるいは窒化ニオブ膜を形成することができる。Nb (NtAm) (NMe 2 ) 3 of the present invention is a novel compound having a vapor pressure about 10 times higher at the same temperature compared to the known Nb (NtBu) (MEt 2 ) 3 .
Therefore, steam can be easily supplied in the ALD method. Since this compound can be easily purified by recrystallization and distillation, it is preferable as an ALD raw material for semiconductor devices. Moreover, since this compound has a melting point of 47 ° C., it can be liquefied by slight heating, so that it can be quantitatively and stably supplied by a liquid mass flow controller.
A good quality niobium oxide film or niobium nitride film can be formed by the ALD method using Nb (NtAm) (NMe 2 ) 3 and water.
本発明のターシャリーアミルイミドトリス（ジメチルアミド）ニオブ（以下、Ｎｂ（ＮｔＡｍ）（ＮＭｅ２）３と表す）は新規化合物である。それは、特許文献１に記載のＴａ（ＮｔＡｍ）（ＮＭｅ２）３の製法をもとにして製造することができる。The tertiary amylimide tris (dimethylamide) niobium (hereinafter referred to as Nb (NtAm) (NMe 2 ) 3 ) of the present invention is a novel compound. It can be produced based on the Ta (NtAm) (NMe 2 ) 3 production method described in Patent Document 1.
４モルのリチウムジメチルアミドと１モルのリチウムターシャリーアミルアミドをヘキサン中に溶解懸濁させ、攪拌水冷しながら粉末状の五塩化ニオブを加えて２昼夜１０〜４０℃で反応させる。次いで副生した塩化リチウム結晶を濾過で取り除き、得られた黄色の液体から溶媒等、低沸点分を減圧で留去する。すると、オレンジ色の粘性液体が残るので、これを１Ｔｏｒｒの減圧蒸留をすると、１１０℃付近で黄紅茶色液体が得られる。この液体をヘキサンから−３０℃で再結晶し、得られた暗黄色結晶を１Ｔｏｒｒの真空蒸留し、１００℃付近で主留分の黄紅茶色液体を得る。この液体は室温で暗黄色の固体となる。五塩化ニオブに対する収率は５８％である。 4 mol of lithium dimethylamide and 1 mol of lithium tertiary amylamide are dissolved and suspended in hexane, powdered niobium pentachloride is added with stirring and water cooling, and the mixture is reacted at 10 to 40 ° C. for 2 days and nights. Next, by-product lithium chloride crystals are removed by filtration, and low-boiling components such as a solvent are distilled off from the obtained yellow liquid under reduced pressure. Then, since an orange viscous liquid remains, if this is distilled under reduced pressure of 1 Torr, a yellow blackish liquid is obtained at around 110 ° C. This liquid is recrystallized from hexane at −30 ° C., and the dark yellow crystals obtained are vacuum distilled at 1 Torr to obtain a yellow tea black liquid of the main fraction at around 100 ° C. This liquid becomes a dark yellow solid at room temperature. The yield based on niobium pentachloride is 58%.
ここで原料とするリチウムジメチルアミドは、ノルマルブチルリチウムのヘキサン溶液とジメチルアミンガスを反応させることにより、白色ヨーグルト状として得られる。リチウムターシャリーアミルアミドはノルマルリチウムのヘキサン溶液とターシャリーアミルアミンとを反応させることにより、白色懸濁液として得られる。この二つの反応生成液をそのまま合わせて用いればよい。
反応溶媒としては、ヘキサンの他、ペプタン、オクタン、トルエン、ジエチルエーテルなどが使える。
使用する五塩化ニオブは、市販されている高純度のものを用いると最終生成物の金属元素不純物を少なくできる。当然のことながらその粒度により、反応速度、反応温度上昇に影響するので、添加速度を制御する。The lithium dimethylamide used here is obtained as white yogurt by reacting a hexane solution of normal butyl lithium with dimethylamine gas. Lithium tertiary amylamide is obtained as a white suspension by reacting a hexane solution of normal lithium with tertiary amylamine. These two reaction product liquids may be used together as they are.
As a reaction solvent, in addition to hexane, peptane, octane, toluene, diethyl ether and the like can be used.
When niobium pentachloride used has a high purity commercially available, the metal element impurities of the final product can be reduced. As a matter of course, the particle size affects the reaction rate and the reaction temperature rise, so the addition rate is controlled.
反応時間は５〜５０時間である。五塩化ニオブ１モルに対する仕込みリチウムジメチルアミドのモル数は４モル、リチウムターシャリーアミルアミドのモル数は１モルであるが、若干の過剰のリチウムジメチルアミド、リチウムターシャリーアミルアミドを加えてもよい。 The reaction time is 5 to 50 hours. The number of moles of charged lithium dimethylamide per mole of niobium pentachloride is 4 moles and the number of moles of lithium tertiary amylamide is 1 mole, but a slight excess of lithium dimethylamide and lithium tertiary amylamide may be added. .
実施例１で得られたＮｂ（ＮｔＡｍ）（ＮＭｅ２）３について、以下に同定結果と物性を述べる。
（１）組成分析
湿式分解し、生成した液のＩＣＰ発光分光分析の結果
Ｎｂ分析値 ２８．６ｗｔ％ （理論値 ２９．９ｗｔ％）
ＣＨＮ分析の結果
Ｃ ４１．９ｗｔ％ （理論値 ４２．６ｗｔ％）
Ｈ ９．２ｗｔ％ （理論値 ９．４ｗｔ％）
Ｎ １７．４ｗｔ％ （理論値 １８．１ｗｔ％）The identification results and physical properties of Nb (NtAm) (NMe 2 ) 3 obtained in Example 1 are described below.
(1) Composition analysis Result of ICP emission spectroscopic analysis of liquid obtained by wet decomposition Nb analysis value 28.6 wt% (theoretical value 29.9 wt%)
Results of CHN analysis C 41.9 wt% (theoretical value 42.6 wt%)
H 9.2wt% (theoretical value 9.4wt%)
N 17.4 wt% (theoretical value 18.1 wt%)
（２）不純物分析
ＩＣＰ発光分光分析の結果（単位ｐｐｍ）
Ａｌ＜１、Ｃａ＜１、Ｆｅ＜１、Ｍｇ＜１、Ｔｉ＜１、Ｌｉ＜１
であり高純度であった。
またＣｌ分析の結果、Ｃｌは１ｐｐｍであった。(2) Impurity analysis Results of ICP emission spectroscopic analysis (unit: ppm)
Al <1, Ca <1, Fe <1, Mg <1, Ti <1, Li <1
And high purity.
As a result of Cl analysis, Cl was 1 ppm.
（３）ＥＩ−ＭＳ
測定条件
装置；ＪＥＯＬ ＡＸ５０５Ｗ、イオン化法；ＥＩ、イオン源温度；２３０℃
イオン化エネルギー；７０ｅＶ
測定結果を図１に示した。
主なｍ／ｚと強度（％）とそのイオン種を以下に列挙した。
ｍ／ｚ＝
３１０（５１％）Ｎｂ［ＮＣ（ＣＨ３）２Ｃ２Ｈ５］［Ｎ（ＣＨ３）２］３分子イオン
２９５（２１％）Ｎｂ［ＮＣ（ＣＨ３）Ｃ２Ｈ５］［Ｎ（ＣＨ３）２］３
２８１（１００％）Ｎｂ［ＮＣ（ＣＨ３）２］［Ｎ（ＣＨ３）２］３
４４（２６％）Ｎ（ＣＨ３）２ (3) EI-MS
Measurement conditions Apparatus; JEOL AX505W, ionization method; EI, ion source temperature; 230 ° C
Ionization energy: 70 eV
The measurement results are shown in FIG.
The main m / z, strength (%) and ionic species are listed below.
m / z =
310 (51%) Nb [NC (CH 3) 2 C 2 H 5] [N (CH 3) 2] 3 molecular ion 295 (21%) Nb [NC (CH 3) C 2 H 5] [N (CH 3 ) 2 ] 3
281 (100%) Nb [NC (CH 3 ) 2 ] [N (CH 3 ) 2 ] 3
44 (26%) N (CH 3 ) 2
（４）１Ｈ−ＮＭＲ
測定条件
装置；ＪＮＭ−ＥＣＡ４００（４００ＭＨｚ）、溶媒；Ｃ６Ｄ６、方法；１Ｄ
測定結果を図２に示した。
δＨ（ｐｐｍ）と（帰属）を以下に列挙する。
３．１４ ｓ （１８Ｈ，Ｎ（ＣＨ ３）２）
２．２０ ｄ （６．５Ｈ，不明）
１．５４ ｑ （２．３Ｈ，ＣＨ３ＣＨ ２Ｃ（ＣＨ３）２Ｎ）
１．３１ ｓ （７．６Ｈ，ＣＨ３ＣＨ２Ｃ（ＣＨ ３）２Ｎ）
１．１１ ｔ （３．４Ｈ，ＣＨ ３ＣＨ２Ｃ（ＣＨ３）２Ｎ）(4) 1 H-NMR
Measurement conditions Apparatus; JNM-ECA400 (400 MHz), solvent; C 6 D 6 , method; 1D
The measurement results are shown in FIG.
δH (ppm) and (assignment) are listed below.
3.14 s (18H, N (C H 3 ) 2 )
2.20 d (6.5H, unknown)
1.54 q (2.3H, CH 3 C H 2 C (CH 3) 2 N)
1.31 s (7.6 H , CH 3 CH 2 C (C H 3 ) 2 N)
1.11 t (3.4H, C H 3 CH 2 C (CH 3 ) 2 N)
（５）蒸気圧
蒸留のデータから、１Ｔｏｒｒ／１００℃であった。
（６）性状と融点
淡黄色の結晶で、その融点は４７℃であった。(5) Vapor pressure It was 1 Torr / 100 degreeC from the data of distillation.
(6) Properties and melting point Pale yellow crystals having a melting point of 47 ° C.
（７）ＴＧ−ＤＴＡ
測定条件
試料重量；２２．８ｍｇ、雰囲気；Ａｒ １気圧、
昇温速度；１０．０ｄｅｇ／ｍｉｎ
測定結果を図３に示した。(7) TG-DTA
Measurement conditions Sample weight; 22.8 mg, atmosphere; Ar 1 atm,
Temperature increase rate: 10.0 deg / min
The measurement results are shown in FIG.
（８）溶液化
Ｎｂ（ＮｔＡｍ）（ＮＭｅ２）３にヘキサンを１０ｗｔ％添加した組成物は、２０℃で完全に溶液となり析出物がなかった。トルエンでも同様であった。(8) Solutionization The composition obtained by adding 10 wt% of hexane to Nb (NtAm) (NMe 2 ) 3 became a complete solution at 20 ° C. and had no precipitate. The same was true for toluene.
以上に述べたうちの主に組成分析、ＥＩ−ＭＳ、１Ｈ−ＮＭＲから総合的に判断して、この化合物はＮｂ（ＮｔＡｍ）（ＮＭｅ２）３と同定した。Of these, the compound was identified as Nb (NtAm) (NMe 2 ) 3 mainly judging from composition analysis, EI-MS, and 1 H-NMR.
次にＮｂ（ＮｔＡｍ）（ＮＭｅ２）３と同じ手法で公知化合物のＮｂ（ＮｔＢｕ）（ＮＥｔ２）３を合成し、融点、蒸気圧を測定し、本発明化合物のＮｂ（ＮｔＡｍ）（ＮＭｅ２）３と比較した。融点と蒸気圧の結果を表１に示した。Next, Nb (NtBu) (NEt 2 ) 3 which is a known compound is synthesized by the same method as Nb (NtAm) (NMe 2 ) 3 , the melting point and vapor pressure are measured, and Nb (NtAm) (NMe 2 ) of the compound of the present invention is measured. ) Compared with 3 . The results of melting point and vapor pressure are shown in Table 1.
表１より本発明のＮｂ（ＮｔＡｍ）（ＮＭｅ２）３が１Ｔｏｒｒを与える温度は１００℃で、Ｎｂ（ＮｔＢｕ）（ＮＥｔ２）３の１５０℃より約５０℃低いことがわかる。またＴａ（ＮｔＢｕ）（ＮＥｔ２）３は８０℃で０．１Ｔｏｒｒしかないので、同じ温度で蒸気圧を比較すると、本発明のＮｂ（ＮｔＡｍ）（ＮＭｅ２）３は約１０倍の高い蒸気圧を与える。よって本発明のＮｂ（ＮｔＡｍ）（ＮＭｅ２）３は、ＡＬＤ原料化合物として蒸気圧の点で非常に好ましい性質を有していることが明らかである。蒸発させるためにソース温度や気化器温度を低くできることは、そこでの熱劣化を少なくすることができ、使用の安定がはかれ、パーティクル発生量を少なくできるという利点を有する。Table 1 shows that the temperature at which Nb (NtAm) (NMe 2 ) 3 of the present invention gives 1 Torr is 100 ° C., which is about 50 ° C. lower than 150 ° C. of Nb (NtBu) (NEt 2 ) 3 . Further, Ta (NtBu) (NEt 2 ) 3 has only 0.1 Torr at 80 ° C. Therefore, when comparing the vapor pressure at the same temperature, Nb (NtAm) (NMe 2 ) 3 of the present invention has a vapor pressure that is about 10 times higher. give. Therefore, it is clear that Nb (NtAm) (NMe 2 ) 3 of the present invention has a very favorable property in terms of vapor pressure as an ALD raw material compound. The ability to lower the source temperature and vaporizer temperature for evaporation has the advantage that thermal degradation there can be reduced, the use is stabilized, and the amount of particles generated can be reduced.
本発明のＮｂ（ＮｔＡｍ）（ＮＭｅ２）３は金属元素不純物が各１ｐｐｍ以下、Ｃｌが１ｐｐｍで高純度であった。蒸留精製により純度はさらに上げられる。Nb (NtAm) (NMe 2 ) 3 of the present invention was highly pure with 1 ppm or less of metal element impurities and 1 ppm of Cl. The purity is further increased by distillation purification.
本発明はＮｂ（ＮｔＡｍ）（ＮＭｅ２）３を原料として用いることを特徴とするＡＬＤ法による窒化ニオブ膜もしくは酸化ニオブ膜の形成方法でもある。
Ｎｂ（ＮｔＡｍ）（ＮＭｅ２）３の供給方法としては、
（１）５０〜１２０℃にソース温度を保ち、発生する蒸気の自圧でベーパーソースマスフローコントローラーにより供給する
（２）融点の４７℃以上、好ましくは５０℃以上にソース温度を保ち、液体とし、キャリアーガスをバブリングすることによりＮｂ（ＮｔＡｍ）（ＮＭｅ２）３を気化させる
（３）ソース温度を５０℃以上に加熱し、液体として６０℃程度に加熱された液体マスフローメーターで供給し、気化器で全量気化させる
（４）Ｎｂ（ＮｔＡｍ）（ＮＭｅ２）３に１０ｗｔ％以上の有機溶媒を添加し、室温で溶液として液体マスフローコントローラーあるいは液体マスフローメーターで供給し、気化器で全量気化させる
等がある。
Ｎｂ（ＮｔＡｍ）（ＮＭｅ２）３は液体状態では約５ｃｐの粘度であり、バブリングやマスフローコントローラー、マスフローメーターで使える。
また（４）の有機溶媒としては、ヘキサン、ヘプタン、オクタン、トルエン、シクロヘキサン等、ＣＶＤ原料溶媒として通常使用されているものが使用できる。The present invention is also a method for forming a niobium nitride film or a niobium oxide film by an ALD method characterized by using Nb (NtAm) (NMe 2 ) 3 as a raw material.
As a supply method of Nb (NtAm) (NMe 2 ) 3 ,
(1) Keep the source temperature at 50 to 120 ° C., and supply it with a vapor source mass flow controller with the self-pressure of the generated steam (2) Keep the source temperature at a melting point of 47 ° C. or higher, preferably 50 ° C. or higher, and make it a liquid, Nb (NtAm) (NMe 2 ) 3 is vaporized by bubbling the carrier gas. (3) The source temperature is heated to 50 ° C. or higher and supplied as a liquid by a liquid mass flow meter heated to about 60 ° C. (4) Add an organic solvent of 10 wt% or more to Nb (NtAm) (NMe 2 ) 3 , supply it as a solution at room temperature with a liquid mass flow controller or a liquid mass flow meter, and evaporate the entire amount with a vaporizer. is there.
Nb (NtAm) (NMe 2 ) 3 has a viscosity of about 5 cp in the liquid state and can be used in bubbling, a mass flow controller, and a mass flow meter.
Further, as the organic solvent (4), hexane, heptane, octane, toluene, cyclohexane and the like which are usually used as CVD raw material solvents can be used.
Ｎｂ（ＮｔＡｍ）（ＮＭｅ２）３の製造
温度計、攪拌子を備えた５００ｍＬ三口フラスコを真空置換後、アルゴン雰囲気下とし、作りたてのＬｉＮＭｅ２ヘキサン懸濁液１５０ｍＬ（ＬｉＮＭｅ２として２０．４ｇ，０．４０ｍｏｌ）と作りたてのＬｉＮＨｔＡｍヘキサン懸濁液５０ｍＬ（ＬｉＮＨｔＡｍとして９．３ｇ，０．１０ｍｏｌ）を仕込み、１時間よく攪拌した。フラスコを水冷しながら粉末状の高純度ＮｂＣｌ５（２７．０ｇ，０．１０ｍｏｌ）を反応液温が２０〜３５℃になるように徐々に加えた。その後、室温にて４８時間攪拌すると、沈降性のよいスラリーとなった。次いで副生したＬｉＣｌ粒子を濾過分離すると、黄色透明液体が得られた。この液をオイルバス温度３０℃で減圧にしてヘキサン溶媒や副生アミン類を留去すると、オレンジ色の粘性液体となった。この液体を１１０℃付近で１Ｔｏｒｒで蒸留し、黄紅茶色の透明液体２２．３ｇを得た。この液体をヘキサン３０ｍＬに溶解し、−３０℃で再結晶した。得られた淡黄色結晶を１Ｔｏｒｒ下で蒸留し、留出温度１００℃付近で黄紅茶色の液体主留分１８．０ｇを得た。この液は室温で暗黄色の結晶に固化した。同定の結果は前述したようにＮｂ（ＮｔＡｍ）（ＮＭｅ２）３であり（０．０５８ｍｏｌ）、収率はＮｂＣｌ５に対して５８％であった。Manufacture of Nb (NtAm) (NMe 2 ) 3 A 500 mL three-necked flask equipped with a thermometer and a stirrer was replaced with a vacuum, and then placed in an argon atmosphere, and 150 mL of a fresh LiNMe 2 hexane suspension (20.4 g as LiNMe 2 , 0 .40 mol) and 50 mL of freshly prepared LiNHtAm hexane suspension (9.3 g, 0.10 mol as LiNHtAm) were added and stirred well for 1 hour. While cooling the flask with water, powdery high-purity NbCl 5 (27.0 g, 0.10 mol) was gradually added so that the reaction solution temperature was 20 to 35 ° C. Then, when it stirred at room temperature for 48 hours, it became a slurry with good sedimentation property. Subsequently, by-product LiCl particles were separated by filtration to obtain a yellow transparent liquid. When this solution was reduced in pressure at an oil bath temperature of 30 ° C. and the hexane solvent and by-product amines were distilled off, an orange viscous liquid was obtained. This liquid was distilled at around 110 ° C. and 1 Torr to obtain 22.3 g of a yellowish black transparent liquid. This liquid was dissolved in 30 mL of hexane and recrystallized at -30 ° C. The obtained pale yellow crystals were distilled under 1 Torr to obtain 18.0 g of a yellow tea black liquid main fraction at a distillation temperature of about 100 ° C. This solution solidified into dark yellow crystals at room temperature. As described above, the result of identification was Nb (NtAm) (NMe 2 ) 3 (0.058 mol), and the yield was 58% with respect to NbCl 5 .
Ｎｂ（ＮｔＡｍ）（ＮＭｅ２）３を用いたＡＬＤ法による酸化ニオブ膜の形成
実施例１で得たＮｂ（ＮｔＡｍ）（ＮＭｅ２）３を入れたシリンダーを８０℃に加熱し、露点−１１０℃のキャリアーガスでバブリングして得たＮｂ（ＮｔＡｍ）（ＮＭｅ２）３の蒸気と水、露点−１１０℃のパージガスを交互にＡＬＤ室に導入した。基板温度３５０℃にて約２０ｎｍの膜を形成した。この膜は膜中の不純物が少ない良質の酸化ニオブ膜であった。 Nb (NtAm) (NMe 2) 3 was heated Nb obtained in forming the first embodiment of the niobium oxide film by the ALD method (NtAm) a cylinder containing the (NMe 2) 3 to 80 ° C. with a dew point -110 ° C. A vapor of Nb (NtAm) (NMe 2 ) 3 obtained by bubbling with a carrier gas and water and a purge gas having a dew point of −110 ° C. were alternately introduced into the ALD chamber. A film having a thickness of about 20 nm was formed at a substrate temperature of 350 ° C. This film was a good quality niobium oxide film with few impurities in the film.
Ｎｂ（ＮｔＡｍ）（ＮＭｅ２）３を用いたＡＬＤ法による窒化ニオブ膜の形成
実施例１で得たＮｂ（ＮｔＡｍ）（ＮＭｅ２）３を入れたシリンダーを８０℃に加熱し、露点−１１０℃のキャリアーガスでバブリングして得たＮｂ（ＮｔＡｍ）（ＮＭｅ２）３の蒸気とアンモニアガス、露点−１１０℃のパージガスを交互にＡＬＤ室に導入した。基板温度３００℃にて約２０ｎｍの膜を形成した。この膜は膜中の不純物が少ない良質の窒化ニオブ膜であった。 Nb (NtAm) (NMe 2) 3 was heated Nb obtained in forming the first embodiment of the niobium nitride layer by the ALD method (NtAm) a cylinder containing the (NMe 2) 3 to 80 ° C. with a dew point -110 ° C. A vapor of Nb (NtAm) (NMe 2 ) 3 obtained by bubbling with a carrier gas of 1 and a purge gas having a dew point of −110 ° C. were alternately introduced into the ALD chamber. A film having a thickness of about 20 nm was formed at a substrate temperature of 300 ° C. This film was a good quality niobium nitride film with few impurities in the film.
本発明は、高い蒸気圧を持ち、５０℃以下の融点である、新規な化合物であり、この原料を用いるＡＬＤ法による窒化ニオブ膜あるいは酸化ニオブ膜は、良質で極微細加工性に優れているので、産業上の利用可能性は極めて大きい。 The present invention is a novel compound having a high vapor pressure and a melting point of 50 ° C. or less. A niobium nitride film or niobium oxide film by this ALD method using this raw material is of high quality and excellent in ultrafine workability. Therefore, industrial applicability is extremely large.
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