KR100834453B1 - Method for forming high dielectric thin layer and high dielectric thin layer - Google Patents
Method for forming high dielectric thin layer and high dielectric thin layer Download PDFInfo
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- KR100834453B1 KR100834453B1 KR1020070010401A KR20070010401A KR100834453B1 KR 100834453 B1 KR100834453 B1 KR 100834453B1 KR 1020070010401 A KR1020070010401 A KR 1020070010401A KR 20070010401 A KR20070010401 A KR 20070010401A KR 100834453 B1 KR100834453 B1 KR 100834453B1
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- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000010409 thin film Substances 0.000 claims abstract description 61
- 239000002019 doping agent Substances 0.000 claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 230000001590 oxidative effect Effects 0.000 claims abstract description 10
- 239000011572 manganese Substances 0.000 claims abstract description 6
- 239000000758 substrate Substances 0.000 claims abstract description 6
- 239000010936 titanium Substances 0.000 claims abstract description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052788 barium Inorganic materials 0.000 claims abstract description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 3
- 239000011733 molybdenum Substances 0.000 claims abstract description 3
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 3
- 239000010937 tungsten Substances 0.000 claims abstract description 3
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000000151 deposition Methods 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 15
- 239000010408 film Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 6
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 238000005229 chemical vapour deposition Methods 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000001272 nitrous oxide Substances 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 238000000427 thin-film deposition Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 238000005137 deposition process Methods 0.000 abstract 1
- 230000008021 deposition Effects 0.000 description 11
- 238000000231 atomic layer deposition Methods 0.000 description 8
- 238000000137 annealing Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 4
- 230000010354 integration Effects 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- ZYLGGWPMIDHSEZ-UHFFFAOYSA-N dimethylazanide;hafnium(4+) Chemical compound [Hf+4].C[N-]C.C[N-]C.C[N-]C.C[N-]C ZYLGGWPMIDHSEZ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 238000007736 thin film deposition technique Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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- 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
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
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- H—ELECTRICITY
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- 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
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
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- 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
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
- H01L21/02175—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
- H01L21/02181—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing hafnium, e.g. HfO2
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
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- 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
- H01L21/28556—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 chemical means, e.g. CVD, LPCVD, PECVD, laser CVD
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Abstract
Description
도 1a 내지 1d는 산소와 질소-산소 혼합가스 플라즈마를 이용하여 원자층 증착법으로 HfO2와 HfOxNy의 증착을 두께별로 조절한 시편의 모식도이다.1A to 1D are schematic diagrams of specimens in which deposition of HfO 2 and HfO x N y is controlled for each thickness by atomic layer deposition using an oxygen and nitrogen-oxygen mixed gas plasma.
도 2는 도 1과 같이 형성된 박막에 대해 누설전류를 측정한 결과를 나타내는 그래프이다.FIG. 2 is a graph illustrating a result of measuring a leakage current of the thin film formed as shown in FIG. 1.
도 3은 도 1과 같이 형성된 박막에 대해 전기용량(capacitance)-전압(voltage)을 측정한 결과를 나타내는 그래프이다.FIG. 3 is a graph illustrating a result of measuring capacitance-voltage of a thin film formed as shown in FIG. 1.
도 4는 도 1과 같이 형성된 박막에 대해 파괴전압(breakdown voltage)을 측정한 결과를 나타내는 그래프이다.4 is a graph illustrating a result of measuring a breakdown voltage of a thin film formed as shown in FIG. 1.
고유전율 박막은 금속 산화물 반도체 전계효과 트랜지스터(MOSFET)의 게이트 산화물이나 커패시터의 유전체에서 SiO2를 대체할 수 있는 물질로 많이 연구되고 있다.High dielectric constant thin films are being studied as a material that can replace SiO 2 in the gate oxide of a metal oxide semiconductor field effect transistor (MOSFET) or the dielectric of a capacitor.
게이트 산화물로 고유전율 박막을 사용할 경우 등가산화물막두께(equivalent oxide thickness)를 줄이면서도 누설전류도 감소시킬 수 있기 때문에, 소자의 집적도를 높이기 위해서 반드시 적용할 필요가 있는 것으로 고려되고 있다.In the case of using a high dielectric constant thin film as the gate oxide, the leakage current can be reduced while reducing the equivalent oxide thickness. Therefore, it is considered to be necessary to apply the device to increase the device integration.
또한 커패시터 유전체도 점차 작은 크기로 많은 전하량을 저장할 필요가 있기 때문에, 같은 크기에서 전기용량을 늘릴 수 있는 고유전율 박막의 증착이 필수적이라 할 수 있다.In addition, since the capacitor dielectric needs to store a large amount of charge in an increasingly small size, it is essential to deposit a high-k dielectric film that can increase capacitance at the same size.
최근에는 이러한 고유전율 박막의 증착용으로 HfO2나 ZrO2, Ta2O5, Al2O3, TiO2나 이들의 화합물, 또는 이들의 나노 적층구조 등이 많이 연구되고 있다.Recently, HfO 2 , ZrO 2 , Ta 2 O 5 , Al 2 O 3 , TiO 2 , compounds thereof, or nano-laminated structures thereof have been studied for the deposition of such high dielectric constant thin films.
상기 산화물들의 증착 방법으로는 원자층 증착법이 많이 사용되고 있지만, 신뢰성이나 누설전류(leakage currents)의 증가, 많은 계면 상태 등이 문제점으로 지적되고 있다. Atomic layer deposition is widely used as the deposition method of the oxides, but reliability, increase of leakage currents, and many interface states have been pointed out as problems.
한편 산화물에 질소나 불소를 집어넣음으로써 상기 문제점을 줄여나갈 수 있음이 알려져 있는데, 이는 질소나 불소와 같은 물질들이 결함(defect)의 발생을 줄여 산화물의 신뢰성을 높이고 누설전류를 줄일 수 있기 때문이다. On the other hand, it is known that the problem can be reduced by injecting nitrogen or fluorine into the oxide, because materials such as nitrogen and fluorine can reduce the occurrence of defects, thereby increasing the reliability of the oxide and reducing leakage current. .
그리고 질소나 불소를 도핑(doping)시키는 방법으로는, 종래 박막을 형성한 후 어닐링(annealing)을 수행하는 방법이 알려져 있는데, 이와 같이 박막을 형성한 후에 어닐링을 실시하는 2단계의 공정으로 진행할 경우, 제조원가나 효율의 측면에서 불리하다.As a method of doping nitrogen or fluorine, a method of performing annealing after forming a thin film is known in the related art. In the case of proceeding to a two-step process of performing annealing after forming the thin film as described above, It is disadvantageous in terms of manufacturing cost and efficiency.
또한, 실제 고유전율 박막을 게이트 산화물로 사용할 경우, 도펀트(dopant) 인 질소는 기판과의 계면(interface)부분에서는 결함을 막아줄 정도의 적은 양이 들어가야 하는 반면, 게이트 쪽은 폴리 실리콘(poly Si)의 도펀트 확산(dopant diffusion)을 막아 줄 수 있도록 많은 양이 들어가야 한다. 즉, 도펀트의 두께별 도핑 프로파일(doping profile)이 정확하게 조절될 필요가 있으나, 상기 어닐링 방법을 통해서는 도핑 프로파일의 조절이 불가능하다.In addition, when a high dielectric constant thin film is used as a gate oxide, nitrogen, a dopant, should be small enough to prevent defects at the interface with the substrate, while the gate side is polysilicon. A large amount should be added to prevent dopant diffusion of That is, the doping profile for each thickness of the dopant needs to be precisely adjusted, but the doping profile cannot be adjusted through the annealing method.
본 발명은 전술한 종래기술의 문제점을 해결하기 위해 창안된 것으로, 도펀트를 박막의 증착과 동시에 형성시킬 수 있으며, 도펀트의 도핑(doping) 프로파일을 박막의 두께별로 정확히 조절할 수 있어, 박막의 특성을 향상시킬 수 있는 고유전율 박막의 형성방법을 제공하는데 그 목적이 있다.The present invention has been made to solve the above-mentioned problems of the prior art, it is possible to form a dopant at the same time as the deposition of the thin film, the doping (dope) profile of the dopant can be precisely adjusted for each thickness of the thin film, thereby controlling It is an object of the present invention to provide a method of forming a high dielectric constant thin film that can be improved.
또한, 본 발명의 다른 목적은 박막의 소자 특성이 현저하게 향상된 고유전율 박막을 제공하는 것이다.In addition, another object of the present invention is to provide a high-k dielectric thin film significantly improved device properties of the thin film.
상기 목적을 달성하기 위한 본 발명에 따른 방법은, 증착법을 통해 기판상에 고유전율 박막을 형성하는 방법으로, (a) 금속 전구체와 상기 금속을 산화시킬 수 있는 물질을 주입하여 박막을 형성하는 단계와, (b) 금속 전구체, 상기 금속을 산화시킬 수 있는 물질 및 도펀트(dopant)를 포함하는 물질을 주입하여 도펀트(dopant)가 포함된 박막을 형성하는 단계를 포함하며, 상기 (b) 단계를 상기 (a)단계의 전, 후 또는 중간에 실시하여, 형성된 박막 상에 도펀트(dopant) 층의 위치 또는 두께 프로파일을 조절함으로써, 소자의 특성을 변화시킬 수 있는데 특징이 있 다.The method according to the present invention for achieving the above object is a method of forming a high dielectric constant thin film on a substrate by a vapor deposition method, (a) forming a thin film by injecting a metal precursor and a material capable of oxidizing the metal And (b) injecting a metal precursor, a material capable of oxidizing the metal, and a material including a dopant to form a thin film including a dopant, the step (b) The characteristics of the device may be changed by adjusting the position or thickness profile of the dopant layer on the formed thin film by performing before, after, or in the middle of the step (a).
본 발명에 있어서, "도펀트(dopant)"란 유전율 박막의 특성을 변화시키기 위해 의도적으로 넣어주는 원소를 의미하며, "도핑(doping)"이란 박막의 질화처리 또는 불화처리와 같이 필요한 원소를 박막 중에 화합물 상태로 첨가하는 것을 의미한다.In the present invention, "dopant" means an element that is intentionally put in order to change the properties of the dielectric film, "doping" means a necessary element such as nitriding or fluorination treatment of the thin film It means adding in a compound state.
상기 본 발명에 따른 제조방법에서는, 금속 전구체, 금속을 산화시킬 수 있는 물질 및 도펀트를 포함하는 물질을 주입하여 박막을 형성하는 단계를 선택적으로 실시함으로써, 도펀트를 박막의 원하는 위치에 원하는 두께로 주입할 수 있어, 박막의 특성을 다양하게 변화시킬 수 있게 된다.In the manufacturing method according to the present invention, by injecting a metal precursor, a material capable of oxidizing a metal and a material containing a dopant to selectively form a thin film, the dopant is injected to a desired position of the thin film in a desired thickness It is possible to change the characteristics of the thin film in various ways.
또한, 도펀트는 박막의 형성시에 함께 주입되기 때문에, 종래의 어닐링과 같은 후속 공정이 필요하지 않게 되어, 공정수가 줄어들고, 제조온도도 낮아지게 되므로, 제조원가가 절감되며 생산성이 향상되게 된다.In addition, since the dopant is implanted together at the time of forming the thin film, subsequent processes such as conventional annealing are unnecessary, so that the number of processes is reduced and the manufacturing temperature is lowered, thereby reducing manufacturing costs and improving productivity.
상기 금속 전구체의 금속은 하프늄(Hf), 지르코늄(Zr), 알루미늄(Al), 탄탈룸(Ta), 티타늄(Ti), 스트론튬(Sr), 란타늄(La), 바륨(Ba), 납(Pb), 크롬(Cr), 몰리브덴(Mo), 텅스텐(W), 이트륨(Y) 및 망간(Mn)으로 이루어진 군에서 선택된 1종 이상일 수 있으나, 이에 제한되지 않는다.The metal of the metal precursor is hafnium (Hf), zirconium (Zr), aluminum (Al), tantalum (Ta), titanium (Ti), strontium (Sr), lanthanum (La), barium (Ba), lead (Pb) , Chromium (Cr), molybdenum (Mo), tungsten (W), yttrium (Y) and manganese (Mn) may be one or more selected from the group consisting of, but is not limited thereto.
또한, 상기 도펀트(dopant)는 별도의 물질을 통해 투입될 수도 있으나, 암모니아수(NH4OH)와 같이 금속을 산화시킬 수 있는 물질에 포함되어 있을 수도 있다. 또한, 상기 도펀트(dopant)로는 유전체의 특성을 변화시킬 수 있는 것이면 어느 것 이나 적용될 수 있으며, 바람직하게는 질소(N) 또는 불소(F)를 사용한다.In addition, the dopant may be added through a separate material, or may be included in a material capable of oxidizing a metal such as ammonia water (NH 4 OH). In addition, the dopant may be applied as long as it can change the characteristics of the dielectric, preferably nitrogen (N) or fluorine (F) is used.
또한, 상기 금속 전구체의 금속을 산화시킬 수 있는 물질로는 산소, 아산화질소, 암모니아수 및 물로 이루어진 군에서 선택된 1종 이상을 사용하나, 이에 제한되지 않는다.In addition, as a material capable of oxidizing the metal of the metal precursor, one or more selected from the group consisting of oxygen, nitrous oxide, ammonia water and water is used, but is not limited thereto.
또한, 상기 증착법은 본 발명의 기술적 사상이 적용될 수 있는 것이면 어느 것이나 사용될 수 있으며, 바람직하게는 원자층 증착법(ALD) 또는 화학적 기상 증착법(CVD)을 사용한다.In addition, the deposition method may be used as long as the technical spirit of the present invention can be applied, preferably using atomic layer deposition (ALD) or chemical vapor deposition (CVD).
또한, 상기 본 발명의 다른 목적을 제공하기 위한 본 발명에 따른 고유전율 박막은, 기판상에 형성된 고유전율 박막으로서, 도펀트가 함유되지 않은 박막층의 사이에 도펀트가 함유된 박막층이 형성되어 있는데 특징이 있다. 이와 같이 도펀트가 함유된 박막층이 도펀트가 함유되어 있지 않는 박막층의 사이에 위치함으로써, 유전상수가 커지고 절연파괴 특성이 개선된다.In addition, the high dielectric constant thin film according to the present invention for providing another object of the present invention is a high dielectric constant thin film formed on the substrate, a thin film layer containing a dopant is formed between the thin film layer containing no dopant have. As such, the thin film layer containing the dopant is positioned between the thin film layers not containing the dopant, thereby increasing the dielectric constant and improving the dielectric breakdown characteristic.
이하, 본 발명의 실시예를 기초로 하여 본 발명을 보다 상세히 설명한다. 그러나 하기 실시예는 단지 예시적인 것으로 본 발명을 한정하는 것이 아니다.Hereinafter, the present invention will be described in more detail based on the embodiments of the present invention. However, the following examples are merely illustrative and do not limit the invention.
[시편 1][Psalm 1]
본 발명의 실시예에서는 원자층 증착(ALD) 장비를 사용하여 증착을 수행하였으며, 금속 전구체로는 Tetrakis(dimethylamino)Hafnium(Hf(NMe2)4)을 사용하였다.In an embodiment of the present invention, deposition was performed using atomic layer deposition (ALD) equipment, and Tetrakis (dimethylamino) Hafnium (Hf (NMe 2 ) 4 ) was used as the metal precursor.
전구체의 캐리어(carrier) 가스로는 아르곤(Ar)을 사용하였고 퍼징 가 스(purging gas)도 동일하게 아르곤을 사용하였다.Argon (Ar) was used as a carrier gas of the precursor, and argon was also used for the purging gas.
베이스 압력은 터보 분자 펌프를 이용, 5×10-7 Torr가 되도록 하였으며 가스의 유량은 MFC로 조절하였다. The base pressure was 5 × 10 −7 Torr using a turbo molecular pump and the flow rate of gas was controlled by MFC.
사용한 원자층 증착 공정의 레시피는 온도 250℃에서 전구체 0.2초, 퍼징 4초, 반응물 4초, 퍼징 4초로 하였다.The recipe of the used atomic layer deposition process was made into the precursor 0.2 second, the purging 4 second, the
먼저, p-type Si 웨이퍼를 RCA세척(H2O, NH4OH, H2O2 의 5:1:1 혼합물) 한 후, 산소 플라즈마만을 이용해 30회 증착하여, 도 1a와 같은 단면을 갖는 HfO2로 이루어진 박막을 형성하였다. 이때 증착 비율은 약 1.3Å/cycle로 전형적인 원자층 증착 특성을 보여주었다. 산화물 박막의 두께는 약 4nm 정도였다.First, the p-type Si wafer is RCA washed (5: 1: 1 mixture of H 2 O, NH 4 OH, and H 2 O 2 ), and then deposited 30 times using only oxygen plasma to have a cross section as shown in FIG. A thin film made of HfO 2 was formed. At this time, the deposition rate was about 1.3 mA / cycle, which showed typical atomic layer deposition characteristics. The thickness of the oxide thin film was about 4 nm.
증착 후 어닐링(post deposition annealing)으로 산소 분위기 상압 400℃에서 10분간 급속열처리(rapid thermal processing)를 행한 후, 게이트 전극으로 백금을 스퍼터링으로 하드 마스크(hard mask)를 이용해서 증착하고, 열증착으로 증착한 금을 백 콘택트(back contact)로 사용하였다. 그리고 형성가스(H2 5% + N2 95%) 어닐링을 400℃에서 30분간 행하였다.After 10 minutes of rapid thermal processing at 400 ° C in an oxygen atmosphere by post deposition annealing, platinum was deposited using a hard mask by sputtering the gate electrode, followed by thermal deposition. The deposited gold was used as a back contact. Forming gas (H 2 5% + N 2 95%) annealing was performed at 400 ° C. for 30 minutes.
[시편 2][Psalm 2]
질소-산소 혼합가스 플라즈마를 이용해서 우선 10회 증착하여 HfOxNy 막을 형성한 후, 이어서 산소 플라즈마만을 이용해서 20회 증착하여 HfO2 막을 형성하여, 도 1b와 같은 단면을 갖는 박막을 형성하였으며, 기타의 공정은 시편 1과 동일하게 하였다. The HfO x N y film was first formed by 10 times deposition using a nitrogen-oxygen mixed gas plasma, followed by 20 times deposition using only oxygen plasma to form an HfO 2 film, thereby forming a thin film having a cross section as shown in FIG. 1B. And other processes were the same as in
[시편 3][Psalm 3]
산소 플라즈마만을 이용해서 10회 증착하여 HfO2 막을 형성한 후, 질소-산소 혼합가스 플라즈마를 이용해 10회 증착하여 HfOxNy 막을 형성하고, 다시 산소 플라즈마를 이용해서 10회 증착하여 HfO2 막을 형성하여, 도 1c와 같은 단면을 갖는 박막을 형성하였으며, 기타의 공정은 시편 1과 동일하게 하였다. After depositing 10 times using only oxygen plasma to form HfO 2 film, it is deposited 10 times using nitrogen-oxygen mixed gas plasma to form HfO x N y film, and then 10 times using oxygen plasma to form HfO 2 film. Thus, a thin film having a cross section as shown in FIG. 1C was formed, and other processes were the same as those in
[시편 4][Psalm 4]
산소 플라즈마만을 이용해서 20회 증착하여 HfO2 막을 형성한 후, 질소-산소 혼합가스 플라즈마를 이용해 10회 증착하여 HfOxNy 막을 형성하여, 도 1d와 같은 단면을 갖는 박막을 형성하였으며, 기타의 공정은 시편 1과 동일하게 하였다.After depositing 20 times using only oxygen plasma to form an HfO 2 film, and then depositing 10 times using a nitrogen-oxygen mixed gas plasma to form an HfO x N y film, a thin film having a cross section as shown in FIG. 1D was formed. The process was the same as that in
이상과 같이 형성된 고유전율 박막에 대해 전기적 특성을 측정하였는데, 누설전류(leakage currents)는 케이슬리(Keithely) 4200 반도체 분석기로 측정하였으며, 전기용량-전압은 HP4284로 측정하였다.The electrical characteristics of the high-k dielectric thin film formed as described above were measured. Leakage currents were measured by a Keisly 4200 semiconductor analyzer, and the capacitance-voltage was measured by HP4284.
도 2에 나타난 바와 같이, 증착한 HfO2-HfOxNy박막의 누설전류를 보여준다. HfOxNy층이 포함된 MOS소자의 누설전류가 그렇지 않은 순수한 HfO2박막으로 이루어진 경우보다 1MV/cm에서 10배 가까이 줄어듦을 확인할 수 있다.As shown in Figure 2, it shows the leakage current of the deposited HfO 2 -HfO x N y thin film. It can be seen that the leakage current of the MOS device including the HfO x N y layer is reduced by 10 times at 1 MV / cm than the case of the pure HfO 2 thin film.
도 3에 나타난 바와 같이, HfOxNy층이 포함된 MOS소자의 경우, 유전상수가 순수한 HfO2박막의 경우보다 증가함을 알 수 있으며, 특히 HfOxNy층이 가운데 증착된 박막인 시편 3의 경우, 계산된 유전상수가 24.8 (EOT=0.63nm)로 아래와 위에 증착한 시편 2 및 시편 3 박막의 22.1과 21.3보다 상당히 증가함을 알 수 있다. 이는 도펀트인 질소를 포함시키는 막의 위치 및 두께를 조절함으로써 등가산화물막두께(equivalent oxide thickness)를 줄일 수 있음을 보여준다. 즉, 본 발명에 따른 방법에 의하면 소자의 집적도를 높일 수 있게 된다.As shown in Figure 3, in the case of HfO x N y layer of a MOS device comprising a, it can be seen that the dielectric constant increases than in the case of pure HfO 2 thin film, in particular HfO x N y layer is a thin film of sample deposition of In the case of 3, the calculated dielectric constant is 24.8 (EOT = 0.63nm), which is considerably increased from 22.1 and 21.3 of the
도 4는 시편 1, 2, 3 및 4에서 각각 10개의 MOS소자의 유전층 절연파괴전압(dielectric breakdown voltage)를 측정한 결과이다. 도 4에 나타난 바와 같이, HfOxNy층이 포함된 MOS소자의 경우 절연파괴가 전체적으로 더 높은 전기장에서 발생하였으며, 특히 HfOxNy층이 가운데 증착된 박막인 시편 3의 경우 50% 파괴가 13MV/cm에서 발생하였고 파괴 분포(failure의 distribution) 역시 가장 샤프한 모습을 보여주었다.FIG. 4 shows the results of measuring dielectric breakdown voltages of 10 MOS devices in
상술한 바와 같이, 본 발명은 원자층 박막 증착법을 이용해서 고유전율 박막 증착시에 도펀트(dopant)의 위치를 조절함으로써 박막의 신뢰성을 높이고 또한 등가산화물막두께(EOT)를 낮추어 소자의 집적도를 향상시킬 수 있다.As described above, the present invention improves the reliability of the thin film by lowering the equivalent oxide film thickness (EOT) by adjusting the position of the dopant during the deposition of the high dielectric constant thin film by using the atomic layer thin film deposition method to improve the device integration. You can.
또한, 본 발명에 따른 제조방법은, 종래의 산화물 증착 후 아산화질소(N2O)나 암모니아(NH3)를 이용한 열 어닐링(thermal annealing) 처리의 2단계로 진행된 공정이 아니라, 박막 증착시에 도펀트가 함께 들어가는 1단계로 제조되기 때문에, 공정수가 줄어들고 공정온도를 낮출 수 있어, 제조원가가 절감되고 생산성이 향상된다.In addition, the manufacturing method according to the present invention is not a process proceeded in two steps of the thermal annealing treatment using nitrous oxide (N 2 O) or ammonia (NH 3 ) after the conventional oxide deposition, at the time of thin film deposition Since the dopant is manufactured in one step that enters together, the number of processes can be reduced and the process temperature can be lowered, thereby reducing manufacturing costs and improving productivity.
또한, 본 발명에 의하면, 필요로 하는 소자의 특성을 고려하여, 질소나 불소 같은 도펀트가 포함되는 위치와 두께 프로파일을 정확하게 조절할 수 있기 때문에, 소자 설계시 하나의 자유도(degree of freedom)를 부여할 수 있게 된다.In addition, according to the present invention, since the position and thickness profile in which dopants such as nitrogen and fluorine are contained can be precisely adjusted in consideration of the required characteristics of the device, a degree of freedom is given when designing the device. You can do it.
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