TWI392760B - Methods for producing silicon nitride films by vapor-phase growth - Google Patents
Methods for producing silicon nitride films by vapor-phase growth Download PDFInfo
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- TWI392760B TWI392760B TW93110330A TW93110330A TWI392760B TW I392760 B TWI392760 B TW I392760B TW 93110330 A TW93110330 A TW 93110330A TW 93110330 A TW93110330 A TW 93110330A TW I392760 B TWI392760 B TW I392760B
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- 238000000034 method Methods 0.000 title claims description 28
- 238000001947 vapour-phase growth Methods 0.000 title claims description 10
- 229910052581 Si3N4 Inorganic materials 0.000 title 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 title 1
- 239000007789 gas Substances 0.000 claims description 135
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 116
- 238000006243 chemical reaction Methods 0.000 claims description 84
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 claims description 63
- 238000004519 manufacturing process Methods 0.000 claims description 32
- 230000015572 biosynthetic process Effects 0.000 claims description 27
- 239000000758 substrate Substances 0.000 claims description 26
- 238000003786 synthesis reaction Methods 0.000 claims description 25
- 239000003701 inert diluent Substances 0.000 claims description 19
- 239000002243 precursor Substances 0.000 claims description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 239000011541 reaction mixture Substances 0.000 claims description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- -1 dimethyl hydrazine amide Chemical class 0.000 claims description 6
- YQYHEXLCJHNXRW-UHFFFAOYSA-N hydrazine methylhydrazine Chemical compound CNN.NN YQYHEXLCJHNXRW-UHFFFAOYSA-N 0.000 claims description 6
- PNKUSGQVOMIXLU-UHFFFAOYSA-N Formamidine Chemical compound NC=N PNKUSGQVOMIXLU-UHFFFAOYSA-N 0.000 claims description 5
- 238000000354 decomposition reaction Methods 0.000 claims description 4
- VMGAPWLDMVPYIA-HIDZBRGKSA-N n'-amino-n-iminomethanimidamide Chemical compound N\N=C\N=N VMGAPWLDMVPYIA-HIDZBRGKSA-N 0.000 claims description 3
- BOLDJAUMGUJJKM-LSDHHAIUSA-N renifolin D Natural products CC(=C)[C@@H]1Cc2c(O)c(O)ccc2[C@H]1CC(=O)c3ccc(O)cc3O BOLDJAUMGUJJKM-LSDHHAIUSA-N 0.000 claims description 3
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 claims description 2
- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical compound NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 claims description 2
- 229930182817 methionine Natural products 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 239000010408 film Substances 0.000 description 57
- 238000005229 chemical vapour deposition Methods 0.000 description 16
- 239000011261 inert gas Substances 0.000 description 15
- RHUYHJGZWVXEHW-UHFFFAOYSA-N 1,1-Dimethyhydrazine Chemical compound CN(C)N RHUYHJGZWVXEHW-UHFFFAOYSA-N 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 8
- FBOZXECLQNJBKD-ZDUSSCGKSA-N L-methotrexate Chemical compound C=1N=C2N=C(N)N=C(N)C2=NC=1CN(C)C1=CC=C(C(=O)N[C@@H](CCC(O)=O)C(O)=O)C=C1 FBOZXECLQNJBKD-ZDUSSCGKSA-N 0.000 description 6
- 101100023111 Schizosaccharomyces pombe (strain 972 / ATCC 24843) mfc1 gene Proteins 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 6
- 229960000485 methotrexate Drugs 0.000 description 6
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 238000005979 thermal decomposition reaction Methods 0.000 description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 4
- 235000019270 ammonium chloride Nutrition 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910052707 ruthenium Inorganic materials 0.000 description 4
- DIIIISSCIXVANO-UHFFFAOYSA-N 1,2-Dimethylhydrazine Chemical compound CNNC DIIIISSCIXVANO-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000012705 liquid precursor Substances 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 3
- YMEKHGLPEFBQCR-UHFFFAOYSA-N 2,2,3,3,5,5-hexachloro-1,4-dioxane Chemical compound ClC1(OC(C(OC1)(Cl)Cl)(Cl)Cl)Cl YMEKHGLPEFBQCR-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- IDBOAVAEGRJRIZ-UHFFFAOYSA-N methylidenehydrazine Chemical compound NN=C IDBOAVAEGRJRIZ-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- HSTYWKYKLFONRQ-UHFFFAOYSA-N 1,2-dichloroguanidine Chemical compound ClNC(N)=NCl HSTYWKYKLFONRQ-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- BCZWPKDRLPGFFZ-UHFFFAOYSA-N azanylidynecerium Chemical compound [Ce]#N BCZWPKDRLPGFFZ-UHFFFAOYSA-N 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 239000003575 carbonaceous material Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000000572 ellipsometry Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- CIGIXQCZEXLNIP-UHFFFAOYSA-N germylhydrazine Chemical group [GeH3]NN CIGIXQCZEXLNIP-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- WDWDWGRYHDPSDS-UHFFFAOYSA-N methanimine Chemical compound N=C WDWDWGRYHDPSDS-UHFFFAOYSA-N 0.000 description 1
- UNASZPQZIFZUSI-UHFFFAOYSA-N methylidyneniobium Chemical compound [Nb]#C UNASZPQZIFZUSI-UHFFFAOYSA-N 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- VOYCMZPGRYEHDB-UHFFFAOYSA-N n,n-bis(methylsulfonyl)methanesulfonamide Chemical compound CS(=O)(=O)N(S(C)(=O)=O)S(C)(=O)=O VOYCMZPGRYEHDB-UHFFFAOYSA-N 0.000 description 1
- BQIGMBPWIKZNQY-UHFFFAOYSA-N n-aminothiohydroxylamine Chemical compound NNS BQIGMBPWIKZNQY-UHFFFAOYSA-N 0.000 description 1
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 239000007845 reactive nitrogen species Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Classifications
-
- 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
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/34—Nitrides
- C23C16/345—Silicon nitride
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Vapour Deposition (AREA)
- Formation Of Insulating Films (AREA)
Description
本發明係關於產生氮化矽薄膜的方法,並且更特別地是關於藉由諸如化學氣相沈積(CVD,chemical vapor deposition)之氣相生長產生氮化矽薄膜的方法。The present invention relates to a method of producing a tantalum nitride film, and more particularly to a method of producing a tantalum nitride film by vapor phase growth such as chemical vapor deposition (CVD).
氮化矽膜具有極佳的阻障性質與極佳的抗氧化性,因而使用於微電子裝置製造(諸如作為蝕刻阻絕層、阻障層或閘極絕緣層)及氧化物/氮化物疊層中。Tantalum nitride film has excellent barrier properties and excellent oxidation resistance, and is therefore used in microelectronic device fabrication (such as as an etch stop layer, barrier layer or gate insulating layer) and an oxide/nitride stack. in.
電漿輔助CVD(PECVD,plasma-enhanced CVD)及低壓CVD(LPCVD,low-pressure CVD)為目前用於形成氮化矽膜的主要方法。Plasma-assisted CVD (PECVD) and low-pressure CVD (LPCVD) are the main methods currently used to form tantalum nitride films.
PECVD的進行通常係藉由在一對平行板電極間導入矽源(通常為矽烷)與氮源(通常為氨氣,但近來為氮氣),並在低溫(約350℃)與低壓(0.001 torr至5 torr)下,於該電極間施加高頻能量,以由矽源與氮源誘發電漿產生。在所形成之電漿中的活性矽物種與活性氮物種會彼此反應,而產生氮化矽薄膜。藉由PECVD而以該方式形成的氮化矽薄膜通常不具有化學計量組成且富含有氫,因而具有低薄膜密度、不佳的階梯覆蓋、快速蝕刻速率及不佳的熱穩定性。PECVD is usually carried out by introducing a helium source (usually decane) and a nitrogen source (usually ammonia, but more recently nitrogen) between a pair of parallel plate electrodes, and at low temperatures (about 350 ° C) and low pressure (0.001 torr). At 5 torr, high frequency energy is applied between the electrodes to induce plasma generation from the helium source and the nitrogen source. The active cerium species and the reactive nitrogen species in the formed plasma react with each other to produce a tantalum nitride film. The tantalum nitride film formed in this manner by PECVD generally does not have a stoichiometric composition and is rich in hydrogen, thus having low film density, poor step coverage, fast etch rate, and poor thermal stability.
LPCVD使用低壓(0.1至2 torr)與高溫(800℃至900℃),而產生品質優於PECVD所產生之氮化矽薄膜的氮化矽薄膜。目前,氮化矽通常藉由LPCVD而由二氯矽 烷與氣態氨的反應產生。然而,在該LPCVD過程中之二氯矽烷與氣態氨的反應會產生副產物氯化氨,該氯化氨會累積於反應器排氣管中並將其阻塞,且亦沈積於晶圓上。再者,現有的LPCVD技術具有氮化矽薄膜成長速率慢的缺點,並具有高熱預算。為降低產生氮化矽薄膜所需的熱預算,近來已發展出藉由將氨氣與六氯二矽烷(作為氮化矽前驅物)進行反應而產生氮化矽薄膜的方法。然而,該方法係因六氯二矽烷中存在有大量的氯而使前揭問題明顯加劇。該方法亦產生含矽微粒,此舉將使排氣管線的壽命實質地降低。最後,雖然該方法可在諸如600℃的反應溫度以極佳的生長速率提供高品質的氮化矽薄膜(良好的階梯覆蓋比例及低氯含量),但是當使用低於550℃的反應溫度時,這些性質會明顯地劣化。LPCVD uses low pressure (0.1 to 2 torr) and high temperature (800 ° C to 900 ° C) to produce a tantalum nitride film that is superior in quality to the tantalum nitride film produced by PECVD. Currently, tantalum nitride is usually made from dichloroguanidine by LPCVD. The reaction of an alkane with gaseous ammonia is produced. However, the reaction of methylene chloride with gaseous ammonia during the LPCVD process produces by-products, ammonium chloride, which accumulates in the reactor exhaust and blocks it and is also deposited on the wafer. Furthermore, the existing LPCVD technology has the disadvantage that the growth rate of the tantalum nitride film is slow and has a high thermal budget. In order to reduce the thermal budget required to produce a tantalum nitride film, a method of producing a tantalum nitride film by reacting ammonia gas with hexachlorodioxane (as a tantalum nitride precursor) has recently been developed. However, this method is significantly exacerbated by the presence of a large amount of chlorine in hexachlorodioxane. This method also produces ruthenium containing particles which will substantially reduce the life of the vent line. Finally, although the method can provide a high quality tantalum nitride film (good step coverage ratio and low chlorine content) at an excellent growth rate at a reaction temperature such as 600 ° C, when a reaction temperature lower than 550 ° C is used These properties will be significantly degraded.
已有人提出使用揮發性含碳矽氮烷、疊氮矽氮烷及胺基矽烷作為氮化矽前驅物,以解決前揭問題(參考非專利參考資料1與2)。然而,這些單獨使用或結合氨氣使用的氮化矽前驅物會使碳化矽和/或大量的碳摻入氮化矽薄膜產物中。It has been proposed to use volatile carbon-containing decane, azide and alkane as a cerium nitride precursor to solve the above problems (see Non-Patent References 1 and 2). However, these tantalum nitride precursors used alone or in combination with ammonia gas may incorporate niobium carbide and/or a large amount of carbon into the tantalum nitride film product.
(非專利參考資料1)Grow等人,Mater.Lett.23,187,1995(Non-patent Reference 1) Grow et al., Mater. Lett. 23, 187, 1995
(非專利參考資料2)Levy等人,J.Mater.Res.,11,1483,1996(Non-patent Reference 2) Levy et al., J. Mater. Res., 11, 1483, 1996
因此,本發明所解決的問題在於提供一種用於產生氮化矽薄膜的氣相生長方法,其中該氣相生長方法可產生具有改良薄膜特性的氮化矽薄膜,而縱使在相當低溫下亦可進行該反應,以及該氣相生長方法不會伴隨產生氯化銨,且不會有明顯的含碳污染物摻入薄膜產物中。Therefore, the problem to be solved by the present invention is to provide a vapor phase growth method for producing a tantalum nitride film, wherein the vapor phase growth method can produce a tantalum nitride film having improved film properties, even at relatively low temperatures. The reaction is carried out, and the vapor phase growth process is not accompanied by the production of ammonium chloride, and no significant carbonaceous contaminants are incorporated into the film product.
根據本發明的第一個觀點,所提供為一種藉由氣相生長產生氮化矽薄膜的方法,該方法的特徵在於:將聯胺氣體與選自由三甲矽烷基胺氣體和甲矽烷基聯胺氣體所組成之族群的至少一種前驅物氣體供給入容納有至少一個基板的反應器內,以及藉由該二種氣體的反應而將氮化矽薄膜形成於該至少一個基板上。According to a first aspect of the present invention, there is provided a method for producing a tantalum nitride film by vapor phase growth, the method characterized by: a hydrazine gas selected from the group consisting of a trimethyl hydrazine alkyl gas and a methyl hydrazine alkylamine At least one precursor gas of the group of gases is supplied into the reactor containing at least one substrate, and a tantalum nitride film is formed on the at least one substrate by the reaction of the two gases.
根據本發明的第二個觀點,所提供為一種藉由氣相生長產生氮化矽薄膜的方法,該方法的特徵在於:將甲矽烷基聯胺氣體供給入容納有至少一個基板的反應器內,以及藉由該甲矽烷基聯胺氣體的分解而將氮化矽薄膜形成於該至少一個基板上。According to a second aspect of the present invention, there is provided a method for producing a tantalum nitride film by vapor phase growth, the method comprising: feeding a methyl hydrazine hydrazine gas into a reactor containing at least one substrate And forming a tantalum nitride film on the at least one substrate by decomposition of the methotrexate hydrazine gas.
本發明係更具體地說明如下。The present invention is more specifically described below.
與藉由諸如CVD之氣相生長過程產生氮化矽薄膜於基板上的方法有關的本發明係使用三甲矽烷基胺((H3 Si)3 N )和/或甲矽烷基聯胺作為氮化矽前驅物。這些前驅物係藉由與聯胺的氣相反應而產生氮化矽薄膜。在這些前驅物當中,甲矽烷基聯胺可藉由本身的熱分解而形成氮化矽薄膜。The present invention relating to a method for producing a tantalum nitride film on a substrate by a vapor phase growth process such as CVD uses trimethylsulfonylamine ((H 3 Si) 3 N ) and/or a mercaptoalkylamine as a nitride.矽Precursor. These precursors produce a tantalum nitride film by gas phase reaction with hydrazine. Among these precursors, the mercapto hydrazine can form a tantalum nitride film by thermal decomposition of itself.
本發明所使用的甲矽烷基聯胺包含有化學式(I)所定義的甲矽烷基聯胺H3 Si(Ra )N-N(Rb )Rc (I)The formazan hydrazine used in the present invention comprises a dimethyl hydrazine H 3 Si(R a )NN(R b )R c (I) as defined by the formula (I).
其中,Ra ,Rb 與Rc 係個別獨立地選自甲矽烷基、氫原子、甲基、乙基及苯基。Wherein R a , R b and R c are each independently selected from the group consisting of a methyl group, a hydrogen atom, a methyl group, an ethyl group and a phenyl group.
與前揭前驅物反應的聯胺包含有化學式(Ⅱ)所定義的聯胺H(R1 )N-N(R2 )R3 (Ⅱ)The hydrazine reacted with the previously disclosed precursor contains the hydrazine H(R 1 )NN(R 2 )R 3 (II) defined by the formula (II)
其中,R1 ,R2 與R3 係個別獨立地選自氫原子、甲基、乙基及苯基。Wherein R 1 , R 2 and R 3 are each independently selected from a hydrogen atom, a methyl group, an ethyl group and a phenyl group.
首先將說明藉由聯胺與前揭前驅物(CVD過程)的反應而產生氮化矽薄膜的方法。在此例中,將預製體氣體、聯胺氣體及視需要而選用的惰性稀釋氣體供給入容納有至少一個基板(特指諸如矽基板的半導體基板)的反應器內,並藉由預製體氣體與聯胺氣體間的反應而將氮化矽薄膜形成於該基板上。First, a method of producing a tantalum nitride film by a reaction of a hydrazine with a precursor (CVD process) will be described. In this case, a preform gas, a hydrazine gas, and optionally an inert diluent gas are supplied into a reactor containing at least one substrate (specifically, a semiconductor substrate such as a ruthenium substrate), and by a preform gas A tantalum nitride film is formed on the substrate by a reaction with a hydrazine gas.
在預製體氣體與聯胺氣體的反應期間,反應室內部可維持在0.1 torr至1,000 torr的壓力,而將反應室內維持在0.1 torr至10 torr的壓力為較佳。During the reaction of the preform gas with the hydrazine gas, the pressure inside the reaction chamber can be maintained at a pressure of 0.1 to rr to 1,000 torr, and it is preferred to maintain the pressure in the reaction chamber at a pressure of 0.1 to rr to 10 torr.
預製體氣體與聯胺氣體的反應通常可在不超過1,000 ℃的溫度(CVD反應溫度)下進行。然而,在低於300℃的溫度下幾乎無氮化矽產生。因此,預製體氣體與聯胺氣體的反應可在300℃至1,000℃進行。縱使在400℃至700℃的低溫下,該預製體與聯胺仍得以足夠高的生長速率(薄膜形成速率)產生氮化矽。此外,當CVD反應溫度為300℃至500℃時,縱使開口的縱橫比為10,其仍可獲得諸如至少約0.8的階梯覆蓋比例。階梯覆蓋比例可定義為位於接梯形體之最小膜厚除以位於平坦或平面區域之膜厚所獲得的數值。CVD反應溫度通常為靠近氮化矽形成於其上之基板的溫度。The reaction of the preform gas with the hydrazine gas can usually be no more than 1,000 The temperature is °C (CVD reaction temperature). However, almost no tantalum nitride is produced at temperatures below 300 °C. Therefore, the reaction of the preform gas with the hydrazine gas can be carried out at 300 ° C to 1,000 ° C. Even at a low temperature of 400 ° C to 700 ° C, the preform and the hydrazine are still capable of producing a tantalum nitride at a sufficiently high growth rate (film formation rate). Further, when the CVD reaction temperature is from 300 ° C to 500 ° C, even if the aspect ratio of the opening is 10, it is still possible to obtain a step coverage ratio such as at least about 0.8. The step coverage ratio can be defined as the value obtained by dividing the minimum film thickness of the trapezoidal body by the film thickness of the flat or planar region. The CVD reaction temperature is usually the temperature of the substrate on which the tantalum nitride is formed.
聯胺氣體與預製體氣體通常可以不超過100的聯胺/預製體流速比供給入反應室中。雖然當聯胺/預製體流速比超過100時仍可產生氮化矽,但是超過100的聯胺/預製體流速比通常為不經濟的。較佳的聯胺/預製體流速比數值為1至80。The hydrazine gas and the preformed gas can typically be fed into the reaction chamber at a hydrazine/preform flow rate ratio of no more than 100. Although tantalum nitride can be produced when the hydrazine/preform flow rate ratio exceeds 100, a hydrazine/preform flow rate ratio of more than 100 is generally uneconomical. Preferred hydrazine/preform flow ratio values are from 1 to 80.
以視需要而選用之方式輸入反應室內的惰性稀釋氣體可為諸如氮氣之惰性氣體或諸如氬氣之稀有氣體。The inert diluent gas input into the reaction chamber in a manner selected as needed may be an inert gas such as nitrogen or a rare gas such as argon.
因為本發明所使用的預製體或聯胺皆未含有氯,所以其反應並不會產生先前造成困擾的氯化銨副產物。再者,雖然本發明所使用的甲矽烷基聯胺和/或聯胺包含有含碳物種,但是縱使在使用該含碳物質的情況下,氮化矽產物中仍僅發現相當低的碳濃度。Since neither the preform nor the hydrazine used in the present invention contains chlorine, the reaction does not produce the previously troubled ammonium chloride by-product. Furthermore, although the formazan hydrazine and/or hydrazine used in the present invention contains a carbonaceous species, even in the case of using the carbonaceous material, only a relatively low carbon concentration is found in the tantalum nitride product. .
現將說明單獨使用甲矽烷基聯胺及利用其熱分解產生氮化矽薄膜的方法。在此例中,將甲矽烷基聯胺氣體及視 需要而選用的任何惰性稀釋氣體輸入反應室內,並藉由甲矽烷基聯胺的熱分解而產生氮化矽薄膜。如同前揭的CVD過程,反應室內的壓力可維持在0.1 torr至1,000 torr,而反應室內的壓力維持在0.1 torr至10 torr為較佳。A method of producing a tantalum nitride bismuth film alone and a thermal decomposition thereof to produce a tantalum nitride film will now be described. In this case, the methotrexate hydrazine gas and Any inert diluent gas selected as needed is fed into the reaction chamber and a tantalum nitride film is produced by thermal decomposition of the methyl hydrazine amide. As in the previously disclosed CVD process, the pressure in the reaction chamber can be maintained at 0.1 torr to 1,000 torr, and the pressure in the reaction chamber is preferably maintained at 0.1 torr to 10 torr.
如同前揭的CVD過程,通常可在300℃至1,000℃進行甲矽烷基聯胺氣體的分解。縱使在400℃至700℃的低溫下,該甲矽烷基聯胺分解仍得以足夠高的生長速率(薄膜形成速率)產生氮化矽。此外,當分解溫度為300℃至500℃時,仍可獲得高階梯覆蓋比例。As in the CVD process previously disclosed, the decomposition of the germyl hydrazine gas can generally be carried out at 300 ° C to 1,000 ° C. Even at a low temperature of 400 ° C to 700 ° C, the carzolidine hydrazine is decomposed to a sufficiently high growth rate (film formation rate) to produce tantalum nitride. Further, when the decomposition temperature is from 300 ° C to 500 ° C, a high step coverage ratio can still be obtained.
對於CVD過程與熱分解過程而言,該甲矽烷基聯胺氣體可預先製備或儲存於密封容器內直至使用為止,或者可當場進行合成,且含有合成甲矽烷基聯胺氣體的氣態反應混合物可輸入反應室內。將甲矽烷基胺氣體與聯胺氣體輸入合成室內,以進行甲矽烷基聯胺氣體的現場合成。此時,亦可將惰性稀釋氣體(諸如前揭可輸入反應室內的惰性稀釋氣體)與前揭反應氣體輸入合成室內。有關輸入甲矽烷基胺氣體與聯胺氣體於合成室內的條件部分,合成室內的壓力應維持在0.1至1,000 torr,且聯胺氣體/甲矽烷基胺氣體的流速比應為10至1,000。該二種氣體可在室溫至500℃的溫度下進行反應。甲矽烷基聯胺係藉此反應產生。其次,可藉由調壓器將合成室內所產生的含甲矽烷基聯胺氣態反應混合物進行壓力調整,並輸入前揭的反應室內。在此所使用的甲矽烷基胺包含有化學式(Ⅲ)所定義的甲矽烷基胺 (H3 Si)m N(H)3-m (Ⅲ)For the CVD process and the thermal decomposition process, the methotrexate hydrazine gas may be prepared in advance or stored in a sealed container until use, or may be synthesized on the spot, and the gaseous reaction mixture containing the synthetic methionine hydrazine gas may be Enter the reaction chamber. The methotrexate gas and the hydrazine gas are fed into the synthesis chamber for on-site synthesis of the methyl hydrazine hydrazine gas. At this time, an inert diluent gas (such as an inert diluent gas previously introduced into the reaction chamber) and a preliminary reaction gas may be introduced into the synthesis chamber. Regarding the conditions for the input of the methotrexate gas and the hydrazine gas in the synthesis chamber, the pressure in the synthesis chamber should be maintained at 0.1 to 1,000 torr, and the flow rate ratio of the hydrazine gas/formamidine gas should be 10 to 1,000. The two gases can be reacted at a temperature of from room temperature to 500 °C. The formylalkylamine is produced by this reaction. Secondly, the methotrexate-containing hydrazine-containing gaseous reaction mixture produced in the synthesis chamber can be pressure-regulated by a pressure regulator and input into the previously exposed reaction chamber. The formalkaneamine used herein comprises a methylideneamine (H 3 Si) m N(H) 3-m (III) as defined by the formula (III).
其中,m為從1至3的整數。輸入合成室內的聯胺包含有化學式(Ⅳ)所定義的聯胺 H(Rx )N-N(Ry )Rz (Ⅳ)Wherein m is an integer from 1 to 3. The hydrazine input into the synthesis chamber contains the hydrazine H(R x )NN(R y )R z (IV) defined by the formula (IV)
其中,Rx ,Ry 與Rz 係個別獨立地選自氫原子、甲基、乙基及苯基。Wherein R x , R y and R z are each independently selected from a hydrogen atom, a methyl group, an ethyl group and a phenyl group.
例如,可藉由甲矽烷基胺(Ⅲ)與聯胺(Ⅳ)的反應產生甲矽烷基聯胺(I)。For example, the formylalkylamine (I) can be produced by the reaction of a mercaptoalkylamine (III) with a hydrazine (IV).
第1圖包含用於產生氮化矽薄膜之CVD基設備的一實施例的方塊圖,其中該CVD基設備便於執行用以產生氮化矽薄膜的本發明方法。實施例1所舉例的係使用含有已製備之預製體氣體的預製體氣體源。1 is a block diagram of an embodiment of a CVD-based device for producing a tantalum nitride film, wherein the CVD-based device facilitates performing the method of the present invention for producing a tantalum nitride film. Example 1 exemplifies the use of a preformed gas source containing the prepared preform gas.
第1圖所示的生產設備10設有反應室11、預製體氣體源12、聯胺氣體源13及惰性稀釋氣體源14,其中該氣體可以符合環境規定的方式輸入。The production apparatus 10 shown in Fig. 1 is provided with a reaction chamber 11, a preform gas source 12, a hydrazine gas source 13, and an inert diluent gas source 14, wherein the gas can be supplied in a manner compliant with the environment.
基座111配置於反應室11內,且諸如矽基板之半導體基板112安裝於基座111上(因為第1圖所舉例的設備為單晶圓設備,所以只有單一個半導體基板安裝於基座111上)。加熱器113設於基座111內,以便將半導體基板112加熱至設定的CVD反應溫度。在批式設備的狀況中,可將數個半導體基板至250個半導體基板容納於反應室內。批式設備內所使用的加熱器與單晶圓設備內所使用的加熱器可具有不同的結構。The susceptor 111 is disposed in the reaction chamber 11, and the semiconductor substrate 112 such as a ruthenium substrate is mounted on the susceptor 111 (since the device illustrated in FIG. 1 is a single wafer device, only a single semiconductor substrate is mounted on the pedestal 111. on). A heater 113 is disposed in the susceptor 111 to heat the semiconductor substrate 112 to a set CVD reaction temperature. In the case of a batch device, a plurality of semiconductor substrates can be housed in the reaction chamber within 250 semiconductor substrates. The heater used in the batch device can have a different structure than the heater used in the single wafer device.
預製體氣體源12包含有容納液化預製體的密封容器。 預製體氣體係經由預製體氣體供給管線L1而由預製體氣體源12輸入,並進入反應室11內。該管線L1內配置有預製體氣體源12的關閉閥V1及諸如質量流量控制器MFC1的流速控制器,其中該質量流量控制器MFC1位於該關閉閥V1的下游。預製體氣體係藉由該質量流量控制器MFC1而控制成設定的流速,並輸入反應室11內。The preformed gas source 12 contains a sealed container containing a liquefied preform. The preformed body gas system is input from the preform gas source 12 via the preform gas supply line L1 and enters the reaction chamber 11. A shut-off valve V1 of the preformed gas source 12 and a flow rate controller such as a mass flow controller MFC1 are disposed in the line L1, wherein the mass flow controller MFC1 is located downstream of the shut-off valve V1. The preformed body gas system is controlled to a set flow rate by the mass flow controller MFC1 and is input into the reaction chamber 11.
聯胺氣體源13包含有容納液化聯胺的密封容器。聯胺氣體係經由聯胺氣體進料管線L2而由聯胺氣體源13輸入,並進入反應室11內。該管線L2內配置有關閉閥V2及諸如質量流量控制器MFC2的流速控制器,其中該質量流量控制器MFC2位於該關閉閥V2的下游。聯胺氣體係藉由該質量流量控制器MFC2而控制成設定的流速,並輸入反應室11內。The hydrazine gas source 13 contains a sealed container containing a liquefied hydrazine. The hydrazine gas system is input from the hydrazine gas source 13 via the hydrazine gas feed line L2 and enters the reaction chamber 11. A shut-off valve V2 and a flow rate controller such as a mass flow controller MFC2 are disposed in the line L2, wherein the mass flow controller MFC2 is located downstream of the shut-off valve V2. The hydrazine gas system is controlled to a set flow rate by the mass flow controller MFC2 and is input into the reaction chamber 11.
惰性稀釋氣體源14包含有容納惰性稀釋氣體的密封容器。如有必要或有所希冀,惰性稀釋氣體係穿經惰性稀釋氣體進料管線L3而由惰性稀釋氣體源14輸入,並進入反應室11內。如第1圖所示,惰性稀釋氣體進料管線L3可接合於預製體氣體進料管線L1,因而可將惰性稀釋氣體與預製體氣體一同輸入反應室11內。該管線L3內配置有關閉閥V3及諸如質量流量控制器MFC3的流速控制器,其中該質量流量控制器MFC3位於該關閉閥V3的出口端。惰性氣體係藉由該質量流量控制器MFC3而控制成設定的流速,並輸入反應室11內。The inert diluent gas source 14 contains a sealed container containing an inert diluent gas. If necessary or desired, the inert diluent gas system is passed through an inert diluent gas feed line L3 and fed from an inert diluent gas source 14 and into the reaction chamber 11. As shown in Fig. 1, the inert diluent gas feed line L3 can be joined to the preform gas feed line L1, so that the inert diluent gas can be introduced into the reaction chamber 11 together with the preform gas. A shut-off valve V3 and a flow rate controller such as a mass flow controller MFC3 are disposed in the line L3, wherein the mass flow controller MFC3 is located at the outlet end of the shut-off valve V3. The inert gas system is controlled to a set flow rate by the mass flow controller MFC3 and is input into the reaction chamber 11.
反應室11的出口係藉由管線L4而連接至廢氣處理裝 置15。該廢氣處理裝置15會移除諸如副產物與未反應物質,且為廢氣處理裝置15所純化的氣體係由該系統排出。管線L4內配置有感壓器PG、諸如蝴蝶閥BV1之調壓器及真空泵PM。藉由各個質量流量控制器將各種氣體輸入反應室11內,而反應室11內的壓力係藉由感壓器PG進行監測,並藉由泵PM的作業與蝴蝶閥BV1的開口控制而建立在設定的壓力值。The outlet of the reaction chamber 11 is connected to the exhaust gas treatment device by a line L4. Set 15. The exhaust gas treatment device 15 removes, for example, by-products and unreacted materials, and the gas system purified by the exhaust gas treatment device 15 is discharged from the system. A pressure sensor PG, a pressure regulator such as a butterfly valve BV1, and a vacuum pump PM are disposed in the line L4. Various gases are introduced into the reaction chamber 11 by respective mass flow controllers, and the pressure in the reaction chamber 11 is monitored by the pressure sensor PG, and is established by the operation of the pump PM and the opening control of the butterfly valve BV1. The set pressure value.
當藉由甲矽烷基聯胺氣體的熱分解產生氮化矽薄膜時,聯胺進料系統的使用(聯胺氣體源13、進料管線L2、關閉閥V2及質量流量控制器MFC2)變得不必要,而無須設置。When a tantalum nitride film is produced by thermal decomposition of a mercaptoalkylamine gas, the use of the hydrazine feed system (the hydrazine gas source 13, the feed line L2, the shut-off valve V2, and the mass flow controller MFC2) becomes Not necessary, no need to set.
第2圖包含有用於產生氮化矽薄膜之設備的方塊圖,該設備含有用於產生甲矽烷基聯胺的現場裝置。與第1圖相同之第2圖中的組成元件係以相同的參考符號標示,並省略其詳細說明。Figure 2 contains a block diagram of an apparatus for producing a tantalum nitride film containing a field device for producing a dimethyl hydrazine. The components in the second drawing that are the same as in the first embodiment are denoted by the same reference numerals, and the detailed description thereof will be omitted.
第2圖所示的生產設備20除了具有與第1圖所示相同的反應室11以外,並包含有用於現場合成甲矽烷基聯胺的合成室21。加熱器211配置於該合成室21周圍,以用於將合成室21內部加熱至設定的反應溫度。The production facility 20 shown in Fig. 2 includes a synthesis chamber 21 for synthesizing a methylenediamine in situ, in addition to the same reaction chamber 11 as shown in Fig. 1. A heater 211 is disposed around the synthesis chamber 21 for heating the inside of the synthesis chamber 21 to a set reaction temperature.
第2圖所示的生產設備20未設有第1圖所示的預製體氣體源12,而包含有將與聯胺反應以產生甲矽烷基聯胺的甲矽烷基胺源22。甲矽烷基胺源22包含有容納液態形式甲矽烷基胺的密封容器。甲矽烷基胺氣體經由進料管線L21而由甲矽烷基胺源22輸入,並進入合成室21內。該 管線L21內配置有關閉閥V21及諸如質量流量控制器MFC21的流速控制器,其中該質量流量控制器MFC21位於該關閉閥V21的下游。甲矽烷基胺氣體係藉由該質量流量控制器MFC21而控制成設定的流速,並輸入合成室21內。The production apparatus 20 shown in Fig. 2 is not provided with the preform gas source 12 shown in Fig. 1, but contains a source of the mercaptoalkylamine 22 which is reacted with a hydrazine to produce a dimethyl hydrazine. The form of the mercaptoalkylamine 22 comprises a sealed container containing the methylformamide in liquid form. The formamidine amine gas is fed from the formamidine source 22 via feed line L21 and enters synthesis chamber 21. The A shut-off valve V21 and a flow rate controller such as a mass flow controller MFC21 are disposed in the line L21, wherein the mass flow controller MFC21 is located downstream of the shut-off valve V21. The formamidine gas system is controlled to a set flow rate by the mass flow controller MFC21, and is input into the synthesis chamber 21.
除了連接至反應室11的進料管線L2以外,聯胺氣體源13設有連接至合成室21的進料管線L22。該管線L22內配置有關閉閥V22及諸如質量流量控制器MFC22的流速控制器,其中該質量流量控制器MFC22位於該關閉閥V22的出口端。聯胺氣體係藉由該質量流量控制器MFC22而控制成設定的流速,並輸入合成室21內。The hydrazine gas source 13 is provided with a feed line L22 connected to the synthesis chamber 21, except for the feed line L2 connected to the reaction chamber 11. A shut-off valve V22 and a flow rate controller such as a mass flow controller MFC 22 are disposed in the line L22, wherein the mass flow controller MFC 22 is located at the outlet end of the shut-off valve V22. The hydrazine gas system is controlled to a set flow rate by the mass flow controller MFC22, and is input into the synthesis chamber 21.
除了連接至反應室11的進料管線L3以外,惰性稀釋氣體源14設有連接至合成室21的進料管線L23。該進料管線L23內配置有關閉閥V23及諸如質量流量控制器MFC23的流速控制器,其中該質量流量控制器MFC23位於該關閉閥V23的出口端。如有必要或有所希冀,惰性稀釋氣體係藉由該質量流量控制器MFC23而控制成設定的流速,並輸入合成室21內。第2圖之設備中的管線L3係直接連接至反應室11。The inert diluent gas source 14 is provided with a feed line L23 connected to the synthesis chamber 21, except for the feed line L3 connected to the reaction chamber 11. A shut-off valve V23 and a flow rate controller such as a mass flow controller MFC23 are disposed in the feed line L23, wherein the mass flow controller MFC23 is located at the outlet end of the shut-off valve V23. If necessary or desired, the inert diluent gas system is controlled to a set flow rate by the mass flow controller MFC 23 and is input into the synthesis chamber 21. The line L3 in the apparatus of Fig. 2 is directly connected to the reaction chamber 11.
合成室21的出口係藉由管線L24而連接至反應室11。管線L24內設有諸如蝴蝶閥BV2之調壓器。在合成室21內的壓力已藉由蝴蝶閥BV2而調整成適於輸入反應室11內的壓力之後,將合成室21所提供的含甲矽烷基聯胺氣體氣態反應混合物輸入反應室11內。The outlet of the synthesis chamber 21 is connected to the reaction chamber 11 by a line L24. A regulator such as a butterfly valve BV2 is provided in the line L24. After the pressure in the synthesis chamber 21 has been adjusted to a pressure suitable for input into the reaction chamber 11 by the butterfly valve BV2, the gaseous reaction mixture containing the methyl hydrazine hydrazine gas supplied from the synthesis chamber 21 is introduced into the reaction chamber 11.
有關第1圖所示之用於產生氮化矽薄膜之設備中的預製體氣體處理部分,氣相材料係由容納有液態形式預製體氣體的預製體氣體源12抽出,並藉由開啟閥門V1及使用質量流量控制器MFC1進行調整而經由管線L1輸入反應室11內。然而,預製體氣體亦可使用起泡器或蒸發器而經由管線L1輸入反應室11內。第3圖表示使用起泡器的預製體氣體進料系統。該進料系統係作用於取代第1圖所示之生產設備中的預製體氣體源12與閥門V1,並設有容納有液態形式預製體氣體31的預製體氣體源32。將管線L31插入該預製體氣體源32中,以便由如前揭之相同惰性氣體源33將惰性氣體起泡輸入容納於預製體氣體源32的預製體氣體31中。關閉閥V31配置於管線L31中。將第1圖所示之生產設備的管線L1插入位於預製體氣體31液面上方的預製體氣體源32中。關閉閥V32配置於管線L1中。當惰性氣體起泡進入預製體時,預製體會混入惰性氣體中,並藉由質量流量控制器MFC1施加流速控制而經由管線L1輸入第1圖所示的反應室11中。With respect to the preform gas treatment portion of the apparatus for producing a tantalum nitride film shown in Fig. 1, the vapor phase material is withdrawn from the preform gas source 12 containing the liquid form preform gas, and by opening the valve V1 It is adjusted by the mass flow controller MFC1 and is input into the reaction chamber 11 via the line L1. However, the preformed gas may also be introduced into the reaction chamber 11 via the line L1 using a bubbler or an evaporator. Figure 3 shows a preformed gas feed system using a bubbler. The feed system acts to replace the preform gas source 12 and valve V1 in the production facility shown in Figure 1 and to provide a preformed gas source 32 containing the preform gas 31 in liquid form. Line L31 is inserted into the preform gas source 32 to bubble the inert gas into the preform gas 31 contained in the preform gas source 32 from the same inert gas source 33 as previously disclosed. The closing valve V31 is disposed in the line L31. The line L1 of the production plant shown in Fig. 1 is inserted into the preform gas source 32 located above the level of the preform gas 31. The shutoff valve V32 is disposed in the line L1. When the inert gas is bubbled into the preform, the preform is mixed into the inert gas and applied to the reaction chamber 11 shown in Fig. 1 via the line L1 by the flow rate control by the mass flow controller MFC1.
第4圖表示使用蒸發器的預製體氣體進料系統。該進料系統係作用於取代第1圖所示之生產設備中的預製體氣體源12與質量流量控制器MFC1,並設有容納有液態形式預製體氣體41的預製體氣體源42。將管線L41設於該預製體氣體源42中,以便以液態預製體氣體31液面為惰性氣體加壓的方式,而由如前揭之相同惰性氣體源43輸入惰性氣體。關閉閥V41配置於管線L41中。此外,將第1 圖所示之生產設備的管線L1插入預製體氣體源42內的預製體氣體41中。該管線L1內配置有關閉閥V42、位於該關閉閥V42出口端的液體質量流量控制器MFC41,及位於該液體質量流量控制器LMFC41下游的蒸發器44。為來自惰性氣體源43的惰性氣體所加壓的液態預製體氣體41會流經管線L1,藉由液體質量流量控制器LMFC41施加流速控制,並輸入蒸發器44中。液態前驅物係於該蒸發器44內蒸發,並輸入第1圖所示的反應室11內。惰性氣體亦可由惰性氣體源45以經由管線L42而輸入蒸發器44內,以便提高蒸發器44內的液態前驅物蒸發。該管線L42內配置有諸如質量流量控制器MFC42及關閉閥V43,其中該質量流量控制器MFC42用於控制來自惰性氣體源45的惰性氣體流速,而該關閉閥V43位於該質量流量控制器MFC42下游。Figure 4 shows a preformed gas feed system using an evaporator. The feed system acts to replace the preform gas source 12 and the mass flow controller MFC1 in the production plant shown in Fig. 1 and to provide a preform gas source 42 containing the preform gas 22 in liquid form. A line L41 is provided in the preform gas source 42 to pressurize the liquid precursor gas 31 as an inert gas, and the inert gas is supplied from the same inert gas source 43 as previously disclosed. The shutoff valve V41 is disposed in the line L41. In addition, will be the first The line L1 of the production plant shown in the drawing is inserted into the preform gas 41 in the preform gas source 42. A shut-off valve V42, a liquid mass flow controller MFC41 at the outlet end of the shut-off valve V42, and an evaporator 44 located downstream of the liquid mass flow controller LMFC41 are disposed in the line L1. The liquid preform gas 41 pressurized for the inert gas from the inert gas source 43 flows through the line L1, is controlled by the liquid mass flow controller LMFC41, and is supplied to the evaporator 44. The liquid precursor is evaporated in the evaporator 44 and is fed into the reaction chamber 11 shown in Fig. 1. The inert gas may also be supplied to the evaporator 44 via the inert gas source 45 via line L42 to enhance evaporation of the liquid precursor within the evaporator 44. The line L42 is provided with, for example, a mass flow controller MFC42 for controlling the flow rate of the inert gas from the inert gas source 45, and a shut-off valve V43, which is located downstream of the mass flow controller MFC42. .
本發明將藉由下列工作實施例而更詳細地進行說明,惟本發明並非僅限於這些工作實施例。The invention will be explained in more detail by the following working examples, but the invention is not limited to these working examples.
本實施例使用具有實施例1所示結構的生產設備。在將進料流速為0.5 sccm或4 sccm的TSA氣體及進料流速為40 sccm的1,1-雙甲基聯胺(UDMH)氣體輸入容納有矽基板的反應室內時,於不同的CVD反應溫度(T)下將氮化矽薄膜產生於矽基板上。反應室內的壓力維持在1 torr。在該製程期間量測氮化矽沈積(生長)速率,並將 所獲得的數值對反應溫度(單位為K)倒數的1,000倍繪製於第5圖中。第5圖中的線段a為進料0.5 sccm TSA氣體(UDMH/TSA進料流速比=80)的結果圖,而線段b為進料4 sccm TSA氣體(UDMH/TSA進料流速比=10)的結果圖。This embodiment uses a production apparatus having the structure shown in Embodiment 1. When a TSA gas having a feed flow rate of 0.5 sccm or 4 sccm and a 1,1-bismethyl hydrazine (UDMH) gas having a feed flow rate of 40 sccm are input into a reaction chamber containing a ruthenium substrate, different CVD reactions are performed. A tantalum nitride film is formed on the tantalum substrate at a temperature (T). The pressure in the reaction chamber is maintained at 1 torr. Measure the rate of deposition (growth) of tantalum nitride during the process and The value obtained is plotted in Figure 5 for 1,000 times the reciprocal of the reaction temperature (in K). Line a in Figure 5 is the result of the feed 0.5 sccm TSA gas (UDMH/TSA feed flow ratio = 80), while line b is the feed 4 sccm TSA gas (UDMH/TSA feed flow ratio = 10) The result graph.
由第5圖的結果得知,氮化矽薄膜生長速率在較低UDMH/TSA進料流速比時會較高,並隨著反應溫度的增加而增加。然而,縱使在低達480℃的溫度下執行時,氮化矽薄膜的生長速率仍夠高。From the results of Fig. 5, it is known that the growth rate of the tantalum nitride film is higher at a lower UDMH/TSA feed flow rate ratio and increases as the reaction temperature increases. However, even when performed at temperatures as low as 480 ° C, the growth rate of the tantalum nitride film is still high enough.
所獲得之氮化矽薄膜的成分經歐傑(Auger)元素分析與橢圓儀量測發現為Si0.8-0.9 N。在80之UDMH/TSA進料流速比下所製備的氮化矽薄膜的碳含量僅為3重量%。藉由0.25%水性氟化氫之各個氮化矽薄膜的蝕刻速率在所有狀況中皆為30-50埃/分鐘,其係實質地低於PECVD氮化矽薄膜的蝕刻速率。The composition of the obtained tantalum nitride film was found to be Si 0.8-0.9 N by Auger elemental analysis and ellipsometry. The carbon nitride content of the tantalum nitride film prepared at a feed rate ratio of UDMH/TSA of 80 was only 3% by weight. The etch rate of each tantalum nitride film by 0.25% aqueous hydrogen fluoride is 30-50 angstroms/minute in all cases, which is substantially lower than the etch rate of the PECVD tantalum nitride film.
在本實施例中,反應室內的氣態反應混合物亦以傅力葉轉換紅外線光譜(FTIR,Fourier transform infrared spectroscopy)進行分析。在二個UDMH/TSA進料流速比下,其已證實:(a)TSA之二個主峰值(在約947 cm-1 的峰值為SiN鍵結,而在約2172 cm-1 的峰值為SiH鍵結)的強度比(I(947)/I(2172))會發生變化(見第6圖),以及(b)SiH鍵結的峰值會由2172 cm-1 遷移至2163 cm-1 。該結果證實雙甲矽烷基甲基聯胺(SiH3 )2 N-N(CH3 )2 係於大於或等於450℃下藉由TSA與UDMH的反應而產生。與 本實施例中之氮化矽薄膜產生有關的關係與合成為:(I)甲矽烷基聯胺可作用為前驅物;(Ⅱ)甲矽烷基聯胺可藉由甲矽烷基胺與聯胺的反應而產生;以及(Ⅲ)可使用藉由甲矽烷基胺與聯胺之反應而產生的含甲矽烷基聯胺氣態反應混合物形成氮化矽。In this embodiment, the gaseous reaction mixture in the reaction chamber is also analyzed by Fourier transform infrared spectroscopy (FTIR). At two UDMH/TSA feed flow ratios, it has been confirmed that: (a) the two main peaks of TSA (the peak at about 947 cm -1 is SiN bonding, and the peak at about 2172 cm -1 is SiH) The intensity ratio of the bond (I(947)/I(2172)) changes (see Figure 6), and (b) the peak of the SiH bond migrates from 2172 cm -1 to 2163 cm -1 . This result confirmed that the bis-decylalkylmethylamine (SiH 3 ) 2 NN(CH 3 ) 2 was produced by the reaction of TSA with UDMH at 450 ° C or higher. The relationship and synthesis related to the production of the tantalum nitride film in the present embodiment are as follows: (I) the methylidene hydrazine can act as a precursor; (II) the methylidene hydrazine can be obtained by the formylamine and the hydrazine. And (III) forming a tantalum nitride using a gaseous reaction mixture containing a methyl hydrazine alkylamine produced by the reaction of a mercaptoalkylamine with a hydrazine.
使用具有第1圖所示結構的生產設備,在不同反應溫度下,在容納有矽基板的反應室內形成氮化矽薄膜,其中該矽基板上形成有縱橫比(深度/直徑)為10的溝渠(直徑:0.6微米)。以40 sccm的流速輸入UDMH;以4 sccm的流速輸入TSA氣體;以及反應室內的壓力為1 torr。在不同溫度下所獲得之氮化矽薄膜的階梯覆蓋比係以掃瞄式電子顯微鏡(SEM,scanning electron microscopy)進行量測,且其結果示於第7圖中。Using a production apparatus having the structure shown in FIG. 1, a tantalum nitride film is formed in a reaction chamber containing a tantalum substrate at a different reaction temperature, wherein a trench having an aspect ratio (depth/diameter) of 10 is formed on the tantalum substrate. (Diameter: 0.6 microns). UDMH was fed at a flow rate of 40 sccm; TSA gas was fed at a flow rate of 4 sccm; and the pressure in the reaction chamber was 1 torr. The step coverage ratio of the tantalum nitride film obtained at different temperatures was measured by a scanning electron microscopy (SEM), and the results are shown in Fig. 7.
第7圖的結果不僅顯示藉由建立500℃的反應溫度可提高氮化矽薄膜產物的階梯覆蓋比,並可預測藉由將反應溫度設定在更低數值便可進一步提高階梯覆蓋比。The results of Fig. 7 show not only that the step coverage ratio of the tantalum nitride film product can be improved by establishing a reaction temperature of 500 ° C, but also that the step coverage ratio can be further improved by setting the reaction temperature to a lower value.
本發明已藉由不同具體實例與工作實施例而說明如上,但本發明並非僅限於此。可將前揭的不同具體實例結合使用。The present invention has been described above by way of various specific examples and working examples, but the invention is not limited thereto. Different specific examples of the foregoing can be used in combination.
如前所述,本發明的方法不會伴隨產生氯化銨,不會有明顯的含碳污染物摻入薄膜產物中,且縱使在相當低的 溫度下亦可產生具有較佳薄膜性質的氮化矽薄膜。As stated previously, the process of the present invention does not concomitantly produce ammonium chloride, and no significant carbonaceous contaminants are incorporated into the film product, and even at relatively low levels. A tantalum nitride film having better film properties can also be produced at a temperature.
10,20‧‧‧氮化矽薄膜生產設備10,20‧‧‧Nitrided Niobium Thin Film Production Equipment
11‧‧‧反應室11‧‧‧Reaction room
12‧‧‧前驅物氣體源12‧‧‧Precursor gas source
13‧‧‧聯胺氣體源13‧‧‧Hydrazine gas source
14‧‧‧惰性稀釋氣體源14‧‧‧Inert diluent source
15‧‧‧廢氣處理裝置15‧‧‧Exhaust gas treatment device
21‧‧‧甲矽烷基聯胺合成室21‧‧‧Methylalkyl hydrazine synthesis room
22‧‧‧甲矽烷基胺氣體源22‧‧‧Mercaptoalkylamine gas source
111‧‧‧基座111‧‧‧Base
112‧‧‧半導體基板112‧‧‧Semiconductor substrate
113,211‧‧‧加熱器113,211‧‧‧heater
L1-L4,L21-L24‧‧‧氣體進料管線L1-L4, L21-L24‧‧‧ gas feed line
V1-V3,V21-V23‧‧‧關閉閥V1-V3, V21-V23‧‧‧Close valve
PG‧‧‧感壓器PG‧‧‧ pressure device
MFC1-MFC3,MFC21-MFC23‧‧‧質量流量控制器MFC1-MFC3, MFC21-MFC23‧‧‧ Mass flow controller
BV1,BV2‧‧‧蝴蝶閥BV1, BV2‧‧‧ butterfly valve
PM‧‧‧真空泵PM‧‧‧vacuum pump
第1圖包含用於產生氮化矽薄膜之設備的實施例的方塊圖。Figure 1 contains a block diagram of an embodiment of an apparatus for producing a tantalum nitride film.
第2圖包含用於產生氮化矽薄膜之設備的另一個實施例的方塊圖。Figure 2 contains a block diagram of another embodiment of an apparatus for producing a tantalum nitride film.
第3圖包含使用起泡器之前驅物氣體進料系統的方塊圖。Figure 3 contains a block diagram of the precursor gas feed system prior to use of the bubbler.
第4圖包含使用蒸發器之前驅物氣體進料系統的方塊圖。Figure 4 contains a block diagram of the precursor gas feed system prior to use of the evaporator.
第5圖包含CVD反應溫度與氮化矽薄膜生長速率間之關係的圖式。Figure 5 contains a graph of the relationship between the CVD reaction temperature and the growth rate of the tantalum nitride film.
第6圖包含TSA之二個主峰值強度比與反應溫度間之關係的圖式。Figure 6 contains a plot of the relationship between the two main peak intensity ratios of the TSA and the reaction temperature.
第7圖包含CVD反應溫度與氮化矽薄膜階梯覆蓋比間之關係的圖式。Figure 7 contains a graph of the relationship between the CVD reaction temperature and the step coverage ratio of the tantalum nitride film.
10‧‧‧氮化矽薄膜生產設備10‧‧‧Nitrided Niobium Thin Film Production Equipment
11‧‧‧反應室11‧‧‧Reaction room
12‧‧‧前驅物氣體源12‧‧‧Precursor gas source
13‧‧‧聯胺氣體源13‧‧‧Hydrazine gas source
14‧‧‧惰性稀釋氣體源14‧‧‧Inert diluent source
15‧‧‧廢氣處理裝置15‧‧‧Exhaust gas treatment device
111‧‧‧基座111‧‧‧Base
112‧‧‧半導體基板112‧‧‧Semiconductor substrate
113‧‧‧加熱器113‧‧‧heater
L1-L4‧‧‧氣體進料管線L1-L4‧‧‧ gas feed line
V1-V3‧‧‧關閉閥V1-V3‧‧‧Close valve
PG‧‧‧感壓器PG‧‧‧ pressure device
MFC1-MFC3‧‧‧質量流量控制器MFC1-MFC3‧‧‧mass flow controller
BV1‧‧‧蝴蝶閥BV1‧‧‧Butterfly Valve
PM‧‧‧真空泵PM‧‧‧vacuum pump
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GB1006803A (en) * | 1963-05-10 | 1965-10-06 | Standard Telephones Cables Ltd | Improvements in or relating to semiconductor devices |
JPH1174485A (en) * | 1997-06-30 | 1999-03-16 | Toshiba Corp | Semiconductor device and manufacture thereof |
US7122222B2 (en) * | 2003-01-23 | 2006-10-17 | Air Products And Chemicals, Inc. | Precursors for depositing silicon containing films and processes thereof |
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2003
- 2003-04-17 JP JP2003113118A patent/JP4354732B2/en not_active Expired - Lifetime
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2004
- 2004-04-08 WO PCT/IB2004/001346 patent/WO2004092441A2/en not_active Application Discontinuation
- 2004-04-14 TW TW93110330A patent/TWI392760B/en not_active IP Right Cessation
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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JPS61234534A (en) * | 1985-04-11 | 1986-10-18 | Semiconductor Energy Lab Co Ltd | Fabrication of silicon nitride coating |
US20010048973A1 (en) * | 1998-06-26 | 2001-12-06 | Yuusuke Sato | Ammonium halide eliminator, chemical vapor deposition system and chemical vapor deposition process |
Also Published As
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TW200500490A (en) | 2005-01-01 |
JP2004319842A (en) | 2004-11-11 |
WO2004092441A3 (en) | 2004-12-02 |
WO2004092441A2 (en) | 2004-10-28 |
JP4354732B2 (en) | 2009-10-28 |
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