US20040234779A1 - Fluorinated aromatic precursors - Google Patents
Fluorinated aromatic precursors Download PDFInfo
- Publication number
- US20040234779A1 US20040234779A1 US10/724,970 US72497003A US2004234779A1 US 20040234779 A1 US20040234779 A1 US 20040234779A1 US 72497003 A US72497003 A US 72497003A US 2004234779 A1 US2004234779 A1 US 2004234779A1
- Authority
- US
- United States
- Prior art keywords
- deposition
- plasma
- precursors
- chamber
- precursor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000002243 precursor Substances 0.000 title claims description 106
- 125000003118 aryl group Chemical group 0.000 title claims description 34
- 229920000642 polymer Polymers 0.000 claims description 78
- 229910052727 yttrium Inorganic materials 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- -1 siloxanes Chemical class 0.000 abstract description 52
- 238000006116 polymerization reaction Methods 0.000 abstract description 51
- 239000000463 material Substances 0.000 abstract description 48
- 239000010409 thin film Substances 0.000 abstract description 27
- 230000004888 barrier function Effects 0.000 abstract description 24
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 15
- 229910052802 copper Inorganic materials 0.000 abstract description 15
- 239000010949 copper Substances 0.000 abstract description 15
- 150000001491 aromatic compounds Chemical class 0.000 abstract description 11
- 230000006870 function Effects 0.000 abstract description 8
- 239000004020 conductor Substances 0.000 abstract description 2
- 238000012885 constant function Methods 0.000 abstract 1
- 238000000151 deposition Methods 0.000 description 101
- 230000008021 deposition Effects 0.000 description 92
- 210000002381 plasma Anatomy 0.000 description 83
- 239000010410 layer Substances 0.000 description 71
- 238000000034 method Methods 0.000 description 63
- 235000012431 wafers Nutrition 0.000 description 63
- 239000010408 film Substances 0.000 description 48
- 229910052751 metal Inorganic materials 0.000 description 45
- 239000002184 metal Substances 0.000 description 45
- 239000000543 intermediate Substances 0.000 description 42
- 230000008569 process Effects 0.000 description 40
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 36
- 238000004519 manufacturing process Methods 0.000 description 35
- 238000005229 chemical vapour deposition Methods 0.000 description 29
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 28
- 239000003989 dielectric material Substances 0.000 description 21
- 230000001965 increasing effect Effects 0.000 description 20
- 239000000203 mixture Substances 0.000 description 19
- 239000007789 gas Substances 0.000 description 18
- 238000010494 dissociation reaction Methods 0.000 description 17
- 230000005593 dissociations Effects 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 230000005855 radiation Effects 0.000 description 16
- 229920000052 poly(p-xylylene) Polymers 0.000 description 15
- 238000012545 processing Methods 0.000 description 15
- 239000000758 substrate Substances 0.000 description 15
- 238000010586 diagram Methods 0.000 description 14
- 239000012048 reactive intermediate Substances 0.000 description 14
- 239000000126 substance Substances 0.000 description 14
- 239000006185 dispersion Substances 0.000 description 12
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 11
- 229910052681 coesite Inorganic materials 0.000 description 11
- 229910052906 cristobalite Inorganic materials 0.000 description 11
- 239000000178 monomer Substances 0.000 description 11
- 239000010453 quartz Substances 0.000 description 11
- 239000000377 silicon dioxide Substances 0.000 description 11
- 229910052682 stishovite Inorganic materials 0.000 description 11
- 229910052905 tridymite Inorganic materials 0.000 description 11
- 229930195733 hydrocarbon Natural products 0.000 description 10
- 229920006254 polymer film Polymers 0.000 description 10
- 238000005336 cracking Methods 0.000 description 9
- 229910052731 fluorine Inorganic materials 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 8
- 230000007423 decrease Effects 0.000 description 8
- 239000000539 dimer Substances 0.000 description 8
- 150000002430 hydrocarbons Chemical group 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 7
- 229910008284 Si—F Inorganic materials 0.000 description 7
- 239000011737 fluorine Substances 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- 238000000137 annealing Methods 0.000 description 6
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 5
- 230000005670 electromagnetic radiation Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910003481 amorphous carbon Inorganic materials 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 238000012552 review Methods 0.000 description 4
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 230000005679 Peltier effect Effects 0.000 description 3
- 229910020177 SiOF Inorganic materials 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 3
- 229910001634 calcium fluoride Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229910021419 crystalline silicon Inorganic materials 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Inorganic materials [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 3
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910016703 F—Si—F Inorganic materials 0.000 description 2
- 229910018540 Si C Inorganic materials 0.000 description 2
- 229910018557 Si O Inorganic materials 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000002178 crystalline material Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- QKCGXXHCELUCKW-UHFFFAOYSA-N n-[4-[4-(dinaphthalen-2-ylamino)phenyl]phenyl]-n-naphthalen-2-ylnaphthalen-2-amine Chemical compound C1=CC=CC2=CC(N(C=3C=CC(=CC=3)C=3C=CC(=CC=3)N(C=3C=C4C=CC=CC4=CC=3)C=3C=C4C=CC=CC4=CC=3)C3=CC4=CC=CC=C4C=C3)=CC=C21 QKCGXXHCELUCKW-UHFFFAOYSA-N 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 2
- OBTZDIRUQWFRFZ-UHFFFAOYSA-N 2-(5-methylfuran-2-yl)-n-(4-methylphenyl)quinoline-4-carboxamide Chemical compound O1C(C)=CC=C1C1=CC(C(=O)NC=2C=CC(C)=CC=2)=C(C=CC=C2)C2=N1 OBTZDIRUQWFRFZ-UHFFFAOYSA-N 0.000 description 1
- CZMRCDWAGMRECN-UHFFFAOYSA-N 2-{[3,4-dihydroxy-2,5-bis(hydroxymethyl)oxolan-2-yl]oxy}-6-(hydroxymethyl)oxane-3,4,5-triol Chemical compound OCC1OC(CO)(OC2OC(CO)C(O)C(O)C2O)C(O)C1O CZMRCDWAGMRECN-UHFFFAOYSA-N 0.000 description 1
- BSYNRYMUTXBXSQ-UHFFFAOYSA-N Aspirin Chemical compound CC(=O)OC1=CC=CC=C1C(O)=O BSYNRYMUTXBXSQ-UHFFFAOYSA-N 0.000 description 1
- WMXCISRMHQHTKI-UHFFFAOYSA-N CN[N](C)(N=C)O[N](NC)(NC)OC Chemical compound CN[N](C)(N=C)O[N](NC)(NC)OC WMXCISRMHQHTKI-UHFFFAOYSA-N 0.000 description 1
- POPACFLNWGUDSR-UHFFFAOYSA-N CO[Si](C)(C)C Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 1
- POSCJTAFAUDKRM-UHFFFAOYSA-N CO[Si](C)(C)C[Si](C)(C)C Chemical compound CO[Si](C)(C)C[Si](C)(C)C POSCJTAFAUDKRM-UHFFFAOYSA-N 0.000 description 1
- 239000004341 Octafluorocyclobutane Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910003828 SiH3 Inorganic materials 0.000 description 1
- 229910004200 TaSiN Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910008807 WSiN Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 229940104869 fluorosilicate Drugs 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- PGFXOWRDDHCDTE-UHFFFAOYSA-N hexafluoropropylene oxide Chemical group FC(F)(F)C1(F)OC1(F)F PGFXOWRDDHCDTE-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000012705 liquid precursor Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 1
- 230000005405 multipole Effects 0.000 description 1
- 150000004950 naphthalene Polymers 0.000 description 1
- 150000002790 naphthalenes Polymers 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- BCCOBQSFUDVTJQ-UHFFFAOYSA-N octafluorocyclobutane Chemical compound FC1(F)C(F)(F)C(F)(F)C1(F)F BCCOBQSFUDVTJQ-UHFFFAOYSA-N 0.000 description 1
- 235000019407 octafluorocyclobutane Nutrition 0.000 description 1
- 238000010943 off-gassing Methods 0.000 description 1
- 230000003534 oscillatory effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000012536 packaging technology Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000010887 waste solvent Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/62—Plasma-deposition of organic layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
-
- 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
-
- 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
- C23C16/40—Oxides
- C23C16/401—Oxides containing silicon
- C23C16/402—Silicon dioxide
-
- 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
- H01L21/02123—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 silicon
- H01L21/02126—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 silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
-
- 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
- H01L21/02123—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 silicon
- H01L21/02126—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 silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
- H01L21/02131—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 silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC the material being halogen doped silicon oxides, e.g. FSG
-
- 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
- H01L21/02208—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 the precursor containing a compound comprising Si
- H01L21/02214—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 the precursor containing a compound comprising Si the compound comprising silicon and oxygen
- H01L21/02216—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 the precursor containing a compound comprising Si the compound comprising silicon and oxygen the compound being a molecule comprising at least one silicon-oxygen bond and the compound having hydrogen or an organic group attached to the silicon or oxygen, e.g. a siloxane
-
- 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
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
- H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
- H01L21/02274—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition in the presence of a plasma [PECVD]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/312—Organic layers, e.g. photoresist
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/312—Organic layers, e.g. photoresist
- H01L21/3121—Layers comprising organo-silicon compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/312—Organic layers, e.g. photoresist
- H01L21/3121—Layers comprising organo-silicon compounds
- H01L21/3122—Layers comprising organo-silicon compounds layers comprising polysiloxane compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/312—Organic layers, e.g. photoresist
- H01L21/3127—Layers comprising fluoro (hydro)carbon compounds, e.g. polytetrafluoroethylene
-
- 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
- H01L21/02118—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 carbon based polymeric organic or inorganic material, e.g. polyimides, poly cyclobutene or PVC
- H01L21/0212—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 carbon based polymeric organic or inorganic material, e.g. polyimides, poly cyclobutene or PVC the material being fluoro carbon compounds, e.g.(CFx) n, (CHxFy) n or polytetrafluoroethylene
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31609—Particulate metal or metal compound-containing
- Y10T428/31612—As silicone, silane or siloxane
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31652—Of asbestos
- Y10T428/31663—As siloxane, silicone or silane
Definitions
- This invention is related to chemical compositions and methods for preparing materials that have low dielectric constants LKD.
- These low K materials, LKD are prepared by photon assisted and/or plasma enhanced transport polymerization or chemical vapor deposition of some selected siloxanes and F-containing aromatic compounds.
- the LKD materials are particularly useful for manufacturing integrated circuits that have features smaller than 0.18 ⁇ m.
- the integrated circuit (IC) device density has doubled in about every 18 months.
- the gate length of integrated circuits is less than 0.18 ⁇ m, the propagation time or delay time is dominated by interconnect delay instead of device gate delay.
- interconnect delay instead of device gate delay.
- Aluminum and copper are the metal of choice for manufacture of integrated circuits with feature sizes of less than 0.18 ⁇ m. Furthermore, as methods for etching copper are developed, integrated circuits with feature sizes of less than 0.13 ⁇ m can be made using copper damascene along with LKD materials.
- titanium nitride is used as barrier layer to improve interfacial adhesion between metal and SiO 2 dielectric materials and to prevent corrosion of the metal by the wet chemicals used during semiconductor processing or from fluorine liberated from fluorinated SiO 2 or other fluorinated polymers in the low dielectric polymer films. Corrosion results in the migration of metal ions from the metal line into the surrounding dielectric material. This results in increased leakage of current from the metal line into the adjacent circuit components, degrading circuit performance.
- the glue layer or barrier layer is to prevent migration of metal ions from the metal lines.
- the metal gap is equal to or smaller than 0.13 ⁇ m and when copper is used as conductor, the dielectric effectiveness of currently available materials is so limited that TiN or any other currently available metal barrier will become unsuitable for protecting against metal corrosion. Furthermore, the potential interfacial corrosion problem for copper will be even more severe than for aluminum.
- Organic polymers are considered an improvement over inorganic low dielectric materials because the K of organic polymers can be as low as 2.0.
- most of the currently available organic polymers have serious problems. Specifically, they are not sufficiently effective as barrier layers.
- siloxane-containing polymers [0015] The mechanisms for superior insulation property of siloxane-containing polymers are remained to be fully elucidated. It was rationalized though siloxanes are permeable to water vapor, they are perfect barriers for liquid water due to their high hydrophobicity. Their near zero water absorption can be attributed to the presence of siloxane derivatives presented in these polymers:
- R′, R′′, R′′′, and R′′′′ are alkyl groups, such as —CH 3 , and wherein n is an integer of from 1 to 5. Due to very high rotational and oscillatory freedom of the substituted siloxanes including R groups such as —CH 3 , these siloxane groups can achieve very close contact with metal. The close contact prevents water from coming between the polymer and metal components thereby providing a watertight seal to prevent the degradation of critical circuit components by water. These siloxanes therefore are suitable for barrier layer materials.
- Si—CH 3 groups siloxanes which contain many Si—CH 3 groups
- inorganic siloxane precursors contain few Si—H groups.
- These precursors produce polymer produce thin films having dielectric-constants in the range of from about 2.7 to 3.0.
- a crack-free SOG dry film is only attainable when its thickness is less than 0.25 to 0.3 ⁇ m. Therefore, it is necessary to perform several sequential SOG steps to manufacture a layer of SOG that is thick enough (about 1 ⁇ m) to provide desirable sealing and dielectric properties.
- the total time needed to make SOG layers of this thickness is about 3 to 4 hours. This makes manufacturing SOG siloxane seals very inefficient.
- the SOG process is expensive due to the high losses (about 80% to 90%) of materials during spin coating.
- SOG deposited precursors also require post-deposition treatments at temperatures higher than 410° C. to reduce out gassing during deposition, reflow or annealing of metals.
- This high temperature treatment results in high residual stress, which ranges from about 200 to about 500 MPa at room temperature. High residual stress can cause delamination art dielectric materials and metal surfaces, and can crack metal features in integrated circuits. Therefore, chemical processes that can deposit other siloxane-containing polymers are desirable.
- the first method described is the modification of SiO 2 by adding carbon and/or fluorine atoms.
- Siloxanes have been deposited using plasma dissociation processes (e.g., H. Yasuda, Plasma Polymerization, Academic Press (1985); M. Shen and A. T. Bell Editors: Plasma Polymerization, ACS Symposium Series, Vol.108, ACS (1979). These references are herein incorporated fully by reference. However, because these siloxane-containing polymers have low thermal stability, none of the mentioned siloxane polymers is adequate for IC fabrication meeting the requirements for small feature size.
- the fluorinated amorphous carbon products had dielectric constants as low as 2.2 but had very poor thermal stability. These materials shrank as much as 45% after annealing at 350° C. for 30 minutes in nitrogen.
- LKD materials with dielectric constants as low as 2.5 were prepared by adding fluorinated aliphatic compounds into high density plasma chemical vapor deposition (HDPCVD).
- HDPCVD high density plasma chemical vapor deposition
- PFTE tetrafluoroethylene
- TeflonTM registered tradename of DuPont Inc.
- dielectric constant of 2.0 has also been made by plasma polymerization of CF 2 ⁇ CF 2 .
- these materials have poor thermal stability.
- Poly(para-xylylenes) or PPX have dielectric constants ranging from of 2.4 to 3.5. They can be deposited at low temperatures.
- the fluorinated PPX (F-PPX; Parylene-FTM, a trademark of Special Coating Systems, Inc.) has greater thermal stability than cross-linked poly(tetrafluoroethylene) due to the presence of phenylene groups in the repeating units.
- F-PPX Parylene-FTM, a trademark of Special Coating Systems, Inc.
- F-PPX Parylene-FTM, a trademark of Special Coating Systems, Inc.
- the precursor molecule is dissociated (or cracked) to yield a reactive radical intermediate.
- the reactive intermediate contains at least one unpaired electron which upon deposition onto the wafer can bind with other reactive intermediate molecules to form a polymer.
- the polymer thus forms a thin film of material on the substrate.
- Wary et al. ( Semiconductor International, June 1996 pp: 211-216) used the precursor ( ⁇ , ⁇ , ⁇ ′, ⁇ ′, tetrafluoro-di-p-xylylene) and a thermal TP process for making polymers of the structural formula: ⁇ —CF 2 —C 6 H 4 —CF 2 — ⁇ ) n .
- Films made from Parylene AF-4TM have a dielectric constant of 2.34 and have increased thermal stability compared to the hydrocarbon dielectric materials mentioned above. Under nitrogen atmosphere, a polymer made of Parylene AF-4TM lost only 0.8% of its weight over 3 hours at 450° C.
- Parylene AF-4TM the melting point of Parylene AF-4TM is about 400° C., which is too low for metal annealing.
- Parylene AF-4TM has poor adhesion to metal and its dimer precursor is too expensive and not readily available for future IC manufacturing.
- transport polymerization (Lee, C. J., Transport Polymerization of Gaseous Intermediates and Polymer Crystal Growth. J. Macromol. Sci. - Rev. Macromol. Chem. C 16:79-127 (1977-1978), avoids several problems by cracking the precursor in one chamber and then transporting the intermediate molecules into a different deposition chamber. By doing this, the wafer can be kept cool, so that metal lines are not disrupted, and multiple layers of semiconductor devices may be manufactured on the same wafer. Further, the conditions of cracking can be adjusted to maximize the cracking of the precursor, ensuring that very little or no precursor is transported to the deposition chamber.
- the density of the transported intermediates may be kept low, to discourage re-dimerization of intermediates.
- the thin films of low dielectric material are more homogeneous and more highly polymerized than films deposited by CVD. Therefore, these films have higher mechanical strength and can be processed with greater precision, leading to more reproducible deposition and more reproducible manufacturing of integrated circuits.
- one objective of this invention is to develop novel dielectric thin films for integrated circuit manufacture.
- Another objective of this invention is the manufacture of gradient thin films in which the composition of the polymer layer differs along the film's thickness to provide changes in dielectric constant.
- Yet another objective of this invention is the manufacture of gradient thin films in which the composition of the polymer layer differs along the film's thickness to provide changes in thermal properties.
- a further objective of this invention is the manufacture of gradient thin films in which the composition of the polymer layer differs along the film's thickness to provide changes in mechanical properties.
- Another of the objectives of this invention is to provide LKD consists of sufficient amount siloxanes for hermetic protection of copper and other metals and materials.
- An additional objective is to provide molecular structures with high rotational flexibility between the silicon atoms and the planar configurations of the aromatic moieties to permit tight bonding of the molecule to the substrate.
- Another objective is to provide processes that result in low residual stress at polymer/metal interfaces.
- Yet another objective is to provide LKD materials that have also sufficient thermal and mechanical properties.
- the invention discloses new precursors and methods for depositing materials with low dielectric constants.
- precursors containing aromatic moieties containing sp 2 -C—F bonds are deposited along with SiO 2 to provide thin films with low dielectric constant, high thermal stability, and high mechanical strength.
- gradient films are made which comprise depositing different layers of low dielectric material sequentially, each layer comprising different compositions of precursors.
- the thin films are made with siloxanes and aromatic hydrocarbons selected to provide adhesion layer, barrier layer, and low dielectric layer functions.
- the siloxanes contain molecular structures with high rotational flexibility between the silicon atoms and the planar configurations of the aromatic moieties to permit tight bonding of the molecule to the metal, thus providing the adhesion layer function.
- the aromatic hydrocarbons are selected to provide low dielectric constant, high thermal stability, and high mechanical stability, thereby providing barrier and low dielectric layer functions.
- the dielectric constant of these materials range from 2.0 to 2.6.
- the residual stress of these materials on copper ranges from 25 to 50 M Pa at room temperatures.
- FIG. 1 depicts structures of some aromatic precursors of this invention.
- FIG. 2 depicts structures of some isomers of one of the precursors of this invention.
- FIG. 3 depicts structures of some side products of this invention.
- FIG. 4 is a schematic diagram of a transport polymerization system using electromagnetic radiation to dissociate precursors.
- FIG. 5 is a schematic diagram of a transport polymerization equipment employing IR radiation.
- FIG. 6 is a schematic diagram of a transport polymerization system employing radio frequencies to generate a plasma.
- FIG. 7 is a schematic diagram of a transport polymerization system employing microwaves to generate a plasma.
- FIG. 8 is a depiction of an inductively coupled high density plasma apparatus.
- FIG. 9 depicts a schematic diagram of a combination transport polymerization and chemical vapor deposition reactor utilizing photon-plasma and infrared radiation.
- FIG. 10 is a depiction of a cluster tool which can be used to deposit step-gradient films of this invention.
- FIG. 11 is a schematic diagram of a step-gradient film of the present invention.
- FIG. 12 is a schematic diagram of a continuous gradient film of the present invention.
- the adhesion and barrier layers made of titanium nitride, titanium oxynitride, or other conventional materials are replaced with siloxanes and aromatic hydrocarbons selected to provide adhesion layer, barrier layer, high thermal stability and low dielectric layer functions.
- the siloxanes contain molecular structures with high rotational flexibility between the silicon and oxygen atoms and the planar configurations of the aromatic moieties to permit tight bonding of the molecule to the metal, thus providing the adhesion layer function.
- the aromatic hydrocarbons are selected to provide low dielectric constant, high thermal stability, and high mechanical stability, thereby providing barrier and low dielectric layer functions.
- the materials with low dielectric constant having high thermal stability and high elastic modulus (E) are prepared by plasma assisted or photon assisted transport polymerization or chemical vapor deposition of some selected siloxanes and fluorine-containing aromatic compounds.
- the dielectric constant of these materials range from 2.0 to 2.6.
- the residual stress of these materials on copper ranges from 25 to 50 M Pa at room temperatures.
- the precursors useful for this invention include selected siloxanes and F-containing aromatic compounds.
- siloxane derivatives useful for this invention comprise the following chemical structures.
- R′ and R′′ are fluorinated alkyl groups; or aromatic mono-, di-, tri- or tetra-radicals and their fluorinated derivatives.
- the siloxanes can be linear or cyclic compounds and n is an integer of at least 1. When n is from 3 to 5 and R′ and R′′ are selected from the group consisting of —H, —CH 3 , —CF 3 , —(CH 2 ) n —CF 3 ,—C 2 H 5 , —C 6 H 5 , —C 6 (CF 3 )H 4 , various commercial siloxane products are available. Other useful siloxanes can be found in some textbooks, such as John Ziegler and F. W.
- siloxane derivatives include cyclic siloxanes, wherein n is between 2 and about 7, preferably about 4 to about 5, or wherein R′ and R′′ are fluorinated alkyl groups, or are fluorinated aromatic groups described below. Siloxanes and fluorinated aromatic precursors have been used separately in plasma deposition of polymers, but not their admixtures for use in IC applications.
- Aromatic precursors useful for this invention include compounds with the following structure: Y—Ar—(Y′) 2 , wherein the Ar is an aromatic compound consisting primarily of sp 2 C to sp 2 C and sp 2 C—Y bonds, and wherein Y and Y′ are a leaving groups selected from the group consisting of —H, —Cl, —Br, —NR, —SR, —SiR 3 , —NR 2 and —SO 2 R and wherein R is —H, an alky group or an aromatic mono-radical, and z is an integer ranging from 1 to 6.
- aromatic compounds are: C 6 F n H (6-n) , CF 3 —C 6 F 5 , CF 3 —C 6 F 4 —CF 3 , CF 3 —C 6 F 4 —C 6 F 5 , CF 3 —C 6 F 4 —C 6 F 4 —CF 3 , and C 10 F 8 .
- FIG. 1 depicts structures of some aromatic moieties useful for this invention.
- the moiety —CF 2 —C 6 H 4 —CF 2 — is used in poly(para-xylylene) ParyleneTM (a trademark of Specialty Coating Systems, Inc.) as a material for manufacturing semiconductor thin films with low dielectric constants.
- precursors of this invention contain aromatic moieties which have from more than about 6 to about 40 carbon atoms.
- Precursors of this invention can be classified according to the following formulas:
- the di-phenylenyl moiety (—C 10 H (8-n) F n —) where n is an integer of from 0 to 8 consists of two phenylenyl moieties covalently linked together.
- the 4-ring pyreneyl (—C 16 H (8-n) F n —) moiety wherein n is an integer of from 0 to 8 are useful.
- covalently linking similar or different aromatic residues together creates larger aromatic moieties.
- linking phenyleneyl and naphthenyl residues into a phenyleneyl-naphthenyl moiety results in an aromatic moiety with the structural formula: (C 6 H 4-n F n )—(C 10 H 6-m F m ), where n and m are integers.
- linking a phenanthrenyl residue and a pyreneyl residue results in an aromatic moiety with the structural formula: —(C 14 H (8-n) F n )—(C 16 H (8-n) F n )—. All such combinations of the aforementioned aromatic moieties which consist of up to about 40 carbon atoms are considered to be part of this invention.
- positional isomer refers to the relative location of the radical-containing moieties on the aromatic groups.
- the chamber is designed to accommodate devices which can redistribute the flow pattern of intermediates onto the wafers. If the chamber is too small, there will be insufficient room to incorporate flow pattern adjusters or diffusion plates into the systems. Moreover, with small chamber dimensions, it is difficult to provide adequate devices for automated wafer handling.
- Asymmetrical isomers with lower extended chain lengths will have higher G and E.
- symmetrical isomers have higher Tg due to the higher cohesive energy, which results from the more complete alignment of aromatic moieties. The more complete alignment results in closer approximation of ⁇ electrons in the adjacent aromatic moieties, which results in the formation of tighter n bonds being formed between adjacent aromatic moieties.
- the arrangement of the reactive groups can be para-para (pp), meta-para (mp), para-ortho (po), meta-ortho (mo), ortho-ortho (oo), para-meta (pm), or meta-meta (mm).
- pp para-para
- mp para-ortho
- po para-ortho
- mo meta-ortho
- oo para-meta
- mm meta-meta
- the oo positional isomer will be constrained to a trans-like configuration, wherein the two radical-containing moieties of Compound IV will not be close together. If they are too close together, they may form a monomer, which will contaminate the polymer. Fortunately, the oo monomer is highly unstable, and does not easily form.
- the bond types present in the new materials have more cohesive energy than the bond types of other, previously used materials.
- sp 2 C ⁇ sp 2 C bonds in aromatic compounds have much higher bond strength and cohesive energy than sp 3 Si-sp 3 C or Si—C bonds in the siloxanes.
- the sp 2 C-sp 3 C bond, or hyperconjugated C—C bond, the sp 2 C—X, or hyperconjugated C—X bond both have higher bonding energy (BE) and cohesive energy than the sp 3 Si-sp 3 C and sp 3 Si—X bonds.
- the hyperconjugation results from participation of the ⁇ -bonds electrons of the C—C or C—X single bond in overlapping with the ⁇ -orbitals of a neighboring C ⁇ C double bond.
- the resonance stabilization of a single bond by a neighboring double bond increases its bonding strength. This is especially effective when the X is an electron withdrawing group such as fluorine atom.
- the bonding energy of the C ⁇ C—F bond is higher than that of the C—C—F and Si—F bonds. Examples of these bond energies are found in Table 1.
- the bond energy (BE) of a sp 3 C—X bond can be higher than that of a sp 3 Si—X bond when X ⁇ H, C and S; however, its opposite is true when X ⁇ F, Cl and O.
- the BE of a sp 3 Si—F bond is 135 kcal/mol. versus 110 kcal/mol. of a sp 3 C—F bond.
- SiOF films consisting of more than 4.2 atomic-F % are found to be very unstable under pressure cooker conditions (Passemard et al. Fluorine Stability in Fluorosilicate Glass and Effects on Dielectric Properties, Proceedings of the 2 d DUMIC, p 145, 1996). It has been theorized that due to higher reactivity of sp 3 Si—F bonds towards fluorination comparing to Si—O bonds, plasma polymerization of precursors containing >4.2% fluorine result in SiOF films comprising mostly F—Si—F. (Takamura et al.
- the sp 3 Si—F bond in a F—Si—F group can be easily hydrolyzed due to the high polarity resulting from presence of the second fluorine on the group. Takamura et al., Proceedings of the 2 d DUMIC p 231, (1996). Hydrolyzed Si—F bonds will release HF acids and corrode metals in integrated circuits.
- organic compounds consisting mostly of sp 2 C—F bonds are used to lower dielectric constant of SiO containing films.
- the sp 2 C—F bond has high thermal stability and excellent hydrolytic stability.
- sp 3 Si—F and sp 3 C—F bonded moieties there is no similar limit for the atomic % of F content for thin films comprising sp 2 C—F bonds.
- Thin films prepared from this invention can have K as low as 2.0-2.3 and excellent thermal stability.
- these new precursors can replace titanium nitride (TiN), TaN, WN, TaSiN, WSiN, and similar materials as barrier layers and adhesion layers.
- TiN titanium nitride
- WN titanium nitride
- TaSiN TaSiN
- WSiN similar materials
- barrier layers and adhesion layers require the development of equipment for low temperature dissociation and deposition. The equipment used is described in the above-described co-pending applications.
- the polymers and siloxane derivatives of this invention can be deposited using any conventional CVD or transport polymerization method which uses “cold dissociation” methods.
- cold dissociation methods are those which do not appreciably heat the precursors.
- Such cold dissociation methods include photon assisted (PA) or plasma enhanced (PE) processes.
- Photon assisted transport polymerization and chemical vapor deposition can use infrared (IR), ultraviolet (UV) or vacuum ultraviolet (VUV) sources, or combinations of the above.
- IR infrared
- UV ultraviolet
- VUV vacuum ultraviolet
- a desirable energy source is incoherent excimer radiation that is derived from a dielectric barrier discharge. UV and VUV photon energies that are in the range from about 3 to about 5 eV are especially useful.
- One option of this invention is to first deposit on metal surfaces a layer of siloxanes ranging from 100 to 500 ⁇ , then switch to deposition of fluorinated aromatic polymers. Another option is to deposit copolymers of siloxanes and fluorinated aromatic compounds by introducing admixtures of these two types of compounds with various mixing ratios. Additionally, gradients of polymers can be made by gradually changing the composition of the precursors introduced into the deposition system during deposition. Another option is to make a damascene dielectric structure with a top layer of PACVD siloxanes for better LKD to copper adhesion. In addition to equipment utilizing thermal methods for dissociating precursors, equipment utilizing electromagnetic radiation is useful for practicing this invention.
- Useful electromagnetic radiation is in the infrared (IR), ultraviolet (UV) and vacuum ultraviolet (VUV) spectra UV and VUV produce no heat, whereas IR produces heat.
- IR and either UV or VUV can dissociate precursors with increased efficiency.
- FIG. 4 is a schematic diagram of a transport polymerization system 400 using electromagnetic radiation as an energy source for cracking precursor molecules.
- Precursors are transported from the precursor tank 404 through a pipe 408 and through a mass flow controller 412 through another pipe 416 and into a tube 420 which is transparent to the types of electromagnetic radiation to be used.
- a glass tube is sufficient.
- quartz tubes are necessary, and preferably are made of a single crystal quartz.
- tubes made of MgF 2 , LiF, or CaF 2 are necessary because the short wavelengths of VUV cannot pass easily through quartz.
- the electromagnetic energy source can be located at a site within the central area of flow of precursors. With this configuration, a large proportion of the electromagnetic energy is directed at the precursors as they flow past. This can increase the efficiency of precursor cracking.
- the reactive intermediates are transported into the deposition chamber 422 surrounded by a heater 436 .
- the wall of the chamber is heated to decrease the deposition of molecules on the chamber wall. This heating can be accomplished by any conventional means, including, but not limited to resistive heating.
- the flow of intermediates is adjusted by a movable flow pattern adjustor 440 .
- Vertical movement of the flow pattern adjustor 440 adjusts the flow rate of intermediates into the chamber 432 and aids in mixing the intermediates more evenly within the chamber 432 .
- Horizontal movement of flow pattern adjustor 440 adjusts the flow distribution of intermediates over the wafer 448 .
- the flow pattern adjuster can be a flat, stainless steel plate, or alternatively can be a porous or honeycomb structure.
- a gas dispersion plate 444 evens the flow of intermediates over the wafer 448 . Dispersion holes between the flow pattern adjuster and the wafer ensure the dispersion of the intermediates.
- the wafer 448 is held by a mechanical or electrostatic cold chuck 452 , which is cooled by any chiller 456 employing any conventional means, including, but not limited to liquid nitrogen or reverse Peltier effect.
- a UV or VUV source also can be directed toward the wafer 448 to permit cross-linking of polymers after their deposition.
- a pipe 460 is for exhausting the chamber 452 , and a pump 472 connected via a pipe 468 to a trap 464 maintain the pressure within the chamber at desired levels.
- Exemplary sources of UV radiation for transport polymerization can include (1) a mercury lamp that provides from 50 to 220 mW/cm 2 of UV ranging from 185 to 450 nm or (2) a metal halide lamp that provides from 40 to 160 mW/cm 2 of UV ranging from 256 nm to 450 nm. These UV sources provide photon energies ranging from 2 to 5 eV, which are sufficient for generating radical intermediates.
- VUV vacuum ultraviolet
- Incoherent excimer radiation can provide a large number of UV and VUV wavelengths for photolytic processing of various chemicals.
- the preferred source is incoherent excimer radiation derived from dielectric barrier discharge. UV and VUV photons that are in the ranges of 3 to 5 eV are especially useful. These energy levels are comparable with the bonding energies of most chemical bonds, thus are very effective for initiating photochemical reactions (see Table 1).
- Table 2 shows the bonding energies in electron volts (eV) corresponding to certain bonds of this invention. This data is from Streitwiesser et al., Introduction to Organic Chemistry, Appendix II, University of California Press, Berkeley, Calif. (1992), incorporated herein fully by reference.
- VUV or incoherent excimer UV sources can be provided by dielectric barrier or silent discharge using a variety of gas or gas mixtures according to methods known in the art.
- VUV can be generated using KrBr, Ar 2 , ArCl, ArBr, Xe 2 and F 2 gases.
- Xe emits at 172 nm
- XeCl emits at 308 nm.
- nearly all of the chemical bonds of interest in polymer manufacture can be broken using photolytic methods. Because excimer radiation is selective for the energy of the specific bonds, excimer radiation from a second source or alternatively, a plasma source may be used simultaneously if it is desired to break other bonds at the same time.
- Such a combination of excimer sources and plasma sources are useful to break bonds of precursors for making cross-linked poly(para-xylylenes). Because the leaving groups of these precursors can be different, it is desirable to break those bonds selectively to generate tri- and tetra-functional reactive intermediates.
- FIG. 5 An alternative transport polymerization equipment employing IR radiation 500 is shown in FIG. 5.
- the precursors are transported from a precursor holder 504 through a pipe 508 and through a mass flow controller 512 and a second pipe 516 into the chamber 520 .
- the chamber contains a quartz chamber 524 , optionally containing a catalyst 528 .
- An infrared radiation source 532 is placed outside the quartz container 524 , and the precursors are dissociated as they pass through the quartz container 524 .
- a diffusion plate 536 is used to optimize the flow pattern of intermediates to the wafer 540 .
- a flow pattern adjuster as shown in FIG. 4 ( 440 ) may be used to adjust the flow of intermediates over the wafer 540 .
- the wafer 540 is held on a mechanical or electrostatic cold chuck 544 , which is cooled by a conventional chiller 548 .
- the pressure in the chamber is maintained by a pump 564 connected via a pipe 560 to and a trap 556 , which is connected to chamber 520 by a pipe 552 .
- the trap 556 protect the pump from deposition of intermediates in the pump 564 .
- IR radiation In IR radiation, a combination of both thermolytic and photolytic reactions are expected. Therefore, it is important to ensure that the IR power is in the range where the reactive intermediates can be dissociated, but where destruction of the polymer network does not occur.
- the IR power should be in the range of from 500 Watts to 3000 Watts, preferably from 1500 Watts to 2500 Watts, and most preferably 2000 Watts.
- Plasma energy is also used to dissociate precursors into reactive intermediates.
- Plasma sources useful for this invention can be provided by various different kinds of equipment. Michael Lieberman and Allan Lichtenberg Principles of Plasma Discharge and Material Processing, Wiley Interscience, (1994). There are generally two types of energy sources for plasma enhanced transport polymerization or chemical vapor deposition. They are radiofrequency (RF) and microwave sources.
- RF radiofrequency
- Plasma enhanced TP is carried out using the novel reactors described herein (FIGS. 6-9).
- the electron density in the plasma is in the range of about 10 12 to about 10 13 electrons/cm 3 .
- Low density plasma TP and CVD can be carried out at about 100 milliTorr to about 100 Torr.
- High density plasma (HDP) is characterized by electron densities in the range of about 10 13 to about 10 14 electrons/cm 3 .
- High density plasma TP and CVD can be carried out at pressures of about 0.1 milliTorr to about 100 milliTorr.
- the higher electron density in HDP increases the formation of cross-linked polymers, because the higher energy density increases the numbers of tri-radical intermediates which can form cross-links between polymer chains.
- the dielectric constant is measured for samples of substrate whose dimensions are about 0.1′′ ⁇ 0.1′′, composed of a layer of polymer sandwiched between two metal layers.
- the capacitance of the polymer layer is measured, and the dielectric constant is calculated from the result of this measurement.
- the error in the estimation of the area of the top metal layer is about 5%-10% of the average value.
- the measurement of capacitance is accurately measured, and the dielectric constant is calculated.
- the total possible error of the calculated value of the dielectric constant is about 10%-20% of the average value.
- composition of the films is characterized by Fourier Transform Infrared Spectroscopy (FTIR, Bio-Rad Systems, Inc.) using methods known in the art, and the methods will not be discussed further.
- FTIR Fourier Transform Infrared Spectroscopy
- the ratio ( ⁇ ) of hydrocarbon CHx to SiO 2 is calculated by comparing the areas under he peaks at 3200 or 1250 cm ⁇ 1 with the area under the peak at 879 cm ⁇ 1 .
- the plasma variables used to control the physical and chemical nature of the deposited polymer film are: excitation power in Watts (W), flow rate (F) of the monomer(s), molar rations of different monomers (for making co-polymers or gradient films), substrate temperature T s , deposition pressure (P), substrate bias (V s ), and monomer temperature (T mo ), the flow rates of the feed gas and/or monomer(s), relative positions and separation of the anode and cathode plates, location of the gas inlet and pump outlet and control of the pump speed. All of these factors have effects on the types and properties of the deposited film. Other factors such as the reactor geometry can play a major role.
- All depositions can be performed after subjecting the surfaces to an in-situ argon plasma pre-cleaning step.
- the films are deposited at RF power ranges of a few tens of Watts to a few hundred Watts with a gas flow rate of between 30-90 SCCM.
- the chamber pressure during deposition ranges from 10 ⁇ 3 Torr to a few Torr. Deposition rates vary from a few hundred ⁇ /min to close to 0.4 ⁇ m/min.
- the useful processing parameters therefore have to be optimized for each composition in order to obtain desirable combinations of dielectric constant, mechanical properties such as Elastic Modulus, thermal properties such as T g and residual stress and sufficient protection of metal/polymer interfaces from moisture.
- the following parameters were found useful for making low K dielectric materials with high thermal stability from siloxanes of this invention: Power levels range from 80 to 300 Watts, or preferably from 120 to 200 Watts under the gas flow rates range from 30 to 90 SCCM, preferably from 50 to 75 standard cubic centimeters per minute (SCCM) and a vacuum pressure of few milliTorr.
- void free thin films with dielectric constants ranging from 2.2 to 2.6 can be obtained at deposition rates ranging from 1200 ⁇ to 2000 ⁇ /min.
- These films have Tgs in the range from 150° C. to 300° C. and have low residual stress ranging from 15 MPas to 50 MPas.
- Electron Spectroscopy for Chemical Analysis is also employed for more quantitative analysis of surface compositions of the deposited films.
- ESCI studies indicated for a flow rate of 30 SCCM, as the power level increased from 80 to 200 Watts, the number of carbon atoms per silicon atom in the polymer film surface wag 1.36 and 1.17, respectively. Because the theoretical C/Si ration in a monomer is 2, this results indicates that in addition to the C—H bond dissociation, there is substantial Si—C bond dissociation during plasma polymerization. For larger wafers, the power should be increased proportionately.
- Step-gradient films of this invention can be manufactured by depositing a first layer of material which contains siloxanes which will adhere to the substrate. This tightly adhering layer functions as an adhesive layer, permitting subsequent layers to adhere to the semiconductor device. On top of this siloxane-rich layer, an additional layer, containing for example, a fluorinated aromatic hydrocarbon can be deposited using either the same deposition chamber, or by using the cluster tool described below (FIG. 10).
- continuous gradient thin films are made by gradually introducing different precursors or combinations of precursors into the apparatus during the plasma deposition process. For instance, first, a siloxane-rich thin layer ranging from a few tens of ⁇ to several hundreds of ⁇ is deposited onto a metal layer. Then, on top of this siloxane-rich layer, a layer of sp 2 C—F bond-rich siloxanes or organic compounds is made by introduced into the deposition apparatus with increasing molar % of fluorinated aromatic compounds toward the centers between the metal lines and away from the metal surfaces.
- the layer making contact with the metal can be composed of a material with a lower dielectric constant (K ⁇ 2.0 to 2.6).
- This type of polymer is desirable if the polymer can withstand the temperatures of the processes, or if a higher K (2.6 to 3.2) is suitable. If the temperatures of the subsequent processing steps are unsatisfactorily high for siloxanes, materials with higher thermal stability will be required. These materials also have higher dielectric constants.
- the siloxane-rich layer is well suited as a water barrier which can seal the metal lines (the “hermetic effect”) preventing their corrosion. This is especially important when copper is used as the metal.
- a SiO 2 -rich layer can be deposited on top of the interlevel dielectric layer. This can be simply achieved by increasing the power level of the plasma to over 300 Watts for a 4 inch diameter wafer ans using admixtures with higher percentages of siloxane precursors.
- the SiO 2 -rich cover layer is helpful for CMP of these materials and metals following deposition.
- FIG. 6 is a schematic diagram of a transport polymerization system 600 employing RF to generate a plasma.
- the precursors are stored in a precursor holder 604 , are transported via a pipe 608 and through a liquid injector for liquid precursors, or a mass flow controller 612 for gasses, then are transported via another pipe 616 into a plasma tube 620 made of quartz.
- the tube 616 is made of a single quartz crystal.
- Precursors are exposed to RF energy generated by a RF generator 626 , through a coil 628 , and a plasma 630 is thereby generated.
- the plasma 630 then flows into a deposition chamber 634 which is surrounded by a heater 638 .
- the heater 638 keeps the walls of the chamber 634 above the condensation temperature of the reactive intermediates. This prevents condensation of intermediates onto the walls of the chamber 634 .
- the flow of intermediates is adjusted by a flow pattern adjuster 642 .
- Vertical movement of the flow pattern adjuster 642 adjusts the flow rate of intermediates into the chamber 634 , and aids in mixing the intermediates in the chamber 634 .
- Horizontal movement of the flow pattern adjuster 642 adjusts the distribution of the intermediates over the surface of wafer 650 .
- a gas dispersion plate 646 with holes distributes the flow of intermediates evenly over the surface of the wafer 650 .
- the wafer 650 is held on a cold chuck 654 , which is kept cool by a chiller 658 employing any conventional cooling method, including liquid nitrogen and reverse Peltier effect.
- the chamber is connected via a pipe 662 to a cold trap 666 , which traps undeposited intermediates.
- the pressure in the chamber 634 is maintained by a pump 676 connected to trap 656 by a pipe 670 .
- Frequencies needed to generate plasmas are in a range of from 1 kHz to 2.5 GHz.
- a preferred range is between 400 kHz and 13.56 MHz, with the most preferred frequency being 13.56 MHz.
- the power should be in the range of 30 to 300 Watts.
- Preferred power range is 100 Watts to 250 Watts, and the most preferred power is 200 Watts of discharge power.
- the pressure should be kept within a range of from 0.001 Torr to 100 Torr, preferably from 50 milliTorr to 500 milliTorr, and most preferably at 100 milliTorr pressure.
- using low frequencies (5 kHz) can result in formation of insoluble poly(para-xylylene) which have higher temperature resistance. Morita et al. Trans. IEEE Japan pp: 65075 (1972).
- a carrier gas such as nitrogen or argon is used, and the flow rates of the carrier gas should be from 30 to 90 SCCM, preferably from 50 to 75 SCCM.
- FIG. 7 is a schematic diagram of a transport polymerization system employing microwaves. Precursors are held in a precursor tank 704 , and are vaporized, pass through a pipe 706 and through a mass flow controller 710 , through a second pipe 714 and into a quartz tube 718 . A microwave generator 722 is attached via a waveguide 726 to one end of the quartz tube 718 . Microwave energy enters the quartz tube 718 where a plasma 728 is generated, which dissociates the precursors into reactive intermediates. After dissociation, the intermediates are transported into a chamber 730 heated by a heating device 734 , including, but not limited to resistive heater.
- a heating device 734 including, but not limited to resistive heater.
- the flow of the intermediates is controlled by a flow pattern adjustor 738 .
- Vertical movement of the a flow pattern adjustor 738 adjusts the flow rate of intermediates into chamber 630 and adjusts the mixing of intermediates in chamber 730 .
- a gas dispersion plate 742 evenly distributes the intermediates over the surface of wafer 746 .
- the intermediates deposit on the wafer 746 , which is held by a cold chuck 750 , which is attached to a chiller 754 employing any conventional cooling means, including, but not limited to liquid nitrogen or reverse Peltier effect.
- the chamber pressure is controlled by a pump 770 , connected via a pipe 766 to a cold trap 762 .
- the trap 762 is connected via a pipe 758 to the chamber 730 .
- the cold trap 762 protects the pump 770 from deposition of intermediates.
- Microwave power density or electron field strength is selected based upon the residence time of the precursors in the chamber.
- the power is generally between 200 and 700 Watts, preferably between 400 and 600 Watts, and most preferably at 500 Watts. Desirable electron energy is chosen to match the bond energy of the leaving group.
- the pressure within the reaction vessel should be below atmospheric pressure. Pressures in the range of 0.001 to 200 Torr work well. Furthermore, to inhibit condensation of chemicals, the walls of the reaction chamber should be kept warm, preferably in the range of 50° C. to 150° C., preferably above 100° C.
- the IR radiation heats the precursors to a threshold temperature, requiring less VUV power to complete the cracking reaction. IR also heats the chamber walls to decrease deposition on them because VUV is a cold light source which does not heat up the chamber.
- Deposition and polymerization of reactive intermediates to form low dielectric polymers is achieved by placing the wafer on a cold chuck.
- the temperature of the cold chuck should be between ⁇ 198° C. and 30° C., preferably at about ⁇ 5° C. Any suitable method for cooling the cold chuck may be used, including reverse Peltier, liquid nitrogen, or conventional refrigeration methods. Reverse Peltier and liquid nitrogen cooling methods are preferred.
- a cold trap is placed between the vacuum pump and the deposition chamber.
- a high density plasma deposition process can also be used to dissociate precursors.
- the electron density is in the range of from about 10 13 to 10 14 electrons/cm 3 . This process must be carried at lower pressures than conventional plasma processes.
- a inductively coupled high density plasma apparatus 800 is shown schematically in FIG. 8.
- a precursor delivery system 804 volatilizes or vaporizes the precursor, which flows through a pipe 808 and an anode gas injector 812 into the deposition chamber 816 .
- the anode gas injector 812 is attached to RF generators 820 which are matched by matching controllers 824 .
- the output of the RF generators 820 passes through inductive coils 828 to produce an electrical field.
- the wafer 832 is held by a cathode electrostatic chuck 836 , which is connected to the RF generator 820 .
- IR sources 840 provide additional heating of precursors to decrease the needed plasma power and to inhibit condensation on the chamber walls.
- the plasma source power needed for a wafer of 8 inch diameter is in the range of about 100 Watts to 4000 Watts, and preferably about 2000 Watts. For wafers of other sizes, power should be adjusted accordingly.
- Power is in the range of about 1 Watt/cm 2 of wafer surface area to about 15 Watts/cm 2 , preferably from about 2 Watts/cm 2 to about 10 Watts/cm 2 , and more preferably about 5 Watts/cm 2 .
- the chamber pressure is maintained in the range of 0.01 milliTorr to 10 milliTorr, and preferably below 5 milliTorr by a pump and cold trap (not shown).
- the wafer temperature is in the range from about 300° C. to 450° C., and is preferably about 350° C.
- a novel chamber design comprising utilization of magnets on the periphery of the chamber wall is used in this invention.
- the magnetic multipole configuration confines the plasma and increases the lifetime of primary electrons, therefore enabling the generation and sustenance of a low pressure plasma. This allows the deposition to occur at lower pressure and higher flow rates and overcomes the problem of powder formation during high deposition rates.
- the upper electrode, attached to the copper electrode is connected to the RF power through a matching network, and the lower electrode is connected to the ground.
- a ring of magnets is used to confine the plasma. These magnets are attached to the outer wall of the deposition chamber. The advantages of locating the magnets outside the chamber are that the powder cannot form on the magnets themselves, and such a reactor has a simpler design.
- FIG. 9 depicts a schematic diagram of a TP and CVD reactor 900 embodying the elements for photon-plasma and IR dissociation and deposition.
- Precursors 904 are stored in a precursor container 908 which is connected via a pipe 912 to a mass flow controller 916 .
- precursors are transported into a dissociation reactor 924 which houses the dissociation chamber 928 .
- the wall of reactor 924 is made of crystalline materials such as LiF, MgF 2 , or CaF 2 , which permits light of vacuum ultraviolet wavelengths to pass.
- Vacuum ultraviolet and ultraviolet light is generated by a silent discharge plasma generators 932 , which are place inside infrared heaters 936 .
- the infrared heaters 936 are placed inside DC magnets 940 and AC magnets 944 .
- the magnets regulate the flow of plasma during dissociation, and the reactive intermediates so generated are transported to a deposition reactor 950 .
- the deposition reactor 950 contains a deposition chamber 960 containing a gas and reactant dispersion manifold 954 , a gas and reactant dispersion plate 958 .
- the walls of the deposition chamber are made of crystalline materials such as LiF, MgF 2 , or CaF 2 , which permits light of vacuum ultraviolet wavelengths to pass.
- the gas dispersion manifold 954 and the gas dispersion plate 958 are used to adjust the distribution and homogeneity of the intermediates.
- the intermediates are directed toward the wafer 962 , which is held on a cold chuck 964 .
- the gas dispersion manifold 954 and dispersion plate 958 are connected in parallel to a DC voltage bias anode 968 , a DC voltage bias cathode 969 , an AC voltage bias anode 970 , and an AC voltage bias cathode 971 .
- Silent discharge plasma generators 972 are placed outside the deposition chamber 960 .
- Infrared heaters 974 are placed outside the silent plasma discharge generators 960 and DC magnets 978 and AC magnets 980 are placed outside the infrared heaters 974 .
- Gasses exit the deposition chamber 960 through a pipe 984 , pass through a cold or reactive trap 988 , pass through another pipe 992 to a vacuum pump 996 .
- the pressure in the systems is maintained at a desired pressure using pump 996 .
- the trap 988 protects the pump from deposition of intermediates.
- the deposition chamber can be used without the dissociation reactor.
- Precursors are placed directly on wafer 962 , and the chuck 964 is not cooled.
- IR, UV, or VUV radiation is directed toward the wafer 962 .
- the radiation dissociates the precursor, and deposition of intermediates and polymerization takes place on the wafer.
- Table 4 shows process conditions for combined photon-plasma assisted precursor dissociation using chamber 928
- Table 5 shows process conditions for combined photon-plasma precursor deposition in deposition chamber 960 .
- TABLE 4 Process Conditions for Photon-Plasma Precursor Dissociation Variable Range Preferred Range Temperature 200° C.-600° C. 350° C.-500° C.
- the plasma density is reported as electron density, but it is to be noted that ion density must be the same to maintain charge neutrality of the plasma. Any non-uniformity of charge distribution can result in plasma damage to the thin film of low dielectric material, as well as imparting charge to the integrated circuit components.
- Control of the plasma is by a magnetic field within the precursor chamber and in the deposition chamber.
- the plasma In the precursor reactor, the plasma is confined to any desired area, such as the center of the reactor. Additionally, alternating the polarity of the magnetic field stirs the plasma, ensuring even energy distribution within the plasma, thereby increasing the efficiency of dissociation of precursor molecules into reactive intermediates.
- the magnetic field In the deposition chamber, the magnetic field is used to control the pattern of distribution of intermediates over the wafer. This would serve two purposes: (1) to direct the deposition of precursor to the desired portion of the surface, thus conserving the precursor, and (2) minimize film deposition on other parts of the reactor chamber, thus minimizing the required cleaning, minimizing particle generation, and simplifying the reactor chamber design.
- Another feature comprises the placement of an electrical bias voltage within the deposition chamber.
- This provides a further means of controlling the flow of plasma-ionized species to the site of deposition on the wafer.
- a bias voltage in the form of direct current (DC) or alternating current (AC) can be applied and modulated. Pulsed voltages can be used to alter the flow pattern of ions to either accelerate, decelerate, or to regulate the density of the plasma ions in the stream reaching the wafer. Optimization of ion velocity and flow, thus can be obtained using various combinations of magnetic field and bias voltage.
- Table 6 shows the ranges of the various magnetic field and bias voltage variables which are regulated in this invention.
- a “hydrogen membrane” For transport polymerization of precursors containing —H as a leaving group, the inclusion of a “hydrogen membrane” may be desired.
- —H When the precursors flow through the cracking apparatus, —H is cleaved from the reactive groups of the precursors, and this —H can dimerize to form molecular hydrogen.
- a membrane with pores of about 3 ⁇ to about 5 ⁇ in diameter To prevent this hydrogen from adsorbing onto the wafer surface, a membrane with pores of about 3 ⁇ to about 5 ⁇ in diameter. Because the size of molecular hydrogen is small enough to penetrate the membrane but the radical intermediates are not small enough, the hydrogen can be effectively removed from the cracking chamber and thereby avoid contaminating the polymer.
- similar membranes with appropriate sized pores can also be used.
- FIG. 10 shows a schematic diagram of a cluster tool 1000 .
- a first station 1004 is a wafer cassette which holds one or more wafers for processing.
- a wafer is transported to a cleaning chamber 1008 where the wafer is exposed to VUV light of wavelengths in the range of from about 180 nm to about 450 nm, or to UV light.
- This pre-treatment is to remove impurities from the wafer surface prior to deposition of material with low dielectric constant.
- the wafer is transported to a first processing station 1012 , where a first deposition occurs.
- the processing station 1012 can be any of the devices depicted in FIGS. 4-9 above.
- the wafer is transported to a second processing station 1016 , where further deposition of low dielectric material occurs. Subsequently, the wafer is transported to a third processing station 1020 , where a third layer of low dielectric material is deposited. It is desirable to deposit several layers of low dielectric material in different processing stations because there are likely to be variations in the flow patterns in the different stations.
- the wafer is transported to a fourth processing station 1024 , where a fourth layer of low dielectric material is deposited. Differences in flow patterns may result in the uneven deposition of films in each station. It is unlikely that the uneven deposition pattern for each station will be the same. Therefore, by depositing multiple layers of polymer, any differences in thickness of precursor resulting from deposition in one station can be at least partially corrected by polymer deposition in another station.
- a step-gradient film can be made by depositing a siloxane-rich precursor mixture at station 1012 , and a second mixture, containing, for example, a mixture rich in fluorinated aromatic precursors at station 1016 . Subsequent additional layers with different compositions may be deposited at subsequent stations.
- the station 1024 can be used for post-deposition treatments, such as thermal annealing, reflow, plasma surface treatments, or cross-linking by exposing the polymer film to VUV of wavelengths in the range from 180 nm to 450 nm.
- post-deposition treatments such as thermal annealing, reflow, plasma surface treatments, or cross-linking by exposing the polymer film to VUV of wavelengths in the range from 180 nm to 450 nm.
- Another advantage of the cluster tool is the possibility of depositing different types of polymers at the different stations.
- a first layer chosen to adhere tightly to the substrate a second layer chosen to have certain dielectric properties, thermal stability, or mechanical stability.
- a third layer may be chosen the have the same or different properties.
- FIG. 11 shows a schematic diagram of the manufacture of a step-gradient film 1100 of this invention.
- Substrate 1104 has a series of metal lines 1108 deposited on its surface.
- FIG. 11 a shows a layer of siloxane-rich polymer 1112 deposited on top of the metal lines and on the exposed substrate 1104 .
- FIG. 11 b shows a second layer of polymer, containing for example, a fluorinated aromatic hydrocarbon 1116 .
- the surface of layer 1116 as shown has been planarized, but planarization need not be carried out, depending on the application.
- another, siloxane-rich layer 1120 is deposited to permit the deposition of additional metal lines. This process can be carried out many times, resulting in the manufacture of a multi-layered semiconductor device.
- FIG. 12 shows a schematic diagram of the manufacture of a continuous gradient film 1200 of this invention.
- Substrate 1204 has a series of metal lines deposited on its surface.
- FIG. 12 a shows the portion of the continuous gradient containing a siloxane-rich layer containing the least amount of fluorinated aromatic hydrocarbon (light shading) 1212 , and the intermediate portion of the polymer film containing an intermediate concentration of fluorinate aromatic hydrocarbon 1216 .
- the relative concentration of fluorinated aromatic hydrocarbon-containing polymer increases relative to the concentration of the siloxane-rich portion, making a portion of the gradient film which has a high concentration of fluorinated aromatic hydrocarbon 1220 .
- the surface of the polymer layer 1220 is shown after planarization, but planarization need not be carried out, depending on the application.
- another, siloxane-rich layer 1224 is deposited to permit the deposition of additional metal lines. This process can be carried out many times, resulting in the manufacture of a multi-layered semiconductor device.
- the parallel plate plasma system with magnetic confinement was used for polymerization of ⁇ Si—(OCH 3 ) 2 ⁇ 4 on a 4 inch diameter wafer.
- the power level was set at 80 Watts
- the precursor flow rate was set at 75 SCCM
- the deposition time was 20 minutes
- the deposition rate was 0.08 ⁇ /min.
- the film had a K of 2.32
- Tg was 240° C.
- the residual stress on silicon substrate was 37 MPa.
- Example 1 The plasma system described in Example 1 above was used for polymerization of an admixture of 60 molar % of ⁇ Si—(OCH 3 ) 2 ⁇ 4 and 40 molar % of CF 3 —C(H 4 —CF 3 .
- the power level was set at 200 Watts
- the precursor flow rate was set at 90 SCCM
- the deposition time was 20 minutes
- the deposition rate was 0.12 ⁇ m/min.
- the film had a K of 2.21, a Tg of 310° C., and a residual stress on a silicon substrate of 40 MPa.
- Example 1 The plasma system described in Example 1 above was used for polymerization of an admixture of 40 molar % of ⁇ Si—(OCH 3 ) 2 ⁇ 4 and 60 molar % of CF 3 —C 6 H 4 —CF 3 .
- the power level was set at 200 Watts
- the precursor flow rate was set at 90 SCCM
- the deposition time was 20 minutes
- the deposition rate was 0.12 ⁇ m/min.
- the film had a K of 2.21, a Tg of 310° C., and a residual stress on a silicon substrate of 32 MPa.
- This invention includes novel precursors and methods for making sealants with low dielectric constant, high thermal stability, and high mechanical strength.
- the polymers include fluorinated aromatic moieties and can be used to manufacture thin films and integrated circuits.
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Plasma & Fusion (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Ceramic Engineering (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Formation Of Insulating Films (AREA)
Abstract
Intermetal dielectric (IMD) and interlevel dielectric (ILD) that have dielectric constants (K) ranging from 2.0 to 2.6 are prepared from plasma or photon assisted CVD (PACVD) or transport polymerization (TP). The low K dielectric (LKD) materials are prepared from PACVD or TP of some selected siloxanes and F-containing aromatic compounds. The thin films combine barrier and adhesion layer functions with low dielectric constant functions, thus eliminating the necessity for separate adhesion and barrier layers, and layers of low dielectric constant. The LKD materials disclosed in this invention are particularly useful for <0.18 μm ICs, or when copper is used as conductor in future ICs.
Description
- Lee et al., Precursors for Making Low Dielectric Constant Materials with Improved Thermal Stability. Attorney Docket No.: QTII 8020 SRM/DBB.
- Lee et al. Chemicals and Processes for Making Fluorinated Poly(Para-Xylylenes). Attorney Docket No.: QTII 8021 SRM/DBB.
- Lee et al., New Deposition Systems and Processes for Transport Polymerization and Chemical Vapor Deposition. Attorney Docket No.: QTII 8022 SRM/DBB.
- Lee et al., Low Dielectric Constant Materials with Improved Thermal and Mechanical Properties. Attorney Docket No.: QTII 8023 SRM/DBB.
- All of the above co-pending applications are incorporated herein fully by reference.
- This invention is related to chemical compositions and methods for preparing materials that have low dielectric constants LKD. These low K materials, LKD, are prepared by photon assisted and/or plasma enhanced transport polymerization or chemical vapor deposition of some selected siloxanes and F-containing aromatic compounds. The LKD materials are particularly useful for manufacturing integrated circuits that have features smaller than 0.18 μm.
- For the past 20 years, the integrated circuit (IC) device density has doubled in about every 18 months. When the gate length of integrated circuits is less than 0.18 μm, the propagation time or delay time is dominated by interconnect delay instead of device gate delay. As the distance between metal lines decreases, the need for materials which can protect the integrity of the circuits also increases.
- Aluminum and copper are the metal of choice for manufacture of integrated circuits with feature sizes of less than 0.18 μm. Furthermore, as methods for etching copper are developed, integrated circuits with feature sizes of less than 0.13 μm can be made using copper damascene along with LKD materials.
- I. Packaging of Integrated Circuits
- When aluminum or copper is used in integrated circuits, titanium nitride (TiN) is used as barrier layer to improve interfacial adhesion between metal and SiO2 dielectric materials and to prevent corrosion of the metal by the wet chemicals used during semiconductor processing or from fluorine liberated from fluorinated SiO2 or other fluorinated polymers in the low dielectric polymer films. Corrosion results in the migration of metal ions from the metal line into the surrounding dielectric material. This results in increased leakage of current from the metal line into the adjacent circuit components, degrading circuit performance. Thus, one purpose of the glue layer or barrier layer is to prevent migration of metal ions from the metal lines. If TiN is used as a barrier layer, it must be about 200 Å to about 300 Å in thickness to be effective to protect against metal corrosion and degradation of circuit performance. Because metal lines are-close together, the distance between them is limited by the thickness of the barrier layer (2×200 Å=400 Å) and by the intervening low dielectric material. In an integrated circuit with 0.13 μm feature size, the thickness of the barrier layer of 400 Å leaves only 900 Å of space available for the low dielectric material. Moreover, as the space available for dielectric material decreases, there is the increased likelihood of gaps or voids being formed in the dielectric layers, further degrading circuit performance. Therefore, currently there is a need for new ways of protecting metal lines from corrosion while still maintaining proper dielectric efficiency.
- Moreover, when the metal gap is equal to or smaller than 0.13 μm and when copper is used as conductor, the dielectric effectiveness of currently available materials is so limited that TiN or any other currently available metal barrier will become unsuitable for protecting against metal corrosion. Furthermore, the potential interfacial corrosion problem for copper will be even more severe than for aluminum.
- To address this problem and others, new adhesion layer and barrier layer materials with low dielectric constants are being developed. Organic polymers are considered an improvement over inorganic low dielectric materials because the K of organic polymers can be as low as 2.0. However, most of the currently available organic polymers have serious problems. Specifically, they are not sufficiently effective as barrier layers.
- A. Siloxane Containing Polymers for Packaging Integrated Circuits
- In the 1980s, very extensive studies have been conducted to find hermetic packaging technologies for copper that used in Multi-Chip Modules (MCM). Due to their excellent electrical and thermal properties, polysiloxanes are among the most prevalent materials currently used in the encapsulation of electronic components. It has been found that only silicone gels and some siloxane containing polymers can prevent increases of leakage currents for encapsulated Triple Track Testers (TM under pressure cooker conditions. C. P. Wong, “High Performance Silicone Gels in IC Device Chip Encapsulation,”Mat. Res. Symp. 108:175-187 (1988). However, most of the conventional polysiloxanes have either gel-like or rubbery in consistency, and therefore have limited applications in areas demanding high mechanical strength of the coating material.
- The mechanisms for superior insulation property of siloxane-containing polymers are remained to be fully elucidated. It was rationalized though siloxanes are permeable to water vapor, they are perfect barriers for liquid water due to their high hydrophobicity. Their near zero water absorption can be attributed to the presence of siloxane derivatives presented in these polymers:
- where R′, R″, R′″, and R″″ are alkyl groups, such as —CH3, and wherein n is an integer of from 1 to 5. Due to very high rotational and oscillatory freedom of the substituted siloxanes including R groups such as —CH3, these siloxane groups can achieve very close contact with metal. The close contact prevents water from coming between the polymer and metal components thereby providing a watertight seal to prevent the degradation of critical circuit components by water. These siloxanes therefore are suitable for barrier layer materials.
- B. Spin On Glass (SOG)
- Currently, spin-on-glass (SOG) processes uses both organic and inorganic compounds as precursors. Organic precursors include siloxanes which contain many Si—CH3 groups and inorganic siloxane precursors contain few Si—H groups. These precursors, produce polymer produce thin films having dielectric-constants in the range of from about 2.7 to 3.0. However, a crack-free SOG dry film is only attainable when its thickness is less than 0.25 to 0.3 μm. Therefore, it is necessary to perform several sequential SOG steps to manufacture a layer of SOG that is thick enough (about 1 μm) to provide desirable sealing and dielectric properties. The total time needed to make SOG layers of this thickness is about 3 to 4 hours. This makes manufacturing SOG siloxane seals very inefficient. Furthermore, the SOG process is expensive due to the high losses (about 80% to 90%) of materials during spin coating.
- These SOG deposited precursors also require post-deposition treatments at temperatures higher than 410° C. to reduce out gassing during deposition, reflow or annealing of metals. This high temperature treatment results in high residual stress, which ranges from about 200 to about 500 MPa at room temperature. High residual stress can cause delamination art dielectric materials and metal surfaces, and can crack metal features in integrated circuits. Therefore, chemical processes that can deposit other siloxane-containing polymers are desirable.
- II. Precursors and Polymers for Manufacturing Low Dielectric Constant Materials
- During the past few years, several types of precursors have been used to manufacture polymers with low dielectric constants for use in manufacture of integrated circuits. Transport Polymerization (TP) and Chemical Vapor Deposition (CVD) methods have been used to deposit low dielectric materials. The starting materials, precursors and end products fall into three groups, based on their chemical compositions. The following examples of these types of precursors and products are taken from Proceedings of theThird International Dielectrics for Ultra Large Scale Integration Multilevel Interconnect Conference (DUMIC), Feb. 10-11 (1997).
- A. Modification of SiO2 by Carbon (C) and Fluorine (F)
- The first method described is the modification of SiO2 by adding carbon and/or fluorine atoms. McClatchie et al., Proc. 3d Int. DUMIC Conference, 34-40 (1997) used methyl silane (CH3—SiH3) as a carbon source, and when reacted with SiH4 and the oxidant H2O2 and deposited using a thermal CVD process, the dielectric constant (K) of the resulting polymer was 3.0. However, this K is too high to be suitable for the efficient miniaturization of integrated circuits.
- Sugahara et al.,Proc. 3d Int. DUMIC Conference, 19-25 (1997) deposited the aromatic precursor, C6H5—Si—(OCH3)3 on SiO2 using a plasma enhanced (PE) CVD process that produced a thin film with a dielectric constant K of 3.1. The resulting polymer had only fair thermal stability (0.9% weight loss at 450° C. in 30 minutes under nitrogen). However, the 30 min heating period is shorter than the time needed to manufacture complex integrated circuits. Multiple deposition steps, annealing, and metalizing steps significantly increase the time during which a wafer is exposed to high temperatures. Thus, this dielectric material is unsuitable for manufacture of multilevel integrated circuits.
- Shimogaki et al.,Proc. 3d Int. DUMIC Conference, 189-196 (1997) modified SiO2 using CF4 and SiH4 with NO2 as oxidant in a PECVD process The process resulted in a polymer with a dielectric constant of 2.6, which is much lower than that of SiO2 (K=4.0). However, one would expect low thermal stability due to low bonding energy of sp3C—F and sp3C—Si bonds (BE=110 and 72 kcal/mol., respectively) in the film. The low thermal stability would result in films which could not withstand the long periods at high temperatures necessary for integrated circuit manufacture.
- Siloxanes have been deposited using plasma dissociation processes (e.g., H. Yasuda,Plasma Polymerization, Academic Press (1985); M. Shen and A. T. Bell Editors: Plasma Polymerization, ACS Symposium Series, Vol.108, ACS (1979). These references are herein incorporated fully by reference. However, because these siloxane-containing polymers have low thermal stability, none of the mentioned siloxane polymers is adequate for IC fabrication meeting the requirements for small feature size.
- B. Amorphous-Carbon (αC)- and Fluorinated Amorphous Carbon (F-αC)-Containing Low Dielectric Materials
- The second approach described involves the manufacture of α-carbon and α-fluorinated carbon films. Robles et al.,Proc. 3d Int. DUMIC Conference, 26-33 (1997) used various combinations of carbon sources including methane, octafluorocyclobutane and acetylene with fluorine sources including C2F6 and nitrogen trifluoride (NF3) to deposit thin films using a high density plasma (HDP) CVD process.
- The fluorinated amorphous carbon products had dielectric constants as low as 2.2 but had very poor thermal stability. These materials shrank as much as 45% after annealing at 350° C. for 30 minutes in nitrogen.
- Recently, LKD materials with dielectric constants as low as 2.5 were prepared by adding fluorinated aliphatic compounds into high density plasma chemical vapor deposition (HDPCVD). Highly cross-linked amorphous poly(tetrafluoroethylene) (PFTE; Teflon™, registered tradename of DuPont Inc.) with a dielectric constant of 2.0 has also been made by plasma polymerization of CF2═CF2. However, these materials have poor thermal stability.
- One theory which could account for the low thermal stability of the fluorinated amorphous carbon products is the presence of large numbers of sp3C—F and sp3C-sp3C bonds in the polymers. These bonds have a bonding energy of 110 kcal/mol and 92 kcal/mol, respectively. Thus, the films cannot withstand the long periods of high temperatures necessary for IC manufacture.
- Poly(para-xylylenes) or PPX have dielectric constants ranging from of 2.4 to 3.5. They can be deposited at low temperatures. The fluorinated PPX (F-PPX; Parylene-F™, a trademark of Special Coating Systems, Inc.) has greater thermal stability than cross-linked poly(tetrafluoroethylene) due to the presence of phenylene groups in the repeating units. However, like cross-linked poly(tetrafluoroethylene), decomposition of F-PPX will potentially cause corrosion of copper in integrated circuits. Decomposition liberates free fluoride ions (F−), which can corrode circuit components. Therefore, there is a need for the development of new materials for sealing integrated circuit components.
- III. Methods for Deposition of Materials with Low Dielectric Constant
- The deposition of low dielectric materials onto wafer surfaces has been performed using spin on glass (SOG), but for newer devices which have features smaller than 0.25 μm, SOG processes cannot fill the small gaps between features. Therefore, vapor deposition methods are preferred. Of these, transport polymerization (TP) and chemical vapor deposition (CVD) are most suitable.
- Commercial organic and inorganic spin on glass (SOG) methods deposit mostly low molecular weight siloxanes. They have disadvantages for integrated circuit manufacture. SOG processes generate waste solvents and also have low deposition efficiencies, resulting in wasting of materials and increased cost of final products.
- In both TP and CVD, in contrast, the precursor molecule is dissociated (or cracked) to yield a reactive radical intermediate. The reactive intermediate contains at least one unpaired electron which upon deposition onto the wafer can bind with other reactive intermediate molecules to form a polymer. The polymer thus forms a thin film of material on the substrate. These processes are more efficient at utilizing precursors than are SOG processes. No extra precursors are needed to overcome the losses due to material spinning off of the wafer. Thus, transport polymerization and chemical vapor deposition are more desirable than SOG processes for depositing sealants to integrated circuits.
- A. Chemical Vapor Deposition
- Chemical vapor deposition has been used to deposit thin films with low dielectric constant. Sharangpani and Singh,Proc. 3d Int. DUMIC Conference, 117-120 (1997) reported deposition of amorphous poly(tetrafluoroethylene) using a liquid injection system. A dispersion of PFTE is sprayed directly on a wafer substrate, which is exposed to ultraviolet light and light from tungsten halogen lamps. Unfortunately, PFTE has a low glass transition temperature (Tg) and cannot be used for IC fabrication requiring temperatures of greater than 400° C. Labelle et al., Proc. 3d Int. DUMIC Conference, 98-105 (1997) reported using pulsed radio frequency (RF) plasma enhanced CVD (PECVD) process for deposition of hexafluoropropylene oxide. However, as with poly(tetrafluoroethylene), the resulting polymers have low Tg values and cannot withstand the high temperatures required for semiconductor processing.
- Kudo et al.,Proc. 3d Int. DUMIC Conference, 85-92 (1997) reported using a PECVD process for deposition of hydrocarbons including C2H2(C2H2+C4F4).
- Lang et al.,Mat. Res. Soc. Symp. Proc. 381:45-50 (1995) reported thermal CVD process for deposition of poly(naphthalene) and poly(fluorinated naphthalene). Although polymers made from these materials have low dielectric constants, the polymers are very rigid, being composed of adjoining naphthalene moieties. Thus, they are prone to shattering with subsequent processing such as CMP.
- Selbrede and Zucker, Proc. 3d Int. DUMIC Conference, 121-124 (1997) reported using a thermal TP process for deposition of Parylene-N™. The dielectric constant of the resulting polymer (K=2.65-2.70) also was not low enough. Furthermore, the decomposition temperature (Td) of the thin film was also too low to withstand temperatures greater than 400° C.
- Wang et al., Proc. 3d Int. DUMIC Conference, 125-128 (1997) reported that annealing a deposited layer of poly(para-xylylene) increases the thermal stability, but even then, the loss of polymer was too great to be useful for future IC manufacturing.
- Wary et al. (Semiconductor International, June 1996 pp: 211-216) used the precursor (α, α, α′, α′, tetrafluoro-di-p-xylylene) and a thermal TP process for making polymers of the structural formula: {—CF2—C6H4—CF2—})n. Films made from Parylene AF-4™ have a dielectric constant of 2.34 and have increased thermal stability compared to the hydrocarbon dielectric materials mentioned above. Under nitrogen atmosphere, a polymer made of Parylene AF-4™ lost only 0.8% of its weight over 3 hours at 450° C. However, the melting point of Parylene AF-4™ is about 400° C., which is too low for metal annealing. In addition, Parylene AF-4™ has poor adhesion to metal and its dimer precursor is too expensive and not readily available for future IC manufacturing.
- All of the aforementioned references are hereby incorporated fully by reference.
- B. Transport Polymerization
- In contrast to a CVD process, transport polymerization (TP) (Lee, C. J., Transport Polymerization of Gaseous Intermediates and Polymer Crystal Growth.J. Macromol. Sci.-Rev. Macromol. Chem. C16:79-127 (1977-1978), avoids several problems by cracking the precursor in one chamber and then transporting the intermediate molecules into a different deposition chamber. By doing this, the wafer can be kept cool, so that metal lines are not disrupted, and multiple layers of semiconductor devices may be manufactured on the same wafer. Further, the conditions of cracking can be adjusted to maximize the cracking of the precursor, ensuring that very little or no precursor is transported to the deposition chamber. Moreover, the density of the transported intermediates may be kept low, to discourage re-dimerization of intermediates. Thus, the thin films of low dielectric material are more homogeneous and more highly polymerized than films deposited by CVD. Therefore, these films have higher mechanical strength and can be processed with greater precision, leading to more reproducible deposition and more reproducible manufacturing of integrated circuits.
- Therefore, one objective of this invention is to develop novel dielectric thin films for integrated circuit manufacture.
- Another objective of this invention is the manufacture of gradient thin films in which the composition of the polymer layer differs along the film's thickness to provide changes in dielectric constant.
- Yet another objective of this invention is the manufacture of gradient thin films in which the composition of the polymer layer differs along the film's thickness to provide changes in thermal properties.
- A further objective of this invention is the manufacture of gradient thin films in which the composition of the polymer layer differs along the film's thickness to provide changes in mechanical properties.
- Another of the objectives of this invention is to provide LKD consists of sufficient amount siloxanes for hermetic protection of copper and other metals and materials.
- An additional objective is to provide molecular structures with high rotational flexibility between the silicon atoms and the planar configurations of the aromatic moieties to permit tight bonding of the molecule to the substrate.
- Another objective is to provide processes that result in low residual stress at polymer/metal interfaces.
- Yet another objective is to provide LKD materials that have also sufficient thermal and mechanical properties.
- Therefore, the invention discloses new precursors and methods for depositing materials with low dielectric constants.
- In one aspect of this invention, precursors containing aromatic moieties containing sp2-C—F bonds are deposited along with SiO2 to provide thin films with low dielectric constant, high thermal stability, and high mechanical strength.
- In another aspect of this invention, methods for transport polymerization and chemical vapor deposition using plasma energy sources are used to deposit novel thin films using siloxane and aromatic hydrocarbon precursors.
- In yet another aspect of this invention, gradient films are made which comprise depositing different layers of low dielectric material sequentially, each layer comprising different compositions of precursors.
- In this invention, the thin films are made with siloxanes and aromatic hydrocarbons selected to provide adhesion layer, barrier layer, and low dielectric layer functions.
- In another aspect of this invention, the siloxanes contain molecular structures with high rotational flexibility between the silicon atoms and the planar configurations of the aromatic moieties to permit tight bonding of the molecule to the metal, thus providing the adhesion layer function.
- In yet another aspect of this invention, the aromatic hydrocarbons are selected to provide low dielectric constant, high thermal stability, and high mechanical stability, thereby providing barrier and low dielectric layer functions.
- In other aspect of this invention, the dielectric constant of these materials range from 2.0 to 2.6.
- In yet another aspect of this invention, the residual stress of these materials on copper ranges from 25 to 50 M Pa at room temperatures.
- In a further aspect of this invention, These polymers form primarily 3-dimensional networks.
- Other objects, aspects and advantages of this invention can be ascertained from the review of the additional detailed disclosure, the examples, the figures and the claims.
- FIG. 1 depicts structures of some aromatic precursors of this invention.
- FIG. 2 depicts structures of some isomers of one of the precursors of this invention.
- FIG. 3 depicts structures of some side products of this invention.
- FIG. 4 is a schematic diagram of a transport polymerization system using electromagnetic radiation to dissociate precursors.
- FIG. 5 is a schematic diagram of a transport polymerization equipment employing IR radiation.
- FIG. 6 is a schematic diagram of a transport polymerization system employing radio frequencies to generate a plasma.
- FIG. 7 is a schematic diagram of a transport polymerization system employing microwaves to generate a plasma.
- FIG. 8 is a depiction of an inductively coupled high density plasma apparatus.
- FIG. 9 depicts a schematic diagram of a combination transport polymerization and chemical vapor deposition reactor utilizing photon-plasma and infrared radiation.
- FIG. 10 is a depiction of a cluster tool which can be used to deposit step-gradient films of this invention.
- FIG. 11 is a schematic diagram of a step-gradient film of the present invention.
- FIG. 12 is a schematic diagram of a continuous gradient film of the present invention.
- In this invention, the adhesion and barrier layers made of titanium nitride, titanium oxynitride, or other conventional materials are replaced with siloxanes and aromatic hydrocarbons selected to provide adhesion layer, barrier layer, high thermal stability and low dielectric layer functions. The siloxanes contain molecular structures with high rotational flexibility between the silicon and oxygen atoms and the planar configurations of the aromatic moieties to permit tight bonding of the molecule to the metal, thus providing the adhesion layer function. The aromatic hydrocarbons are selected to provide low dielectric constant, high thermal stability, and high mechanical stability, thereby providing barrier and low dielectric layer functions. The materials with low dielectric constant having high thermal stability and high elastic modulus (E) are prepared by plasma assisted or photon assisted transport polymerization or chemical vapor deposition of some selected siloxanes and fluorine-containing aromatic compounds. The dielectric constant of these materials range from 2.0 to 2.6. The residual stress of these materials on copper ranges from 25 to 50 M Pa at room temperatures. These polymers form primarily 3-dimensional networks.
- I. Precursors
- The precursors useful for this invention include selected siloxanes and F-containing aromatic compounds.
- A. Siloxane Derivatives
-
- where R′ and R″ are fluorinated alkyl groups; or aromatic mono-, di-, tri- or tetra-radicals and their fluorinated derivatives. The siloxanes can be linear or cyclic compounds and n is an integer of at least 1. When n is from 3 to 5 and R′ and R″ are selected from the group consisting of —H, —CH3, —CF3, —(CH2)n—CF3,—C2H5, —C6H5, —C6(CF3)H4, various commercial siloxane products are available. Other useful siloxanes can be found in some textbooks, such as John Ziegler and F. W. Gordon Fearson, Ed. Silicon-Based Polymer Science Adv. Chem. Series No 224, ACS (1990). Although these siloxanes have been previously described, none of them has been used to replace a barrier layer or adhesion layer in the manufacture of integrated circuits.
- The most useful siloxane derivatives include cyclic siloxanes, wherein n is between 2 and about 7, preferably about 4 to about 5, or wherein R′ and R″ are fluorinated alkyl groups, or are fluorinated aromatic groups described below. Siloxanes and fluorinated aromatic precursors have been used separately in plasma deposition of polymers, but not their admixtures for use in IC applications.
- B. Fluorinated Aromatic Moieties
- Aromatic precursors useful for this invention include compounds with the following structure: Y—Ar—(Y′)2, wherein the Ar is an aromatic compound consisting primarily of sp2C to sp2C and sp2C—Y bonds, and wherein Y and Y′ are a leaving groups selected from the group consisting of —H, —Cl, —Br, —NR, —SR, —SiR3, —NR2 and —SO2R and wherein R is —H, an alky group or an aromatic mono-radical, and z is an integer ranging from 1 to 6. Some examples of the aromatic compounds are: C6FnH(6-n), CF3—C6F5, CF3—C6F4—CF3, CF3—C6F4—C6F5, CF3—C6F4—C6F4 —CF3, and C10F8.
- Additional aromatic structures can be found in the attached FIGS.1 to 3. FIG. 1 depicts structures of some aromatic moieties useful for this invention. The moiety —CF2—C6H4—CF2— is used in poly(para-xylylene) Parylene™ (a trademark of Specialty Coating Systems, Inc.) as a material for manufacturing semiconductor thin films with low dielectric constants.
- Other precursors of this invention contain aromatic moieties which have from more than about 6 to about 40 carbon atoms. Precursors of this invention can be classified according to the following formulas:
- —C10H(6-n)Fn—, wherein n is an integer ranging from 0 to 6;
- —C12H(8-n)Fn—, wherein n is an integer ranging from 0 to 8;
- —C13H(7-n)Fn—, wherein n is an integer ranging from 0 to 7;
- —C14H(8-n)Fn—, wherein n is an integer ranging from 0 to 8;
- —C16H(10-n)Fn—, wherein n is an integer ranging from 0 to 10.
- The di-phenylenyl moiety (—C10H(8-n)Fn—) where n is an integer of from 0 to 8 consists of two phenylenyl moieties covalently linked together. The anthracenyl (—C14H(8-n)Fn—) moiety wherein n is an integer of from 0 to 6, the phenanthrenyl (—C14H(8-n)Fn—) moiety wherein n is an integer of from 0 to 8, the 4-ring pyreneyl (—C16H(8-n)Fn—) moiety wherein n is an integer of from 0 to 8 are useful. Further, more complex aromatic structures such as a naphthenyl moiety connected to a phenylene moiety (—C16H(10-n)Fn—) wherein n is an integer from 0 to 10 are useful in this invention. Furthermore, a three-ring structure (—C13H(7-n)Fn—) also is useful.
- Moreover, covalently linking similar or different aromatic residues together creates larger aromatic moieties. For example, linking phenyleneyl and naphthenyl residues into a phenyleneyl-naphthenyl moiety results in an aromatic moiety with the structural formula: (C6H4-nFn)—(C10H6-mFm), where n and m are integers. Similarly, linking a phenanthrenyl residue and a pyreneyl residue results in an aromatic moiety with the structural formula: —(C14H(8-n)Fn)—(C16H(8-n)Fn)—. All such combinations of the aforementioned aromatic moieties which consist of up to about 40 carbon atoms are considered to be part of this invention.
- Numerous positional isomers exist for each of the above formulas. The term positional isomer refers to the relative location of the radical-containing moieties on the aromatic groups. In addition to positional isomers, the location of the fluorine atoms also may be different for each of the positional isomers. For instance, when the aromatic group has the general formula: —C10H(6-n)Fn—, there are 9 and 39 positional isomers for n=0 and 1 respectively (see FIG. 2). For each of the positional isomers shown in FIG. 2, there are several fluorine-isomers. The number of these mono-fluoro-isomers is shown in parentheses. All partially or fully fluorinated aromatic moieties and all of the positional isomers are included in this invention.
- However, not all of these positional isomers are equally useful in transport polymerization for the preparation of thin films for IC fabrication. Isomers, when formed into reactive intermediate di-radicals, may not form polymers at all. For example, for the (1, 2) isomer as shown in FIG. 2, the radical groups are too close together on the aromatic moiety, and the reactive intermediates will mostly form undesirable side products such as monomers and dimers (FIG. 3), and will not form polymers. When these monomers and dimers deposit on wafers along with polymers, the resulting thin films will be contaminated with liquid or powdered side products, and thereby becoming useless for integrated circuit fabrication. For the same reason, the (1, 8) isomer also is not useful.
- These powdery dimers form on wafers when the vapor pressure is too high or/and its residence time, τ, inside the chamber is too long. Attempts to increase deposition rate by increasing the chamber pressure resulted in more dimer formation and concomitant loss of dielectric efficiency unless the residence time in the chamber is very low. The sufficiently short residence time needed to avoid powder formation on cold wafers can only be obtained by using small deposition chambers: Because the smallest chamber size is limited by the wafer diameter, the height of the chamber should be very small. Constraints on the dimensions of the chamber can lead to poor deposition patterns if the flow of intermediates is focused on a particular portion of the wafer. In some of the new deposition systems of co-pending application, the chamber is designed to accommodate devices which can redistribute the flow pattern of intermediates onto the wafers. If the chamber is too small, there will be insufficient room to incorporate flow pattern adjusters or diffusion plates into the systems. Moreover, with small chamber dimensions, it is difficult to provide adequate devices for automated wafer handling.
- On the another hand, intermediate di-radicals generated from the (1, 6) isomer will not form dimers because of the stearic hindrance of its bulky Ar group as shown in FIG. 3. For the same reason, except for the (1, 2) and (1, 8) isomers, other C-10 di-radicals will tend to not form side products on wafers even though they have a high residence time and/or under high vapor pressure. Therefore, these polymer precursors are favored for potentially getting much higher deposition rates.
- Therefore, it is desirable to chose isomers in which the formation of dimers or monomers is not favored. By selecting the positional isomers such that the reactive groups are sufficiently far apart, dimer or monomer formation is minimized. It is desirable for the end-to-end length (Im) to be at least 4 Å, and preferably, Im should be at least 6 Å. End-to-end length is calculated using bond angle and bond length of repeating units in the polymers.
- Asymmetrical isomers with lower extended chain lengths will have higher G and E. However, symmetrical isomers have higher Tg due to the higher cohesive energy, which results from the more complete alignment of aromatic moieties. The more complete alignment results in closer approximation of π electrons in the adjacent aromatic moieties, which results in the formation of tighter n bonds being formed between adjacent aromatic moieties.
- For the di-phenylene moiety, there are several positional isomers. In these positional isomers, the arrangement of the reactive groups can be para-para (pp), meta-para (mp), para-ortho (po), meta-ortho (mo), ortho-ortho (oo), para-meta (pm), or meta-meta (mm). Note that the oo positional isomer will be constrained to a trans-like configuration, wherein the two radical-containing moieties of Compound IV will not be close together. If they are too close together, they may form a monomer, which will contaminate the polymer. Fortunately, the oo monomer is highly unstable, and does not easily form.
- Some of the naphthenyl (C10) isomers, such as the (1, 5) and (3, 7) isomers, have a symmetric configuration, therefore they are likely to form highly crystalline polymers. For the same polymer, thin films with higher degrees of crystalinity have higher thermal stability, higher Elastic Modulus and higher Tg and lower Coefficient of Thermal Expansion (CTE). For this reason, Parylene AF-4™ deposited at higher wafer temperatures resulted in higher Tg and E and lower CTE than those of films deposited at lower wafer temperatures.
- When the aromatic compounds are used in conjunction with siloxanes, one theory which may account for the improved thermal stability and improved mechanical properties of the resulting materials is that the bond types present in the new materials have more cohesive energy than the bond types of other, previously used materials. First, sp2C═sp2C bonds in aromatic compounds have much higher bond strength and cohesive energy than sp3Si-sp3C or Si—C bonds in the siloxanes. For single bonds, the sp2C-sp3C bond, or hyperconjugated C—C bond, the sp2C—X, or hyperconjugated C—X bond both have higher bonding energy (BE) and cohesive energy than the sp3 Si-sp3C and sp3 Si—X bonds. This is due to the so called “hyperconjugation” effect. The hyperconjugation results from participation of the σ-bonds electrons of the C—C or C—X single bond in overlapping with the π-orbitals of a neighboring C═C double bond. The resonance stabilization of a single bond by a neighboring double bond increases its bonding strength. This is especially effective when the X is an electron withdrawing group such as fluorine atom. For the above reason, the bonding energy of the C═C—F bond is higher than that of the C—C—F and Si—F bonds. Examples of these bond energies are found in Table 1.
TABLE 1 Bond Type sp3C—Si sp2C—Si sp3C—sp3C sp2C—H sp2C—F Bond 72 92 92 111 126 Energy (BE) (kcal/ mol) Bond Type Si—O sp2C—sp3C sp2C═sp2C sp3C—F Si—F Bond 98 102 145 110 135 Energy (BE) (kcal/ mol) - The date of Table 1 is taken from Streitwiesser et al.,Introduction to Organic Chemistry, Appendix II, University of California Press, Berkeley, Calif. (1992), incorporated herein fully by reference. The bond energy (BE) of a sp3C—X bond can be higher than that of a sp3Si—X bond when X═H, C and S; however, its opposite is true when X═F, Cl and O. For instance, the BE of a sp3Si—F bond is 135 kcal/mol. versus 110 kcal/mol. of a sp3C—F bond. Despite its high BE, SiOF films consisting of more than 4.2 atomic-F % are found to be very unstable under pressure cooker conditions (Passemard et al. Fluorine Stability in Fluorosilicate Glass and Effects on Dielectric Properties, Proceedings of the 2d DUMIC, p 145, 1996). It has been theorized that due to higher reactivity of sp3Si—F bonds towards fluorination comparing to Si—O bonds, plasma polymerization of precursors containing >4.2% fluorine result in SiOF films comprising mostly F—Si—F. (Takamura et al. Preparation of Stable Fluorine-Doped Silicon Oxide Film by Biased Helicon Plasma CVD, Proceedings of the 2d DUMIC p 231, 1996). Due to these reasons, stable SiOF films are limited to those having a dielectric constant of 3.5 or higher.
- After polymerization, the sp3Si—F bond in a F—Si—F group can be easily hydrolyzed due to the high polarity resulting from presence of the second fluorine on the group. Takamura et al., Proceedings of the 2d DUMIC p 231, (1996). Hydrolyzed Si—F bonds will release HF acids and corrode metals in integrated circuits.
- In this invention, organic compounds consisting mostly of sp2C—F bonds are used to lower dielectric constant of SiO containing films. The sp2C—F bond has high thermal stability and excellent hydrolytic stability. Unlike for sp3Si—F and sp3C—F bonded moieties, there is no similar limit for the atomic % of F content for thin films comprising sp2C—F bonds. Thin films prepared from this invention can have K as low as 2.0-2.3 and excellent thermal stability.
- Therefore, these new precursors can replace titanium nitride (TiN), TaN, WN, TaSiN, WSiN, and similar materials as barrier layers and adhesion layers. However, the use of these new precursors as barrier and adhesion layers requires the development of equipment for low temperature dissociation and deposition. The equipment used is described in the above-described co-pending applications.
- II. Deposition of Precursors
- The polymers and siloxane derivatives of this invention can be deposited using any conventional CVD or transport polymerization method which uses “cold dissociation” methods. As used herein, the term “cold dissociation” methods are those which do not appreciably heat the precursors. Such cold dissociation methods include photon assisted (PA) or plasma enhanced (PE) processes.
- A. Photon Assisted Transport Polymerization
- Photon assisted transport polymerization and chemical vapor deposition can use infrared (IR), ultraviolet (UV) or vacuum ultraviolet (VUV) sources, or combinations of the above. A desirable energy source is incoherent excimer radiation that is derived from a dielectric barrier discharge. UV and VUV photon energies that are in the range from about 3 to about 5 eV are especially useful.
- One option of this invention is to first deposit on metal surfaces a layer of siloxanes ranging from 100 to 500 Å, then switch to deposition of fluorinated aromatic polymers. Another option is to deposit copolymers of siloxanes and fluorinated aromatic compounds by introducing admixtures of these two types of compounds with various mixing ratios. Additionally, gradients of polymers can be made by gradually changing the composition of the precursors introduced into the deposition system during deposition. Another option is to make a damascene dielectric structure with a top layer of PACVD siloxanes for better LKD to copper adhesion. In addition to equipment utilizing thermal methods for dissociating precursors, equipment utilizing electromagnetic radiation is useful for practicing this invention. Useful electromagnetic radiation is in the infrared (IR), ultraviolet (UV) and vacuum ultraviolet (VUV) spectra UV and VUV produce no heat, whereas IR produces heat. When used in combination, IR and either UV or VUV can dissociate precursors with increased efficiency.
- 1. Transport Polymerization Using Combined IR, UV, and VUV Sources
- FIG. 4 is a schematic diagram of a
transport polymerization system 400 using electromagnetic radiation as an energy source for cracking precursor molecules. Precursors are transported from theprecursor tank 404 through apipe 408 and through amass flow controller 412 through anotherpipe 416 and into atube 420 which is transparent to the types of electromagnetic radiation to be used. For IR irradiation, a glass tube is sufficient. For UV irradiation, quartz tubes are necessary, and preferably are made of a single crystal quartz. For VUV irradiation, tubes made of MgF2, LiF, or CaF2 are necessary because the short wavelengths of VUV cannot pass easily through quartz. - In another embodiment of the invention, the electromagnetic energy source can be located at a site within the central area of flow of precursors. With this configuration, a large proportion of the electromagnetic energy is directed at the precursors as they flow past. This can increase the efficiency of precursor cracking.
- After dissociating in
tube 420, the reactive intermediates are transported into the deposition chamber 422 surrounded by aheater 436. The wall of the chamber is heated to decrease the deposition of molecules on the chamber wall. This heating can be accomplished by any conventional means, including, but not limited to resistive heating. After enteringchamber 432, the flow of intermediates is adjusted by a movableflow pattern adjustor 440. Vertical movement of theflow pattern adjustor 440 adjusts the flow rate of intermediates into thechamber 432 and aids in mixing the intermediates more evenly within thechamber 432. Horizontal movement offlow pattern adjustor 440 adjusts the flow distribution of intermediates over thewafer 448. The flow pattern adjuster can be a flat, stainless steel plate, or alternatively can be a porous or honeycomb structure. Agas dispersion plate 444 evens the flow of intermediates over thewafer 448. Dispersion holes between the flow pattern adjuster and the wafer ensure the dispersion of the intermediates. Thewafer 448 is held by a mechanical or electrostaticcold chuck 452, which is cooled by anychiller 456 employing any conventional means, including, but not limited to liquid nitrogen or reverse Peltier effect. A UV or VUV source also can be directed toward thewafer 448 to permit cross-linking of polymers after their deposition. Apipe 460 is for exhausting thechamber 452, and apump 472 connected via apipe 468 to atrap 464 maintain the pressure within the chamber at desired levels. - Exemplary sources of UV radiation for transport polymerization can include (1) a mercury lamp that provides from 50 to 220 mW/cm2 of UV ranging from 185 to 450 nm or (2) a metal halide lamp that provides from 40 to 160 mW/cm2 of UV ranging from 256 nm to 450 nm. These UV sources provide photon energies ranging from 2 to 5 eV, which are sufficient for generating radical intermediates.
- An alternative to conventional UV light is vacuum ultraviolet (VUV). (See Van Zant,Microchip Fabrication, 3d edition, McGraw Hill, New York, 1996). Incoherent excimer radiation can provide a large number of UV and VUV wavelengths for photolytic processing of various chemicals. The preferred source is incoherent excimer radiation derived from dielectric barrier discharge. UV and VUV photons that are in the ranges of 3 to 5 eV are especially useful. These energy levels are comparable with the bonding energies of most chemical bonds, thus are very effective for initiating photochemical reactions (see Table 1).
TABLE 2 Bond Energies of Selected Bonds Chemical Bonds Bonding Energies (eV) φ-CH2Br 2.52 φ-CH2—OR 3.52 φ-CH2—CH3 3.30 φ-CH2—NH 3.09 φ-CH2—F 4.17 φ-CH2—SR 3.20 φ-CH2—H 3.83 - Table 2 shows the bonding energies in electron volts (eV) corresponding to certain bonds of this invention. This data is from Streitwiesser et al.,Introduction to Organic Chemistry, Appendix II, University of California Press, Berkeley, Calif. (1992), incorporated herein fully by reference.
- However, the energies of mercury vapor or metal halide UV radiation are too small to be useful for rapid transport polymerization. The desired residence time within the cracking chamber, which is the time available for photolysis should be in the range of a few milliseconds to several hundred milliseconds. Therefore, VUV is the most desirable form of energy for photon assisted transport polymerization.
- VUV or incoherent excimer UV sources can be provided by dielectric barrier or silent discharge using a variety of gas or gas mixtures according to methods known in the art. For example, VUV can be generated using KrBr, Ar2, ArCl, ArBr, Xe2 and F2 gases. Xe emits at 172 nm, Kr at 222 nm, and XeCl emits at 308 nm. As can be seen from Table 2, nearly all of the chemical bonds of interest in polymer manufacture can be broken using photolytic methods. Because excimer radiation is selective for the energy of the specific bonds, excimer radiation from a second source or alternatively, a plasma source may be used simultaneously if it is desired to break other bonds at the same time. Such a combination of excimer sources and plasma sources are useful to break bonds of precursors for making cross-linked poly(para-xylylenes). Because the leaving groups of these precursors can be different, it is desirable to break those bonds selectively to generate tri- and tetra-functional reactive intermediates.
- Using photon-assisted processes of this invention, it is also possible to cross-link the novel polymers after their deposition. By directing the photons toward the surface of the polymer, the electromagnetic energy disrupts some of the C—F or C—H bonds, creating radicals, which can bond with nearby polymer chains, resulting in a cross-linked film of polymers. This can be accomplished by exposing the wafer to UV or VUV for several seconds up to several minutes.
- 2. Transport Polymerization Using Infrared (IR) Radiation
- An alternative transport polymerization equipment employing
IR radiation 500 is shown in FIG. 5. The precursors are transported from aprecursor holder 504 through apipe 508 and through amass flow controller 512 and asecond pipe 516 into thechamber 520. The chamber contains aquartz chamber 524, optionally containing acatalyst 528. Aninfrared radiation source 532 is placed outside thequartz container 524, and the precursors are dissociated as they pass through thequartz container 524. Adiffusion plate 536 is used to optimize the flow pattern of intermediates to thewafer 540. Optionally, a flow pattern adjuster as shown in FIG. 4 (440) may be used to adjust the flow of intermediates over thewafer 540. Thewafer 540 is held on a mechanical or electrostaticcold chuck 544, which is cooled by aconventional chiller 548. The pressure in the chamber is maintained by apump 564 connected via apipe 560 to and atrap 556, which is connected tochamber 520 by apipe 552. Thetrap 556 protect the pump from deposition of intermediates in thepump 564. - In IR radiation, a combination of both thermolytic and photolytic reactions are expected. Therefore, it is important to ensure that the IR power is in the range where the reactive intermediates can be dissociated, but where destruction of the polymer network does not occur. The IR power should be in the range of from 500 Watts to 3000 Watts, preferably from 1500 Watts to 2500 Watts, and most preferably 2000 Watts.
- B. Plasma Enhanced Transport Polymerization
- Plasma energy is also used to dissociate precursors into reactive intermediates. Plasma sources useful for this invention can be provided by various different kinds of equipment. Michael Lieberman and Allan LichtenbergPrinciples of Plasma Discharge and Material Processing, Wiley Interscience, (1994). There are generally two types of energy sources for plasma enhanced transport polymerization or chemical vapor deposition. They are radiofrequency (RF) and microwave sources.
- Plasma enhanced TP is carried out using the novel reactors described herein (FIGS. 6-9). With low density plasma, the electron density in the plasma is in the range of about 1012 to about 1013 electrons/cm3. Low density plasma TP and CVD can be carried out at about 100 milliTorr to about 100 Torr. High density plasma (HDP) is characterized by electron densities in the range of about 1013 to about 1014 electrons/cm3. High density plasma TP and CVD can be carried out at pressures of about 0.1 milliTorr to about 100 milliTorr. The higher electron density in HDP increases the formation of cross-linked polymers, because the higher energy density increases the numbers of tri-radical intermediates which can form cross-links between polymer chains.
- Several comprehensive reviews and texts have appeared on plasma polymerization which incorporate many of the methods currently in the art. Yasuda,Plasma Polymerization, Academic Press, 1985; d'Agostino, Ed.: Plasma Deposition, Treatment and Etching of Polymers, Academic Press, 1990; Hollahan and Bell, Ed., Techniques and Applications of Plasma Chemistry, John Wily and Sons, 1974; Morita et al, Pure Appl. Chem. 57:1277 (1985). Each of these is incorporated herein fully by reference.
- C. Measurement of Polymer Properties
- To describe the effects of polymer composition and process conditions on polymer properties, measurements of dielectric constant and polymer composition are measured and correlated with process conditions.
- 1. Dielectric Constant
- The dielectric constant is measured for samples of substrate whose dimensions are about 0.1″×0.1″, composed of a layer of polymer sandwiched between two metal layers. The capacitance of the polymer layer is measured, and the dielectric constant is calculated from the result of this measurement. The error in the estimation of the area of the top metal layer is about 5%-10% of the average value. The measurement of capacitance is accurately measured, and the dielectric constant is calculated. The total possible error of the calculated value of the dielectric constant is about 10%-20% of the average value.
- 2. Film Composition
- The composition of the films is characterized by Fourier Transform Infrared Spectroscopy (FTIR, Bio-Rad Systems, Inc.) using methods known in the art, and the methods will not be discussed further. The ratio (γ) of hydrocarbon CHx to SiO2 is calculated by comparing the areas under he peaks at 3200 or 1250 cm−1 with the area under the peak at 879 cm−1.
- D. Regulation of Physical and Chemical Properties of Polymer Films
- 1. Regulation of Process Conditions
- The plasma variables used to control the physical and chemical nature of the deposited polymer film are: excitation power in Watts (W), flow rate (F) of the monomer(s), molar rations of different monomers (for making co-polymers or gradient films), substrate temperature Ts, deposition pressure (P), substrate bias (Vs), and monomer temperature (Tmo), the flow rates of the feed gas and/or monomer(s), relative positions and separation of the anode and cathode plates, location of the gas inlet and pump outlet and control of the pump speed. All of these factors have effects on the types and properties of the deposited film. Other factors such as the reactor geometry can play a major role.
- Among all plasma parameters, the flow rate and power level have the most profound effects on the properties of deposited products. For instance, under the same flow rate, increasing power levels resulted in thin films of higher dielectric constants, high glass transition temperatures and thermal resistance for a given composition of siloxane chemicals. On the another hand, under the same power level, increasing flow rates will result in lower dielectric constant and thermal stability of the products due to presence of large amounts of —CHx— groups (X=1 to 3). This is because CHx— containing polymers such as polyethylene (K=2.0) have lower dielectric constants than does SiO2 (K=4.0).
- All depositions can be performed after subjecting the surfaces to an in-situ argon plasma pre-cleaning step. The films are deposited at RF power ranges of a few tens of Watts to a few hundred Watts with a gas flow rate of between 30-90 SCCM. The chamber pressure during deposition ranges from 10−3 Torr to a few Torr. Deposition rates vary from a few hundred Å/min to close to 0.4 μm/min.
- The useful processing parameters therefore have to be optimized for each composition in order to obtain desirable combinations of dielectric constant, mechanical properties such as Elastic Modulus, thermal properties such as Tg and residual stress and sufficient protection of metal/polymer interfaces from moisture. The following parameters were found useful for making low K dielectric materials with high thermal stability from siloxanes of this invention: Power levels range from 80 to 300 Watts, or preferably from 120 to 200 Watts under the gas flow rates range from 30 to 90 SCCM, preferably from 50 to 75 standard cubic centimeters per minute (SCCM) and a vacuum pressure of few milliTorr. Using these conditions, void free thin films with dielectric constants ranging from 2.2 to 2.6 can be obtained at deposition rates ranging from 1200 Å to 2000 Å/min. These films have Tgs in the range from 150° C. to 300° C. and have low residual stress ranging from 15 MPas to 50 MPas.
- For a 4 inch diameter wafer and power levels below about 20 Watts, most of the hydrocarbons of the precursor introduced into the chamber are intact. However, as the power level increases to about 40 to 50 Watts, the hydrocarbon content decreases rapidly. Increasing the power level further above about 100 Watts decreases the hydrocarbon contents is greatly reduced for the gas flow rates studied. For larger wafers, the power should be increased proportionately.
- Also, for 4 inch diameter wafers, for the precursor is {Si—OCH3)2}4, and when γ (1250/870 cm−1) decreases from 0.08 top 0.37, the dielectric constant of the resulting film increases from 2.0 to 3.5. Therefore, when the flow rates is 30 SCCM, K increases from 2.3 to 2.8 as the power level increases from 80 Watts to 250 Watts. At higher flow rates of 75 SCCM, K increase from 2.25 to 2.4 as the power level increases from 80 to 150 Watts. For larger wafers, the power should be increased proportionately.
- Additionally, for 4 inch diameter wafers coated with the above films, Electron Spectroscopy for Chemical Analysis (ESCM) is also employed for more quantitative analysis of surface compositions of the deposited films. ESCI studies indicated for a flow rate of 30 SCCM, as the power level increased from 80 to 200 Watts, the number of carbon atoms per silicon atom in the polymer film surface wag 1.36 and 1.17, respectively. Because the theoretical C/Si ration in a monomer is 2, this results indicates that in addition to the C—H bond dissociation, there is substantial Si—C bond dissociation during plasma polymerization. For larger wafers, the power should be increased proportionately.
- 2. Manufacture of Co-Polymers
- Although materials with low dielectric constant (K=2.2 to 3.2) can be achieved by plasma or photon assisted polymerization of siloxanes, the resulting low dielectric films usually have poorer thermal stability due to presence of large proportion of sp3 C—H and sp3 Si-sp3C bonds. To improve the thermal stability of the above films without compromising their dielectric properties, one can use admixtures of siloxanes and fluorinated aromatic compounds that disclosed in this invention. For example, admixtures of CF3—C6F4—CH3 and {Si—(OCH3)2}4 can be used together. In general, under the conditions described above, the thermal stability and the dielectric constant of the polymer increases as the molar ratio of the CF3—C6F4—CH3 increases.
- These co-polymer films are pinhole free, possess high mechanical strength and adhesion and can be deposited conformally onto any surfaces. The plasma variables can be so adjusted so as to yield a film with relatively low residual stress. Thin firms on silicon with residual stress as low as 5 to 30 MPa at room temperature can be achieved for film thicknesses up to a about 5 μm. The coefficient of thermal expansion perpendicular to the film (Z-CTE) of this film was estimated to be about 10 to 25 ppm/° C. One of the drawbacks of plasma polymerization for hydrocarbons in the past has been the low deposition rates. However, with the presence of siloxanes, we have been able to achieve deposition rates close to 0.2 μ/min routinely and can achieve deposition rates of up to 0.4 μm/min.
- Using admixtures of precursors at low precursor flow rates and low power levels, there is a sharper increase in the dielectric constant than for higher flow rates at higher power levels. Increasing the flow rate does not further increase dielectric constant, rather, the dielectric constant levels off. The former can be classified as a “power rich” region, and the latter, a “power deficient” region. This result is consistent with the increases in C—H bond dissociation , which results in increased ratio of SiO2 to CHx (where X=1 to 3) contents, as derived from FTIR and ESCA studies described above.
- 3. Manufacture of Gradient Polymer Films
- Step-gradient films of this invention can be manufactured by depositing a first layer of material which contains siloxanes which will adhere to the substrate. This tightly adhering layer functions as an adhesive layer, permitting subsequent layers to adhere to the semiconductor device. On top of this siloxane-rich layer, an additional layer, containing for example, a fluorinated aromatic hydrocarbon can be deposited using either the same deposition chamber, or by using the cluster tool described below (FIG. 10).
- In another option of this invention, continuous gradient thin films are made by gradually introducing different precursors or combinations of precursors into the apparatus during the plasma deposition process. For instance, first, a siloxane-rich thin layer ranging from a few tens of Å to several hundreds of Å is deposited onto a metal layer. Then, on top of this siloxane-rich layer, a layer of sp2C—F bond-rich siloxanes or organic compounds is made by introduced into the deposition apparatus with increasing molar % of fluorinated aromatic compounds toward the centers between the metal lines and away from the metal surfaces. The layer making contact with the metal can be composed of a material with a lower dielectric constant (K<2.0 to 2.6). This type of polymer is desirable if the polymer can withstand the temperatures of the processes, or if a higher K (2.6 to 3.2) is suitable. If the temperatures of the subsequent processing steps are unsatisfactorily high for siloxanes, materials with higher thermal stability will be required. These materials also have higher dielectric constants. The siloxane-rich layer is well suited as a water barrier which can seal the metal lines (the “hermetic effect”) preventing their corrosion. This is especially important when copper is used as the metal.
- On the other hand, by increasing the molar % of sp2C—F bonds in the polymer away from the metal features, materials with lower dielectric constants and increased thermal stability are desirable. The gradient polymer scheme increases the effective insulation properties, while achieving better interfacial protection of metal features.
- In another option of this invention, on top of the interlevel dielectric layer, a SiO2-rich layer can be deposited. This can be simply achieved by increasing the power level of the plasma to over 300 Watts for a 4 inch diameter wafer ans using admixtures with higher percentages of siloxane precursors. The SiO2-rich cover layer is helpful for CMP of these materials and metals following deposition.
- E. Equipment Used To Generate Plasmas for Transport Polymerization and Chemical Vapor Deposition
- 1. Plasma Enhanced Transport Polymerization Using a Radio Frequency Plasma Generator
- FIG. 6 is a schematic diagram of a
transport polymerization system 600 employing RF to generate a plasma. The precursors are stored in aprecursor holder 604, are transported via apipe 608 and through a liquid injector for liquid precursors, or amass flow controller 612 for gasses, then are transported via anotherpipe 616 into aplasma tube 620 made of quartz. Preferably, thetube 616 is made of a single quartz crystal. Precursors are exposed to RF energy generated by aRF generator 626, through acoil 628, and aplasma 630 is thereby generated. Theplasma 630 then flows into adeposition chamber 634 which is surrounded by aheater 638. Theheater 638 keeps the walls of thechamber 634 above the condensation temperature of the reactive intermediates. This prevents condensation of intermediates onto the walls of thechamber 634. The flow of intermediates is adjusted by aflow pattern adjuster 642. Vertical movement of theflow pattern adjuster 642 adjusts the flow rate of intermediates into thechamber 634, and aids in mixing the intermediates in thechamber 634. Horizontal movement of theflow pattern adjuster 642 adjusts the distribution of the intermediates over the surface ofwafer 650. Agas dispersion plate 646 with holes distributes the flow of intermediates evenly over the surface of thewafer 650. - The
wafer 650 is held on acold chuck 654, which is kept cool by achiller 658 employing any conventional cooling method, including liquid nitrogen and reverse Peltier effect. The chamber is connected via apipe 662 to acold trap 666, which traps undeposited intermediates. The pressure in thechamber 634 is maintained by apump 676 connected to trap 656 by apipe 670. - Frequencies needed to generate plasmas are in a range of from 1 kHz to 2.5 GHz. A preferred range is between 400 kHz and 13.56 MHz, with the most preferred frequency being 13.56 MHz. The power should be in the range of 30 to 300 Watts. Preferred power range is 100 Watts to 250 Watts, and the most preferred power is 200 Watts of discharge power. The pressure should be kept within a range of from 0.001 Torr to 100 Torr, preferably from 50 milliTorr to 500 milliTorr, and most preferably at 100 milliTorr pressure. Alternatively, using low frequencies (5 kHz) can result in formation of insoluble poly(para-xylylene) which have higher temperature resistance. Morita et al.Trans. IEEE Japan pp: 65075 (1972). A carrier gas such as nitrogen or argon is used, and the flow rates of the carrier gas should be from 30 to 90 SCCM, preferably from 50 to 75 SCCM.
- 2. Plasma Enhanced Transport Polymerization of Polymers Using a Microwave Generator
- Microwave sources can also be used to generate plasmas for generating the reactive intermediates. FIG. 7 is a schematic diagram of a transport polymerization system employing microwaves. Precursors are held in a
precursor tank 704, and are vaporized, pass through apipe 706 and through amass flow controller 710, through asecond pipe 714 and into a quartz tube 718. Amicrowave generator 722 is attached via awaveguide 726 to one end of the quartz tube 718. Microwave energy enters the quartz tube 718 where aplasma 728 is generated, which dissociates the precursors into reactive intermediates. After dissociation, the intermediates are transported into achamber 730 heated by aheating device 734, including, but not limited to resistive heater. The flow of the intermediates is controlled by aflow pattern adjustor 738. Vertical movement of the aflow pattern adjustor 738 adjusts the flow rate of intermediates intochamber 630 and adjusts the mixing of intermediates inchamber 730. Agas dispersion plate 742 evenly distributes the intermediates over the surface ofwafer 746. The intermediates deposit on thewafer 746, which is held by acold chuck 750, which is attached to achiller 754 employing any conventional cooling means, including, but not limited to liquid nitrogen or reverse Peltier effect. The chamber pressure is controlled by apump 770, connected via a pipe 766 to acold trap 762. Thetrap 762 is connected via apipe 758 to thechamber 730. Thecold trap 762 protects thepump 770 from deposition of intermediates. - Microwave power density or electron field strength is selected based upon the residence time of the precursors in the chamber. The power is generally between 200 and 700 Watts, preferably between 400 and 600 Watts, and most preferably at 500 Watts. Desirable electron energy is chosen to match the bond energy of the leaving group.
- To prevent condensation of precursor, intermediates, or products on the chamber walls, the pressure within the reaction vessel should be below atmospheric pressure. Pressures in the range of 0.001 to 200 Torr work well. Furthermore, to inhibit condensation of chemicals, the walls of the reaction chamber should be kept warm, preferably in the range of 50° C. to 150° C., preferably above 100° C. The IR radiation heats the precursors to a threshold temperature, requiring less VUV power to complete the cracking reaction. IR also heats the chamber walls to decrease deposition on them because VUV is a cold light source which does not heat up the chamber.
- Deposition and polymerization of reactive intermediates to form low dielectric polymers is achieved by placing the wafer on a cold chuck. The temperature of the cold chuck should be between −198° C. and 30° C., preferably at about −5° C. Any suitable method for cooling the cold chuck may be used, including reverse Peltier, liquid nitrogen, or conventional refrigeration methods. Reverse Peltier and liquid nitrogen cooling methods are preferred. To prevent condensation of chemicals on the pump, a cold trap is placed between the vacuum pump and the deposition chamber.
- 3. High Density Plasma Chemical Vapor Deposition
- A high density plasma deposition process can also be used to dissociate precursors. In contrast to the low density plasma process described above, in high density plasmas, the electron density is in the range of from about 1013 to 1014 electrons/cm3. This process must be carried at lower pressures than conventional plasma processes. In this embodiment, a inductively coupled high
density plasma apparatus 800 is shown schematically in FIG. 8. Aprecursor delivery system 804 volatilizes or vaporizes the precursor, which flows through apipe 808 and ananode gas injector 812 into thedeposition chamber 816. Theanode gas injector 812 is attached toRF generators 820 which are matched by matchingcontrollers 824. The output of theRF generators 820 passes throughinductive coils 828 to produce an electrical field. Thewafer 832 is held by a cathodeelectrostatic chuck 836, which is connected to theRF generator 820.IR sources 840 provide additional heating of precursors to decrease the needed plasma power and to inhibit condensation on the chamber walls. The plasma source power needed for a wafer of 8 inch diameter is in the range of about 100 Watts to 4000 Watts, and preferably about 2000 Watts. For wafers of other sizes, power should be adjusted accordingly. Power is in the range of about 1 Watt/cm2 of wafer surface area to about 15 Watts/cm2, preferably from about 2 Watts/cm2 to about 10 Watts/cm2, and more preferably about 5 Watts/cm2. The chamber pressure is maintained in the range of 0.01 milliTorr to 10 milliTorr, and preferably below 5 milliTorr by a pump and cold trap (not shown). The wafer temperature is in the range from about 300° C. to 450° C., and is preferably about 350° C. - 4. Combined Transport Polymerization and CVD Apparatus Utilizing Combined Photon and Plasma Processes
- To improve deposition rate, a novel chamber design comprising utilization of magnets on the periphery of the chamber wall is used in this invention. The magnetic multipole configuration confines the plasma and increases the lifetime of primary electrons, therefore enabling the generation and sustenance of a low pressure plasma. This allows the deposition to occur at lower pressure and higher flow rates and overcomes the problem of powder formation during high deposition rates. The upper electrode, attached to the copper electrode is connected to the RF power through a matching network, and the lower electrode is connected to the ground. A ring of magnets is used to confine the plasma. These magnets are attached to the outer wall of the deposition chamber. The advantages of locating the magnets outside the chamber are that the powder cannot form on the magnets themselves, and such a reactor has a simpler design.
- FIG. 9 depicts a schematic diagram of a TP and
CVD reactor 900 embodying the elements for photon-plasma and IR dissociation and deposition.Precursors 904 are stored in aprecursor container 908 which is connected via apipe 912 to amass flow controller 916. For TP, precursors are transported into adissociation reactor 924 which houses thedissociation chamber 928. The wall ofreactor 924 is made of crystalline materials such as LiF, MgF2, or CaF2, which permits light of vacuum ultraviolet wavelengths to pass. Vacuum ultraviolet and ultraviolet light is generated by a silentdischarge plasma generators 932, which are place insideinfrared heaters 936. Theinfrared heaters 936 are placed insideDC magnets 940 andAC magnets 944. The magnets regulate the flow of plasma during dissociation, and the reactive intermediates so generated are transported to adeposition reactor 950. - The
deposition reactor 950 contains adeposition chamber 960 containing a gas andreactant dispersion manifold 954, a gas andreactant dispersion plate 958. The walls of the deposition chamber are made of crystalline materials such as LiF, MgF2, or CaF2, which permits light of vacuum ultraviolet wavelengths to pass. Thegas dispersion manifold 954 and thegas dispersion plate 958, are used to adjust the distribution and homogeneity of the intermediates. The intermediates are directed toward thewafer 962, which is held on acold chuck 964. Thegas dispersion manifold 954 anddispersion plate 958 are connected in parallel to a DCvoltage bias anode 968, a DC voltage biascathode 969, an ACvoltage bias anode 970, and an AC voltage biascathode 971. Silentdischarge plasma generators 972 are placed outside thedeposition chamber 960.Infrared heaters 974 are placed outside the silentplasma discharge generators 960 andDC magnets 978 andAC magnets 980 are placed outside theinfrared heaters 974. Gasses exit thedeposition chamber 960 through apipe 984, pass through a cold orreactive trap 988, pass through anotherpipe 992 to avacuum pump 996. The pressure in the systems is maintained at a desiredpressure using pump 996. Thetrap 988 protects the pump from deposition of intermediates. - For CVD, the deposition chamber can be used without the dissociation reactor. Precursors are placed directly on
wafer 962, and thechuck 964 is not cooled. IR, UV, or VUV radiation is directed toward thewafer 962. The radiation dissociates the precursor, and deposition of intermediates and polymerization takes place on the wafer. - Table 4 shows process conditions for combined photon-plasma assisted precursor
dissociation using chamber 928, and Table 5 shows process conditions for combined photon-plasma precursor deposition indeposition chamber 960.TABLE 4 Process Conditions for Photon-Plasma Precursor Dissociation Variable Range Preferred Range Temperature 200° C.-600° C. 350° C.-500° C. Photon Wavelength 100 nm-400 nm 140 nm-300 nm Photon Energy 2.5 eV-12 eV 4 eV-9 eV Photon Flux 10 milliW/cm2-5 W/cm2 40-100 milliW/cm2 Plasma Density 1012-1014 electrons/ cm 31013 electrons/cm3 Pressure 0.1 milliTorr-10 Torr 1 milliTorr-100 milliTorr -
TABLE 5 Process Conditions for Photon-Plasma Precursor Deposition Variable Range Preferred Range Temperature −20° C.-300° C. −10° C. Photon Wavelength 100 nm-400 nm 250 nm Photon Energy 2.5 eV-12 eV 4.5 eV Photon Flux 10 milliW/cm2-5 W/cm2 10-100 milliW/cm2 Plasma Density 1012-1014 electrons/ cm 31013 electrons/cm3 Pressure 0.1 milliTorr-10 Torr 1 milliTorr-100 milliTorr -
TABLE 6 Process Conditioned for Chemical Vapor Deposition Variable Range Preferred Range DC Bias Voltage 100-2000 V 500 V AC Bias Voltage 10-200 V 50 V Pulsed Bias Voltage 100-4000 V 500 V Pulse Width 10-1000 msec 1 msec Pulse Frequency 10 Hz-1000 Hz 60 Hz DC Magnetic Field Strength 100-2000 Gauss 700 Gauss AC Magnetic Field Strength 100-1000 Gauss 500 Gauss AC frequency 10 Hz-500 Hz 50 Hz-60 Hz Pressure in Silent 100 Torr-1500 Torr 760 Torr Discharge Generator AC Power to Silent 100 Watts-2000 Watts 500 Watts Discharge Generator - The plasma density is reported as electron density, but it is to be noted that ion density must be the same to maintain charge neutrality of the plasma. Any non-uniformity of charge distribution can result in plasma damage to the thin film of low dielectric material, as well as imparting charge to the integrated circuit components.
- Control of the plasma is by a magnetic field within the precursor chamber and in the deposition chamber. In the precursor reactor, the plasma is confined to any desired area, such as the center of the reactor. Additionally, alternating the polarity of the magnetic field stirs the plasma, ensuring even energy distribution within the plasma, thereby increasing the efficiency of dissociation of precursor molecules into reactive intermediates. In the deposition chamber, the magnetic field is used to control the pattern of distribution of intermediates over the wafer. This would serve two purposes: (1) to direct the deposition of precursor to the desired portion of the surface, thus conserving the precursor, and (2) minimize film deposition on other parts of the reactor chamber, thus minimizing the required cleaning, minimizing particle generation, and simplifying the reactor chamber design.
- Another feature comprises the placement of an electrical bias voltage within the deposition chamber. This provides a further means of controlling the flow of plasma-ionized species to the site of deposition on the wafer. A bias voltage, in the form of direct current (DC) or alternating current (AC) can be applied and modulated. Pulsed voltages can be used to alter the flow pattern of ions to either accelerate, decelerate, or to regulate the density of the plasma ions in the stream reaching the wafer. Optimization of ion velocity and flow, thus can be obtained using various combinations of magnetic field and bias voltage. Table 6 shows the ranges of the various magnetic field and bias voltage variables which are regulated in this invention.
TABLE 7 Optimization of Electrical and Magnetic Field Variables for Association Preferred Variable Range Range Pressure in Silent Discharge 100 Torr-1500 Torr 500 Torr Generator AC Power to Silent Discharge 100 Watts-2000 Watts 500 Watts Generator AC Magnetic Field Strength 100 Gauss-1000 Gauss 500 Gauss DC Magnetic Field Strength 100 Gauss-2000 Gauss 700 Gauss -
TABLE 8 Optimization of Electrical and Magnetic Field Variables for Deposition Variable Range Preferred Range DC Bias Voltage 100-2000 V 500 V AC Bias Voltage 10-200 V 50 V Pulsed Bias Voltage 100-4000 V 500 V Pulse Width 10-1000 msec 1 msec Pulse Frequency 10 Hz-1000 Hz 60 Hz DC Magnetic Field Strength 100-2000 Gauss 700 Gauss AC Magnetic Field Strength 100-1000 Gauss 500 Gauss AC frequency 10 Hz-500 Hz 50 Hz-60 Hz - For transport polymerization of precursors containing —H as a leaving group, the inclusion of a “hydrogen membrane” may be desired. When the precursors flow through the cracking apparatus, —H is cleaved from the reactive groups of the precursors, and this —H can dimerize to form molecular hydrogen. To prevent this hydrogen from adsorbing onto the wafer surface, a membrane with pores of about 3 Å to about 5 Å in diameter. Because the size of molecular hydrogen is small enough to penetrate the membrane but the radical intermediates are not small enough, the hydrogen can be effectively removed from the cracking chamber and thereby avoid contaminating the polymer. For other leaving groups, similar membranes with appropriate sized pores can also be used.
- D. Cluster Tool for Multiple Depositions on Wafers
- Several of the above processes can be carried out using a single piece of equipment. FIG. 10 shows a schematic diagram of a
cluster tool 1000. Afirst station 1004 is a wafer cassette which holds one or more wafers for processing. A wafer is transported to acleaning chamber 1008 where the wafer is exposed to VUV light of wavelengths in the range of from about 180 nm to about 450 nm, or to UV light. This pre-treatment is to remove impurities from the wafer surface prior to deposition of material with low dielectric constant. After cleaning, the wafer is transported to afirst processing station 1012, where a first deposition occurs. Theprocessing station 1012 can be any of the devices depicted in FIGS. 4-9 above. After a first processing step atstation 1012, the wafer is transported to asecond processing station 1016, where further deposition of low dielectric material occurs. Subsequently, the wafer is transported to athird processing station 1020, where a third layer of low dielectric material is deposited. It is desirable to deposit several layers of low dielectric material in different processing stations because there are likely to be variations in the flow patterns in the different stations. After the deposition steps have been completed, the wafer is transported to afourth processing station 1024, where a fourth layer of low dielectric material is deposited. Differences in flow patterns may result in the uneven deposition of films in each station. It is unlikely that the uneven deposition pattern for each station will be the same. Therefore, by depositing multiple layers of polymer, any differences in thickness of precursor resulting from deposition in one station can be at least partially corrected by polymer deposition in another station. - A step-gradient film can be made by depositing a siloxane-rich precursor mixture at
station 1012, and a second mixture, containing, for example, a mixture rich in fluorinated aromatic precursors atstation 1016. Subsequent additional layers with different compositions may be deposited at subsequent stations. - Alternatively, the
station 1024 can be used for post-deposition treatments, such as thermal annealing, reflow, plasma surface treatments, or cross-linking by exposing the polymer film to VUV of wavelengths in the range from 180 nm to 450 nm. - Another advantage of the cluster tool is the possibility of depositing different types of polymers at the different stations. Thus, it is possible to deposit a first layer chosen to adhere tightly to the substrate, a second layer chosen to have certain dielectric properties, thermal stability, or mechanical stability. A third layer may be chosen the have the same or different properties.
- E. Gradient Thin Films of Siloxanes and Fluorinated Hydrocarbons
- FIG. 11 shows a schematic diagram of the manufacture of a step-
gradient film 1100 of this invention.Substrate 1104 has a series ofmetal lines 1108 deposited on its surface. FIG. 11a shows a layer of siloxane-rich polymer 1112 deposited on top of the metal lines and on the exposedsubstrate 1104. FIG. 11b shows a second layer of polymer, containing for example, a fluorinatedaromatic hydrocarbon 1116. The surface oflayer 1116 as shown has been planarized, but planarization need not be carried out, depending on the application. On top of this layer, another, siloxane-rich layer 1120 is deposited to permit the deposition of additional metal lines. This process can be carried out many times, resulting in the manufacture of a multi-layered semiconductor device. - FIG. 12 shows a schematic diagram of the manufacture of a continuous gradient film1200 of this invention.
Substrate 1204 has a series of metal lines deposited on its surface. FIG. 12a shows the portion of the continuous gradient containing a siloxane-rich layer containing the least amount of fluorinated aromatic hydrocarbon (light shading) 1212, and the intermediate portion of the polymer film containing an intermediate concentration of fluorinatearomatic hydrocarbon 1216. Further from the metal lines, and further from thesubstrate 1204, the relative concentration of fluorinated aromatic hydrocarbon-containing polymer increases relative to the concentration of the siloxane-rich portion, making a portion of the gradient film which has a high concentration of fluorinatedaromatic hydrocarbon 1220. The surface of thepolymer layer 1220 is shown after planarization, but planarization need not be carried out, depending on the application. On top of this layer, another, siloxane-rich layer 1224 is deposited to permit the deposition of additional metal lines. This process can be carried out many times, resulting in the manufacture of a multi-layered semiconductor device. - The parallel plate plasma system with magnetic confinement was used for polymerization of {Si—(OCH3)2}4 on a 4 inch diameter wafer. The power level was set at 80 Watts, the precursor flow rate was set at 75 SCCM, the deposition time was 20 minutes, and the deposition rate was 0.08 μ/min. The film had a K of 2.32, Tg was 240° C., and the residual stress on silicon substrate was 37 MPa.
- The plasma system described in Example 1 above was used for polymerization of an admixture of 60 molar % of {Si—(OCH3)2}4 and 40 molar % of CF3—C(H4—CF3. The power level was set at 200 Watts, the precursor flow rate was set at 90 SCCM, the deposition time was 20 minutes, the deposition rate was 0.12 μm/min. The film had a K of 2.21, a Tg of 310° C., and a residual stress on a silicon substrate of 40 MPa.
- The plasma system described in Example 1 above was used for polymerization of an admixture of 40 molar % of {Si—(OCH3)2}4 and 60 molar % of CF3—C6H4—CF3. The power level was set at 200 Watts, the precursor flow rate was set at 90 SCCM, the deposition time was 20 minutes, the deposition rate was 0.12 μm/min. The film had a K of 2.21, a Tg of 310° C., and a residual stress on a silicon substrate of 32 MPa.
- The foregoing descriptions and Examples are included for illustrative purposes only, and are not intended to limit the scope of the invention. Other features, aspects and objects of the invention can be obtained from a review of the figures and the claims. It is to be understood that other embodiments of the invention can be developed and fall within the spirit and scope of the invention and claims.
- Each of the references cited above in this application is herein incorporated fully by reference.
- This invention includes novel precursors and methods for making sealants with low dielectric constant, high thermal stability, and high mechanical strength. The polymers include fluorinated aromatic moieties and can be used to manufacture thin films and integrated circuits.
- Other features, aspects and objects of the invention can be obtained from a review of the figures and the claims.
Claims (8)
1-70. Cancel.
71. A precursor for making a polymer, said precursor having the formula: Y—Ar—(Y′)z, wherein z is an integer of 1 to about 6, wherein Y and Y′ are leaving groups, and Ar is a compound containing an aromatic moiety having from greater than 6 to about 40 carbon atoms, and having at least one sp2C-sp2C double bond and one or more of a sp2C—F bond or a sp2 C—H bond.
72. The precursor of claim 71 , wherein Ar is selected from the group consisting of
—(CH(2-n)Fn)—(C6H(4-m)Fm)—, wherein n is 1 or 2 and m is an integer ranging from 1 to 4,
—(CH(2-n)Fn)—(C6H(4-m)Fm)—(CH(2-o)Fo)— wherein n is 1 or 2 and m is an integer ranging from 1 to 4 and o is 1 or 2,
—(CH(2-n)Fn)—(C6H(4-m)Fm)—(C6H(4-o)Fo)— wherein n is 1 or 2 and m is an integer ranging from 1 to 4 and o is an integer ranging from 1 to 4,
—(CH(2-n)Fn)—(C6H(4-m)Fm)—(C6H(4-o)Fo)—(CH(2-p)Fp)— wherein n is 1 or 2 and m is an integer ranging from 1 to 4 and o is an integer ranging from 1 to 4 and p is 1 or 2,
—C10H(6-n)Fn—, wherein n is an integer ranging from 0 to 6,
—C12H(8-n)Fn—, wherein n is an integer ranging from 0 to 8,
—C13H(7-n)Fn—, wherein n is an integer ranging from 0 to 7,
—C14H(8-n)Fn—, wherein n is an integer ranging from 0 to 8,
—C16H(10-n)Fn—, wherein n is an integer ranging from 0 to 10,
—C10H(8-n)Fn— wherein n is an integer ranging from 0 to 8,
—C16H(8-n)Fn—, wherein n is an integer ranging from 0 to 8,
—(C6H4-nFn)—(C10H6-mFm)—, where n is an integer ranging from 1 to 4 and m is an integer ranging from 1 to 6,
—(C14H(8-n)Fn)—(C16H(8-n)Fn)—, wherein n and m are independently integers ranging from 1 to 8, and
—(C14H(8-n)Fn)—(C16H(10-m)Fm)—, wherein n is an integer ranging from 1 to 8 and m is an integer ranging from 1 to 10;
—(C10H6-mFm)—(C10H6-nFn)—(C10H6-oFo)—, wherein m, n and o are integers independently selected from 1 to 6;
—C14H(8-m)Fm—(C10H6-nFn)—C14H(8-o)Fo—, wherein m and o are integers independently selected from 1 to 8 and n is an integer from 1 to 6, and
a positional isomer of any of the above.
73. The precursor of claim 71 , wherein Y and Y′ are independently selected from the group consisting of —H, —Cl, —Br, —NR, —SR, —SiR3, —NR2 and —SO2R, wherein R is —H, an alkyl group or an aromatic group.
74. The precursor of claim 71 , wherein Y is a leaving group selected from the group consisting of —H, —Br and —F.
75. The precursor of claim 71 , wherein Y and Y′ are Br.
76. The precursor of claim 71 , wherein Ar is selected from the group consisting of:
—CF2—(C6F4)—,
—CF2—(C6F4)—(C6F4)—,
—CF2—(C6F4)—(C6F4)—CF2—,
—(CF2)—(C6F4)—(C6F4)—,
—(CF2)—(C6F4)—(C6F4)—(CF2)—,
—C10F6—,
—C12F8—,
—C13F7—,
—C14F8—,
—C10F8—,
—C16F8—,
—(C6F4)—(C10F6)—,
—(C14F8)—(C16F8)—,
—(C14F8)—(C16F10)—,
—(C10F6)—(C10F6)—(C10F6)—, and
—(C14F8)—(C10F6)—(C14F8)—,
—(C10F6)—(C10F6)—(C10F6)—,
—(C10F6)—(C10F6)—(C10F6)—(C10F6)—,
a combination of one or more of the above Ar groups, with the proviso that the total number of carbon atoms is said Ar group is less than about 40, and
a positional isomer of any of the above.
77. The precursor of claim 71 having a formula selected from the group consisting of:
Br—CF2—(C6F4)—Br,
Br—CF2—(C6F4)—(C6F4)—Br,
Br—(CF2)—(C6F4)—(C6F4)—(CF2)—Br,
Br—C10F6—Br,
Br—C12F8—Br,
Br—C13F7—Br,
Br—C14F8—Br,
Br—C16F10—Br,
Br—C10F8—Br,
Br—C16F8—Br, and
a positional isomer of the above.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/724,970 US20040234779A1 (en) | 1997-10-24 | 2003-12-01 | Fluorinated aromatic precursors |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/957,480 US6051321A (en) | 1997-10-24 | 1997-10-24 | Low dielectric constant materials and method |
US09/468,378 US6663973B1 (en) | 1997-10-24 | 1999-12-20 | Low dielectric constant materials prepared from photon or plasma assisted chemical vapor deposition and transport polymerization of selected compounds |
US10/724,970 US20040234779A1 (en) | 1997-10-24 | 2003-12-01 | Fluorinated aromatic precursors |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/468,378 Continuation US6663973B1 (en) | 1997-10-24 | 1999-12-20 | Low dielectric constant materials prepared from photon or plasma assisted chemical vapor deposition and transport polymerization of selected compounds |
Publications (1)
Publication Number | Publication Date |
---|---|
US20040234779A1 true US20040234779A1 (en) | 2004-11-25 |
Family
ID=25499622
Family Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US08/957,480 Expired - Fee Related US6051321A (en) | 1997-10-24 | 1997-10-24 | Low dielectric constant materials and method |
US09/468,378 Expired - Fee Related US6663973B1 (en) | 1997-10-24 | 1999-12-20 | Low dielectric constant materials prepared from photon or plasma assisted chemical vapor deposition and transport polymerization of selected compounds |
US10/724,970 Abandoned US20040234779A1 (en) | 1997-10-24 | 2003-12-01 | Fluorinated aromatic precursors |
Family Applications Before (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US08/957,480 Expired - Fee Related US6051321A (en) | 1997-10-24 | 1997-10-24 | Low dielectric constant materials and method |
US09/468,378 Expired - Fee Related US6663973B1 (en) | 1997-10-24 | 1999-12-20 | Low dielectric constant materials prepared from photon or plasma assisted chemical vapor deposition and transport polymerization of selected compounds |
Country Status (5)
Country | Link |
---|---|
US (3) | US6051321A (en) |
JP (1) | JP2001521061A (en) |
KR (1) | KR100573708B1 (en) |
AU (1) | AU1087999A (en) |
WO (1) | WO1999021706A1 (en) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040255862A1 (en) * | 2001-02-26 | 2004-12-23 | Lee Chung J. | Reactor for producing reactive intermediates for low dielectric constant polymer thin films |
US20060201426A1 (en) * | 2004-05-25 | 2006-09-14 | Lee Chung J | Reactor for Producing Reactive Intermediates for Transport Polymerization |
US20060274474A1 (en) * | 2005-06-01 | 2006-12-07 | Lee Chung J | Substrate Holder |
US20070023868A1 (en) * | 2005-07-28 | 2007-02-01 | Dongbu Electronics Co., Ltd. | Method of forming copper metal line and semiconductor device including the same |
US20110081503A1 (en) * | 2009-10-06 | 2011-04-07 | Tokyo Electron Limited | Method of depositing stable and adhesive interface between fluorine-based low-k material and metal barrier layer |
US20110081500A1 (en) * | 2009-10-06 | 2011-04-07 | Tokyo Electron Limited | Method of providing stable and adhesive interface between fluorine-based low-k material and metal barrier layer |
WO2011044053A1 (en) * | 2009-10-06 | 2011-04-14 | Tokyo Electron Limited | Method of providing stable and adhesive interface between fluorine-based low-k material and metal barrier layer |
US20130266472A1 (en) * | 2012-04-04 | 2013-10-10 | GM Global Technology Operations LLC | Method of Coating Metal Powder with Chemical Vapor Deposition for Making Permanent Magnets |
WO2014145043A1 (en) | 2013-03-15 | 2014-09-18 | Hzo Inc. | Combining different types of moisture -resistant materials |
Families Citing this family (127)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6243112B1 (en) * | 1996-07-01 | 2001-06-05 | Xerox Corporation | High density remote plasma deposited fluoropolymer films |
US5989998A (en) * | 1996-08-29 | 1999-11-23 | Matsushita Electric Industrial Co., Ltd. | Method of forming interlayer insulating film |
US6020458A (en) | 1997-10-24 | 2000-02-01 | Quester Technology, Inc. | Precursors for making low dielectric constant materials with improved thermal stability |
US6432846B1 (en) | 1999-02-02 | 2002-08-13 | Asm Japan K.K. | Silicone polymer insulation film on semiconductor substrate and method for forming the film |
US6514880B2 (en) | 1998-02-05 | 2003-02-04 | Asm Japan K.K. | Siloxan polymer film on semiconductor substrate and method for forming same |
US6383955B1 (en) | 1998-02-05 | 2002-05-07 | Asm Japan K.K. | Silicone polymer insulation film on semiconductor substrate and method for forming the film |
US6852650B2 (en) * | 1998-02-05 | 2005-02-08 | Asm Japan K.K. | Insulation film on semiconductor substrate and method for forming same |
TW437017B (en) | 1998-02-05 | 2001-05-28 | Asm Japan Kk | Silicone polymer insulation film on semiconductor substrate and method for formation thereof |
US6881683B2 (en) | 1998-02-05 | 2005-04-19 | Asm Japan K.K. | Insulation film on semiconductor substrate and method for forming same |
US6287990B1 (en) | 1998-02-11 | 2001-09-11 | Applied Materials, Inc. | CVD plasma assisted low dielectric constant films |
US6054379A (en) * | 1998-02-11 | 2000-04-25 | Applied Materials, Inc. | Method of depositing a low k dielectric with organo silane |
US6303523B2 (en) * | 1998-02-11 | 2001-10-16 | Applied Materials, Inc. | Plasma processes for depositing low dielectric constant films |
US6660656B2 (en) | 1998-02-11 | 2003-12-09 | Applied Materials Inc. | Plasma processes for depositing low dielectric constant films |
US6593247B1 (en) | 1998-02-11 | 2003-07-15 | Applied Materials, Inc. | Method of depositing low k films using an oxidizing plasma |
JP3469771B2 (en) * | 1998-03-24 | 2003-11-25 | 富士通株式会社 | Semiconductor device and manufacturing method thereof |
AU3870899A (en) * | 1998-05-01 | 1999-11-23 | Seshu B. Desu | Oxide/organic polymer multilayer thin films deposited by chemical vapor deposition |
JP3706027B2 (en) * | 1998-09-18 | 2005-10-12 | 東京エレクトロン株式会社 | Plasma processing method |
US5994778A (en) * | 1998-09-18 | 1999-11-30 | Advanced Micro Devices, Inc. | Surface treatment of low-k SiOF to prevent metal interaction |
US6444593B1 (en) | 1998-12-02 | 2002-09-03 | Advanced Micro Devices, Inc. | Surface treatment of low-K SiOF to prevent metal interaction |
US6252303B1 (en) | 1998-12-02 | 2001-06-26 | Advanced Micro Devices, Inc. | Intergration of low-K SiOF as inter-layer dielectric |
US6362115B1 (en) * | 1998-12-09 | 2002-03-26 | Applied Materials, Inc. | In-situ generation of p-xylyiene from liquid precursors |
JP4351755B2 (en) * | 1999-03-12 | 2009-10-28 | キヤノンアネルバ株式会社 | Thin film forming method and thin film forming apparatus |
US6204202B1 (en) * | 1999-04-14 | 2001-03-20 | Alliedsignal, Inc. | Low dielectric constant porous films |
US6709715B1 (en) * | 1999-06-17 | 2004-03-23 | Applied Materials Inc. | Plasma enhanced chemical vapor deposition of copolymer of parylene N and comonomers with various double bonds |
SG93210A1 (en) | 1999-06-29 | 2002-12-17 | Univ Singapore | Method for lamination of fluoropolymer to metal and printed circuit board (pcb) substrate |
US6495208B1 (en) * | 1999-09-09 | 2002-12-17 | Virginia Tech Intellectual Properties, Inc. | Near-room temperature CVD synthesis of organic polymer/oxide dielectric nanocomposites |
US6399489B1 (en) * | 1999-11-01 | 2002-06-04 | Applied Materials, Inc. | Barrier layer deposition using HDP-CVD |
WO2001046458A1 (en) * | 1999-12-20 | 2001-06-28 | The Penn State Research Foundation | Deposited thin films and their use in detection, attachment, and bio-medical applications |
US6541367B1 (en) * | 2000-01-18 | 2003-04-01 | Applied Materials, Inc. | Very low dielectric constant plasma-enhanced CVD films |
EP1123991A3 (en) * | 2000-02-08 | 2002-11-13 | Asm Japan K.K. | Low dielectric constant materials and processes |
JP2001267310A (en) | 2000-03-17 | 2001-09-28 | Tokyo Electron Ltd | Method and device for film forming plasma |
US6558755B2 (en) | 2000-03-20 | 2003-05-06 | Dow Corning Corporation | Plasma curing process for porous silica thin film |
US6576300B1 (en) * | 2000-03-20 | 2003-06-10 | Dow Corning Corporation | High modulus, low dielectric constant coatings |
EP1138804A3 (en) | 2000-03-27 | 2003-06-25 | Infineon Technologies AG | Component with at least two contiguous insulating layers and manufacturing method therefor |
US6458718B1 (en) | 2000-04-28 | 2002-10-01 | Asm Japan K.K. | Fluorine-containing materials and processes |
US6521546B1 (en) | 2000-06-14 | 2003-02-18 | Applied Materials, Inc. | Method of making a fluoro-organosilicate layer |
DE10034737C2 (en) * | 2000-07-17 | 2002-07-11 | Fraunhofer Ges Forschung | Process for producing a permanent release layer by plasma polymerization on the surface of a molding tool, a molding tool which can be produced by the process and its use |
US6764958B1 (en) * | 2000-07-28 | 2004-07-20 | Applied Materials Inc. | Method of depositing dielectric films |
US6573196B1 (en) | 2000-08-12 | 2003-06-03 | Applied Materials Inc. | Method of depositing organosilicate layers |
JP2002075980A (en) * | 2000-08-30 | 2002-03-15 | Miyazaki Oki Electric Co Ltd | Method for depositing low dielectric film by vacuum ultraviolet cvd |
CN1100162C (en) * | 2000-09-26 | 2003-01-29 | 复旦大学 | Alpha-SiCoF film as insulating dielectric with low dielectric constant and its preparation |
US6448186B1 (en) | 2000-10-06 | 2002-09-10 | Novellus Systems, Inc. | Method and apparatus for use of hydrogen and silanes in plasma |
EP1275133A1 (en) * | 2000-10-19 | 2003-01-15 | Robert Bosch Gmbh | Device and method for the etching of a substrate by means of an inductively coupled plasma |
US6531398B1 (en) | 2000-10-30 | 2003-03-11 | Applied Materials, Inc. | Method of depositing organosillicate layers |
US6905981B1 (en) | 2000-11-24 | 2005-06-14 | Asm Japan K.K. | Low-k dielectric materials and processes |
JP3545364B2 (en) * | 2000-12-19 | 2004-07-21 | キヤノン販売株式会社 | Semiconductor device and manufacturing method thereof |
US6537733B2 (en) * | 2001-02-23 | 2003-03-25 | Applied Materials, Inc. | Method of depositing low dielectric constant silicon carbide layers |
US7192645B2 (en) | 2001-02-26 | 2007-03-20 | Dielectric Systems, Inc. | Porous low E (<2.0) thin films by transport co-polymerization |
US6797343B2 (en) | 2001-12-20 | 2004-09-28 | Dielectric Systems, Inc. | Dielectric thin films from fluorinated precursors |
US20050274322A1 (en) * | 2001-02-26 | 2005-12-15 | Lee Chung J | Reactor for producing reactive intermediates for low dielectric constant polymer thin films |
US20040055539A1 (en) * | 2002-09-13 | 2004-03-25 | Dielectric Systems, Inc. | Reactive-reactor for generation of gaseous intermediates |
US6825303B2 (en) * | 2001-02-26 | 2004-11-30 | Dielectric Systems, Inc. | Integration of low ε thin films and Ta into Cu dual damascene |
US6881447B2 (en) | 2002-04-04 | 2005-04-19 | Dielectric Systems, Inc. | Chemically and electrically stabilized polymer films |
US7026052B2 (en) | 2001-02-26 | 2006-04-11 | Dielectric Systems, Inc. | Porous low k(<2.0) thin film derived from homo-transport-polymerization |
KR100926722B1 (en) * | 2001-04-06 | 2009-11-16 | 에이에스엠 저펜 가부시기가이샤 | The siloxane polymer film on a semiconductor substrate and its manufacturing method |
US6777171B2 (en) | 2001-04-20 | 2004-08-17 | Applied Materials, Inc. | Fluorine-containing layers for damascene structures |
US6740601B2 (en) * | 2001-05-11 | 2004-05-25 | Applied Materials Inc. | HDP-CVD deposition process for filling high aspect ratio gaps |
US6486082B1 (en) | 2001-06-18 | 2002-11-26 | Applied Materials, Inc. | CVD plasma assisted lower dielectric constant sicoh film |
US6926926B2 (en) * | 2001-09-10 | 2005-08-09 | Applied Materials, Inc. | Silicon carbide deposited by high density plasma chemical-vapor deposition with bias |
US6759327B2 (en) * | 2001-10-09 | 2004-07-06 | Applied Materials Inc. | Method of depositing low k barrier layers |
US6656837B2 (en) * | 2001-10-11 | 2003-12-02 | Applied Materials, Inc. | Method of eliminating photoresist poisoning in damascene applications |
US6887578B2 (en) * | 2001-10-30 | 2005-05-03 | Massachusetts Institute Of Technology | Fluorocarbon-organosilicon copolymers and coatings prepared by hot-filament chemical vapor deposition |
DE10153288A1 (en) * | 2001-10-31 | 2003-05-15 | Infineon Technologies Ag | Manufacturing process for a semiconductor device |
JP3701626B2 (en) * | 2001-12-06 | 2005-10-05 | キヤノン販売株式会社 | Manufacturing method of semiconductor device |
US6720561B2 (en) * | 2001-12-06 | 2004-04-13 | General Electric Company | Direct CsI scintillator coating for improved digital X-ray detector assembly longevity |
US7091137B2 (en) * | 2001-12-14 | 2006-08-15 | Applied Materials | Bi-layer approach for a hermetic low dielectric constant layer for barrier applications |
US6890850B2 (en) * | 2001-12-14 | 2005-05-10 | Applied Materials, Inc. | Method of depositing dielectric materials in damascene applications |
US6838393B2 (en) * | 2001-12-14 | 2005-01-04 | Applied Materials, Inc. | Method for producing semiconductor including forming a layer containing at least silicon carbide and forming a second layer containing at least silicon oxygen carbide |
US6974970B2 (en) * | 2002-01-17 | 2005-12-13 | Silecs Oy | Semiconductor device |
US6849562B2 (en) * | 2002-03-04 | 2005-02-01 | Applied Materials, Inc. | Method of depositing a low k dielectric barrier film for copper damascene application |
US6936309B2 (en) | 2002-04-02 | 2005-08-30 | Applied Materials, Inc. | Hardness improvement of silicon carboxy films |
US20030211244A1 (en) * | 2002-04-11 | 2003-11-13 | Applied Materials, Inc. | Reacting an organosilicon compound with an oxidizing gas to form an ultra low k dielectric |
US20030194495A1 (en) * | 2002-04-11 | 2003-10-16 | Applied Materials, Inc. | Crosslink cyclo-siloxane compound with linear bridging group to form ultra low k dielectric |
US20030194496A1 (en) * | 2002-04-11 | 2003-10-16 | Applied Materials, Inc. | Methods for depositing dielectric material |
US6815373B2 (en) * | 2002-04-16 | 2004-11-09 | Applied Materials Inc. | Use of cyclic siloxanes for hardness improvement of low k dielectric films |
US9061317B2 (en) | 2002-04-17 | 2015-06-23 | Air Products And Chemicals, Inc. | Porogens, porogenated precursors and methods for using the same to provide porous organosilica glass films with low dielectric constants |
US8951342B2 (en) | 2002-04-17 | 2015-02-10 | Air Products And Chemicals, Inc. | Methods for using porogens for low k porous organosilica glass films |
US8293001B2 (en) | 2002-04-17 | 2012-10-23 | Air Products And Chemicals, Inc. | Porogens, porogenated precursors and methods for using the same to provide porous organosilica glass films with low dielectric constants |
US7384471B2 (en) | 2002-04-17 | 2008-06-10 | Air Products And Chemicals, Inc. | Porogens, porogenated precursors and methods for using the same to provide porous organosilica glass films with low dielectric constants |
US20030206337A1 (en) * | 2002-05-06 | 2003-11-06 | Eastman Kodak Company | Exposure apparatus for irradiating a sensitized substrate |
US7056560B2 (en) * | 2002-05-08 | 2006-06-06 | Applies Materials Inc. | Ultra low dielectric materials based on hybrid system of linear silicon precursor and organic porogen by plasma-enhanced chemical vapor deposition (PECVD) |
US6936551B2 (en) * | 2002-05-08 | 2005-08-30 | Applied Materials Inc. | Methods and apparatus for E-beam treatment used to fabricate integrated circuit devices |
US7060330B2 (en) * | 2002-05-08 | 2006-06-13 | Applied Materials, Inc. | Method for forming ultra low k films using electron beam |
US7307343B2 (en) * | 2002-05-30 | 2007-12-11 | Air Products And Chemicals, Inc. | Low dielectric materials and methods for making same |
US7256467B2 (en) * | 2002-06-04 | 2007-08-14 | Silecs Oy | Materials and methods for forming hybrid organic-inorganic anti-stiction materials for micro-electromechanical systems |
US6746970B2 (en) * | 2002-06-24 | 2004-06-08 | Macronix International Co., Ltd. | Method of forming a fluorocarbon polymer film on a substrate using a passivation layer |
US6927178B2 (en) * | 2002-07-11 | 2005-08-09 | Applied Materials, Inc. | Nitrogen-free dielectric anti-reflective coating and hardmask |
US7105460B2 (en) * | 2002-07-11 | 2006-09-12 | Applied Materials | Nitrogen-free dielectric anti-reflective coating and hardmask |
US7749563B2 (en) * | 2002-10-07 | 2010-07-06 | Applied Materials, Inc. | Two-layer film for next generation damascene barrier application with good oxidation resistance |
EP1568071B1 (en) * | 2002-11-29 | 2019-03-20 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Wafer comprising a separation layer and a support layer and its manufacturing method |
US6790788B2 (en) * | 2003-01-13 | 2004-09-14 | Applied Materials Inc. | Method of improving stability in low k barrier layers |
US6897163B2 (en) | 2003-01-31 | 2005-05-24 | Applied Materials, Inc. | Method for depositing a low dielectric constant film |
US6740602B1 (en) * | 2003-03-17 | 2004-05-25 | Asm Japan K.K. | Method of forming low-dielectric constant film on semiconductor substrate by plasma reaction using high-RF power |
TW200421483A (en) * | 2003-03-17 | 2004-10-16 | Semiconductor Leading Edge Tec | Semiconductor device and method of manufacturing the same |
US20040253378A1 (en) * | 2003-06-12 | 2004-12-16 | Applied Materials, Inc. | Stress reduction of SIOC low k film by addition of alkylenes to OMCTS based processes |
US6919636B1 (en) * | 2003-07-31 | 2005-07-19 | Advanced Micro Devices, Inc. | Interconnects with a dielectric sealant layer |
US20050037153A1 (en) * | 2003-08-14 | 2005-02-17 | Applied Materials, Inc. | Stress reduction of sioc low k films |
KR100545169B1 (en) * | 2003-09-03 | 2006-01-24 | 동부아남반도체 주식회사 | Electro-static chuck of semi conductor manufacturing equipment and method for chucking wafer using the same |
US7008882B2 (en) * | 2003-11-28 | 2006-03-07 | United Microelectronics Corp. | Method and structure for the adhesion between dielectric layers |
US7030041B2 (en) * | 2004-03-15 | 2006-04-18 | Applied Materials Inc. | Adhesion improvement for low k dielectrics |
US20050214457A1 (en) * | 2004-03-29 | 2005-09-29 | Applied Materials, Inc. | Deposition of low dielectric constant films by N2O addition |
US7094661B2 (en) * | 2004-03-31 | 2006-08-22 | Dielectric Systems, Inc. | Single and dual damascene techniques utilizing composite polymer dielectric film |
US7309395B2 (en) | 2004-03-31 | 2007-12-18 | Dielectric Systems, Inc. | System for forming composite polymer dielectric film |
US6962871B2 (en) * | 2004-03-31 | 2005-11-08 | Dielectric Systems, Inc. | Composite polymer dielectric film |
US7229911B2 (en) * | 2004-04-19 | 2007-06-12 | Applied Materials, Inc. | Adhesion improvement for low k dielectrics to conductive materials |
US20050233555A1 (en) * | 2004-04-19 | 2005-10-20 | Nagarajan Rajagopalan | Adhesion improvement for low k dielectrics to conductive materials |
US7384693B2 (en) * | 2004-04-28 | 2008-06-10 | Intel Corporation | Diamond-like carbon films with low dielectric constant and high mechanical strength |
US20050245693A1 (en) * | 2004-05-03 | 2005-11-03 | Bhatt Sanjiv M | Fluorinated aromatic polymers |
US20050277302A1 (en) * | 2004-05-28 | 2005-12-15 | Nguyen Son V | Advanced low dielectric constant barrier layers |
JP4512779B2 (en) * | 2004-06-21 | 2010-07-28 | 独立行政法人産業技術総合研究所 | Low dielectric constant insulating film forming material and forming method |
US7229041B2 (en) * | 2004-06-30 | 2007-06-12 | Ohio Central Steel Company | Lifting lid crusher |
US7288205B2 (en) * | 2004-07-09 | 2007-10-30 | Applied Materials, Inc. | Hermetic low dielectric constant layer for barrier applications |
US20060046044A1 (en) * | 2004-08-24 | 2006-03-02 | Lee Chung J | Porous composite polymer dielectric film |
US7422776B2 (en) * | 2004-08-24 | 2008-09-09 | Applied Materials, Inc. | Low temperature process to produce low-K dielectrics with low stress by plasma-enhanced chemical vapor deposition (PECVD) |
US7335608B2 (en) | 2004-09-22 | 2008-02-26 | Intel Corporation | Materials, structures and methods for microelectronic packaging |
US7465475B2 (en) * | 2004-11-09 | 2008-12-16 | Eastman Kodak Company | Method for controlling the deposition of vaporized organic material |
US7265437B2 (en) * | 2005-03-08 | 2007-09-04 | International Business Machines Corporation | Low k dielectric CVD film formation process with in-situ imbedded nanolayers to improve mechanical properties |
US7425350B2 (en) * | 2005-04-29 | 2008-09-16 | Asm Japan K.K. | Apparatus, precursors and deposition methods for silicon-containing materials |
US20060275547A1 (en) * | 2005-06-01 | 2006-12-07 | Lee Chung J | Vapor Phase Deposition System and Method |
US20070134435A1 (en) * | 2005-12-13 | 2007-06-14 | Ahn Sang H | Method to improve the ashing/wet etch damage resistance and integration stability of low dielectric constant films |
US20070278682A1 (en) * | 2006-05-31 | 2007-12-06 | Chung-Chi Ko | Self-assembled mono-layer liner for cu/porous low-k interconnections |
US7297376B1 (en) | 2006-07-07 | 2007-11-20 | Applied Materials, Inc. | Method to reduce gas-phase reactions in a PECVD process with silicon and organic precursors to deposit defect-free initial layers |
US20090026924A1 (en) * | 2007-07-23 | 2009-01-29 | Leung Roger Y | Methods of making low-refractive index and/or low-k organosilicate coatings |
JP5501807B2 (en) * | 2009-03-31 | 2014-05-28 | 東京エレクトロン株式会社 | Processing equipment |
JP5387627B2 (en) * | 2011-07-28 | 2014-01-15 | ルネサスエレクトロニクス株式会社 | Manufacturing method of semiconductor device |
CN103105736A (en) * | 2011-11-11 | 2013-05-15 | 中芯国际集成电路制造(上海)有限公司 | Photolithography method and etching method |
US8980740B2 (en) | 2013-03-06 | 2015-03-17 | Globalfoundries Inc. | Barrier layer conformality in copper interconnects |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5283378A (en) * | 1990-10-18 | 1994-02-01 | Bayer Aktiengesellschaft | Process for the dechlorination and/or debromination of fluorine-and chlorine- and/or bromine-containing aromatic compounds |
Family Cites Families (33)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3274267A (en) * | 1963-09-23 | 1966-09-20 | Union Carbide Corp | Cyclic alpha-perfluoro-di-p-xylylenes |
US3332891A (en) * | 1963-09-23 | 1967-07-25 | Union Carbide Corp | Process for the preparation of alpha-per-fluoro-p-xylylene polymers |
US3440277A (en) * | 1965-12-13 | 1969-04-22 | Us Air Force | Fluoroaromatic compounds |
US3342754A (en) * | 1966-02-18 | 1967-09-19 | Union Carbide Corp | Para-xylylene polymers |
US4291244A (en) * | 1979-09-04 | 1981-09-22 | Union Carbide Corporation | Electrets |
US4737379A (en) | 1982-09-24 | 1988-04-12 | Energy Conversion Devices, Inc. | Plasma deposited coatings, and low temperature plasma method of making same |
DE3240303C1 (en) * | 1982-10-30 | 1984-01-19 | Merck Patent Gmbh, 6100 Darmstadt | Process for the preparation of [2,2] -paracyclophane |
JPS601846A (en) | 1983-06-18 | 1985-01-08 | Toshiba Corp | Multilayer interconnection structure semiconductor device and manufacture thereof |
US5714029A (en) * | 1984-03-12 | 1998-02-03 | Nitto Electric Industrial Co., Ltd. | Process for working a semiconductor wafer |
JPS60231442A (en) * | 1984-04-28 | 1985-11-18 | Toyota Central Res & Dev Lab Inc | Water-repellent glass |
US4911992A (en) | 1986-12-04 | 1990-03-27 | Dow Corning Corporation | Platinum or rhodium catalyzed multilayer ceramic coatings from hydrogen silsesquioxane resin and metal oxides |
US5139813A (en) * | 1990-09-28 | 1992-08-18 | Union Carbide Chemicals & Plastics Technology Corporation | Method for inducing fluorescence in parylene films by an active plasma |
US5230929A (en) * | 1992-07-20 | 1993-07-27 | Dow Corning Corporation | Plasma-activated chemical vapor deposition of fluoridated cyclic siloxanes |
US5210341A (en) * | 1991-12-20 | 1993-05-11 | Union Carbide Chemicals & Plastics Technology Corporation | Processes for the preparation of octafluoro-[2,2]paracyclophane |
US5324813A (en) * | 1992-07-22 | 1994-06-28 | International Business Machines Corporation | Low dielectric constant fluorinated polymers and methods of fabrication thereof |
US5268202A (en) * | 1992-10-09 | 1993-12-07 | Rensselaer Polytechnic Institute | Vapor deposition of parylene-F using 1,4-bis (trifluoromethyl) benzene |
US5424097A (en) * | 1993-09-30 | 1995-06-13 | Specialty Coating Systems, Inc. | Continuous vapor deposition apparatus |
JP3407086B2 (en) | 1994-06-17 | 2003-05-19 | 日本テキサス・インスツルメンツ株式会社 | Method for manufacturing semiconductor device |
KR100474128B1 (en) * | 1995-10-18 | 2005-07-11 | 스페셜티 코팅 시스템즈, 인코포레이티드 | Method for preparing octafluoro- [2,2] paracyclophane |
US5536892A (en) * | 1995-10-18 | 1996-07-16 | Specialty Coating Systems, Inc. | Processes for the preparation of octafluoro-[2,2]paracyclophane |
EP0769788A3 (en) * | 1995-10-20 | 1998-01-14 | W.L. Gore & Associates, Inc. | Low dielectric constant material for use as an insulation element in an electronic device |
US5538758A (en) * | 1995-10-27 | 1996-07-23 | Specialty Coating Systems, Inc. | Method and apparatus for the deposition of parylene AF4 onto semiconductor wafers |
US5556473A (en) * | 1995-10-27 | 1996-09-17 | Specialty Coating Systems, Inc. | Parylene deposition apparatus including dry vacuum pump system and downstream cold trap |
US5536322A (en) * | 1995-10-27 | 1996-07-16 | Specialty Coating Systems, Inc. | Parylene deposition apparatus including a heated and cooled support platen and an electrostatic clamping device |
EP0862664B1 (en) * | 1995-10-27 | 2003-01-02 | Specialty Coating Systems, Inc. | Method and apparatus for the deposition of parylene af4 onto semiconductor wafers |
US5534068A (en) * | 1995-10-27 | 1996-07-09 | Specialty Coating Systems, Inc. | Parylene deposition apparatus including a tapered deposition chamber and dual vacuum outlet pumping arrangement |
US5536319A (en) * | 1995-10-27 | 1996-07-16 | Specialty Coating Systems, Inc. | Parylene deposition apparatus including an atmospheric shroud and inert gas source |
US5536321A (en) * | 1995-10-27 | 1996-07-16 | Specialty Coating Systems, Inc. | Parylene deposition apparatus including a post-pyrolysis filtering chamber and a deposition chamber inlet filter |
TW297147B (en) * | 1995-10-27 | 1997-02-01 | Specialty Coating Systems Inc | Multi-level circuit structure including fluorinated parylene polymer dielectric interlayers |
US5536317A (en) * | 1995-10-27 | 1996-07-16 | Specialty Coating Systems, Inc. | Parylene deposition apparatus including a quartz crystal thickness/rate controller |
US6284933B1 (en) * | 1996-10-23 | 2001-09-04 | William R. Dolbier, Jr. | TFPX synthesis |
US5783614A (en) * | 1997-02-21 | 1998-07-21 | Copytele, Inc. | Polymeric-coated dielectric particles and formulation and method for preparing same |
US5841005A (en) * | 1997-03-14 | 1998-11-24 | Dolbier, Jr.; William R. | Parylene AF4 synthesis |
-
1997
- 1997-10-24 US US08/957,480 patent/US6051321A/en not_active Expired - Fee Related
-
1998
- 1998-10-15 AU AU10879/99A patent/AU1087999A/en not_active Abandoned
- 1998-10-15 JP JP2000517840A patent/JP2001521061A/en active Pending
- 1998-10-15 KR KR1020007004418A patent/KR100573708B1/en not_active IP Right Cessation
- 1998-10-15 WO PCT/US1998/021755 patent/WO1999021706A1/en active IP Right Grant
-
1999
- 1999-12-20 US US09/468,378 patent/US6663973B1/en not_active Expired - Fee Related
-
2003
- 2003-12-01 US US10/724,970 patent/US20040234779A1/en not_active Abandoned
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5283378A (en) * | 1990-10-18 | 1994-02-01 | Bayer Aktiengesellschaft | Process for the dechlorination and/or debromination of fluorine-and chlorine- and/or bromine-containing aromatic compounds |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040255862A1 (en) * | 2001-02-26 | 2004-12-23 | Lee Chung J. | Reactor for producing reactive intermediates for low dielectric constant polymer thin films |
US20060201426A1 (en) * | 2004-05-25 | 2006-09-14 | Lee Chung J | Reactor for Producing Reactive Intermediates for Transport Polymerization |
US20060274474A1 (en) * | 2005-06-01 | 2006-12-07 | Lee Chung J | Substrate Holder |
US20070023868A1 (en) * | 2005-07-28 | 2007-02-01 | Dongbu Electronics Co., Ltd. | Method of forming copper metal line and semiconductor device including the same |
US20110081503A1 (en) * | 2009-10-06 | 2011-04-07 | Tokyo Electron Limited | Method of depositing stable and adhesive interface between fluorine-based low-k material and metal barrier layer |
US20110081500A1 (en) * | 2009-10-06 | 2011-04-07 | Tokyo Electron Limited | Method of providing stable and adhesive interface between fluorine-based low-k material and metal barrier layer |
WO2011044053A1 (en) * | 2009-10-06 | 2011-04-14 | Tokyo Electron Limited | Method of providing stable and adhesive interface between fluorine-based low-k material and metal barrier layer |
US20130266472A1 (en) * | 2012-04-04 | 2013-10-10 | GM Global Technology Operations LLC | Method of Coating Metal Powder with Chemical Vapor Deposition for Making Permanent Magnets |
CN103366942A (en) * | 2012-04-04 | 2013-10-23 | 通用汽车环球科技运作有限责任公司 | Method of coating metal powder with chemical vapor deposition for making permanent magnets |
WO2014145043A1 (en) | 2013-03-15 | 2014-09-18 | Hzo Inc. | Combining different types of moisture -resistant materials |
EP2969259A4 (en) * | 2013-03-15 | 2016-11-23 | Hzo Inc | Combining different types of moisture -resistant materials |
Also Published As
Publication number | Publication date |
---|---|
KR20010031401A (en) | 2001-04-16 |
US6051321A (en) | 2000-04-18 |
WO1999021706A1 (en) | 1999-05-06 |
US6663973B1 (en) | 2003-12-16 |
JP2001521061A (en) | 2001-11-06 |
KR100573708B1 (en) | 2006-04-26 |
AU1087999A (en) | 1999-05-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6663973B1 (en) | Low dielectric constant materials prepared from photon or plasma assisted chemical vapor deposition and transport polymerization of selected compounds | |
US6086679A (en) | Deposition systems and processes for transport polymerization and chemical vapor deposition | |
KR100602222B1 (en) | Precursors for making low dielectric constant materials with improved thermal stability | |
KR100767246B1 (en) | Method for enhancing deposition rate of chemical vapor deposition films | |
US6140456A (en) | Chemicals and processes for making fluorinated poly(para-xylylenes) | |
US20070299239A1 (en) | Curing Dielectric Films Under A Reducing Atmosphere | |
US20030196680A1 (en) | Process modules for transport polymerization of low epsilon thin films | |
US20030134039A1 (en) | Electron beam modification of CVD deposited films, forming low dielectric constant materials | |
CN101316945B (en) | A method to improve the ashing/wet etch damage resistance and integration stability of low dielectric constant films | |
KR20120073190A (en) | Porogens, porogenated precursors and methods for using the same to provide porous organosilica glass films with low dielectric constants | |
US7192645B2 (en) | Porous low E (<2.0) thin films by transport co-polymerization | |
US20110313184A1 (en) | Insulating film material, and film formation method utilizing the material, and insulating film | |
WO2001036703A1 (en) | System and method for depositing inorganic/organic dielectric films | |
US20030188683A1 (en) | UV reactor for transport polymerization | |
US7718544B2 (en) | Method of forming silicon-containing insulation film having low dielectric constant and low diffusion coefficient | |
KR100494194B1 (en) | Porogens, porogenated precursors and methods for using the same to provide porous organosilica glass films with low dielectric constants |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |