GB2397947A - Method of using a (hfac)Cu(I)(DMB) precursor to form copper wiring - Google Patents
Method of using a (hfac)Cu(I)(DMB) precursor to form copper wiring Download PDFInfo
- Publication number
- GB2397947A GB2397947A GB0410696A GB0410696A GB2397947A GB 2397947 A GB2397947 A GB 2397947A GB 0410696 A GB0410696 A GB 0410696A GB 0410696 A GB0410696 A GB 0410696A GB 2397947 A GB2397947 A GB 2397947A
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- forming
- semiconductor device
- copper wiring
- copper
- vaporizer
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- 239000010949 copper Substances 0.000 title claims abstract description 233
- 238000000034 method Methods 0.000 title claims abstract description 158
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 138
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 137
- 239000002243 precursor Substances 0.000 title claims description 46
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 title description 2
- 239000006200 vaporizer Substances 0.000 claims abstract description 78
- 239000004065 semiconductor Substances 0.000 claims abstract description 77
- 230000008569 process Effects 0.000 claims abstract description 69
- 238000000151 deposition Methods 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 30
- 238000005137 deposition process Methods 0.000 claims abstract description 28
- 230000008020 evaporation Effects 0.000 claims abstract description 15
- 238000001704 evaporation Methods 0.000 claims abstract description 15
- 238000002347 injection Methods 0.000 claims abstract description 13
- 239000007924 injection Substances 0.000 claims abstract description 13
- 239000007921 spray Substances 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims description 42
- 229910052739 hydrogen Inorganic materials 0.000 claims description 42
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 40
- 239000010410 layer Substances 0.000 claims description 29
- 230000009467 reduction Effects 0.000 claims description 26
- 239000012159 carrier gas Substances 0.000 claims description 25
- 230000004888 barrier function Effects 0.000 claims description 22
- 239000011229 interlayer Substances 0.000 claims description 21
- 238000009792 diffusion process Methods 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- 239000000654 additive Substances 0.000 claims description 18
- 238000004140 cleaning Methods 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 13
- 230000000996 additive effect Effects 0.000 claims description 13
- 238000005240 physical vapour deposition Methods 0.000 claims description 11
- 239000001307 helium Substances 0.000 claims description 10
- 229910052734 helium Inorganic materials 0.000 claims description 10
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 10
- 238000011065 in-situ storage Methods 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 238000005229 chemical vapour deposition Methods 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- 230000009977 dual effect Effects 0.000 claims description 6
- 238000007517 polishing process Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 101100456896 Drosophila melanogaster metl gene Proteins 0.000 claims 1
- 244000309466 calf Species 0.000 claims 1
- 230000004927 fusion Effects 0.000 claims 1
- 229940099990 ogen Drugs 0.000 claims 1
- 230000008021 deposition Effects 0.000 abstract description 19
- 239000012691 Cu precursor Substances 0.000 abstract description 18
- 239000010409 thin film Substances 0.000 abstract description 9
- 238000005516 engineering process Methods 0.000 abstract description 6
- NTWRVTYVHDNXDY-UHFFFAOYSA-N [Cu+].CC(C=C)(C)C Chemical compound [Cu+].CC(C=C)(C)C NTWRVTYVHDNXDY-UHFFFAOYSA-N 0.000 abstract description 2
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 57
- 239000011344 liquid material Substances 0.000 description 22
- 239000010408 film Substances 0.000 description 17
- 210000003128 head Anatomy 0.000 description 11
- 235000012431 wafers Nutrition 0.000 description 10
- 230000015556 catabolic process Effects 0.000 description 9
- 238000006731 degradation reaction Methods 0.000 description 9
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- 230000008016 vaporization Effects 0.000 description 5
- 238000007747 plating Methods 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- 239000008186 active pharmaceutical agent Substances 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
- 230000008859 change Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- 238000009834 vaporization Methods 0.000 description 3
- 230000010354 integration Effects 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- -1 4BJ compound Chemical class 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 241000332141 Iris fulva Species 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 241001486863 Sprattus sprattus Species 0.000 description 1
- 241001122767 Theaceae Species 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 101100099158 Xenopus laevis rela gene Proteins 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 210000000941 bile Anatomy 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 101150014174 calm gene Proteins 0.000 description 1
- CMDYHTIDHSNRGW-UHFFFAOYSA-L copper;2-acetyloxybenzoate Chemical compound [Cu+2].CC(=O)OC1=CC=CC=C1C([O-])=O.CC(=O)OC1=CC=CC=C1C([O-])=O CMDYHTIDHSNRGW-UHFFFAOYSA-L 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- BADXJIPKFRBFOT-UHFFFAOYSA-N dimedone Chemical compound CC1(C)CC(=O)CC(=O)C1 BADXJIPKFRBFOT-UHFFFAOYSA-N 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- GCSJLQSCSDMKTP-UHFFFAOYSA-N ethenyl(trimethyl)silane Chemical compound C[Si](C)(C)C=C GCSJLQSCSDMKTP-UHFFFAOYSA-N 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 210000000554 iris Anatomy 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002674 ointment Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- MBYLVOKEDDQJDY-UHFFFAOYSA-N tris(2-aminoethyl)amine Chemical compound NCCN(CCN)CCN MBYLVOKEDDQJDY-UHFFFAOYSA-N 0.000 description 1
- 210000000623 ulna Anatomy 0.000 description 1
Classifications
-
- 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
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
- H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
- H01L21/28512—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table
- H01L21/28556—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table by chemical means, e.g. CVD, LPCVD, PECVD, laser CVD
-
- 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
- C23C16/06—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 metallic material
- C23C16/18—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 metallic material from metallo-organic compounds
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/448—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
- C23C16/4481—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials by evaporation using carrier gas in contact with the source material
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (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)
- Electrodes Of Semiconductors (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
A method of forming a copper wiring in a semiconductor device, uses metal organic chemical vapour deposition (MOCVD) process technology 400, in which 1 ,1 1, 5, 5, 5-hexafluoro-2, 4-pentadionato (3,3-dimethyl-1-butene)-copper(I) ((hfac)Cu(DMB)) is used as a copper precursor. The deposition process used copper deposition equipment 100 comprising a direct liquid injection (DLI) system, a control evaporation mixer (CEM) or a vaporizer of an orifice type or a spray type. Accordingly, it can realize reproducibility of the copper deposition process and obtain a copper thin film of good quality.
Description
TITLE OF'1:HE INVENTION
METHon OF FORMING A COPPER WIRING IN A SEMIC'ONDlJ('TOR
DEVICE
BACKGROIJI OF 1 INVENTION
Field of the Invention:
The invention relates generally to a method of forming a copper wiring in a semiconductor device, and more particularly to, a method of forming a copper wiring in a semiconductor device capable of not only realizing, reappearance ', lso expressed as reproducibility) of the copper deposition process but also obtaining a copper thin film having a good film quality, by establishing a metal organic chemical vapor deposition t1\.40C57D) rroces.s technology in which 1,7i,5,,5-heafluoro-2, 4- pentadionato (3,3-dimethyl-1-butene)-copper(I) (hereinafter called (hfac) Cu(DM13)) compound is used as a copper precursor.
Description ofthePrior Art:
As semiconductor industries move into an ultra large scale integration, the geoetrv of devices reduces to a sub-half-micron region, while the circuit density thereof become increased in view of improved performance and reliability. Due to these reasons. a copper thin fihn is usually employed as an intercomection material useful in an integration circuit since the melting point of the copper thin fikn is higher than that of an aluminum thin film in forming a metal wiring in a seniconclcoi- device. Tlus intecoimectioni made loom copper thin film improves the re]iabili of a semiconductor device due to its higher resistance against electro migration (EM) and also increases signal transfer speed due to its low resistivity.
a method of forming a copper twining, the copper deposition process is an rt-pGrtant process in realizing higher deN ice reliability and higher integrated device signal transfer speed. Thus the copper deposition process employs various deposition methods such as physical vapor deposition (PVD), electroplating, electrolcss-plating and metal organic chemical vapor deposition (MOCVD). Because deposition methods, such as the MOCVD method, are significantly affected by a co,}-,ei precuisoi. a delivers, system by which tl.e copper cai:1 be safely moved must also be developed.
The MOCVD method of copper deposition may employ several types of liquid clively,ystcms Le-eilla*.el called LDS), i.lcladi..g: an LnS employing a bubbler method; an LDS such as direct liquid injection (hereinafter called DL1:); an LDS such as control evaporation nixing (hereinafter called CEM); and an LDS having a vaporizer of an orifice type or a spray tvpe. A compound comprising a copper metal called a precursor in an LDS is degraded to forth a copper deposition.
In the copper precursor used in MOCVD two compounds were developed. These compounds were copper II valence (Cut') compound such as 1,1,1,5, 5,5hexa:Lluoro- .1-ient-dionato-copper(II) and Cu (hfac), compound. each haNing a low vapor press; c. I- !l l ONN in o the development of these two compounds. another compound.
copper I \Talcnce (Cui) has keen developed. Copper I valence (Cui) has a high deposition speed since it has a higher vapor pressure than the copper IT valence compound and allows Leigh quality copper thin Ulna deposition at a low temperature of' I SO - 25() C. The I, 1,1, 5,5,5-hefluoro-9 4pentadionato(trimethylvinylsilane) - copper(T) (hereinat'ter called (ht'ac)Cu(TMVS)) compound of the currently- developed V.'io.!s copper I,.alence compounds is a representati,.e copper precursor for use in AOC\'D that l,as been Fidel used since it remains at a liquid phase at room temperature and allows a high quality copper thin film at a low temperature. Even with these advantages, however, the (hfac) Cu(TMVS) compound has a problem that it is degraded at room temperature. Thus, the (hfac)Cu(TMVS) compound has reappearance problems when applied to the process of manufacturing a seiricor,ductor de\ice. Accordingly, although the (hf'ac)Cu(TVS) compound is high in vapor pressure among the developed several precursors, it is low in securing reappearance in the conventional LDS. As such, the (hfac)Cu(TMVS) compound .rill have great difficlulty in securin^;, reappearance unless a new; T DS that can he safely carried is developed. Further, as the range between the vaporization temperature and the condensation temperature in the (hfac)Cu(TMVS) compound is extremely narrow, there is a problem that it has to keep the temperature constant.
Also. Schumacher reported that the (hfac)Cu(TMVS) compound can he safely used t'or about one year if it is used with a stabilizer.
In order to solve the problems with is, the above mentioned (hfac)Cu(TMVS) compound. a ('hfac)Cu('DMB') compound has been developed as a precursor. The (ht'ac)Cu(Dx.IB! compound is a nets compound that is de\ieloped using, 3. 3- dinethy]-l-butene (hereinafter called DMB) as Lewis base ligand. DMB used in this compound has a low molecular weight and high vapor pressure. Because the (hfac Cu(DMB) compound uses DM13 instead of a methyl group of TAMS as a T. ei7is base ligand' the compound has a higher vapor pressure than the (hf:'ac)(:u(TMVS). Therefore, the (hfac)Cu(DMB) compound is a good precursor since 't cal1 significantly improve a poor deposition speed, which is one of the ire. test problem in a MOCVD Cu precursor. However, because a MOCW) process technology using the (hfac)Cu(DMB) precursor in a conventional LDS has not been established. the (hfac)Cu(DMB) compound has not been commercialized.
Further, a LDS comprising a bubbler is not suitable for use with a liquid material having a low vapor pressure such as a copper liquid material. Specially, because the temperature of the bubbler must remain constant, the copper liquid material is degraded and particles are thus generated from it. The problem with this degradation is that it adversely affects the semiconductor deposition film, lowers its reappearance and causes a fiery lo.. deposition speed, etc. StlMl\Y OF THE INVENTION It is therefore an object of the present invention to provide a method of forming a copper wiring in a semiconductor device capable of not only realizing reappearance of' copper deposition process without developing a new LDS but also obtaining a copper thin fhn having a good Olin quality deposition process, by optimally setting the conditions of the copper deposition apparatus to thus establish a.1OCVD process technology in >> ihich a (hf'ac')Cu(DMB) compound is used as a precursor.
in order to accomplish the above object, a method of forming a copper wiring in a semiconductor device according to the present invention is characterized in that it comprises the steps of forming an interlayer insulating film on a semiconductor substrate in which various components for forming a semiconductor device are ic-r me d: flown no a contact hole and a trench on said interla:er insulating film and then -.;orming a diffusion barrier layer on the surface of said interlayer insulating film including said contact hole and said trench; depositing Cu so that said contact hole and said trench can be sufficiently filled; using a (hfac) Cu(DM:B) precursor by metal organic chemical vapor deposition (MOCVD) method in a direct liquid injection system, a control evaporation mixer or a liquid delivery system having a vaporizer of an. c,;ificc type or a spray type; and forming a copper wiring by performing a chemical mechanical polishing process.
In the case of using a direct liquid injection system provided with a reactive channbcr, the temperatlJre of the,.arorizer in the direct liquid infection- is in the range of 40 - 120 C. The temperature of the carrier gas induced into the vaporizer of the direct liquid injection is controlled to be about 20 C higher than that of the vaporizer of the direct liquid in jection. The carrier gas is at least one of helium (He), hydrogen (H.), argon (Ar) etc. and the flow rate thereof is in the range of 10 70Gsccm. the temperature of all the gas lines and the source lines from the vaporizer of the direct liquid injection to the reactive chamber are kept the saline as that of the v a.porizer. The internal temperature of the reactive chamber and the temperature of the sho\N Erich head in the reactive chamber are kept the same as that of tl-Ze vaporizer of the direct liquid injection.
In the case of using a control evaporation mixer provided with a reactive chamber. the temperature of a control valve in -the vaporizer of the control evaporation mixer is kept at a room temperature. The temperature of a heat exchanger in the vaporizer is in the range of 40 - 120 C. The temperature of the carrier gas induced into the control valise in the vaporizer Of the control evaporation mixci is conti-olled to be 20 - 120 C lower or higher than that of the heat exchanger of the vaporizer. The carrier gas is at least one of helium (He), hydrogen Em), argon (Ar) etc. and the flow rate thereof is in the range of lO - 700sccm. The temperature of all the gas lines and the source lines from the vaporizer of the control evaporation mixer to the reactive chamber are kept the same as or 5 - 20 C higher than that of the lied exchanger of tl,e - vaporizer. The internal temperature of the reactive chamber and the temperature of the showering head are kept the same as that of the heat exchanger in the vaporizer of the control evaporation mixer.
In the case of using a liquid delivery s,stem riro.ided Wick a reactive chamber and having a vaporizer of an orifice type or a spray types the temperature of the vaporizer is in the range of 20 - 120 C. The temperature of the carrier gas induced into the vaporizer is controlled to be 40 - 140 C which is 20 C higher than that of the vaporize.. The carrier gas is at least one of helium (He), hydrogen (Ha), argon (Ar! etc. and the flow rate thereof is in the range of 10 - 700sccm. The temperature of all the gas lines and the source lines from the vaporizer to the reactive chamber are lust the same as that of the vaporizer. The internal temperature of the reactive chamber and the temperature of the shouiering head are kept the same as that of the vaporizer.
Meanwhile. the (hfac)Cu(DMB) precursor can be used without any additives.
o:-weN-er, when any additive is used in the (hfac)Cu(DMB) precursor, the DMB of (1! - >0 o can be added or Hhfac of (). I - 20% can he added or a combination of DMP and llhiac can be added, as a additive.
BRIEF DESCRIPTION OF THE DRAWINGS
The aforementioned aspects and other features of the present invention will be explained in the hollowing description, taken in conjunction with the accompanying drawings, wherein: F ig. 1 is a flowchart for explaining a method of forming a copper wiring in a semlicullductor device according to the present invention; Fig. is a schematic view of a DLI including a reactive chamber, for explaining a method of forming a copper wiring in a semiconductor device according to the pr;sen.t i!e'ti off; ant Fig. 3 is a schematic view of a CEM including a reactive chamber, for explaining a method of forming a copper wiring in a semiconductor device according to the present invention.
DETAII,ED DESCRIPTION OF PREFERRED ElOOIl\IENS
The present invention will be described in detail by way of a preferred embodiment with reference to accompanying drawings, in which like reference numerals are used to identify the same or similar parts.
Referring now to Fig. 1, there is shown a flowchart for explaining a method of forming a copper -iris in a semiconductor device according to the present invention.
copper deposition process according to the present invention begins with t:hc step of initializing a copper deposition (step 100). When the initializing step is complete, a wafers on Enrich ccp,er.'ill be deposited, is loaded into a rea.cti,Te cl.a.iiber (step ()()). After the loafer is placed in, the chamber, the deposition process c-'ndili::ns are set in the copper deposition equipment (step 300). Finally, when the deposition process conditions are set, copper is deposited on the wafer by means of MOC'VD process using a (hfac)Cu(DMB) precursor (step 400).
Among the process steps, the step of setting deposition process conditions IT! the clapper deposition equipment (step 300) is an important step for accomplishing the object of the present invention. In other words, only when the deposition process conditions are optimally set, the MOCVD process technology using the (hlcLcJCu(4BJ compound cat. be establishers.
In order to optimally set the deposition process conditions in the copper deposition equipment, it is required that the characteristics of the copper deposition equipment must be letdown as well as the characteristics of the (hfac)Cu(DMB) compound being a copper precursor.
Firsts the characteristics of the (hfac)Cu(DMB) compound of a copper precursor are as follows: Wlien the (hfac)Cu(l)MB) precursor is compared with the (hfac)Cu(TMVS) 1,rec.i sor in sti-ucture. there is no difference in structure except for the conuitioil that Si is replaced With C in the middle of neutral lioand in the (hfac)Cu(DMB) precursor.
Reviewing the results of TGA/DSC on the (hfac)Cu(TMVS) precursor and the ('hiiac)C-u(DMB) precursor, it has been found that the (hfac)Cu(TMVS) precursor is degraded at the temperature of 63 C while the (hfac)Cu(DMB) precursor is degraded at the temperature of about 90 C. Thus, it can be seen that the (lfacJCu(l)l\4B) precursor has good thermal stability. belong Tith the.n. nai stability, or.c of'the most important factors affecting the characteristics of a precursor is vapor pressr.re. After reviewing the results of measuring vapor pressure, ii is found that the (hfac)Cu(DMB) precursor has nearly a I order higher vapor pressure than the (hfac)Cu('I'MVS) precursor. In concrete, it is found that the vapor pressure of the (hl'ac)Cu(TMVS) precursor is 0.67 at the temperature of 55 C while the vapor pressure ofthe (hfac)Cu(DM]3) precursor is 2.01 at the temperature of 43.5 C, 3.10 at the temperature of 54 C, 5.26 at the temperature of 66 C, 8.75 at the temperature ol' 78 C and 19.93 at the temperature of 88 C. Also, it is reported that the iLfac>Cu(D.'rB precursor ener+es degradation deposits at the temperature of' about 96 C. Thus, it can be seen that the degradation temperature of the (hfac)Cu(DMB) precursor is higher than that of the (hfac)Cu(TMVS) precursor.
Considering these results, as the degradation temperature of the (hfac) Cu(DM]B) precursor is much higher than that of the (hfac)Cu(TMVS) precursor, it has the potential by which much higher vaporization temperature can be available. Also, as the (hfac')Cu(DMB) precursor has much higher vapor pressure, it can easily obtain the deposition speed of more than] 000 A /min (1.67109m/s).
The characteristics of the copper deposition equipment for performing a MOCVD process using the (hfac)Cu(DMB) compound is as follows: The copper deposition equipment used in the MOCKED process is generally consisted of a l.DS and a reactive chainher. A representative LDS currently applied lo carry a copper precursor includes a DLT, CEM and an I DS having a vaporizer of an orifice type or a spray type.
t-'ig. 2 is a schematic View Of a DLT s,NTste.r. including a reactive cha!nber, for ex,la.ining' a method of forming a copper aspirin=, in a semiconductor device according to the present invention.
The DLI system 230 consists of a micro-pump 20 and a vaporizer 30 and has a structure in which liquid materials are vaporized from a metal disk 32. The liquid material of an ampule 19 is pressurized at the pressure of about 20psi and then transtcrrcd to the miclo-pu.np 20 via a first salve 21. At this time, while a first stepping motor 22 raises a first piston 23, the liquid material fills in the first cylinder 24. Then, while the first valve 21 is closed, a second valve 25 is opened, the first piston. 73 is!oered and the second steprpin-g, motor 2.6 sim'ultanenqly raises the second piston 27. This enables the liquid material filled in the first cylinder 24 to fill the second cylinder 28 via the second valve 25. Thereafter, as the second valve 25 is closed, the third valve 29 is opened and the second piston 27 is lowered, the liquid material is transferred to the vaporizer 3Q via the third Valve 29. At this time, as the first valve 21 is opened and the first piston is raised, the liquid material fills in the first cylinder 24 again. With these repeating operations, the liquid material is supplied into the Na. porizer 30 via the micro-punp 20. The flow control is determined by the number of cycles of the first and second stepping motors 22 and 26. The liquid material thus supplied fi-on the nicro-pump 20 is induced into the 99 stacked metal disks 32 via the delivery valve 31 provided on the liquid infloNv line 34. anti tired vaporized by a healing zone 33. The vaporized gas is induced into the reactive. e chamber 890 aria the evaporation Eras int1Ow, /outfloT line 36 alone' with a carrier gas induced via the carrier gas inflow line 35.
The react) e chamber Sgn consists of a shovNerirlg head 8Q for sprat> i id the Naporized material supplied from the DLI s,N,stem 23Q and a susceptor plate 90 for loading the wafer 111.
l'he Dl,T system 230 is constructed in which the liquid material therein is induced between the 99-stacked metal disks 32 and then vaporized at the vaporizer 30. Tlus, the DLI system 230 has good thermal exchange efficiency since it has a very wide thermal excliane and can transfer the induced liquid material in a wide range of pressures. including several tens through several hundreds psi. However, because the internal pressure of the vaporizer 30 is maintained at a very low prcssre Of al,oL t several Tour, the DLT system 230 can give the o!u,e expanding el't'ect depending on the difference of the pressure. Thus, the DLI system 230 can maximize the vaporizations efficiency. However, the Dl,l system 230 has the disadvantage that it is dii'fcult to maintain the pressure of the liquid material constant and it takes a very long time to get the pressure of the liquid material at a state of equilibrium. Reaching equilibrium takes a long' time because the DLI system relies on the induced liquid material to drive the metal disks 32 and it is constructed so that the micro-puml:> 20 can Finn the pressure. Further when the liquid material its suctioned at an initial state. there is a problem that the vaporizer 30 is clogged since a large amount ot'liquid material induced into the metal disks 32 remained un vaporized.
Fig. is a schematic Vienna- of a (: EM including a reactive chamber, for explaining a method of forming a copper attiring in a semiconductor device according lo the present invention.
The CEM 567 coi.sists of a liquid rllass flop controller 49 (he.eina0.er called LMI-C) and a vaporizer 50, wherein a liquid inaterial is vaporized at a heat exchanger 70. The vaporizer 50 consists of a control valve 60 and a heat exchanger 70. The control valve 60 consists of an orifice 61, a mixer 62 and actuator 63, a liquid inflow line 64 for supplying a. liquid material, a carrier gas inflow line 65 for supplying a carrier gas and a liquid vent line 66. The heat exchanger 70 is provided with a spiral tulle 7t. Wl,en the carrier gas passes through the ircr 62, a severe spiral flow is formed, so that the liquid material passed through the orifice 61 is transferred to the heat exchanger 70 at the form of mist. The liquid material mixed with the carrier gas , +1.; A A,;mr1 1;1= :'Cr;1 - tlrr - h fhm onir1 1-.lhP 71 'l'hn the L L1 I I I JO I LIJ I I I [ 11 1 1 A, =1.À 1 _.1. I, _. A _ vaporized gas is induced into the reactive chamber 890 via the vaporized gas inflo/out:1Ow line 72.
I he reactive chamber 890 consists of a showering head 80 for spraying the v aporized material supplied fiom the CEM 567 and a susceptor plate 90 for loading the wafer 1 l 1.
In the Vaporizer 50 of the CEM 67, the orifice 6i will be r arely clogged since it is not directly, heated. TTowever because the orifice has a very low conductance and -aporization is generated at the lono spiral tube 71 there is the problem that particles are likely Lo forth due to condensation and degradation of the liquid material.
In the case of depositing copper by MOC'vrl) method using a (hfac)Cu(DMB) compound as a copper precursor find the:C)I T system 230 provided with the reactive chamber 890 shown in Fig. 2, the copper deposition process conditions for realizing rea.pearance of copper deposition process are as follows: In order to vaporize the (hfac)Cu(DMB) compound being a copper precursor, the temperature of the vaporizer 30 is kept in the range of 40 - 1200C. The temperature of the carrier gas induced into the vaporizer 30 is controlled to be in the range of 60 - 140 C which is 20 TIC higher than that of the vaporizer 30, so that the compound can be completely evacuated. At this time, available carrier gases rear ir,c'ude helium (He) ? hydrogen (Hz)' argon (Ar) etc. and the flow rate thereof is in the range of 10 - 700sccm. In order to improve the conductance of the (hfac)Cu(DMB) compound while preventing the degradation and condensation thereof that is 'arnori.ed at the Vaporizer to, the temnerat,-!re of al! the gas lines and the source lines frown the vaporizer 30 to the reactive chamber 890 are kept the same as that of the vaporizer 30. In Odes tea completely evacuate impurities while the vaporized (hfac)Cu(DMB) compound induced into the reactive chamber 890 is degraded and then pure copper components can be deposited on the wafer 111, the internal temperature of the reactive chamber 890 and the temperature of the shQvvering head 80 are kept the same as that of the vaporizer 30. At this time, the temperature of the susceptor plate 90 into which the wafer 111 is loaded is latest in Ike range of i:0 980CC. N!so, the internal prcssu2-e of the reactive chamber 890 is latest in the range of 0.1 - ton. Tile distance between the showering head 80 and the susceptor plate 90 is l - 50mm. The flow rate of the (hfac)Cu(DMB) compound is in the range of O.l - l.O sccm. in the above process, the (hfac)Cu(DMB) compound being a copper precursor can be used vithout any additives. However, when any additive is used in the (hfac)Cu(DMB) compound, the DMB of O.l - 30 /0 can be adUcd or llllfac of O. 1 - 0 /0 can be added or a combination of Dam and Hhfac can be added, as a additive.
In the case of depositing copper by a MOCVD method using a (hfac)Cu(DMB) compound as a copper precursor and the CEM 567 provided with the reactive chamber 890 shown in Fig. 3, the copper deposition process conditions for realizing reappearance of a copper deposition process are as follows: When else carrier eras passes through the mixer 62 in the vaporizer 50 for vaporizing the (hfac)Cu(DMB) compound, a severe spiral flow is formed, so that the (hfac)Cu(DMB) compound passed through the orifice 61 is transferred to the heat exchlallgel 7n at the forms of mist. Thus, the temperature of the heat echanGrer 7n is kept in the range of 40 - l 20 C while the temperature of the control valve 60 is kept at room temperature. The temperature of the carrier gas induced into the control valve 60 ol the vaporizer 0 may be controlled to be higher or lower than that of the heat exchanger 70 of the vaporizer 50, that is in the range of 40 C. At this time. available carrier gases Nay include helium (He), hydrogen (H:), argon (Ar) etc. and the flow rate thereof is in the range of lO - 700sccm. In order to improve the conductance Off the (hfac)Cu(DMB) compound \vYile preventing the degradation and condensation thei eof that is vaporized at the heat exchanger 70 of the vaporizer 50, the temperature of all the gas lines and the source lines fiom the vaporizer 50 to the reactive chamber 890 are kept the same as that of the heat exchanger 70 of the vaporizer 50 or in the range of 5 - 20C. In order to completely evacuate impurities while the vaporized (hfac)Cu(Dl\:B) compound induced into the reactive chamber 890 is degrraded and then pure copper components can be deposited on the waler- I 11. tee,i-,teinal te,n, peiatuic of the reactive chamber S90 and the temperature cuff the showering Lead 80 are latest the sainc as that of the heat exchanger 70 Of the vaporizer 50. At this tine, the temperature of the susceptor plate 90 into which the wafer 111 is loaded is kept in the range of 120 - 280 C. Also, the internal pressure of the reactive chamber 890 is kept in the range of 0.1 - Storr. The distance between the showering head 80 and the susceptor plate 90 is 1 - 50mm. The flow rate of the (hf-ac)Cu(DMB) compound being a copper precursor is in the range of 0.1 - 1.0 sccm.
In the above process, the (hfac)Cu(DMB) compound being a copper precursor can be used without any additives. However, when any additive is used in the (hfac)Cu(Dvn) cui-lluoulld, the MOB of 0. - 3Q can be added Or Hhfic Of 0.1 - 90 .
can be added or a combination of DMB and Hhfac can be added, as a additive.
In the case of depositing copper by MOCVD method using a (hfac)Cu(DMB) compound as a copper precursor and a liquid delivery system having a vaporizer of an orifice type or a spray type, with which a reactive chamber (not shown) is provided. the copper deposition process conditions for realizing reappearance of a copper deposition process are as follows: The tcngerature of the v aporizer for vaporizing the (hfac)Cu(DMB) compound being a copper precursor is kept in the range of 20 - l9OOC. The temperature of the carrier gas induced into the vaporizer is controlled to be in the range of 40 - 140 C which is 20C higher than that of the vaporizer. so that the compound can be completely evacuated. At this time. available cattier gases may include helium (He)- hydrogen (Ha) argon (Ar) etc. and the flow rate thereof is in the range of 10 - 700sccm. TO order to improve the conductance of the (hfac)Cu(DMB) c^ Upon id IN bile preventing the degradation and condensation thereof that is v.,porized at the aporizer, the temperature of all the gas lines and the source lines -frown the vaporizer to the reactive chamber arc kept the same as that of the vaporizer.
TO order to completely evacuate impurities while the vaporized (hfac) Cu(DMB) compound induced into the reactive chamber is degraded and then pure copper components can be deposited on the wafer, the internal temperature of the reactive cLalnlDcr and the tc;nperature of the showering head ale kept same to that of the vaporizer. At this tine, the temperature of the susceptor plate into which the wafer is loaded is kept in the range of 120 - 280 C. Also, the internal pressure of the reactive chamber is kept in the range of 0. - storr. Me distance between the showering head and the susceptor plate is 1 - 50mm. The flow rate of the (hfac)Cu(DMB) compound is in the range of 0.] - 1.0 sccm. In the above process, the (hfac)Cu(I)MB) compound being a copper precursor can be used without any additives. HoN;eNTer, when any additive is used in the (hfac) Cu(DMB) compound, the DMB of 0.1 - 30 /, can be added or Hhiac of 0.1 20% can be added or a combination of DMB and Hhfac can be added, as a additive.
leased on the above copper deposition conditions. a method ol forming a copper w irises in a semiconductor device shill be nose; explained in a way by which a DLT. CEM or a liquid delivery system having a vaporizer of an orifice type or a spray type is applied.
In the case of depositing copper for a copper thin film by use of the (hfac)Cu(OMB) precursor by a MOCVD method using a DLI system provided with the reactive chamber shown in Fiat. 2, a method of forming a copper wiring in a s-TAiconducto1^ device according to the present invention is as follows: On inter]ayer insulating film is formed on a semiconductor substrate in which Nario:s components for forming a semiconductor device are formed. Then, a contact hole and a trench are longed on the interlayer insulating lam using a mask and are then experienced by cleaning process. Next, a diffusion barrier layer is formed on the surface of the interlayer insulating film including the contact hole and the trench.
In the DLI provided with the reactive chamber, Cu is plated enough to fill the contact hole and the trench using the (hfac)Cu(DMB) precursor by MOCVD method.
When the Cu plating is finished, the Cu plated surface is experienced by hydrogen rel1'ctioTn Theresa! process and then. is experienced by achemical m-echan-ica polishing (hereinafter called CMP) process, thus fonning a copper wiring.
In the above process, the interlayer insulating film is donned of an insulating hhn having a low dielectric constant. The contact hole and the trench are fonned in a dual damascene method. The cicanin, process may use a FU-' plasma in case that a bottom layer is made of metals such as tungsten (TV) or aluminum (Al), and may use a inactive cleaning method ill case blat the bottom layer is made of copper (Cu).
I'he diffusion barrier layer may be formed of at least one of ionized PVD TiN, (CVD TINT. MOCK VT TiN. ionized PVD Ta, ionized P\O TaN, CVD Ta, CVD TaN' CVD Vow.
The copper deposition process ensures that the temperature of the vaporizer 30 in the DLI 230 is kept in the range of 40 - 120 C, and that the temperature of the cattier gas induced into iLe Vaporizer 30 is controlled to be in the range of 60 - 140C which is OOC higher than that of the vaporizer 30 wherein available carrier gases may include helium (He), hydrogen (H2), argon (Ar) etc. and the flow +e thereof is in, the range Of 1Ci - 700sccm. to. order to irnpro>e the conductance of hc (hfac)Cu(DMB) precurso: while preventing, the degradation and condensation then cof that is vaporized at the vaporizer 30, the temperature of all the gas lines and the source lines from the vaporizer 30 to the reactive chamber 890 are kept the same as that of the vaporizer 30. At this Lime, the temperature of the susceptor plate 90 into which the wafer 10 is loaded is kept in the range of 150 - 280 C. Also, the internal pressure of the reactive chamber 89n is kept in the range of 0.1 - 5torr. The distance between the showering head 80 and the susceptor plate 90 is 1 - 50mm.
The flow rate of the (hfac)Cu(DMB) precursor is in the rang of 01. - 1.0 sccm. The (lfac>CuttMB conpo'Jnd of a copper precursor vised in the Conner deposition process can be used without any additives. However, when any additive is used in the (hfac)Cu(DMB) compound, the DMB of 0.1 - 30% can be added or Hhfac of 0.1 90'>0 can be added or a combination of DMB and Hhfac can be added, as a additive.
The hydrogen reduction thermal process includes performing a thermal process in tle range of room temperature - 350 GC for 30 minutes - 3 hours under hydrogen reduction atmosphere in order to change the (hfac) Cu(DMB) compound into a grain mQrphol.>gN. At this time. the hydrogen reduction atmosphere may use hydrogen (Hi) only or a hydrogen mixed g as such as Eat --Ar(1-95 z'o), He + N. (1- 950/,,) etc. Nt^ter CMP process a post-cleaning process may be performed. The cleaning process and the diffusion barrier donning process are perfor, ning in-situ with no time deia)i. Also, the C u platting process and the hydrogen reduction thermal process may be performed in-situ with no time delay.
In the case of depositing copper for a copper thin film by use of the hfac)Cu(MB precursor by, MOCNv'D Rod USillg CENT] provided Zenith fee reactivate clamber shown in Fig. 3, a method of forming a copper wiring in a semiconductor device according to the present invention is as follows: Ail interlayer insulating film is formed on a semiconductor substrate in which various components for forming a semiconductor device are for,;ned. Then a contact hole and a trench are fonned on the interlayer insulating film using a mask and are then experienced by cleaning process. lN'ext, a diffusion barrier layer is foamed on the surface of the interlayer insulating film including the contact hole and the trench.
In the CEM provided with the reactive chamber, a copper layer is donned enough to all Ah of - lo c'=A the trmnrh en fbih the rliffilcirn hrrir taffy in fry I J] I_ 1 1 JO 1 l 1, 'J - using, the (hfac)Cu(DMB) precursor by MOCVD method. When formation of the copper layer is finished, the copper layer is experienced by hydrogen reduction thermal process and then is experienced by CMP process, thus fonning a copper >s irino in the contact and the trench.
In the above process' the interlayer insulating film is formed of an insulating film having a low dielectric constant. The contact hole and the trench are formed in a dual damasccne method. l he cleaning process may use a RF plasma in case that a bottom layer is made of metals such as tungsten (W) or aluminum (Al), and may use a reactive cleanin_ method in case that the bottom layer is made of copper (Cu).
The diffusion barrier layer may be fonned of at least one of ionized PVD TiN.
Cow TiN, MOCKED Tiled ionized PAD Ta, ionized P\l) TaN, CVD Ta, COD TaN, AVID WN. IJpon a copper deposition process. the conditions of the CEM provided with the reactive chamber are same to the above mentioned.
The hydrogen reduction thermal process includes performing- a thermal process in the range of room temperature - 350 C for 30 minutes - 3 hours under hydrogen reduction atmosphere in order to change the (hfac)Cu(DMB) compound into a grain morphology. At this tine, the hydrogen reduction atmosphere may use hydrogen (H:) only or a hydrogen mixed gas such as H2 + Ar(1-95%), H2 + N2 (1-95%) etc. After CMP process, a post-cleaning process may be perfonned. The cleaning process and the diffi.lsion barrier fonning process are perfonned in-situ with no tune delay. Also, the Cu plating process and the hydrogen reduction thermal process may be performed in-situ with no time delay.
In the case of depositing confer for a confer thin film by use of the (hfac)Cu(DMB) precursor by MOCVD method using all of the LDSs provided with the reactive chamber and having a vaporizer of an orifice type or a spray type, a method of fonning a copper wiring in a semiconductor device according to the present invention is as follows: An interiayer insulating film is donned on a semiconductor substrate in which various components for fanning a semiconductor device are fanned. Then. a contact hole and a trench are formed on the interlayer insulating film using a mask and are then experienced by cleaning process. Next, a diffusion barrier layer is formed on the surface of the interlayer insulating Olin including the contact hole and the trench.
In the LOS provided with the r eactive chamber and having a vaporizer of an orifice type or a spray type, a copper layer is fonned enough to fill the contact hole and the trench on which the diffusion barrier layer is formed, using the (hfac)Cu(DM:) precursor by MOCVD method. When connation of the copper layer is finished, the cooper layer is experienced by hydrogen reduction ther-rl.a process and then is experienced by CMP process, thus forming a copper retiring in the contact and the tren ch.
in the above process, the interlayer insulating him is tonned ol an insulating film having a low dielectric constant below 2.7. The contact hole and the trench are formed in a dual danascene method. The cleaning process may use a RF plasma in case that a bottom layer is made of metals such as tungsten (W) or alurninurn AI), and may use a reactive c]ea.ning method in case that the bottom layer is made of copper (Cu). The diffusion barrier layer may be formed of at least one of ionized pVI) TiN7 CVr) TiN, MOCVr) TiN' ionizer pVL) Tat ionizecl PVO TaN; (:::VE) Ta; (my) TaN. con WE. Upon a copper deposition process, the conditions of the CEM provided with the reactive chamber and having a vaporizer of an orifice type or a spray type are same to the above mentioned. The hydrogen reduction thermal process includes performing a thermal process in the range of room temperature - 3() C for 30 minutes - 3 hours under hydrogen reduction atmosphere in order to change the (hfac)Cu(DMR) compound into a grain morphology. At this time, the hydrogen reduction atmosphere may use hydrogen (hi,) only or a hydrogen Nixed gas such as IT, ,-Ar(]-9%). HI No (]-9%) e-c. After CMP process, a. post- cleanin process may be performed. The cleaning process and the diffusion battier forming process are performed in-situ with no time delay. Also, the Cu plating pi ocess and the hydrogen reduction iLennal process may be performed in-situ with no time delay.
As can be understood Mom the above description, the present invention can n.n halls. realize reappearance ol the copper deposition process hut also obtain a copper thin film having a good film quality, by optionally settin;, the deposition process conditions of the copper deposition equipment to thus establish a MOCKS process technology in which a (hfac) Cu(DMB) compound is used as a precursor.
The present invent) on has been described with reference to particular embodiments in connection with particular applications. Those having ordinary skill in Be art and access to the teachings of the present invention will recognize additional modifications and applications within the scope thereof.
It is therefore intended by the appended claims to cover any and all such applications modifGation.q? an-d embodies entc within the scope of the present i nvention.
Claims (1)
- MAT IS CLAIMED IS: ]. A method of forming a copper Nearing in asemiconductor device. comprising the steps of: !onming an inrerlayer insulating film on a semiconductor substrate in which V!riOtiS components for forming a semiconductor device are formed; forming a contact hole and a trench on said interlayer insulating fihn; forming a ditfuson barrier layer on the surface ot said interlayer insulating film including said contact hole and said trench; depositing Cu so that said contact hole and said trench are filled, using a (hfac)Cu(DMB) precursor bid metal organic chemical vapor deposition (MOC57D) method in a liquid delivery system provided with a reactive chamber; wherein said liquid delivery system is selected from the group comprising: direct liquid injection; control evaporation mixer, liquid delivery system having a vaporizer of an orifice type or spray type; and forming a copper wiring by performing a chemical mechanical polishing process.2. A method of forming a copper wiring in a semiconductor device, comprising the steps of: forming an interlayer insulating film on a semiconductor sulstra.te in which various components for forming a semiconductor device are fonned; forming a contact hole and a trench on said interlaver insulating' 1lrn; fonning a diffusion balkier layer on the surface of said interloper insulating f:ilm including said contact hole and said trench; depositing (flu so that said contact hole and said trench are lolled, using a (hfac)Cu(DMl3) precursor by metal organic chemical vapor deposition (MOCVD) method in a direct liquid injection system provided with a reactive chamber; and forming a copper \N'iring by performing a chemical mechanical polishing process.The method of fondling a canner wiring in a semiconductor device a. ccordin to claim 2, wherein said contact hole and said trench are formed in a dual damascene method.4. The method of l'orming a copper wiring in a semiconductor device according to claim 2. wherein said diffusion barrier layer is donned of at least one of ionized PVD TiN, CVD Tiny MOCVD TiN. ionized PVD Ta, ionized PVD TaN, CVD Ta, CVD TaN and CVD WN.I. The method of Conning a copper wiring in a semiconductor device according to claim 2. -vi-hereiri Tic temperature of a. Vaporizer in said direct liquid injection system is in the range of 40 - 20 C 6. The method of f6^min=7 a copper.viring in seniconduetor device according 7.' claim 0. wherein the temperature of a carrier gas induced into a vaporizer in said direct liquid injection system is controlled to be about 20 C higher than that of the temperature of the vaporizer in said direct liquid in jection system.7. The method of forming a copper wiring in a semiconductor device according to claim; is. vvhcrein said carrier gas is at leas' one of helium (He), hydrogen (Ha), argon (Ar) gas and the Low rate thereof is in the range of 10 - 700sccm.8. The method of for!ni!o a copper Trio in a. semicondluetor device according to claim 2, wherein the temperature of gas lines and source lines extending from a vaporizer in said direct liquid injection system to said reactive chamber are kept the same as that of said vaporizer.9. The method of iorning a copper wiring in a semiconductor device according to claiTrt I. wherein the internal temperature oi said reactive chamber and the temperature of a showering head in said reactive chamber are kept the same as that of a Vaporizer in said direct liquid injection.10. The method of forming a copper wiring in a semiconductor device according to claim 2. wherein the temperature of a susceptor plate ilk said reactive chamber is in the range of 150 - 980 C I i. The metl,od of, i.onnirg a copper.Tirin in a seniconduc+or device according to, claim 2, 'vherein the internal pressure of said reactive chamber is kept in the range of 0. - Stow.]2. The method of forming a copper wiring in a semiconductor device according to claim 2. wherein the distance between a showering head and a susceptor plate in said react) v e cha;,nber is in the range of] - 50mml.13. The method of forming a copper wiring in a semiconductor device according to claim Wherein the Item rate of said thfac)Cu(D>.'rR) precursor is in the range of 0. l - 1.() sccm.14. The method of forming a copper wiring in a semiconductor device according to claim 9, Herein OMB of 0.1 - 30% is added or Hhfac of 0.1 00% is added or a combination of DMB and Hhfac is added to the (hfac) (:u(DMB) precursor, as an additive.] it. The method of forming a copper wiring in a semiconductor device according lo claim 2- wherein after said Cu deposition process. a hydrogen reduction thermal process is performed in situ with no time delay, wherein the hydrogen reduction thermal process is performed in a temperature range of room temperature - 350C for a dime frame of 3n minutes - 3 honors, tinder a hydrogen reduction atrmoshere.I6. The method of forming a copper wiring in a semiconductor device according to claim]5, wherein said hydrogen reduction atmosphere uses any one of H2, H2 --Art] -95%) and H2 + N:: (1-95%).17. The method of forming a copper miring in a semiconductor device according to claim 2, wherein after the process of forming said diffusion barrier, a cleaning process is performed, and wherein said cleaning process and said diffusion barrier fO' fling process He pe'-forled insitu Edith no tine delay.18. A method of forming a copper wiring in a semiconductor device, comprising the steps of: forming an interlayer insulating film on a semiconductor substrate in which various components for forming a semiconductor device are formed; fQrminD a contact hole and a trench on said interlayer insulating' films; i'orminD a diffusion barrier layer on the surface of said interlayer insulating film including said contact hole and said trench; forming a copper layer so that said contact hole and said trench are fil]ed7 Using a (hI'ac)Cu(DMB) precursor by metal organic chemical vapor deposition (MOCVD) method in a. control evaporation mixer provided with a reactive chamber; and forming a copper wiring by performing a chemical mechanical polishing process.]9. The method of forming a copper wiring in a semiconductor device according to claim] 8. wherein said contact hole and said trench are formed in a dual damascene method.20. 'I'le method of l:orming a copper wiring in a semiconductor device according to claim 1 S. wherein said dii'-fusioi: barrier layer is informed of at least one of ionized Palm TiN. CVD TiN. MOCVI) TiN. ionized PVD Ta. ionized PVD TaN. C.VI:) Ta, CVD T aN and CVD CHIN.21. The method of forming a copper wiring in a semiconductor device according to claim 18, wheicin the te'peraure of a control valve in a vaporizer of said control evaporation mixer is kept at room temperature and the temperature of a heat exchanger in said vaporizer is in the range of 40 - 120 C 00. The method offonning a copper wiring in a semiconductor device according to claim 18- wherein the temperature of a carrier gas induced into a control valve in a vapoi izer of the control evaporation mixer is controlled to be in the range of 20 C 140 C, wherein the temperature of the carrier gas is lower or higher than that of the heat exchanger in said vaporizer.73. The method of forming a copper wiring in a semiconductor device according to claim 22, wherein said carrier gas is at least one of helium (He), hydrogen (H:), 27-gol (jeer) gas and the floral rate thereof is in the range of 10 - 700sccn.Ad. The method of donning a copper wiring in a semiconductor device according to claim 18, wherein the temperature of gas lines and source lines extending from a vaporizer of the control evaporation mixer to said reactive chamber are kept the same as or 5 - 2() C higher than that of a heat exchanger in said vaporizer.5. The method of forming a copper wiring in a semiconductor device according to, claim 'S. Therein the internal temperature of said reactive chamber and the temperature:-'f a showering head in said reactive chamber are kept the same as that of a heat exchanger in the vaporizer of a control evaporation mixer.6. The method of fonning a copper wiring in a semiconductor device according to claim] 8, wherein the temperature of a susceptor plate in said reactive chamber is in cite range of i 0 - 280^C 27. The method of forming a copper wiring in a semiconductor device according to claim 18, 1 erein the internal pressure of said reactive chamber is kept in the range of 0.1 - Story.28. The method of fondling a copper wirin_ in a semiconductor device according to claim 18, wherein the distance between a showering head and a susceptor plate in said reactive chamber is in the range of 1 - 50mm 99. The method of forming a copper wiring in a semiconductor device according k' claim IS, wherein L)MB of 0.1 - 30% is added or Hhfac of O.i - 200/o is added or a combination of DMB and Hhlac is added to the (hfac) Cu(DMB) precursor, as an additive.30. The method of forming a copper wiring in a semiconductor device according Lo claim i 8, wherein after said Cu deposition process, a Hydrogen reduction thermal process is performed in situ with no time delay. wherein the hydrogen reduction thermal process is performed in a temperature range of room temperature - 35() C 9.l a time frame of 3() minutes - 3 hours, '!.der a hvd!ogen reduction atmosphere.[he method of fonning a copper attiring in a semiconductor device according to ciao:()' wherein said hydrogen reduction atmosphere uses any one of id:, 11: Art 1-95%) and H: + N: (1-95%).30. The method o f forming a copper spiring in a semiconductor device according to claim 18, wherein after the process of forming said diffusion barrier, a cleaning process is performed, and wherein said cleaning process and said diffusion barrier forming process are performed in-situ with no time delay: 33. A method of forming a copper wiring in a semiconductor device, comprising the sines or: fonning an interlayer insulating f;]m. on a semiconductor substrate in which various components for forming a semiconductor device are formed; forming a con.ta.ct hole and a trench or said interlayer insulatin=, film; forming, a diffusion barrier layer on He surface of said interlayer insulating hln including said contact hole and said trench; fonning a copper layer so that said contact hole and said trench are filled, using a (hfac)Cu(DMB) precursor by metal organic chemical vapor deposition (MOCVD) method in a liquid delivery system provided with a reactive chamber and ha; ing a vaporizer of an orifice type or a spray type; and forming a copper wiring by performing a chemical mechanical polishing process.34. The method of forming a copper wiring in a semiconductor device according to claim 33, wherein said contact hole and said trench are formed in a dual damascene method.35. 'I'he method of forming a copper wiring in a semiconductor device according to claim 33, wherein said dil'fusion barrier layer is formed of at least one of ionized PVV'l'ilNT. CVD TiN. MOCVD TiN. ionized PVV Ta. ionized PVD TaN, CVV Ta. CVD TaN and CV:D Am. Oh. The method of forming a copper wiring in a semiconductor device according to elai-r, ,, wherein the temperature of the vaporizer is in the range of 00 - 10 C 37. The method of forming a copper wiring in a semiconductor device according in cl;-!ii.n À3 wherein the teinperatl-!re of a carrier gas induced into the vaporizer is c::ntrolled le. be in the range ni 40 - 14() C which is 20C higher than that of the aporizer.38. The method offorming a copper wiring in a semiconductor device according to claim 37- wherein said carrier gas is at least one of helium (He), hydrogen (He), argon / A Ace anal the Fen l'tf thrfOf in in t5P runes of 1 n - 70nscrm 39. The method of forming a copper wiring in a semiconductor device according to claim I. wherein the temperature of gas lines and source]ine. s extending from said vaporizer to said reactive chamber are kept the same as that of the temperature of said Vaporizer.40. The method of forming a copper wiring in a semiconductor device according to claim 33. wherein the internal temperature of said reactive chamber and the temperature of a showering head are l;ept the same as that of said vaporizer.41. The method of forming a copper wiring in a semiconductor device according to Elaine I, .\lcrcin the i,em,perature of a suscepior plate in said reactive chamber is in the range calf 190 - 28() C 49 Tlle nethoci Of f'nl-Dl jug;J copper wiring in a semiconductor device according to claim 33. wherein the inte!nal press.!e ol said reactive chamber is kept in the range of ().1 - Ston.43. The method of forming a copper wiring in a semiconductor device according to claim 33, wherein the distance between a showering head and a. susceptor plate in said r ea.cti>e chanter is in the range of I - A. Oml.n.44. The method of forming a copper wiring in a semiconductor device according to claim So. wherein the flow rate of said (hfac)(:u(DMB) precursor is in the range of 0.1- 1.0 sccm.4. the method of forming a copper wiring in a semiconductor device according to claim 33. wherein DMB of 0.1 - 30% is added or Hhfa.c of 0.1 - 20% is added or a combination of DME; and Hhf;ac is added to the (hfac) Cu(DMB) precursor, as an additive.6. The method of forming a copper wiring in a semiconductor device according id clL,irn 33. wherein after said Cu deposition process, a hydrogen reduction thermal process is performed in situ with no' time delay. wherein the hydrogen reduction thermal process is performed in a temperature range of room temperature - 350 for a time fragile oi 30 minutes - 3 hours, lander a hydrogen reduction atmosphere.47. The method of forming a copper wiring in a semiconductor device according to claim 46, wherein said hydrogen reduction atmosphere uses any one of t1:, t1: Ar(1-95%) and H: + NO (1-95%).48. I'he method of forming a copper retiring in a semiconductor device according to claim 33, wherein after the process of forming said diffusion barrier, a cleaning process is performed, and wherein said cleaning process and said diffusion barrier formi71g process are nerforTned in-sit7.7 with no time delay
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019990060562A KR100358045B1 (en) | 1999-12-22 | 1999-12-22 | Method of forming a copper wiring in a semiconductor device |
| GB0029435A GB2363678B (en) | 1999-12-22 | 2000-12-04 | Method of forming a copper wiring in a semiconductor device |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB0410696D0 GB0410696D0 (en) | 2004-06-16 |
| GB2397947A true GB2397947A (en) | 2004-08-04 |
| GB2397947B GB2397947B (en) | 2004-10-06 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB0410696A Expired - Fee Related GB2397947B (en) | 1999-12-22 | 2000-12-04 | Method of forming a copper wiring in a semiconductor device |
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| Country | Link |
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| GB (1) | GB2397947B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0898308A2 (en) * | 1997-08-22 | 1999-02-24 | Samsung Electronics Co., Ltd. | A method for forming a metal interconnection in a semiconductor device |
| WO1999053117A2 (en) * | 1998-04-14 | 1999-10-21 | Cvd Systems, Inc. | Film deposition system |
| WO2000071550A1 (en) * | 1999-05-25 | 2000-11-30 | Advanced Technology Materials, Inc. | Copper source reagent compositions, and method of making and using same for microelectronic device structures |
-
2000
- 2000-12-04 GB GB0410696A patent/GB2397947B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0898308A2 (en) * | 1997-08-22 | 1999-02-24 | Samsung Electronics Co., Ltd. | A method for forming a metal interconnection in a semiconductor device |
| WO1999053117A2 (en) * | 1998-04-14 | 1999-10-21 | Cvd Systems, Inc. | Film deposition system |
| WO2000071550A1 (en) * | 1999-05-25 | 2000-11-30 | Advanced Technology Materials, Inc. | Copper source reagent compositions, and method of making and using same for microelectronic device structures |
Non-Patent Citations (1)
| Title |
|---|
| Thin solid films (Switzerland), vol 350, 15th August 1999, Elsevier, Switzerland, Kang et al, pages 10 to 13. * |
Also Published As
| Publication number | Publication date |
|---|---|
| GB0410696D0 (en) | 2004-06-16 |
| GB2397947B (en) | 2004-10-06 |
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Effective date: 20131204 |