CN107338116A - A kind of cleaning agent, its preparation method and application - Google Patents
A kind of cleaning agent, its preparation method and application Download PDFInfo
- Publication number
- CN107338116A CN107338116A CN201710613213.5A CN201710613213A CN107338116A CN 107338116 A CN107338116 A CN 107338116A CN 201710613213 A CN201710613213 A CN 201710613213A CN 107338116 A CN107338116 A CN 107338116A
- Authority
- CN
- China
- Prior art keywords
- cleaning agent
- corrosion inhibitor
- preparation
- mass fraction
- agent
- 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.)
- Granted
Links
- 239000012459 cleaning agent Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 230000007797 corrosion Effects 0.000 claims abstract description 36
- 238000005260 corrosion Methods 0.000 claims abstract description 36
- 239000003112 inhibitor Substances 0.000 claims abstract description 34
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 150000004040 pyrrolidinones Chemical class 0.000 claims abstract description 15
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011630 iodine Substances 0.000 claims abstract description 13
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000003647 oxidation Effects 0.000 claims abstract description 10
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 10
- 239000004094 surface-active agent Substances 0.000 claims abstract description 10
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 9
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012964 benzotriazole Substances 0.000 claims abstract description 6
- 150000007857 hydrazones Chemical class 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims description 7
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 claims description 3
- UOFGSWVZMUXXIY-UHFFFAOYSA-N 1,5-Diphenyl-3-thiocarbazone Chemical group C=1C=CC=CC=1N=NC(=S)NNC1=CC=CC=C1 UOFGSWVZMUXXIY-UHFFFAOYSA-N 0.000 claims description 2
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical class CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- ZRDJERPXCFOFCP-UHFFFAOYSA-N azane;iodic acid Chemical group [NH4+].[O-]I(=O)=O ZRDJERPXCFOFCP-UHFFFAOYSA-N 0.000 claims description 2
- URGYLQKORWLZAQ-UHFFFAOYSA-N azanium;periodate Chemical compound [NH4+].[O-]I(=O)(=O)=O URGYLQKORWLZAQ-UHFFFAOYSA-N 0.000 claims description 2
- DXWSZLNAWOWMAN-UHFFFAOYSA-N boric acid;tetrabutylazanium Chemical compound OB(O)O.CCCC[N+](CCCC)(CCCC)CCCC DXWSZLNAWOWMAN-UHFFFAOYSA-N 0.000 claims description 2
- QGKPFZYVJCURLK-UHFFFAOYSA-N boric acid;tetramethylazanium Chemical compound OB(O)O.C[N+](C)(C)C QGKPFZYVJCURLK-UHFFFAOYSA-N 0.000 claims description 2
- IRCSOVSHHCMPLH-UHFFFAOYSA-N boric acid;tetrapropylazanium Chemical compound OB(O)O.CCC[N+](CCC)(CCC)CCC IRCSOVSHHCMPLH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- CPSCIFXVLXCFIQ-NTCAYCPXSA-N n-[(e)-1-phenylethylideneamino]aniline Chemical group C=1C=CC=CC=1C(/C)=N/NC1=CC=CC=C1 CPSCIFXVLXCFIQ-NTCAYCPXSA-N 0.000 claims description 2
- PZYDAVFRVJXFHS-UHFFFAOYSA-N n-cyclohexyl-2-pyrrolidone Chemical class O=C1CCCN1C1CCCCC1 PZYDAVFRVJXFHS-UHFFFAOYSA-N 0.000 claims description 2
- HLQAWDQQEJSALG-UHFFFAOYSA-N periodic acid tetramethylazanium Chemical compound C[N+](C)(C)C.I(=O)(=O)(=O)O HLQAWDQQEJSALG-UHFFFAOYSA-N 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 2
- RXMRGBVLCSYIBO-UHFFFAOYSA-M tetramethylazanium;iodide Chemical compound [I-].C[N+](C)(C)C RXMRGBVLCSYIBO-UHFFFAOYSA-M 0.000 claims description 2
- -1 ammonium tetrafluoroborate Chemical compound 0.000 claims 2
- GUOVBFFLXKJFEE-UHFFFAOYSA-N 2h-benzotriazole-5-carboxylic acid Chemical class C1=C(C(=O)O)C=CC2=NNN=C21 GUOVBFFLXKJFEE-UHFFFAOYSA-N 0.000 claims 1
- 230000003213 activating effect Effects 0.000 claims 1
- 150000003233 pyrroles Chemical class 0.000 claims 1
- 230000001629 suppression Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 16
- 238000004140 cleaning Methods 0.000 abstract description 10
- 238000005530 etching Methods 0.000 abstract description 10
- 239000004065 semiconductor Substances 0.000 abstract description 7
- 238000004380 ashing Methods 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 150000004767 nitrides Chemical class 0.000 description 5
- 229910052715 tantalum Inorganic materials 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000001259 photo etching Methods 0.000 description 3
- 238000001020 plasma etching Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012956 testing procedure Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/042—Acids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/046—Salts
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/28—Heterocyclic compounds containing nitrogen in the ring
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/34—Organic compounds containing sulfur
- C11D3/349—Organic compounds containing sulfur additionally containing nitrogen atoms, e.g. nitro, nitroso, amino, imino, nitrilo, nitrile groups containing compounds or their derivatives or thio urea
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3942—Inorganic per-compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/22—Electronic devices, e.g. PCBs or semiconductors
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Cleaning Or Drying Semiconductors (AREA)
Abstract
The invention discloses a kind of cleaning agent, its preparation method and application.The preparation method of the cleaning agent of the present invention, it comprises the following steps, following raw materials are mixed, you can；Described raw material includes the component of following masses fraction：0.5% 20% agent containing iodine oxidation, 0.5% 20% boracic etchant, 1% 50% pyrrolidinone compounds solvent, 1% 20% corrosion inhibitor, the surfactant and water of 0.01% 5% not metal ion, each component mass fraction sum is 100%；The pH value of the cleaning agent is 7.5 13.5；Described corrosion inhibitor is the one or more in benzotriazole corrosion inhibitor, hydrazone class corrosion inhibitor, carbazones class corrosion inhibitor and thiocarbohydrazone class corrosion inhibitor.In application in semiconductor chip of the cleaning agent made from the preparation method of the present invention after etching ashing, cleaning quality and effect are good.
Description
Technical field
The present invention relates to a kind of cleaning agent, its preparation method and application.
Background technology
During the dual-inlaid processing of integrated circuit, photoetching process is used to pattern being imaged on device wafer.Photoetching skill
Art includes coating, exposed and developed step.Then covered with positivity or negative photoresist coating substance chip and with mask, it is described
Mask limits pattern that is to be held or removing in subsequent technique.After mask is suitably placed, mask is by a branch of monochromatic spoke
Penetrate, such as ultraviolet (UV) light or deep UV (DUV) light (≈ 250nm or 193nm) are directed through mask, so that the photoetching glue material of exposure
Material is more or less dissolved in the rinse solution of selection.Then removal or " development " soluble Other substrate materials, so as to leave
With mask identical pattern.
Then, gaseous plasma is etched for the pattern of the photoresist coating of development to be transferred to following layer, it can
With including hard mask (hardmask), interlayer dielectric and/or etching stopping layer.Residue after plasma etching generally deposits
In the structure of rear end wiring, if not removing may hinder subsequent silication or contact to be formed.After plasma etching ashing
Residue generally include the various residues such as hard mask residue, polymer residues, other particles.Clean these grades from
, it is necessary to which cleaning agent has higher selectivity, for example, can be to metal and low k dielectric when son etches the residue after ashing
The nitride of hard mask residue is expeditiously removed in the case of Effect of Materials is less.With the lasting contracting of equipment critical dimension
Small and corresponding requirements for high efficiency and reliable apparatus performance are, it is necessary to such improved Cleasing compositions.
Currently used for selectivity remove titaniferous, tungstenic, etching mask containing tantalum cleaning agent patent it is more, it is as shown in the table
Patent or patent application：
Although various cleaning selectivity are disclosed in these patents, for the clear of the hard mask component of this etching of tantalum nitride
Wash effect and remove selectivity, these patents are ineffective.The especially patent of EKC Science ＆ Tech Co., Ltd.
It is explicitly pointed out in CN105874568A claim and removes the alternative removal tantalum nitride of composition, but is not had in its specification
Have and provide the related etching experimental data of tantalum nitride.The present inventor is carried out real using the multiple formulations in its protection domain
Test, it is found that its composition and cleaning method remove titaniferous for selectivity and tungstenic etching mask effect is preferable, but for containing tantalum
Etching mask material (such as tantalum nitride) it is ineffective, tantalum nitride can not be removed effectively.This will have a strong impact on cleaning agent
Cleaning performance.
Therefore, need a kind of cleaning agent of exploitation badly, its can high selectivity move nitride etch mask, while and copper, cobalt,
Tantalum, tungsten, titanium and low-k materials are compatible and it is necessary to effectively remove ashing etch residue simultaneously.
The content of the invention
The technical problems to be solved by the invention be in order to overcome existing cleaning agent for the material of etching mask containing tantalum (such as
Tantalum nitride) ineffective, the defects of tantalum nitride can not be removed effectively, and provide a kind of cleaning agent, its preparation method
And application.Cleaning agent produced by the present invention can expeditiously move in the case of less on metal and low k dielectric influence
Except the nitride of hard mask residue, selectivity is good, has boundless market application foreground.
The present invention mainly solves above-mentioned technical problem by following technological means：
The invention provides a kind of cleaning agent, and it is made by following raw materials, and described raw material includes following masses fraction
Component：0.5%-20% agent containing iodine oxidation, 0.5%-20% boracic etchant, 1%-50% pyrrolidinone compounds solvent,
The surfactant and water of 1%-20% corrosion inhibitor, 0.01%-5% not metal ion, each component mass fraction
Sum is 100%；The pH value of the cleaning agent is 7.5-13.5；Described corrosion inhibitor is that benzotriazole corrosion suppresses
One or more in agent, hydrazone class corrosion inhibitor, carbazones class corrosion inhibitor and thiocarbohydrazone class corrosion inhibitor.
Wherein, the mass fraction of the agent containing iodine oxidation is preferably 1%-10%, more preferably 1.5%-5%.It is described
The mass fraction of boracic etchant be preferably 1%-10%, more preferably 1.5%-5%.Described pyrrolidinone compounds solvent
Mass fraction is preferably 5%-35%, more preferably 10%-30%.The mass fraction of described corrosion inhibitor is preferably 3%-
15%, more preferably 5%-10%.The mass fraction of described surfactant is preferably 0.1%-4%, more preferably
0.2%-3%.The pH value of the cleaning agent is preferably 8-12, more preferably 9-11.
Wherein, in described cleaning agent, the dosage that each component mass fraction sum is 100%, Gu Shui is preferably each to supply
Constituent mass fraction sum is 100% meter.
Wherein, the agent containing iodine oxidation is preferably one kind or more in acid iodide, iodate, periodic acid and periodates
Kind.Described iodate is preferably ammonium iodate and/or acid iodide tetramethylammonium.Described periodates be preferably periodic acid ammonium and/or
Periodic acid tetramethylammonium.
Wherein, described boracic etchant can be the conventional boracic etchant in this area, preferably tetrafluoro boric acid, tetrafluoro boron
Sour ammonium, tetrafluoro boric acid tetramethylammonium, tetrafluoro boric acid etamon, tetrafluoro boric acid tetrapropylammonium and one kind or more in tetrafluoro boric acid tetrabutylammonium
Kind.
Wherein, described pyrrolidinone compounds solvent is the conventional pyrrolidinone compounds solvent in this area, the hydrogen quilt preferably on N
Substituted pyrrolidinone compounds solvent.The substituted pyrrolidinone compounds solvent of hydrogen on described N be preferably 1-METHYLPYRROLIDONE,
One or more in N- ethyl pyrrolidones, N- cyclohexyl pyrrolidones and NHP.
Wherein, the benzotriazole corrosion inhibitor is preferably BTA, methyl benzotriazazole and 5- carboxylics
One or more in base BTA.The hydrazone class corrosion inhibitor is preferably acetophenone phenylhydrazone.The thiocarbohydrazone
Class corrosion inhibitor is preferably Diphenylthiocarbazone.
Wherein, the surfactant of described not metal ion is that the surface of the conventional not metal ion in this area is lived
Property agent, preferably polyvinylpyrrolidone and/or DBSA.
Described pH value can be adjusted according to the actual conditions of each component in cleaning agent and content.Such as usable organic acid,
One or more in inorganic acid, inorganic base, strong base-weak acid salt and cushioning liquid.If avoid the pH value of glue-dispenser that violent ripple occurs
Dynamic, the cushioning liquid that can be used this area conventional is adjusted.Described organic acid optimization citric acid.Described inorganic acid is preferred
Boric acid.The preferred tetramethylammonium hydroxide of described strong base-weak acid salt.
Wherein, the one or more (such as two kinds) in the preferred deionized water of the water, distilled water, pure water and ultra-pure water.
In a preferred embodiment of the invention, described cleaning agent, it is made by following raw materials, described raw material components
By 1%-10% agent containing iodine oxidation, 1%-10% boracic etchant, 5%-35% pyrrolidinone compounds solvent, 3%-15%
Corrosion inhibitor, 0.1%-4% not metal ion surfactant and water composition, each component mass fraction sum is
100%；The pH value of the cleaning agent is 8-12；Described corrosion inhibitor is benzotriazole corrosion inhibitor, the corruption of hydrazone class
One or more in corrosion inhibitor, carbazones class corrosion inhibitor and thiocarbohydrazone class corrosion inhibitor.
Present invention also offers a kind of preparation method of described cleaning agent, it comprises the following steps：By described raw material
Mixing, you can.Described mixing is preferably that the solid constituent in described raw material components is added in liquid component, and stirring is equal
It is even, you can.The temperature of described mixing is room temperature.After described mixing, vibration, the behaviour of filtering are preferably further comprised
Make.The purpose of vibration is that hunting speed and time are unlimited in order that each raw material components are sufficiently mixed.Filtering is insoluble in order to remove
Thing.
Present invention also offers the application in a kind of semiconductor chip of described cleaning agent after etching ashing.Institute
The semiconductor chip stated is preferably the semiconductor chip of copper-connection or aluminium interconnection structure.
Described application preferably includes the following steps：The semiconductor chip after being ashed and described etch cleaner will be etched
Contact.More preferably comprise the following steps：The semiconductor chip etched after being ashed is contacted with described etch cleaner, shaken
Swing, wash, drying.
Wherein, preferably 10 DEG C -90 DEG C of the temperature of described contact, preferably 20 DEG C -60 DEG C, such as 40-45 DEG C.Described connects
Tactile operation will preferably etch the semiconductor chip after being ashed and immerse in described cleaning fluid.Described vibration is preferably shaken in constant temperature
Swing in device and vibrate.Preferably 10 DEG C -90 DEG C, preferably 20 DEG C -60 DEG C, such as 40-45 DEG C of the temperature of described vibration.Described washing
It is preferred that washed with water (such as one or more in deionized water, distilled water, pure water and ultra-pure water).The method of described drying
It is preferred that dried up with high-purity nitrogen.
Room temperature refers to 10-30 DEG C in the present invention.
It on the basis of common sense in the field is met, above-mentioned each optimum condition, can be combined, it is each preferably real to produce the present invention
Example.
Agents useful for same and raw material of the present invention are commercially available.
The positive effect of the present invention is：Cleaning agent made from the preparation method of the present invention can be to metal and low
Nitride is expeditiously removed in the case of k dielectric Effect of Materials is less, selectivity is good, and cleaning effect is good, has boundless
Market application foreground, solve problem for microelectronics, the development for promoting China's microelectronic industry has been served it is positive,
Also there is higher economic benefit.
Embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to described reality
Apply among a scope.The experimental method of unreceipted actual conditions in the following example, conventionally and condition, or according to business
Product specification selects.
In following embodiments and comparative example, the preparation method of cleaning agent comprises the following steps：Corresponding raw material is mixed, i.e.,
Can.
In following embodiments, concrete operations temperature is not limited, is each meant and is carried out at ambient temperature.
Embodiment 1-10
Each raw material components of the cleaning agent of table 1
The mass fraction and cleaning agent pH value of 2 each raw material components of table
Comparative example 1-33
Each raw material components of the cleaning agent of table 3
The mass fraction and cleaning agent pH value of 4 each raw material components of table
Wherein, the dosage upper limit of each component is explored in comparative example 1-2；Explored in comparative example 3-8 and do not add oxygen containing iodine
The effect of agent；The effect for not adding boracic etchant is explored in comparative example 9-14；Comparative example 15-21, which explores to use, contains iodine
The effect of other oxidants outside oxidant；Comparative example 22-27 is explored using other etchants outside boracic etchant
Effect；Comparative example 28-29 explores the effect using other classification organic solvents outside pyrrolidinone compounds solvent；Comparative example
30-31 explores the effect using other corrosion inhibitors outside corrosion inhibitor in the present composition；Comparative example 32-33
Explore the effect of the surfactant using metal ion.
Effect example
Testing procedure：
By various chips, (it respectively has with the various nitride, metal, the dielectric material that are deposited on silicon chip
Layer thickness) be immersed at 50 DEG C in cleaning agent 15 minutes, and the wafer thickness before and after impregnation is determined, wherein making
With Four Dimensions Four Point Probe Meter 333A measure TiN, TaN, WN, Cu, Co, Ta, Ti and W
Thickness, TEOS is measured using derived from HORIBA JOBIN YVON Auto SE Spectroscopic Ellipsometer
Thickness.Etch-rate is calculated as thickness change (before and after chemical treatment) divided by chemical process time.Chemical solution pH makes
Counted with Beckman 260pH/Temp/mV to measure.And the copper for cleaning each cleaning fluid after plasma etching ashing at 50 DEG C
Chip is interconnected, residue removes effect and evaluated by SEM results (Hitachi S-5500).
Every test result is shown in Table 5.
Etch-rate (at 50 DEG C), unit：
Table 5
Cleaning situation
From above-mentioned contrast effect example 1-33 with implementation result example 1-10 it can also be seen that the cleaning agent of the present invention compares contrast
The cleaning agent of example, either etching selectivity, or cleaning performance, there is lifting.
Claims (10)
1. a kind of preparation method of cleaning agent, it is characterised in that it comprises the following steps：Following raw materials are mixed, you can；It is described
Raw material include the component of following masses fraction：0.5%-20% agent containing iodine oxidation, 0.5%-20% boracic etchant,
1%-50% pyrrolidinone compounds solvent, 1%-20% corrosion inhibitor, 0.01%-5% not metal ion surface
Activating agent and water, each component mass fraction sum are 100%；The pH value of the cleaning agent is 7.5-13.5；Described corrosion suppression
Preparation is benzotriazole corrosion inhibitor, hydrazone class corrosion inhibitor, carbazones class corrosion inhibitor and thiocarbohydrazone class
One or more in corrosion inhibitor.
2. the preparation method of cleaning agent as claimed in claim 1, it is characterised in that
The mass fraction of the described agent containing iodine oxidation is 1%-10%；
And/or the mass fraction of described boracic etchant is 1%-10%；
And/or the mass fraction of described pyrrolidinone compounds solvent is 5%-35%；
And/or the mass fraction of described corrosion inhibitor is 3%-15%；
And/or the mass fraction of described surfactant is 0.1%-4%；
And/or the pH value of the cleaning agent is 8-12.
3. the preparation method of cleaning agent as claimed in claim 2, it is characterised in that
The mass fraction of the described agent containing iodine oxidation is 1.5%-5%；
And/or the mass fraction of described boracic etchant is 1.5%-5%；
And/or the mass fraction of described pyrrolidinone compounds solvent is 10%-30%；
And/or the mass fraction of described corrosion inhibitor is 5%-10%；
And/or the mass fraction of described surfactant is 0.2%-3%；
And/or the pH value of the cleaning agent is 9-11.
4. the preparation method of cleaning agent as claimed in claim 1, it is characterised in that
The benzotriazole corrosion inhibitor is in BTA, methyl benzotriazazole and 5- carboxy benzotriazoles
One or more；
And/or the hydrazone class corrosion inhibitor is acetophenone phenylhydrazone；
And/or the thiocarbohydrazone class corrosion inhibitor is Diphenylthiocarbazone.
5. the preparation method of cleaning agent as claimed in claim 1, it is characterised in that described agent containing iodine oxidation is acid iodide, iodine
One or more in hydrochlorate, periodic acid and periodates.
6. the preparation method of cleaning agent as claimed in claim 5, it is characterised in that
Described iodate is ammonium iodate and/or acid iodide tetramethylammonium；
And/or described periodates is periodic acid ammonium and/or periodic acid tetramethylammonium.
7. the preparation method of cleaning agent as claimed in claim 1, it is characterised in that described boracic etchant is tetrafluoro boron
In acid, ammonium tetrafluoroborate, tetrafluoro boric acid tetramethylammonium, tetrafluoro boric acid etamon, tetrafluoro boric acid tetrapropylammonium and tetrafluoro boric acid tetrabutylammonium
One or more；
And/or the surfactant of described not metal ion is polyvinylpyrrolidone and/or DBSA.
8. the preparation method of cleaning agent as claimed in claim 1, it is characterised in that described pyrrolidinone compounds solvent is on N
The substituted pyrrolidinone compounds solvent of hydrogen.
9. the preparation method of cleaning agent as claimed in claim 8, it is characterised in that the pyrroles that the hydrogen on described N is substituted
Alkane ketones solvent is 1-METHYLPYRROLIDONE, N- ethyl pyrrolidones, N- cyclohexyl pyrrolidones and NHP
In one or more.
10. the preparation method of the cleaning agent as described in claim any one of 1-9, it is characterised in that described cleaning agent, its by
Following raw materials are made, and described raw material components are by 1%-10% agent containing iodine oxidation, 1%-10% boracic etchant, 5%-
35% pyrrolidinone compounds solvent, 3%-15% corrosion inhibitor, 0.1%-4% not metal ion surfactant
Formed with water, each component mass fraction sum is 100%；The pH value of the cleaning agent is 8-12.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109207287A (en) * | 2018-05-22 | 2019-01-15 | 深圳市伯斯特科技有限公司 | Chip cutting cleaning solution and the cleaning solution manufacture craft |
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| CN101366107A (en) * | 2005-10-05 | 2009-02-11 | 高级技术材料公司 | Oxidizing aqueous cleaner for the removal of post-etch residues |
| WO2009101588A2 (en) * | 2008-02-11 | 2009-08-20 | Ecolab Inc. | Use of activator complexes to enhance lower temperature cleaning in alkaline peroxide cleaning systems |
| WO2012051380A2 (en) * | 2010-10-13 | 2012-04-19 | Advanced Technology Materials, Inc. | Composition for and method of suppressing titanium nitride corrosion |
| CN106010826A (en) * | 2015-03-31 | 2016-10-12 | 气体产品与化学公司 | Selectively Removing Titanium Nitride Hard Mask and Etch Residue Removal |
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2017
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101366107A (en) * | 2005-10-05 | 2009-02-11 | 高级技术材料公司 | Oxidizing aqueous cleaner for the removal of post-etch residues |
| WO2009101588A2 (en) * | 2008-02-11 | 2009-08-20 | Ecolab Inc. | Use of activator complexes to enhance lower temperature cleaning in alkaline peroxide cleaning systems |
| WO2012051380A2 (en) * | 2010-10-13 | 2012-04-19 | Advanced Technology Materials, Inc. | Composition for and method of suppressing titanium nitride corrosion |
| CN106010826A (en) * | 2015-03-31 | 2016-10-12 | 气体产品与化学公司 | Selectively Removing Titanium Nitride Hard Mask and Etch Residue Removal |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109207287A (en) * | 2018-05-22 | 2019-01-15 | 深圳市伯斯特科技有限公司 | Chip cutting cleaning solution and the cleaning solution manufacture craft |
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