CN107229193B - A kind of cleaning agent, preparation method and application - Google Patents
A kind of cleaning agent, preparation method and application Download PDFInfo
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- CN107229193B CN107229193B CN201710612659.6A CN201710612659A CN107229193B CN 107229193 B CN107229193 B CN 107229193B CN 201710612659 A CN201710612659 A CN 201710612659A CN 107229193 B CN107229193 B CN 107229193B
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- Prior art keywords
- corrosion inhibitor
- mass fraction
- cleaning agent
- application
- semiconductor chip
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- 239000012459 cleaning agent Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 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
- 238000005530 etching Methods 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 150000004040 pyrrolidinones Chemical class 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 239000004065 semiconductor Substances 0.000 claims abstract description 15
- 238000004380 ashing Methods 0.000 claims abstract description 14
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000004140 cleaning Methods 0.000 claims abstract description 12
- 239000011630 iodine Substances 0.000 claims abstract description 12
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004094 surface-active agent Substances 0.000 claims abstract description 11
- 230000003647 oxidation Effects 0.000 claims abstract description 10
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 10
- 239000012964 benzotriazole Substances 0.000 claims abstract description 9
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 9
- 150000007857 hydrazones Chemical class 0.000 claims abstract description 6
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000010355 oscillation Effects 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
- 239000004327 boric acid Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 claims description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 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 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000001035 drying Methods 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
- WDQFELCEOPFLCZ-UHFFFAOYSA-N 1-(2-hydroxyethyl)pyrrolidin-2-one Chemical compound OCCN1CCCC1=O WDQFELCEOPFLCZ-UHFFFAOYSA-N 0.000 claims description 2
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 claims description 2
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-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
- IRCSOVSHHCMPLH-UHFFFAOYSA-N boric acid;tetrapropylazanium Chemical compound OB(O)O.CCC[N+](CCC)(CCC)CCC IRCSOVSHHCMPLH-UHFFFAOYSA-N 0.000 claims description 2
- 229940060296 dodecylbenzenesulfonic acid Drugs 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 compound O=C1CCCN1C1CCCCC1 PZYDAVFRVJXFHS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 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
- MOFINMJRLYEONQ-UHFFFAOYSA-N [N].C=1C=CNC=1 Chemical class [N].C=1C=CNC=1 MOFINMJRLYEONQ-UHFFFAOYSA-N 0.000 claims 1
- -1 ammonium tetrafluoroborate Chemical compound 0.000 claims 1
- 230000005764 inhibitory process Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 18
- 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
- 229910052715 tantalum Inorganic materials 0.000 description 5
- 150000004767 nitrides Chemical class 0.000 description 4
- 238000001020 plasma etching Methods 0.000 description 4
- 239000000243 solution Substances 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
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000001259 photo etching Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000007853 buffer solution 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
- 238000001914 filtration Methods 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
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- QGKPFZYVJCURLK-UHFFFAOYSA-N boric acid;tetramethylazanium Chemical compound OB(O)O.C[N+](C)(C)C QGKPFZYVJCURLK-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 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
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003989 dielectric material Substances 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
- 238000003384 imaging method Methods 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
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 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
- 239000012266 salt solution Substances 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
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
- G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Cleaning Or Drying Semiconductors (AREA)
- Detergent Compositions (AREA)
Abstract
The invention discloses a kind of cleaning agent, preparation method and applications.In application disclosed by the invention, the cleaning agent, it is made by following raw materials, the raw material includes the component of following mass fraction: the agent containing iodine oxidation of 0.5%-20%, the boracic etchant of 0.5%-20%, the pyrrolidinone compounds solvent of 1%-50%, the corrosion inhibitor of 1%-20%, 0.01%-5% not metal ion surfactant and water, the sum of each component mass fraction be 100%；The pH value of the cleaning agent is 7.5-13.5；The corrosion inhibitor is one of benzotriazole corrosion inhibitor, hydrazone class corrosion inhibitor, carbazones class corrosion inhibitor and thiocarbohydrazone class corrosion inhibitor or a variety of.For cleaning agent of the invention in the application in the semiconductor chip after etching ashing, cleaning quality and effect are good.
Description
Technical field
The present invention relates to a kind of cleaning agent, preparation method and applications.
Background technique
During the dual-inlaid processing of integrated circuit, photoetching process is used to pattern being imaged on device wafer.Photoetching skill
Art includes coating, exposure and imaging step.It is then covered with positivity or negative photoresist coating substance chip and with mask, it is described
Mask limits to be held or removal pattern in subsequent technique.After mask is suitably placed, mask is by a branch of monochromatic spoke
It penetrates, such as ultraviolet (UV) light or depth UV (DUV) light (≈ 250nm or 193nm) are directed through mask, so that the photoetching glue material of exposure
Material more or less dissolves in the rinse solution of selection.Then removal or " development " soluble Other substrate materials, to leave
Pattern identical with mask.
Then, it is used for gaseous plasma etching that the pattern of the photoresist coating of development to be transferred to following layer, it can
To include hard exposure mask (hardmask), interlayer dielectric and/or etching stopping layer.Residue after plasma etching usually deposits
In the structure of rear end wiring, if not removing may interfere subsequent silication or contact to be formed.After plasma etching ashing
Residue generally include the various residues such as hard exposure mask residue, polymer residues, other particles.Clean these it is equal from
When son etches the residue after ashing, cleaning agent selectivity with higher is needed, for example, can be to metal and low k dielectric
The nitride of hard exposure mask residue is expeditiously removed in the lesser situation of Effect of Materials.With the lasting contracting of equipment critical dimension
Corresponding requirements small and for high efficiency and reliable apparatus performance, need such improved cleaning compositions.
It is more that titaniferous, tungstenic, the cleaning agent patent of etching mask containing tantalum are removed currently used for selectivity, as shown in the table
Patent or patent application:
Although various cleaning selectivity are disclosed in these patents, for the clear of the hard exposure mask component of this etching of tantalum nitride
It washes effect and removes selectivity, these patents are ineffective.The especially patent of EKC Science & Tech Co., Ltd.
It is explicitly pointed out in the claim of CN105874568A and removes composition alternative removal tantalum nitride, but is not had in its specification
Provide the relevant etching experimental data of tantalum nitride.The present inventor is carried out real using the multiple formulations in its protection scope
It tests, 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 seriously affect cleaning agent
Cleaning effect.
Therefore, need to develop a kind of cleaning agent, can highly selective shifting nitride etch exposure 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.
Summary of the invention
The technical problem to be solved by the present invention is 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, preparation method
And application.For cleaning agent of the invention in the application of the semiconductor chip after etching ashing, cleaning quality and effect are good.
The present invention is mainly to solve above-mentioned technical problem by following technological means:
The present invention provides a kind of cleaning agents, are made by following raw materials, and the raw material includes following mass fraction
Component: the agent containing iodine oxidation of 0.5%-20%, the boracic etchant of 0.5%-20%, 1%-50% pyrrolidinone compounds solvent,
The surfactant and water of the corrosion inhibitor of 1%-20%, the not metal ion of 0.01%-5%, each component mass fraction
The sum of be 100%；The pH value of the cleaning agent is 7.5-13.5；The corrosion inhibitor is that benzotriazole corrosion inhibits
One of agent, hydrazone class corrosion inhibitor, carbazones class corrosion inhibitor and thiocarbohydrazone class corrosion inhibitor are a variety of.
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%.The pyrrolidinone compounds solvent
Mass fraction is preferably 5%-35%, more preferably 10%-30%.The mass fraction of the corrosion inhibitor is preferably 3%-
15%, more preferably 5%-10%.The mass fraction of the 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 the cleaning agent, the dosage that the sum of each component mass fraction is 100%, Gu Shui is preferably each to supply
The sum of constituent mass score is 100% meter.
Wherein, the agent containing iodine oxidation is preferably one of acid iodide, iodate, periodic acid and periodates or more
Kind.The iodate is preferably ammonium iodate and/or acid iodide tetramethylammonium.The periodates be preferably periodic acid ammonium and/or
Periodic acid tetramethylammonium.
Wherein, the boracic etchant can be the boracic etchant of this field routine, preferably tetrafluoro boric acid, tetrafluoro boron
One of sour ammonium, tetrafluoro boric acid tetramethylammonium, tetrafluoro boric acid etamon, tetrafluoro boric acid tetrapropylammonium and tetrafluoro boric acid tetrabutylammonium are more
Kind.
Wherein, the pyrrolidinone compounds solvent is the pyrrolidinone compounds solvent of this field routine, the hydrogen quilt on preferably N
Substituted pyrrolidinone compounds solvent.The substituted pyrrolidinone compounds solvent of hydrogen on the N be preferably N-Methyl pyrrolidone,
One of N- ethyl pyrrolidone, N- cyclohexyl pyrrolidone and n-hydroxyethyl pyrrolidone are a variety of.
Wherein, the benzotriazole corrosion inhibitor is preferably benzotriazole, methyl benzotriazazole and 5- carboxylic
One of base benzotriazole is a variety of.The hydrazone class corrosion inhibitor is preferably acetophenone phenylhydrazone.The thiocarbohydrazone
Class corrosion inhibitor is preferably Diphenylthiocarbazone.
Wherein, the surfactant of the not metal ion is that the surface of the not metal ion of this field routine is living
Property agent, preferably polyvinylpyrrolidone and/or dodecyl benzene sulfonic acid.
The pH value can be adjusted according to the actual conditions of each component in cleaning agent and content.Such as usable organic acid,
One of inorganic acid, inorganic base, strong base-weak acid salt and buffer solution are a variety of.If avoiding the pH value of glue-dispenser that violent wave occurs
It is dynamic, it the buffer solution of this field routine can be used to be adjusted.The organic acid optimization citric acid.The inorganic acid is preferred
Boric acid.The preferred tetramethylammonium hydroxide of the strong base-weak acid salt.
Wherein, one of the preferred deionized water of the water, distilled water, pure water and ultrapure water or a variety of (such as two kinds).
In a preferred embodiment of the invention, the cleaning agent is made by following raw materials, the raw material components
By the agent containing iodine oxidation of 1%-10%, the boracic etchant of 1%-10%, 5%-35% pyrrolidinone compounds solvent, 3%-15%
Corrosion inhibitor, 0.1%-4% not metal ion surfactant and water composition, the sum of each component mass fraction is
100%；The pH value of the cleaning agent is 8-12；The corrosion inhibitor is benzotriazole corrosion inhibitor, hydrazone class corruption
One of corrosion inhibitor, carbazones class corrosion inhibitor and thiocarbohydrazone class corrosion inhibitor are a variety of.
The present invention also provides the preparation methods of the cleaning agent described in one kind comprising the following steps: by the raw material
Mixing.Solid component in the raw material components is preferably added in liquid component by the mixing, and stirring is equal
It is even.The mixed temperature is room temperature.After the mixing, oscillation, the behaviour of filtering are preferably further comprised
Make.The purpose of oscillation is to be sufficiently mixed each raw material component, and hunting speed and time are unlimited.Filtering is insoluble in order to remove
Object.
The present invention also provides application of the cleaning agent described in one kind in the semiconductor chip after etching ashing.Institute
The semiconductor chip stated is preferably the semiconductor chip of copper-connection or aluminium interconnection structure.
The application preferably includes the following steps:, by the semiconductor chip and the etch cleaner after etching ashing
Agent contact.More preferably include the following steps: will etching ashing after semiconductor chip contacted with the etch cleaner,
Oscillation, washing, drying.
Wherein, preferably 10 DEG C -90 DEG C of the temperature of the contact, preferably 20 DEG C -60 DEG C, such as 40-45 DEG C.Described connects
The operation of touching preferably immerses the semiconductor chip after etching ashing in the cleaning solution.The oscillation is preferably shaken in constant temperature
It swings in device and vibrates.Preferably 10 DEG C -90 DEG C of the temperature of the oscillation, preferably 20 DEG C -60 DEG C, such as 40-45 DEG C.The washing
It is preferred that being washed with water (such as one of deionized water, distilled water, pure water and ultrapure water or a variety of).The method of the drying
It is preferred that being dried up with high-purity nitrogen.
Room temperature refers to 10-30 DEG C in the present invention.
On the basis of common knowledge of the art, above-mentioned each optimum condition, can any combination to get each preferable reality of the present invention
Example.
The reagents and materials used in the present invention are commercially available.
The positive effect of the present invention is that: the application of the semiconductor chip of the invention after etching ashing
In, cleaning quality and effect are good.Cleaning solution of the invention can influence height in lesser situation to metal and low k dielectric
Nitride is efficient removed, selectivity is good, has boundless market application prospect, solve problem for microelectronics,
It is positive to promoting the development of China's microelectronic industry to serve, it may have higher economic benefit.
Specific embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to the reality
It applies among a range.In the following examples, the experimental methods for specific conditions are not specified, according to conventional methods and conditions, or according to quotient
The selection of product specification.
In following embodiment and comparative examples, the preparation method of cleaning agent includes the following steps: to mix corresponding raw material, i.e.,
It can.
In following embodiments, concrete operations temperature is not limited, is each meant and is carried out at room temperature.
Embodiment 1-10
The each raw material component of 1 cleaning agent of table
The mass fraction and cleaning agent pH value of 2 each raw material component of table
Comparative example 1-33
The each raw material component of 3 cleaning agent of table
The mass fraction and cleaning agent pH value of 4 each raw material component of table
Wherein, the dosage upper limit of each component is explored in comparative example 1-2；It is explored in comparative example 3-8 and does 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 is explored using containing iodine
The effect of other oxidants except oxidant；Comparative example 22-27 is explored using other etchants except boracic etchant
Effect；Comparative example 28-29 explores the effect using other classification organic solvents except pyrrolidinone compounds solvent；Comparative example
30-31 explores the effect using other corrosion inhibitors except 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 has various nitride, metal, the dielectric material being deposited on silicon wafer, respectively has
Layer thickness) be immersed at 50 DEG C in cleaning agent 15 minutes, and the wafer thickness before and after impregnation is measured, wherein making
With Four Dimensions Four Point Probe Meter 333A measurement TiN, TaN, WN, Cu, Co, Ta, Ti and W
Thickness measures TEOS using the Auto SE Spectroscopic Ellipsometer derived from HORIBA JOBIN YVON
Thickness.Etch-rate is calculated as thickness change (before and after chemical treatment) divided by chemical process time.Chemical solution pH makes
It is counted with Beckman 260pH/Temp/mV to measure.And each cleaning agent is cleaned to the copper after plasma etching ashing at 50 DEG C
Chip is interconnected, residue removes effect and evaluated by SEM result (Hitachi S-5500).
Every test result is shown in Table 5.
Etch-rate (at 50 DEG C), unit:
Table 5
Clean situation
From above-mentioned contrast effect example 1-33 with implementation result example 1-10 it can also be seen that cleaning agent of the invention compares comparison
The cleaning agent of example, either etching selectivity or cleaning effect, there is promotion.
Claims (10)
1. a kind of application of cleaning agent in the semiconductor chip after etching ashing, which is characterized in that the cleaning agent
It is made by following raw materials, the raw material includes the component of following mass fraction: the agent containing iodine oxidation of 0.5%-20%, 0.5%-
20% boracic etchant, the pyrrolidinone compounds solvent of 1%-50%, the corrosion inhibitor of 1%-20%, 0.01%-5% are not
Surfactant, the He Shui of metal ion, the sum of each component mass fraction are 100%；The pH value of the cleaning agent is 7.5-
13.5；The corrosion inhibitor is benzotriazole corrosion inhibitor, hydrazone class corrosion inhibitor, the corrosion inhibition of carbazones class
One of agent and thiocarbohydrazone class corrosion inhibitor are a variety of；The agent containing iodine oxidation is acid iodide, iodate, periodic acid
With one of periodates or a variety of；The boracic etchant is tetrafluoro boric acid, ammonium tetrafluoroborate, tetrafluoro boric acid tetramethyl
One of ammonium, tetrafluoro boric acid etamon, tetrafluoro boric acid tetrapropylammonium and tetrafluoro boric acid tetrabutylammonium are a variety of.
2. application as described in claim 1, which is characterized in that
The mass fraction of the agent containing iodine oxidation is 1%-10%；
And/or the mass fraction of the boracic etchant is 1%-10%；
And/or the mass fraction of the pyrrolidinone compounds solvent is 5%-35%；
And/or the mass fraction of the corrosion inhibitor is 3%-15%；
And/or the mass fraction of the surfactant is 0.1%-4%；
And/or the pH value of the cleaning agent is 8-12.
3. application as claimed in claim 2, which is characterized in that
The mass fraction of the agent containing iodine oxidation is 1.5%-5%；
And/or the mass fraction of the boracic etchant is 1.5%-5%；
And/or the mass fraction of the pyrrolidinone compounds solvent is 10%-30%；
And/or the mass fraction of the corrosion inhibitor is 5%-10%；
And/or the mass fraction of the surfactant is 0.2%-3%；
And/or the pH value of the cleaning agent is 9-11.
4. application as described in claim 1, which is characterized in that
The pyrrolidinone compounds solvent is the substituted pyrrolidinone compounds solvent of hydrogen on N；
And/or the benzotriazole corrosion inhibitor is benzotriazole, methyl benzotriazazole and 5- carboxyl benzo three
One of nitrogen azoles is a variety of；
And/or the hydrazone class corrosion inhibitor is acetophenone phenylhydrazone；
And/or the thiocarbohydrazone class corrosion inhibitor is Diphenylthiocarbazone；
And/or the surfactant of the not metal ion is polyvinylpyrrolidone and/or dodecyl benzene sulfonic acid.
5. application as claimed in claim 4, which is characterized in that
And/or the iodate is ammonium iodate and/or acid iodide tetramethylammonium；
And/or the periodates is periodic acid ammonium and/or periodic acid tetramethylammonium；
And/or the substituted pyrrolidinone compounds solvent of hydrogen on the N be N-Methyl pyrrolidone, N- ethyl pyrrolidone,
One of N- cyclohexyl pyrrolidone and n-hydroxyethyl pyrrolidone are a variety of.
6. application as described in any one in claim 1-5, which is characterized in that the cleaning agent is made by following raw materials,
The raw material components by the agent containing iodine oxidation of 1%-10%, the boracic etchant of 1%-10%, 5%-35% pyrrolidones
The surfactant and water of the not metal ion of class solvent, the corrosion inhibitor of 3%-15%, 0.1%-4% form, each group
Dividing the sum of mass fraction is 100%；The pH value of the cleaning agent is 8-12.
7. application as described in claim 1, which is characterized in that the semiconductor chip is copper-connection or aluminium interconnection structure
Semiconductor chip；
And/or the application includes the following steps: with the cleaning solution to contact the semiconductor chip after etching ashing i.e.
It can.
8. the use as claimed in claim 7, which is characterized in that the application will include the following steps: after etching ashing
Semiconductor chip is contacted with the cleaning agent, is vibrated, washing, is dry.
9. application as claimed in claim 8, which is characterized in that
The temperature of the contact is 10 DEG C -90 DEG C；
And/or the operation of the contact is that will etch the semiconductor chip after being ashed to immerse in the cleaning solution；
And/or the oscillation is vibrated in constant temperature oscillator；
And/or the temperature of the oscillation is 10 DEG C -90 DEG C；
And/or the washing is to be washed with water；
And/or the method for the drying is to be dried up with high-purity nitrogen.
10. application as claimed in claim 9, which is characterized in that
The temperature of the contact is 20 DEG C -60 DEG C；
And/or the temperature of the oscillation is 20 DEG C -60 DEG C.
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