CN101529559B - A cleaning method for use in post etch and ashing a semiconductor wafer - Google Patents
A cleaning method for use in post etch and ashing a semiconductor wafer Download PDFInfo
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- CN101529559B CN101529559B CN200780037535.4A CN200780037535A CN101529559B CN 101529559 B CN101529559 B CN 101529559B CN 200780037535 A CN200780037535 A CN 200780037535A CN 101529559 B CN101529559 B CN 101529559B
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- 238000004140 cleaning Methods 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 47
- 238000004380 ashing Methods 0.000 title claims abstract description 31
- 239000004065 semiconductor Substances 0.000 title abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 82
- 239000002184 metal Substances 0.000 claims abstract description 82
- 239000007788 liquid Substances 0.000 claims abstract description 68
- 238000005260 corrosion Methods 0.000 claims abstract description 31
- 230000007797 corrosion Effects 0.000 claims abstract description 31
- 239000003112 inhibitor Substances 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 64
- 238000005530 etching Methods 0.000 claims description 45
- 239000012530 fluid Substances 0.000 claims description 38
- 239000008367 deionised water Substances 0.000 claims description 34
- 229910052757 nitrogen Inorganic materials 0.000 claims description 32
- 239000013078 crystal Substances 0.000 claims description 30
- 239000004020 conductor Substances 0.000 claims description 29
- 239000002002 slurry Substances 0.000 claims description 15
- 229920002125 Sokalan® Polymers 0.000 claims description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 14
- 239000004584 polyacrylic acid Substances 0.000 claims description 13
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 10
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 10
- 239000011976 maleic acid Substances 0.000 claims description 10
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000007921 spray Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 229920001519 homopolymer Polymers 0.000 claims description 6
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 4
- 229920006243 acrylic copolymer Polymers 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 239000002738 chelating agent Substances 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- -1 halogen ions Chemical class 0.000 abstract description 14
- 229910052736 halogen Inorganic materials 0.000 abstract description 5
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 230000001681 protective effect Effects 0.000 abstract description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052794 bromium Inorganic materials 0.000 abstract description 2
- 229920002120 photoresistant polymer Polymers 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract 1
- 229920005646 polycarboxylate Polymers 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 33
- 229910021641 deionized water Inorganic materials 0.000 description 31
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 27
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 24
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 12
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 12
- 239000005695 Ammonium acetate Substances 0.000 description 12
- 229940043376 ammonium acetate Drugs 0.000 description 12
- 235000019257 ammonium acetate Nutrition 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 238000001020 plasma etching Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 239000001177 diphosphate Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 150000003009 phosphonic acids Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- NLVWBYNKMPGKRG-ODZAUARKSA-N azane;(z)-but-2-enedioic acid Chemical compound N.OC(=O)\C=C/C(O)=O NLVWBYNKMPGKRG-ODZAUARKSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
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- 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
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
- H01L21/02071—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers the processing being a delineation, e.g. RIE, of conductive layers
-
- 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
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0073—Anticorrosion compositions
-
- 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
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
- H01L21/02074—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers the processing being a planarization of conductive layers
-
- C11D2111/22—
Abstract
The present invention provides a cleaning method for use in post etch and ashing a semiconductor wafer. The method comprises the following steps: after treating the wafer with photoresist cleaning solution, clean the wafer with a metal protective liquid containing water-solubility metal corrosion inhibitor, and dry it. The water-solubility metal corrosion inhibitor may be a polycarboxylate metal corrosion inhibitor. By employing the metal protective liquid, the method prevents metal corrosion from halogen ions, oxygen ions, bromine ions, OH- ions, H ions etc. generated from the plasma etch process and the atmosphere.
Description
Technical field
The present invention relates to semiconductor wafer manufacturing technique, be specifically related to the cleaning method after a kind of conductor crystal round etching ashing.
Technical background
In common semiconductor fabrication process, by form the mask of photoresist at metal level, form the pattern of conductive metal layer after the exposure with plasma etching.Because in the metal level plasma etching, use a lot of Halogen gas, activated plasma comes the etching metal.On wafer, the material that much contains the halogen family element is particularly arranged in the etch residue, these halogen elements, particularly chloride material with process that water contacts in, can cause serious corrosion to metal.OH-ion independent in the higher water of pH also can corroding metal.Removing in the process of residue behind the metal etch with chemical cleaning solution, corrosion of metals is a very general and very serious problem, can cause the decline of wafer yield.
Therefore, the corrosion of metals problem in the cleaning process is extremely urgent after the ashing of solution conductor crystal round etching.But existing technology all exists defective separately, fundamentally head it off.Utilize first the chemical cleaning solution that contains amine to remove to remove the residue that plasma etching produces on the wafer such as: patent documentation US5175124, then come chemical residual liquid on the cleaning wafer with the deionized water that adds CO2, thus the generation of corroding on the minimizing metal level; Patent documentation US522637 passes into CO2 in the deionized water of overflow (Over Flow) device, clean the wafer at least 5 minutes that contains chemical cleaning solution, reaches the purpose that reduces corrosion of metals.The main policies of these two patents is to pass into CO2 in deionized water, makes the deionized water acidity that dies down, and reduces hydroxide ion to corrosion of metal.But the adding speed of CO2 is difficult to effective control, and can not reduce like this chloride ion to corrosion of metal, and the corrosion of chloride ion is only the main cause of semiconductor alloy corrosion.And for example: patent documentation JP618191 is by adding the cleaning of a step organic solvent before washing, reduces on the wafer chlorine element and other can cause the content of the material of corrosion of metals, and then reduces corrosion of metal.But organic solvent has increased cost and has brought environment. problem, can not fundamentally remove the etch residue that contains halogen element.For another example: patent documentation US5533635 is full of the interior 5-60 of the cavity second of carbon tetrafluoride and oxygen by wafer being put into a temperature at 150-250 ℃, and the etch residue of chloride element is changed into stable chlorine-containing polymer, prevents corrosion of metals.Be difficult to so all chlorine is all changed into stable form, invalid to the concentration that reduces hydroxide ion, also reduced the equipment throughput of board, and complicated operation, be difficult to carry out.For another example: patent documentation CN1466173A utilizes the fast prompt drop liquid of heat of at least one circulation to embathe the content that (QDR) reduces chlorine on the wafer after removing etch residue with the chemical cleaning solution of alkalescence, reduces corrosion of metal.Wherein the temperature of deionized water is at 70-80 ℃.Although along with the rising of temperature can strengthen the cleaning performance of chemical cleaning solution, reduced the solubility of CO2, be unfavorable for the reduction of pH value, can not effectively reduce the corrosion of chlorine element, and complicated operation, be difficult to carry out.
Brief summary of the invention
The objective of the invention is fundamentally to solve the corrosion of metals problem in the cleaning process after the conductor crystal round etching ashing, a kind of cleaning method that operates after simple and easy and the significant conductor crystal round etching ashing of effect is provided.
Above-mentioned purpose of the present invention realizes by following technical proposal: after etch residue on the usefulness photoresistance cleaning fluid removal wafer, with the metal protection liquid cleaning wafer that contains the water-soluble metal corrosion inhibiter, afterwards drying gets final product.
In example of the present invention, what described water-soluble metal corrosion inhibiter was better is the polycarboxylic acid metal inhibitor.Described polycarboxylic acid metal inhibitor is carboxylic homopolymers and/or copolymer.In preferred embodiment of the present invention, described carboxylic homopolymers and/or copolymer are selected from one or more in following: ammonium salt, sylvite and the sodium salt of HPMA (HPMA), polyacrylic acid (PAA), polymethylacrylic acid, acrylic acid and maleic acid, styrene and acrylic copolymer, styrene and maleic acid, acrylonitrile and maleic acid and above-mentioned polymer.That described carboxylic homopolymers and/or the weight percent of copolymer in metal protection liquid are better is 0.001-10%.
In example of the present invention, described metal protection liquid also can comprise in addition: other corrosion inhibitors, surfactant and/or chelating agent.
In the example of the present invention, described metal protection liquid treatment step preferred nitrogen bubbling or spray cleaning way, what the time was better is 0.1 to 15 minute.
In the present invention, described photoresistance cleaning fluid is the general designation of a class common agents well known in the art, generally comprises amine, azanol class or semi-aqueous cleaning fluid.In example of the present invention, better is semi-aqueous cleaning fluid.Described photoresistance cleaning fluid treatment step preferably adopts low-temperature operation photoresistance cleaning fluid, and temperature is better is room temperature to 40 ℃, and what the time was better is 0.5-30 minute.
In the example of the present invention, behind the metal protection liquid cleaning wafer, can add in addition a step: wafer is cleaned with deionized water.The fast prompt drop liquid of employing or spray mode that the mode of its cleaning is better, what the time was better is 0.1 to 15 minute.
In the example of the present invention, what drying step was better carries out under nitrogen, and that rotating speed is better is 500～6000RPM, and that better is 500～3000RPM, and that best is 1000～2000RPM, and what the time was better is 0.1～10 minute.
Nitrogen bubble cleans, spray cleans and fast prompt drop liquid cleaning way is techniques well known.Fast prompt drop liquid cleans (Quick Dump Rinse, QDR) refer to: after wafer is put into rinse bath, cleaning fluid is gushed out by the bottom or simultaneously by the nozzle ejection on top, be full of whole rinse bath Deng cleaning fluid, the overflow fixed time, open the door of bottom of rinse bath, fast solution is drained, then repeat above action several times, finish the task of whole cleaning.
Positive progressive effect of the present invention is: the metal protection liquid in the cleaning process can reduce the anionic ion content such as crystal column surface chlorine, bromine; the thick metal protective film of which floor molecule that forms in the metal surface simultaneously; can stop chloride ion; oxygen; hydroxide ion is to the attack of metal, thereby greatly reduced corrosion of metal.The method is easy and simple to handle, and effect is remarkable, has solved the technical barrier that prior art is difficult to fundamentally solve because of separately defective.Its effect will further specify by the contrast experiment among the embodiment.
Summary of the invention
Mode below by embodiment further specifies the present invention, does not therefore limit the present invention among the described scope of embodiments.
The percentage composition of each material all is weight percentage in the following example.
The method that adopts metal protection liquid to clean after [embodiment 1] conductor crystal round etching ashing
Concrete steps:
1. at room temperature clean wafer 0.5 minute after the plasma electrically slurry etching with the photoresistance cleaning fluid.This photoresistance cleaning fluid is: 74% methyl pyrrolidone (NMP), 1.20% ammonium fluoride, 2.6% ammonium acetate, 2% acetic acid and 20.2% deionized water.
2. with metal protection liquid the wafer spray was cleaned 0.1 minute.This metal protection liquid is the aqueous solution of 10% ammonium polyacrylate.
3. with deionized water wafer being carried out 0.1 minute spray process cleans.
4. carry out High Rotation Speed under the nitrogen and dry, rotating speed is 6000RPM, and the time is 0.1 minute.
The method that adopts metal protection liquid to clean after [embodiment 2] conductor crystal round etching ashing
Concrete steps:
1. use the wafer of photoresistance cleaning fluid after 20 ℃ of lower cleaning plasma electricallies slurry etchings 5 minutes.This photoresistance cleaning fluid is: 74% methyl pyrrolidone (NMP), 1.20% ammonium fluoride, 2.6% ammonium acetate, 2% acetic acid and 20.2% deionized water.
2. with metal protection liquid the wafer nitrogen bubble was cleaned 2 minutes.This metal protection liquid is: the aqueous solution of 0.001% HPMA.
3. with deionized water wafer being carried out 2 minutes fast prompt drop liquid cleans.
4. carry out High Rotation Speed under the nitrogen and dry, rotating speed is 3000RPM, and the time is 4 minutes.
The method that adopts metal protection liquid to clean after [embodiment 3] conductor crystal round etching ashing
Concrete steps:
1. use the wafer of photoresistance cleaning fluid after 25 ℃ of lower cleaning plasma electricallies slurry etchings 10 minutes.This photoresistance cleaning fluid is: 74% methyl pyrrolidone (NMP), 1.20% ammonium fluoride, 2.6% ammonium acetate, 2% acetic acid and 20.2% deionized water.
2. with metal protection liquid the wafer nitrogen bubble was cleaned 5 minutes.This metal protection liquid is: the aqueous solution that contains 1% polymethylacrylic acid.
3. with deionized water wafer being carried out 5 minutes fast prompt drop liquid cleans.
4. carry out High Rotation Speed under the nitrogen and dry, rotating speed is 2000RPM, and the time is 5 minutes.
The method that adopts metal protection liquid to clean after [embodiment 4] conductor crystal round etching ashing
Concrete steps:
1. use the wafer of photoresistance cleaning fluid after 30 ℃ of lower cleaning plasma electricallies slurry etchings 15 minutes.This photoresistance cleaning fluid is: 60% methyl pyrrolidone (NMP), 1.20% ammonium fluoride, 7.8% ammonium acetate, 1.6% acetic acid, 1.1% ethylene glycol, 0.3% polyacrylic acid (molecular weight 600) and 28% deionized water.
2. with metal protection liquid the wafer nitrogen bubble was cleaned 8 minutes.This metal protection liquid is: 0.5% styrene and acrylic copolymer and 0.3% phosphonic acids butane, 1,2, the 4 tricarboxylic aqueous solution.
3. deionized water carries out fast prompt drop liquid cleaning in 8 minutes to wafer.
4. carry out High Rotation Speed under the nitrogen and dry, rotating speed is 1000RPM, and the time is 8 minutes.
The method that adopts metal protection liquid to clean after [embodiment 5] conductor crystal round etching ashing
Concrete steps:
1. use the wafer of photoresistance cleaning fluid after 35 ℃ of lower cleaning plasma electricallies slurry etchings 20 minutes.This photoresistance cleaning fluid is: 60% methyl pyrrolidone (NMP), 1.20% ammonium fluoride, 7.8% ammonium acetate, 1.6% acetic acid, 1.1% ethylene glycol, 0.3% polyacrylic acid (molecular weight 600) and 28% deionized water.
2. with metal protection liquid the wafer nitrogen bubble was cleaned 10 minutes.This metal protection liquid is: the aqueous solution of 2% acrylic acid and maleic acid and 0.5% dodecyl sodium sulfate.
3. with deionized water wafer being carried out 10 minutes fast prompt drop liquid cleans.
4. carry out High Rotation Speed under the nitrogen and dry, rotating speed is 500RPM, and the time is 10 minutes.
The method that adopts metal protection liquid to clean after [embodiment 6] conductor crystal round etching ashing
Concrete steps:
1. use the wafer of photoresistance cleaning fluid after 40 ℃ of lower cleaning plasma electricallies slurry etchings 25 minutes.This photoresistance cleaning fluid is: 60% methyl pyrrolidone (NMP), 1.20% ammonium fluoride, 7.8% ammonium acetate, 1.6% acetic acid, 1.1% ethylene glycol, 0.3% polyacrylic acid (molecular weight 600) and 28% deionized water.
2. with metal protection liquid the wafer nitrogen bubble was cleaned 12 minutes.This metal protection liquid is: the aqueous solution of 5% styrene and maleic acid and 0.8% hydroxy ethylidene-diphosphate.
3. with deionized water wafer being carried out 12 minutes fast prompt drop liquid cleans.
4. carry out High Rotation Speed under the nitrogen and dry, rotating speed is 1500RPM, and the time is 6 minutes.
The method that adopts metal protection liquid to clean after [embodiment 7] conductor crystal round etching ashing
Concrete steps:
1. use the wafer of photoresistance cleaning fluid after 25 ℃ of lower cleaning plasma electricallies slurry etchings 30 minutes.This photoresistance cleaning fluid is: 60% methyl pyrrolidone (NMP), 1.20% ammonium fluoride, 7.8% ammonium acetate, 1.6% acetic acid, 1.1% ethylene glycol, 0.3% polyacrylic acid (molecular weight 600) and 28% deionized water.
2. with metal protection liquid the wafer nitrogen bubble was cleaned 15 minutes.This metal protection liquid is: the aqueous solution of 5% acrylonitrile and maleic acid, 0.2% phosphonic acids butane, 1,2,4 tricarboxylic acids, 0.5% dodecyl sodium sulfate and 0.8% hydroxy ethylidene-diphosphate.
3. with deionized water wafer being carried out 15 minutes fast prompt drop liquid cleans.
4. carry out High Rotation Speed under the nitrogen and dry, rotating speed is 2000RPM, and the time is 7 minutes.
The method that adopts metal protection liquid to clean after [embodiment 8] conductor crystal round etching ashing
Concrete steps:
1. use the wafer of photoresistance cleaning fluid after 30 ℃ of lower cleaning plasma electricallies slurry etchings 20 minutes.This photoresistance cleaning fluid is: 60% methyl pyrrolidone (NMP), 1.20% ammonium fluoride, 7.8% ammonium acetate, 1.6% acetic acid, 1.1% ethylene glycol, 0.3% polyacrylic acid (molecular weight 600) and 28% deionized water.
2. with metal protection liquid the wafer nitrogen bubble was cleaned 5 minutes.This metal protection liquid is: the aqueous solution of 10% acrylic acid and maleic acid and 0.001% styrene and acrylic copolymer.
3. with deionized water wafer being carried out 6 minutes fast prompt drop liquid cleans.
4. High Rotation Speed dries, and rotating speed is 2000RPM, and the time is 6 minutes.
The method that adopts metal protection liquid to clean after [embodiment 9] conductor crystal round etching ashing
Concrete steps:
1. use the wafer of photoresistance cleaning fluid after 30 ℃ of lower cleaning plasma electricallies slurry etchings 20 minutes.This photoresistance cleaning fluid is: 60% methyl pyrrolidone (NMP), 1.20% ammonium fluoride, 7.8% ammonium acetate, 1.6% acetic acid, 1.1% ethylene glycol, 0.3% polyacrylic acid (molecular weight 600) and 28% deionized water.
2. with metal protection liquid the wafer nitrogen bubble was cleaned 5 minutes.This metal protection liquid is: the aqueous solution of 0.5% HPMA, 0.3% polyacrylic acid and 0.2% polymethylacrylic acid.
3. carry out High Rotation Speed under the nitrogen and dry, rotating speed is 2000RPM, and the time is 7 minutes.
The method that adopts metal protection liquid to clean after [embodiment 10] conductor crystal round etching ashing
Concrete steps:
1. use ACT-930 (commercial disignation: ACT-930 is purchased from U.S. Air product company), the wafer after 70 ℃ of lower cleaning plasma electricallies slurry etchings 30 minutes.This wafer is AlSiCu (aluminium copper silicon) metallic film.
2. with the organic solvent isopropyl alcohol wafer nitrogen bubble was cleaned 5 minutes.
3. with metal protection liquid the wafer nitrogen bubble was cleaned 5 minutes.This metal protection liquid is: 0.3% polyacrylic acid potassium, 0.5% Sodium Polyacrylate and 0.2% acrylonitrile and maleic acid ammonium aqueous copolymers solution.
4. with deionized water wafer being carried out 6 minutes fast prompt drop liquid cleans.
5. High Rotation Speed dries under the nitrogen, and rotating speed is 2000RPM, and the time is 10 minutes.
The method that adopts metal protection liquid to clean after [embodiment 11] conductor crystal round etching ashing
Concrete steps:
1. use the wafer of photoresistance cleaning fluid after 30 ℃ of lower cleaning plasma electricallies slurry etchings 20 minutes.This photoresistance cleaning fluid is: 60% methyl pyrrolidone (NMP), 1.20% ammonium fluoride, 7.8% ammonium acetate, 1.6% acetic acid, 1.1% ethylene glycol, 0.3% polyacrylic acid (molecular weight 600) and 28% deionized water.
2. with metal protection liquid the wafer nitrogen bubble was cleaned 5 minutes.This metal protection liquid is: the aqueous solution of 1% triethanolamine.
3. with deionized water wafer being carried out 6 minutes fast prompt drop liquid cleans.
4. carry out High Rotation Speed under the nitrogen and dry, rotating speed is 2000RPM, and the time is 10 minutes.
The method that adopts metal protection liquid to clean after [embodiment 12] conductor crystal round etching ashing
Concrete steps:
1. use the wafer of photoresistance cleaning fluid after 30 ℃ of lower cleaning plasma electricallies slurry etchings 20 minutes.This photoresistance cleaning fluid is: 60% methyl pyrrolidone (NMP), 1.20% ammonium fluoride, 7.8% ammonium acetate, 1.6% acetic acid, 1.1% ethylene glycol, 0.3% polyacrylic acid (molecular weight 600) and 28% deionized water.This wafer is AlSiCu (aluminium copper silicon) metallic film.
2. with metal protection liquid the wafer nitrogen bubble was cleaned 5 minutes.This metal protection liquid is: the aqueous solution of 0.5% polyacrylic acid (molecular weight 600).
3. with deionized water wafer being carried out 6 minutes fast prompt drop liquid cleans.
4. carry out High Rotation Speed under the nitrogen and dry, rotating speed is 2000RPM, and the time is 10 minutes.SEM photo through AlSiCu (aluminium copper silicon) metallic film after the above-mentioned steps processing is seen Fig. 1, and A, B are metallic film sidewall photo among the figure, and C, D are metallic film surface picture.Sidewall and surface all do not have poroid corrosion as seen from the figure.Projection on the sidewall is that the plasma etching by front step operation causes.
Do not carry out the method that solution cleans after [comparative example 1] conductor crystal round etching ashing
Concrete steps:
1. use the wafer of photoresistance cleaning fluid after 30 ℃ of lower cleaning plasma electricallies slurry etchings 20 minutes.This photoresistance cleaning fluid is: 60% methyl pyrrolidone (NMP), 1.20% ammonium fluoride, 7.8% ammonium acetate, 1.6% acetic acid, 1.1% ethylene glycol, 0.3% polyacrylic acid (molecular weight 600) and 28% deionized water.This wafer is AlSiCu (aluminium copper silicon) metallic film.
2. with deionized water wafer nitrogen being carried out 6 minutes fast prompt drop liquid cleans.
3. carry out High Rotation Speed under the nitrogen and dry, rotating speed is 2000RPM, and the time is 10 minutes.SEM photo through AlSiCu (aluminium copper silicon) metallic film after the above-mentioned steps processing is seen Fig. 2, and A, B are metallic film sidewall photo among the figure, and C, D are metallic film surface picture.Institute's collar region is the position of heavy corrosion among the figure.
The method that adopts organic solvent I PA to clean after [comparative example 2] conductor crystal round etching ashing
Concrete steps:
1. use ACT-930 (commercial disignation: ACT-930 is purchased from U.S. Air product company), the wafer after 70 ℃ of lower cleaning plasma electricallies slurry etchings 30 minutes.This wafer is AlSiCu (aluminium copper silicon) metallic film.
2. with the organic solvent isopropyl alcohol wafer nitrogen bubble was cleaned 5 minutes.
3. with deionized water wafer being carried out 6 minutes fast prompt drop liquid cleans.
4. carry out High Rotation Speed under the nitrogen and dry, rotating speed is 2000RPM, and the time is 10 minutes.Through above-mentioned
The SEM photo of the AlSiCu after the step process (aluminium copper silicon) metallic film is seen Fig. 3, and institute's collar region is slight poroid corrosion location among the figure.
Description of drawings
Fig. 1 is the SEM photo of AlSiCu (aluminium copper silicon) metallic film after processing according to embodiment 12 methods, and A, B are metallic film sidewall photo among the figure, and C, D are metallic film surface picture.As seen from the figure, sidewall and surface all do not have poroid corrosion.Projection on the sidewall is that the plasma etching by front step operation causes.
Fig. 2 is the SEM photo of AlSiCu (aluminium copper silicon) metallic film after processing according to comparative example 1 method, and A, B are metallic film sidewall photo among the figure, and C, D are metallic film surface picture.Institute's collar region is the position of heavy corrosion among the figure.
Fig. 3 is the SEM photo of AlSiCu (aluminium copper silicon) metallic film after processing according to comparative example 2 method, and institute's collar region is the position of slight poroid corrosion among the figure.
Claims (10)
1. the cleaning method after the conductor crystal round etching ashing is characterized in that: with the metal protection liquid that contains the water-soluble metal corrosion inhibiter, the wafer after the photoresistance cleaning fluid processed cleans, and dries afterwards;
Wherein: described water-soluble metal corrosion inhibiter is carboxylic homopolymers and/or copolymer, wherein, described carboxylic homopolymers and/or copolymer are selected from one or more in following: the ammonium salt of HPMA, polyacrylic acid, polymethylacrylic acid, acrylic acid and maleic acid, styrene and acrylic copolymer, styrene and maleic acid, acrylonitrile and maleic acid and above-mentioned polymer, sylvite and sodium salt; Wherein, described carboxylic homopolymers and/or the percentage by weight of copolymer in metal protection liquid are 0.001-10%;
Wherein, described metal protection liquid cleaning step adopts nitrogen bubble or spray mode to clean, and the time of described metal protection liquid cleaning step is 0.1 to 15 minute;
Wherein, described photoresistance cleaning fluid is semi-aqueous cleaning fluid, and described photoresistance cleaning fluid treatment step is, with low-temperature operation photoresistance cleaning fluid, and the wafer after cleaning plasma electrically slurry etching under the temperature of room temperature to 40 ℃;
Wherein, described drying step is carried out under nitrogen.
2. the cleaning method after the conductor crystal round etching ashing according to claim 1, it is characterized in that: described metal protection liquid also comprises other corrosion inhibitors, surfactant and/or chelating agent.
3. the cleaning method after the conductor crystal round etching ashing according to claim 1, it is characterized in that: the time of described photoresistance cleaning fluid treatment step is 0.5-30 minute.
4. the cleaning method after the conductor crystal round etching ashing according to claim 1 is characterized in that: after wafer process metal protection liquid cleans, use washed with de-ionized water again.
5. the cleaning method after the conductor crystal round etching ashing according to claim 4, it is characterized in that: described washed with de-ionized water step adopts fast prompt drop liquid or spray mode to clean.
6. the cleaning method after the conductor crystal round etching ashing according to claim 4, it is characterized in that: the time of described washed with de-ionized water step is 0.1 to 15 minute.
7. the cleaning method after the conductor crystal round etching ashing according to claim 1, it is characterized in that: described drying step rotating speed is 500～6000RPM.
8. the cleaning method after the conductor crystal round etching ashing according to claim 7, it is characterized in that: described drying step rotating speed is 500～3000RPM.
9. the cleaning method after the conductor crystal round etching ashing according to claim 8, it is characterized in that: described drying step rotating speed is 1000～2000RPM.
10. the cleaning method after the conductor crystal round etching ashing according to claim 1, it is characterized in that: the time of described drying step is 0.1～10 minute.
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| CN200780037535.4A CN101529559B (en) | 2006-10-13 | 2007-10-12 | A cleaning method for use in post etch and ashing a semiconductor wafer |
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| CN200610117137.0 | 2006-10-13 | ||
| CNA2006101171370A CN101162684A (en) | 2006-10-13 | 2006-10-13 | Cleaning method afterSemi-conductor crystal round etching ashing |
| CN200780037535.4A CN101529559B (en) | 2006-10-13 | 2007-10-12 | A cleaning method for use in post etch and ashing a semiconductor wafer |
| PCT/CN2007/002934 WO2008046304A1 (en) | 2006-10-13 | 2007-10-12 | A cleaning method for use in post etch and ashing a semiconductor wafer |
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| CN101529559A CN101529559A (en) | 2009-09-09 |
| CN101529559B true CN101529559B (en) | 2013-01-16 |
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| CN200780037535.4A Expired - Fee Related CN101529559B (en) | 2006-10-13 | 2007-10-12 | A cleaning method for use in post etch and ashing a semiconductor wafer |
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| CN101748409A (en) * | 2008-11-28 | 2010-06-23 | 安集微电子（上海）有限公司 | Semiconductor wafer metal base protection liquid and use method thereof |
| CN102399648B (en) * | 2010-09-10 | 2015-04-15 | 安集微电子（上海）有限公司 | Fluorine-containing cleaning solution |
| CN103208416B (en) * | 2013-04-03 | 2016-06-22 | 无锡华润上华半导体有限公司 | Clean and dry method after a kind of cavity structure etching |
| KR20160141249A (en) * | 2015-05-29 | 2016-12-08 | 세메스 주식회사 | Nozzle, Apparatus and method for treating a substrate with the same |
| WO2017063188A1 (en) * | 2015-10-16 | 2017-04-20 | Ecolab Usa Inc. | Maleic anhydride homopolymer and maleic acid homopolymer and the method for preparing the same, and non-phosphorus corrosion inhibitor and the use thereof |
| CN109545662A (en) * | 2018-11-21 | 2019-03-29 | 合肥新汇成微电子有限公司 | A kind of plasma-based cleaning in crystal round etching processing procedure |
| CN110508549B (en) * | 2019-08-12 | 2022-07-26 | 锦州神工半导体股份有限公司 | Cleaning method of monocrystalline silicon gasket with aluminum nitride film deposited on surface |
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| CN1326217A (en) * | 2001-06-13 | 2001-12-12 | 旺宏电子股份有限公司 | Method for washing semiconductor without corrosion to metal |
| CN1500130A (en) * | 2001-03-27 | 2004-05-26 | Aqueous cleaning compsn. contg. copper-specific corrosion inhibitor for cleaning inorganic residues on semiconductor substrate | |
| CN1527364A (en) * | 2003-04-29 | 2004-09-08 | ̨������·����ɷ�����˾ | Wafer cleaning method and apparatus |
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| KR100543457B1 (en) * | 2003-06-02 | 2006-01-23 | 삼성전자주식회사 | Cleaning agent with a corrosion inhibitor in a process of forming a semiconductor device |
| KR20050044085A (en) * | 2003-11-07 | 2005-05-12 | 삼성전자주식회사 | Aqueous cleaning solution for integrated circuit device and cleaning method using the cleaning solution |
| US20050205835A1 (en) * | 2004-03-19 | 2005-09-22 | Tamboli Dnyanesh C | Alkaline post-chemical mechanical planarization cleaning compositions |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1500130A (en) * | 2001-03-27 | 2004-05-26 | Aqueous cleaning compsn. contg. copper-specific corrosion inhibitor for cleaning inorganic residues on semiconductor substrate | |
| CN1326217A (en) * | 2001-06-13 | 2001-12-12 | 旺宏电子股份有限公司 | Method for washing semiconductor without corrosion to metal |
| CN1527364A (en) * | 2003-04-29 | 2004-09-08 | ̨������·����ɷ�����˾ | Wafer cleaning method and apparatus |
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| Publication number | Publication date |
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| CN101529559A (en) | 2009-09-09 |
| CN101162684A (en) | 2008-04-16 |
| WO2008046304A8 (en) | 2009-05-28 |
| WO2008046304A1 (en) | 2008-04-24 |
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