CN117925325A - High-adsorptivity semiconductor chip cleaning agent and preparation method and application thereof - Google Patents
High-adsorptivity semiconductor chip cleaning agent and preparation method and application thereof Download PDFInfo
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- CN117925325A CN117925325A CN202311821501.1A CN202311821501A CN117925325A CN 117925325 A CN117925325 A CN 117925325A CN 202311821501 A CN202311821501 A CN 202311821501A CN 117925325 A CN117925325 A CN 117925325A
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- 239000012459 cleaning agent Substances 0.000 title claims abstract description 67
- 239000004065 semiconductor Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 238000004140 cleaning Methods 0.000 claims abstract description 39
- 238000005260 corrosion Methods 0.000 claims abstract description 33
- 230000007797 corrosion Effects 0.000 claims abstract description 33
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 32
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 16
- 239000012498 ultrapure water Substances 0.000 claims abstract description 16
- 239000003223 protective agent Substances 0.000 claims abstract description 14
- 239000003112 inhibitor Substances 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 claims description 16
- FZAQROFXYZPAKI-UHFFFAOYSA-N anthracene-2-sulfonyl chloride Chemical compound C1=CC=CC2=CC3=CC(S(=O)(=O)Cl)=CC=C3C=C21 FZAQROFXYZPAKI-UHFFFAOYSA-N 0.000 claims description 15
- SQVRNKJHWKZAKO-UHFFFAOYSA-N beta-N-Acetyl-D-neuraminic acid Natural products CC(=O)NC1C(O)CC(O)(C(O)=O)OC1C(O)C(O)CO SQVRNKJHWKZAKO-UHFFFAOYSA-N 0.000 claims description 15
- SQVRNKJHWKZAKO-OQPLDHBCSA-N sialic acid Chemical compound CC(=O)N[C@@H]1[C@@H](O)C[C@@](O)(C(O)=O)OC1[C@H](O)[C@H](O)CO SQVRNKJHWKZAKO-OQPLDHBCSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 10
- 229930195725 Mannitol Natural products 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 239000000594 mannitol Substances 0.000 claims description 10
- 235000010355 mannitol Nutrition 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000005792 Geraniol Substances 0.000 claims description 8
- GLZPCOQZEFWAFX-YFHOEESVSA-N Geraniol Natural products CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 claims description 8
- 238000011010 flushing procedure Methods 0.000 claims description 8
- 229940113087 geraniol Drugs 0.000 claims description 8
- 229910001868 water Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 229940088594 vitamin Drugs 0.000 claims description 6
- 239000011782 vitamin Substances 0.000 claims description 6
- 229930003231 vitamin Natural products 0.000 claims description 6
- 235000013343 vitamin Nutrition 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- COBPKKZHLDDMTB-UHFFFAOYSA-N 2-[2-(2-butoxyethoxy)ethoxy]ethanol Chemical compound CCCCOCCOCCOCCO COBPKKZHLDDMTB-UHFFFAOYSA-N 0.000 claims description 4
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 150000001720 carbohydrates Chemical class 0.000 claims description 4
- OVBPIULPVIDEAO-LBPRGKRZSA-N folic acid Chemical compound C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)N[C@@H](CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-LBPRGKRZSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 3
- KIUKXJAPPMFGSW-DNGZLQJQSA-N (2S,3S,4S,5R,6R)-6-[(2S,3R,4R,5S,6R)-3-Acetamido-2-[(2S,3S,4R,5R,6R)-6-[(2R,3R,4R,5S,6R)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylic acid Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 KIUKXJAPPMFGSW-DNGZLQJQSA-N 0.000 claims description 2
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 2
- 229940018563 3-aminophenol Drugs 0.000 claims description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 2
- 239000004386 Erythritol Substances 0.000 claims description 2
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 claims description 2
- OVBPIULPVIDEAO-UHFFFAOYSA-N N-Pteroyl-L-glutaminsaeure Natural products C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)NC(CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-UHFFFAOYSA-N 0.000 claims description 2
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- 235000019414 erythritol Nutrition 0.000 claims description 2
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 claims description 2
- 229940009714 erythritol Drugs 0.000 claims description 2
- 229960000304 folic acid Drugs 0.000 claims description 2
- 235000019152 folic acid Nutrition 0.000 claims description 2
- 239000011724 folic acid Substances 0.000 claims description 2
- 229920002674 hyaluronan Polymers 0.000 claims description 2
- 229960003160 hyaluronic acid Drugs 0.000 claims description 2
- 239000000832 lactitol Substances 0.000 claims description 2
- 235000010448 lactitol Nutrition 0.000 claims description 2
- VQHSOMBJVWLPSR-JVCRWLNRSA-N lactitol Chemical compound OC[C@H](O)[C@@H](O)[C@@H]([C@H](O)CO)O[C@@H]1O[C@H](CO)[C@H](O)[C@H](O)[C@H]1O VQHSOMBJVWLPSR-JVCRWLNRSA-N 0.000 claims description 2
- 229960003451 lactitol Drugs 0.000 claims description 2
- 229960001855 mannitol Drugs 0.000 claims description 2
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 229940079877 pyrogallol Drugs 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- 229960002920 sorbitol Drugs 0.000 claims description 2
- 235000010356 sorbitol Nutrition 0.000 claims description 2
- 150000005846 sugar alcohols Chemical group 0.000 claims description 2
- 150000003722 vitamin derivatives Chemical class 0.000 claims description 2
- 239000000811 xylitol Substances 0.000 claims description 2
- 235000010447 xylitol Nutrition 0.000 claims description 2
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 2
- 229960002675 xylitol Drugs 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 15
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052751 metal Inorganic materials 0.000 abstract description 12
- 239000002184 metal Substances 0.000 abstract description 11
- 239000002131 composite material Substances 0.000 abstract description 9
- 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 abstract description 5
- 150000002739 metals Chemical class 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 12
- 230000002195 synergetic effect Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- -1 amine compounds Chemical class 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- 238000001312 dry etching Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 150000003384 small molecules Chemical class 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000003670 easy-to-clean Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 238000005935 nucleophilic addition reaction Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
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Abstract
The invention relates to a high-adsorptivity semiconductor chip cleaning agent which comprises the following components in parts by weight: 0.1-1 part of emulsifying agent; 3-5 parts of pH regulator; 0.1-1 part of corrosion inhibitor; 0.1-1 part of protective agent; 0.5-1 part of hydrofluoric acid; 0.5-2 parts of ammonium fluoride; 20-40 parts of organic solvent; 40-60 parts of ultrapure water; the invention also discloses a preparation method of the cleaning agent. The high-adsorptivity semiconductor chip cleaning agent adopts a composite emulsifier to form a new structure, and the structure forms intrasystem adsorption and becomes an efficient residue-containing capture carrier. The emulsifier has better corrosion resistance, effectively improves the cleaning capability of the cleaning agent on metals, has excellent corrosion resistance, and further improves the cleaning effect by adding the corrosion inhibitor and the protective agent.
Description
Technical Field
The invention belongs to the field of semiconductor manufacturing processes, and particularly relates to a high-adsorptivity semiconductor chip cleaning agent, a preparation method and application thereof.
Background
Aluminum processes require cleaning of post-etch residues, while cleaning agents are an important wet chemistry that is critical in the post-metal interconnect of integrated circuit fabrication. The cleaning agent is required to prevent the corrosion of the metal polar plate and achieve a good cleaning effect in the process.
Post-etch residue cleaner products currently used in integrated circuit fabrication typically include hydroxylamine, organic solvents, corrosion inhibitors, water, and the like. Hydroxylamine reacts with polymers containing metal, carbon, oxygen and other elements to break polymer molecular chains into small molecules, and then other amine compounds in the product react with some of the small molecules to form substances dissolved in the cleaning agent. Other small molecules containing metal elements are complexed with phenolic compounds, so that the small molecules are dissolved in the cleaning agent. The water in the system provides protons, which improves the reactivity of hydroxylamine. However, the cleaning agent of the system still cannot thoroughly clean the residues after etching in the aluminum process.
As the size of integrated circuit manufacturing technology is reduced, the cleaning requirements for photoresist films and ashed residues are becoming more stringent, and therefore cleaning agents are required to have higher wetting ability.
The dry etching cleaning agent generally reduces the surface tension of residues and the substrate after dry etching by adding a surfactant, but the bubble property of the dry etching cleaning agent can cause the dry etching cleaning agent to generate foam so that the substrate is not easy to clean thoroughly.
Therefore, not only is the balance of surface tension required to be improved, but also the peeling property of the residue is required to be improved, so that the peeling of the residue is more complete, rapid and thorough.
Disclosure of Invention
The invention solves the technical problems that: the cleaning agent can not effectively reduce the surface tension of the solution, has poor solution balance and corrosion resistance, has weak stripping performance on residues and has unsatisfactory cleaning effect.
In view of the technical problems in the prior art, the invention designs a high-adsorptivity semiconductor chip cleaning agent, and a preparation method and application thereof.
In order to solve the technical problems, the invention adopts the following scheme:
The high-adsorptivity semiconductor chip cleaning agent is characterized by comprising the following components in parts by weight:
Wherein the emulsifier is a mixture of vitamins and saccharides;
the vitamin is one or two of folic acid and beta-nicotinamide mononucleotide;
The saccharide is one or two of hyaluronic acid or sialic acid;
The protective agent is sugar alcohol.
Further, the emulsifier is a mixture of beta-nicotinamide mononucleotide and sialic acid.
Further, in the emulsifier, the mass ratio of the beta-nicotinamide mononucleotide to the sialic acid is 1:1-1:3.
Further, the corrosion inhibitor is one or more of geraniol, pyrogallol, pyridine and m-aminophenol;
The organic solvent is one or more of diethylene glycol butyl ether, ethylene glycol butyl ether and triethylene glycol butyl ether.
Further, the protective agent is one or more of sorbitol, xylitol, mannitol, lactitol and erythritol.
Further, the protective agent is mannitol;
the corrosion inhibitor is geraniol;
The organic solvent is triethylene glycol butyl ether;
the pH regulator is sulfuric acid or phosphoric acid.
Further, the pH regulator is phosphoric acid.
The invention also discloses a preparation method of the high-adsorptivity semiconductor chip cleaning agent, which is characterized by comprising the following steps of:
step 1: weighing each component in parts by mass respectively;
Step 2: adding all components except ultrapure water and an emulsifying agent into a container, and stirring until all materials are completely dissolved; and (3) adding 1/2 of the amount of the emulsifying agent and all the ultrapure water at the same time under stirring, continuing stirring, adding the rest 1/2 of the amount of the emulsifying agent after stirring for 3-5min, and stirring until the solution is clear and transparent, thus obtaining the high-adsorptivity semiconductor chip cleaning agent.
The invention also discloses a cleaning method of the high-adsorptivity semiconductor chip cleaning agent, which is characterized by comprising the following steps of:
Step 1: preparing the prepared high-adsorptivity semiconductor chip cleaning agent into an aqueous solution with the mass percent concentration of 10-30% by using ultrapure water;
step 2: soaking the semiconductor chip in the water solution prepared in the step 1 at 20-50 ℃ for 5-15min to obtain a soaked semiconductor chip;
Step 3: and (3) placing the soaked semiconductor chip into ultrapure water for washing at least twice, and then washing by using absolute ethyl alcohol and drying by using nitrogen gas to finish the washing of the semiconductor chip.
The invention also discloses application of the high-adsorptivity semiconductor chip cleaning agent in cleaning semiconductor chips.
In the invention, the selection of the emulsifier component takes the vitamin compound as a main body, and the selection has the scientificity:
Pi electrons and carboxyl groups in the vitamin compound can improve the efficiency of the emulsifier. The emulsifier has hydrophilic and oleophilic amphiphilic properties, so that the surface property of the cleaning solution can be changed during cleaning, and the emulsifier has lower surface tension and better wettability and foamability.
In the invention, beta-nicotinamide mononucleotide and sialic acid are added as a composite emulsifier in the preparation process, so that the cleaning capability of the cleaning on metals can be effectively improved, and the cleaning effect and the corrosion resistance are balanced.
In the cleaning agent system of the invention, the beta-nicotinamide mononucleotide and the sialic acid composite emulsifier have synergistic effect:
Wherein, the lipophilic group points to oil and the hydrophilic group points to water, thereby reducing the surface tension of the water and enabling the surface of the substrate to be easily wetted. The directionality changes the adhesion condition of pollution, so that pollution rolling, dispersion, emulsification, suspension and other phenomena occur, pollution particles such as water-coated fat and the like, namely emulsified particles, are further formed, and finally cleaned and removed. The cleaning effect can be enhanced in the emulsification stage, the components of the composite emulsifier can also avoid redeposition of emulsified particles on the surface of the substrate.
Wherein, the molecular structure of the beta-nicotinamide mononucleotide in the emulsifier is shown in the following chart:
Wherein the molecular structure of sialic acid in the emulsifier is shown in the following figure:
Further, the hydrogen phosphate in the beta-nicotinamide mononucleotide and the carboxyl in sialic acid undergo esterification reaction, and the specific reaction mechanism is as follows:
RCOOH+RPO(OH)2 -→RCOO-RPO(OH)2
Phosphorus hydroxyl is a functional group containing phosphorus and oxygen that can react with carboxyl groups to form esters. This reaction requires acid catalysis, usually with sulfuric acid or phosphoric acid as catalysts, and the pH regulator in the present invention can also serve this function precisely. In the reaction, one hydrogen ion of the phosphorus hydroxyl group is substituted with a hydroxyl group of the carboxyl group, forming an ester bond. Meanwhile, another hydrogen ion of the phosphorus hydroxyl group is replaced by an acid ion in the catalyst to form a phosphate ion.
By esterification, the two materials can be combined together, and phosphate esters can be formed structurally.
Further, the amide group in the β -nicotinamide mononucleotide may undergo an esterification reaction with the hydroxyl group in sialic acid. In this reaction, nucleophilic addition reaction occurs between the amide group and the hydroxyl group, resulting in an amide ester compound.
The resulting product undergoes further hydrolysis by the following reaction mechanism:
RC(O)NR'2+H20→RC(O)OH+R'2NH
Wherein R and R' 2 are hydrocarbyl or substituted hydrocarbyl.
After the above reaction, the hydrogen phosphate end and the amide group end in the β -nicotinamide mononucleotide structure may be respectively linked to the carboxyl end and the hydroxyl end of sialic acid. The end-to-end connection results in a capsule-like structure formed inside the two macromolecules, which forms an intra-system adsorption and becomes an efficient residue-containing capture carrier.
Due to the formation and existence of the structure, the chip cleaning agent liquid can effectively improve the stripping and cleaning capacities of metals, and has excellent corrosion resistance.
Meanwhile, the composite emulsifying agent can also effectively clean the residues after etching, limit the residues in the capture carrier, improve the stripping performance of the residues, enable the stripping of the residues to be more complete, rapid and thorough, and further improve the cleaning effect of the chip cleaning agent.
In the invention, the protective agent and the corrosion inhibitor are added simultaneously, and the synergistic effect is achieved: the protective agent and the corrosion inhibitor can effectively reduce the corrosion of hydrofluoric acid to Al.
Wherein, the molecular structure of mannitol is shown in the following figure:
wherein the molecular structure of geraniol is shown in the following figure:
the mechanism of action of the synergistic protection Al of mannitol and geraniol is as follows:
Since mannitol has a plurality of hydroxyl groups, and the hydroxyl groups have higher activity, the hydroxyl groups of mannitol can be substituted with hydrogen on carbon with hydroxyl groups on geraniol, so that a multi-opening continuous pocket structure with better capturing and binding performance is formed.
The formation of the structure is more beneficial to controlling the concentration of hydrofluoric acid and ammonium fluoride in the system, thereby reducing corrosion to Al and better protecting metallic Al.
In the invention, the synergistic effect of the composite emulsifier beta-nicotinamide mononucleotide and sialic acid is fully utilized, so that etching residues in a system are efficiently captured and restrained, the corrosion resistance is increased, and the cleaning effect is improved; meanwhile, the concentration of hydrofluoric acid and ammonium fluoride in the system is continuously controlled by further utilizing the synergistic effect of the protecting agent and the corrosion inhibitor, so that the protection of metal Al is better realized while the cleaning effect is improved.
It should be noted that, in the present invention, unless otherwise specified, reference to the specific meaning of "comprising" as defined and described by the composition includes both the open meaning of "comprising", "including" and the like, and the closed meaning of "consisting of …" and the like.
The invention provides a high-adsorptivity semiconductor chip cleaning agent, a preparation method and application thereof, and the cleaning agent has the following beneficial effects:
(1) The high adsorptivity semiconductor chip cleaning agent adopts composite emulsifying agent beta-nicotinamide mononucleotide and sialic acid. After the reaction of the two, the two are connected end to end structurally, a saccular-like structure can be formed inside the two macromolecules, and the structure forms the intra-system adsorption and becomes a high-efficiency capturing carrier for containing residues. Due to the formation and existence of the structure, the chip cleaning agent can effectively improve the cleaning capability of metal, and meanwhile, the cleaning agent has excellent corrosion resistance.
(2) The composite emulsifying agent can also effectively clean the residues after etching, limit the residues in the capture carrier, effectively improve the balance of surface tension, and improve the stripping performance of the residues, so that the residues are stripped more completely, rapidly and thoroughly, and the cleaning effect of the chip cleaning agent is improved.
(3) The invention selects the protective agent and the corrosion inhibitor to be added simultaneously, which has synergistic effect: since mannitol has a plurality of hydroxyl groups and the activity degree of the hydroxyl groups is higher, the hydroxyl groups of mannitol can be substituted with hydrogen on carbon with hydroxyl groups on geraniol, so that a multi-opening continuous pocket structure with better capturing and binding properties is formed, and meanwhile, the concentration of hydrofluoric acid and ammonium fluoride in a system can be effectively controlled by adding a protective agent and a corrosion inhibitor, and the corrosion to Al is reduced.
(4) The high-adsorptivity semiconductor chip cleaning agent can still maintain extremely excellent cleaning efficiency only under the pure soaking process condition of cleaning without matching an ultrasonic process.
Drawings
Fig. 1: amplifying 1000 times of pictures under a scanning electron microscope before cleaning an etched Al chip;
Fig. 2: the picture of the Al chip scanning electron microscope which is cleaned by the semiconductor chip cleaning agent prepared in the embodiment 1 of the invention is amplified 1000 times;
Fig. 3: the Al chip scanning electron microscope after being cleaned by the cleaning agent prepared in the comparative example 1 is used for amplifying 1000 times of pictures.
Detailed Description
The invention is further described with reference to specific examples and figures:
table 1 example
Table 2 comparative example
Table 3 test results
The preparation method of the high-adsorptivity semiconductor chip cleaning agent comprises the following steps:
step 1: weighing each component in parts by mass respectively;
Step 2: adding all components except ultrapure water and an emulsifying agent into a container, and stirring until all materials are completely dissolved; and (3) adding 1/2 of the emulsifier and all ultrapure water at the same time under stirring, continuing stirring, adding the rest 1/2 of the emulsifier after stirring for 3min, and stirring until the solution is clear and transparent, thus obtaining the high-adsorptivity semiconductor chip cleaning agent.
The preparation method of the cleaning agent in the examples of the present invention is as described above, and the preparation method of the cleaning agent of the comparative example is referred to examples.
The cleaning method of the high-adsorptivity semiconductor chip cleaning agent comprises the following steps:
Step 1: preparing the prepared high-adsorptivity semiconductor chip cleaning agent into an aqueous solution with the mass percent concentration of 20% by using ultrapure water;
step 2: soaking the semiconductor chip in the aqueous solution prepared in the step 1 at 35 ℃ for 10min to obtain a semiconductor chip after soaking;
Step 3: and (3) placing the soaked semiconductor chip into ultrapure water for flushing twice, flushing with absolute ethyl alcohol, and drying with nitrogen to finish the cleaning of the semiconductor chip.
Regarding performance testing and description:
The test method of the cleaning effect of the performance 1 comprises the following steps:
Step 1: preparing the prepared high-adsorptivity semiconductor chip cleaning agent into an aqueous solution with the mass percent concentration of 20% by using ultrapure water;
Step 2: soaking the Al chip in the aqueous solution prepared in the step 1 at 35 ℃ for 10min to obtain the soaked Al chip;
Step 3: and (3) placing the soaked Al chip into ultrapure water for flushing twice, flushing by using absolute ethyl alcohol, and drying by using nitrogen to finish the cleaning of the Al chip.
The test method of the performance 2 metal corrosion comprises the following steps:
the four-probe method is adopted to test the corrosion performance of different cleaning agents to metals, and the specific test method comprises the following steps: the initial film thickness before immersion was measured on a 2X 2cm wafer under a four-probe tester. The method comprises the steps of ensuring that the environment of an instrument is kept consistent when four probes are tested each time, immersing a wafer in a cleaning agent at 35 ℃ for 10min, immediately flushing the wafer with ultrapure water and absolute ethyl alcohol, drying the wafer by nitrogen after flushing twice, testing the wafer which is just cleaned by a four-probe tester again after cleaning the wafer to obtain the film thickness, and carrying out corrosion rate according to the change of the film thickness of the front and rear times /Min).
Analysis of test results shows that:
As can be seen from the test data in table 3, the surface of the chip cleaned by the semiconductor chip cleaning agent prepared by the embodiment of the invention is clean and has no residue. The surface of the chip cleaned by the cleaning agent prepared by the comparative example has obvious impurity residues.
Secondly, the corrosion rates of the Al chips cleaned by the semiconductor chip cleaning agent prepared by the embodiment of the invention are all equal toAnd/min.
The Al chip corrosion rate after being cleaned by the cleaning agent prepared in the comparative example is higher than that of the Al chip/min。
From the corrosion rate, the semiconductor chip cleaning agent prepared by the embodiment of the invention has better corrosion resistance.
Further contrasted by the attached drawings in the specification:
fig. 1 is a photograph of an etched Al chip before cleaning at a magnification of 1000 times under a scanning electron microscope. And FIG. 2 is a 1000-fold magnification image of an Al chip scanning electron microscope cleaned with the semiconductor chip cleaning agent prepared in example 1 of the present invention.
As can be seen from the comparison between fig. 1 and fig. 2, the surface of the Al chip cleaned by the semiconductor chip cleaning agent prepared in example 1 of the present invention is clean and has no residue. Meanwhile, the diameter of the hole wall is changed greatly, which proves that the cleaning is not corroded to cause loss.
FIG. 3 is a photograph of an Al chip scanning electron microscope at 1000 times magnification after cleaning using the cleaning agent prepared in comparative example 1 of the present invention.
As can be seen from fig. 3, the surface of the Al chip washed with the cleaning agent prepared in comparative example 1 of the present invention has impurities remaining. And the diameter of the inner wall of the hole becomes larger, which proves that slight corrosion occurs during the cleaning process and loss is caused.
In the invention, the synergistic effect of the composite emulsifier beta-nicotinamide mononucleotide and sialic acid is fully utilized, so that etching residues in a system are efficiently captured and restrained to increase corrosion resistance and improve cleaning effect; meanwhile, the concentration of hydrofluoric acid and ammonium fluoride in the system is continuously consumed by further utilizing the synergistic effect of the protecting agent and the corrosion inhibitor, so that the protection of metal Al is better realized while the cleaning effect is improved. The cleaning performance is improved, the cleaning effect is improved, and meanwhile, solid particle residues are removed more rapidly and thoroughly.
While the present invention has been described above by way of example with reference to the embodiments and the accompanying drawings, it is apparent that the implementation of the present invention is not limited by the above manner, and it is within the scope of the present invention to apply the inventive concept and technical solution to other situations as long as various improvements are adopted by the inventive concept and technical solution, or without any improvement.
Claims (10)
1. The high-adsorptivity semiconductor chip cleaning agent is characterized by comprising the following components in parts by weight:
Wherein the emulsifier is a mixture of vitamins and saccharides;
the vitamin is one or two of folic acid and beta-nicotinamide mononucleotide;
The saccharide is one or two of hyaluronic acid or sialic acid;
The protective agent is sugar alcohol.
2. The high adsorptivity semiconductor chip cleaning agent as defined in claim 1, characterized in that: the emulsifier is a mixture of beta-nicotinamide mononucleotide and sialic acid.
3. The high adsorptivity semiconductor chip cleaning agent as defined in claim 2, characterized in that: in the emulsifier, the mass ratio of the beta-nicotinamide mononucleotide to sialic acid is 1:1-1:3.
4. The high-adsorptivity semiconductor chip cleaning agent according to claim 3, characterized in that: the corrosion inhibitor is one or more of geraniol, pyrogallol, pyridine and m-aminophenol;
The organic solvent is one or more of diethylene glycol butyl ether, ethylene glycol butyl ether and triethylene glycol butyl ether.
5. The high-adsorptivity semiconductor chip cleaning agent as defined in claim 4, characterized in that: the protective agent is one or more of sorbitol, xylitol, mannitol, lactitol and erythritol.
6. The high-adsorptivity semiconductor chip cleaning agent according to claim 5, characterized in that: the protective agent is mannitol;
the corrosion inhibitor is geraniol;
The organic solvent is triethylene glycol butyl ether;
the pH regulator is sulfuric acid or phosphoric acid.
7. The high-adsorptivity semiconductor chip cleaning agent as defined in claim 6, characterized in that: the pH regulator is phosphoric acid.
8. A method for preparing the high adsorptivity semiconductor chip cleaning agent according to any one of claims 1 to 7, characterized by comprising the steps of:
step 1: weighing each component in parts by mass respectively;
Step 2: adding all components except ultrapure water and an emulsifying agent into a container, and stirring until all materials are completely dissolved; and (3) adding 1/2 of the amount of the emulsifying agent and all the ultrapure water at the same time under stirring, continuing stirring, adding the rest 1/2 of the amount of the emulsifying agent after stirring for 3-5min, and stirring until the solution is clear and transparent, thus obtaining the high-adsorptivity semiconductor chip cleaning agent.
9. A cleaning method of the high adsorptivity semiconductor chip cleaning agent as described in any one of claims 1 to 7, characterized by comprising the steps of:
Step 1: preparing the prepared high-adsorptivity semiconductor chip cleaning agent into an aqueous solution with the mass percent concentration of 10-30% by using ultrapure water;
step 2: soaking the semiconductor chip in the water solution prepared in the step 1 at 20-50 ℃ for 5-15min to obtain a soaked semiconductor chip;
step 3: and (3) flushing the soaked semiconductor chip by using ultrapure water at least twice until the surface cleaning agent is completely flushed, flushing by using absolute ethyl alcohol, and then drying by using nitrogen gas to finish the cleaning of the semiconductor chip.
10. Use of the high-adsorptivity semiconductor chip cleaning agent according to any one of claims 1-7 for cleaning semiconductor chips.
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| CN202311821501.1A CN117925325A (en) | 2023-12-27 | 2023-12-27 | High-adsorptivity semiconductor chip cleaning agent and preparation method and application thereof |
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| CN202311821501.1A CN117925325A (en) | 2023-12-27 | 2023-12-27 | High-adsorptivity semiconductor chip cleaning agent and preparation method and application thereof |
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