CN117778119A - Cleaning agent for chip after chemical mechanical polishing and preparation method and application thereof - Google Patents
Cleaning agent for chip after chemical mechanical polishing and preparation method and application thereof Download PDFInfo
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- CN117778119A CN117778119A CN202311825082.9A CN202311825082A CN117778119A CN 117778119 A CN117778119 A CN 117778119A CN 202311825082 A CN202311825082 A CN 202311825082A CN 117778119 A CN117778119 A CN 117778119A
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- 239000012459 cleaning agent Substances 0.000 title claims abstract description 53
- 238000005498 polishing Methods 0.000 title claims abstract description 22
- 239000000126 substance Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title description 8
- 239000002738 chelating agent Substances 0.000 claims abstract description 29
- 239000000654 additive Substances 0.000 claims abstract description 21
- 230000000996 additive effect Effects 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 15
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical class OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims abstract description 15
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 11
- 230000007797 corrosion Effects 0.000 claims abstract description 11
- 238000005260 corrosion Methods 0.000 claims abstract description 11
- 239000003112 inhibitor Substances 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 4
- 239000004065 semiconductor Substances 0.000 claims description 35
- 238000004140 cleaning Methods 0.000 claims description 32
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 11
- 239000012498 ultrapure water Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000001116 FEMA 4028 Substances 0.000 claims description 6
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims description 6
- 229960004853 betadex Drugs 0.000 claims description 6
- CQOZJDNCADWEKH-UHFFFAOYSA-N 2-[3,3-bis(2-hydroxyphenyl)propyl]phenol Chemical compound OC1=CC=CC=C1CCC(C=1C(=CC=CC=1)O)C1=CC=CC=C1O CQOZJDNCADWEKH-UHFFFAOYSA-N 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 5
- 150000007530 organic bases Chemical class 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 4
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000007865 diluting Methods 0.000 claims description 4
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- ODLHGICHYURWBS-LKONHMLTSA-N trappsol cyclo Chemical compound CC(O)COC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](COCC(C)O)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](COCC(C)O)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](COCC(C)O)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](COCC(C)O)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)COCC(O)C)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1COCC(C)O ODLHGICHYURWBS-LKONHMLTSA-N 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
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- 238000005406 washing Methods 0.000 claims description 3
- IVHXFSFLCMNTQP-UHFFFAOYSA-N 1,3-benzothiazole-4-thiol Chemical compound SC1=CC=CC2=C1N=CS2 IVHXFSFLCMNTQP-UHFFFAOYSA-N 0.000 claims description 2
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 2
- DJEFWCDUJJUZGY-UHFFFAOYSA-N 3-sulfanyl-2h-1,3-benzothiazole Chemical compound C1=CC=C2N(S)CSC2=C1 DJEFWCDUJJUZGY-UHFFFAOYSA-N 0.000 claims description 2
- CMSMOCZEIVJLDB-UHFFFAOYSA-N Cyclophosphamide Chemical compound ClCCN(CCCl)P1(=O)NCCCO1 CMSMOCZEIVJLDB-UHFFFAOYSA-N 0.000 claims description 2
- GHASVSINZRGABV-UHFFFAOYSA-N Fluorouracil Chemical compound FC1=CNC(=O)NC1=O GHASVSINZRGABV-UHFFFAOYSA-N 0.000 claims description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-O N-dimethylethanolamine Chemical compound C[NH+](C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-O 0.000 claims description 2
- -1 carboxyethyl diamine Chemical class 0.000 claims description 2
- 229960004397 cyclophosphamide Drugs 0.000 claims description 2
- 229960002949 fluorouracil Drugs 0.000 claims description 2
- 150000002334 glycols Chemical class 0.000 claims description 2
- 229940097346 sulfobutylether-beta-cyclodextrin Drugs 0.000 claims description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 11
- 229910001431 copper ion Inorganic materials 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 10
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 abstract description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 229920001353 Dextrin Polymers 0.000 abstract 1
- 239000004375 Dextrin Substances 0.000 abstract 1
- 235000019425 dextrin Nutrition 0.000 abstract 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 23
- 239000012964 benzotriazole Substances 0.000 description 23
- 239000010949 copper Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 11
- 229910052802 copper Inorganic materials 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 230000002209 hydrophobic effect Effects 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000013522 chelant Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000000879 optical micrograph Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- FJHBVJOVLFPMQE-QFIPXVFZSA-N 7-Ethyl-10-Hydroxy-Camptothecin Chemical group C1=C(O)C=C2C(CC)=C(CN3C(C4=C([C@@](C(=O)OC4)(O)CC)C=C33)=O)C3=NC2=C1 FJHBVJOVLFPMQE-QFIPXVFZSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
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Abstract
The invention relates to a cleaning agent for chips after chemical mechanical polishing, which comprises the following components in parts by mass: 1-10 parts of chelating agent; 1-5 parts of an additive; 0.1-0.5 part of corrosion inhibitor; 1-10 parts of organic alkali; 80-90 parts of deionized water; the method is characterized in that: both the chelating agent and the additive are beta-cyclodextrin derivatives. The polyhydroxy beta-ring of the inventionThe chelating agent and the additive of the dextrin derivative comprise beta-cyclodextrin-polyethylene glycol as hydrophilic groups, and the cyclodextrin has the cavity structure and polyhydroxy structure characteristics of cyclodextrin to produce synergistic effect with the beta-cyclodextrin-polyethylene glycol to further remove Cu-BTA, and meanwhile, the hydrophilic groups formed by ethylene oxide groups in the polyethylene glycol point to water to act together to lead BTA ‑ Wrap up and prevent BTA ‑ Then combines with copper ions to achieve the effect of thoroughly removing Cu-BTA.
Description
Technical Field
The invention relates to the field of cleaning for chip preparation, in particular to a cleaning agent for chips after chemical mechanical polishing, a preparation method and application thereof.
Background
In very large scale integrated circuits (GLSI), the damage of impurities to devices is remarkable due to the continuous decrease of feature sizes, and thus, wafer surface cleanliness becomes an important factor affecting device yield.
The post-polishing cleaning of copper is a crucial step in the chemical mechanical planarization process, and a large amount of polishing liquid abrasive and organic residues exist on the surface of copper after polishing, and the residual organic substances are mainly Benzotriazole (BTA) and Cu-BTA generated by copper ions. Cu-BTA residues cause hydrophobicity of the copper surface and affect the removal of the abrasive. An important function of post-copper polishing cleaning is to effectively remove organic residues without increasing surface roughness.
Furthermore, the main cleaning targets in copper post-CMP cleaning are inhibitors and SiO adsorbed on the wafer surface 2 And (3) particles. The inhibitor belongs to organic matters, the integrity of film deposition can be damaged when the inhibitor is adsorbed on the surface of a wafer, meanwhile, the organic matters are easy to decompose and deteriorate under the environment of illumination high-temperature oxidation and the like, and decomposition products are complex and various, so that immeasurable influence can be caused on a semiconductor device.
Regarding the mechanism by which BTA inhibits Cu, it is believed that 2 BTA molecules bridge Cu atoms to form a continuous insoluble polymer Cu-BTA covering the Cu surface inhibits Cu corrosion. However, the Cu-BTA film is difficult to desorb, and the BTA molecular structure contains a benzene ring with hydrophobic property, so that the surface is highly hydrophobic due to adsorption on the copper surface. The adsorption of BTA also produces pores on the wafer surface, which causes copper ions to diffuse into the medium, resulting in electromigration and leakage current, affecting the reliability of copper interconnection and the performance of semiconductor devices. Cu-BTA can be cracked and volatilized in a high-temperature environment, and toxic gas is released, so that the Cu-BTA is harmful to the environment and human body. Therefore, for cleaning semiconductor chips, a cleaning agent is required to maintain a good cleaning effect under simple and mild process conditions.
In the current chip cleaning field, urgent needs still exist for novel chip cleaning agents and cleaning methods, and particularly, more urgent industrial application needs exist for novel cleaning agents which are free of damage, thorough and complete in cleaning, free of chip corrosion and the like.
Disclosure of Invention
The invention designs a cleaning agent for chips after chemical mechanical polishing, a preparation method and application thereof, and solves the technical problem that the existing cleaning agent can not completely remove Cu-BTA and form a protective film on the metal surface.
In order to solve the technical problems, the invention adopts the following scheme:
the cleaning agent for the chip after chemical mechanical polishing is characterized by comprising the following components in parts by weight:
wherein the chelating agent is a beta-cyclodextrin derivative containing polyhydroxy;
the additive is polyethylene glycol derivative containing beta-cyclodextrin.
Further, the chelating agent is selected from one of sulfobutyl ether-beta-cyclodextrin, isocyanate-beta-cyclodextrin-trimellitic aldehyde triphenol (MDI-beta-CD-Tp) and hydroxypropyl-beta-cyclodextrin (HP-beta-CD).
Further, the additive is selected from one of beta-cyclodextrin polyethylene glycol cyclophosphamide, beta-cyclodextrin-polyethylene glycol-7-ethyl-10-hydroxycamptothecin and beta-cyclodextrin polyethylene glycol fluorouracil.
Further, the corrosion inhibitor is one or more of beta-amino ketone, 2-mercaptobenzothiazole, 3-mercaptobenzothiazole and 4-mercaptobenzothiazole.
Further, the organic base is one or more of 2-amino-2-methyl-1, 3-propanediol, tetramethyl ethylenediamine, N-dimethylethanolamine and carboxyethyl diamine.
Further, the chelating agent is isocyanate-beta-cyclodextrin-m-trimellitic aldehyde triphenol (MDI-beta-CD-Tp);
the additive is beta-cyclodextrin-polyethylene glycol-7-ethyl-10-hydroxycamptothecin;
the corrosion inhibitor is beta-amino ketone;
the organic base is tetramethyl ethylenediamine.
The invention also discloses a preparation method of the cleaning agent after chip chemical mechanical polishing, which comprises the following steps:
s1: weighing each component with the respective dosage;
s2: and sequentially adding all the components into a container, stirring at normal temperature until all the materials are completely dissolved, and obtaining the cleaning agent after the chip is subjected to chemical mechanical polishing.
The invention also discloses an application of the cleaning agent after the chip chemical mechanical polishing to cleaning Cu-BTA on the surface of the semiconductor chip.
The invention also discloses a cleaning method of the cleaning agent after the chip chemical mechanical polishing, which comprises the following steps:
s1: diluting the chip chemically and mechanically polished cleaning agent to 10-100 times by using ultrapure water, and then soaking the semiconductor chip by using the aqueous solution at normal temperature for 50-150 seconds to obtain a soaked semiconductor chip;
s2: and (3) placing the soaked semiconductor chip into ultrapure water for washing at least twice, and then drying the surface of the semiconductor chip by using nitrogen gas to finish the cleaning treatment of the semiconductor chip.
In the present invention, the chelating agent may be preferably 2 to 9 parts for further optimizing the cleaning effect; the additive may preferably be 1-4 parts; the corrosion inhibitor can be preferably 0.2 to 0.4 part; the organic base may preferably be 2 to 6 parts; deionized water may preferably be 80-85 parts;
in the cleaning method of the present invention, the cleaning agent may be diluted with ultrapure water to any multiple of 10 to 100 times, for example, 20 times, 30 times, 40 times, 55 times, 60 times, 78 times, 99 times, etc., and the soaking time may be any time of 50 to 150 seconds, for example, 60 seconds, 70 seconds, 88 seconds, 92 seconds, 100 seconds, 120 seconds, 145 seconds, etc., and a good cleaning effect may be achieved.
In the present invention, the preferred chelating agent MDI-beta-CD-Tp has the following formula;
isocyanate-beta-cyclodextrin-trimellitic aldehyde triphenol (MDI-beta-CD-Tp) can be synthesized by the following method:
2g of beta-CD and 1.64g of MDI are weighed and dissolved in 20mL of DMF, the mixture is heated, refluxed and stirred for 3 hours at 80 ℃ under the protection of nitrogen, and after the reaction is finished, acetone is added to precipitate, the mixture is filtered, and vacuum drying is carried out at 50 ℃ for 12 hours, thus obtaining the milky product MDI-beta-CD.
Weighing Tp 0.107g and MDI-beta-CD 1.038g, respectively dissolving in 15mL of DMF, placing in a single-neck flask, heating and refluxing at 70 ℃ under nitrogen protection, stirring for 8 hours, adding acetone to precipitate after the reaction is finished, filtering, and drying in vacuum at 50 ℃ to obtain a white target product.
The inventors have found that the polyhydroxy and chelate ring contained in the chelating agent can break the chemical bond between Cu-BTA, effectively complex copper ions, and that the chelating agent has a cavity structure with BTA - And compared with the method, the method is easier to combine with copper ions, so that Cu-BTA is removed.
The separated BTA molecules are organic matters, the main component of the cleaning agent is organic alkali, the main component of the cleaning agent and the cleaning agent are in accordance with the principle of similar structure compatibility, and the reacted products are dissolved in the surface of the copper carried away by the cleaning agent, and the reaction mechanism is as follows:
Cu-BTA＝Cu 2+ +BTA - 。
in the present invention, the most preferred additive β -cyclodextrin-polyethylene glycol-7-ethyl-10-hydroxycamptothecin has the structure:
the inventor discovers that the beta-cyclodextrin-polyethylene glycol in the additive is a hydrophilic group part, and has the synergistic effect with the chelating agent due to the cavity structure of cyclodextrin and the structural characteristics of polyhydroxy, thereby removing Cu-BTA, and simultaneously the ethylene oxide (-CH) in the polyethylene glycol 2 CH 2 The hydrophilic group formed by O-) points to water, and the two groups act together to lead BTA - Wrap up and prevent BTA - Then combined with copper ions to achieve the effect of removing Cu-BTA. The hydrophobic group contained in the composition, 7-ethyl-10-hydroxycamptothecin part, can form a hydrophobic film on the metal surface, thereby preventing BTA - Combined with copper ions.
Compared with the prior art, the cleaning agent for the chip after chemical mechanical polishing and the preparation method and the application thereof have the following beneficial effects:
(1) The chelating agent and the additive of the polyhydroxy beta-cyclodextrin derivative comprise beta-cyclodextrin-polyethylene glycol as hydrophilic groups, and have the synergistic effect with the cavity structure of cyclodextrin and the structural characteristics of polyhydroxy to further remove Cu-BTA, and simultaneously the ethylene oxide (-CH) in the polyethylene glycol 2 CH 2 The hydrophilic group formed by O-) points to water, and the two groups act together to lead BTA - Wrap up and prevent BTA - And the copper ions are combined again, so that the effect of thoroughly removing Cu-BTA is achieved. The addition of the chelating agent and the additive can obviously reduce the surface tension of the cleaning agent, enhance the wettability and the permeation effect of the cleaning agent on the surface of the wafer, and enable the additive molecules to be more effectively adsorbed on the surface of the wafer, thereby effectively removing the SiO remained on the surface 2 And (3) particles.
(2) The invention adopts the beta-cyclodextrin derivative, which is suitable for BTA due to the moderate size of the molecular hole of the beta-CD - And the structure is relatively stable and firm.
(3) The polyhydroxy and chelate ring contained in the chelating agent can break the chemical bond between Cu-BTA, thus effectivelyComplexing copper ions, and due to the cavity structure of the chelating agent and BTA - And compared with the method, the method is easier to combine with copper ions, so that Cu-BTA is removed. The separated BTA molecules are organic matters, the main component of the cleaning agent is organic alkali, the two are in accordance with the principle of similar structure compatibility, and the reacted products are dissolved in the cleaning agent and carried away from the copper surface.
(4) The chelating agent containing the beta-cyclodextrin derivative can enhance the coordination capacity with metal ions in an alkaline environment, thereby improving the removal capacity of BTA. Meanwhile, the cleaning agent is adsorbed and wrapped on the surfaces of the wafer and the particles by means of permeation adsorption, so that the particles are changed while steric hindrance is formed, electrostatic repulsive force is generated between the particles, and the particles are removed.
(5) The additive can be fully spread on the water interface of the Cu wafer to form a protective film, and further combination of the chelating agent and the surface of the Cu wafer is blocked, so that the corrosion of the chelating agent on the Cu surface is reduced.
(6) The cleaning agent is environment-friendly, pollution-free and low in volatilization loss, and can be washed by ultrapure water after the cleaning is finished, so that the cleaning agent is harmless to the environment and human bodies.
Drawings
Fig. 1: attaching Cu-BTA to the surface of the semiconductor chip before cleaning and amplifying the Cu-BTA by 50 times of an optical microscope picture;
fig. 2: an optical microscope image of the surface of the semiconductor chip after cleaning by using the cleaning agent of the embodiment 1 of the invention is magnified 50 times;
FIG. 3 is a photograph of a 50-magnification optical microscope of the surface of a semiconductor chip washed with the cleaning agent of comparative example 1 of the present invention;
fig. 4: is an infrared spectrum of the chelating agent MDI-beta-CD-Tp.
Detailed Description
The invention is further described below with reference to the examples and figures 1 to 4:
table 1 example
Table 2 comparative example
Table 3 test results
The preparation method of the cleaning agent comprises the following steps of
S1: weighing each component with the respective dosage;
s2: and sequentially adding all the components into a container, stirring at normal temperature until all the materials are completely dissolved, and obtaining the cleaning agent after the chip is subjected to chemical mechanical polishing.
The examples in the present invention were prepared according to the above-described method, and comparative examples were prepared with reference to the method.
The cleaning method of the invention comprises the following steps of
S1: diluting the chip chemically and mechanically polished cleaning agent to 20 times by using ultrapure water, and then soaking the semiconductor chip by using the aqueous solution at normal temperature for 60 seconds to obtain a soaked semiconductor chip;
s2: and (3) placing the soaked semiconductor chip into ultrapure water for flushing twice, and then drying the surface of the semiconductor chip by using nitrogen gas to finish the cleaning treatment of the semiconductor chip.
Regarding the performance test method:
the test method of the cleaning effect of the property 1 comprises the following steps:
after the grinding and polishing steps of the subsequent process, a large amount of wax, polishing powder residue, polishing liquid residue and the like remain on the semiconductor chip, and the chip is cleaned by using the cleaning agent of the above-mentioned examples and comparative examples of the present invention.
The cleaning treatment method comprises the following steps:
step 1: diluting the chip chemically and mechanically polished cleaning agent to 20 times by using ultrapure water, and then soaking the semiconductor chip by using the aqueous solution at normal temperature for 60 seconds to obtain a soaked semiconductor chip;
step 2: and (3) placing the soaked chip into ultrapure water to be washed twice, and then drying the surface of the semiconductor chip by using nitrogen gas, thus completing the cleaning treatment of the semiconductor chip.
The ultrapure water used in both of the steps 1 and 2 is deionized water having a resistance of at least 18mΩ.
In the experimental process, the contact angle is tested under the influence of the surface oxide layer and external factors, and the surface of the chip is pretreated. The pretreatment used chemical mechanical polishing in this part of the experiment.
Property 2 contact angle test method:
and (3) dripping deionized water on the surface of the semiconductor chip, and analyzing the angle by using a contact angle tester to judge the hydrophilicity and the hydrophobicity of the surface of the chip. And judging the BTA removal condition according to the hydrophilicity and the hydrophobicity of the chip surface.
The fresh chip surface is hydrophilic, the contact angle of deionized water on the chip surface is small, when the BTA film exists on the chip surface, the chip surface is hydrophobic, and the contact angle of deionized water on the chip surface is large.
Analysis of test results:
from the test data of table 3, it can be seen that:
firstly, the surfaces of chips cleaned by the cleaning agent provided by the embodiment of the invention have good hydrophilicity, and the surfaces of chips cleaned by the cleaning agent provided by the comparative example have poor hydrophilicity.
In comparative example 1, the contact angle was increased without adding a chelating agent, and the loss of this component resulted in Cu-BTA remaining on the surface and increased hydrophobicity.
The loss of this component also resulted in surface residual Cu-BTA and increased hydrophobicity due to the increased contact angle without the addition of the additive in comparative example 2.
Secondly, the cleaning agents in the embodiment of the invention have better cleaning effect, and no Cu-BTA residue exists after cleaning.
In comparative example 1, cu-BTA remained after washing due to the loss of chelating agent.
In comparative example 2, cu-BTA remained after cleaning due to the lack of additives.
Further description is made by the accompanying drawings:
FIG. 1 is a photograph of a 50-fold optical microscope of Cu-BTA attached to the surface of a semiconductor chip before cleaning; FIG. 2 is a 50-magnification optical microscope image of the surface of a semiconductor chip cleaned with the cleaning agent of example 1 of the present invention; FIG. 3 is a photograph of a 50-magnification optical microscope of the surface of a semiconductor chip washed with the cleaning agent of comparative example 1 of the present invention.
As shown in FIG. 1, a large number of Cu-BTA black spots are attached to the surface of a semiconductor chip before cleaning, the Cu-BTA film is difficult to desorb, and the BTA molecular structure contains benzene rings with hydrophobic property, so that the surface is highly hydrophobic due to adsorption on the surface of the chip.
As shown in FIG. 2, the surface of the semiconductor chip cleaned by the cleaning agent of example 1 of the present invention has no Cu-BTA.
As shown in FIG. 3, the surface of the semiconductor chip cleaned by the cleaning agent of comparative example 1 still has Cu-BTA residues.
FIG. 4 is an infrared spectrum of the chelator MDI-beta-CD-Tp of the invention.
In FIG. 4, the characteristic peak of DI- β -CD-Tp was shown to be substantially vanished for-N-C=O compared to MDI- β -CD, and 1660cm -1 The absorption peak of c=o becomes large, indicating that MDI- β -CD was introduced at Tp, and MDI- β -CD-Tp was successfully synthesized.
The chelating agent and the additive of the polyhydroxy beta-cyclodextrin derivative of the invention contain beta-cyclodextrin-polyethylene glycol as hydrophilic groups, and have synergistic effect due to the cavity structure of cyclodextrin and the structural characteristics of polyhydroxyFurther removing Cu-BTA, simultaneously directing hydrophilic groups formed by ethylene oxide groups in polyethylene glycol to water, and combining the two groups to react with BTA - Wrap up and prevent BTA - Then combines with copper ions to achieve the effect of thoroughly removing Cu-BTA. The additive can be fully spread on the water interface of the Cu wafer to form a protective film, and further combination of the chelating agent and the surface of the Cu wafer is blocked, so that the corrosion of the chelating agent on the Cu surface is reduced.
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 (9)
1. The cleaning agent for the chip after chemical mechanical polishing is characterized by comprising the following components in parts by weight:
1-10 parts of chelating agent;
1-5 parts of an additive;
0.1-0.5 part of corrosion inhibitor;
1-10 parts of organic alkali;
80-90 parts of deionized water;
wherein the chelating agent is a beta-cyclodextrin derivative containing polyhydroxy;
the additive is polyethylene glycol derivative containing beta-cyclodextrin.
2. The post-cmp cleaning agent of claim 1 wherein: the chelating agent is selected from one of sulfobutyl ether-beta-cyclodextrin, isocyanate-beta-cyclodextrin-trimellitic aldehyde triphenol (MDI-beta-CD-Tp) and hydroxypropyl-beta-cyclodextrin (HP-beta-CD).
3. The post-cmp cleaning agent of claim 2, wherein: the additive is selected from one of beta-cyclodextrin polyethylene glycol cyclophosphamide, beta-cyclodextrin-polyethylene glycol-7-ethyl-10-hydroxycamptothecin and beta-cyclodextrin polyethylene glycol fluorouracil.
4. The post-cmp cleaning agent of claim 3 wherein: the corrosion inhibitor is one or more of beta-amino ketone, 2-mercaptobenzothiazole, 3-mercaptobenzothiazole and 4-mercaptobenzothiazole.
5. The post-cmp cleaning agent of claim 4 wherein: the organic base is one or more of 2-amino-2-methyl-1, 3-propanediol, tetramethyl ethylenediamine, N-dimethyl ethanolamine and carboxyethyl diamine.
6. The post-cmp cleaning agent of claim 5 wherein:
the chelating agent is isocyanate-beta-cyclodextrin-m-trimellitic aldehyde triphenol (MDI-beta-CD-Tp);
the additive is beta-cyclodextrin-polyethylene glycol-7-ethyl-10-hydroxycamptothecin;
the corrosion inhibitor is beta-amino ketone;
the organic base is tetramethyl ethylenediamine.
7. A method for preparing the post-cmp cleaning agent for chips according to any one of claims 1 to 6, comprising the steps of:
s1: weighing each component with the respective dosage;
s2: and sequentially adding all the components into a container, stirring at normal temperature until all the materials are completely dissolved, and obtaining the cleaning agent after the chip is subjected to chemical mechanical polishing.
8. Use of the post-cmp cleaning agent of any one of claims 1-6 for cleaning Cu-BTA on a semiconductor chip surface.
9. A method of cleaning the post-cmp cleaning agent for chips as defined in any one of claims 1 to 6, comprising the steps of:
s1: diluting the chip chemically and mechanically polished cleaning agent to 10-100 times by using ultrapure water, and then soaking the semiconductor chip by using the aqueous solution at normal temperature for 50-150 seconds to obtain a soaked semiconductor chip;
s2: and (3) placing the soaked semiconductor chip into ultrapure water for washing at least twice, and then drying the surface of the semiconductor chip by using nitrogen gas to finish the cleaning treatment of the semiconductor chip.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311825082.9A CN117778119A (en) | 2023-12-27 | 2023-12-27 | Cleaning agent for chip after chemical mechanical polishing and preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311825082.9A CN117778119A (en) | 2023-12-27 | 2023-12-27 | Cleaning agent for chip after chemical mechanical polishing and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117778119A true CN117778119A (en) | 2024-03-29 |
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| CN202311825082.9A Pending CN117778119A (en) | 2023-12-27 | 2023-12-27 | Cleaning agent for chip after chemical mechanical polishing and preparation method and application thereof |
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| Country | Link |
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| CN (1) | CN117778119A (en) |
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2023
- 2023-12-27 CN CN202311825082.9A patent/CN117778119A/en active Pending
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