CN117806139A - Photoresist cleaning solution - Google Patents
Photoresist cleaning solution Download PDFInfo
- Publication number
- CN117806139A CN117806139A CN202311600916.6A CN202311600916A CN117806139A CN 117806139 A CN117806139 A CN 117806139A CN 202311600916 A CN202311600916 A CN 202311600916A CN 117806139 A CN117806139 A CN 117806139A
- Authority
- CN
- China
- Prior art keywords
- photoresist
- aza
- crown ether
- cleaning solution
- ether
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 46
- 238000004140 cleaning Methods 0.000 title claims abstract description 35
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 11
- 239000002738 chelating agent Substances 0.000 claims abstract description 11
- 150000004292 cyclic ethers Chemical class 0.000 claims abstract description 11
- 229920000642 polymer Polymers 0.000 claims abstract description 11
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 11
- 239000000654 additive Substances 0.000 claims abstract description 10
- 230000000996 additive effect Effects 0.000 claims abstract description 10
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims abstract description 8
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims abstract description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 claims abstract description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 11
- 239000002184 metal Substances 0.000 abstract description 11
- -1 aza crown ether Chemical class 0.000 abstract description 7
- 239000007788 liquid Substances 0.000 abstract description 7
- 238000005260 corrosion Methods 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 5
- 239000003814 drug Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 238000011109 contamination Methods 0.000 abstract description 3
- 150000001768 cations Chemical class 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract description 2
- 239000006260 foam Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000012634 fragment Substances 0.000 description 3
- 229910000449 hafnium oxide Inorganic materials 0.000 description 3
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
Abstract
The invention relates to a photoresist cleaning solution. The cleaning solution consists of PGMEA, saturated cyclic ether, carboxylic acid polymer chelating agent, additive and deionized water. The saturated cyclic ether is at least one of dioxane, tetrahydrofuran, tetrahydropyran and dioxane. The carboxylic acid polymer chelating agent is maleimide monoamide-DTPA. The additive is aza crown ether selected from at least one of aza-18-crown ether-6, aza-15-crown ether-5, aza-12-crown ether-4, aza-10-crown ether-3. The cleaning solution is suitable for cleaning positive photoresist and negative photoresist simultaneously. Wherein PGMEA and saturated cyclic ether cooperate to make the photoresist expand and foam and peel off, and the addition of the additive enhances the wettability and solubility of the liquid medicine to the photoresist. The aza crown ether and carboxylic acid polymer chelating agent cooperate to complex metal cations or positive ions, so that the corrosion of photoresist cleaning liquid on bottom metal and dielectric layer materials is inhibited, and the metal contamination on the surface of the wafer is well cleaned.
Description
Technical Field
The invention belongs to the technical field of semiconductor cleaning, and particularly relates to a photoresist cleaning solution.
Background
Photolithography is a widely used technique for forming a desired image pattern on a substrate using light or other electromagnetic radiation. Along with the iterative updating of the photoetching technology, the device structure is complicated and refined, and positive photoresist and negative photoresist are often used in the same process. The photoresist removing cleaning liquid known in the industry often has defects on removing negative photoresist with good positive photoresist removing effect, has residues on removing the positive photoresist with obvious negative photoresist cleaning effect, and can not be used together, so that the liquid medicine is required to be continuously switched, the process is complex, and the process cost is high.
Meanwhile, the existing cleaning solution for removing photoresist mainly comprises a strong alkaline substance or a compound containing halogen atoms. In the cleaning liquid, free radicals-OH and halogen in the alkaline substances have certain corrosion effects on metal substrates or underlying dielectric layer materials, and sometimes the front-side circuits cannot be effectively protected due to over-strong alkalinity.
Aiming at the problems of different degrees in the prior art, a photoresist cleaning solution which is simultaneously applicable to positive photoresist and negative photoresist is to be developed, and the photoresist cleaning solution has higher protection performance on metal layers such as copper, aluminum, titanium nitride and the like, silicon dioxide low-k dielectric layers, aluminum oxide, zirconium oxide or hafnium oxide and the like, and high-k dielectric layers such as silicon dioxide low-k dielectric layers and hafnium oxide and the like.
Disclosure of Invention
The invention aims to provide a photoresist cleaning solution which can be simultaneously applied to removing photoresist of positive photoresist and negative photoresist.
The second object of the present invention is to provide a photoresist stripping solution which has high protection performance for metal layers such as copper, aluminum, titanium nitride, etc., silicon dioxide low-k dielectric layers, and high-k dielectric layers such as aluminum oxide, zirconium oxide or hafnium oxide, etc.
In order to achieve the above purpose, the technical scheme of the invention provides a photoresist cleaning solution, which contains PGMEA, saturated cyclic ether, carboxylic acid polymer chelating agent, additive and deionized water. The content of PGMEA is 60% -80%, the content of saturated cyclic ether is 5% -10%, the content of carboxylic acid polymer chelating agent is 1% -3%, the content of additive is 0.1% -1%, and the rest is deionized water.
Wherein the saturated cyclic ether is at least one of dioxane, tetrahydrofuran, tetrahydropyran and dioxane.
The carboxylic acid polymer chelating agent is maleimide monoamide-DTPA.
The additive is aza crown ether, and is at least one of aza-18-crown ether-6, aza-15-crown ether-5, aza-12-crown ether-4 and aza-10-crown ether-3.
According to the technical scheme, PGMEA and saturated cyclic ether are synergistic, so that the photoresist is expanded, foamed and stripped, and the wettability and the solubility of the liquid medicine to the photoresist are enhanced by adding the additive, so that the cleaning effect of the photoresist is further improved. Meanwhile, the aza crown ether and the carboxylic acid polymer chelating agent are synergistic to complex metal cations or positive ions, so that the photoresist cleaning solution is inhibited from corroding bottom metal and dielectric layer materials, and meanwhile, the aza crown ether and the carboxylic acid polymer chelating agent have excellent cleaning effect on metal contamination on the surface of a wafer.
The beneficial effects of the invention are that
The invention has the advantages and beneficial effects that: in the invention, the photoresist cleaning solution solves the problem of simultaneous application to positive and negative photoresist through the double matching of PGMEA and saturated cyclic ether, and the aza crown ether is introduced to enhance the wettability and solubility of the liquid medicine, so that the cleaning effect is enhanced, and meanwhile, the cleaning solution and the maleimide monoamide-DTPA cooperate to obtain obvious effects on the aspects of corrosion resistance of bottom metal materials and low-k and high-k dielectric layers and the removal of metal contamination on the surface of a wafer.
Drawings
Fig. 1 shows the surface state under a super depth of field microscope after removal.
Fig. 2 is an EDS diagram with the complete back surface removed.
Fig. 3 is a view showing the state of the surface of a super depth microscope with cleaning residues.
Fig. 4 is an EDS diagram of a surface with cleaning residue.
Detailed Description
For a better understanding of the present invention, reference will now be made in detail to the drawings and examples, which are illustrated in the accompanying drawings, but are not intended to limit the scope of the invention.
The photoresist cleaning solution of the invention is prepared by simply and uniformly mixing the components shown in the table 1.
Table 1 shows the components and contents of the stripping solutions of examples 1 to 9 and comparative examples 1 to 15.
Cutting the test piece covered with a layer of positive photoresist film and the test piece covered with a layer of negative photoresist film after high-temperature curing into 1.6x1.6cm 2 The fragments of the size were immersed in the photoresist cleaning solutions described in examples and comparative examples, respectively, and the stripping temperature was 25℃and the cleaning time was recorded until the removal was completed, after the stripping treatment, the fragments were rinsed with ultrapure water and dried with nitrogen, and then it was judged whether the removal was completed by means of a super depth electron microscope and energy spectrum analysis, and if the removal was not completed, the cleaning time was further prolonged and the time until the complete removal was recorded, namely the sol efficiency, and the results of examples and comparative examples are summarized in Table 2.
Table 2 shows the sol efficiencies of the photoresists on the test pieces of examples 1 to 9 and comparative examples 1 to 15.
Will be plated with Al, cu, ti, tiN, oxide, al 2 O 3 、HfO 2 、ZrO 2 Test pieces of the film were cut 1.6x1.6cm 2 Fragments of the same size were immersed in the photoresist cleaning solutions described in examples and comparative examples, respectively, and etched at 25℃for 30 minutes, after etching, rinsed with ultrapure water, blown dry with nitrogen, and the thickness of each film before and after etching was measured by a four-probe resistance tester, and the etching rate of each solution to each film was calculated, and the results of examples and comparative examples are summarized in Table 3.
Table 3 shows the corrosion of the respective metals and the respective dielectric layers in examples 1 to 9 and comparative examples 1 to 15.
According to the experimental results of the embodiment, the photoresist cleaning solution provided by the invention can remove positive photoresist and negative photoresist at the same time under the normal temperature condition, and has no corrosion to the base material.
Claims (4)
1. The photoresist cleaning solution is characterized by comprising PGMEA, saturated cyclic ether, carboxylic acid polymer chelating agent, additive and deionized water; the content of PGMEA is 60% -80%, the content of saturated cyclic ether is 5% -10%, the content of carboxylic acid polymer chelating agent is 1% -3%, the content of additive is 0.1% -1%, and the rest is deionized water.
2. The photoresist cleaning solution of claim 1, wherein the saturated cyclic ether is at least one of dioxane, tetrahydrofuran, tetrahydropyran, and dioxane.
3. The photoresist cleaning solution of claim 1, wherein the carboxylic acid polymer chelating agent is maleimide monoamide-DTPA.
4. The photoresist cleaning solution of claim 1, wherein the additive is an aza-crown ether selected from at least one of aza-18-crown ether-6, aza-15-crown ether-5, aza-12-crown ether-4, aza-10-crown ether-3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311600916.6A CN117806139A (en) | 2023-11-24 | 2023-11-24 | Photoresist cleaning solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311600916.6A CN117806139A (en) | 2023-11-24 | 2023-11-24 | Photoresist cleaning solution |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117806139A true CN117806139A (en) | 2024-04-02 |
Family
ID=90424289
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311600916.6A Pending CN117806139A (en) | 2023-11-24 | 2023-11-24 | Photoresist cleaning solution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117806139A (en) |
-
2023
- 2023-11-24 CN CN202311600916.6A patent/CN117806139A/en active Pending
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