Cleaning agent and preparation method and use thereof

Abstract

Provided are a cleaning agent and a preparation method and the use thereof. The cleaning agent is prepared from the following raw materials comprising the following mass fraction of components: 0.5%-20% of an oxidant containing iodine, 0.5%-20% of an etchant containing boron, 1%-50% of a pyrrolidinone solvent, 1%-20% of a corrosion inhibitor, 0.01%-5% of a metal ion-free surfactant, and water, with the sum of the mass fraction of each component being 100%, the pH of the cleaning agent is 7.5-13.5, and the corrosion inhibitor is one or more of a benzotriazole corrosion inhibitor, a hydrazone corrosion inhibitor, a carbazone corrosion inhibitor and a thiocarbohydrazone corrosion inhibitor. The cleaning agent can efficiently remove nitrides from hard mask residues with little effects on metals and low-κ dielectric materials, and has a good selectivity.

Claims

1. A cleaning agent, wherein the cleaning agent is prepared from the following raw materials comprising the following mass fraction of components: 1.5%-5% of an oxidant containing iodine; 1.5%-5% of an etchant containing boron; 10%-30% of a pyrrolidinone solvent; 5%-10% of a corrosion inhibitor; 0.2%-3% of a metal ion-free surfactant; and water, with the sum of the mass fraction of each component being 100%; the pH of the cleaning agent is 9-11; the corrosion inhibitor is selected from the group consisting of a benzotriazole corrosion inhibitor, a hydrazone corrosion inhibitor, a carbazone corrosion inhibitor and a thiocarbazone corrosion inhibitor.

2. The cleaning agent according to claim 1, wherein, the benzotriazole corrosion inhibitor is selected from the group consisting of benzotriazole, methylbenzotriazole and 5-carboxybenzotriazole; and/or, the hydrazone corrosion inhibitor is acetophenone phenylhydrazone; and/or, the thiocarbazone corrosion inhibitor is diphenylthiocarbazone.

3. The cleaning agent according to claim 1, wherein the oxidant containing iodine is selected from the group consisting of iodic acid, iodate, periodic acid and periodate.

4. The cleaning agent according to claim 3, wherein the iodate is ammonium iodate and/or tetramethylammonium iodate; and/or, the periodate is ammonium periodate and/or tetramethylammonium periodate.

5. The cleaning agent according to claim 1, wherein the etchant containing boron is selected from the group consisting of tetrafluoroboric acid, ammonium tetrafluoroborate, tetramethylammonium tetrafluoroborate, tetraethylammonium tetrafluoroborate, tetrapropylammonium tetrafluoroborate and tetrabutylammonium tetrafluoroborate; and/or, the metal ion-free surfactant is polyvinylpyrrolidinone and/or dodecylbenzenesulfonic acid.

6. The cleaning agent according to claim 1, wherein the pyrrolidinone solvent is N-hydrogen-substituted pyrrolidinone solvent.

7. The cleaning agent according to claim 6, wherein the N-hydrogen-substituted pyrrolidinone solvent is selected from the group consisting of N-methylpyrrolidinone, N-ethylpyrrolidinone, N-cyclohexylpyrrolidinone, and N-hydroxyethylpyrrolidinone.

8. The cleaning agent according to claim 1, wherein the raw materials consisting of 1.5%-5% of oxidant containing iodine, 1.5%-5% of etchant containing boron, 10%-30% of pyrrolidinone solvent, 5%-10% of corrosion inhibitor, 0.2%-3% of metal ion-free surfactant, and water, with the sum of the mass fraction of each component being 100%; the pH of the cleaning agent is 9-11.

9. A method for preparing the cleaning agent according to claim 1, which comprises mixing the raw materials of claim 1.

10. Use of the cleaning agent of claim 1 in cleaning an etched and ashed semiconductor chip.

11. The use according to claim 10, wherein, the semiconductor chip is preferably a semiconductor chip of a copper interconnect structure or an aluminum interconnect structure; and/or, the use comprises contacting the etched and ashed semiconductor chip with the etching cleaning agent.

12. The use according to claim 10, which comprises: contacting the etched and ashed semiconductor chip with the etching cleaning agent followed by vibration, washing, and drying.

13. The use according to claim 12, wherein, the contacting temperature is 10-90° C.; and/or, the operation of contacting is immersing the etched and ashed semiconductor chip in the cleaning liquid; and/or, the vibration is carried out in a vortex mixer with constant temperature; and/or, the vibration temperature is 10-90° C.; and/or, the drying method is blowing dry with high purity nitrogen.

Description

EMBODIMENT

(1) In the following embodiments and comparative embodiments, the method for preparing the cleaning agent comprises mixing the corresponding raw materials.

(2) In the following embodiments, the operations are all carried out at room temperatures unless otherwise specified.

Embodiments 1-10

(3) TABLE-US-00002 TABLE 1 Components of the cleaning agent Oxidant containing Etchant Pyrrolidinone Corrosion Metal ion-free iodine containing boron solvent inhibitor surfactant No. Type Type Type Type Type 1 Periodic acid Tetrafluoroboric acid N-methylpyrrolidinone Benzotriazole Polyvinyl pyrrolidone 2 Tetramethylammonium Ammonium N-ethylpyrrolidinone Methylbenzotriazole Polyvinyl periodate tetrafluoroborate pyrrolidone 3 Ammonium periodate Tetrabutylammonium N-cyclohexylpyrrolidinone 5-carboxybenzotriazole Dodecyl tetrafluoroborate benzenesulfonic acid 4 Iodic acid Tetramethylammonium N-hydroxyethylpyrrolidinone Acetophenone Polyvinyl tetrafluoroborate phenylhydrazone pyrrolidone 5 Ammonium iodate Tetraethylammonium N-methylpyrrolidinone Diphenylthiocarbazone Dodecyl tetrafluoroborate benzenesulfonic acid 6 Tetramethylammonium Tetrapropylammonium N-ethylpyrrolidinone Benzotriazole Dodecyl iodate tetrafluoroborate benzenesulfonic acid 7 Periodic acid Tetrafluoroboric acid N-methylpyrrolidinone Benzotriazole Polyvinyl pyrrolidone 8 Periodic acid Tetrafluoroboric acid N-methylpyrrolidinone Benzotriazole Polyvinyl pyrrolidone 9 Periodic acid Tetrafluoroboric acid N-methylpyrrolidinone Benzotriazole Polyvinyl pyrrolidone 10 Periodic acid Tetrafluoroboric acid N-methylpyrrolidinone Benzotriazole Polyvinyl pyrrolidone

(4) TABLE-US-00003 TABLE 2 Mass fraction of each component and the pH of the cleaning agent Oxidant Etchant Pyrrolidone Corrosion Metal ion-free containing iodine containing boron solvent inhibitor surfactant Water No. Mass fraction % pH 1 1.5 1.5 10 5 0.2 81.8 9 2 1 1 15 6 0.5 76.5 9.5 3 2 4 20 7 1 68 9.2 4 3 2 25 8 2 59 10 5 4 3 27 9 2.5 53.5 10.5 6 5 5 30 10 3 47 11 7 0.5 0.5 1 1 0.01 96.99 9 8 1 1 5 3 0.1 89.9 9 9 10 10 50 20 4 6 9 10 20 20 35 15 5 5 9

Comparative Embodiments 1-33

(5) TABLE-US-00004 TABLE 3 Components of the cleaning agent Oxidant containing Etchant Pyrrolidinone Corrosion Metal ion-free iodine containing boron solvent inhibitor surfactant No. Type Type Type Type Type 1 Periodic acid Tetrafluoroboric acid N-methylpyrrolidinone Benzotriazole Polyvinyl pyrrolidone 2 Periodic acid Tetrafluoroboric acid N-methylpyrrolidinone Benzotriazole Polyvinyl pyrrolidone 3 Periodic acid Tetrafluoroboric acid N-methylpyrrolidinone Benzotriazole Polyvinyl pyrrolidone 4 Tetramethylammonium Ammonium N-ethylpyrrolidinone Methylbenzotriazole Polyvinyl periodate tetrafluoroborate pyrrolidone 5 Ammonium periodate Tetrabutylammonium N-cyclohexylpyrrolidinone 5-carboxybenzotriazole Dodecyl tetrafluoroborate benzene sulfonic acid 6 Iodic acid Tetramethylammonium N-hydroxyethylpyrrolidinone 1-hydroxybenzotriazole Polyvinyl tetrafluoroborate pyrrolidone 7 Ammonium iodate Tetraethylammonium N-methylpyrrolidinone 4-carboxybenzotriazole Dodecyl tetrafluoroborate benzene sulfonic acid 8 Tetramethylammonium Tetrapropylammonium N-ethylpyrrolidinone Benzotriazole Dodecyl iodate tetrafluoroborate benzene sulfonic acid 9 Periodic acid Tetrafluoroboric acid N-methylpyrrolidinone Benzotriazole Polyvinyl pyrrolidone 10 Tetramethylammonium Ammonium N-ethylpyrrolidinone Methylbenzotriazole Polyvinyl periodate tetrafluoroborate pyrrolidone 11 Ammonium periodate Tetrabutylammonium N-cyclohexylpyrrolidinone 5-carboxybenzotriazole Dodecyl tetrafluoroborate benzene sulfonic acid 12 Iodic acid Tetramethylammonium N-hydroxyethylpyrrolidinone 1-hydroxybenzotriazole Polyvinyl tetrafluoroborate pyrrolidone 13 Ammonium iodate Tetraethylammonium N-methylpyrrolidinone 4-carboxybenzotriazole Dodecyl tetrafluoroborate benzene sulfonic acid 14 Tetramethylammonium Tetrapropylammonium N-ethylpyrrolidinone Benzotriazole Dodecyl iodate tetrafluoroborate benzene sulfonic acid 15 Hydrogen peroxide Tetrafluoroboric acid N-methylpyrrolidinone Benzotriazole Polyvinyl pyrrolidone 16 Ammonium persulfate Tetrafluoroboric acid N-methylpyrrolidinone Benzotriazole Polyvinyl pyrrolidone 17 Peracetic acid Tetrafluoroboric acid N-methylpyrrolidinone Benzotriazole Polyvinyl pyrrolidone 18 Ammonium chlorite Tetrafluoroboric acid N-methylpyrrolidinone Benzotriazole Polyvinyl pyrrolidone 19 Ammonium perborate Tetrafluoroboric acid N-methylpyrrolidinone Benzotriazole Polyvinyl pyrrolidone 20 Nitric acid Tetrafluoroboric acid N-methylpyrrolidinone Benzotriazole Polyvinyl pyrrolidone 21 Tetramethylammonium Tetrafluoroboric acid N-methylpyrrolidinone Benzotriazole Polyvinyl chlorate pyrrolidone 22 Periodic acid Hydrofluoric acid N-methylpyrrolidinone Benzotriazole Polyvinyl pyrrolidone 23 Periodic acid Fluorosilicic acid N-methylpyrrolidinone Benzotriazole Polyvinyl pyrrolidone 24 Periodic acid Ammonium fluorosilicate N-methylpyrrolidinone Benzotriazole Polyvinyl pyrrolidone 25 Periodic acid Ammonium hydrogen N-methylpyrrolidinone Benzotriazole Polyvinyl fluoride pyrrolidone 26 Periodic acid Tetramethylammonium N-methylpyrrolidinone Benzotriazole Polyvinyl fluoride pyrrolidone 27 Periodic acid Trishydroxyethylammonium N-methylpyrrolidinone Benzotriazole Polyvinyl fluoride pyrrolidone 28 Periodic acid Tetrafluoroboric acid Ethylene glycol Benzotriazole Polyvinyl pyrrolidone 29 Periodic acid Tetrafluoroboric acid Sulfolane Benzotriazole Polyvinyl pyrrolidone 30 Periodic acid Tetrafluoroboric acid N-methylpyrrolidinone 1,2-dihydroxyphenol Polyvinyl pyrrolidone 31 Periodic acid Tetrafluoroboric acid N-methylpyrrolidinone Pyrogallol Polyvinyl pyrrolidone 32 Periodic acid Tetrafluoroboric acid N-methylpyrrolidinone Benzotriazole Sodium isooctyl sulfate 33 Periodic acid Tetrafluoroboric acid N-methylpyrrolidinone Benzotriazole Sodium dodecyl benzene sulfonate

(6) TABLE-US-00005 TABLE 4 Mass fraction of each component and the pH of the cleaning agent Oxidant Etchant Corrosion Metal ion-free containing iodine containing boron Pyrrolidinone solvent inhibito surfactant Water No Mass fraction % pH 1 0.1 21 0.5 0.5 0 77.9 9 2 21 0.1 51 21 6 0.9 9 3 0 1.5 10 5 0.2 83.3 9 4 0 1 15 6 0.5 77.5 9.5 5 0 2 20 7 1 70 9.2 6 0 3 25 8 2 62 10 7 0 4 27 9 2.5 57.5 10.5 8 0 5 30 10 3 52 11 9 1.5 0 10 5 0.2 83.3 9 10 1 0 15 6 0.5 77.5 9.5 11 2 0 20 7 1 70 9.2 12 3 0 25 8 2 62 10 13 4 0 27 9 2.5 57.5 10.5 14 5 0 30 10 3 52 11 15 1.5 1.5 10 5 0.2 81.8 9 16 2.5 2.5 11 6 0.2 81.8 9 17 3.5 3.5 12 7 0.2 81.8 9 18 4.5 4.5 13 8 0.2 81.8 9 19 5.5 5.5 14 9 0.2 81.8 9 20 6.5 6.5 15 10 0.2 81.8 9 21 7.5 7.5 16 11 0.2 81.8 9 22 1.5 1.5 10 5 0.2 81.8 9 23 1.5 1.5 10 5 0.2 81.8 9 24 1.5 1.5 10 5 0.2 81.8 9 25 1.5 1.5 10 5 0.2 81.8 9 26 1.5 1.5 10 5 0.2 81.8 9 27 1.5 1.5 10 5 0.2 81.8 9 28 1.5 1.5 10 5 0.2 81.8 9 29 1.5 1.5 10 5 0.2 81.8 9 30 1.5 1.5 10 5 0.2 81.8 9 31 1.5 1.5 10 5 0.2 81.8 9 32 1.5 1.5 10 5 0.2 81.8 9 33 1.5 1.5 10 5 0.2 81.8 9

(7) Among the above embodiments, Comparative embodiments 1-2 explored the upper limit of the amount of each component. Comparative embodiments 3-8 explored the effect without adding the oxidant containing iodine. Comparative embodiments 9-14 explored the effect without adding the etchant containing boron. Comparative embodiments 15-21 explored the effect of using the oxidizing agents other than the oxidant containing iodine. Comparative embodiments 22-27 explored the effects of using the etchant other than the etchant containing boron. Comparative embodiments 28-29 explored the effect of using the organic solvents other than the pyrrolidinone. Comparative embodiments 30-31 explored the effects of using the corrosion inhibitors other than corrosion inhibitors in the components of the present invention. Comparative embodiments 32-33 explored the effect of using surfactants containing metal ions.

Effect Embodiments

(8) Testing Procedures:

(9) Various wafers (with various nitrides, metals, dielectric materials deposited on the silicon wafer, each having a material layer thickness of 1000 Å) were immersed in the cleaning agent at 50° C. for 15 minutes. The thickness of the wafers was measured before and after the immersion treatment, wherein the thickness of TiN, TaN, WN, Cu, Co, Ta, Ti, and W was measured by Four Dimensions Four Point Probe Meter 333A, and the thickness of TEOS was measured by an Auto SE Spectroscopic Ellipsometer from HORIBA JOBIN YVON. The etching rate was calculated as the change of the thickness (before and after chemical treatment) divided by the chemical treatment time. The pH of the chemical solution was measured using a Beckman 260 pH/Temp/mV meter. The cleaning liquids were used to clean the plasma etched and ashed copper interconnect chips at 50° C., and the residue removal effect was evaluated by SEM results (Hitachi S-5500).

(10) The test results are shown in Table 5.

(11) Etching rate (at 50° C.) in Å/min.

(12) TABLE-US-00006 TABLE 5 Cleaning / TaN TiN WN Cu Co Ta W Ti TEOS effect / 40-100 100-200 60-100 0-2 0-1 0-1 0-1 0-1 0-1 ⊚ Application effect 46 156.1 75.8 1.8 0.2 0.8 0.2 0.4 0.5 ⊚ embodiment 1 Application effect 54.1 116.6 90.3 0.7 0.4 0.4 0.3 0.2 0.3 ⊚ embodiment 2 Application effect 60.2 137 72.1 1.8 0.6 1 0.2 0.2 0.5 ⊚ embodiment 3 Application effect 91.1 102.2 87.1 1.2 0.7 0 0 0.3 0.9 ⊚ embodiment 4 Application effect 91.5 134.7 85.9 0.4 0.6 0.2 1 1 0.9 ⊚ embodiment 5 Application effect 69.6 100.3 96.4 0.6 0.2 0.3 0.9 1 0 ⊚ embodiment 6 Application effect 54.1 111.9 72 1.7 0 1 0.7 0.1 1 ⊚ embodiment 7 Application effect 50.8 191.8 73.2 1.3 0.1 0.7 0.2 0.5 0.9 ⊚ embodiment 8 Application effect 73.3 186.6 92.4 1.8 0.1 0.5 0.5 0.9 0.9 ⊚ embodiment 9 Application effect 88.4 164.2 90.8 0.5 0.9 1 0.1 1 0.7 ⊚ embodiment 10 Comparative 4.2 15.1 6.5 0.2 0.8 0 1.2 1.6 0.8 X effect embodiment 1 Comparative 50.1 75.3 44.8 3.9 3.5 3 1.3 1.6 2.8 X effect embodiment 2 Comparative 4.6 4.3 3.3 2.2 1.4 2.7 0 4.9 1.4 Δ effect embodiment 3 Comparative 3.2 1.8 4 2.5 4.4 3.9 1.7 3.9 2.9 X effect embodiment 4 Comparative 0.6 0.8 4.8 0.9 4 3.8 2.2 2.2 4.5 X effect embodiment 5 Comparative 4.5 4.3 4.2 3.8 2.8 3.5 0.5 0.9 1.2 X effect embodiment 6 Comparative 1.8 3.3 4.4 0.6 0.9 4.6 0.9 2 1.8 Δ effect embodiment 7 Comparative 3.3 5 3.5 3.7 3.2 4.2 1 1.6 2 X effect embodiment 8 Comparative 43.8 45.2 44.3 4 4.7 5 5 4.8 4.3 Δ effect embodiment 9 Comparative 48.7 40.9 41.1 4.2 4.6 4.5 4.7 4.2 4.4 X effect embodiment 10 Comparative 48.4 45.8 47.4 4.6 4.1 4.1 4.3 4 4.8 Δ effect embodiment 11 Comparative 40.1 48.2 48.1 4.8 4.2 4.5 4.8 4.3 4.9 X effect embodiment 12 Comparative 47.5 48.1 40.8 4 5 4.3 4 4.7 4.6 Δ effect embodiment 13 Comparative 45.6 40.1 44.4 4.3 5 4.6 4.3 4.8 4.5 X effect embodiment 14 Comparative 54.6 53.8 53.8 5 7.6 7.5 7.4 6.9 6.4 X effect embodiment 15 Comparative 57.2 50.2 54 7.4 7.4 6 5.7 8 6.9 X effect embodiment 16 Comparative 57.5 59.4 58.7 7.9 5.9 7.5 7 5.5 6.4 X effect embodiment 17 Comparative 52.9 53.8 54.3 8 6.9 6 7.9 7.6 7.3 X effect embodiment 18 Comparative 53.4 51.7 58.2 6 5.3 6.4 5.7 5.8 7.7 Δ effect embodiment 19 Comparative 59.7 58.5 59.7 5.5 5.4 5.7 6.6 6.2 7.6 X effect embodiment 20 Comparative 56.8 56.6 52.2 8 7.8 8 5.8 7 5 Δ effect embodiment 21 Comparative 57.4 50.5 59.7 6 5.3 5.4 6.4 8 7.8 Δ effect embodiment 22 Comparative 53.9 54.7 56.7 6.8 5 5.3 5.7 7.7 5.1 Δ effect embodiment 23 Comparative 52.3 52.4 59.4 5.3 7.1 5.4 6.5 6.8 6.6 Δ effect embodiment 24 Comparative 57.1 52.9 50.6 5.1 7.8 5 6.7 7.1 6.3 X effect embodiment 25 Comparative 52.9 56.5 56.9 5.3 5.3 6 7.4 7.4 6.2 X effect embodiment 26 Comparative 52.4 52.7 56 5.1 6.1 5 7.6 6.9 7.6 X effect embodiment 27 Comparative 54.4 50.6 53.7 6.9 6.6 5.6 7.9 5.3 5.8 X effect embodiment 28 Comparative 52.1 53.6 58.8 7.8 7 6.6 5.9 5.6 8 Δ effect embodiment 29 Comparative 54 51.9 59.4 5.4 6.5 6.2 8 5.1 5.7 ⊚ effect embodiment 30 Comparative 59.3 50.8 50.4 6.4 5.7 6.8 6.2 7.9 6.8 Δ effect embodiment 31 Comparative 53.7 58.4 53.1 5.9 5.6 6.6 6.4 6 6.9 ⊚ effect embodiment 32 Comparative 50.8 55.7 50.4 6.6 5.2 7.6 7.8 5 7.6 Δ effect embodiment 33

Cleaning Effect

(13) TABLE-US-00007 ⊚ Completely removed ◯ A small amount of residue Δ Some residue X A large amount of residue

(14) Comparative effect embodiments 1-33 and Effect embodiments 1-10 show that the cleaning agents of the present invention improve both etching selectivity and cleaning effect compared with the cleaning agents of the comparative embodiments.

(15) Although the specific embodiments of the present invention are described above, a person skilled in the art should understand that these are only examples and can be changed or modified in a variety of ways without deviating from the principle and essence of the present invention. Accordingly, the scope of the present invention is defined by the appended claims.