CN114369462A - Etching solution for selectively etching titanium nitride and tungsten - Google Patents
Etching solution for selectively etching titanium nitride and tungsten Download PDFInfo
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- CN114369462A CN114369462A CN202111546681.8A CN202111546681A CN114369462A CN 114369462 A CN114369462 A CN 114369462A CN 202111546681 A CN202111546681 A CN 202111546681A CN 114369462 A CN114369462 A CN 114369462A
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- 238000005530 etching Methods 0.000 title claims abstract description 313
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 179
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 179
- 239000010937 tungsten Substances 0.000 title claims abstract description 179
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 title claims abstract description 152
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 23
- -1 hydrogen ions Chemical class 0.000 claims abstract description 14
- 239000003112 inhibitor Substances 0.000 claims abstract description 13
- 239000004094 surface-active agent Substances 0.000 claims abstract description 12
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 4
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 50
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 28
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 21
- 229910017604 nitric acid Inorganic materials 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 17
- 229920002401 polyacrylamide Polymers 0.000 claims description 14
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 8
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 8
- 239000003518 caustics Substances 0.000 claims description 7
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 7
- 235000011046 triammonium citrate Nutrition 0.000 claims description 7
- 239000001393 triammonium citrate Substances 0.000 claims description 7
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 6
- ILRSCQWREDREME-UHFFFAOYSA-N dodecanamide Chemical compound CCCCCCCCCCCC(N)=O ILRSCQWREDREME-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 3
- LLOHIFXFHGMBNO-UHFFFAOYSA-N azane;2-hydroxyethanesulfonic acid Chemical compound [NH4+].OCCS([O-])(=O)=O LLOHIFXFHGMBNO-UHFFFAOYSA-N 0.000 claims description 3
- ZSNUOIONTCOONQ-UHFFFAOYSA-M hexadecyl(trimethyl)azanium;fluoride Chemical compound [F-].CCCCCCCCCCCCCCCC[N+](C)(C)C ZSNUOIONTCOONQ-UHFFFAOYSA-M 0.000 claims description 3
- 235000013024 sodium fluoride Nutrition 0.000 claims description 3
- 239000011775 sodium fluoride Substances 0.000 claims description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- ILRKKHJEINIICQ-OOFFSTKBSA-N Monoammonium glycyrrhizinate Chemical compound N.O([C@@H]1[C@@H](O)[C@H](O)[C@H](O[C@@H]1O[C@H]1CC[C@]2(C)[C@H]3C(=O)C=C4[C@@H]5C[C@](C)(CC[C@@]5(CC[C@@]4(C)[C@]3(C)CC[C@H]2C1(C)C)C)C(O)=O)C(O)=O)[C@@H]1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@H]1O ILRKKHJEINIICQ-OOFFSTKBSA-N 0.000 claims description 2
- QMKBSUASRATAHH-UHFFFAOYSA-N N.N.N1=NN=NC1=C1N=NN=N1 Chemical compound N.N.N1=NN=NC1=C1N=NN=N1 QMKBSUASRATAHH-UHFFFAOYSA-N 0.000 claims description 2
- DFPAKSUCGFBDDF-ZQBYOMGUSA-N [14c]-nicotinamide Chemical compound N[14C](=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-ZQBYOMGUSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- TXBULBYASDPNNC-UHFFFAOYSA-L tetraethylazanium;sulfate Chemical compound [O-]S([O-])(=O)=O.CC[N+](CC)(CC)CC.CC[N+](CC)(CC)CC TXBULBYASDPNNC-UHFFFAOYSA-L 0.000 claims description 2
- PKDWAUXITAOJHD-UHFFFAOYSA-N 2-acetylbenzamide Chemical compound CC(=O)C1=CC=CC=C1C(N)=O PKDWAUXITAOJHD-UHFFFAOYSA-N 0.000 claims 1
- DOZZSWAOPDYVLH-UHFFFAOYSA-N 2-phenylpropanamide Chemical compound NC(=O)C(C)C1=CC=CC=C1 DOZZSWAOPDYVLH-UHFFFAOYSA-N 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 29
- 239000002184 metal Substances 0.000 abstract description 29
- 239000010936 titanium Substances 0.000 abstract description 7
- 229910052719 titanium Inorganic materials 0.000 abstract description 7
- 239000007800 oxidant agent Substances 0.000 abstract description 6
- 230000001590 oxidative effect Effects 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 230000001737 promoting effect Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 60
- 229910021642 ultra pure water Inorganic materials 0.000 description 45
- 239000012498 ultrapure water Substances 0.000 description 45
- 239000000523 sample Substances 0.000 description 32
- 229910052581 Si3N4 Inorganic materials 0.000 description 31
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 31
- 229910052757 nitrogen Inorganic materials 0.000 description 30
- 238000010926 purge Methods 0.000 description 30
- 238000005406 washing Methods 0.000 description 30
- 230000008859 change Effects 0.000 description 15
- 238000005520 cutting process Methods 0.000 description 15
- 239000011521 glass Substances 0.000 description 15
- 238000002791 soaking Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 6
- 230000004888 barrier function Effects 0.000 description 4
- CPSUAFUQJBJMPO-UHFFFAOYSA-N 2-phenylpropanediamide Chemical compound NC(=O)C(C(N)=O)C1=CC=CC=C1 CPSUAFUQJBJMPO-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229940116335 lauramide Drugs 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- KGGRQKDGRGUWAT-UHFFFAOYSA-N n-acetylbenzamide Chemical compound CC(=O)NC(=O)C1=CC=CC=C1 KGGRQKDGRGUWAT-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- ing And Chemical Polishing (AREA)
- Weting (AREA)
Abstract
The invention relates to an etching solution for selectively etching titanium nitride and tungsten, which mainly comprises hydrogen peroxide, inorganic acid, corrosive, etching inhibitor, surfactant and deionized water. Hydrogen peroxide is used as an oxidant in the etching solution; inorganic acid is used as a secondary oxidant in the etching solution, so that the oxidability of hydrogen peroxide is increased, hydrogen ions are provided for the etching solution, and the stability of the etching rate is ensured; in the process of etching titanium nitride and tungsten by the etching solution, the titanium nitride can be selectively etched, and the stability of the speed is ensured. The etchant may form a complex with the oxidized titanium ions, promoting further reaction of the titanium nitride; the etching inhibitor can inhibit the oxidation of the metal tungsten; the etching inhibitor is adsorbed on the surface of the metal tungsten in a coordination bond form to form a dense film to prevent the etching solution from etching the metal tungsten; the surface active agent can adjust the surface tension between the etching solution and different phases, so as to adjust the selection ratio of the etching solution in two phases of titanium nitride and tungsten. The etching solution of the invention can selectively etch the titanium nitride with high etching rate.
Description
Technical Field
The invention belongs to the technical field of etching solutions, and particularly relates to a low-foam etching solution with uniform etching.
Background
Tungsten, which is widely used for metal conductive layers, gates, barrier layers, or reticles in integrated circuits due to its good semiconductor compatibility and adhesion, and titanium nitride materials are widely used in integrated circuit fabrication. Similarly, titanium nitride (titanium-based metal) is often used as a material for a bottom layer, a barrier layer or a bonding layer of other metal layers in integrated circuits due to its excellent conductive and superconducting properties, and particularly in logic circuit manufacturing, although very large scale integrated circuits are developed toward a higher copper process, the current MOCVD technology for depositing titanium nitride is an irreplaceable technology for using titanium nitride as a bonding layer and a barrier layer for tungsten filling.
The existing titanium nitride and tungsten etching solution is mostly used for simultaneously etching titanium nitride and tungsten layers, and both patent 1(CN109328394A) and patent 2(CN 110195229A) disclose the etching solution for simultaneously etching a tungsten metal layer and a titanium nitride layer, and the effect of ensuring the consistent etching rate of tungsten and titanium nitride can be ensured by regulating and controlling. Patent 3(CN 110095952 a) uses an etchant composition of 1-10% of an oxidizing agent, 5-20% of a polyamine compound, 2-10% of an ammonium salt, and 0.1-2% of a corrosion inhibitor, the etchant being selected from tungsten capable of selectively removing titanium nitride, copper, and TEOS silicon oxide on a wafer. Patent 4(CN 105936822 a) uses 80% -90% of at least one compound selected from sulfuric acid and alkyl sulfonic acid, 1% -5% of peroxide, 0.001% -1% of inorganic ammonium salt, the etching solution can selectively etch titanium nitride and tungsten, but the selectivity ratio is only 10.5, and the etching rate of titanium nitride is only up to
In summary, the existing literature for titanium nitride and tungsten mainly etches both simultaneously, and the etching rate can be ensured to be consistent by regulation, while the literature for selectively etching titanium nitride and tungsten has a lower selection ratio and lower etching rate, and a titanium nitride and tungsten etching solution with a high selection ratio and a high etching rate is required to be developed.
Disclosure of Invention
The invention provides an etching solution for selectively removing titanium nitride and tungsten, which can be used for selectively etching titanium nitride and forming a metal interconnection line in a logic circuit process in an integrated circuit.
In order to achieve the purpose, the invention adopts the following technical scheme:
an etching solution for selectively etching titanium nitride and tungsten comprises the following components in percentage by mass: the mass fraction of the hydrogen peroxide is 1-30%; the mass fraction of the inorganic acid is 1-50%; the mass fraction of the corrosive agent is 1-10%; the mass fraction of the etching inhibitor is 1-5%; the mass fraction of the surfactant is 0.001-1%; the balance being deionized water.
Preferably, the corrosive agent is one or a combination of more of fluoride, hydrofluoric acid, ammonium fluoride, sodium fluoride, fluosilicic acid and sodium fluosilicate.
Preferably, the inorganic acid is one or more of sulfuric acid, nitric acid and hydrochloric acid.
Preferably, the etching inhibitor ammonium salt compound is one or more of ammonium sulfate, ammonium persulfate, tetraethylammonium sulfate, triammonium citrate, hexadecyltrimethylammonium fluoride, ammonium isethionate, monoammonium glycyrrhizinate, diammonium 5,5' -bitetrazole, and ammonium nitrate.
Preferably, the surfactant is an amide compound, and is one or more of polyacrylamide, nicotinamide, 2-furfuryl amide, crotonamide, lauramide, 2-phenyl malonamide, acetyl benzamide and diacetone acrylamide.
The preparation method of the etching solution for selectively etching the titanium nitride and the tungsten comprises the following steps:
s1: adding hydrogen peroxide, deionized water and inorganic acid in sequence;
s2: adding a corrosive agent, an etching inhibitor and a surfactant, adding water to adjust the total amount of the etching solution, and ultrasonically stirring uniformly to obtain the etching solution.
Preferably, when the inorganic acid is nitric acid and sulfuric acid, the nitric acid is added firstly, then the sulfuric acid is added in three times, and after the sulfuric acid is added every time, the mixture is placed into an ice bath to be cooled to room temperature, the sulfuric acid is added again, and the steps are repeated for three times.
The using method of the etching solution for selectively etching the titanium nitride and the tungsten is characterized in that the titanium nitride and the tungsten are soaked in the etching solution and etched at the temperature of 40-80 ℃ for 1-20min to complete the etching.
The invention has the advantages of
In the formula of the invention, the hydrogen peroxide is used as an oxidant in the etching solution; the inorganic acid is used as a secondary oxidant in the etching solution, so that the oxidability of hydrogen peroxide is increased, hydrogen ions are provided in the etching solution, and the stability of the etching rate is ensured; in the process of etching titanium nitride and tungsten by the etching solution, the titanium nitride can be selectively etched, and the stability of the speed is ensured. The corrosive agent can form a complex with the oxidized titanium ions to promote further reaction of the titanium nitride; the etching inhibitor can inhibit the oxidation of the metal tungsten, and is adsorbed on the surface of the metal tungsten in a coordination bond form to form a dense film so as to inhibit the etching of the etching solution on the metal tungsten; the surfactant can adjust the surface tension between the etching solution and different phases, so as to adjust the selection ratio of the etching solution in two phases of titanium nitride and tungsten.
The specific implementation mode is as follows:
the invention will be further illustrated with reference to the following specific examples.
Example 1
An etching solution for selectively etching titanium nitride and tungsten, comprising:
15 wt% of hydrogen peroxide, 12.8 wt% of nitric acid, 21.8 wt% of sulfuric acid, 4.4 wt% of hydrofluoric acid, 2 wt% of ammonium sulfate, 0.1 wt% of polyacrylamide and the balance of ultrapure water.
The etching temperature and etching time were 50 ℃ and 5min, respectively.
Preparing the etching solution in a beaker according to the composition of the etching solution, putting the ultrasonically-stirred etching solution beaker into a constant-temperature water bath kettle at 50 ℃, and after the temperature of the etching solution reaches 50 ℃ and is stable for a period of time; cutting titanium nitride and tungsten metal sheets into the same size by using a glass cutter, washing with ultrapure water, and purging with nitrogen; the method comprises the following steps of measuring the film thickness of silicon nitride and tungsten sheets before etching by using a four-probe thickness gauge, fixing the titanium nitride or tungsten sheets by using a frame, suspending and soaking the titanium nitride or tungsten sheets in an etching solution at 50 ℃, taking out the titanium nitride or tungsten sheets after etching for 5 minutes, washing the titanium nitride or tungsten sheets by using ultrapure water, purging the titanium nitride or tungsten sheets by using nitrogen, testing the film thickness of the silicon nitride and tungsten sheets after etching by using the four-probe thickness gauge, and calculating the etching rate according to the change of the film thickness before and after etching.
Example 2
An etching solution for selectively etching titanium nitride and tungsten, comprising:
15 wt% of hydrogen peroxide, 34.6 wt% of sulfuric acid, 4.4 wt% of hydrofluoric acid, 2 wt% of ammonium sulfate, 0.1 wt% of polyacrylamide and the balance of ultrapure water.
The etching temperature and etching time were 50 ℃ and 5min, respectively.
Preparing the etching solution in a beaker according to the composition of the etching solution, putting the ultrasonically-stirred etching solution beaker into a constant-temperature water bath kettle at 50 ℃, and after the temperature of the etching solution reaches 50 ℃ and is stable for a period of time; cutting titanium nitride and tungsten metal sheets into the same size by using a glass cutter, washing with ultrapure water, and purging with nitrogen; the method comprises the following steps of measuring the film thickness of silicon nitride and tungsten sheets before etching by using a four-probe thickness gauge, fixing the titanium nitride or tungsten sheets by using a frame, suspending and soaking the titanium nitride or tungsten sheets in an etching solution at 50 ℃, taking out the titanium nitride or tungsten sheets after etching for 5 minutes, washing the titanium nitride or tungsten sheets by using ultrapure water, purging the titanium nitride or tungsten sheets by using nitrogen, testing the film thickness of the silicon nitride and tungsten sheets after etching by using the four-probe thickness gauge, and calculating the etching rate according to the change of the film thickness before and after etching.
Example 3
An etching solution for selectively etching titanium nitride and tungsten, comprising:
15 wt% of hydrogen peroxide, 34.6 wt% of nitric acid, 4.4 wt% of hydrofluoric acid, 2 wt% of ammonium sulfate, 0.1 wt% of polyacrylamide and the balance of ultrapure water.
The etching temperature and etching time were 50 ℃ and 5min, respectively.
Preparing the etching solution in a beaker according to the composition of the etching solution, putting the ultrasonically-stirred etching solution beaker into a constant-temperature water bath kettle at 50 ℃, and after the temperature of the etching solution reaches 50 ℃ and is stable for a period of time; cutting titanium nitride and tungsten metal sheets into the same size by using a glass cutter, washing with ultrapure water, and purging with nitrogen; the method comprises the following steps of measuring the film thickness of silicon nitride and tungsten sheets before etching by using a four-probe thickness gauge, fixing the titanium nitride or tungsten sheets by using a frame, suspending and soaking the titanium nitride or tungsten sheets in an etching solution at 50 ℃, taking out the titanium nitride or tungsten sheets after etching for 5 minutes, washing the titanium nitride or tungsten sheets by using ultrapure water, purging the titanium nitride or tungsten sheets by using nitrogen, testing the film thickness of the silicon nitride and tungsten sheets after etching by using the four-probe thickness gauge, and calculating the etching rate according to the change of the film thickness before and after etching.
Example 4
An etching solution for selectively etching titanium nitride and tungsten, comprising:
15 wt% of hydrogen peroxide, 20 wt% of nitric acid, 21.8 wt% of sulfuric acid, 4.4 wt% of hydrofluoric acid, 2 wt% of ammonium sulfate, 0.1 wt% of polyacrylamide and the balance of ultrapure water.
The etching temperature and etching time were 50 ℃ and 5min, respectively.
Preparing the etching solution in a beaker according to the composition of the etching solution, putting the ultrasonically-stirred etching solution beaker into a constant-temperature water bath kettle at 50 ℃, and after the temperature of the etching solution reaches 50 ℃ and is stable for a period of time; cutting titanium nitride and tungsten metal sheets into the same size by using a glass cutter, washing with ultrapure water, and purging with nitrogen; the method comprises the following steps of measuring the film thickness of silicon nitride and tungsten sheets before etching by using a four-probe thickness gauge, fixing the titanium nitride or tungsten sheets by using a frame, suspending and soaking the titanium nitride or tungsten sheets in an etching solution at 50 ℃, taking out the titanium nitride or tungsten sheets after etching for 5 minutes, washing the titanium nitride or tungsten sheets by using ultrapure water, purging the titanium nitride or tungsten sheets by using nitrogen, testing the film thickness of the silicon nitride and tungsten sheets after etching by using the four-probe thickness gauge, and calculating the etching rate according to the change of the film thickness before and after etching.
Example 5
An etching solution for selectively etching titanium nitride and tungsten, comprising:
15 wt% of hydrogen peroxide, 12.8 wt% of nitric acid, 21.8 wt% of sulfuric acid, 7.9 wt% of ammonium fluoride, 2 wt% of ammonium sulfate, 0.1 wt% of polyacrylamide and the balance of ultrapure water.
The etching temperature and etching time were 50 ℃ and 5min, respectively.
Preparing the etching solution in a beaker according to the composition of the etching solution, putting the ultrasonically-stirred etching solution beaker into a constant-temperature water bath kettle at 50 ℃, and after the temperature of the etching solution reaches 50 ℃ and is stable for a period of time; cutting titanium nitride and tungsten metal sheets into the same size by using a glass cutter, washing with ultrapure water, and purging with nitrogen; the method comprises the following steps of measuring the film thickness of silicon nitride and tungsten sheets before etching by using a four-probe thickness gauge, fixing the titanium nitride or tungsten sheets by using a frame, suspending and soaking the titanium nitride or tungsten sheets in an etching solution at 50 ℃, taking out the titanium nitride or tungsten sheets after etching for 5 minutes, washing the titanium nitride or tungsten sheets by using ultrapure water, purging the titanium nitride or tungsten sheets by using nitrogen, testing the film thickness of the silicon nitride and tungsten sheets after etching by using the four-probe thickness gauge, and calculating the etching rate according to the change of the film thickness before and after etching.
Example 6
An etching solution for selectively etching titanium nitride and tungsten, comprising:
15 wt% of hydrogen peroxide, 12.8 wt% of nitric acid, 21.8 wt% of sulfuric acid, 4.4 wt% of sodium fluoride, 2 wt% of ammonium sulfate, 0.1 wt% of polyacrylamide and the balance of ultrapure water.
The etching temperature and etching time were 50 ℃ and 5min, respectively.
Preparing the etching solution in a beaker according to the composition of the etching solution, putting the ultrasonically-stirred etching solution beaker into a constant-temperature water bath kettle at 50 ℃, and after the temperature of the etching solution reaches 50 ℃ and is stable for a period of time; cutting titanium nitride and tungsten metal sheets into the same size by using a glass cutter, washing with ultrapure water, and purging with nitrogen; the method comprises the following steps of measuring the film thickness of silicon nitride and tungsten sheets before etching by using a four-probe thickness gauge, fixing the titanium nitride or tungsten sheets by using a frame, suspending and soaking the titanium nitride or tungsten sheets in an etching solution at 50 ℃, taking out the titanium nitride or tungsten sheets after etching for 5 minutes, washing the titanium nitride or tungsten sheets by using ultrapure water, purging the titanium nitride or tungsten sheets by using nitrogen, testing the film thickness of the silicon nitride and tungsten sheets after etching by using the four-probe thickness gauge, and calculating the etching rate according to the change of the film thickness before and after etching.
Example 7
An etching solution for selectively etching titanium nitride and tungsten, comprising:
15 wt% of hydrogen peroxide, 12.8 wt% of nitric acid, 21.8 wt% of sulfuric acid, 4.4 wt% of hydrofluoric acid, 2 wt% of triammonium citrate, 0.1 wt% of polyacrylamide and the balance of ultrapure water.
The etching temperature and etching time were 50 ℃ and 5min, respectively.
Preparing the etching solution in a beaker according to the composition of the etching solution, putting the ultrasonically-stirred etching solution beaker into a constant-temperature water bath kettle at 50 ℃, and after the temperature of the etching solution reaches 50 ℃ and is stable for a period of time; cutting titanium nitride and tungsten metal sheets into the same size by using a glass cutter, washing with ultrapure water, and purging with nitrogen; the method comprises the following steps of measuring the film thickness of silicon nitride and tungsten sheets before etching by using a four-probe thickness gauge, fixing the titanium nitride or tungsten sheets by using a frame, suspending and soaking the titanium nitride or tungsten sheets in an etching solution at 50 ℃, taking out the titanium nitride or tungsten sheets after etching for 5 minutes, washing the titanium nitride or tungsten sheets by using ultrapure water, purging the titanium nitride or tungsten sheets by using nitrogen, testing the film thickness of the silicon nitride and tungsten sheets after etching by using the four-probe thickness gauge, and calculating the etching rate according to the change of the film thickness before and after etching.
Example 8
An etching solution for selectively etching titanium nitride and tungsten, comprising:
15 wt% of hydrogen peroxide, 12.8 wt% of nitric acid, 21.8 wt% of sulfuric acid, 4.4 wt% of hydrofluoric acid, 2 wt% of ammonium isethionate, 0.1 wt% of polyacrylamide and the balance of ultrapure water.
The etching temperature and etching time were 50 ℃ and 5min, respectively.
Preparing the etching solution in a beaker according to the composition of the etching solution, putting the ultrasonically-stirred etching solution beaker into a constant-temperature water bath kettle at 50 ℃, and after the temperature of the etching solution reaches 50 ℃ and is stable for a period of time; cutting titanium nitride and tungsten metal sheets into the same size by using a glass cutter, washing with ultrapure water, and purging with nitrogen; the method comprises the following steps of measuring the film thickness of silicon nitride and tungsten sheets before etching by using a four-probe thickness gauge, fixing the titanium nitride or tungsten sheets by using a frame, suspending and soaking the titanium nitride or tungsten sheets in an etching solution at 50 ℃, taking out the titanium nitride or tungsten sheets after etching for 5 minutes, washing the titanium nitride or tungsten sheets by using ultrapure water, purging the titanium nitride or tungsten sheets by using nitrogen, testing the film thickness of the silicon nitride and tungsten sheets after etching by using the four-probe thickness gauge, and calculating the etching rate according to the change of the film thickness before and after etching.
Example 9
An etching solution for selectively etching titanium nitride and tungsten, comprising:
15 wt% of hydrogen peroxide, 12.8 wt% of nitric acid, 21.8 wt% of sulfuric acid, 4.4 wt% of hydrofluoric acid, 2 wt% of hexadecyl trimethyl ammonium fluoride, 0.1 wt% of polyacrylamide and the balance of ultrapure water.
The etching temperature and etching time were 50 ℃ and 5min, respectively.
Preparing the etching solution in a beaker according to the composition of the etching solution, putting the ultrasonically-stirred etching solution beaker into a constant-temperature water bath kettle at 50 ℃, and after the temperature of the etching solution reaches 50 ℃ and is stable for a period of time; cutting titanium nitride and tungsten metal sheets into the same size by using a glass cutter, washing with ultrapure water, and purging with nitrogen; the method comprises the following steps of measuring the film thickness of silicon nitride and tungsten sheets before etching by using a four-probe thickness gauge, fixing the titanium nitride or tungsten sheets by using a frame, suspending and soaking the titanium nitride or tungsten sheets in an etching solution at 50 ℃, taking out the titanium nitride or tungsten sheets after etching for 5 minutes, washing the titanium nitride or tungsten sheets by using ultrapure water, purging the titanium nitride or tungsten sheets by using nitrogen, testing the film thickness of the silicon nitride and tungsten sheets after etching by using the four-probe thickness gauge, and calculating the etching rate according to the change of the film thickness before and after etching.
Example 10
15 wt% of hydrogen peroxide, 12.8 wt% of nitric acid, 21.8 wt% of sulfuric acid, 4 wt% of hydrofluoric acid, 2 wt% of triammonium citrate, 0.3 wt% of polyacrylamide and the balance of ultrapure water.
The etching temperature and etching time were 50 ℃ and 5min, respectively.
Preparing the etching solution in a beaker according to the composition of the etching solution, putting the ultrasonically-stirred etching solution beaker into a constant-temperature water bath kettle at 50 ℃, and after the temperature of the etching solution reaches 50 ℃ and is stable for a period of time; cutting titanium nitride and tungsten metal sheets into the same size by using a glass cutter, washing with ultrapure water, and purging with nitrogen; the method comprises the following steps of measuring the film thickness of silicon nitride and tungsten sheets before etching by using a four-probe thickness gauge, fixing the titanium nitride or tungsten sheets by using a frame, suspending and soaking the titanium nitride or tungsten sheets in an etching solution at 50 ℃, taking out the titanium nitride or tungsten sheets after etching for 5 minutes, washing the titanium nitride or tungsten sheets by using ultrapure water, purging the titanium nitride or tungsten sheets by using nitrogen, testing the film thickness of the silicon nitride and tungsten sheets after etching by using the four-probe thickness gauge, and calculating the etching rate according to the change of the film thickness before and after etching.
Example 11
15 wt% of hydrogen peroxide, 12.8 wt% of nitric acid, 21.8 wt% of sulfuric acid, 4.4 wt% of hydrofluoric acid, 2 wt% of triammonium citrate, 0.1 wt% of lauramide and the balance of ultrapure water.
The etching temperature and etching time were 50 ℃ and 5min, respectively.
Preparing the etching solution in a beaker according to the composition of the etching solution, putting the ultrasonically-stirred etching solution beaker into a constant-temperature water bath kettle at 50 ℃, and after the temperature of the etching solution reaches 50 ℃ and is stable for a period of time; cutting titanium nitride and tungsten metal sheets into the same size by using a glass cutter, washing with ultrapure water, and purging with nitrogen; the method comprises the following steps of measuring the film thickness of silicon nitride and tungsten sheets before etching by using a four-probe thickness gauge, fixing the titanium nitride or tungsten sheets by using a frame, suspending and soaking the titanium nitride or tungsten sheets in an etching solution at 50 ℃, taking out the titanium nitride or tungsten sheets after etching for 5 minutes, washing the titanium nitride or tungsten sheets by using ultrapure water, purging the titanium nitride or tungsten sheets by using nitrogen, testing the film thickness of the silicon nitride and tungsten sheets after etching by using the four-probe thickness gauge, and calculating the etching rate according to the change of the film thickness before and after etching.
Example 12
15 wt% of hydrogen peroxide, 12.8 wt% of nitric acid, 21.8 wt% of sulfuric acid, 4.4 wt% of hydrofluoric acid, 2 wt% of triammonium citrate, 0.1 wt% of 2-phenyl malonamide and the balance of ultrapure water.
The etching temperature and etching time were 50 ℃ and 5min, respectively.
Preparing the etching solution in a beaker according to the composition of the etching solution, putting the ultrasonically-stirred etching solution beaker into a constant-temperature water bath kettle at 50 ℃, and after the temperature of the etching solution reaches 50 ℃ and is stable for a period of time; cutting titanium nitride and tungsten metal sheets into the same size by using a glass cutter, washing with ultrapure water, and purging with nitrogen; the method comprises the following steps of measuring the film thickness of silicon nitride and tungsten sheets before etching by using a four-probe thickness gauge, fixing the titanium nitride or tungsten sheets by using a frame, suspending and soaking the titanium nitride or tungsten sheets in an etching solution at 50 ℃, taking out the titanium nitride or tungsten sheets after etching for 5 minutes, washing the titanium nitride or tungsten sheets by using ultrapure water, purging the titanium nitride or tungsten sheets by using nitrogen, testing the film thickness of the silicon nitride and tungsten sheets after etching by using the four-probe thickness gauge, and calculating the etching rate according to the change of the film thickness before and after etching.
Comparative example 1
15 wt% of hydrogen peroxide, 12.8 wt% of nitric acid, 21.8 wt% of sulfuric acid, 4.4 wt% of hydrofluoric acid, 0.1 wt% of polyacrylamide and the balance of ultrapure water.
The etching temperature and etching time were 50 ℃ and 5min, respectively.
Preparing the etching solution in a beaker according to the composition of the etching solution, putting the ultrasonically-stirred etching solution beaker into a constant-temperature water bath kettle at 50 ℃, and after the temperature of the etching solution reaches 50 ℃ and is stable for a period of time; cutting titanium nitride and tungsten metal sheets into the same size by using a glass cutter, washing with ultrapure water, and purging with nitrogen; the method comprises the following steps of measuring the film thickness of silicon nitride and tungsten sheets before etching by using a four-probe thickness gauge, fixing the titanium nitride or tungsten sheets by using a frame, suspending and soaking the titanium nitride or tungsten sheets in an etching solution at 50 ℃, taking out the titanium nitride or tungsten sheets after etching for 5 minutes, washing the titanium nitride or tungsten sheets by using ultrapure water, purging the titanium nitride or tungsten sheets by using nitrogen, testing the film thickness of the silicon nitride and tungsten sheets after etching by using the four-probe thickness gauge, and calculating the etching rate according to the change of the film thickness before and after etching.
Comparative example 2
15 wt% of hydrogen peroxide, 12.8 wt% of nitric acid, 21.8 wt% of sulfuric acid, 4.4 wt% of hydrofluoric acid, 2 wt% of triammonium citrate and the balance of ultrapure water.
The etching temperature and etching time were 50 ℃ and 5min, respectively.
Preparing the etching solution in a beaker according to the composition of the etching solution, putting the ultrasonically-stirred etching solution beaker into a constant-temperature water bath kettle at 50 ℃, and after the temperature of the etching solution reaches 50 ℃ and is stable for a period of time; cutting titanium nitride and tungsten metal sheets into the same size by using a glass cutter, washing with ultrapure water, and purging with nitrogen; the method comprises the following steps of measuring the film thickness of silicon nitride and tungsten sheets before etching by using a four-probe thickness gauge, fixing the titanium nitride or tungsten sheets by using a frame, suspending and soaking the titanium nitride or tungsten sheets in an etching solution at 50 ℃, taking out the titanium nitride or tungsten sheets after etching for 5 minutes, washing the titanium nitride or tungsten sheets by using ultrapure water, purging the titanium nitride or tungsten sheets by using nitrogen, testing the film thickness of the silicon nitride and tungsten sheets after etching by using the four-probe thickness gauge, and calculating the etching rate according to the change of the film thickness before and after etching.
Comparative example 3
15 wt% of hydrogen peroxide, 12.8 wt% of nitric acid, 21.8 wt% of sulfuric acid, 0.1 wt% of polyacrylamide and the balance of ultrapure water.
The etching temperature and etching time were 50 ℃ and 5min, respectively.
Preparing the etching solution 1 in a beaker, placing the ultrasonically-stirred etching solution beaker into a constant-temperature water bath kettle at 50 ℃, and after the temperature of the etching solution reaches 50 ℃ and is stable for a period of time; cutting titanium nitride and tungsten metal sheets into the same size by using a glass cutter, washing with ultrapure water, and purging with nitrogen; the method comprises the following steps of measuring the film thickness of silicon nitride and tungsten sheets before etching by using a four-probe thickness gauge, fixing the titanium nitride or tungsten sheets by using a frame, suspending and soaking the titanium nitride or tungsten sheets in an etching solution at 50 ℃, taking out the titanium nitride or tungsten sheets after etching for 5 minutes, washing the titanium nitride or tungsten sheets by using ultrapure water, purging the titanium nitride or tungsten sheets by using nitrogen, testing the film thickness of the silicon nitride and tungsten sheets after etching by using the four-probe thickness gauge, and calculating the etching rate according to the change of the film thickness before and after etching.
The detection method comprises the following steps:
titanium nitride
And fixing the etching time, and measuring the film thickness of the silicon nitride before and after etching by using a four-probe thickness gauge to obtain the etching rate of the titanium nitride.
Tungsten
And fixing the etching time, and measuring the film thickness of the tungsten plate before and after etching by using a four-probe thickness gauge to obtain the etching rate of the tungsten.
Selection ratio: the ratio of the etch rate of titanium nitride to the etch rate of tungsten.
The results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the etching rates of titanium nitride in examples 1 to 4 were substantially the same
The etching selection ratio is more than 33, which indicates that nitric acid or sulfuric acid is used as a secondary oxidant in the etching solution, can increase the oxidability of hydrogen peroxide, provides hydrogen ions in the etching solution and ensures that the stability of the etching rate is maintained. Titanium nitride etch rates in examples 5 and 6
The etching selectivity ratio is more than 40, which indicates that the corrosive agent can form a complex with the oxidized titanium ions and can promote the further reaction of the titanium nitride; etch rates of titanium nitride in examples 7-9
The etching selectivity ratio is more than 39, which shows that the etching inhibitor can inhibit the oxidation of the metal tungsten, and is adsorbed on the surface of the metal tungsten to form a dense film in the form of coordination bonds, so that the etching of the metal tungsten by the etching solution can be inhibited; the etch rates of titanium nitride in examples 10-12 were substantially equal
The etching selectivity ratio is more than 32, which shows that the surfactant can adjust the surface tension between the etching solution and different phases to adjust the selectivity ratio of the etching solution in two phases of titanium nitride and tungsten, but in example 10, the excessive surfactant is not easily dissolved in the etching solution and suspended on the surface of the etching solution, which is not beneficial to adjusting the selectivity ratio of the etching solution to two phases.
No etching inhibitor was used in comparative example 1, since there was no etching inhibitorThe agent inhibits the etching of tungsten, a compact barrier film cannot be formed on the surface of the tungsten, and the etching rate of the tungsten is
The etch selectivity ratio of titanium nitride to tungsten was 1.4. In comparative example 2, no surfactant was present, the surface tension between the etching solution and the different phases could not be adjusted, the wettability of the etching solution was poor, the selectivity of the etching solution between the titanium nitride and tungsten phases could not be adjusted, and the etching selectivity was 6.6. Comparative example 3, which is an anticorrosive agent, cannot form a complex with oxidized titanium ions, so that the oxidized titanium ions are dissociated, inhibiting further oxidation of titanium nitride, and cannot promote etching in further reaction of titanium nitride, the etching rate of titanium nitride is
The etch selectivity ratio was 19.6.
The above embodiments are merely preferred technical solutions of the present invention, and should not be construed as limiting the present invention, and features in the embodiments and examples in the present application may be arbitrarily combined with each other without conflict. The protection scope of the present invention is defined by the claims, and includes equivalents of technical features of the claims. I.e., equivalent alterations and modifications within the scope hereof, are also intended to be within the scope of the invention.
Claims (8)
1. The etching solution for selectively etching titanium nitride and tungsten is characterized by comprising the following components in percentage by mass: the mass fraction of the hydrogen peroxide is 1-30%; the mass fraction of the inorganic acid is 1-50%; the mass fraction of the corrosive agent is 1-10%; the mass fraction of the etching inhibitor is 1-5%; the mass fraction of the surfactant is 0.001-1%; the balance being water.
2. The etching solution for selectively etching titanium nitride and tungsten according to claim 1, wherein the etchant is one or more of fluoride, hydrofluoric acid, ammonium fluoride, sodium fluoride, fluorosilicic acid, and sodium fluorosilicate.
3. The etching solution for selectively etching titanium nitride and tungsten according to claim 1, wherein the inorganic acid is one or more of sulfuric acid, nitric acid and hydrochloric acid.
4. The etching solution for selectively etching titanium nitride and tungsten according to claim 1, wherein the etching inhibitor ammonium salt compound is one or more of ammonium sulfate, ammonium persulfate, tetraethylammonium sulfate, triammonium citrate, cetyltrimethylammonium fluoride, ammonium isethionate, monoammonium glycyrrhizinate, diammonium 5,5' -bitetrazole, and ammonium nitrate.
5. The etching solution for selectively etching titanium nitride and tungsten according to claim 1, wherein the surfactant is an amide compound selected from one or more of polyacrylamide, nicotinamide, 2-furfurylamide, crotonamide, laurylamide, 2-phenylpropionamide, acetylbenzamide, and diacetoneacrylamide.
6. The method for preparing an etching solution for selectively etching titanium nitride and tungsten according to any one of claims 1 to 5, wherein the method comprises the following steps:
s1: adding hydrogen peroxide, deionized water and inorganic acid in sequence;
s2: adding a corrosive agent, an etching inhibitor and a surfactant, adding water to adjust the total amount of the etching solution, and ultrasonically stirring uniformly to obtain the etching solution.
7. The method as claimed in claim 6, wherein the inorganic acid is nitric acid or sulfuric acid, nitric acid is added first, sulfuric acid is added three times, the mixture is cooled in an ice bath to room temperature, and sulfuric acid is added again and the steps are repeated three times.
8. The use of the etching solution for selectively etching titanium nitride and tungsten as claimed in any one of claims 1 to 5, wherein the etching is completed by immersing titanium nitride and tungsten in the etching solution and etching at a temperature of 40 to 80 ℃ for 1 to 20 min.
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