CN114381770A - Copper electroplating solution applied to dry etching method copper interconnection Damascus and copper electroplating method thereof - Google Patents
Copper electroplating solution applied to dry etching method copper interconnection Damascus and copper electroplating method thereof Download PDFInfo
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 156
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 145
- 239000010949 copper Substances 0.000 title claims abstract description 145
- 238000009713 electroplating Methods 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 56
- 238000001312 dry etching Methods 0.000 title claims abstract description 28
- 238000007747 plating Methods 0.000 claims abstract description 39
- 239000002131 composite material Substances 0.000 claims abstract description 29
- 239000006258 conductive agent Substances 0.000 claims abstract description 21
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 15
- 239000008139 complexing agent Substances 0.000 claims abstract description 11
- 150000001879 copper Chemical class 0.000 claims abstract description 10
- 239000004094 surface-active agent Substances 0.000 claims abstract description 10
- 239000006084 composite stabilizer Substances 0.000 claims abstract description 9
- 238000007664 blowing Methods 0.000 claims description 37
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical group [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 229940099596 manganese sulfate Drugs 0.000 claims description 15
- 239000011702 manganese sulphate Substances 0.000 claims description 15
- 235000007079 manganese sulphate Nutrition 0.000 claims description 15
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 15
- -1 cerium ions Chemical class 0.000 claims description 14
- 229940046892 lead acetate Drugs 0.000 claims description 14
- 229910052684 Cerium Inorganic materials 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 11
- 235000010265 sodium sulphite Nutrition 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- CWVRJTMFETXNAD-FWCWNIRPSA-N 3-O-Caffeoylquinic acid Natural products O[C@H]1[C@@H](O)C[C@@](O)(C(O)=O)C[C@H]1OC(=O)\C=C\C1=CC=C(O)C(O)=C1 CWVRJTMFETXNAD-FWCWNIRPSA-N 0.000 claims description 10
- PZIRUHCJZBGLDY-UHFFFAOYSA-N Caffeoylquinic acid Natural products CC(CCC(=O)C(C)C1C(=O)CC2C3CC(O)C4CC(O)CCC4(C)C3CCC12C)C(=O)O PZIRUHCJZBGLDY-UHFFFAOYSA-N 0.000 claims description 10
- CWVRJTMFETXNAD-KLZCAUPSSA-N Neochlorogenin-saeure Natural products O[C@H]1C[C@@](O)(C[C@@H](OC(=O)C=Cc2ccc(O)c(O)c2)[C@@H]1O)C(=O)O CWVRJTMFETXNAD-KLZCAUPSSA-N 0.000 claims description 10
- CWVRJTMFETXNAD-JUHZACGLSA-N chlorogenic acid Chemical compound O[C@@H]1[C@H](O)C[C@@](O)(C(O)=O)C[C@H]1OC(=O)\C=C\C1=CC=C(O)C(O)=C1 CWVRJTMFETXNAD-JUHZACGLSA-N 0.000 claims description 10
- 229940074393 chlorogenic acid Drugs 0.000 claims description 10
- FFQSDFBBSXGVKF-KHSQJDLVSA-N chlorogenic acid Natural products O[C@@H]1C[C@](O)(C[C@@H](CC(=O)C=Cc2ccc(O)c(O)c2)[C@@H]1O)C(=O)O FFQSDFBBSXGVKF-KHSQJDLVSA-N 0.000 claims description 10
- 235000001368 chlorogenic acid Nutrition 0.000 claims description 10
- BMRSEYFENKXDIS-KLZCAUPSSA-N cis-3-O-p-coumaroylquinic acid Natural products O[C@H]1C[C@@](O)(C[C@@H](OC(=O)C=Cc2ccc(O)cc2)[C@@H]1O)C(=O)O BMRSEYFENKXDIS-KLZCAUPSSA-N 0.000 claims description 10
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 9
- 229910001431 copper ion Inorganic materials 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- FLBAYUMRQUHISI-UHFFFAOYSA-N 1,8-naphthyridine Chemical compound N1=CC=CC2=CC=CN=C21 FLBAYUMRQUHISI-UHFFFAOYSA-N 0.000 claims description 8
- BRBXDQGNQPEQOW-UHFFFAOYSA-N 4-methyl-4-(1H-pyrrolo[3,2-b]pyridin-2-yl)-5H-1,3-thiazol-2-amine Chemical compound CC1(CSC(=N1)N)C2=CC3=C(N2)C=CC=N3 BRBXDQGNQPEQOW-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 229920000128 polypyrrole Polymers 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 7
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical group [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 7
- 238000001179 sorption measurement Methods 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical group [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 6
- 230000010355 oscillation Effects 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 230000004888 barrier function Effects 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000003381 stabilizer Substances 0.000 claims description 4
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical group CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000007740 vapor deposition Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 abstract description 17
- 239000010703 silicon Substances 0.000 abstract description 17
- 238000009792 diffusion process Methods 0.000 abstract description 13
- 230000008569 process Effects 0.000 abstract description 11
- 230000008021 deposition Effects 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 16
- 238000012360 testing method Methods 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 208000033999 Device damage Diseases 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical group [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 4
- 230000003749 cleanliness Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000008719 thickening Effects 0.000 description 4
- 229910052581 Si3N4 Inorganic materials 0.000 description 3
- 230000004075 alteration Effects 0.000 description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 3
- 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 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910001437 manganese ion Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/12—Process control or regulation
- C25D21/14—Controlled addition of electrolyte components
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
Abstract
The invention discloses an electrolytic copper plating solution applied to copper interconnection Damascus by a dry etching method and an electrolytic copper plating method thereof, wherein the electrolytic copper plating solution comprises the following components in mass concentration: copper salt is 5-20 g/L; 30-90mg/L of composite conductive agent; 10-15mg/L of accelerator; 1-8g/L of complexing agent; 20-60mg/L of surfactant; 15-45mg/L of composite stabilizer; 0.1-0.5g/L of reducing agent. The solution ensures that the phenomenon of device performance damage caused by atomic diffusion does not occur between copper and silicon; the technical scheme uses the chlorine-free accelerator, so that the base material is not damaged, and the electroplating can be realized under the normal temperature condition; the step of conducting copper deposition is not required to be carried out in advance, and the process flow is shortened.
Description
Technical Field
The invention relates to the technical field of copper electroplating, in particular to an electroplating copper solution applied to copper interconnection Damascus by a dry etching method and an electroplating copper method thereof.
Background
The damascene technique, i.e. the damascene technique, is to etch a pattern film for metal wires on a dielectric layer and then refill the metal with the pattern film. The main feature of the damascene technique is that no etching of the metal layer is required. When the material of the metal wire is converted from aluminum to copper with lower resistivity, the damascene technique is very important for copper process because of the difficulty of dry etching of copper, and the damascene process using Cu-CMP is the only copper patterning process that is currently mature and has been successfully used in IC fabrication. By the 0.1 μm process stage, 90% of the semiconductor production lines will adopt the copper wiring process. In the multilayer wiring three-dimensional structure, global planarization of each layer is required to be guaranteed, and the Cu-CMP can realize global planarization and local planarization of a silicon wafer.
As copper interconnects get smaller, tantalum nitride dielectric layers are relatively thicker because it is difficult to scale liners down to thinner than 1 nm, chenille et al in patent CN113106506A propose electroplating cobalt to solve the problem of copper electromigration, but this approach currently requires market evaluation for reliability and risk.
In addition, the formulation of the copper electroplating proposed in patent CN113388869A by Yaoyu et al, the glyoxylic acid used in the formulation can be oxidized and reduced with copper to cause copper instability, because disodium EDTA is not enough to stabilize copper ions at 70 ℃, and the pH of the solution is 12-13, which damages both the silicon layer and the dielectric layer.
Therefore, there is a need in the market for an electrolytic copper plating solution that can ensure that the device performance will not be damaged due to atomic diffusion between copper and silicon layer.
Disclosure of Invention
Aiming at the defects in the technology, the invention provides the copper electroplating solution applied to the copper interconnection Damascus adopting the dry etching method and the copper electroplating method thereof, and the solution ensures that the phenomenon of device performance damage caused by atomic diffusion between copper and a silicon layer can not occur; the technical scheme uses the chlorine-free accelerator, so that the base material is not damaged, and the electroplating can be realized under the normal temperature condition; the step of conducting copper deposition is not required to be carried out in advance, and the process flow is shortened.
In order to achieve the aim, the invention provides an electroplating copper solution applied to copper interconnection Damascus by a dry etching method, which comprises the following components in mass concentration:
copper salt 5-20g/L
Composite conductive agent 30-90mg/L
10-15mg/L of chlorine-free accelerator
1-8g/L complexing agent
20-60mg/L of surfactant
15-45mg/L composite stabilizer
0.1-0.5g/L of reducing agent
The balance being pure water
The pH is 6.5-8.5
The operation temperature is 25-35 DEG C
The current density is 2.0-3.5A/dm2
The composite stabilizer is a composite of manganese sulfate and lead acetate, when in use, the mass concentration ratio of the manganese sulfate to the lead acetate is 3:2, the manganese sulfate is 9-27mg/L, and the lead acetate is 6-18 mg/L;
the composite conductive agent is a composite of three substances of dibenzopyrrolo [1, 2-a ] [1, 8] naphthyridine, polypyrrole and 2-amino- (4-azaindolyl) -4-methylthiazoline, and the mass concentration ratio of the three substances in use is 1:1: 1; during electroplating, the substrate is soaked in the solution, a layer of organic film can be rapidly formed on the medium barrier layer, the organic film can adsorb the reducing agent and reduce copper through adsorption, a seed copper layer is formed in a short time, circuit conduction is realized, thickening is realized under the electroplating condition, and meanwhile, the diffusion of copper atoms to the silicon layer is also hindered.
Wherein the copper salt is copper sulfate and provides copper ions; the complexing agent is one or two of chlorogenic acid or chlorogenic acid; the pH is adjusted by a solution of 10% by mass sodium hydroxide and 10% by volume concentrated sulfuric acid.
Wherein, the accelerator is cerium sulfate or cerium oxide to provide cerium ions for catalysis.
Wherein the surfactant is dodecyl benzene sulfonic acid.
Wherein the reducing agent is sodium sulfite.
The preparation method of the electroplating copper solution applied to the copper interconnection Damascus by the dry etching method comprises the following steps of:
firstly, dissolving the composite conductive agent with the mass concentration in a solution with the volume concentration of 10% concentrated sulfuric acid of about 50 mL, cooling, adding the composite stabilizing agent with the mass concentration, adding pure water, and uniformly stirring to prepare 500mL of the composite conductive agent with the volume of 300-;
secondly, preparing the reducing agent and the surfactant according to the mass concentration, adding pure water, and uniformly stirring, wherein the preparation volume is 100-200mL;
thirdly, preparing copper salt, complexing agent and accelerator according to the mass concentration, adding pure water, and uniformly stirring to prepare the mixture with the volume of 50-100mL;
fourthly, mixing the three volume solutions, adding pure water to dilute the solution by nearly one liter, and then adjusting the pH value by using 10% sodium hydroxide and 10% concentrated sulfuric acid solution, wherein the operations are all carried out at normal temperature.
In order to realize the purpose, the invention also provides a copper electroplating method applied to the copper interconnection Damascus by the dry etching method, which comprises the following specific steps:
and step 3, closing the switch, conducting the circuit, and continuously blowing until the electroplating is finished.
Wherein, the specific conditions used in the ultrasonic oscillation in the step 1 are as follows: the time is 3-5min and the frequency is 25-35KHz, so that the impurities are removed completely, the silicon nitride medium is prevented from being decomposed and damaged under the action of ultrasonic waves, the appearance can be observed, and if the medium layer is damaged, the surface of the medium layer is blackened, has chromatic aberration, and is bright, clean and lossless.
Wherein, the specific conditions of the blowing in the step 2 are as follows: the blowing gas is nitrogen, the blowing gas is sprayed from the blowing holes, the bottom of the bath solution of the copper plating bath is opened to blow upwards, and the pressure is set to be 3-4.5kg/cm2(ii) a The air blowing has the function of quickly stirring liquid and accelerating the deposition of seed copper; meanwhile, oxygen in the copper electroplating solution is rapidly removed, and copper is prevented from being oxidized.
Wherein, the specific conditions of the blowing in the step 3 are as follows: the gas is also nitrogen, and the copper electroplating is promoted under the electrifying condition, so that the plating layer is thickened continuously; the purpose of air blowing is to prevent copper from being oxidized on the one hand and to realize uniform transmission of ions to a plating piece on the other hand; at the air blowing stripAnd (3) carrying out vertical copper electroplating under the workpiece, wherein the specific parameters of the air blowing are as follows: the sizes of the upper and lower side holes of the bath solution of the copper electroplating bath are uniform, and the upper pressure is set to be 1-1.5kg/cm2The pressure is set to 1.5-2.0kg/cm2(ii) a The blowing direction is that the upper surface and the lower surface of the bath solution are blown to the surface of the board in the direction of a vertical angle in the middle, and the aim is to improve the uniformity of the ion transmission speed, thereby improving the uniformity of the electroplated copper layer on the surface of the substrate of the plated part.
The invention has the beneficial effects that: compared with the prior art, the copper electroplating solution and the copper electroplating method thereof for the copper interconnection damascene adopting the dry etching method have the following advantages:
1) adding composite conductive agent into the plating solution, wherein the composite conductive agent is dibenzopyrrolo [1, 2-a ] [1, 8] naphthyridine, polypyrrole and 2-amino- (4-azaindolyl) -4-methyl thiazoline, the mass concentration ratio of the three is 1:1:1, when in use, the matrix is soaked in the solution during electroplating, so that an organic film can be quickly formed on the medium barrier layer, the organic film can adsorb the reducing agent and reduce copper through adsorption, can form a seed copper layer in a short time, realizes circuit conduction, thereby realizing thickening under the electroplating condition and simultaneously having the function of hindering the diffusion of copper atoms to the silicon layer, therefore, the process flow can be shortened, and the seed copper layer has better dispersibility due to the ordered characteristic of the film.
2) The components of the scheme comprise composite stabilizers of manganese sulfate and lead acetate, and trace manganese ions and lead ions can be doped between metal plating layers, so that on one hand, the conductivity of the plating layers can be improved, the diffusivity of copper atoms can be reduced, and on the other hand, a good effect on the stability of the plating solution is achieved.
3) In the electrolytic copper plating solution adopted by the scheme, the accelerator is cerium ions to realize catalysis, replaces chloride ions used in the current market, when the common circuit board or IC carrier plate is electroplated with copper, because the circuit is wider, generally more than 25 microns, a small amount of chloride ions can not greatly affect the circuit, but in the chip manufacturing process, the circuit reaches the level of several microns, a small amount of chloride ions can also cause great damage to the copper circuit, therefore, the selection of the accelerator for replacing chloride ions is a market demand, and researches show that the conduction effect of cerium ions on copper ions is very obvious, the principle is that cerium ions can be adsorbed on a seed copper layer to accelerate the adsorption of sodium sulfite, the sodium sulfite and the cerium ions generate electronic exchange to generate reduced cerium atoms, and the reduced cerium atoms and the copper ions are subjected to displacement reaction under the action of electrification to obtain copper simple substance deposition.
4) The electroplating method adopted by the scheme adopts a nitrogen blowing method, so that the problem that a seed copper layer is easy to oxidize during electroplating can be effectively solved, and the deposition of seed copper is accelerated; and the uniformity of the ion transmission speed is improved, so that the uniformity of the electroplated copper layer on the surface of the substrate is improved.
Drawings
FIG. 1 is a schematic illustration of an electrolytic copper plating process applied to a dry etch copper interconnect damascene. A drawing;
FIG. 2 is a graph showing the results of the uniformity test of the electroplated copper layer for three examples and one comparative example;
FIG. 3 is a graph of conductivity data for copper for three examples and one comparative example;
fig. 4 is a graph of conductivity data for silicon layers for three examples and one comparative example.
Detailed Description
In order to make the invention more clear, the invention is further described below with reference to the text and the accompanying drawings.
The invention provides an electroplating copper solution for copper interconnection damascene by using a dry etching method, which comprises the following components in mass concentration:
in per liter of bath:
copper salt 5-20g/L
Composite conductive agent 30-90mg/L
10-15mg/L of chlorine-free accelerator
1-8g/L complexing agent
20-60mg/L of surfactant
15-45mg/L composite stabilizer
0.1-0.5g/L of reducing agent
The balance being pure water
The pH is 6.5-8.5
The operation temperature is 25-35 DEG C
The current density is 2.0-3.5A/dm2
The composite stabilizer is a composite of manganese sulfate and lead acetate, when in use, the mass concentration ratio of the manganese sulfate to the lead acetate is 3:2, the manganese sulfate is 9-27mg/L, and the lead acetate is 6-18 mg/L;
the composite conductive agent is a composite of three substances of dibenzopyrrolo [1, 2-a ] [1, 8] naphthyridine, polypyrrole and 2-amino- (4-azaindolyl) -4-methylthiazoline, and the mass concentration ratio of the three substances in use is 1:1: 1; during electroplating, the substrate is soaked in the solution, a layer of organic film can be rapidly formed on the medium barrier layer, the organic film can adsorb the reducing agent and reduce copper through adsorption, a seed copper layer is formed in a short time, circuit conduction is realized, thickening is realized under the electroplating condition, and meanwhile, the diffusion of copper atoms to the silicon layer is also hindered.
In this embodiment, the copper salt is copper sulfate, providing copper ions; the complexing agent is one or two of chlorogenic acid or chlorogenic acid; the pH is adjusted by a solution of 10% by mass sodium hydroxide and 10% by volume concentrated sulfuric acid.
In this embodiment, the accelerator is cerium sulfate or cerium oxide to provide cerium ions for catalysis.
In this example, the surfactant is dodecylbenzene sulfonic acid; the reducing agent is sodium sulfite.
In this embodiment, the preparation method of the electrolytic copper plating solution applied to dry etching copper interconnect damascene is as follows, and is measured by per liter of bath solution:
firstly, dissolving the composite conductive agent with the mass concentration in a solution with the volume concentration of 10% concentrated sulfuric acid of about 50 mL, cooling, adding the composite stabilizing agent with the mass concentration, adding pure water, and uniformly stirring to prepare 500mL of the composite conductive agent with the volume of 300-;
secondly, preparing the reducing agent and the surfactant according to the mass concentration, adding pure water, and uniformly stirring, wherein the preparation volume is 100-200mL;
thirdly, preparing copper salt, complexing agent and accelerator according to the mass concentration, adding pure water, and uniformly stirring to prepare the mixture with the volume of 50-100mL;
fourthly, mixing the three volume solutions, adding pure water to dilute the solution by nearly one liter, and then adjusting the pH value by using 10% sodium hydroxide and 10% concentrated sulfuric acid solution, wherein the operations are all carried out at normal temperature.
The preparation method is adopted in the invention because the composite conductive agent is dissolved under an acidic condition, then copper ions are coordinated with the complexing agent and then can be combined with the composite conductive agent and the accelerator, and an association is formed through an electron pair, so that the composite conductive agent cannot be separated out after the pH value is increased.
In order to achieve the above object, the present invention further provides a copper electroplating method applied to a copper interconnect damascene of a dry etching method, which comprises the following specific steps as shown in fig. 1:
s1, after the medium layer is subjected to vapor deposition, washing for three times and ultrasonic vibration, wherein the ultrasonic vibration aims to thoroughly clean adsorbed dust and impurities;
s2, after entering an electrolytic copper plating tank with electrolytic copper plating solution, connecting a cathode and an anode, and blowing air for 3-8min before electrifying;
and S3, closing the switch, conducting the circuit, and continuously blowing until the electroplating of the plated part is finished.
In this embodiment, the specific conditions used in the ultrasonic oscillation in step S1 are as follows: the time is 3-5min and the frequency is 25-35KHz, so that the impurities are removed completely, the silicon nitride medium is prevented from being decomposed and damaged under the action of ultrasonic waves, the judgment can be carried out by observing the appearance, and if the medium layer is damaged, the surface of the silicon nitride medium is blackened, has chromatic aberration, and is bright, clean and lossless.
In this embodiment, the specific conditions of the air blowing in step S2 are: the blowing gas is nitrogen, the blowing gas is sprayed from the blowing holes, the bottom of the bath solution of the copper plating bath is opened to blow upwards, and the pressure is set to be 3-4.5kg/cm2The purpose is to play a role in quickly stirring liquid, accelerate the deposition of seed copper, quickly eliminate oxygen in the solution and prevent the deposition of seed copperThe copper is prevented from being oxidized.
In this embodiment, the specific conditions of the air blowing in step S3 are: the gas is also nitrogen, but the condition of circular telegram at this moment, and the cladding material is constantly thickened, and the purpose of blowing is on the one hand to prevent copper oxidation, and on the other hand realizes that the ion evenly transmits to the piece of plating, carries out perpendicular electro-coppering under the condition of blowing, and the concrete parameter setting of this blowing is: the sizes of the upper and lower side holes of the bath solution of the copper electroplating bath are uniform, and the pressure intensity on the copper electroplating bath is set to be 1-1.5kg/cm2The pressure intensity below the copper electroplating tank is set to be 1.5-2.0kg/cm2(ii) a The blowing direction is that the upper surface and the lower surface of the bath solution are blown to the surface of the board in the direction of a vertical angle in the middle, and the aim is to improve the uniformity of the ion transmission speed, thereby improving the uniformity of the electroplated copper layer on the surface of the substrate of the plated part.
The invention has the beneficial effects that: compared with the prior art, the copper electroplating solution and the copper electroplating method thereof for the copper interconnection damascene adopting the dry etching method have the following advantages:
1) adding composite conductive agent into the plating solution, wherein the composite conductive agent is dibenzopyrrolo [1, 2-a ] [1, 8] naphthyridine, polypyrrole and 2-amino- (4-azaindolyl) -4-methyl thiazoline, the mass concentration ratio of the three is 1:1:1, when in use, the matrix is soaked in the solution during electroplating, so that an organic film can be quickly formed on the medium barrier layer, the organic film can adsorb the reducing agent and reduce copper through adsorption, can form a seed copper layer in a short time, realizes circuit conduction, thereby realizing thickening under the electroplating condition and simultaneously having the function of hindering the diffusion of copper atoms to the silicon layer, therefore, the process flow can be shortened, and the seed copper layer has better dispersibility due to the ordered characteristic of the film.
2) The components of the scheme comprise composite stabilizers of manganese sulfate and lead acetate, and trace manganese ions and lead ions can be doped between metal plating layers, so that on one hand, the conductivity of the plating layers can be improved, the diffusivity of copper atoms can be reduced, on the other hand, a good effect on the stability of the plating solution can be achieved, and the MTO can reach more than 5.
3) The electroplating solution adopted by the scheme has the chlorine-free accelerator which realizes the catalysis effect for cerium ions and replaces the chloride ions used in the current market, when the common circuit board or IC carrier plate is electroplated with copper, because the circuit is wider, generally more than 25 microns, a small amount of chloride ions can not greatly affect the circuit, but in the chip manufacturing process, the circuit reaches the level of several microns, a small amount of chloride ions can also cause great damage to the copper circuit, therefore, the selection of the accelerator for replacing chloride ions is a market demand, and researches show that the conduction effect of cerium ions on copper ions is very obvious, the principle is that cerium ions can be adsorbed on a seed copper layer to accelerate the adsorption of sodium sulfite, the sodium sulfite and the cerium ions generate electronic exchange to generate reduced cerium atoms, and the reduced cerium atoms and the copper ions are subjected to displacement reaction under the action of electrification to obtain copper simple substance deposition.
4) The electroplating method adopted by the scheme can effectively solve the problem that a seed copper layer is easy to oxidize during electroplating by a nitrogen blowing method, and accelerates the deposition of seed copper; and the uniformity of the ion transmission speed is improved, so that the uniformity of the electroplated copper layer on the surface of the substrate is improved.
The following are several specific examples of the invention
Example 1
An electroplating copper solution applied to copper interconnection Damascus of a dry etching method comprises the following components in percentage by liter of bath solution:
copper sulfate 10g/L
Dibenzopyrrolo [1, 2-a ] [1, 8] naphthyridine 30mg/L
Polypyrrole 30mg/L
2-amino- (4-azaindolyl) -4-methylthiazoline 30mg/L
Cerium sulfate 10mg/L
Chlorogenic acid 5g/L
Manganese sulfate 30mg/L
Lead acetate 15mg/L
Sodium sulfite 0.3g/L
The balance being pure water
The pH was 6.5
The operation temperature is 30 DEG C
The time is 40min
The current density is 2.5A/dm2
The criteria are as follows
A. The uniformity of the electroplated copper layer is a, which indicates that the appearance is bright and has no color difference, three groups of five-point method data in the middle of four sides are taken, and the difference value of each group is not more than 5 percent compared with the average value; b represents that the appearance is bright and has no color difference, and the difference value is in the range of 5-10% compared with the average value; c indicates that the appearance is slightly dark, slightly has chromatic aberration, and the difference value is more than 10 percent compared with the average value; d represents obvious color difference and blackened appearance; e indicates that the copper surface is blackened seriously.
B. Conducting three groups of experiments on the conductivity test of the electroplated copper layer, wherein the experimental amount of each group is 10, the time period is half a year, and a represents that the conductivity is reduced by less than 3 percent within half a year; b represents that the conductivity is reduced by 3-8% within half a year to be good; c represents that the conductivity is reduced by 8-15% in half a year to be poor; d represents a 15-25% decrease in conductivity as a difference; e represents a decrease in conductivity of 25% or more in half a year.
C. The device damage test caused by copper atom diffusion mainly comprises a silicon layer conductivity test and element copper and silicon appearance change, three groups of experiments are carried out, the experimental amount of each group is 10, the time period is half a year, wherein a represents that the conductivity is reduced by less than 3% in half a year, and the appearance is bright and clean; b represents that the conductivity is reduced by 3-8% within half a year, and the appearance is uniform, bright and clean; c represents that the conductivity is reduced by 8-15% within half a year, and the appearance is slightly blackened; d represents a 15-25% reduction in conductivity and a marked blackening in appearance; e indicates that the conductivity is reduced by 25% or more in half a year, and that the blackening corrosion is very poor.
D. The bath stability includes a being 5 MTOs, b being 4 MTOs, c being 3 MTOs, d being 2 MTOs, e being 1 MTO.
Example 2
An electroplating copper solution applied to copper interconnection Damascus of a dry etching method comprises the following components in percentage by liter of bath solution:
copper sulfate 10g/L
Dibenzopyrrolo [1, 2-a ] [1, 8] naphthyridine 20mg/L
Polypyrrole 20mg/L
2-amino- (4-azaindolyl) -4-methylthiazoline 20mg/L
Cerium sulfate 10mg/L
Chlorogenic acid 5g/L
Manganese sulfate 15mg/L
Lead acetate 10mg/L
Sodium sulfite 0.3g/L
The balance being pure water
pH of 7
The operation temperature is 30 DEG C
The time is 40min
The current density is 2.5A/dm2
Example 3
An electroplating copper solution applied to copper interconnection Damascus of a dry etching method comprises the following components in percentage by liter of bath solution:
copper sulfate 10g/L
10mg/L of dibenzopyrrolo [1, 2-a ] [1, 8] naphthyridine
Polypyrrole 10mg/L
2-amino- (4-azaindolyl) -4-methylthiazoline 10mg/L
Cerium sulfate 10mg/L
Chlorogenic acid 5g/L
Manganese sulfate 18mg/L
Lead acetate 12mg/L
Sodium sulfite 0.3g/L
The balance being pure water
The pH was 7.5
The operation temperature is 30 DEG C
The time is 40min
The current density is 2.5A/dm2
Comparative example
An electroplating copper solution applied to copper interconnection Damascus of a dry etching method comprises the following components in percentage by liter of bath solution:
copper sulfate 30g/L
Sodium polydithio-dipropyl sulfonate 10mg/L
Chlorogenic acid 5g/L
Manganese sulfate 15mg/L
Sodium sulfite 0.3g/L
The balance being pure water
pH of 7
The operation temperature is 30 DEG C
The time is 40min
The current density is 4.5A/dm2
From fig. 2-4, the following conclusions can be drawn:
in example 1, test results were obtained: the plating uniformity is a, the half-year conductivity of the copper-plated layer is a, and the test for the device damage caused by copper atom diffusion comprises the half-year conductivity of the silicon layer is a, the appearance brightness cleanliness is a, and the bath stability is a.
In example 2, test results were obtained: the plating uniformity is a, the half-year conductivity of the copper-plated layer is a, and the test for the device damage caused by copper atom diffusion comprises the half-year conductivity of the silicon layer is a, the appearance brightness cleanliness is a, and the bath stability is a.
In example 3, test results were obtained: the plating uniformity is a, the half-year conductivity of the copper-plated layer is a, and the test for the device damage caused by copper atom diffusion comprises the half-year conductivity of the silicon layer is a, the appearance brightness cleanliness is a, and the bath stability is a.
Comparative example compared to the examples, the comparative example lacks the conductive agent, stabilizer, accelerator is the conventional sodium polydithio dipropyl sulfonate, the current density is too high, and the test results are obtained: the plating uniformity is b, the half-year conductivity of the copper-plated layer is c, the device damage caused by copper atom diffusion is c, the half-year conductivity of the silicon layer is c, the appearance brightness cleanliness is c, and the bath stability is d.
As can be seen by comparing the three embodiment examples and the comparative example, the solution of the invention ensures that the phenomenon of device performance damage caused by atomic diffusion between copper and silicon does not occur, a chlorine-free accelerator is used, the base material is not damaged, and electroplating can be realized under the normal temperature condition; the step of conducting copper deposition is not required to be carried out in advance, and the process flow is shortened.
The above disclosure is only an example of the present invention, but the present invention is not limited thereto, and any variations that can be made by those skilled in the art should fall within the scope of the present invention.
Claims (10)
1. The electrolytic copper plating solution applied to copper interconnection Damascus by a dry etching method is characterized by comprising the following components in mass concentration:
copper salt 5-20g/L
Composite conductive agent 30-90mg/L
10-15mg/L of chlorine-free accelerator
1-8g/L complexing agent
20-60mg/L of surfactant
15-45mg/L composite stabilizer
0.1-0.5g/L of reducing agent
The balance being pure water
The pH is 6.5-8.5
The operation temperature is 25-35 DEG C
The current density is 2.0-3.5A/dm2
The composite stabilizer is a composite of manganese sulfate and lead acetate, when in use, the mass concentration ratio of the manganese sulfate to the lead acetate is 3:2, the manganese sulfate is 9-27mg/L, and the lead acetate is 6-18 mg/L;
the composite conductive agent is a composite of three substances of dibenzopyrrolo [1, 2-a ] [1, 8] naphthyridine, polypyrrole and 2-amino- (4-azaindolyl) -4-methylthiazoline, and the mass concentration ratio of the three substances in use is 1:1: 1; during electroplating, the substrate is soaked in the copper electroplating solution with the components, and an organic film is rapidly formed on the medium barrier layer; the organic film adsorbs the reducing agent and reduces copper through adsorption, and a seed copper layer is formed in 3-8 min.
2. The electrolytic copper plating solution for dry etching copper interconnect damascene according to claim 1, wherein the chlorine-free accelerator is cerium sulfate and provides cerium ions for catalysis.
3. The electrolytic copper plating solution for dry etching copper interconnect damascene according to claim 1, wherein the copper salt is copper sulfate, providing copper ions; the complexing agent is one or two of chlorogenic acid or chlorogenic acid; the pH is adjusted by a solution of 10% by mass sodium hydroxide and 10% by volume concentrated sulfuric acid.
4. The electrolytic copper plating solution for dry etching copper interconnect damascene according to claim 1, wherein the surfactant is dodecylbenzene sulfonic acid.
5. The electrolytic copper plating solution for dry etching copper interconnect damascene according to claim 1, wherein the reducing agent is sodium sulfite.
6. The electrolytic copper plating solution applied to copper interconnect damascene of dry etching method according to claim 1, wherein the electrolytic copper plating solution is prepared by the following method, in terms of per liter of bath:
firstly, dissolving the composite conductive agent with the mass concentration in a solution with the volume concentration of 10% concentrated sulfuric acid of about 50 mL, cooling, adding the composite stabilizing agent with the mass concentration, adding pure water, and uniformly stirring to prepare 500mL of the composite conductive agent with the volume of 300-;
secondly, preparing the reducing agent and the surfactant according to the mass concentration, adding pure water, and uniformly stirring, wherein the preparation volume is 100-200mL;
thirdly, preparing copper salt, complexing agent and accelerator according to the mass concentration, adding pure water, and uniformly stirring to prepare the mixture with the volume of 50-100mL;
fourthly, mixing the three volume solutions, adding pure water to dilute the solution by nearly one liter, and then adjusting the pH value by using 10% sodium hydroxide and 10% concentrated sulfuric acid solution, wherein the operations are all carried out at normal temperature.
7. A copper electroplating method applied to copper interconnection Damascus by a dry etching method is characterized by comprising the following specific steps:
step 1, after a plated part passes through a vapor deposition medium layer, washing for three times and performing ultrasonic oscillation;
step 2, after a plating piece enters an electrolytic copper plating tank with the electrolytic copper plating solution of any one of claims 1 to 6, connecting a cathode and an anode, and blowing air for 3 to 8min before electrifying;
and step 3, closing the switch, conducting the circuit, and continuously blowing until the electroplated copper of the plated part is finished.
8. The copper electroplating method applied to copper interconnect damascene of dry etching method according to claim 7, wherein the specific conditions used in the ultrasonic oscillation in the step 1 are as follows: the time is 3-5min and the frequency is 25-35 KHz.
9. The electrolytic copper plating method applied to copper interconnect damascene of dry etching method according to claim 7, wherein the specific conditions of the step 2 blowing gas are as follows: the blowing gas is nitrogen, the blowing gas is sprayed from the blowing holes, the bath solution bottom of the copper plating bath is opened to blow upwards, and the blowing pressure is set to be 3-4.5kg/cm2。
10. The electrolytic copper plating method applied to copper interconnect damascene of dry etching method according to claim 7, wherein the specific conditions of the step 3 blowing gas are as follows: the blowing gas is nitrogen; carrying out vertical copper electroplating under the condition of air blowing, wherein the specific parameters of the air blowing are as follows: the sizes of the upper and lower side holes of the bath solution of the copper electroplating bath are uniform, and the upper pressure is set to be 1-1.5kg/cm2The pressure is set to 1.5-2.0kg/cm2(ii) a The blowing direction is that the upper surface and the lower surface of the bath solution blow towards the plate surface in the direction of the middle vertical angle.
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| CN112593219A (en) * | 2020-12-09 | 2021-04-02 | 昆山成功环保科技有限公司 | Solution for direct electroless copper plating of aluminum substrates and application method thereof |
| CN113789553A (en) * | 2021-11-17 | 2021-12-14 | 深圳市创智成功科技有限公司 | Nickel plating solution applied to printed circuit board and nickel electroplating method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112593219A (en) * | 2020-12-09 | 2021-04-02 | 昆山成功环保科技有限公司 | Solution for direct electroless copper plating of aluminum substrates and application method thereof |
| CN113789553A (en) * | 2021-11-17 | 2021-12-14 | 深圳市创智成功科技有限公司 | Nickel plating solution applied to printed circuit board and nickel electroplating method thereof |
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| CN114934302A (en) * | 2022-04-27 | 2022-08-23 | 深圳市联合蓝海黄金材料科技股份有限公司 | Cyanide-free electrogilding liquid and application thereof |
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