CN113130292A - Plasma etching residue cleaning solution - Google Patents
Plasma etching residue cleaning solution Download PDFInfo
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- CN113130292A CN113130292A CN201911407714.3A CN201911407714A CN113130292A CN 113130292 A CN113130292 A CN 113130292A CN 201911407714 A CN201911407714 A CN 201911407714A CN 113130292 A CN113130292 A CN 113130292A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
- H01L21/02071—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers the processing being a delineation, e.g. RIE, of conductive layers
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31105—Etching inorganic layers
- H01L21/31111—Etching inorganic layers by chemical means
Abstract
The invention provides a plasma etching residue cleaning solution which comprises an oxidant, a pH regulator, a stabilizer, an organic acid ammonium salt, a metal corrosion inhibitor and water. The invention provides a plasma etching residue cleaning solution, which can effectively remove the plasma etching residues in the wafer cleaning process, and has less residues in metal channels; the method has high selectivity on the etching of the titanium nitride, and can efficiently remove the titanium nitride hard mask; in addition, the corrosion rate to metal materials, non-metal materials and Low-k medium materials is Low in the process of cleaning the high-speed single chip microcomputer; the operation window is large; the cleaning liquid does not contain fluorine, and even if the cleaning liquid is a wafer with the thickness less than 14nm, the electrical property of the wafer is not influenced.
Description
Technical Field
The invention relates to the field of wafer cleaning liquid in a semiconductor manufacturing process, in particular to a plasma etching residue cleaning liquid.
Background
Wafer cleaning is the most repeated process in the integrated circuit process, and the quality of the cleaning effect greatly affects the quality problems of the chip process, the integrated circuit characteristics and the like. Various chemicals used in the cleaning solution seriously pollute the environment due to improper treatment, and a large amount of chemicals and water are consumed for various times of cleaning. In the face of IC processes with finer lines and higher integration, more efficient cleaning schemes are also being investigated. Photoresist masks are commonly used in the semiconductor industry to pattern materials such as semiconductors or electrolytes. In one application, photoresist masks are used in dual damascene processes to form interconnects in back-end metallization of microelectronic devices. Dual damascene processes involve forming a photoresist mask on a Low dielectric constant (Low-k, or Low-k) dielectric layer above a metal conductor layer, such as a copper (Cu) layer. The Low-k dielectric layer is then etched according to the photoresist mask to form vias and/or trenches to expose the metal conductor layer. The vias and trenches, commonly referred to as dual damascene structures, are typically defined using two lithography. The photoresist mask is then removed from the Low-k dielectric layer and a conductive material is then deposited into the vias and/or trenches to form the interconnects.
As microelectronic device dimensions decrease, it becomes more difficult to achieve critical dimensions for vias and trenches. Copper metal and Low-k dielectric materials are increasingly used in the field of semiconductor manufacturing. Especially, under the condition that the copper dual damascene process is more and more extensive, it is more and more important to find a cleaning solution which can effectively remove etching residues and simultaneously protect Low-k dielectric materials, non-metallic materials and metallic materials. Meanwhile, as the size of the semiconductor process is smaller and smaller, the cleaning method is more and more widely used for cleaning the high-speed rotating single chip. Thus, a metal hard mask is used to provide better profile control of the vias and trenches. The metal hard mask is made of titanium or titanium nitride and is removed by wet etching after forming the vias and/or trenches of the dual damascene structure, typically by cleaning/rinsing/de-ionized water rinsing. In this process, only the residual polymer photoresist layer and inorganic substances can be removed, and the metal layer cannot be attacked and damaged. It is critical that the wet etch process use a removal chemistry that effectively removes the metal hard mask and/or photoresist etch residues without affecting the underlying metal conductive layer and Low-k dielectric material. In other words, the removal chemistry needs to have a high selectivity to the metal conductive layer and the Low-k dielectric layer.
At home and abroad, reports on semiconductor cleaning liquid are more, US20150027978A1 discloses high-selectivity etching TiN, the etching rate of TiN is improved mainly by adding ammonium salt and hydrogen peroxide for decomposition, 5-methylbenzotriazole is added for inhibiting the corrosion of copper, and ammonium fluoride is added for improving the cleaning capacity. Although the formula has good protection on copper, the 5-methylbenzotriazole is adsorbed on the surface of the wafer, is difficult to desorb and can cause great influence on electrical property. Further research is carried out on the basis of WO201603729A1, and the method discloses that the etching rate of metal and nonmetal is adjusted by fluosilicic acid, ammonium iodate, vanadium oxide, ammonium vanadate and the like, the method can further improve the etching rate of TiN, and has good protection on copper, but the problem of corrosion inhibitor adsorption on the surface of a wafer is still not solved, and new metal ions are introduced, so that the electrical property is influenced, and the control condition of metal corrosion caused by cleaning liquid under high-speed rotation is also not solved. The formula disclosed in US20179546321B2 contains fluorine-containing components, organic or inorganic acid and the like, can well solve the problem of wafer surface adsorption, but is difficult to completely remove a thick TiN hard mask, incomplete in etching and unclean in cleaning, and the electrical property is influenced. Recently, the company EKC, US patent US10155921B2, disclosed a method for removing titanium nitride by an oxidizing agent, a carboxylate salt, and a metal corrosion inhibitor while being compatible with copper and low-k dielectric materials. Hydrogen peroxide is used as an oxidant, pyrrole, pyrazole, indazole and derivatives thereof are used as metal corrosion inhibitors, ammonium salt is used as a titanium nitride etching reinforcing agent, and the hard mask and residues thereof are selectively removed under the condition of pH value of 7-12 and temperature of 20-60 ℃ without affecting the underlying metal conducting layer and the low-k dielectric layer, so that better profile control can be obtained. The patent explicitly states that the products do not contain fluorine, and thus the cleaning effect of the products is poor, especially for wafers with 14nm technology nodes and smaller, and the electrical performance is greatly influenced.
Disclosure of Invention
In order to solve the technical problem that a cleaning solution in the wafer cleaning process in the prior art cannot simultaneously and effectively remove etching residues and protect low-k dielectric materials, non-metallic materials and metallic materials, the invention provides a plasma etching residue cleaning solution which comprises an oxidant, a pH regulator, a stabilizer, an organic acid ammonium salt, a metal corrosion inhibitor and water.
Further, the mass concentration of the oxidant is 0.1 wt% -30 wt%.
Further, the oxidant is H2O2N-methylmorpholine oxide (NMMO or NMO), benzoyl peroxide, tetrabutylammonium peroxymonosulfate, ozone, permanganic acid, perchloric acid, iodic acid, periodic acid, persulfuric acid, ammonium peroxodisulfate, peracetic acid (CH)3(CO) OOH), carbamide peroxide ((CO (NH)2)2)H2O2) One or more of nitric acid, ammonium hypochlorite, ammonium chlorate, ammonium iodate, ammonium perchlorate, ammonium periodate, tetramethylammonium chlorite, tetramethylammonium chlorate, tetramethylammonium iodate, tetramethylammonium perborate, tetramethylammonium perchlorate, tetramethylammonium periodate, tetramethylammonium persulfate, peracetic acid, perbenzoic acid, and alloxan. The oxidizing agent is preferably H2O2。
Further, the mass concentration of the organic acid ammonium salt is 0.01 wt% -50 wt%.
Further, the organic acid ammonium salt is one or more of ammonium formate, ammonium oxalate, ammonium lactate, ammonium tartrate, triammonium citrate, ammonium acetate, ammonium carbamate, ammonium carbonate, ammonium benzoate, tetraammonium ethylenediaminetetraacetic acid (tetraammonium EDTA), triammonium ethylenediaminetetraacetate (triammonium EDTA), diammonium ethylenediaminetetraacetate (diammonium EDTA), ammonium succinate, 1-H-pyrazole-3-ammonium formate, ammonium malonate, ammonium adipate, ammonium iminodiacetate. Preferably, the organic acid ammonium salt is an organic acid ammonium salt with strong chelating ability.
Further, the mass concentration of the pH regulator is 0.1 wt% -20 wt%.
Further, the pH regulator is an alkaline regulator.
Further, the pH regulator is one or more of quaternary amine hydroxide, organic amine and organic alcohol amine.
Further, the quaternary amine hydroxide is one or more of tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), trimethylphenylammonium hydroxide, benzyltrimethylammonium hydroxide (BTMAH), benzyltriethylammonium hydroxide (BTEAH), tetrabutylammonium hydroxide, tetrabutylphosphonium hydroxide (TBPH), choline hydroxide, ammonium hydroxide, dodecyltrimethylammonium hydroxide (DTAH), hexadecyltrimethylammonium hydroxide (CTOH).
Further, the organic amine is one or more of monoethylamine, diethylamine, triethylamine, tripropylamine, N' N-diethylethylenediamine, hydroxyethylethylenediamine, cyclohexylamine, 1, 2-propylenediamine and pentamethyldiethylenetriamine.
Further, the organic alcohol amine is one or more of Monoethanolamine (MEA), Diethanolamine (DEA), Triethanolamine (TEA), Diglycolamine (DGA), isopropanolamine and N-methylethanolamine.
Further, the pH regulator is an alkaline pH regulator with a small metal ion content. Preferably an alkaline pH adjusting agent having a metal ion content of < 50 ppb.
Further, the mass concentration of the stabilizer is 0.05-1000 ppm. The mass concentration of the stabilizer is preferably 0.1 to 100 ppm.
Further, the stabilizer is one or more of glycine, ethylenediaminetetraacetic acid (EDTA), trans-1, 2-cyclohexanediaminetetraacetic acid (CDTA), uric acid, picolinic acid, nitrilotriacetic acid (NTA), ethylenediamine-N, N '-disuccinic acid (EDDS), glutamic acid, diethylenetriaminepentaacetic acid (DTPA), hydroxyethylethylenediaminetriacetic acid (HEDTA), hydroxyethylidene diphosphonic acid (HEDP), iminodiacetic acid (IDA), nitrilotriacetic acid, nicotinic acid, tartaric acid, citric acid, 1,4,7, 10-tetraazacyclododecane-1, 4,7, 10-tetraacetic acid (DOTA), ethyleneglycol tetraacetic acid (EGTA), 1, 2-bis (o-aminophenoxy) ethane-N, N' -tetraacetic acid, sulfonamide, propylenediaminetetraacetic acid.
Further, the mass concentration of the metal corrosion inhibitor is 0.02 wt% -29 wt%.
Further, the metal corrosion inhibitor is a mixture of a polyol and a heterocyclic compound containing at least one nitrogen element. Preferably, the polyol is a polyol having a high number of hydroxyl groups.
Further, the heterocyclic compound containing at least one nitrogen element is Benzotriazole (BTA), 1,2, 4-triazole, 5-methylbenzotriazole (TTA), hydroxybenzotriazole, pyrazole, tolyltriazole, 3, 5-dimethylpyrazole, tetrazole, 4-amino-1, 2, 4-triazole, benzothiazole, methyl-1H-benzotriazole (TTL), 2-aminobenzothiazole, 2-mercaptobenzothiazole, 3-amino-5-hydroxypyrazole, 1-phenylpyrazole, mercaptobenzimidazole, 5-aminotetrazole, 3-mercapto-1, 2, 4-triazole, 3-isopropyl-1, 2, 4-triazole, 2- (5-amino-pentyl) -benzotriazole, 5-benzenethiol-benzotriazole, methyltetrazole, 5-phenyl-benzotriazole, 5-nitro-benzotriazole, 3-amino-5-mercapto-1, 2, 4-triazole, 1-amino-1, 2, 4-triazole, hydroxybenzotriazole, 1-amino-1, 2, 3-benzotriazole, and thiazole. The heterocyclic compound containing at least one nitrogen element is preferably Benzotriazole (BTA).
Further, the structural general formula of the polyalcohol is CnH2n+2Om(n≥2，m≥2)。
Further, the polyhydric alcohol is one or more of glycerol, pentaerythritol, xylitol, Trimethylolethane (TME), Trimethylolpropane (TMP), Ethylene Glycol (EG), propylene glycol, 1, 2-propanediol (1,2-PG), 1, 4-Butanediol (BDO), dipropylene glycol, neopentyl glycol (NPG), diethylene glycol, 1, 6-hexanediol, vinpocetine, glucitol, fructose, ribose, erythritol, pentanol, hexitol, polyethylene glycol 400(PEG-400), polyethylene glycol 600(PEG-600), polypropylene glycol 400(PPG-400), mannitol, and sorbitol.
Further, the mass concentration of the water is 28.4 wt% -96.9 wt%.
Further, the pH value of the plasma etching residue cleaning solution is 7-12.
All reagents of the invention are commercially available.
Ppm in the present invention means a mass concentration expressed in terms of parts per million of solute mass in the total solution mass, and is referred to as a ppm concentration; the wt% of the invention is mass percentage concentration.
Compared with the prior art, the invention has the advantages that:
the invention provides a plasma etching residue cleaning solution, which can effectively remove the plasma etching residue in the wafer cleaning process, for example, the polyhydric alcohol can further reduce the adsorption of BTA and derivatives thereof on the copper surface, and the residue in a metal pore channel is less; the method has high selectivity on the etching of the titanium nitride, and can efficiently remove the titanium nitride hard mask; in addition, the cleaning of the high-speed single chip microcomputer has smaller corrosion rate to metal materials (such as Cu, Co and the like), nonmetal materials and Low-k dielectric materials (such as SiON, TEOS, BDII (Low dielectric constant silicon oxide) and the like), for example, the corrosion of metal copper and cobalt can be well controlled through the synergistic effect of BTA and derivatives thereof and polyhydric alcohol; the operation window is large, the cleaning temperature range is wide, and the cleaning agent can be used at the temperature of 20-80 ℃; the cleaning liquid does not contain fluorine, and even if the cleaning liquid is a wafer with the thickness less than 14nm, the electrical property of the wafer is not influenced. The plasma etching residue cleaning solution has good application prospect in the field of microelectronics such as semiconductor wafer cleaning.
Detailed Description
The advantages of the invention are explained in detail below with reference to specific embodiments.
The cleaning liquid composition according to the present invention is illustrated in detail below by examples and test results, but is not limited to the results shown in these examples and various tests. The cleaning solution compositions of the present invention may be embodied in a variety of specific formulations, wherein the specific components of the composition are discussed in weight percent for all such cleaning solution compositions.
Examples
The preparation method comprises the following steps: the components were simply mixed according to the formulations (specific components and their corresponding specific contents) of the respective examples and comparative examples in the following table 1.
TABLE 1 formulation and cleaning temperature for different examples and comparative examples
Effects of the embodiment
Test objects and their sources for testing etch rates:
TiN (titanium nitride) blank wafer-Ramco Specialties Inc. (Lambda specialty Co., USA)
Cu (copper) blank wafer — Ramco Specialties Inc.
Co (cobalt) blank wafer-Shanghai Huali Microelectronics Corporation (Shanghai Huali Microelectronics, Inc.)
SiON (silicon oxynitride) blank wafer — Ramco Specialties Inc.
TEOS (silicon dioxide) blank wafer — Ramco Specialties Inc.
BDII (Low dielectric constant silica) blank wafer — Ramco Specialties Inc.
The testing method of the etching rate of TiN, Cu, Co and other metals comprises the following steps:
(1) testing initial resistance values (Rs1) of 5 x 5cm metal blanks (TiN blanks, Cu blanks, Co blanks) by using a Napson four-point probe instrument;
(2) placing the 5 x 5cm metal blank wafer on a mini single chip microcomputer mini-SWT at 400rpm, treating the TiN blank wafer for 5min by cleaning solution, and chemically treating the Cu blank wafer and the Co blank wafer for 10 min;
(3) taking out the 5 x 5cm metal blank wafer, cleaning the 5 x 5cm metal blank wafer by using deionized water (DIW), drying the 5 x 5cm metal blank wafer by using high-purity nitrogen, and testing the resistance value (Rs2) of the 5 x 5cm metal blank wafer by using a Napson four-point probe instrument;
(4) the etching rate of the metal can be calculated by inputting the resistance value and the etching time into a proper program.
Non-metal etching Rate (Etch Rate) test methods such as SiON, TEOS, BDII and the like:
1) starting a Nanospec6100 thickness meter according to the standard, selecting a proper test program, putting 5 x 5cm nonmetal blank wafers (SiON blank wafer, TEOS blank wafer and BDII blank wafer) on the Nanospec6100 thickness meter to test the thickness of the nonmetal blank wafers, rotating the nonmetal blank wafers by 90 degrees to continue the test, continuously testing for 4 times, and recording the numerical value;
2) if the non-metal blank wafer is BDII, washing the BDII by water, treating the BDII for 20min at 350 ℃ in a muffle furnace, cooling the BDII to room temperature by a dryer, and testing the previous value; (other wafers do not require step 2)
3) Treating the 5 x 5cm nonmetal blank wafer on a mini-SWT at 400rpm for 10min by using a cleaning solution;
4) taking out the 5 x 5cm nonmetal blank wafer, cleaning with DIW, drying with high-purity nitrogen, testing the thickness of the wafer on a Nanospec6100 thickness meter according to the procedure 1, and recording the numerical value;
5) if the non-metal blank wafer is BDII, washing the BDII by water, treating the BDII for 20min at 350 ℃ in a muffle furnace, cooling the BDII to room temperature by a dryer, and testing the BDII; (other wafers do not require step 5)
6) The above-mentioned before and after thickness values and etching time are inputted into an appropriate program, and the etching rate is calculated as the change in thickness divided by the chemical treatment time.
Different cleaning solutions prepared according to the embodiment and the comparative example in the table 1 are tested for the etching rates of different blank chips according to the etching rate testing method, the adsorption condition of the metal corrosion inhibitor on the surface of the copper wafer is tested by X-ray photoelectron spectroscopy, meanwhile, a mini-SWT single chip microcomputer is used for cleaning the pattern wafer for 90s at the temperature of 50 ℃ and the speed of 400rpm/min, and the pattern wafer is rinsed by water and dried by nitrogen. The media used were: TiN-titanium nitride; cu-copper; co-cobalt; SiON-silicon oxynitride; TEOS-a low dielectric material; BDII-Low dielectric Material. The etching rates, surface adsorption results, and cleaning effects of the different blank wafers are shown in Table 2.
TABLE 2 etch Rate, surface adsorption results, and cleaning results for various examples and comparative examples
| Surface adsorption results (XPS) | Wafer cleaning results |
| Very good basic no adsorption | Basic cleaning |
| Slight adsorption of O | Small amount of residue |
| Adsorption of more delta | High residue of delta |
| X heavy adsorption | X large amount of residue |
As can be seen from table 2: the cleaning solution of the invention is basically used for metal (such as Cu and Co) and nonmetal (SiON, TEOS, BDII) used in semiconductor processingDoes not corrode, and the corrosion condition of the alloy can meet the requirement of the semiconductor industry under the condition of high rotating speed under the condition of single chip high-speed rotating cleaning
And the titanium nitride etching selectivity and etching rate are high. Comparative example 1 in comparison to example 18 shows that: in comparative example 1, without addition of BTA and polyol rinse, the metals Cu and Co were severely corroded and had a large residue in the metal channels. Comparative example 2 compared with comparative example 1, the addition of the polyhydric alcohol alone in comparative example 2 has a certain control effect on corrosion of Cu and Co, but compared with example 18 in comparative example 2, the cleaning solution of comparative example 2 still has a higher corrosion rate on Cu and Co and is still difficult to meet the requirement, but the metal pore channel is basically cleaned and has no residue. Compared with comparative examples 1 and 2, in comparative example 3, the BTA is added alone to effectively inhibit the corrosion of Cu and Co, and the inhibition effect is better than that of the polyhydric alcohol added alone in comparative example 2, but the cleaning solution of comparative example 3 with BTA added alone has poor removal capability of adsorbates on the surface of copper, namely, the surface of copper has more BTA adsorption. In comparative example 3, there is room for further reduction in the corrosion rate of Cu and Co corrosion as compared with example 18. Combining comparative example 18 with comparative examples 1-3, it can be shown that the polyol and BTA provide synergistic control of metal corrosion. Compared with comparative example 3 without the addition of the polyhydric alcohol, in addition, the cleaning solution with the addition of the polyhydric alcohol (such as comparative example 2 and example 18) has relatively less BTA adsorption on the copper surface, which shows that the addition of the polyhydric alcohol can promote the desorption of the BTA from the copper surface, reduce the residue on the copper surface and is beneficial to improving the yield of the semiconductor device. Comparative example 4 compared to example 18, the etch rate of titanium nitride was much lower without the addition of the organic acid ammonium salt cleaning solution, indicating that the organic acid ammonium salt can facilitate the removal of the titanium nitride hard mask.
In conclusion, the positive progress effects of the invention are as follows: the plasma etching residue cleaning solution developed by the invention can well control the corrosion of metal copper and cobalt through the synergistic effect of BTA and derivatives thereof and polyhydric alcohol, and the polyhydric alcohol can further reduce the adsorption of the BTA and the derivatives thereof on the surface of copper. The cleaning solution can remove TiN hard masks efficiently, has Low corrosion rate to non-metal materials and Low-k dielectric materials (such as SiON, TEOS, BDII and the like) in the cleaning of a high-speed single chip microcomputer, has a large operation window, and has good application prospect in the microelectronic field of semiconductor wafer cleaning and the like.
The embodiments of the present invention have been described in detail, but the embodiments are merely examples, and the present invention is not limited to the embodiments described above. Any equivalent modifications and substitutions to those skilled in the art are also within the scope of the present invention. Accordingly, equivalent changes and modifications made without departing from the spirit and scope of the present invention should be covered by the present invention.
Claims (24)
1. A plasma etching residue cleaning solution is characterized by comprising an oxidant, a pH regulator, a stabilizer, an organic acid ammonium salt, a metal corrosion inhibitor and water.
2. The plasma etching residue cleaning solution of claim 1, wherein the mass concentration of the oxidizing agent is 0.1 wt% to 30 wt%.
3. The plasma etch residue cleaning solution of claim 1, wherein the oxidizing agent is H2O2One or more of N-methylmorpholine oxide, benzoyl peroxide, tetrabutylammonium peroxymonosulfate, ozone, permanganate, perchloric acid, iodic acid, periodic acid, persulfuric acid, ammonium peroxodisulfate, peracetic acid, urea peroxide, nitric acid, ammonium hypochlorite, ammonium chlorate, ammonium iodate, ammonium perchlorate, ammonium periodate, tetramethylammonium chlorite, tetramethylammonium chlorate, tetramethylammonium iodate, tetramethylammonium perborate, tetramethylammonium perchlorate, tetramethylammonium periodate, tetramethylammonium persulfate, peracetic acid, perbenzoic acid, and alloxan.
4. The plasma etch residue cleaning solution of claim 3,characterized in that the oxidant is H2O2。
5. The plasma etching residue cleaning solution of claim 1, wherein the mass concentration of the ammonium salt of the organic acid is 0.01 wt% to 50 wt%.
6. The plasma etch residue cleaning solution of claim 1, wherein the organic acid ammonium salt is one or more of ammonium formate, ammonium oxalate, ammonium lactate, ammonium tartrate, triammonium citrate, ammonium acetate, ammonium carbamate, ammonium carbonate, ammonium benzoate, tetraammonium ethylenediaminetetraacetate, triammonium ethylenediaminetetraacetate, diammonium ethylenediaminetetraacetate, ammonium succinate, 1-H-pyrazole-3-ammonium formate, ammonium malonate, ammonium adipate, ammonium iminodiacetate.
7. The plasma etching residue cleaning solution of claim 1, wherein the pH adjuster has a mass concentration of 0.1 wt% to 20 wt%.
8. The plasma etch residue cleaning solution of claim 1, wherein the pH adjustor is an alkaline adjustor.
9. The plasma etch residue cleaning solution of claim 8, wherein the pH adjusting agent is one or more of a quaternary amine hydroxide, an organic amine, and an organic alcohol amine.
10. The plasma etch residue cleaning solution of claim 9, wherein the quaternary amine hydroxide is one or more of tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, trimethylphenyl ammonium hydroxide, benzyltrimethyl ammonium hydroxide, benzyltriethyl ammonium hydroxide, tetrabutyl phosphonium hydroxide, choline hydroxide, ammonium hydroxide, dodecyl trimethyl ammonium hydroxide, hexadecyl trimethyl ammonium hydroxide.
11. The plasma etch residue cleaning solution of claim 9, wherein the organic amine is one or more of monoethylamine, diethylamine, triethylamine, tripropylamine, N' N-diethylethylenediamine, hydroxyethylethylenediamine, cyclohexylamine, 1, 2-propylenediamine, pentamethyldiethylenetriamine.
12. The plasma etch residue cleaning solution of claim 9, wherein the organic alcohol amine is one or more of monoethanolamine, diethanolamine, triethanolamine, diglycolamine, isopropanolamine, N-methylethanolamine.
13. The plasma etching residue cleaning solution of claim 9, wherein the pH adjustor is an alkaline pH adjustor having a metal ion content of less than 50 ppb.
14. The plasma etching residue cleaning solution of claim 1, wherein the mass concentration of the stabilizer is 0.05-1000 ppm.
15. The plasma etching residue cleaning solution of claim 14, wherein the stabilizer has a mass concentration of 0.1 to 100 ppm.
16. The plasma etch residue cleaning solution of claim 1, wherein the stabilizer is one or more of glycine, ethylenediaminetetraacetic acid, trans-1, 2-cyclohexanediaminetetraacetic acid, uric acid, picolinic acid, nitrilotriacetic acid, ethylenediamine-N, N '-disuccinic acid, glutamic acid, diethylenetriaminepentaacetic acid, hydroxyethylethylenediaminetriacetic acid, hydroxyethylidene diphosphonic acid, iminodiacetic acid, nitrilotriacetic acid, nicotinic acid, tartaric acid, citric acid, 1,4,7, 10-tetraazacyclododecane-1, 4,7, 10-tetraacetic acid, ethylene glycol tetraacetic acid, 1, 2-bis (o-aminophenoxy) ethane-N, N' -tetraacetic acid, sulfonamide, propylenediaminetetraacetic acid.
17. The plasma etching residue cleaning solution of claim 1, wherein the mass concentration of the metal corrosion inhibitor is 0.02 wt% to 29 wt%.
18. The plasma etch residue cleaning solution of claim 1, wherein the metal corrosion inhibitor is a mixture of a polyol and a heterocyclic compound comprising at least one nitrogen element.
19. The plasma etch residue cleaning solution of claim 18, wherein the heterocyclic compound comprising at least one nitrogen element is benzotriazole, 1,2, 4-triazole, 5-methylbenzotriazole, hydroxybenzotriazole, pyrazole, tolyltriazole, 3, 5-dimethylpyrazole, tetrazole, 4-amino-1, 2, 4-triazole, benzothiazole, methyl-1H-benzotriazole, 2-aminobenzothiazole, 2-mercaptobenzothiazole, 3-amino-5-hydroxypyrazole, 1-phenylpyrazole, mercaptobenzimidazole, 5-aminotetrazole, 3-mercapto-1, 2, 4-triazole, 3-isopropyl-1, 2, 4-triazole, 2- (5-amino-pentyl) -benzotriazole, tolyltriazole, or a mixture thereof, 5-benzenethiol-benzotriazole, methyltetrazole, 5-phenyl-benzotriazole, 5-nitro-benzotriazole, 3-amino-5-mercapto-1, 2, 4-triazole, 1-amino-1, 2, 4-triazole, hydroxybenzotriazole, 1-amino-1, 2, 3-benzotriazole, and thiazole.
20. The plasma etch residue cleaning solution of claim 19, wherein the heterocyclic compound comprising at least one nitrogen element is benzotriazole.
21. The plasma etch residue cleaning solution of claim 18, wherein the polyol has a general structural formula of CnH2n+2Om(n≥2，m≥2)。
22. The plasma etch residue cleaning solution of claim 21, wherein the polyol is one or more of glycerol, pentaerythritol, xylitol, trimethylolethane, trimethylolpropane, ethylene glycol, propylene glycol, 1, 2-propanediol, 1, 4-butanediol, dipropylene glycol, neopentyl glycol, diethylene glycol, 1, 6-hexanediol, vinpocetine, fructose, ribose, erythritol, pentatol, hexitol, polyethylene glycol 400, polyethylene glycol 600, polypropylene glycol 400, mannitol, and sorbitol.
23. The plasma etching residue cleaning solution of claim 1, wherein the water has a mass concentration of 28.4 wt% to 96.9 wt%.
24. The plasma etch residue cleaning solution of claim 1, wherein the pH is 7-12.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911407714.3A CN113130292A (en) | 2019-12-31 | 2019-12-31 | Plasma etching residue cleaning solution |
| PCT/CN2020/133610 WO2021135804A1 (en) | 2019-12-31 | 2020-12-03 | Cleaning solution for plasma etching residue |
| TW109143515A TW202134421A (en) | 2019-12-31 | 2020-12-09 | Cleaning solution for plasma etching residues |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911407714.3A CN113130292A (en) | 2019-12-31 | 2019-12-31 | Plasma etching residue cleaning solution |
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| CN113130292A true CN113130292A (en) | 2021-07-16 |
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| CN201911407714.3A Pending CN113130292A (en) | 2019-12-31 | 2019-12-31 | Plasma etching residue cleaning solution |
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| Country | Link |
|---|---|
| CN (1) | CN113130292A (en) |
| TW (1) | TW202134421A (en) |
| WO (1) | WO2021135804A1 (en) |
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| WO2023103853A1 (en) * | 2021-12-09 | 2023-06-15 | 安集微电子科技（上海）股份有限公司 | Cleaning fluid and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116218611A (en) * | 2021-12-06 | 2023-06-06 | 上海新阳半导体材料股份有限公司 | Polyimide cleaning fluid |
| CN116218610A (en) * | 2021-12-06 | 2023-06-06 | 上海新阳半导体材料股份有限公司 | Preparation method of polyimide cleaning liquid |
| CN116218612A (en) * | 2021-12-06 | 2023-06-06 | 上海新阳半导体材料股份有限公司 | Application of polyimide cleaning solution in cleaning semiconductor device |
| CN115011348B (en) * | 2022-06-30 | 2023-12-29 | 湖北兴福电子材料股份有限公司 | Aluminum nitride etching solution and application thereof |
| CN115895792B (en) * | 2022-11-11 | 2024-02-23 | 上海新阳半导体材料股份有限公司 | Cleaning solution and kit |
| CN116042331B (en) * | 2022-11-11 | 2024-03-08 | 上海新阳半导体材料股份有限公司 | Application of cleaning liquid |
| CN115710536B (en) * | 2022-11-11 | 2024-03-08 | 上海新阳半导体材料股份有限公司 | Preparation method of cleaning liquid |
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| US6103680A (en) * | 1998-12-31 | 2000-08-15 | Arch Specialty Chemicals, Inc. | Non-corrosive cleaning composition and method for removing photoresist and/or plasma etching residues |
| US8361237B2 (en) * | 2008-12-17 | 2013-01-29 | Air Products And Chemicals, Inc. | Wet clean compositions for CoWP and porous dielectrics |
| JP2013533631A (en) * | 2010-07-16 | 2013-08-22 | アドバンスド テクノロジー マテリアルズ，インコーポレイテッド | Aqueous cleaning agent to remove residues after etching |
| US9546321B2 (en) * | 2011-12-28 | 2017-01-17 | Advanced Technology Materials, Inc. | Compositions and methods for selectively etching titanium nitride |
| KR20200034830A (en) * | 2013-12-06 | 2020-03-31 | 후지필름 일렉트로닉 머티리얼스 유.에스.에이., 아이엔씨. | Cleaning formulation for removing residues on surfaces |
| CN105785725A (en) * | 2014-12-23 | 2016-07-20 | 安集微电子（上海）有限公司 | Photoresist residue cleaning liquid |
| KR102372109B1 (en) * | 2017-01-17 | 2022-03-08 | 엔테그리스, 아이엔씨. | Post-etch residue removal for advanced node beol processing |
| CN110095952A (en) * | 2018-01-29 | 2019-08-06 | 张家港奥擎电子化学有限责任公司 | A kind of composition removing titanium nitride hard mask and/or etch residues for selectivity |
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| WO2023103853A1 (en) * | 2021-12-09 | 2023-06-15 | 安集微电子科技（上海）股份有限公司 | Cleaning fluid and use thereof |
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| WO2021135804A1 (en) | 2021-07-08 |
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