TW201012922A - Residue cleaning solution after plasma etching and ashing - Google Patents

Abstract

The present invention provides a cleaning solution for plasma etching and ashing residue removal. The residue cleaning solution includes fluoride, organic amine, solvent and water, which has a good cleaning capacity that can remove the residues after plasma etching and ashing on metals, channels and the pad wafer. The residue cleaning solution has a low corrosion speed toward non-metallic materials (e.g., SiO2, PETEOS, silicon and materials with low dielectric constants) and some metals (e.g., Ti, Al and Cu). The residue cleaning solution can be applied to wet bench, batch-spray and single wafer tool with larger operating window. The residue cleaning solution will be well applied in microelectronics industry field such as semiconductor chip cleaning.

Description

201012922 IX. Description of the Invention: [Technical Field] The present invention relates to a cleaning fluid for semiconductor manufacturing, and a special etching residue cleaning solution. Electric Power [Prior Art] In the manufacturing process of a semiconductor component, the patterning of the coating of the photoresist layer is a necessary process step. In the figure, the layer, imaging, ion implantation and diligence Ϊ = 2 worms will harden the photoresist layer polymer, due to the resistance f; ashing removes most of the photoresist layer (PR). Step: Step ί

ί^ίί i (4) side / parental return to the remaining layer, 1 body + t wash cleaning / rinsing / deionized water rinse. In this process, 聚合物, J polymer photoresist layer and inorganic substances, and can not attack the damage of gold ΐ 水性 water-based code, the cleaning liquid has the following several kinds of amine cleaning liquid, half of the first two types (four) ^ performance cleaning solution. Among them, there are all the sub-buffers of the general genus, generally between 60c and 8 (between rc, _clean ίίίΐϊ, for example, can not simultaneously control the metal and non-three-variable semiconductors, and the valley features change. , and so on.,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, The gas is washed between 1 and the acidic buffer consists of a salt with a _ p value of 3 to 7. The composition ratio is 1〇: i to j 5 2 夂 夂, and the corresponding record of the record is disclosed. Fluorine-containing cleaning solution, special f = liquid dryness and surface tension are reported large, from plastic $ m 5,972,862, quality mineral or organic acid, quarterly salt and organic =

11, because the cleaning effect is not very stable, there are various ^Up in order to overcome the defects of the existing cleaning solution: = two: trapping - heart [invention] The technical problem to be solved according to the present invention is to overcome the existing = (4) The cleaning liquid has a large lying rate, and the (4) metal (4) metal and non-window small 'cleaning ability is insufficient and the cleaning effect is unstable, etc., and provides a strong cleaning ability, and the corrosion rate /, can be the same Control the corrosion of metal and non-metal, clean the plasma etching residue cleaning liquid with large window and stable cleaning effect. According to a specific embodiment of the present invention, the plasma etching residue cleaning liquid of the present invention contains a fluoride, an organic amine, a solvent and water. Among them, the fluoride is preferably selected from the group consisting of hydrogen fluoride, or a salt formed by hydrogen fluoride and a base, preferably hydrogen fluoride (HF), ammonium fluoride (NH4F), ammonium hydrogen fluoride (NH4HF2), tetrakis-based ammonium sulfate (N(CH3)). One or more of 4F) and trishydroxyethylated gasification i(CH20H)3HF). The above base is preferably selected from the group consisting of ammonia quaternary ammonium oxime oxides and alcohol amines. Preferably, the content of the above-mentioned image compound is from 201012922 to 0.01% by weight to 20% by weight. Preferably, the above-mentioned nitramine may be one or more selected from the group consisting of a mercapto group, an amino group and an imide organic amine. Preferably, the above-mentioned secret organic amine is an alcohol amine such as ethanolamine, diethanolamine, triethanolamine, isopropanolamine, ...N-dimethylethanolamine, N'N-methylethylethanolamine and &; methyl di- _ female. Preferably, the above amino group-containing organic amine may be an organic polyamine such as an amine, pentamethyldiethylenetriamine and a polyethene polyamine. Preferably, the organic amine of the reciprocating group may be an amino group-containing organic acid such as 2-aminoacetic acid, acid, iminodiacetic acid, aminotriacetic acid and ethylenediaminetetraacetic acid. ^ 'It is preferred to use the above three organic amines (that is, the alcohol amine amine amine material. Compared with 2, the ratio of 2 to 35%. The presence of polyamines is beneficial to the ΡΗ ^, to improve the age and weight of the green touch) For example: each: ^ car above the chelating agent can be a stone, stone, sputum, ketone,

The above hardening may be one or more of dimethyl hydrazine and diethyl 4 S. Preferably, the above enthalpy may be one or more of lutet winds in the sulfone. Preferably, the above imidazolidinone, 1,3-dimethyl-2-imidazolidinone and 13_^^ two kinds of r-ethyl; Preferably, the above-mentioned one of the ketones of each hospital is touched. Difficult, ethyl: than 1 methyl 3 醯 H group; 2 imipoline network. Preferably, the above guanamine may be methotrexate and/or dimethylacetamide. Preferably, the above-mentioned one or more of methyl ΐ ΪΓ ΪΓ ΪΓ ΪΓ 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 ^ ^ tί ί diol diol single-yard ether can be one or more of ethylene glycol monomethyl _, , B- Ϊ 和Preferably, 7 201012922 一种 one or more of diethylene glycol mono(tetra), diethylene glycol monoethyl ether and two. Preferably, the above-mentioned dibutyl sulfonium mono-, di-propylene glycol monoethyl ether and dipropylene glycol mono-tripropylene glycol monomorphic may be tripropylene glycol, the above-mentioned solution _ content can be a percentage of riding Φ chest ^ compared to the money, the above water The content may be a percentage by weight of the anti-iirf cleaning (four) may include other f-additive additives in the field, such as a preservative such as copper: benzotriazinium; and, as a preservative, the cleaning solution of the present invention is simply mixed with the above components. Washing is used in a wide temperature range, generally in the = to ic target range, and can be applied to various cleaning methods such as, bench, batch-spray (batch_spray) and (wafertool). The reagents and raw materials used in the present invention are all commercially available, smg e

, cleaning and cleaning, effectively removing the residue on the electropolymerization side, while two (such as SiO 2 , ion-enhanced tetraethoxy decane dioxide, and low dielectric materials) and metal materials (such as Ti, A1 and C rates) At the same time, it controls the corrosion of t1 metal and non-metal. In addition, the 清-turning type of Qing dynasty, with the record of the big ···w miscellaneous and early film doubt 8 201012922 ❹ The advantages and spirit of the present invention can be as follows The invention is further described in the following description. The embodiments of the invention are further illustrated by the following examples, but are not intended to limit the invention to the scope of the embodiments. 1 Embodiment 1 to 33 of the plasma residue residue cleaning liquid according to the present invention is prepared by uniformly mixing the components according to the formulation in the table, and the cleaning liquid of each of the examples can be obtained. Electro-destructive cooking, 土, soil, Άι n Example T23 4 5 6 7 8 910111213 溶剂 Solvent specific reagent dimethyl hydrazine • ethyl arylene 1 methyl ethyl sulfene methyl hard ethyl chlorocyclobutene 2- Imidazolidinone oxime-dimethyl-2-mime» sit ketone 1,3-diethyl-2- Azolidinone oxime-methylpyrrolidone oxime-ethylpyrrolidine-ketone __ Ν-cyclohexylpyrrolidone oxime-hydroxyethylpyrrolidinium 1,3-dimethyl-2-amiline network fluoride content wt% 53 Specific reagent content wt% Hydrogenated hydrogen 0.01 Ammonium fluoride ammonium hydrogen fluoride trishydroxyethyl tetramethylammonium fluoride trihydroxy group ammonium fluoride _ trihydroxy 23⁄4 ammonium fluoride deionized water content 19.89 - 45 organic amine specific reagent Ethanolamine-ethylamine content wt% 0.1 0.5 29 Isoproscinamine 35 ammonium fluoride

39 64.5 68.5 58 Ammonium fluoride pentamethyldiethylenetriamine

50 29.4 Ethylenediaminetetraacetic acid 20 0.1 Ν ' N-monomethylethanolamine 25 Trishydroxyethyl ammonium fluoride 55 Trishydroxyethyl ammonium fluoride 15 N-methyldiethanolamine 15 16 dimethylformamide 44 Fluorine Ammonium-methylacetamide 59 ammonium fluoride 40 32Τ 15 1 methyl diethyl 7.5 9 201012922 17 ethylene glycol mono f ether 59.5 ammonium fluoride 0.5 35 pentamethyldiethylene triamine 5 18 ethylene glycol single Ether 64.5 Ammonium fluoride 0.5 30 Pentamethyldiethylenetriamine 5 19 Ethylene glycol monobutyl ether 64.5 Ammonium fluoride 0.5 32 Pentamethyldiethylenetriamine 3 20 Diethylene glycol monomethyl bond 49.5 Ammonium fluoride 0.5 40 Triethanolamine 10 21 Diethylene glycol monoethyl ether 40 Ammonium fluoride 1 29 Triethanolamine 30 22 Diethylene glycol monobutyl mystery 53 Ammonium fluoride 1 45 Iminodiacetic acid 1 23 Propylene glycol monomethyl ether 35 Trishydroxyethyl fluoride Ammonium 9 40 Triethanolamine 16 24 Propylene glycol Monoethyl ether 35 Trishydroxyethyl ammonium fluoride 10 35 Triethanolamine 20 25 Propylene glycol monobutyl ether 39 Trishydroxyethyl ammonium fluoride 15 45 Iminodiacetic acid 1 26 Dipropylene glycol monomethyl ether 47 Trihydroxyethylammonium fluoride 3 45 pentamethyldiethylenetriamine 5 27 dipropylene glycol monoethyl ether 44 trishydroxyethyl Ammonium fluoride 1 42.5 Pentamethyldiethylenetriamine 12.5 28 Dipropylene glycol monobutyl ether 60 Trishydroxyethyl ammonium fluoride 3 35 Pentamethyldiethylenetriamine 2 29 Tripropylene glycol monomethyl ether 44 Trishydroxyethyl fluoride Ammonium 0.5 45 pentamethyldiethylenetriamine 10.5 30 dimethyl-hardened 60 ammonium fluoride 2 30 iminodiacetic acid 2 tetramethylammonium fluoride 2 triethanolamine 2 polythylene polyamine 2 31 1,3-two曱基-2-咪11 sit 1 forest leisure 30 trishydroxyethyl ammonium fluoride 5 30 iminodiacetic acid 5 dipropylene glycol monoethyl ether 30 32 dimethyl sulphate 30 trishydroxyethyl ammonium fluoride 5 30 imino Acetic acid 2 Dipropylene glycol Monoethyl ether 25 Ammonium hydrogen fluoride 1 Triethanolamine 2 Pentamethyldiethylene triterpene 5 33 Cyclobutane 15 Ammonium fluoride 3 35 Iminodiacetic acid 2 Propylene glycol monobutyl ether 15 Triethanolamine 5 N-hydroxyethylpyrrolidone 20 Pentamethyldiethylenetriamine 5 Effect Example Test method for metal corrosion rate of cleaning solution: 1) Test the initial value of resistance (Rsl) of 4*4cm blank Shishixi Tablet using Napson four-point probe instrument; 2) The 4*4 cm aluminum blank is immersed in a solution that has been previously thermostated to 35 ° C for 30 minutes; 201012922 ~ The 4Mem charm white column, washed with deionized water, high purity, dry mouth, and then use the Napson four-point probe instrument to test the resistance value of the aluminum empty film (Rs2); 4) repeat the first and second Step retest - times, the resistance value is recorded as Rs3; 5) Turn the above resistance value and soak time into the appropriate program to determine the corrosion rate. Non-metallic corrosion rate test method for mountain cleaning fluid: φ

1) Test the thickness of the 4*4 cm PETEOS Shixi tablet (T1) using a Nanospec 6100 thickness gauge; 2) Soak the 4*4 cm PETEOS wafer to a temperature of 35 beforehand. 30 minutes in the solution of sputum; Friends 4^ Take out the 4*4cinPETEOS plaque, wash it with deionized water, dry it with high purity nitrogen and then test the thickness of the 4*4cm PETEOS 矽 piece with the Nan〇spec6100 thickness gauge (T2) 4) Repeat the second and third steps and test the thickness again as T3; 5) Enter the above thickness value and soak time into the appropriate program to calculate the decay rate. Table 2 presents the cleaning effect and the rate of decay of the cleaning liquids 13, 32 and 33 according to the present invention. 11 201012922 Rate of corrosion of clear metal (A/r is) nin) Corrosion rate of non-metal (tetraethoxy shi xi shuang gasification PET, PETEOS) (human / min) Different 頬 type wafer cleaning result liquid S - 30 minutes also a 30 minute first 30 minutes second 30 minutes metal wire channel -- metal pad 13 1.70 0.85 0.22 0.15 clean, no corrosion, no change 诵i was ten clean, no corrosion 32 1.25 0.65 0.63 0.72 Clean, not corroded, no change, clean size, no corrosion 33 1.30 0.72 0.49 0.43 Clean, not corroded, no change in channel size clean 'no corrosion

It can be seen from Table 2 that the cleaning liquid of the present invention does not substantially invade the metal (such as metal) and non-metal (such as pETE〇s) used in the semiconductor process, and the corrosion rate is close to or less than that of the semiconductor industry. Usually required 2 angstroms per minute. When the plasma etching residue was cleaned with the cleaning liquid in Table 2, the residue on the plasma side was removed, and substantially no metal and non-metal were observed. The detailed description of the preferred embodiments of the present invention is intended to provide a better understanding of the preferred embodiments of the present invention. #欠月的范咛 is restricted. On the contrary, the purpose is to hope that the scope of the invention and the equivalence of the patents to be applied for in the present invention 12 201012922 [Simplified illustration] [Major component symbol description]

Claims (1)

201012922 X. Patent application scope: 1. A plasma etching residue cleaning solution comprising: fluoride; organic amine; solvent; and water. 2. The patent wastes the cleaning residue of the plasma residue residue according to the first item, wherein the f fluoride is selected from the group consisting of hydrogen fluoride, ammonium hydrogen fluoride, tetramethylammonium and tris(hydroxyethyl) ammonium hydride. At least one of a group consists of one group. 3. For example, please use the cleaning solution of the electric hybrids in the full-scale phantom item, wherein the content of δH fluoride is 重量~2〇% by weight. 4. The plasma etch residue cleaning solution according to claim 1, wherein the amine is selected from at least one of the group consisting of a base group, an amino group and a lining organic amine. 5. The plasma etching residue cleaning solution according to claim 4, wherein the organic amine containing a radical is an alcohol amine; the amino group-containing organic amine is an organic compound; The organic amine is an amino acid-containing organic acid. 6. A cleaning residue for a plasma residue residue as described in claim 5, wherein the alcohol amine is selected from the group consisting of ethanolamine, diethanolamine, triethanolamine, propylene glycolamine, N,N-dimethylethanolamine. And at least one of a group consisting of N, N-methylethylethanolamine and hydrazine methyldiethanol j, the organopolysaccharide selected from the group consisting of: ethylene triamine, pentadecyl diethylene triamine, and a composition consisting of at least one of a group consisting of polyethene polyamines; the organic acid of the amino group consisting of 2: glycine, 2-aminobenzoic acid, iminodiacetic acid, ammonia triacetic acid, and ethylenediaminetetraacetic acid At least one of the groups is composed of one. 14 201012922 7. The electro-polymerization residue cleaning solution described in the above item, wherein the above-mentioned alcohol amine, organic polyamine and amino-containing polyamine organic system. 8. For example, please refer to the slurry polishing residue cleaning solution described in item 1 of the full-time division, wherein the content of the organic amine is 01 to 35% by weight. 9, Shen Qing patent Ιϋ circumference! The electropolymerization residue cleaning solution according to the invention, wherein the U system is selected from the group consisting of at least one of the group consisting of sub-H oxime, linalone, guanamine and ether. 10. The electrical erosion as described in claim 9 of the patent application is selected from the group consisting of at least one of a group consisting of dimethyl (tetra), diethyl sub-like and methyl ethyl slate. The stone wind is selected from at least one of the group consisting of methyl hydrazine, ethyl hydrazine and cyclobutyl hydrazine, and the sulphur ketone is selected from the group consisting of 2-flavosulfone and benzyl-2. _ 峻 炫 酮 所 - - 群体 群体 群体 群体 群体 対 対 対 対 対 対 対 対 対 対 対 対 対 対 対 対 対 対 対 対 対 対 対 対 対 対 対 対 対 対 対 対 対 対 対 対 対 対 対 対 対 対 対 対 対 対 対At least one of a group consisting of pyrrolidone, which is 1,3-methyl-2-mylinone, which is dimercaptocaramine and / dimethyl Ethyl amide, which is selected from the group consisting of ethylene glycol monoalkyl ether, diethylene glycol ether, propylene glycol monoalkyl ether, dipropylene glycol monoalkyl ether, and tripropylene glycol monoalkyl ether. At least one of its components. 1U is a plasma etching residue cleaning solution according to claim 10, wherein the substrate is selected from the group consisting of ethylene glycol monomethyl ether, ethylene glycol mono-mystery, and ethyl, monobutyl ether. At least one of a group consisting of the diethylene glycol monoalkyl ether selected from the group consisting of diethylene glycol monoterpene ether, diethylene glycol monoethyl ether, and dioxetane monobutyl ether At least one of the components, the propanol monoalkyl group is selected from at least one of the group consisting of propargyl monomethyl hydrazine, propylene glycol monoethyl ether, and propylene glycol monobutyl ether; 15 201012922 The diol monoalkyl ether is selected from at least one of a group consisting of dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether and dipropylene glycol monobutyl ether; the tripropylene glycol monoalkyl ether is tripropylene glycol single Ether ether. 12. The plasma #刻 residue cleaning solution according to claim 1, wherein the solvent is contained in an amount of 35 to 80% by weight. 13. The plasma etching residue cleaning solution according to claim 1, wherein the water content is 10 to 45% by weight. Reference 16