TWI329139B - Corrosion inhibitor composition for cleaning semiconductor chip - Google Patents

Description

IX. Description of the invention: [Technical field to which the invention pertains] The invention is directed to a retardant composition which is washed in a semiconductor manufacturing process. π牛牛日日片清 [Prior Art] In the manufacturing process of semiconductor components, in the manufacture of optical components, it is necessary for the flow exposure and imaging pair X a; nTt#f 0 ^7m7: lt step to use dry The ash is removed to remove the photoresist layer and the photoresist layer is removed. The first - cleaning / cleaning step removes and cleans away the remaining U light ^ two slow = = Wenqing knows the metal layer (such as Shao layer). In the pass, and in order to remove the secret light barrier layer, the high temperature gf is lost. It is necessary to remedy the prior art, such as U.S. Patent Bulletin No. 5334332, U.S. Patent No. 5,417,877, U.S. Patent Notice No. 2, U.S., No. 6,635,186, etc., and the US Patent Publication No. The composition has a slow-removing agent for removing the photoresist layer and is ιί strong. However, the composition is usually used at a high concentration to the temperature tau, which is not friendly to the environment and produces a large substance r 1 . It is urgent to develop a new type of corrosion inhibitor combination 1329139. The main purpose of the invention is to provide a retardant composition for cleaning semiconductor wafers to solve the above problems. [Summary of the Invention] Group > 4 issued - Guan Ke Lai The sample composition comprises water and/or a solvent, characterized by comprising a polymer, wherein at least one monomer which synthesizes the silk-containing polymer contains a plurality of groups. The buffering agent for semiconductor wafer cleaning comprises a carboxyl group-containing poly-p-metal such as A1 or the like, or a non-metal Si, or a non-metal oxide=〇2, etc., which is contained in the slow-acting composition. Lin's things can be mixed Side effects, surfactants, and chelation freshness. This & cleansing side-effect composition not only has environmentally friendly, '^ no, health-promoting characteristics' but also a combination of fluorine-containing and non-fluorine-containing Inhibition effect. The use of the slow-axis composition of the present invention can reduce the residual rate of the 'and hardly attack Sio々si. The buffering agent composition for semiconductors of the present invention can be used between room temperature and 85T: Key tool and single wafer processing. In the present invention, the carboxyl group-containing polymer is a carboxyl group-containing homopolymer, a beautiful copolymer, a carboxyl group-containing homopolymer salt, and/or a carboxyl group-containing copolymer salt. In a preferred embodiment of the present invention, the yttrium, the poly(acrylic acid) and/or the polymethyl propyl group are = ground, and the county-containing polymer is a polyfilament _ and/or Polyacrylic acid. Another preferred embodiment of the present invention is a copolymer of silk-containing monomers (such as acrylic acid and maleic acid copolymer, f-based acrylic acid and silk). 'or a copolymer between a vinyl monomer and a carboxyl group-containing monomer (eg PI and propylene, , styrene, benzoic acid, (10) nitrite, copolymer of ethylene and acrylic acid, copolymer of acrylonitrile and acrylic acid, styrene ^ 6 1329139 based acrylic copolymer, ethylene and methacrylic acid copolymer and / Or a copolymer of acrylonitrile and methacrylic acid, etc.. Preferably, the carboxyl group-containing copolymer is a copolymer of acrylic acid and maleic acid. In another preferred embodiment of the invention, the buffer-containing group The homopolymer salt and/or the carboxyl group-containing copolymer salt is an ammonium salt, a potassium salt and/or a sodium salt. Preferably, the mercapto-containing homopolymer salt and/or the tet-containing copolymer salt are recorded. Salts, such as polyacrylic acid (SD), in the present invention, may be used in the corrosion inhibitor compositions of the present invention as long as they are conventionally available in the prior art. The molecular weight of the carboxyl group-containing polymer is not affected, and the object of the present invention is achieved. If the corrosion inhibitor composition of the present invention has a polymer of a certain quality/density, the retarder composition also relatively has a certain concentration of retardation f. 11 is because for a polymer of a certain quality concentration, if the molecular weight f of the polymer is large, the number of moles of the polymer in the retarder composition is relatively small; if the amount of the polymer is small, The number of moles of the polymer in the corrosion inhibitor composition is relatively constant, that is, a certain polymer is formed, and the polymer of a certain quality concentration contains a concentration of sulfhydryl groups. If the molecular weight of the polymer is not large, the carboxyl group on the polymer may reach a certain concentration in the corrosion inhibitor composition, and the ruthenium complex of the ruthenium reticulating compound can be suppressed by cleaning the semiconductor wafer. Such as Α 1), non-metal (such as si) and scrap metal oxide (such as 〇 2, etc.). In the corrosion inhibitor composition of the present invention, the concentration of the carboxyl group on the polymer is preferably from 25 ppm to 50, 〇〇〇 ppm. In another preferred embodiment of the invention, the corrosion inhibition comprises a small molecule acid and/or a small molecule base. 4 is the heart. The small molecule acid may be various small molecule acids, preferably, it may be an organic acid, and more may be a small molecule acid containing f or more filaments. The organic acid may preferably be 2-

If), oxalic acid (〇A), citric acid and/or no acid. More preferably, it may be butane-1,2,4-tricarboxylic acid (PBTCA) and/or grass 7 1329139. The small molecule base may be various small molecular bases, preferably, it may contain single or multiple Molecularly, more preferably, ammonia and/or tetramethyl hydroxide can be recorded in the corrosion inhibitor composition of the present invention. 'The concentration of the carboxyl group-containing polymer can be various concentrations, preferably, The concentration of the small molecule acid and/or the small molecule base may preferably be 〇1 to 10%, more preferably 5% to 1%, more preferably H5/°. The water and/or solvating concentration may be various concentrations of the prior art, preferably from 80 to 99 99999%, and more preferably from 92 to (four) states. The above concentrations all refer to the mass concentration of the entire buffer composition. , 昆人Ϊ本 in the solvent means that the organic solvent 'can be a variety of organic solvents or its: such as N-methyl ketolone (ΝΜΡ), butane (, 〇, - diethylene glycol monobutyl (10) (10) Cong) and; or erythroamine (ΕΑ) ' Preferably, it may be NMP, DGMBE and/or hydrazine. Na: The secret agent composition may additionally contain other genus or non-metal which is used for semiconductor crystal cleaning, and has a good effect of the 7-effect rat and the gas-free composition of the cap. The ride can be obtained from the following statement [Embodiment] In order to achieve the above-mentioned scope of the present invention ^ ^ ^ ^ ^ The remaining effects, a number of (four) implementation of second-hand and second to explain as follows: 4 夂霄 Example 1 ~ 22 Plus 8 1329139 Table 1 The slow-acting composition and the comparative composition of the present invention (without the defeat composition)

Example DI (%) GBL (%) NM P (%) EA (%) DGMBE (%) Small molecule acid and / or carboxyl group-containing polymer component concentration (%) Component concentration (%) 1' 16.1 9.8 11.8 16.1 46.2 NA ΝΑ 2' 17.9 NA 13.1 17.9 51.1 NA ΝΑ 3' 18.0 NA 13.1 17.8 51.0 PBTC A 0.1 ΝΑ 1 29.8 NA 70 NA NA PBTC A 0.1 ΗΡΜΑ 0.1 2 16.8 NA 12.3 16.8 48.1 PBTC A 3 ΗΡΜΑ 3 3 17.8 NA 13.1 17.8 51.0 PBTC A 0.1 ΗΡΜΑ 0.2 4 17.5 NA 12.8 17.5 50.2 PBTC A 1 ΗΡΜΑ 1 5 9.75 NA NA NA 85 OA 0.25 ΗΡΜΑ 5 6 15.1 9.2 11.1 15.1 43.5 PBTC A 3 ΗΡΜΑ 3 7 15.8 9.5 11.6 15.8 45.3 PBTC A 1 ΗΡΜΑ 1 8 15.9 9.6 11.6 15.9 45.6 PBTC A 0.7 ΗΡΜΑ 0.7 9 15.6 10.4 11.6 15.6 44.8 PBTC A 1 SD 1 10 20 10 NA 10 49.99999 Ammonia 10 Copolymer of acrylic acid and maleic acid 0.0000 1 11 10 10 40 7 30 NA SD 3 12 15 NA 9.9 15 50 TMAH 0.1 SD 10 13 98 NA NA NA NA NA NA SD 2 14 NA NA 95 NA 4 NA NA Phenyl E 1 1329139 Ene and maleic anhydride copolymer DI · Deionized water; NA is not added to this ingredient 2 hair loss, the composition of the retardant and the pair Composition (including composition) Example DI NMP SD nh3h2o PBTCA ΗΡΜΑ NH4F % % % % % % % 4' 29 70 NA ΝΑ ΝΑ ΝΑ 1.0 15 —*' · 29.4 70 NA ΝΑ 0.1 0.1 0.4 16 29.8 70 NA ΝΑ 0.1 0.1 ΝΑ 17 28.3 70 NA 0.5 0.1 0.1 1.0 18 28.4 70 NA 0.5 ΝΑ 0.1 1.0 19 28.2 70 0.1 0.5 0.2 ΝΑ 1.0 20 28.8 70 0.1 ΝΑ 0.1 ΝΑ 1.0 21 ~ 28.9 70 0.1 ΝΑ ΝΑ ΝΑ 1.0 22 28.4 70 0.1 0.5 ΝΑ ΝΑ 1.0 DI: Deionized water; ΝΑ is not added to this ingredient.

The present invention was prepared by mixing the components of the above Tables 1 and 2 in a uniform ratio of the retardant composition and the comparative composition. Effect Example 1: Example 丨 '~3' conjugate and solid thief 1~9 of the slow side combination: The cleaning side is empty from A1 ". The method and the bar % shaker for the mother minute 60 rpm" time is 30 minutes. The etching rate is calculated by 诵G = gamma test before and after the surface resistance change, and the results are as shown in Table 3. The composition of the composition in the non-fluorinated composition on the blank A1 wafer secret rate 1329139

In the semiconductor cleaning process, if the gold eyebrow A/min, it means that the buffering agent composition has a phase of 2 〇 or less, and does not contain a cerium-containing polymer. From the side of Table 3, the rate tends to 2. A/min. The W-containing wafer of the present invention is used for cleaning an empty (10) wafer, and the slow _ combination significantly reduces the etching rate of A1, and even A/mm, which can be used. Therefore, it is explained that the lining of the present invention suppresses the AI rot and suppresses the Α1 impurity, and further facilitates the 1, 2, and retarder composition to exhibit inorganic residue (IV). (5) Fine layer: residue and / or effect Example 2: The former ft described Example 4 retardant composition for cleaning money blank SiO? Japanese film, M NANOSPEC NANO me^s

The etching rate was calculated from the change in surface film thickness before and after the Sl〇2aa sheet etching. The side rate of (10)2 is G.78A/_, and its si〇H, ugly' indicates that the slow-reacting composition of the present invention can also inhibit 1329139. Effect Example 3: Comparative Example 4' The composition and implementation of the life _ to A1 (9). The results of the surface resistance change after the occupation and age were calculated, and the results are shown in Table 4. m from the rest

Table 4 Rate The relaxation combination of the present invention is finer than the meal of the gas-containing composition dispersed from the A1 wafer.

=Rate side group; _ rate is 贞 value, the side rate of the yang is almost the phase fluoride in the semiconductor cleaning process to assist in removing the wafer, but the fluoride tends to increase the etch rate of the metal at the same time. As shown in Table 4 =

It is shown that in the fluoride-containing composition, the present invention is used for the main blank A1 wafer, and the A1 etching rate is also small, and the etching of A1 can be made to be less than 2.0 A/min. The corrosion of the A1 etched 1.88 A/min 'A1 was completely suppressed even if it contained only the money wicking composition containing the mascaraic acid and the uric acid of the money filament family (as in Example 21). The features and spirit of the invention are more apparent from the detailed description of the preferred embodiments of the invention, which is not limited by the scope of the invention disclosed herein. On the contrary, the intention is to cover various modifications and equivalents within the scope of the invention as claimed. Therefore, the scope of the patent application of the invention should be construed broadly in the light of the above description, so that it covers all possible changes and equivalent arrangements. 12 1329139 [Simple description of the diagram] None [Key component symbol description]

Claims (1)

X. The scope of application for patents: 丨 “^, 'charged for the semiconductor wafer cleaning of the slow surname j (C〇rr〇si〇n wrist watch) composition, = corrosion inhibitor composition contains water, its characteristics Wherein: the corrosion inhibitor composition comprises a dicarboxyl group-containing polymer and an organic acid selected from the group consisting of 2-phosphonic acid butane 4,2,4•tricarboxylic acid, oxalic acid, citric acid, gallic acid, and a base selected from the group consisting of ammonia water and tetramethylammonium hydroxide. A corrosion inhibitor composition for semiconductor wafer cleaning, the corrosion inhibitor composition comprising water and a solvent, characterized in that the corrosion inhibitor Composition 1 includes a second carboxyl group-containing polymer and an organic acid selected from the group consisting of 2-phosphonic butane-1 and tricarboxylic acid, oxalic acid, citric acid, gallic acid, and selected from the group consisting of ammonia water and tetramethyl hydroxide. An ammonium base, wherein the solvent is Ν·methylpyrrolidone, 7-butyrolactone, N,N•dimethylacetamide, diethylene glycol monobutyl ether and/or ethanolamine. The corrosion inhibitor composition according to Item 1 or 2, wherein the carboxyl group-containing polymer is a carboxyl group-containing homopolymer or a carboxyl group-containing copolymer. A carboxyl group-containing homopolymer salt and/or a carboxyl group-containing copolymer salt. 4. The corrosion inhibitor composition according to claim 1 or 2, wherein the carboxyl group-containing homopolymer is poly Maleic anhydride, polyacrylic acid and/or polymethacrylic acid; the carboxyl group-containing copolymer is a copolymer of acrylic acid and maleic acid, a copolymer of styrene and acrylic acid, a copolymer of styrene and maleic acid and/or propylene a copolymer of a nitrile and a maleic acid; the carboxyl group-containing homopolymer salt and/or a carboxyl group-containing copolymer salt is an ammonium salt, and/or a sodium salt. 5. A vaginal agent as described in claim 4 The composition is characterized in that the concentration of the carboxyl group-containing polymer is 0.00001 to 10%, the concentration of the organic acid and/or alkali is 0 to 10%, and the concentration of the water and/or solvent is 8 to 99.99999%. Further, the composition of the retardant according to claim 4, wherein the concentration of the slow-group-containing polymer is 0.01 to 3 Å/〇. 1329139 7. The corrosion inhibitor composition according to the invention, characterized in that the concentration of the acid and/or alkali of the food is 0 to 5%. 15