TW200813211A - Cleaning formulation for removing residues on surfaces - Google Patents

Abstract

The present disclosure provides a non-corrosive cleaning composition that is useful for removing residues from a semiconductor substrate. The composition can comprise water, at least one hydrazinocarboxylic acid ester, at least one water soluble carboxylic acid, optionally, at least one fluoride-containing compound, and optionally, at least one corrosion inhibitor not containing a carboxyl group. The present disclosure also provides a method of cleaning residues from a semiconductor substrate using the non-corrosive cleaning composition.

Description

200813211 IX. INSTRUCTIONS: [Mings 3] Field of the Invention The present invention relates to a novel I-cleaning composition for a semiconductor substrate and a method of cleaning a semiconductor substrate. In particular, the present disclosure relates to plasma etching residues formed on a semiconductor substrate after plasma etching of a metal layer or a dielectric material layer deposited on a substrate, and chemical mechanical polishing (CMP) treatment. Thereafter, a cleaning composition of the residue remaining on the substrate is removed. 0 [Prior Art] BACKGROUND OF THE INVENTION In the manufacture of integrated circuit components, a photoresist is used as an intermediate mask for utilizing a series of micro The original reticle mask pattern is transferred to the wafer substrate by the shadowing step and the plasma etching step. One of the main steps in the fabrication of integrated circuit components is the removal of the patterned photoresist film from the wafer substrate. In general, this step is performed in one of two ways. One method involves a wet removal step in which a substrate covered by a photoresist is contacted with a solution of a hindrance agent, which comprises an organic solvent and an amine. However, the remover solution cannot completely and reliably remove the photoresist film. This is especially true when the photoresist film has been exposed to ultraviolet light and plasma during the manufacturing process. A number of photoresist films have such a treatment that =+ is more difficult to dissolve in the remover solution. In addition, such a habit == plasmons are ineffective. It is not possible to remove inorganic residual materials or organic gold during the use of a gas containing 4 gases or an oxide layer. Another method of removing the photoresist film involves exposing the photoresist coated wafer to an oxygen-based plasma to burn the photoresist film from the substrate during a process known as plasma ashing. However, plasma ashing is not completely effective in removing the aforementioned by-products. Instead, the removal of such plasma etch byproducts must be accomplished by subsequently exposing the treated metal and dielectric film to a cleaning fluid. Metal substrates are generally susceptible to corrosion. For example, substrates such as aluminum, steel, aluminum steel alloys, tungsten nitride, and other metals and tungsten metal nitrides will be readily available for use in clean chemical etching. In addition, as component geometries shrink, the amount of corrosion that matrix circuit component manufacturers can tolerate is getting smaller and smaller. Hydroxylamines and hydroxyammonium salts are known to have excellent cleaning power for the removal of residues on semiconductor substrates. However, recent reports have raised concerns about the safe use of these materials, which has led to the replacement of hydroxylamine-type components in semiconductor components. This requires 15 more environmentally friendly materials. Therefore, the cleaning fluid must be effective in removing the plasma etching residue, and the cleaning t must also be non-corrosive to the entire exposed substrate material. The ability to clean a wide residue and impart non-corrosive properties to the exposed substrate material can be achieved by using the cleaning compositions of the present disclosure. The cleaning composition of the present disclosure can have a clean effect on the semiconductor substrate, and the metal contained on the non-corrosion semiconductor substrate, the original composition is that the cleaning composition of the present invention is a weakly acidic formulation, and the reason is that there is a water-soluble organic A composition of compounds which is passed through an oxygen 1 and a reduction machine to enhance the cleaning efficiency of the residue and to be water-soluble and organic. The presence of the substance also plays a role in the function of the rot and the function of the trace metal chelate. 6 200813211 Double function. SUMMARY OF THE INVENTION Summary of the Invention 5 10 15 20 The present disclosure is a (4) frontal clearing core which can be used primarily to remove electropolymerized residue and/or electropolymerized ash residue from a semiconductor substrate as a multi-step An intermediate step in the manufacturing process. Such residues include a range of relatively insoluble organic compound present compounds' such relatively insoluble organic compound mixtures such as residual photoresists, organometallic compounds, and by exposure metals such as copper, titanium, group, crane, starter, metal nitride (4) Titanium and nitrogen (10), and other materials, such as reaction by-products formed by exposure to gold. According to the disclosure of this disclosure (4) the composition of a (four) contains water, at least Γ肼 Γ肼 纽 纽 § 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 Privately selected at least one other type of non-corrosive cleaning composition - water-soluble sulfhydryl group, which is selected from the group consisting of: γ: water; at least one formic acid gambling, thioglycolic acid, Benzyl arsenic acid benzyl ester; to Φ a # ^^ 弟一丁 S曰, and 肼基甲群: 有为量: Γ selected from the group consisting of - _ class, and a certain amount of acid a gas-containing material having two or more additional ligands, a scallop, and an additional ligand, which is selected from the group consisting of: 至少; at least - water-soluble money, tetrabutyl fluoride, or fluorine Groups of trimethyl fluorinated at least - a type of rot-free / ▲ ammonium; and optionally, 7 200813211. The third embodiment of the non-corrosion cleaning composition comprises from wt% to about 15, and scoop 0·〇1 to the attack. To Λ - (10) at least - seed water: t acid; about _wt% to about 5 5 10 15 20 / gluten δ fluorinated material, and optionally at least _ 6 carboxyl containing corrosion inhibitor. A rich > μ / provide " 'species from the semiconductor substrate cleaning residue ^. The method comprises the following steps: providing - a semi-conductive material; contacting the substrate with a cleaning composition comprising a water body: a sulphuric acid vinegar, at least one water-soluble "acid, optionally: one a carbon-soluble fluoride material; and (d) at least two kinds of pastes; cleaning the semiconductor substrate with a suitable cleaning solvent: optionally, removing the cleaning solvent by any means without detracting from the beauty and integrity of the semiconductor The means of drying the semiconductor. In the method of cleaning a residue by a semiconductor substrate, the method comprises the steps of: providing a semiconductor substrate; contacting the cleaning composition with a cleaning solvent; and cleaning the semiconductor with a suitable cleaning solvent. Substrate; and optionally, drying the cleaning composition of the semiconductor embodiment using any means that removes the cleaning solvent without the integrity of the semiconductor substrate comprises: water·$, Leyi" The group consisting of: a water-soluble bismuth ruthenate ruthenium/, a system of U in the lower group: ethyl thioglycolate, thioglycolic acid H and thioic acid 34; From the group consisting of one of the following: one of the two types or more additional ligands, and the additional ligands, at least one type of water-soluble gasified material, which is 2 8 200813211 = A group consisting of tetramethylammonium fluoride, tetrabutylmethylethyl fluoride, at least one species, and, optionally, a reductant-free inhibitor. [F-method] Detailed description of the embodiment of the car father, as defined herein, unless otherwise noted, it should be understood that all hundred/knife ratios expressed must be the weight percentage relative to the total weight of the cleaning composition. "Solvent" is not allowed to dissolve the components of the clearing material at a temperature of 10 ° °. In addition, the temperature is defined as Celsius to about 27 (. 本. This is not intended for one main use. Removing a non-corrosive composition of electric=insect residue and/or ash residue from a semiconductor substrate, package (A) Jc '(8) at least _ a kind of water-soluble decyl citrate; A water-soluble acid, and (D) optionally, at least one of which does not contain a few groups, inhibits 15 agents. The pH of the cleaning composition is from about 2 to about 6. 20 The present disclosure contains at least one of the key ingredients Water-soluble sulfhydryl sulphate S (also known as carbazic acid (8) or (iv) bismuth), it is believed that arable vinegar can be used as a selective oxidation/reducing agent to improve a wide range, otherwise it is a relatively insoluble plasma sculpt residue The dissolution rate. The mercapto citrate particles can assist the removal of the plasma remnant residue and have no rot resistance to the metal. The thioglycolate used in the cleaning composition of the present invention is described by the formula (1): R1OCO-NH-NH2 (I) wherein R1 is a linear or branched group which may be substituted as needed Ci_C2. Recorded, if necessary, a substituted direct bond or a K3_C2() Wei group, or a optionally substituted 200813211 linear or branched C6-C!4 aryl group. Examples of the R1 group include, but are not limited to, A , trifluoromethyl, ethyl, 2,2,2-trifluoroethyl, 2,2,2-trichloroethyl, hydroxyethyl, propyl, isopropyl, cyclopropyl, n-butyl , isobutyl, tert-butyl, t-butyl, cyclobutyl, pentyl, 1-hydroxypentyl, isopentyl, neopentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, cyclo Hexylmethyl, cycloheptyl, 2-cyclohexylethyl, octyl, decyl, decyl, decyl, benzyl and phenyl. Preferred R1 is a linear or branched group which may be substituted as desired. a CVCw alkyl group, or a linear or branched C3-C1() cycloalkyl group which may be substituted as desired. Examples of preferred R1 groups include, but are not limited to, methyl, trifluoromethyl, ethyl, 2,2 , 2-trifluoroethyl, 2,2,2-trichloroethyl, hydroxyethyl, propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, tert-butyl, second Base, cyclobutyl, pentyl, 1-hydroxypentyl, isopentyl, neopentyl, cyclopentyl, hexyl Further, cyclohexyl, heptyl, cyclohexylmethyl, cycloheptyl, 2-cyclohexylethyl, octyl, decyl, and benzyl-15. More preferably R1 is a linear or branched CrC5 which may be substituted as desired. An alkyl group, or a C3-C6 cycloalkyl group. Examples of more preferred R1 groups include, but are not limited to, decyl, ethyl, propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, tert-butyl Base, second butyl, cyclobutyl, pentyl, isopentyl, neopentyl, cyclopentyl, cyclo 20 hexyl, and benzyl. Most preferably R1 is decyl, ethyl, tert-butyl or benzyl Examples of suitable mercaptocarboxylic acid esters include, but are not limited to, methyl carbazate, ethyl carbazate, propyl methacrylate, isopropyl carbazate, butyl decyl decanoate, decyl carboxylic acid Tributyl ester, amyl carbazate, decyl carbazate, pentadecyl decyl decanoate, decyl carbazate, thiol carboxylic acid ester, 10 200813211 phenyl carbazate, and thioglycolic acid 2-hydroxyethyl ester. Preferred examples of the thiol-lowering acid include, but are not limited to, methyl carbazate, ethyl thioglycolate, propyl methacrylate, isopropyl carbazate, butyl decyl phthalate, thioglycolic acid Tributyl vinegar, thioglycolic acid pentyl, hydrazide hydrazide, thioglycolic acid 2 _ yl 5 ethyl ester, and thiol carboxylic acid ester. More preferred examples of mercaptocarboxylic acid esters include, but are not limited to, methyl carbazate, ethyl carbazate, decyl decanoate, isopropyl carbazate, butyl carbazate, decyl carboxylic acid Sanding §, mentyl decyl decanoate and benzyl carbazate. Methyl carbazate, ethyl thioglycolate, tert-butyl carbazate, and decyl carboxylic acid ester are the most preferred mercaptocarboxylic esters. The 10 mercaptocarboxylic acid ester can be a blend of two or more mercaptocarboxylic acid esters. If this is the case, the mercaptocarboxylic acid ester can be blended in any of up to about 99% by weight of at least one of the compounds. Preferably, the mixture contains up to about 95% by weight of at least one component in the binary mixture. More preferably, the binary mixture contains up to about 75 wt% of a compound. The most preferred binary mixture contains up to about 15 5% by weight of various compounds. In the ternary mixture or a more diverse mixture, the citric acid S can be mixed in any suitable ratio. The thioglycolic acid vinegar is commercially available or can be prepared by this method as described in U.S. Patent No. 5,756, 824, incorporated herein by reference. The present disclosure further encompasses at least one water soluble carboxylic acid. Adding a carboxylic acid to the aqueous composition in a preferred weight range of 20, fixing the pH of the composition to an acidic pH, thereby producing an acidic aqueous composition in which important metal oxides such as copper oxide and aluminum oxide (and The oxide of the alloy) dissolves rapidly based on thermodynamic equilibrium. The carboxylic acids disclosed herein have several advantageous functions including: 1) enhancing the solubility properties of the residue of the composition, 2) adjusting the pH of the solution with a high buffering capacity 11 200813211, 3) forming an organic metal chelate through a clean exposed metal surface The species provides a higher degree of anti-purity, and/or 4) provides the chelating and capturing ability of undesired trace amounts of metallic wood that would otherwise be deposited back onto the surface of the semiconductor substrate. 5 10 15 The main effect of including a plurality of water-soluble carboxylic acids in the cleaning compositions of the present disclosure is to provide a metal chelate function. The chelating agents disclosed herein are believed to reduce metal impurities. A chelating agent is a compound which forms a plurality of bonds to a single metal ion. The metal rider is referred to as a core atom, and the anion or molecule of the metal cation with which it forms a coordination compound will be referred to as a ligand. If the system is composed of several atoms, the atom responsible for the basic or nucleophilic nature of the ligand is referred to as a ligand atom. If a test contains more than one ligand atom, it can occupy more than one coordinate position in the complex, and is referred to as a multidentate complex forming agent. The ligands occupying the first, second and third positions are respectively referred to as one tooth, two teeth, three teeth and the like. The complex formation with the polydentate ligand is referred to as chelation, and the complex is referred to as a chelate. A compound containing a group such as a hydroxyl group, an amine group, a thio group, a thiol group, a thiol group, a thiol group, or the like has a metal chelate property f. In particular, the carboxylic acid containing a hydroxyl group can effectively inhibit the corrosion of aluminum, copper, aluminum and copper alloys, titanium, neon, crane, and other metals exposed to metal materials and intermediate materials such as metal nitrides. In the description of the water-soluble carboxylic acid sub-classes in the following paragraphs, substituents having a nitrogen atom or a sulfur atom are not encompassed unless otherwise stated. In one embodiment of the cleaning composition of the present disclosure, the at least one water/gluten carboxylic acid comprises at least one carboxylic acid that does not contain an additional ligand. Examples of such carboxylic acid sub-classes include, but are not limited to, acetic acid, formic acid, butyric acid, propionic acid, benzoic acid 12 200813211 acid, acrylic acid, valeric acid, isovaleric acid, trimethyl acetic acid, and mixtures thereof. In another embodiment of the cleaning composition of the present disclosure, the at least one water soluble carboxylic acid comprises at least one carboxylic acid having one additional ligand. Examples of such carboxylic acid sub-classes include, but are not limited to, pyruvic acid, lactic acid, glycolic acid, crotonic acid, ethoxylated acetic acid, 3-hydroxybutyric acid, 2-hydroxyisobutyric acid, 2-ketopropionic acid, and Its mixture. In another embodiment of the cleaning composition of the present disclosure, the at least one water soluble carboxylic acid comprises at least one monocarboxylic acid having two or more additional ligands. Examples of such carboxylic acid subclasses include, but are not limited to, glyceric acid, gluconic acid, 10 galacturonic acid, and mixtures thereof. In another embodiment of the cleaning composition of the present disclosure, the at least one water-soluble carboxylic acid comprises at least one dicarboxylic acid free of additional ligands. Examples of such carboxylic acids include, but are not limited to, oxalic acid, malonic acid, maleic acid, butenedioic acid, methylmalonic acid, succinic acid, methyl succinic acid, glycolic acid, 15-maleic acid, pimelic acid, phthalic acid, sebacic acid, glutaric acid, and mixtures thereof. In still another example of the cleaning composition of the present disclosure, the at least one water-soluble carboxylic acid comprises at least one dicarboxylic acid having an additional ligand. Examples of subclasses of the present carboxylic acid include, but are not limited to, malic acid, oxalic acid, lyophilic acid, ketoglutaric acid, and mixtures thereof. In still another example of the cleaning composition of the present disclosure, the at least one water soluble carboxylic acid comprises at least one dicarboxylic acid having two or more additional ligands. Examples of such carboxylic acid subclasses include, but are not limited to, tartaric acid, dihydroxy phthalic acid, saccharin acid, and mixtures thereof. 13 200813211 In another example of the cleaning composition disclosed herein, at least one of the water-soluble tickacid inclusions has at least two acid-cracking groups (polycystic acid) without any additional ligands. Compound. Examples of such acid-sorting sub-classes include, but are not limited to, trimethoprimic acid, stearic acid, stupid triacid, and mixtures thereof. In another embodiment of the cleaning composition of the present disclosure, the at least one water-soluble carboxylic acid comprises at least one polycarboxylic acid having an additional ligand. Examples of such carboxylic acid subclasses include, but are not limited to, citric acid, alginic acid, and mixtures thereof. In another embodiment of the cleaning composition of the present disclosure, the at least one water-soluble tickic acid comprises at least one of the at least one nitrogen moiety. Examples of this sub-10 subclass include, but are not limited to, glycine, trycine, N-ethylglycine, alanine, sarcosine, 3-aminobutyric acid, sigmacarboxylic acid , serine, homoserine, aspartame 'threonine, creatinine, fatty acid, indole acetic acid, 2,3-diaminopropionic acid, cis-butyl diamine, butyl-diamine, amine -orotic acid, 5-amino-pyrazole I carboxylic acid, nitro-pyrazole-3-carboxylic acid, 2-imidazolidinium 15 winter carboxylic acid, 4-amino-2-hydroxybutyric acid, 3_ Amino-pyridin-2-carboxylic acid, σ ratio σ well 1 Wei acid, and mixtures thereof. Preferred examples of such a carboxylic acid subclass are serine, homoserine, aspartame, threonine, creatinine, citric acid, indole acetic acid, 2, > diaminopropionic acid, maleic acid Aminic acid, butyric acid, amino-orotic acid, 5-aminopyrazole-4-carboxylic acid, 5-nitro-pyrazole-3-carboxylic acid, 2-imidazolidinone-4-carboxyl 20 Acid, 4-amino 1 hydroxybutyric acid, 3-amino group _ tar carboxylic acid, pyridin carboxylic acid, and fullness thereof. More preferred examples of such carboxylic acid subclasses are serine, felsic acid, threonine, 4-amino-2-butyric acid and mixtures thereof. In another embodiment of the cleaning composition of the present disclosure, the at least one water-soluble carboxylic acid comprises at least one dicarboxylic acid or more than one 200893811 carboxylic acid each having at least one nitrogen moiety. Examples of such carboxylic acid sub-classes include, but are not limited to, Ethylenediaminetetraacetic acid, N-(2-hydroxyethyl)ethylidene diamine-N,N',N'-triacetic acid, 5H-D-B Triamine pentaacetic acid, 1-amino-cis-cyclopentane-1,3-dicarboxylic acid, and mixtures thereof. In another embodiment of the cleaning composition of the present disclosure, the at least one water-soluble carboxylic acid comprises at least one carboxylic acid having at least one sulfur moiety. Examples of such carboxylic acid subclasses include, but are not limited to, thiolactic acid, thiophenecarboxylic acid, mercaptopropionic acid, mercapto-pyruvate, sulfosuccinic acid, mercapto succinic acid, thiodiglycolic acid, and mixtures thereof. Preferred examples of such carboxylic acid subclasses are sulfosuccinic acid, mercaptobutyric acid, thiodiglycolic acid, and mixtures thereof. More preferred examples of such carboxylic acid subclasses are mercapto succinic acid, thiodiglycolic acid, and mixtures thereof. In another embodiment of the cleaning composition of the present disclosure, the at least one water-soluble carboxylic acid comprises at least one sulfur moiety and at least one nitrogen moiety of at least one monocarboxylic acid. Examples of such carboxylic acid sub-classes include, but are not limited to, oxidized cysteamine 15 acid, oxidized cysteine, cysteine, thiazopyridinecarboxylic acid, homocysteine, cystine, and mixtures thereof. Preferred examples of such carboxylic acid subclasses are cysteine, thiazopyridinecarboxylic acid, homocysteine, cystine and mixtures thereof. A more preferred example of this carboxylic acid subclass is cystine. Preferred examples of at least one water-soluble carboxylic acid are 20 monocarboxylic acid having one additional ligand, one carboxylic acid having two or more additional ligands, a dicarboxylic acid containing no additional ligand, and an additional compound. a dicarboxylic acid, a dicarboxylic acid having two or more additional ligands, a polycarboxylic acid containing no additional ligand, a polycarboxylic acid having an additional ligand, a carboxylic acid having at least one nitrogen moiety, and A dicarboxylic acid or polycarboxylic acid having at least one nitrogen moiety. 15 200813211 A better example of a less water-soluble carboxylic acid a ancient y ^ t 』 』 horse has an additional ligand - carboxylic acid, two or more external ligands, dicarboxyl without additional ligand An acid, a di-wei with an additional ligand, a two- or two-additional ligand, an acid with an additional ligand, and a carboxylic acid having at least one gas moiety. The best examples of the lack of a water-soluble tracing acid are - an additional ligand - tickic acid, __ with two or more additional ligands, a dicarboxylic acid without additional ligands, with additional ligands It is mostly acid and has at least one nitrogen moiety. The water-soluble conjugate added to the cleaning composition of the present disclosure may be a blend of two or more kinds of acid. If this is the case, the m acid can be as high as about 995 10

Any ratio of an acid of Wt% is blended. In a mixture, preferably

The mixture contains up to about 95% by weight of an acid. A good binary mixture of p A contains up to about 8 G wt% of the acid. The best binary compounds contain up to (10) 15 wt% of various acids. In the three-reduced multi-component mixture, the linings are mixed in any suitable ratio. This step does not include - water. Preferably, the water is deionized water and ultrapure water which are free of organic contaminants. Preferably, the water has an optimum enthalpy and a factor of from a few million megahms to about 17 million ohms. More preferably, the resistivity of water is at least one million ohms. 2 〇 The present disclosure package δ consists of blending (A) water; (9) at least one water-soluble thiol oxalate; (C) at least one water-soluble carboxylic acid; and (D) optionally at least one carboxyl-free rot a mixture of inhibitors. The water-soluble mercaptocarboxylic acid _ is present in the cleaning composition of the present disclosure in the range of grade 01 Wt% sm5 Wt%. Preferably, there are about 16 in the cleaning composition. 200813211 wtwt% to 赖wt%. More preferably, the thioglycolic vinegar is added to the clearing agent, and the amount of the agent composition is (U wt% to 75 wt%. The optimum range of cultivating vinegar is from about 0.1 wt% to about 5 wt0 / 〇. In the cleaning composition, the water-soluble, _acid addition 1 is from about 01 to about 2 〇 wt%, preferably from about 5% to about 15 w (9) and further from main wt/° to about 10 wt%. The m acid is included in the cleansing composition >month cleansing composition, the optimum concentration of the mirror is cut to "to the range of 6." 10 a of the irr clean domain, depending on (9) may include - or species a few base corrosion inhibitors. These rot or inhibit semiconductor element strains to reduce the alloys such as aluminum, & (4) read layer H scale metal layer = help:: metal and other exposed metals. The ligand of the compound, 1 two machine rotation: 1) These compounds contain silk outside the basket 'such as the base, 15 have a chewing spell. Earth, melon, sulfhydryl, and carbonyl, so have: force to oxidize Nature can prevent an effect J', plus one or more optional sulphur inhibitors can also improve cleaning rot, including but not limited to 20 saliva, tris, glucose, „1 butyl diol a class, benzotrihexenylacetone and 3_wife, 2·butyne-1,4·diol, hydrazine such as a cyclic derivative such as methyl syrup 1: techamisole (te-^ ethyl cultivating, Propyl ketone, ethyl hydrazine, propyl propyl hydrazine, di-ethyl fluorene methyl hydrazine, hydrazine hydrazide and phenyl hydrazine; two types of hydrazine, cis-butene m-hydrazine Anthraquinone and butanone 17 200813211, an aromatic compound and an oxidation inhibitor such as hydroquinone, o-benzotrizene, toluene, 2-methoxybenzene, and 4-methylmethyl; Alcohols such as mystery ethanol, heart propylene "thiol, thioglycerol, salivation, W-based saliva, Weiyl thiophene, 2_Werki · residual quinine sitting, and 2_ thiobarbite (Wbiturie add) ; 贞 贞 and its derivatives such as t Yang Chun and 4 令 (4); 甘二二缩缩_, especially glycolaldehyde diethyl acetal and mixtures thereof. /Residue inhibitors used in the cleaning of the present disclosure The dosage form is added in an amount of 0.001 Wt / 〇 to about i 5 wt%. The preferred concentration of the rot inhibitor is from about 10 _ 5 wt% to about 10 wt%, more preferably 丨 wt% To about 8. In this disclosure, the optimum concentration range of the decay button inhibitor is 0.01 Wt% to about 6

Wt〇/〇〇 In one embodiment of the present disclosure, the cleaning group 15 for removing the electro-etched residue and/or the money ashing residue formed on a semiconductor substrate comprises: 0) Water; , (), force 0.01 wt% to about 15 wt% of at least _ species (丨) water-soluble 肼, soil peek from 'the towel Rl is as needed to be substituted linear or branched CVC20 burning base, depending Relating to a Cvc20 cycloalkyl group which may be substituted, or a C6-C14 aryl group which may be substituted as desired; (C) from about 0.01 wt% to about 20 wt% of at least one water-soluble carboxylic acid; At least one of about 0.001 wt% to about 15 wt% is a corrosion inhibitor that does not contain a carboxyl group. In one preferred embodiment of the invention, a cleaning composition for removing plasma etch residues and/or plasma ashing residues formed on a body substrate of a half-guide 18 200813211 comprises: (a) water; (b) from about 0.05% by weight to about 1% by weight of at least one of the formula (1) water-soluble 肼5-based vinegar vinegar, wherein R1 is a linear or branched crc10 alkyl group which may be substituted as desired or may be substituted as needed C3-Ci()cycloalkyl; (C) from about 0.05 wt% to about 15 wt% selected from one of the additional ligands of formic acid, one or more additional ligands, one of the carboxylic acids, Containing one of the additional ligands of formic acid, a dicarboxylic acid with an additional ligand, a secondary acid with two or more ex-10 external ligands, a polycarboxylic acid without additional ligands, and an additional ligand a polycarboxylic acid, a carboxylic acid having at least one nitrogen moiety, and at least one of a dicarboxylic acid or a polycarboxylic acid having at least one nitrogen moiety; and () any k 'about 0.005 wt% to about At least one of the wt% of the carboxyl group-free residual inhibitor. In a preferred embodiment of the present invention, the composition for removing plasma etch residues and/or plasma ashing residues formed on a semiconductor substrate comprises: '(8) water; (b) at least one of the formulas (1) to about 7.5 wt% of the formula (1) water-soluble mercaptocarboxylic acid H wherein R1 is purely a linear or branched alkyl group which may be substituted or may be substituted as needed c3_ClG ring; 1 , (4), , , spoon 0.1% to _ plus % is selected from an additional carboxy oxime, with two or more additional ligands - mirror Μ ^ ^ Θ additional Once, there are two or more additional ligands _ and there are additional allocations for the 2008 20081111 body and (d) the selection of the toasts of the two. From 1 wt% to about 8 wt% of at least one type of carboxy-free on the substrate, in the preferred embodiment, for removal from the semi-conductive composition comprising electrical f-etch residues and/or Cleaning of the plasma ashing residue (a) water; (iv) at least 1 wt% to about 5 wt% of the formula - (1) water-soluble mercapto citrate, wherein R1 is methylethyl; 10 15 20 ^ wt /^ to about 6 wt% selected from the group consisting of (4) oxime with one additional ligand, two additional ligands - Wei and polycarboxylic acids with additional ligands; and () optionally, about 〇 〇 1 wt% to about 6 wt% of at least one of the Wei-based residual inhibitors. Further, inclusion of a chelating agent m such as a pH adjuster, a surfactant, a carboxyl group-free, and a suicide additive are optional components. The cleaning compositions of the present disclosure may include one or more pH adjusting agents as needed. If there is a desired 'pH adjustment' to adjust the pH range of the composition from about 2 to about 6. A preferred pH range is from about 2 to about 5. A more preferred pH range is from about 2 to about 4. The optimum pH range is from about 2.2 to about 35. The type of the modulating agent which can be used in the present disclosure (4) includes, but is not limited to, the secret, the alcoholic amine, the silky amine, the oxidized _ itpH rhyme, the example yarn is not limited to the transamine, the diethyl amine, Ethanolamine, Diethanolamine, Tri-B, "Diethylethylethanolamine, (tetra)ethylethyl, -methylamine, 20 200813211 Dimethylamine, Trimethylamine, Monoethylamine, Diethylamine, B Methylamine, isopropylamine, diisopropylamine, n-propylamine, n-butylamine, cyclohexyl, N,N-methyl-1,3-propanediamine, N,N_ : methylcyclohexylamine, sugar amine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethyl-based base gas ammonium oxide and methyltris(hydroxyethyl)ammonium hydroxide. The surfactant may also include the cleaning compositions of the present disclosure as needed, thereby even promoting wetting of the semiconductor surface, increasing the ability of the plasma residue to dissolve and the ability of the residue to be removed from the semiconductor substrate. These interfacial surfactants can be nonionic surfactants, cationic surfactants, anionic 10 surfactants, zwitterionic surfactants, or amphiphilic surfactants or mixtures thereof. Preferably, the surfactants disclosed herein contain low levels of metallic impurities. One example is a nonionic surfactant of the alkylphenol polyglycidyl ether type available from Arch Chemicals Inc. under the trade name OHS. If added, the surfactant is present in the cleansing compositions of the present disclosure in amounts up to about 0.5% by weight (5000 parts per million). Preferably, the surfactant of the present disclosure is present in the cleansing composition at a level of from about 0.0005 wt% (5 ppm) to about 0.22 wt% (2200 ppm). More preferably, the surfactant of the present disclosure comprises from about 0.001 wt% (10 ppm) to about 0.1 wt% (1000 ppm) of the cleansing composition. Most preferably, the surfactant of the present disclosure comprises from about wt·〇〇1 wt% (10 ppm) to about 〇·〇5 wt% (500 ppm). The cleaning compositions of the present disclosure further include additives designed to reduce foaming. When used, the antifoaming agent can be used in an amount up to about 20% by weight of the total surfactant concentration. Examples of suitable defoamers include, but are not limited to, DeFoamer WB 500 (available from Tech Sales Co., 21 200813211 NoFoam 1971 (available from Oujn Technology) Oil Chem Technology)), Tego Foaqmex (from DeGusa), Surfynol 104 (from Air-Products), SAG 10 The cleansing compositions disclosed in Osset Corporation (OSi Specialties, 5 Inc.) and Advantage 831 (from Hercules) also include antimicrobial additives (eg fungicides). , algicide or fungicide. Examples of useful antimicrobial agents include, but are not limited to, Kathon CG, Hungry CG II, and NEOLONE 10 950 fungicide (from Rohm and Haas) Company (R〇hm and Hass), methylisoxazole °olinone and AQUCAR products company (from Dow Chemical). Antimicrobial agents used in this cleaning composition The typical concentration range of the antimicrobial agent is from about 0.0001 wt% to about 〇5 wt〇/〇. It is disclosed that it can be used in the manufacturing method of integrated circuit components, so it is prudent to provide 15 cleaning compositions having low metal impurities. Preferably, the cleaning composition of the present disclosure does not exceed the total metal ion contamination level of 1 〇 ppm. More preferably, it has a total A cleaning composition having a metal ion contamination degree of 5 ppm or less. Most preferably, it is a cleaning composition having a total metal ion contamination degree of 1 ppm or less. An example of the cleaning composition of the present invention includes: 20 (a) (b) from about 0. 1 wt% to about 7.5 wt% of thioglycolate; and (c) from about 0.1 wt% to about 10 wt% of a 3:1 mixture by weight of citric acid and lactic acid Another example of a cleaning composition of the present disclosure comprises 22 200813211 (a) water; (b) from about 0.1 wt ° / 〇 to about 5 wt % of thioglycolate; (c) from about 0.1 wt% to about 6 wt% 1:1 mixture of citric acid and lactic acid by weight; and 5 (d) optionally, from about 0.01 wt% to about 6 wt% of ascorbic acid. Another example of the cleaning composition of the present disclosure comprises (8) water; (b) from about 0.1 wt% to about 7.5 wt% of a mixture of methyl carbazate and ethyl decyl decanoate by weight: 1:1 mixture; 10 (c) about 0 .1 wt% to about 10 wt% citric acid; and (d) about 10 ppm to 1000 ppm nonionic surfactant. Another example of a cleaning composition of the present disclosure comprises (a) water; (b) from about 0.05 wt% to about 10 wt% thioglycolate; 15 (c) from about 0.05 wt% to about 15 wt% lactic acid; And (d) a sufficient amount of tetramethylammonium hydroxide to adjust the pH of the composition to a range of from about 2 to about 5. Another example of a cleaning composition of the present disclosure comprises (a) water; 20 (b) from about 0.1 wt% to about 5 wt% of decyl decanoic acid; (c) from about 0.1 wt% to about 6 wt% The pH of the composition is adjusted to a range of from about 2.2 to about 3.5 with a 1:3 mixture of citric acid and lactic acid by weight; and (d) a sufficient amount of tetramethylammonium hydroxide. 23 200813211 Another example of a cleaning composition of the present disclosure comprises (a) water; (b) from about 1% to about 15% by weight of hydrazinium hydrazide @ (4) about 0. 01 wt% to about 20 wt% of a 4:1 mixture of citric acid and D-gluconic acid at 5 weights; and (d) optionally, from about 0.001 wt% to about 15 wt% of cis-butanose spleen; (e) foot The amount of tetramethylammonium hydroxide is adjusted to adjust the pH of the composition to a range of from about 2 to about 6. The cleaning compositions of the present disclosure are not specifically designed to remove the photoresist film from the semiconductor substrate. Rather, the cleaning composition of the present disclosure is designed to remove the photoresist from the semiconductor substrate by dry removal or wet removal, and remove the electricity (4) insects to smash ~ π 々広 1 1 main 仃 仃 仃 仃 去除 removal process . 15 20

Appropriate dry removal methods can be used, including oxygen plasma ashing method U = phase processing method, (4) cooking method, hot money processing case 569117, the full text is incorporated by reference in 4 丨田六闼专利文乂) . In addition, any of the known organic wet removal solutions known to those skilled in the art can be used. The preferred removal method for the Japanese technology is /j. This dry removal method is an oxygen electricity ashing method. This kind of *: temperature rise (typically 2, under vacuum conditions (ie: from the lifetime reduction of the '' semiconductor substrate to remove most of the photoresist ° reverse = this method of oxidation, and organic materials used in organic materials : In addition to the inorganic contaminants or organics of the semiconductor substrate: genus: need to subsequently remove the residues using the cleaning composition of the present disclosure 24 200813211. One embodiment of the present disclosure is a semiconductor substrate A method of cleaning a residue comprising the steps of: (a) providing a semi-conductor substrate comprising a post-etching residue and/or a post-ashing residue; (b) contacting the semiconductor substrate with a cleaning composition, the cleaning The composition comprises: water, at least one water-soluble mercaptocarboxylic acid ester, at least one water-soluble carboxylic acid, and optionally at least one carboxyl-free corrosion inhibitor; (C) cleaning the semiconductor substrate with a suitable cleaning solvent; And drying the semiconductor by means of a means for removing the cleaning solvent without impairing the integrity of the semiconductor substrate. Further, the cleaning composition for the step (b) of the method of the present disclosure Additional may be included as needed Additives such as pH adjusters, surfactants, carboxyl-free chelating agents, antifoaming agents and biocides. 15 Semiconductor substrates to be cleaned by this method contain organic residues and organometallic residues, in addition, a certain range The metal oxide needs to be removed. The semiconductor substrate is typically composed of a ruthenium, osmium, m-v compound such as a combination of any of the above. The semiconductor substrate additionally contains an exposed integrated circuit structure such as an interconnect structure. , for example, metal wires and dielectric materials. Metals and metal alloys used to interconnect 〇, ”, including but not limited to alloys of Ming, Ming and copper, copper, titanium, niobium, sui, and Shi Xi, titanium nitride The nitride substrate also contains a oxidized stone layer, a nitride layer, a carbonized stone layer, and a carbon-doped oxidized second layer. The semiconductor substrate can be attached to the cleaning composition by any suitable method. 25 200813211 Touch, such as placing a cleaning composition in a bath, soaking and/or immersing the semiconductor substrate in a cleaning composition, spraying the cleaning composition onto a semiconductor substrate, and steaming the semiconductor substrate The cleaning composition on the material or any combination thereof. Preferably, the semiconductor substrate is immersed in the cleaning composition. 5 The cleaning composition of the present disclosure can be effectively used at temperatures up to about 90 ° C. Preferred cleaning composition It is used from about 16 ° C to about 70 ° C. A more preferred cleaning composition is used in a temperature range from about 18 t to about 5 (TC). The cleaning composition of the present disclosure has the advantage of being effective for ambient temperature. Depending on the particular cleaning method used, the cleaning time can vary widely. When cleaning in an immersion batch type, the appropriate time is, for example, up to about 60 minutes. The preferred range of the batch method is about 2 Minutes to about 40 minutes. The preferred range of batch-type methods is from about 3 minutes to about 30 minutes. The optimum range for batch-type methods is from about 3 minutes to about 20 minutes. The cleaning time for a single wafer process ranges from about 10 seconds to about 5 minutes. The preferred cleaning time for a single wafer process is in the range of from about 15 seconds to about 4 minutes. A better cleaning time for a single wafer process is in the range of from about 15 seconds to about 3 minutes. The optimum cleaning time for a single wafer process is in the range of from about 20 seconds to about 2 minutes. To further enhance the cleaning ability of the cleaning compositions of the present disclosure, mechanical agitation can be employed. Examples of suitable agitation means that the cleaning composition circulates on the substrate, the cleaning composition is steamed or sprayed onto the substrate, and ultrasonic agitation or ultra high frequency sonic agitation during cleaning. The directivity of the semiconductor substrate relative to the earth can be any angle. It is preferably horizontal or vertical. 26 200813211 The cleaning composition of the present disclosure can be used in conventional cleaning tools such as Ontrak Systems, DSS, SEZ single wafer spray cleaning system, Verteq single wafer ultra high frequency sound wave gold Finger (G〇ldfinger), Semitool Millenmm single-wafer spray cleaning system, 5 and other tool sets. One of the great advantages of the disclosed compositions is that all or part of it consists of relatively non-toxic, non-corrosive and non-reactive components, so that the composition is highly stable over a wide temperature range and processing time range. The compositions of the present disclosure are chemically compatible with virtually all of the materials used in batch cleaning and single wafer cleaning to form existing and emerging semiconductor wafer cleaning method tools. After cleaning, the semiconductor substrate is cleaned with or without agitation means for about 5 seconds to about 5 minutes with a suitable cleaning solvent. Examples of suitable cleaning solvents include, but are not limited to, deionized water (〇1 water), methanol, ethanol, isopropanol, N-methylpyrrolidone, butyrolactone, dimethyl hydrazine, ethyl lactate, and propylene glycol I5 bond acetic acid. Preferred examples of the cleaning solvent include, but are not limited to, deionized water, methanol, ethanol, and isopropanol. More preferred cleaning solvents are deionized water and isopropanol. The best cleaning solvent is deionized water. The solvent can be applied in a manner similar to that used to apply the cleansing composition. The cleaning composition can be removed from the semi-V body substrate prior to the start of the cleaning step, or the cleaning composition can be contacted with the semiconductor substrate at the beginning of the cleaning step. Preferably, the temperature used is 16. 〇 to m. Optionally, the semiconductor substrate is subsequently dried. Any suitable drying means known to the artisan may be employed. Examples of suitable drying means include centrifugal drying, dry residual gas flowing through the semiconductor substrate; or heating of the semi-conducting material by heating means such as a hot plate or an infrared lamp, Mamgoni drying, Lotta 27 200813211 Rotagoni drying, IPA drying or any combination thereof. The drying time will depend on the particular method employed, but typical drying times will range from about 3 seconds to several minutes. This disclosure is also directed to the removal of slurry and metal particles and other residual organic residues and metal oxide residues on 5 copper substrates and low-k dielectric substrates that have been subjected to chemical mechanical polishing. A non-corrosive post-CMp cleaning method. Any suitable chemical mechanical polishing treatment can be used. For examples of suitable chemical mechanical polishing methods, reference is made to U.S. Patent Nos. 6,384, 430, 6, 517, 413, 6, 524, 950, 6, 476, 769, and 6, 438, 414, the entireties of each of which is incorporated herein by reference. Between the chemical mechanical polishing step and the cleaning step, there may be an optional step of the step of using a pre-buffer cleaning step on the polished substrate, such as disclosed in U.S. Patent Nos. 6,454,432 and 6,436,832, the disclosures of each of 'Or with or without agitation; remove the residual slurry particles and other contaminants by cleaning with a suitable solvent. Examples of suitable solvents include deionized water and alcohols. The substrate can be dried using a drying means or directly subjected to cleaning. V. One embodiment of the present disclosure is a method of cleaning a semiconductor substrate containing a post CMP residue, comprising the steps of: (1) providing a semiconductor substrate containing a post CMP residue; 20 (2) the semiconductor substrate and Cleaning the composition contact, the cleaning composition comprising: water, at least one water-soluble mercaptocarboxylic acid ester, at least one water-soluble carboxylic acid, and optionally at least one carboxyl-free corrosion inhibitor; (3) Cleaning the semiconductor substrate with a cleaning solvent; and (4) optionally drying the semiconductor by means of removing the cleaning solvent without damaging the integrity of the semiconductor 28 200813211. Further, in the steps of the method of the present disclosure (9) The materials used in the (9) can be used as the external additive Lu p = into the mixture, defoamer and biocide. 5 10 15 20 The post-CMP residue is contained in the chemical mechanical polishing process. (10) The residue left in the slurry, the (4) recordings and the removal of the remaining material from the surface. The substrates may contain metal interconnects = materials such as copper wires interlaced in low dielectric constant materials or in non-conductive shoddy stacks, such as composites (4) such as HDp oxide, τ-cut, carbon-cut stack push carbon Cut with organic polymer. Examples of carbon-doped oxides include _ 克 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( Aurora (ASM International) and Orion (ο-(Trikon Industries).) Used as an organic polymerization of dielectric-like materials, examples including but not limited to benzophenone (10) Chemical company), poly-aryl ether (FLARE from Allied signd) and Silk (SiLK) (Dow Chemical). Other metal materials and surfaces of semiconductor materials such as Ta, tilt, TiN, or other metal oxides, metal materials, and metal nitride materials may also be present. The copper component can be a full copper material or a full copper alloy material. The cleaning compositions of the present disclosure may be contacted with the substrate to be cleaned in any suitable manner, such as by spraying, soaking, or steaming, and may be delivered to the substrate via a nozzle, hose, tube, brush or equivalent. To aid cleaning, mechanical means can be used. Appropriate (d) means (iv) that the cleaning agent is circulated on the surface of 29 200813211 or steamed or sprayed with detergent on the surface, ultrasonic agitation or ultra-high frequency sonic agitation, or brushing. It is better to brush and ultra-high frequency sound wave agitation. The directionality of the substrate relative to the earth can be any angle. However, it is preferable to be horizontal or vertical. The contact time is from about 15 seconds to about 120 seconds. Preferably, the contact time is from 15 seconds to about 60 seconds. The temperature for cleaning is not particularly limited, but the cleaning result may vary with temperature. Preferred temperatures range from about 16^ to about 27°C. After exposure to the cleaning compositions of the present disclosure, the substrate may be cleaned with a suitable cleaning solvent for about 5 seconds to about 120 seconds with or without a search means. Examples of suitable cleaning solutions include, but are not limited to, deionized water, decyl alcohol, ethanol, isopropanol, and propylene glycol monoacetate. Examples of preferred cleaning solvents include, but are not limited to, deionized water, methanol, ethanol, and isopropanol. More preferred cleaning solvents are deionized water and isopropanol. Yuan Jia cleaning solvent is deionized water. The cleaning solvent can be applied using a device similar to that used to apply the cleaning composition. The cleaning solution may have been removed before the start of the cleaning step, or the cleaning solution is still in contact with the substrate at the beginning of the cleaning step. In a preferred embodiment, the substrate is cleaned using an agitation device for about 10 seconds to about 30 seconds without first removing the cleaning composition, followed by cleaning without agitation means for about 20 seconds to about 90 seconds. The temperature of the cleaning step can be any suitable temperature for the processing equipment below the boiling point of the cleaning solvent. The preferred temperature is from 16 ° C to 27 ° G. The substrate is then dried. Any suitable drying means known to the artisan can be used. Examples of suitable drying means include centrifugal drying, drying gas flowing through the substrate, or heating means using a heating means such as a hot plate or an infrared lamp, or a combination thereof. The drying time is determined by the particular method used, 30 200813211 but typically from about 3 seconds to about several minutes. After the post-etching and/or ashing treatment, the chemical composition of the residue on the semiconductor substrate is determined by the sculpt method or ashing method used and the type of material exposed to the method. The cleaning composition must be modified as appropriate depending on the type of residue or the type of substrate. It is only used for the removal of the plasma side residue and/or the plasma ash residue of the fluoride-containing cleaning composition, including: (A Water; (8) at least - 10 hydrazinyl acid ester; (c) at least one water soluble nucleus; (9) at least - seed water: sexual gasification material; get pro, ((4) - species = inhibitor. The pH of the chemical cleaning composition is about rot. ^ ^ ^ ^ l 夂 的 的 的 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 15 15 15 15 15 15 15 15 15 15 This embodiment of the present disclosure further includes to β

Material. The fluorinated material is stored in the U.S. </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> <RTIgt; After this type of cremation residue or post-etching residue or metal oxalate salt mixture _ compound insoluble metal oxo bow * 丨 V coffee, go two, 6 ^ now in order to fix the core in a short processing time (four) The remaining fine is dissolved, and there is a free state in the range of 10,000 ppm. The fluorine contained in the readings includes, but is not limited to, a monoamine, and the second amine is typically used in the water-soluble fluorinated material salt of the present disclosure such as ammonium fluoride, fluorinated base money, or laver population 31st 200813211 and a salt formed by the reaction of a triamine with HF; a gas salt of a metal salt (m/vi), a cesium fluoride, a tin fluoride (π) or a fluorinated gas, a chlorine acid, and a mixture thereof. These septic materials are not contained in (4) 5 10 15 20 ions. More preferably, the gasification materials are ammonium fluoride and gasified four burning base. The best fluorinated material is unsubstituted and shaped. Examples of fluorinated materials are ammonium fluoride, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrabutylammonium hydride, methylated fluorinated, fluorinated di, ammonium amide, fluorine m Ammonium, fluorinated triethanolammonium, fluorinated ethanolic ammonium, fluorinated ammonium methoxide, fluorinated trimethylol, fluorinated methyldiethanol, fluorinated diethylene glycol ammonium, hydrogen gasification, four gas , sodium tetrafluoroborate, IUt_I/VI), cesium fluoride, tin (π) fluoride or fluorinated. Preferred examples of fluorinated materials are ammonium fluoride, tetramethyl fluoride, and tetraethyl fluoride. base , tetrabutylammonium fluoride, methylammonium fluoride, dimethylammonium fluoride, trimethylethylammonium fluoride, Dunhua three: base ethanol, triethanol ammonium, fluorinated ethanol, I methanol Record, fluorinated trimethylammonium fluoride, fluorinated methyldiethanolammonium fluoride, ammonium diethylene glycol fluoride, ammonium hydrogen difluoride or read lysine. Better fluoride content (4) fluorinated money · Dunhua tetramethyl Ammonium, tetraethylammonium tetrachloride, tetrabutylammonium fluoride or trimethylethylammonium fluoride or trimethylethanolammonium fluoride. The best example of the material containing 4 is ammonium tetramethylammonium fluoride. Tetraethyl chloride, tetrabutylammonium fluoride or trimethylethyl fluoride. The water-soluble fluorine-containing material can conveniently be from about 5 wt% (5 μm) to about 5.0 wt% ( Addition of 5_〇ppm). Preferably, read about $plus% (5〇PPm) to about 3.0 wt% (3_〇ppm), and more preferably about 加ι plus % (10) PPm) to about 2.0 wt. % (2_〇ppm) containing gasification material is included in the cleaning composition containing gasification 32 200813211. The optimum concentration of the fluoride containing material in the fluoride containing cleaning composition is about 0.05 wt% (500 卯 to to) 5 wt% (15〇〇〇ppm). The disclosure includes via blending (A) water; (B) at least one water-soluble mercaptocarboxylic acid ester, (C) at least one water-soluble carboxylic acid; (D) at least one water-soluble fluorine-containing material; and, optionally, (6) at least - a mixture obtained from an age-inhibiting inhibitor. In one embodiment of the present disclosure, for removing plasma (4) residues and/or plasma ashing residues formed on a semiconductor substrate The cleaning composition of the vapor includes: · 10 (8) water; rWt%&quot;^15 'The towel should be chain-chained μ ===_ instead of C3_C2g ring wire, or if necessary, can be substituted 15 20 (= 1Wt% to about domain (4) to select from about 2% to about 5% of the fluorine-containing material; and silk u (four) preparation. Regarding at least one of the weight-free to about 15% of the weight-free pure implementation, the material is recorded in the cleansing of the semi-conducting material and/or the gas containing the gas (8) water; (b)约 〇 她, ^ = to about 1G wt% of at least - of the formula (1) water-soluble oxime, 4 as desired, can be substituted linear or branched C1-C10 33 200813211 alkyl or optionally substituted C3- C10 cycloalkyl; (c) from about 0. 〇 5 wt% to about 15 wt% selected from one carboxylic acid having one additional g hexane, one carboxylic acid having two or more additional ligands, Diterpenic acid with additional ligand, diremediate acid with one additional ligand, dicarboxylic acid with two or more additional ligands, polycarboxylic acid without additional ligand, polycarboxylate with additional ligand An acid, a carboxylic acid having at least one nitrogen moiety, and at least one water-soluble carboxylic acid having at least one gas-distilled dicarboxylic acid or polycarboxylic acid; (d) from about 0.005 wt% to about 3 wt% Fluorinated material; and 10 (e) optionally, from about 0.005 wt% to about 10 wt% of at least one of the non-human Wei's residual inhibitors. - In a preferred embodiment of the present disclosure, the cleaning composition for removing the plasma residue and/or the electro-accumulated ash formed on the semiconductor substrate comprises: Water; 15 (9) about 0·1 wt% to about 7.5 Wt% of at least _ ji ★ n, carboxylic acid ester, I + a a formula (1) water-soluble thiol or (4) to be recorded 4 chain or The C3_C5it base which can be substituted by -B; (c) about 0.1 wt% to about 1 〇 plus % of one carboxylic acid, right, from a steroid containing an additional ligand - 绫 / Solid or multiple additional ligands of 1 acid, with an additional ligand; 2;, with two or more additional ligands, two with an additional ((:)) =: base corrosion inhibition Agent. At least one of the .01^ to about 8 jobs does not contain 竣34 200813211. In one preferred embodiment of the present disclosure, the utility model is used to remove electric paddle engraving residues and/or electropolymers formed on a semiconductor substrate. The vapor-containing cleaning composition of the ash residue comprises: (a) water; 5 (b) at least one of the formula (1) water-soluble thiol-derived vinegar of about o·1 wt% to about 5 wt% Wherein R1 is methyl or ethyl; (c) from about 1 wt% to about 6 wt% selected from the group consisting of one carboxylic acid having one additional ligand, one or more carboxylic acids having one or more additional ligands And a polycarboxylic acid having an additional ligand; 10 (d) from about 0 〇 5 wt% to about 1.5 wt% of the fluorinated material; and (e) optionally, from about 1 wt% to about 6 wt% At least one of the % does not contain a Wei's corrosion inhibitor. The fluoride-containing cleaning composition of the present disclosure may optionally include one or more pH adjusting agents, one or more surfactants, one or more foam 15 reducing agents, and/or one or more antimicrobial additives, all as previously described Description. Since the present disclosure can be applied to a method of manufacturing an integrated circuit component, it is prudent to provide a cleaning composition containing a fluoride containing a low metal impurity. Preferably, the fluoride-containing cleaning composition of the present disclosure does not exceed a total metal ion contamination level of 1 〇 20 PPm. More preferably, it is a cleaning composition containing a fluoride having a total metal ion contamination degree of 5 Ppm or less. Most preferably, it is a cleaning composition containing a fluoride having a total metal ion contamination degree of 1 ppm or less. An example of a fluoride-containing cleaning composition of the present disclosure comprises: (a) water; 35 200813211 (b) from about 0.1% by weight to about 7.5 wt% of methyl carbazate; (c) about 0.1 wt% % to about 10 wt% by weight of a 3:1 mixture of citric acid and lactic acid; and (d) from about 0.001 wt% to about 3 wt% of tetramethylammonium fluoride. 5 Another example of the disclosed fluoride containing cleaning composition comprises (a) water; (b) from about 0.1 wt% to about 5 wt% of methyl methacrylate; (c) from about 0.1 wt% to A 1:1 mixture of about 6 wt% citric acid and lactic acid by weight; 10 (d) from about 0.001 wt% to about 3 wt% ammonium fluoride; and (e) optionally, from about 0.01 wt% to about 6 wt. %ascorbic acid. Another example of a fluoride containing cleaning composition of the present disclosure comprises (a) water; (b) from about 0.1 wt% to about 7.5 wt% methyl carbazate and ethyl propyl carbazate 1 by weight: 1 mixture; (c) from about 0.1 wt% to about 10 wt% citric acid; (d) from about 0.01 wt/〇 to about 2 wt% of fluorinated tetradecylammonium; and (e) from about 10 ppm to 1000 ppm Nonionic surfactant. Another example of a fluoride containing cleaning composition of the present disclosure comprises 20 (a) water; (b) from about 0.05 wt% to about 10 wt% carbazide; (c) from about 0.05 wt% to about 15 wt% % lactic acid; (d) from about 0.01 wt% to about 2 wt% | L tetramethylammonium; and (e) a sufficient amount of tetramethylammonium hydroxide to adjust the pH of the composition to about 2 36 200813211 to about The scope of 5. Another example of a fluoride-containing cleaning composition of the present disclosure comprises (a) water; (b) from about 0.1 wt/〇 to about 5 wt% of tert-butyl carbazate; 5 (c) about 0.1 wt% Up to about 6 wt% of a 1:3 mixture of citric acid and lactic acid by weight; (d) from about 0.001 wt% to about 3 wt% of tetramethylammonium fluoride; and (e) a sufficient amount of tetramethylammonium hydroxide The pH of the composition is adjusted to range from about 2.2 to about 3.5. 10 Another example of the disclosed fluoride containing cleaning composition comprises (a) water; (b) from about 1% to about 15% by weight of methyl carbazate; (c) about 〇·〇 1 wt% to about 20 wt% of a 4:1 mixture of citric acid and D-gluconic acid by weight; (d) from about 0.001 wt% to about 3 wt% of tetramethylammonium hydroxide and hydrofluoric acid 1: 1 molar ratio; and (e) arbitrarily, about o oQi wt% to about 15 wt% cis-butane dioxime. The fluoride containing cleaning compositions of the present disclosure are not specifically designed to remove the photoresist film from the semiconductor substrate. Instead, the vapor-containing cleaning product disclosed herein. Further, after removing the photoresist from the semiconductor substrate by dry removal or wet removal, the plasma etching residue is removed. (4) The cleaning method disclosed herein preferably has a photoresist removal procedure. k field spear, program is as explained above. Another embodiment of the present invention is a method for cleaning residue 37 200813211 from a semiconductor substrate, comprising the steps of: (4) providing a semiconductor substrate comprising a post-(four) residue and/or a ashing residue, (9) the semiconductor The county material is contacted with a fluoride-containing cleaning composition comprising: (4) water; (B) at least one water-soluble cultivating vinegar; (C) at least one water-soluble (four); D) a water-soluble gasified material; and (E) optionally at least one non-reactive corrosion inhibitor; (c) cleaning the semiconductor substrate with a suitable cleaning solvent; and (4) optionally, age-species The semiconductor is dried by means of a cleaning solution that does not detract from the integrity of the semiconductor 10 substrate. In addition, the vapor-containing cleaning composition used in step (b) of the method of the present disclosure may additionally contain additives such as a pH adjuster, a surfactant, a carboxyl-free chelating agent, an antifoaming agent, and a biocide as needed. Agent. The semiconductor substrate to be cleaned by the method contains organic residues and organic 15 metal residues, and in addition, a range of metal oxides needs to be removed. The semiconductor substrate is typically composed of a combination of a stone, a second, a compound, or a combination thereof. The semiconductor substrate additionally contains exposed integrated circuit structures such as interconnect structures such as metal lines and dielectric materials. Metals and metal alloys used in interconnect structures include, but are not limited to, copper, titanium, button, cobalt, tantalum, titanium dioxide, nitride buttons, and tungsten. The semiconductor substrate also contains a ruthenium oxide layer, a tantalum nitride layer, a tantalum carbide layer, and a carbon-doped ruthenium oxide layer. The steps b, c and d are as described above. The present disclosure is also directed to another type of non-corrosion that can be used to remove slurry and metal age from copper and low-k dielectric substrates that have undergone chemical mechanical polishing. The method of cleaning after the money. The Optimum chemical mechanical polishing process includes an optional buffering step, both prior to the cleaning of the post CMP residue, as previously described. SUMMARY OF THE INVENTION - One embodiment is a method of cleaning a semiconducting 5-body substrate containing a post-CMp residue, comprising the steps of: (1) providing a semiconductor substrate containing a post-CMP residue; (2) disabling the semiconductor substrate The material is contacted with a fluorochemical cleaning composition comprising: (4) water; (8) at least one water-soluble thiol-acid S, (C) at least one water-soluble wenic acid; D) a water-soluble fluoride-containing ruthenium material; and (6) optionally at least one kind of odor-free inhibitor; (3) washing the semiconductor substrate with a suitable cleaning solvent; and (4) optionally, borrowing A method of removing the cleaning solvent without damaging the integrity of the semiconductor substrate to dry the semiconductor. In addition, the cleaning composition of the fluoride 15 used in the step of the method of the present invention may optionally contain additional additives such as a pH adjuster, a surfactant, a carboxyl-free chelating agent, an antifoaming agent, and a killing agent. Biological agent. Suitable substrates and the processing procedures of steps 2 and 3, and optionally step 4, are as previously described. EXAMPLES The details of the present invention are illustrated by the following examples, which are intended to be illustrative only and not to limit the scope of the invention. All percentages listed are by weight (wt%) unless otherwise stated. Unless otherwise noted, the controlled agitation during the test was carried out at rpm using a stir bar. 39 200813211 General Procedure 1 Formulation Blending 1000 grams of the cleansing composition was prepared by first completely dissolving the formic acid in ultrapure deionized water (DI) water. Then, an oxidizing/reducing agent (i.e., 肼5 曰, sulphuric acid, and optionally a residual inhibitor) is added and completely dissolved. At this point, a pH adjuster (if used) is added and completely dissolved. All other additives (if used) are added at the end. After all the components were completely dissolved, the pH was measured at ambient temperature. All ingredients are commercially available and of high purity. 10 Approximate Procedure 2 Formulation Blending The fluoride containing cleaning composition was prepared by first completely dissolving the carboxylic acid in ultrapure deionized water (DI) water. Then, an oxidizing/reducing agent (i.e., a mercaptocarboxylic acid ester, a hydroxylammonium sulfate, and an optional residual inhibitor) is added and completely dissolved. The fluorinated material is then added and completely dissolved. A nonionic surfactant (OHS) is then added and completely dissolved. At this point, a pH adjuster (if used) is added and completely dissolved. After all the components were completely dissolved, the pH was measured at ambient temperature. All ingredients are commercially available and of high purity. 20 General procedure 3 Electrochemical measurements Electrochemical data were obtained using an EG&amp;G PARC 263A constant potentiometer/constant cesium fuel gauge. The electrochemical test cell has a solution volume of about 12 〇 ml. Controlled agitation and temperature settings were maintained throughout the test. Electrochemistry 40 200813211 The test cell uses a saturated calomel reference electrode with a potential of +242 millivolts relative to a standard hydrogen electrode, and a platinum counter electrode containing (a) a Si/Si〇2/Ta/Cu film stack or (b) The 200 mm 矽 wafer substrate of the Si/SiCVTi/Al-V/oCu film stack is cut into 1.5 cm wide and 5 cm long by a diamond knife. The test length is 5. The Cu metal film or the Al-4% Cu metal film is exposed. The test solution is used as the surface of the working electrode and has a film thickness of at least 1 μm, but not more than 15 μm. The working electrode area of all the tests is 〇·33 cm 2 . The copper test strip and the Cui Lu test strip are soaked with a dilute acid solution. After about 3 seconds of treatment, followed by a brief deionized water wash, followed by a test to remove the native oxide, leaving 10 bare metal test surfaces. The area of all test strips was covered to avoid exposure to the test solution, but Except for the working electrode area and the dry front metal electrical contact point. The test strip is vertically immersed in the test solution, the working electrode area is completely exposed to the test solution, and the upper part of the test strip is maintained in the air as dry electrical contact. Samples were tested in the following sequence: 丨) open circuit potential measurement, built on the stability of the stationary potential (Ecorr), 2) linearly polarized broom at a fixed scan rate from quiescent at +/- 20 millivolts And 3) at a scan rate of 5 millivolts per second from the Tafel polarization of the stationary electricity at +85 250 volts. Corrosion current density (microamperes per square centimeter / 20 m) was calculated from the Stern-Geary equation using the Tarver slope (/5 a and /3 c), the polarization resistance (RP), and the working electrode surface area. The Faraday's law is used to determine the copper and aluminum etch rates (see M. Stern and A. Geary, Electrochemical Polarization, Journal of Electrochemistry, Vol. 104, No. 1, 1957, p. 56). The electrochemical etch rate is accurately correlated with both the physical weight loss measurement and the inductively coupled plasma (1 (^>) measurement. 200813211 The corrosion ranking of the cleaning composition is evaluated in 1-10 points, with 10 Preferably, a copper etch rate greater than or equal to 5 angstroms per minute is considered unacceptable. A copper etch rate of less than or equal to 1 angstrom/minute is considered good. An etch rate of less than or equal to 0.5 angstrom/minute is considered absolute. Refer to Table 1 for definition of row 5. Table 1: Corrosion row definition copper etch rate [A/min] Copper rot #排行&gt;5 1 &gt;4-^5 2 &gt;3.5 £4 3 &gt;3.0- ^3.5 4 &gt;2.5-^3.0 5 &gt;2.0-^2.5 6 &gt;1.5-^2.0 7 &gt;1-&lt;^0.5 8 &gt;0.5-^ 1 9 ^0.5 10 Examples 1-4 and Comparative Examples 1-3 Examples 1 - 4 and Comparative Examples 1 - 3 were prepared by using the cleaning composition as listed in Table 2, 10 using the approximate procedure 1. 42 200813211

Table 2 · Example 1_4 and Comparative Example 1-3 Composition and pH Example 1·4 Comparative Example 1-3 Solution Composition El Ε2 Ε3 Ε4 C1 C2 C3 Citrate 40 g 40 g 10 g 10 g 40 g 40 g 10 g Lactic acid 1U g 11.1 g 11.1 g 1 U g 11.1 g 11.1 g 11.1 g Me-Carb 10 g 10 g 10 g Et-Carb 10 g HAS 2.3 g 2.3 g 2.3 g ascorbic acid 10 g 10 g 10 g 10 g 10 g TMAH 1.9 g OHS 〇·1g 〇.〇1 gram DI water 938.9g 928.9g 958.9g 958.9g 946.5g 934.7g 966.6g pH (@18°〇2.71 2.68 3.19 3.18 2.00 2.12 2.20··(10)W,Et_c erythritol bismuth Vinegar; interesting = sulfuric acid record; tmaH4 tetramethylammonium; OHS = non-ionic interface activity obtained from Axa Chemical Co., Ltd.; financial = high-purity deionized water tank. lactic acid is about 9 〇 wt% activity; TMAH ( The pH adjuster is added in a 2·5 Wei aqueous solution and 5 is added. The rate of the copper rot is determined according to the approximate procedure 3 by electrochemical test, and the composition is cleaned. (^Wen set silk and 2 mA/sec. Scanning rate. The working electrode is a wafer strip (4). The copper rot rate is listed in Table 3. The cleaning test system contains The dielectric value is transmitted through a substrate of 10 stacks of exposed copper, a porous low-k material, a TEOS layer, and a TiN layer. The stack also contains an etch treatment derived from fluoride and an oxygen-containing poly volume anti-reagent removal treatment. The wafer was originally studied by optical microscopy and then cut into approximately 1 x 1 square centimeter square test strips for cleaning tests. The lxl square centimeter test strip was set using 15 lengths of _ lock extrusion (four) The test strip is suspended into a plastic containing a volume of 25 liters of the cleaning composition of the present invention. The test strip is preheated to 2 before being soaked into the cleaning composition. 5 10 15 20 , accompanied by Controlled agitation. Then, by placing the plastic: pliers: 疋 钱 钱 置于 置于 置于 置于 置于 置于 置于 置于 置于 置于 置于 置于 置于 置于 置于 置于 置于 置于 置于 置于 置于 置于 置于 置于 经由 经由 经由 经由 经由 经由 经由 经由 经由 经由 经由 经由At the time, the composition is maintained at the test temperature maintained at:::=:.-- Once the test strip is exposed to the composition, the test time is met, and the composition of the swimming composition is gently removed and placed in a packed bed of about 15 liters of deionized 7 々 two fine ML plastic cup At the ambient temperature (about lrc) accompanied by the victory. Chi _ in the deionized water of the beaker, about to buy, and remove 'placed with about 15G ml of deionized water in the surrounding ^ dish and accompanied by (four) Lin second 2 liters _ cup. Test strips;: - Wash the cup for 60 seconds, then remove. When removed, the test was carried out from a nitrogen stream that was blown by a nitrogen gas, causing two droplets on the surface of the test strip to be blown away from the test strip, into the step. After the last nitrogen drying step, the test strip is placed on the plastic vehicle covered by the warrior with plastic ===, and the component is exposed upwards; the spoon is stored for 2 hours in a short time. The neo-test strips were lightly coated with a thickness of the object == layer&apos; for the SEM image on the surface of the cleaned test strip element. The cleaning results are listed in Table 3. 44 200813211 Table 3: Copper Corrosion Rate and Residue Cleaning Results Test Reference Number Copper Etching Rate [Angstrom/Minute] Copper Corrosion Ranking* Cleaning Ranking** Total Ranking *** E1 0.6 9 10 9.5 E2 0.5 10 9 9.5 E3 0.7 9 9 9 E4 0.4 10 10 10 C1 2.8 5 5 5 C2 5 1 6 3.5 C3 12 1 7 4 * Refer to the definition of approximate procedure 2. ** Cleanliness is performed with a score of M0, with 10 being the best. The cleaning results are based on the residue removal efficiency as observed by SEMs. 5 *** Total row behavior The average of copper corrosion rankings and cleaning rankings. As is known from Table 3, in both the substrate cleaning and the copper rot # rate test, the cleaning performance of all the cleaning compositions containing the carbazate component (Examples 1-4) was superior to the other compositions (Comparative Example) 1 -3). 10 Examples 5-6 and Comparative Examples 4-5 Examples 5-6 and Comparative Examples 4-5 were prepared using the procedure 1 and using the cleaning compositions listed in Table 4. 45 200813211

Table 4: Compositions and pH of Examples 5-6 and Comparative Examples 4-5 Examples 5-6 Comparative Examples 4-5 '^' Solution Composition E5 Ε6 C4 C5 Citric Acid 40 g 40 g 40 g Lactate 11.1 g 1 U g 11.1 g Me-Carb 10 g Et-Carb 10 g HAS ι〇ϊ^' DI water 938.9 g 938.9 g 948.9 g 938iJ' pH (@18 ° C) 2.73 2.64 1.86 1.94 Refer to Note 2 and Note 2 of Table 2 Copper and The aluminum corrosion rate was determined according to General Procedure 3 using an electrochemical test with a constant temperature set at 50 ° C and a linear polarization scan rate of 2 millivolts 5 / sec. The working electrode is a wafer test strip (a) for copper rot | insect rate test and (b) for the mortal rate test. The copper and Mingfu surname rates are listed in Table 5. The cleaning test was carried out using a substrate comprising a dielectric stack having an exposed A1-〇.5% Cii line and a TiN layer, a Ti layer and a TEOS layer. The stack also contains residues from the fluorine-containing etch process and the oxygen plasma volume resist removal process. The test methods were similar to those of Examples 1-4 and Comparative Examples 1-3. The test conditions were maintained at 60 °C. The results of aluminum residue cleaning are listed in Table 5.

46 200813211 Both ethyl carbazate and HAS are highly effective in removing residues from aluminum substrates. All measured aluminum corrosion rates are extremely low. However, only formulations containing a thioglycolate component can be used as a cleaning composition for aluminum and copper technology with a low substrate rot rate. 5 Examples 7-11 and Comparative Examples 6-8 Examples 7-11 and Comparative Examples 6-8 were prepared using the procedure 15 and the fluoride-containing cleaning compositions listed in Table 6. The copper corrosion rate was determined using an electrochemical test, according to Procedural 3, with a constant temperature setting of 60 ° C +/- 2 t: and a linear polarization scan rate of 〇 16 mV / sec. The results are also shown in Table 6. 1〇表6: Example: Composition of Ml and Comparative Example 6_8, pH and copper corrosion cleaner composition E7 E8 E9 E10 E11 C6 C7 C8 Citric acid (g) 30 30 30 30 30 30 40 40 90% lactic acid solution (g) 33.33 33.33 33.33 33.33 33.33 33.33 11.11 11.11 Ammonium carboxylic acid vinegar (g) 10 2.5 10 10 10 0 0 0 HAS (g) 0 0 0 0 0 0.1 0 2.3 20% TMAF (g) 2.5 2.5 2.5 2.5 2.5 2.5 2.5 10 25% TMAH (g) 0 0 110.92 0 110.92 0 112.6 0 OHS (g) 0.1 0.1 0.1 0.01 0.01 0.1 0.01 0.01 DI water (g) 924.07 931.57 813.15 924.16 813.24 933.97 833.78 936.58 Fluoride-containing g Cleansing composition pH And copper money engraving rate pH@18 °C 2.7 2.2 4.0 2.7 4.0 2.0 4.0 2.2 Copper rot # @60 °C (A / min) 1.0 1.0 2.0 1.0 1.8 1.2 1.5 3.8 even 1: Me^CarbaZate = methyl carbazate ;HAS=hydroxyammonium sulfate; TMAF=tetramethylammonium fluoride; TMAH=tetramethylammonium hydroxide; 〇Hs=nonionic surfactant obtained from Aquila Chemical Co.; di water=Southern purity deionized water 47 200813211 Use of a substrate containing a double-pass metal-inlaid structure with exposed copper wire, based on a complete 200 mm or 300 mm The copper technology of the substrate is subjected to a cleaning test. The uncleaned surface structure of the substrate contains a significant amount of punctiform residue. The substrate was initially observed under an optical microscope, and then the substrate was cut into approximately 1 x 1 square centimeter test strips to be subjected to a cleaning test. A 1 x 1 cm2 test strip placed the surface of the element "up" on the bottom of a 2 ml plastic bottle containing about 100 ml of the fluoride containing cleaning composition. Prior to placing the test strip in the fluoride-containing cleaning composition, the fluoride-containing cleaning composition is preheated to the test in a vibrator/water bath set to about 8 Torr per second for controlled solution agitation. Conditional temperature 10 degrees (typically 4 ° ° C to 70 ° 〇. Then carry out the cleaning test, the test strip "facing up", placed in the heated fluoride containing cleaning composition, leaving the test strip in the fluorine The cleaning composition of the compound is subjected to constant agitation through the test conditions (typically 2 minutes to 10 minutes). Once the test strip is exposed to the fluoride, the cleaning composition is subjected to the test conditions, and the test strip uses a plastic 15 The "lock" clamp of the glue is quickly taken out of the test solution and placed in the ambient temperature (about H ° C) 'filled in a second 25 ml plastic cup filled with about 200 ml of ultrapure deionized water. The test strip is left in deionized water. About 1 〇 15 seconds in the cup, accompanied by gentle agitation, then removed and placed in a second 250 ml plastic cup, which is also filled with about 200 ml of ultrapure deionized water at ambient temperature. Leave 2 〇 in the plastic cup 6 Seconds, accompanied by gentle agitation, and then removed. When removed, the test strip is immediately exposed to nitrogen from hand-held nitrogen ventilation, causing any droplets on the surface of the test strip to be blown away, further completely dry = surface of the inspection element And the back side. After the final nitrogen drying step, the test strip is removed from the plastic clamp holder and placed on the covered plastic carrier, and the component faces up to 48 200813211 I for less than about 2 hours of short-term storage time. Then test The strips were coated with a splash bond of about 30-50 angstroms thick to collect scanning electron microscopy (s EM) images of the critical structures on the surface of the cleaned test strip elements. The processing conditions and results are listed in Table 7. Table 7 ·· Cleaning Results and Fluoride-Containing Cleaning Compositions Example 7-11 and Comparative Example 6_8 Ranking Copper Corrosion Ranking* Cleaning Rating** (Immersion at 50°C for 2 minutes) Cleaning Rating** (Immersed in 50°C _ 4 minutes) Cleaning rating** (immersed in 60°c 2 minutes) Total ranking E7 9 4 10 10 6.5 E8 9 4 10 10 6.5 E9 7 3 10 6 5.0 E10 9 10 9.5 E11 7 8 7.5 C6 8 7 10 10 7.5 C7 8 2 5.0 C8 3 10 6.5 * Refer to the definition of approximation procedure 3. The cleanliness rating is determined by the ι-ίο fraction, with 10 being the best. The cleaning results are based on the SEM to observe the removal efficiency of the residue. 10 *** Total row behavior copper The average of the cleanliness of the rot (10) row and the thief soak for 2 minutes. It shows that the mercaptocarboxylic acid ester (carbazate) is an effective substitution of the hydroxylamine type compound in the cleaning composition of the acidic fluoride. The methyl formate combination TMAF 'successfully cleans spot-type residuals 15 at low temperatures and short processing times while maintaining low corrosivity of the steel. The composition containing the fluorine-containing compound prepared by using the carbazate is preferable because it is safer to use and more environmentally friendly than the composition containing the HAS. 49 200813211 Examples 12-19 and Comparative Examples 9-10 Examples 12-20 and Comparative Example 9 were prepared using the procedure 15 for the cleaning compositions of the fluorides listed in Table 8. Table 8. Fluoride-containing cleaning composition Example number carboxylic acid (g) decyl decanoic acid (g) fluoride (g) OHS (g) additive (g) water (g) pH@ 22〇C E12 CA (30.0 LA (33.3) MC (10.0) NH4F(1.2) (5.0) None (920.4) 2.7 E13 ΜΑ (30.0) DTPA(0.5) MC (5.0) EC (5.0) NH4F(1.2) (5.0) None (953.3) 2.4 E14 ΜΑ (30.0) Glyc. (10) EC (10.0) TMAF (2.5) (5.0) None (942.5) 2.4 E15 ΜΑ (30.0) Glycine (10) EC (10.0) NH4F(1.2) (5.0) None (943.8) 2.4 E16 ΜΑ (30.0) EC (10.0) NH4F(0.6) IMAF(1.3) (5.0) Ascorb.(lO.O) TMAH (938.1) 2.4 E17 ΜΑ (63.2) Malic (10.0) DTPA(0.5) MC (5.0) EC (5.0) NH4F(1.2) (5.0) None (910.1) 3.2 E18 CA(30.0) GlycA(42.9) MC (10.0) IMAF (2.5) (5.0) None (909.6) 2.7 E19 CA(30.0) LA (33.3) MC (10.0) TMAF (2.5) (5.0) None (919.2) 2.75 C9 CA(30.0) LA (33.3) MC (10.0) None (5.0) None (921.7) 2.7 C10 CA (50.0) No no flaws (600· 0) DMSO (250.0) (100) 11.5 5 Note: MO methyl carbazate; EC = ethyl thioglycolate; CA = citric acid; LA = 90% lactic acid; MA = malonic acid; DTPA = di extended Triamine Pentaacetic acid; Malic=malic acid; Ascorb.=ascorbic acid; GA=gluconic acid; GlycA=glycolic acid; NH4F=40.6% ammonium fluoride; TMAF=20% tetramethylammonium fluoride; TMAH=25% tetramethylammonium hydroxide Base ammonium; 〇HS = 0.2% nonionic surfactant from Aquila Chemical Company. A 200 mm substrate based on copper technology was used to perform a cleaning test with a through-hole test structure. The stack contains exposed SiO 2 , SiC, black diamond tantalum and TiN hard masks and contains residues from the volume resist removal (plasma ashing) process 5 . The surface structure of the uncleaned elements of these substrates contains a considerable amount of sidewall polymer type residue of 200813211. The test procedure was similar to Example 7-n and Comparative Examples 6-8. The fluoride containing cleaning composition was maintained at a thief constant temperature test strip immersed in the fluoride containing cleaning composition _ minutes. It is then assessed how much of the sidewall residue is removed, as well as the excessive surname of the hard cover. The results of the treatment 5 conditions are listed in Table 9. Fruit and fluoride containing cleaning composition ranking example PH cleaning line 1 hard mask over-etching E12 2.7 10 light E13 2A 7 / very slight E14 ~ 2A 10 extremely light E15 2.4 10 extremely slight E16 2.4 9 Yi E17 3 1 mountain i 9 Slight E18 2.7 9 E19 2.7 10 EQ9 2.7 0 No C10 11.5 0 1 Rank: 10 [Best] means that the sidewall residue is completely removed and the hard mask/dielectric material interface is 100% exposed. 5 [Intermediate] means approximately 50°/❽ sidewall residue removal and exposure of hard mask/dielectric material =, material interface. 〇 [Worst] means that 0% of the sidewall residue is removed and exposed, and there is no visible hard/dielectric material interface. The addition of fluoride clearly improves the ability of the disclosed fluoride containing cleaning composition to remove sidewall residues. This effect can be achieved without causing a significant reduction in the quality of the dielectric material or hard cover. The present disclosure has been described with reference to the specific embodiments thereof, and it is to be understood that changes, modifications, and changes may be made without departing from the spirit and scope of the invention disclosed herein. Thus, it is intended that the present invention cover the modifications and 5 [Simple description of the diagram] (None) [Description of main component symbols] (None) 52

Claims (1)

200813211 X. Patent application scope: 1. A non-corrosive cleaning composition comprising: water; at least one water-soluble mercaptocarboxylic acid ester; 5 at least one water-soluble carboxylic acid; optionally, at least one water-soluble fluorine-containing a material; and optionally, at least one desulfonation-free inhibitor. 2. The non-corrosive cleaning composition of claim 1, wherein the cleaning composition has a pH of from about 2 to about 6. 10. The non-corrosive insecticidal cleaning composition of claim 1, further comprising an additive selected from the group consisting of a surfactant, a defoaming agent, a biocide, and any combination thereof. 4. A non-corrosive cleaning composition according to claim 1, wherein the water-soluble mercaptocarboxylic acid ester has the following formula (I): 15 rLo.cO-NH-N^ (1) wherein R1 is a linear chain Or a branched CrC20 alkyl group, a C3-C20 cycloalkyl group, or a C6-14 aryl group. 5. A non-corrosive cleaning composition according to item 4 of the patent application, wherein R1 is selected from the group consisting of methyl, trifluoromethyl, ethyl, 20 2, 2, 2_ Gas ethyl, 2,2,2-diethylene ethyl, transethyl, propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, tert-butyl, second butyl, ring Butyl, pentyl, 1-hydroxypentyl, isopentyl, neopentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, cyclohexylmethyl, cycloheptyl, 2-cyclohexylethyl, octyl , mercapto, fifteen, pyrenyl, benzyl, phenyl and 53 200813211 any combination thereof. 6. The non-corrosive cleaning composition of claim 4, wherein R1 is a linear CrC1G alkyl group, a branched CVQo alkyl group, or a C3-C1G cycloalkyl group. 7. The non-corrosive cleaning composition of claim 4, wherein the 5 water-soluble mercaptocarboxylic acid ester is at least one selected from the group consisting of methyl mercaptocarboxylate, ethyl carbazate, Propyl carbazate, isopropyl methacrylate, butyl carbazate, tert-butyl carbazate, amyl carbazate, decyl carbazate, pentadecyl carbazate, thioformic acid A decyl ester, a thiol carboxylic acid ester, a decyl decyl decanoate, and a 2-hydroxyethyl carbazate. 10. The non-corrosive cleaning composition of claim 7, wherein the water-soluble mercaptocarboxylic acid ester is at least one selected from the group consisting of methyl mercaptocarboxylate, ethyl carbazate, Tert-butyl carbazate, and benzyl carbazate. 9. The non-corrosive cleaning composition of claim 1, wherein the 15 water-soluble mercaptocarboxylic acid ester is present in an amount of from about 0.01% by weight to about 15% by weight based on the cleansing composition. 10. The non-corrosive cleaning composition of claim 9, wherein the water-soluble mercaptocarboxylic acid ester is present in an amount of from about 0.1% by weight to about 5% by weight based on the cleansing composition. 20. The non-corrosive cleaning composition of claim 1, wherein the water-soluble mercaptocarboxylic acid ester is one of two water-soluble mercaptocarboxylic acid esters and one of the water-soluble mercaptocarboxylic acid esters. A ratio of up to 99 wt% is blended into the binary mixture. 12. The non-corrosive cleaning composition of claim 11, wherein the binary mixture of the two water-soluble decyl carboxylates is as high as one of the water-soluble thiol carboxylates. Blended in a ratio of 95 wt%. 13. The non-corrosive cleaning composition of claim 12, wherein the binary mixture of the two water-soluble mercaptocarboxylic esters is one of the water-soluble decyl carboxylates up to 75 The ratio of wt% is blended. 14. A non-corrosive cleaning composition according to claim 13 wherein the binary mixture of the two water-soluble mercaptocarboxylic esters is up to 50 wt% of one of the water-soluble mercaptocarboxylic esters The proportion of % is blended. 15. The non-corrosive cleaning composition of claim 1, wherein the 10 water-soluble carboxylic acid is at least one selected from the group consisting of: one carboxylic acid having one additional ligand, There are two or more additional ligands of a carboxylic acid, a dicarboxylic acid with an additional ligand, a dicarboxylic acid with two or more additional ligands, and a polycarboxylic acid with additional ligand. 16. The non-corrosive cleaning composition of claim 15, wherein the 15 water-soluble carboxylic acid is at least one selected from the group consisting of: one carboxylic acid having one additional ligand, There are two or more additional ligands, one carboxylic acid, and a polycarboxylic acid with additional ligands. 17. The non-corrosive cleaning composition of claim 1, wherein the water-soluble Wei acid is present in an amount of from about 0.01% by weight to about 20% by weight of the composition. 18. The non-corrosive cleaning composition according to claim 17, wherein the water-soluble Wei acid is present in an amount of from about λ 1 wt% to about 6 wt%. 19. The non-corrosive cleaning composition of item 1, wherein the inhibitor of the group 2008 20081111 is present in a composition of about 15 wt/^ from about 〇._ - to, ,, spoon. 20 Non-corrosive cleaning composition, wherein the non-carboxyl corrosion inhibitor 5 10 15 20 is present in an amount of about 6 wt%, and the composition is from G1 wt% to the application patent (4). Non-corrosive pure cleaning = bismuth material is selected from the group consisting of: chemical recording, gasification (9) basic record, gasification tetraethyl record, Dunhua four gasification three f-ethyl record, or oxidation three Ethylethanolammonium. A group 22. The water-soluble i-containing material is selected from the group consisting of tetradecyl ammonium fluoride, as claimed in the patent application. Tetrabutyl fluoride or fluorinated trimethylethyl. 23 · Non-corrosion button of the sixth patent (4) The cleaning composition, wherein the water-soluble fluoride-containing material is present in an amount of from about 0.0005 wt% to about 5 wt% of the composition. 24. A non-corrosive cleaning composition according to claim 23, wherein The water-soluble fluoride-containing material is present in an amount of from about t% to about 1.5% 〇/0. The non-corrosive cleaning composition comprises: water; at least one water-soluble hydrazine The carboxylic acid ester is selected from the group consisting of methyl carbazate, ethyl methacrylate, tert-butyl carbazate, and benzyl carbazate; at least one water-soluble carboxylic acid; Selected from the group consisting of 56 200813211 Group: one with an additional ligand - a member, two or more additional ligands - a class of acids, and an additional acid with a further ligand. At least one water soluble The gasification-containing material is selected from the group consisting of: methyltetraethylammonium (IV), methyl ethylammonium; and tetrabutylene or gasification, optionally at least one Containing the county's corrosion inhibitors. 26·—a non-corrosive cleaning composition, Containing ··· water; 10 15 20 vinegar, about wt% to about 15 wt%, at least one kind of water-soluble hydrazine, about 0.01 wt% to about 20 wt, about 嶋崎, L w ;; To a water-soluble containing Dunhua optionally 'at least one kind of corrosion-inhibiting agent that is rich in slow-base. 27. For example, please refer to the non-corrosive cleaning composition of Article 26 of the patent scope, Lizhong? The composition is composed of about 15 wt% of the composition of the coffee. The main 28--the semiconductor substrate cleaning step: the method of money, the financial method comprises providing a semiconductor substrate; the semiconductor base (4) - the cleaning composition contains water, at least - 肼 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ At least one carboxyl-free corrosion inhibitor; prim. 57 200813211 cleaning the semiconductor substrate with a suitable cleaning solvent; and optionally, by means of a means of removing the cleaning solvent without detracting from the integrity of the semiconductor substrate The semiconductor is dried. 29. The method of claim 28, wherein the semiconductor substrate comprises a 5 post residue and/or a post ash residue. 30. The method of claim 28, wherein the semiconductor substrate comprises a post-chemical mechanical polishing residue. 31. The method of claim 28, wherein the cleaning method is carried out at a temperature of from about 18 ° C to about 25 ° C. 10 32. A method of cleaning a residue from a semiconductor substrate, the method comprising the steps of: providing a semiconductor substrate; contacting the semiconductor substrate with a cleaning composition; cleaning the semiconductor substrate with a suitable cleaning solvent; Optionally, the semiconductor is dried by any means that removes the cleaning solvent without impairing the integrity of the semiconductor substrate, wherein the cleaning composition comprises: water; at least one water-soluble thiol carboxylate It is selected from the group consisting of methyl carbazate, ethyl methacrylate, tert-butyl carbazate, and benzyl carbazate; at least one water-soluble carboxylic acid is selected from a group consisting of one carboxylic acid having one additional ligand, one carboxylic acid having two or more additional ligands, and a polycarboxylic acid having an additional ligand; 58 200813211 at least one water-soluble fluorine-containing The material is selected from the group consisting of tetramethylammonium fluoride, tetrabutylammonium fluoride, or trimethylethylammonium fluoride, at least one mercaptocarboxylic acid ester; and optionally Ground, At least one corrosion inhibitor that does not contain a carboxyl group. 59 200813211 VII. Designated representative map: (1) The representative representative of the case is: (). (None) (2) A brief description of the symbol of the representative figure: 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: