TW201207100A - Cleaning composition, cleaning method using the same and fabricating method of semiconductor device - Google Patents

Abstract

A cleaning composition, cleaning method using the same, and fabricating method of semiconductor device are provided. The cleaning composition can solve specific problems of the specific cleaning agent-containing cleaning composition substantially adjusted to neutrality, and the corrosion of metal layers of semiconductor substrates and silicon caused by cleaning can be prevented, and the plasma etching residue or ashing residue generated during the fabricating process (of a semiconductor device) can be adequately removed. A cleaning composition, wherein a cleaning agent, a basic compound and an acid organic compound are contained in water, is adjusted to neutrality substantially, and further includes polymer compound.

Description

201207100 SUMMARY OF THE INVENTION [Technical Field] The present invention relates to a cleaning composition, a cleaning method using the same, and a method of manufacturing a semiconductor device. [Prior Art] In the manufacture of an integrated circuit, a positive photoresist is used as an intermediate mask. Specifically, in a series of photolithography and plasma etching processes, a semiconductor substrate (wafer substrate) is used as a medium for moving the mask pattern of the photomask. The patterned photoresist film can be removed from the substrate at a specified stage of the manufacturing process of the integrated circuit. In general, the removal of the photoresist film can be carried out by the following two methods. The first method is a method comprising a step of "wet stripping" a substrate coated with a photoresist first with a stripper solution containing a fine agent composed of a solvent and an amine. However, in the method of using the stripper solution, there is a phenomenon that the photoresist film cannot be completely removed when the photoresist is subjected to ultraviolet light irradiation or money treatment in the production. The reason for this is that, in the photoresist film, it is deteriorated by the above-described irradiation treatment or the like, and it becomes difficult to transfer it to the solution. Further, the solvent used in such a wet stripping method is, in many cases, an inorganic residue formed in the etching of a gas. (A) ashing is exemplified. In this method, first, the anti-side film is burned on the surface of the semiconductor substrate, and the coated light is exposed to an oxygen-based electric charge with a circle of 2012a. This treatment is carried out in a vacuum chamber, and thus is hardly affected by the contamination of particles or metals in the air. Based on the advantages of § hai, the above-mentioned plasma ashing is widely utilized in the manufacturing steps of integrated circuits. However, in terms of removing the above-mentioned plasma-etched by-products, plasma ashing cannot be said to be completely effective. Therefore, even if the plasma ashing or the above-described wet detachment is performed, the removal of the plasma etching by-product (residue) is additionally required to be washed and removed by washing the solution or the like. Further, in the plasma ashing, it is also necessary to wash and remove the by-products (residues) thus produced. Several commercial products are now available (for example, EKC 265 (trade name) manufactured by EKC Tedm〇1〇gy Inc., ACT 935 (trade name) manufactured by Ashland Chemical Co., Ltd., ELM C- manufactured by Mitsubishi Gas Chemical Co., Ltd. 30 (trade name)), which is used to remove the plasma etching by-product (residue) remaining after the plasma ashing remains due to the electric power. These products are also disclosed as patent documents (see Patent Document! - Patent Document 3, Patent Document 4). However, the pH of these commercially available products is as high as 11 or more, and contains a fluorine compound. Although the plasma etching residue can be effectively decomposed, there is a phenomenon in which the vapor deposition pattern of the metal or oxide on the substrate is also attacked. Although corrosion inhibitors are suitable for these products, it is difficult to obtain only sufficient corrosion prevention. In this regard, a cleaning composition which does not adversely affect the semiconductor substrate has been developed (see Patent Document 5 to Patent Document 7). It is a component of the water system C cleaning liquid, and contains an acid such as a hydroxylamine compound, a basic compound or an organic acid, and 201207100 can maintain the detergency from the surface, and the surface is prevented from being cured. In addition, the cleaning liquid is a water-based cleaning liquid which is a water-based medium, and is low in cost with respect to the organic cleaning liquid, and is excellent in environmental compatibility [Patent Document] [Patent Document 1] U.S. Patent No. 5,297,771 [Patent Document 2] U.S. Patent No. 5,419,779 [Patent Document 3] US Patent No. 563〇9〇4 [Patent Document 4] Japanese Patent No. 3891768 Specification 曰 [Patent Document 5] Japanese Patent [Patent Document 6] Japanese Patent No. 3,351,349 [Patent Document 7] Japanese Patent No. 414,732A (Invention), a new technology disclosed in Patent Documents 5 to 7, and a semiconductor The metal ship in the cleaning composition of the substrate is highly sturdy and high. However, the inventors of the present invention have continued to develop the ninth development in order to achieve higher performance. In particular, the following attempts have been made to promote the cleaning composition: the cleaning composition In a region where the specific cleaning agent exhibits a high detergency in a substantially neutral state, not only does the metal have high corrosion prevention, but also further develops A high corrosion prevention property of the present invention. It is an object of the present invention to provide a cleaning composition, a cleaning method using the same, and a method of manufacturing a semiconductor device which can be solved as being qualitatively adjusted to be neutral. Contains specific problems in specific and clear impurities, which can prevent the metal phase of the semi-conducting plate due to 6 201207100

JL is cleaned by corrosion and can sufficiently remove the residue or ash residue generated in the manufacturing process. Further, it is an object of the invention to provide a cleaning composition which is low in cost and environmentally compatible from a water-based cleaning composition, a cleaning method using the same, and a method for producing a semiconductor element, in addition to the above advantages. The above-mentioned rush can be solved by the following means. (1) A cleaning composition for a semiconductor substrate which is substantially neutral and which is characterized by comprising: water, a nitrogen-containing compound detergent, an organic compound, a monofunctional, a bifunctional, a trifunctional or a tetrafunctional Organic acid, polymer compound. (2) Preferably, the polymer compound of the cleaning composition according to (1) is at least selected from the group consisting of polyethylene glycol, polyethylene stellate, polyethylene glycol, polyacrylic acid, and series (4). A high molecular compound. σ 酸 2 is compared with the listener as described in (1) or (2): ii i lactic acid, acetic acid, propionic acid, malic acid, tartar 酉夂 I I, grass 酉夂, 琥 、, glucose Acid, acid, maleic acid, benzoic acid, 龅婪一田杂^ Li Yiji and Nei Mo #本—formic acid, salicylic acid, lyophilic acid, phthalhydroxamic acid At least one compound. (1) The cleaning group (4) according to any one of the above-mentioned groups, wherein the basic compound such as (1) to 201207100 is an alkaline organic compound having a carbon number of 4 to 30. (5) It is preferable that the basic compound of the cleaning composition according to any one of (1) to (4) is at least one selected from the group consisting of organic amines and quaternary ammonium hydroxides. Compound. (6) Preferably, the test compound of the cleaning composition according to any one of (1) to (5) is an organic amine having no hydroxyl group. (7) Preferably, the basic compound of the cleaning composition according to any one of (1) to (6) is a tetraalkylammonium hydroxide. (8) Preferably, the nitrogen-containing compound detergent of the cleaning composition according to any one of (7) is an amine compound or a urethane compound. (9) The nitrogen-containing compound detergent of the cleaning composition according to any one of (1) to (8), which is selected from the group consisting of hydroxylamine, hydroxylamine sulfate, hydroxylamine hydrochloride, hydroxylamine nitrate and hydroxylamine. At least one compound of the group consisting of phosphates. (10) Preferably, the nitrogen-containing compound detergent of the cleaning composition according to any one of (1) to (9) is hydroxylamine sulfate. (11) Preferably, the cleaning composition according to (1) to (1G) + any of the items is used for removing the slurry side residue and/or ashing apricot of the semiconductor element manufacturing step. (12) The method of cleaning the semiconductor substrate which has been cleaned by the composition of the (1) to (11) towel, and includes the exposed layer or (13): a cleaning method, characterized in that: The plasma etch residue 8 201207100 slag and/or ash residue on the semiconductor substrate is washed by the cleaning composition as described in (1) to (η) 壬-. ~ Washing method, preferably is the manufacturing method of the following red-leading parts, the ship is included in the (ϋ) meal engraving step, electro-injection of the semiconductor substrate, H step 'anti-resistance on the semiconductor substrate _ Performing a ash (b) cleaning step, by using the cleaning composition as in any of (1) to (12), the plasma formation formed on the substrate and/or the ashing step substrate Residual and/or ashing residue [Effect of the invention] g The cleaning composition of the invention can prevent the metal layer of the semiconductor substrate and the ruin caused by the L-J cleaning, and can be sufficiently removed in the semiconductor element step. The electricity _ engraved _ or ash New Zealand. Further, in addition to the advantages, it is possible to simultaneously achieve cost reduction and environmental suitability of the water-based cleaning composition. 2: By the cleaning method of the present invention using the cleaning composition described above, the manufacturing method of the 7L member can realize the environment-adaptive red and inexpensive manufacture of a semiconductor element of a good quality. The above and other objects, features and advantages of the present invention will become more apparent from 201207100 [Embodiment] The composition is a cleaning composition containing a nitrogen-containing compound detergent (b) and an organic compound (7) in water (a), and is substantially adjusted to a neutral cleaning composition in a specific month, and is characterized in that Containing ^ m (e) ° to achieve extremely high residue cleaning at the same time; with metal rot. Regarding its mechanism of action, it is inferred as follows. First of all, in the case of this fortune, the choice of pH is very important, and this point is washed with _ amine and other special nitrogen compound detergents, the PKa of the brewing is in a specific range, if the cleaning composition is too ph = then wash net? reduce. On the other hand, when the pH is too high, the detergency f is f. In the case of considering only the washing performance, it is preferred that the pH is high. However, if the pH is too high, a rot is generated in the metal layer or the like; if the pH exceeds 9 Å, satisfactory anti-recording energy cannot be achieved. In recent years, the structure of semiconductor elements or applicable components have been further diversified, and the requirements for miniaturization and fine wiring have been increasing. In response to this situation, the washing of the semi-conducting plate is also strictly required for the corrosion prevention of the metal layer or the enamel layer (in the present invention, when referring to Shi Xi or Shi Xi layer, Insulator (layer) or semiconductor (layer) such as a weide (membrane) or a weide (10)) is considered. In view of this, the amount of the acidic compound is increased, and the pH of the cleaning composition is lowered to improve the corrosion resistance. However, if this is the case, in the cleaning composition using the specific nitrogen-containing compound cleaner described above, as described above, inevitably causing a decrease in the washing power. In the present invention, the use of the dilemma is overcome. The pH is maintained as a neutral region, and the composition of the specific 201207100, t compound (polymer) is further contained in the cleaning composition. As a result, it is found that the cleaning power of the specific money compound detergent is maintained in the solid area, and the prevention of the metal layer is simultaneously improved. The principle of action still contains an unknown point, but there is a possibility that the hydrophobic property of the polymer = compound has a possibility of arboring. For example, the surface of the semi-body precursor becomes hydrophobic, and the surface thereof is polymerized. It is coated to form a molecular protective film unique to the above components. Hereinafter, the cleaning composition of the present invention, the cleaning method using the same, and the manufacturing operation of the semiconductor device will be described in detail with reference to a part of the drawings. [Residue] In the manufacturing process of a semiconductor device, there is a step of charging a metal layer or the like on a semiconductor substrate by using an anti-money agent pattern or the like as a mask. Specifically, the metal layer, the semiconductor layer, the insulating layer, and the like are etched to pattern the metal layer or the semiconductor layer, or the opening portion α such as a via hole or a wiring trench is formed in the insulating layer. A metal layer, a semiconductor layer, and an insulating layer derived from a resist used as a mask or a second layer are formed on a semiconductor substrate. In the present invention, the residue generated by plasma etching as described above is referred to as "plasma etching slag". χ Moreover, the resist pattern used as a mask is removed after etching. The removal of the resist pattern can be carried out as follows: a wet method using a stripper solution, or a dry method using ashing such as plasma, ozone or the like. In the above ashing, a residue obtained by modifying the plasma etching residue generated by plasma etching in 201207100 or a residue derived from the removed anti-# agent is generated on the semiconductor substrate. In the present invention, the residue generated by ashing as described above is referred to as "ashing residue". Further, the term "plasma" may be referred to as a residue of a plasma-etched residue and an ashing residue which are to be washed and removed on a semiconductor substrate. It is preferable to use a cleaning composition as a plasma residue or an ash residue as a post-etch residue (resEtchResidue) to be washed and removed. The cleaning composition of the present invention is particularly suitable as a virgin composition for removing plasma etching residue due to plasma etching and/or ashing residue due to ashing. The cleaning composition of the present invention can also be suitably used in a cleaning method (use) for removing plasma etching residue and/or ashing residue. Among them, it is preferred that the plasma etching residue and the ash residue are removed immediately after the electric discharge (four) electric currentization. [Cleaning composition] The cleaning composition of the present invention contains vaporization in water as described above. A detergent, a secret organic compound, and a specific organic acid, and are substantially adjusted to be neutral. Hereinafter, it is preferable to add (water) to the respective components to the respective components, water, as the age f, and it is preferred that each of the components has a water content which is uniformly dissolved in t minutes. (4) Total weight of the compound in the Qing Dynasty The content of t is preferably 50 wt% to 99 5 wt%. As described above, there is a cleaning composition which is mainly composed of water 2 (5 Gwt% or more), and it is particularly preferable to use a cleaning composition having a high ratio of two early to machine solvent, which is cheaper and more preferable. . As the water, 12 1 201207100 may be an aqueous medium containing a dissolved component in a range that does not impair the effects of the present invention, or may contain an unavoidable trace mixed component. Among them, preferred are hydrazine water or ion-exchanged water, or water subjected to purification treatment called ultrapure water, and particularly preferred is ultrapure water used in semiconductor manufacturing. (nitrogen-containing compound detergent) and the like. More preferably, the cleaning composition of the present invention comprises a nitrogen-containing compound cleaner (a detergent composed of a compound containing a nitrogen atom). Among them, the detergent is preferably an amine compound cleaner (the so-called amine compound is ammonia, a primary amine, a secondary amine, a secondary amine, a quaternary ammonium salt, a ruthenium, a general term for a compound containing Ν·Η, etc.), More preferably, the oxime has an amine compound detergent of -2, and particularly preferably an amine compound cleaner having an oxygen atom in the molecule. Specifically, it is preferred that the amine (pKa=6) compound or the carbamic add hydroxylamine salt is preferably a mineral acid salt or an organic acid salt of hydroxylamine, more preferably 疋Cl, S, N, A salt of a non-metal such as P and a mineral acid which has been synthesized, and a salt of any acid of hydrochloric acid, sulfuric acid or nitric acid. The urethane compound may, for example, be a carbamate. Among them, a methyl carbamate is preferred. Included is a hydroxylammonium ion, a hydroxylamine, and/or a salt thereof, typically representing a face

When a compound is referred to in the specification, it means that a salt thereof, an ion thereof or an organic acid thereof is contained in addition to the compound itself. Typically, the compound and/or its salt is represented. Therefore, when referring to the upper lysine compound, the organic acid salt of hydroxylamine of Table 13 201207100 can be exemplified by hydroxylamine citrate, hydroxylamine oxalate or the like. The shots of the hydroxylamines are preferably referred to as salts, sulphates, shovels, minerals by amines and hydrochloric acids, and by copper and titanium. In particular, it is better than amine lysine and _ sulphate. These amine-containing compounds may be used alone or in combination of two or more. In the present invention, the detergent is not limited to the above-mentioned amine compound, and may be suitably selected from a compound having a difficult function. . Typically, as a function for transferring the fascinating component, a compound which functions as a nucleophile can be cited. From the viewpoint of this, the following compounds can be exemplified. • A nucleophile having a pKa of 5 or more and 8 or less (more preferably a nucleophile having a PKa of 5.5 or more and 7 or less) is provided. • It has an α effect (if an electron donor atom is present at the α position, the nucleophilicity is higher. a nucleophile having a higher nucleophilicity (preferably based on pKa), a nucleophile having a high ER (etching rate) of Τι〇2, preferably relative to the total weight of the cleaning composition of the present invention, About 〇·〇ι wt%~ about 30 wt% of the range containing the compound containing the cleaning you better is containing ai wt% ~ 15 wt%. In particular, the cleaning agent shows that it is easy to remove the electric engraving and prevent the corrosion of the metal substrate from being made into the above range, and it is particularly suitable to exhibit a high detergency and obtain a good metal corrosion prevention effect. It is preferred in this respect. Further, in the present invention, it is preferred that the fluorine-containing compound such as ammonium fluoride is not used. It is that the money compound cleaner often has a corrosion of the metal I layer, which is used to obtain a detergency, and it is also difficult to ensure sufficient corrosion resistance of the metal layer 201207100 or the layer. (Experimental Compound) The composition of the present invention comprises an inspective compound. In the present invention, the "monthly test compound" means that the upper amine compound or the amine ruthenium compound is not contained, and the __ compound is not used as the "test compound". It is difficult to test compound compounds. It is made up of carbon and IU乍 as its constituent elements, and it has a county. Specifically, the organic compound is at least one compound selected from the group consisting of an organic amine and a quaternary ammonium hydroxide. Correction, the so-called _ is an amine containing carbon as a constituent element. The carbon number of the basic organic compound is preferably 4 to 3 Å, and more preferably 6 to 16 from the viewpoint of boiling point or solubility in water. The organic amine used as the organic compound for cleaning the composition of the present invention comprises: an alkanolamine such as monoethanolamine, diethanolamine, triethanolamine, diethylene glycolamine or N-hydroxyethylpiperazine, and/or Amine, benzoguanamine, diethyl fe, n-butylamine, 3-methoxypropylamine, tert-butylamine, n-hexylamine, cyclohexylamine, n-octylamine, 2-ethylhexylamine , o-diphenylene diamine, m-diphenylene diamine, decyl butylamine, ethylenediamine (EDA), 1,3-propanediamine, 2-aminobenzylamine, N-benzyl An organic amine having no hydroxyl group such as diamine, diethylenetriamine or triethylenetetramine. From the viewpoint of corrosion prevention of metals, an organic amine having no hydroxyl group is more preferable than an alkanolamine. Further, ethylenediamine, u-propylenediamine, o-xylenediamine, and m-xylenediamine may be particularly preferably coordinated to a metal. The quaternary ammonium hydroxide used as the basic compound is preferably a tetraalkylammonium hydroxide, and more preferably a lower (carbon number of 1 to 4) alkyl group 15 201207100 Specific examples of the oxide include tetramethyl hydride (TMAH), tetraethylammonium hydroxide (TEAH), silk fibroin (tetrahydrocarbazine), and tetrabutylammonium hydroxide (hydrazine). In addition, the quaternary ammonium hydroxide can also be exemplified by triammonium hydroxide (bi-test), ruthenium hydroxide-based (by ethyl), tetra-hydrogen (by ethyl), and hydroxide Base trimethyl money (ΒΤΜΑΗ) and so on. In addition to this, a combination of a hydroxide or a type of one or more quaternary ammonium hydroxides may also be used. More preferred among these are TMAH, TEAH, TPAH, TBAH, choline, and particularly preferred are TMAH, TBAH. These organic amines and quaternary ammonium hydroxides may be used singly or in combination of two or more. The amount of the basic compound is preferably from about 1% by weight to about 20.0% by weight based on the total weight of the cleaning composition of the present invention, more preferably 1. 〇wt〇/0 〜10·0 wt °/〇. By setting it as the above-mentioned range, the pH adjustment effect can be sufficiently exhibited in accordance with the content of the specific nitrogen-containing compound detergent such as the above-described hydroxylamine compound, and a high cleaning power and a metal corrosion prevention effect can be achieved, which is preferable. (Organic acid) The cleaning composition of the present invention contains at least one organic acid (also referred to as an acid organic compound), and is, for example, a monofunctional, bifunctional, trifunctional or tetrafunctional organic acid. The number of functional groups is not particularly limited, and among them, preferred is monofunctional or bifunctional or trifunctional. The 'carboxylic acid compound in the organic acid is effective for preventing corrosion of aluminum, copper and metals of the alloys, and the hydroxycarboxylic acid compound having a hydroxyl group is particularly useful as a metal rot. The acid retarding compound has a chelation effect on the metals. The preferred carboxylic acid compound comprises a monodecanoic acid compound and a polycarboxylic acid compound. The carboxylic acid compound is not limited to these compounds, and examples thereof include formic acid, acetic acid, propionic acid, valeric acid, isovaleric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, maleic acid, fumaric acid, and o-benzene. Dicarboxylic acid, phthalic acid, glycolic acid, lactic acid, citric acid, salicylic acid, tartaric acid, gluconic acid, oxydiacetic acid, malic acid, acetohydroxamic acid, alum hydroxy citric acid, willow hydroxy Capric acid, phthalic acid, benzoic acid, dihydroxybenzoic acid, and mixtures thereof. Among them, citric acid, malic acid, tartaric acid, glycolic acid, gluconic acid, and lactic acid which are hydroxycarboxylic acids can be preferably used. Further, the carboxylic acid compound preferably has a constituent element of only C, H and hydrazine, and more preferably has no amine group. Further, these organic acids may be used alone or in combination of two or more. From the viewpoint of effectively preventing corrosion of metals, it is preferred to use two or more kinds in combination. Preferably, the acidic organic compound is added between about G.G1 wt% and about 2 G.G wt%, more preferably about 0.05 wt% to about 2 Torr, relative to the total weight of the cleaning composition of the present invention. 〇wt%, further better 1 is to add 0.1 wt% to 1% by weight. By setting it as the above range, it is preferable to obtain a good gambling effect in accordance with the above-mentioned preferable content of the hydroxylamine compound and the basic organic compound, and to reduce the cleaning power. Further, the definition of the organic acid is the same as the "compound" described above, and is a concept including a salt thereof. (pH of cleaning composition) The cleaning composition of the present invention is substantially adjusted to be neutral. In the present invention, 17 201207100. Neutral in neutrality means that it is desirable to clean the composition. The cation of the composition is in the vicinity of 7. Specifically ΡΗ ^ ~ ^, mouth ~ ^ better is '^ into the step is better. 疋 7.2 ~ 8.0. If the pH is within the above numerical range, the photoresist can be removed in abundance, and the metal and the ashing residue can be simultaneously taken care of. By setting it as the pH range, it is possible to sufficiently remove the remnant when the nitride layer 11 and the gold layer are plasma-like to form a via pattern. The measurement method of the pH can be carried out by using a commercially available pH meter. In the present invention, the pH is a value measured under the conditions shown in the examples unless otherwise specified. The adjustment of the cleaning composition to a predetermined pH' can be carried out by adjusting the titration of the additive amount of the organic compound. (Polymer Compound) A cleaning composition of the present invention contains a ruthenium molecular compound in addition to the essential component. The polymer compound is not particularly limited, and is preferably a polymer compound which can be uniformly dispersed or dissolved in an aqueous medium, and more preferably a polymer compound which is uniformly dissolved in a predetermined amount. Specifically, polyethylene glycol, polyethylene coffee, bite _, polyethylene glycol, polyacrylic acid 'polyethylene imimine, poly hope, or polyallylamine 4 are preferred. Pyridone, polyethylene glycol, polyvinyl alcohol. The molecular weight of the polymer compound is not particularly limited, and is preferably 400 to 30 Å, more preferably 5 Å to 90000. If the molecular weight is small, satisfactory corrosion resistance cannot be obtained. Further, if the molecular weight is too large, the corrosion resistance can be achieved, but the detergency is impaired. In the present invention, when the molecular weight is referred to, unless otherwise specified, it means 18 201207100 a. The weight average molecular weight, molecular weight and degree of dispersion refer to values measured by the following measurement methods. [Method for Measuring Molecular Weight and Dispersion] The amount of the knife and the degree of dispersion are not particularly limited, and can be measured by GPC (gel over chromatography). The gel filled with the lining of the GP C towel is preferably a gel having an aromatic compound in the repeating unit, and for example, a gel composed of a styrene-divinylbenzene copolymer may be mentioned. . The tube plate is preferably used by connecting two to six pieces. The solvent to be used may, for example, be an ether solvent such as tetrahydrofuran or a guanamine solvent such as N-decylpyrrolidone, and an ether solvent such as tetrahydrofuran is preferred. Preferably, the measurement is carried out at a flow rate of the solvent of from 0.1 mL/min to 2 mL/min, and most preferably in the range of from 5 UiL/min to 1.5 mL/min. By performing measurement in this range, it is possible to perform measurement more efficiently without burdening the device. It is preferably carried out at a measurement temperature of from 10 ° C to 50 ° C, most preferably at 2 ° C to 4 ° C. The specific conditions for molecular weight measurement are shown below. Device: HLC-8220GPC (manufactured by Tosoh Corporation) Detector: differential refractometer (RI detector) Front column: TSKGUARDCOLUMN MP (XL) 6 mm><40 mm (manufactured by Tosoh Corporation) Side pipe column: directly connect the following two (all manufactured by Tosoh Corporation) • TSK-GEL Multipore-HXL-M 7.8mmx300mm reference side pipe column. Same as sample side pipe column 201207100 Temperature bath temperature: 40°C movement Bed: tetrahydrofuran sample side moving bed flow: l. 〇mL / min reference side moving bed flow: 0.3mL / min s pattern concentration: 0.1 wt%

Sample injection amount: l〇〇pL Data acquisition time: 16 min to 46 min after sample injection Sampling pitch: 300 msec The above polymer compounds may be used singly or in combination of two or more. Preferably, the polymer compound is added between 3 wt% and 0.000001 wt%, more preferably 1 wt% to 0.000001 wt%, more preferably added, relative to the total weight of the cleaning composition of the present invention. 〇1 Wt%~0.0001 wt%. By setting it as the above range, it is preferable to maintain a high cleaning power and sufficiently obtain a good metal and anticorrosive effect. The polymer compound can be improved by increasing its content. However, excessive levels become detrimental to the ability to clean. (Water-Soluble Organic Solvent) The cleaning composition of the present invention may also contain a water-soluble organic soluble tearing rot, and may be read as follows, such as = A = ethanol, 1-propanol, 2-propanol, 2_ Butanol, ethylene glycol alcohol, ?, 1,6-hexanediol, cyclohexanediol, sorbitol, xylitol, formazan: triamyl glycol, i, 3-butanediol, M_ Alcohol solvent such as butanediol, ethylene-2, 4-ether, diethylene glycol, dipropylene glycol, propylene glycol monomethyl hydrazine, - dry methyl ether, triethylene glycol, polyethylene glycol, propylene glycol, single ethyl alcohol monomethyl 7 ether, dipropylene glycol monomethyl 201207100, ether solvent such as ether, tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether, decylamine, monomethylformamide, dimethyl decylamine, acetamide , monomethyl acetamide, dimercaptoacetamide, monoethyl acetamide, diethyl acetamide, guanidine ketone ketone and other amide solvent, dimercapto ruthenium, dihydrazino A sulfur-containing solvent such as a sub-hard or a ring-shaped stone, a vinegar solvent such as γ·butyrolactone or δ_pentane vinegar. Preferred among these solvents are alcohol-based and ether-based, and more preferred are hydrazine, 6-hexanediol, diethylene glycol, propylene glycol, dipropylene glycol, propylene glycol monodecyl ether, and dipropylene glycol monoterpene ether. The water-soluble organic solvent may be used singly or in combination of two or more kinds as appropriate. The content of the water-soluble organic solvent in the cleaning composition is preferably from 0% by weight to 40% by weight based on the total weight of the cleaning composition, more preferably from 〇wt% to 20% by weight. Concentration is used. Further preferably, it is used in a concentration of from 0.01 wt% to 15 wt%. By adding a water-soluble organic solvent to the cleaning composition, the cleaning power for the carbon-rich residue can be improved, and it is also preferable from the viewpoint of improving the corrosion prevention property of the metal film. (Other components) • Amino group-containing carboxylic acid compound The cleaning composition of the present invention may further contain an amine group-containing carboxylic acid compound. The amine group-containing carboxylic acid compound is preferred in terms of efficiently preventing metal corrosion. Among the amino group-containing carboxylic acid compounds, preferred are arginine, histidine, glutamine, butyl ketone, 0 butyl octagonal, and 1110, and more preferred are arginine and histidine. These amine group-containing acid compounds may be used singly or in combination of two or more. In the case where the cleaning composition of the present invention contains an amine group-containing carboxylic acid compound, the amount thereof may be appropriately selected, and it is preferably about wt% of the total weight of the cleaning composition of the present invention with respect to 21 201207100. About 5.00 wt% is more preferably 〇〇1 wt%~3 wt〇/〇. • Surfactant and The cleaning composition of the present invention may also contain a surfactant. The surfactant can be used as a nonionic, anionic, cationic surfactant and amphoteric Φ live (4). For the total weight of the clarified product, the content of the surfactant in the cleaning composition is preferably 〇 _ wt %~5 wt% 'Better is 〇·〇_(4) ❶ wt%. By adding a surfactant to the cleaning composition towel, the weaving of the composition can be woven, and the adhesion to the object to be cleaned can be improved, so that the two are further recorded from the substrate or the insulating film. The more excellent aspects are also considered. Such an interface activity can be obtained commercially. These interfacial activities are used in combination or in various combinations. • Antifungal Agent The cleaning composition of the present invention may also contain an antifungal agent. The preferred ones are the heterocyclic compounds, and the more (4) are the benzoquinones. The derivative is preferably 5,6-dimercapto H3.benzotriazole (Dbta), 1 (1,2-dicarboxyethyl)benzotriazole (DCEBTA), • double (hydroxyl) Aminomethyl]benzoquinone triazole (ΗΕΑΒΤΑ), ^(hydroxydecyl)benzoquinone triterpene (ΗΜΒΤΑ). The antifungal agent used in the present invention may be used singly or in combination of two or more. Further, the antifungal agent used in the present invention may be synthesized in accordance with a general method, and a commercially available product may be used. Further, the amount of the antifungal agent added is preferably wt. 〇1 wt% or more and 0.2 wt% or less, more preferably 0.05 wt% or more 〇·2 wt% or less 〇 22 201207100

The composition of each component of L may be suitably determined by a general method. For example, ion chromatography or H_NMR or a spectrosorber can be used. [Washing method] Next, a preferred embodiment of the washing method of the present invention will be described. The cleaning method of the present embodiment is a method including a cleaning step of cleaning the plasma etching residue and/or the ash residue formed on the semiconductor substrate by using the cleaning composition of the present invention described above. . In the cleaning method, in order to effectively exhibit the high cleaning power which is the advantage of the cleaning composition of the present invention and the corrosion prevention property of the metal layer or the tantalum layer, it is preferably in the semiconductor substrate. A metal layer such as a via or a wiring is formed and exposed, and the residue is deposited therein. As the metal layer, the metal layer containing aluminum or copper can exert the effect of the above-described cleaning composition of the present invention, and therefore is more preferable. If the surface of the semiconductor substrate in which the at least the plasma button is broken and/or the ash residue is in contact with the cleaning composition of the present invention, the cleaning state in the cleaning step is not In particular, it is preferred that the semiconductor substrate is impregnated into the cleaning composition of the present invention. The cleaning method of the present embodiment is preferably carried out in a state where the cleaning composition is heated in the cleaning step. The heating temperature in the washing step of the cleaning composition is not particularly limited, and is preferably 50 ° C to 90 ° C, more preferably 55 ° C to 80 ° C. Therefore, according to the present embodiment, the composition is heated and used within the above range. Therefore, it is preferred to contain a compound which does not decompose, volatilize or react at this temperature. Further, it is preferable that the pH of the composition of the temperature is not changed greatly, and the change of the cleaning composition of the above-mentioned embodiment 23 201207100 state from the room temperature to the temperature at the time of the above washing is not large and substantially Neutral. [Method of Manufacturing Semiconductor Element] Next, a preferred embodiment of the method for manufacturing a semiconductor device of the present invention will be described in detail. The method of the fourth aspect (4) includes the following steps: (a-1) side step of electrically (four) etching the semiconductor substrate, and/or (ashing step, ashing the anti-reflection on the semiconductor substrate; and (7) step by The composition is cleaned as above, and will be sprayed in the ship's engraving step tlf, and the plasmonic silver residue/disproportionation_washing formed on the material guide plate is removed. Specifically (4), preferably ^ form a via hole or The manufacturing method of the above-mentioned cleaning composition is applied to the washing material of the g&amp; </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> The "semiconductor = substrate" in the present invention refers to the middle semiconductor in the middle of manufacturing a semiconductor element (final product). The element precursor)' is not limited to the wafer unless it is specifically limited, and includes, for example, a film or a tungsten plug, a via, a wiring, and the like. In the first embodiment, the first embodiment of the present invention is shown in FIG. 1 (0 to 3 (4) is a schematic cross-sectional view. </ br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br> The formation of Ray sβ廿, the circular domain electric solar cell and other components or 1 layer or 2 24 201207100 2 followed by the formation of the semiconductor substrate 10', the film, and the like, followed by, for example, CVD (Chemical Vapor) The PCT 1: &quot;Chemical Rolling Deposition Method) sequentially deposits, for example, a film enamel on the entire surface, an A1 alloy film 12, for example, a titanium nitride having a film thickness of about 50 legs, and is sequentially formed into an A1 alloy film 12 and liquefied. The film of the film is formed into a conductor film. In addition, the 'A1 alloy (4) is an alloy film of A1 and Cu containing, for example, 加3 plus% to wt/o of Cu. The material is mixed with the dry method and the ship is patterned / ιό ^ The A1 alloy film 12 and the titanium nitride film 14 are formed as follows: CVD method is formed on the entire surface, for example, a film thickness ^ 5 CMp (C Hemical

Me-P camphor ing, chemical mechanical polishing method, the surface of the oxidized stone enamel is ground and polished to flatten the surface of the oxidized ray 18 . After the order, the semiconductor substrate a shown in Fig. 1(a) is obtained. • Step b: Referring to Fig. 1 (b), the light _ R of the via pattern is formed by the optical domain method on the oxidation frequency 18. Finely, the photoresist film is used as a mask 1 to engrave the oxidized stone film 18 by plasma. At this time, the upper part of the nitride film 14 under the oxidized film is also engraved. Thereby, a via hole (Mei A A) 20 which reaches the titanium nitride film 14 of the wiring 16 is formed on the oxide film (see Fig. 1 (8)). A well-known method = a graph of the ruthenium oxide film 18 and the upper portion of the titanium nitride film 14 can be used. Performing • Step c: Referring to Fig. 1 (c) Next, the photoresist film used as the mask 25 201207100 is removed by, for example, ashing using plasma, oxygen, or the like. Ashing of the photoresist film can be carried out by a known method. In the plasma etching for forming the via hole 20 and the ashing for removing the photoresist film, a photoresist film derived from deterioration and yttrium oxide are attached to the surface of the substrate including the surface around the via hole 20 The film 18 and the residue (plasma etching residue and ashing residue) G of the titanium nitride film 14 exposed at the bottom of the via hole 2〇. The state in which the residue G exists is shown in Fig. 1 (c). • Step d: Referring to FIG. 1(d), after the ashing for removing the photoresist film, the semiconductor base phase 10 formed with the via hole 2 is formed by the cleaning composition of the present embodiment. Wash. Thereby, the plasma etching residue and the ashing residue adhering to the surface of the semiconductor substrate 10 on which the via hole 2 is formed are removed. As a result, the surface of the semiconductor substrate d is extremely clean, and the surface of each (4) having an excellent electrical characteristic is exposed (see (4)). Next, a tungsten film is formed on the entire surface by, for example, a CVD method. Further, the tungsten film is polished by, for example, a CMP method until the surface of the yttrium oxide film 18 is exposed. Thereby, a via window composed of cranes is embedded in the via hole 20. As a result, a high-quality semiconductor element having no such ashing residue is obtained at the interface of the component. (Second Embodiment) Next, an outline of a method of manufacturing a semiconductor device according to a first aspect of the present invention will be described with reference to FIGS. 2(a) to 2(d). A method of manufacturing a semiconductor device of the form f is as follows.半导体 Semiconductor package of the embodiment (4) Manufacturing method ·························· (Step a) Referring to Fig. 2 (a) First, in the same manner as the method of manufacturing the semiconductor device of the first embodiment, the wiring formed by forming the 纟A1 coin 12 and the nitriding film 14 on the material substrate 1 is performed. 16 and yttrium oxide film 18 (refer to Fig. 约 (about). • Step b: refer to Fig. 2 (b). Next, a photoresist film having a via pattern is formed on the yttrium oxide film 18 by photolithography. Then, the ruthenium oxide film 18 and the titanium nitride film 14 are etched by plasma etching using the photoresist film as a mask. At this time, the upper portion of the A1 alloy film 12 under the titanium nitride film 14 is also etched. Thus, the "layer έ hole 2G (via window pattern b) of the A1 alloy film reaching the wiring 16 is formed on the yttrium oxide film 18 and the titanium nitride film 14. The yttrium oxide film 18 can be separately formed by a usual method. The titanium nitride film 14 and the upper portion of the A1 alloy film 12. Pulp • Step c: Referring to Fig. 2 (c) Next, a photoresist film used as a mask is used by, for example, ashing using plasma, oxygen, or the like. The ashing of the light can be carried out by a known method. In the case of the present embodiment, the 阙(10) layered window hole is as dry button and used to remove the photoresist. In the ashing, the surface of the substrate including the surface of the via hole 2〇 and the wall surface of the via hole 20 are adhered with a residue of the pulverized rice residue and the ashing ruth. In the case of this form, the electric secret residue And the ashing residue is not derived from the metamorphic light _, the oxidized pin 18 and the nitriding film 14' but also originates from the A1 alloy film 12 exposed at the bottom of the via hole 20. • Step d: Refer to FIG. (d), 27 201207100 Therefore, after the ashing for removing the photoresist film, the semiconductor substrate 1A having the via hole 20 formed thereon is cleaned by the cleaning composition of the present embodiment. The plasma etching residue and the ashing residue adhering to the surface of the semiconductor substrate 10 on which the via hole 2 is formed are removed. As a result, the surface of the semiconductor substrate d is extremely clean, and each has excellent electrical characteristics. In the present embodiment, in particular, the surface of the aluminum (A1) alloy film 12 which is in contact with the bottom of the via hole is sufficiently washed to expose the clean surface. The manufacturing method of the semiconductor device of the embodiment is the same Further, a via window is formed which is embedded in the via hole 2, thereby obtaining a high-quality semiconductor element having no ash residue as described in the component interface of the tl device. (Third embodiment) ^Second An outline of a method of manufacturing a semiconductor device according to a third embodiment of the present invention will be described with reference to Fig. 3 (a) to Fig. 3 (d). Step (a): Refer to Fig. 3 (a) First, the first embodiment In the same manner as in the method of manufacturing a semiconductor device, an interlayer insulating film (oxidized oxide film) 24 is formed on a semiconductor substrate on which a device or the like is formed. Next, for example, a film thickness of about 5 Q is sequentially formed over the entire surface by, for example, a CVD method. The titanium nitride film 26 of nm, for example, a titanium film 28 having a film thickness of about 2 Å, for example, an A1 alloy film 30 having a film thickness of about 500 nm, for example, a titanium nitride film 32 having a film thickness of about 50 nm. Further, the A1 alloy film 3 is, for example, an alloy film of A1 and Cu containing 0, 1% to 5% of Cu. The above dimensions are merely examples - and the present embodiment is to be construed as being limited thereto. 28 201207100. • Step b: Referring to Fig. 3 (b) Next, a photoresist film having a wiring pattern is formed on the titanium nitride film 32 by photolithography. Then, the photoresist film is used as a mask, and the titanium nitride film 32, the Al alloy film 30, and the titanium film 28 i titanium nitride film 26 are sequentially etched by plasma etching. Thereby, the titanium nitride film 32, the A1 alloy film 3A, the titanium film 28, and the titanium nitride film 26 are patterned to form wirings (wiring patterns) 34 composed of the conductor films. • Step c: Referring to Fig. 3 (c) Next, most of the photoresist film used as a mask is peeled off by wet processing using a chemical. Then, the remaining portion of the photoresist film is removed by, for example, ashing using plasma, oxygen or the like (refer to Fig. 3 (c)). In the ash etching for forming the wiring 34 and the ashing for removing the remaining portion of the photoresist film, as shown in FIG. 3(c), the residue adheres to the surface of the substrate including the upper surface and the side surface of the wiring 34. (plasma etching residue and ashing residue) G. This residue G is derived from a deteriorated photoresist film, a titanium nitride film 32, a μ alloy film 30, a titanium film 28, and a titanium nitride film 26. • Step d: Referring to FIG. 3(d), after the ashing for removing the remaining portion of the photoresist film, the semiconductor device 1 形成 formed with the wiring 34 is washed by the cleaning composition of the present invention. net. As a result, the plasma adhering to the surface of the conductor substrate 10 on which the wiring 34 is formed is removed and removed by ashing. As a result, the surface of the semiconductor substrate d is extremely clean, and the surface of each material which is an ideal electrical property is exposed (see Fig. 3, (4)). In particular, according to the present embodiment, it is preferable to prevent the metal rot in the groove (the groove between the source and the gate 29 201207100) 29. Further, in the above embodiment, the case where the wirings 16 and 34 including the A1 alloy films 12 and 30 are formed will be described, but the material of the wiring is not limited to the above materials. As the wiring, in addition to the wiring made of A1 or the A1 alloy and mainly composed of A1, a wiring made of Cu or a Cu alloy and mainly composed of Cu may be formed. Further, the cleaning composition of the present invention can be widely used in a step of cleaning a plasma etching residue and/or an ash residue from a semiconductor substrate containing aluminum or copper, preferably a wiring formed on a substrate for a semiconductor. The structure contains aluminum or copper. As described above, in the semiconductor manufacturing process of various forms and conditions, the cleaning liquid of the present embodiment has a result that the component interface of the semiconductor element manufactured by the cleaning using the liquid of the moon liquid does not have the residue. A semiconductor component of extremely high quality can be obtained. [Examples] Hereinafter, the present invention will be described in more detail by way of examples. However, the invention is not limited to the examples. &lt;Examples, Comparative Examples&gt; The components shown in the following Table 1 were contained in water in the composition shown in the same table (Wt%) to prepare a liquid for cleaning the composition 1G1 to the cleaning composition 115 (example) . Water is used for ultrapure water as used in semiconductor manufacturing steps. Moreover, as opposed to the above examples, such as the table! The composition of the composition is changed as shown, and the liquid composition H of the cleaning composition eU, the cleaning composition (1) (comparative example), the cleaning composition s11, and the cleaning composition sl2 (reference example) is contained in the table and expressed in the table. (wt%) The component '201207100' contains an organic compound in an amount to be the pH expressed for each sample. In the above, 'the composition (wt%) containing water is a total of 100% by weight. The pH in the table is a value measured by F-51 (trade name) manufactured by H〇RiBA Co., Ltd. at room temperature (2)^). &lt;washing test&gt; _ in the above-mentioned 帛1 real state and 帛2 embodiment, after forming a via hole&apos; by scanning electron microscopy (SEM: s_ing mectr〇n

When the pattern wafer was observed, the plasma etching residue and the ash residue were confirmed on the wall surface of the via window (see FIG. 丨 (c) and FIG. 2 (Ο). Further, regarding the third embodiment, After the wiring was formed, the SEM wafer was observed, and the plasma etching residue and the ash residue were confirmed on the upper surface and the side surface of the wiring (see FIG. 3(c)). The temperature was adjusted as shown in Table 1. In each of the above-mentioned cleaning compositions at a temperature, a slice (about 2 cm x 2 cm) of the pattern wafer to which the residue adhered was impregnated, and the pattern wafer slice was taken out from each of the cleaning compositions described in Table 1, and immediately The ultrapure water was washed with water and dried by n2. The cross section and surface of the pattern wafer slice after the impregnation test were observed by SEM, and the photoresist and the residue (plasma etching residue and ash residue) were determined according to the following criteria. The removability and the residual property of A1 and TiN were evaluated. The evaluation results of the removability and rosin resistance are shown in Table 1. <Residue removal on the surface around the window hole> AA: Photoresist and The residue was completely removed. A: Photoresist And the residue is almost completely removed. B: Residual dissolved matter of photoresist and residue remains. 31 201207100 c: The photoresist and the residue are not substantially removed. &lt;Corrosion of the metal layer at the bottom of the via hole&gt; AA: No corrosion of TiN was observed. A: Corrosion of TiN is 5% or less with respect to wiring. B: Corrosion of TiN is 10% or less with respect to wiring. C : TiN disappears completely. &lt; Corrosion of the layer of the bottom of the hole&gt; AA: No residue was found. A: The corrosion of the crucible was 5% or less with respect to the wiring. B: The corrosion of the crucible was 10% or less with respect to the wiring. In addition, in the third embodiment, the state in which the residue on the side surface and the upper surface of the wiring is removed is not observed on the surface around the via hole, and the metal layer is corroded by A1 ( The evaluation was performed in the same manner as above. [Table 1] 32 201207100 $ % 5 &lt; i % $ &lt; $ % % % % %

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MU s2 gt 51 °32 601 0- 5 -s 33 201207100 The abbreviation in the table indicates the contents as shown below. • "%" means wt%. (Cleanser) • HAS: Hydroxylamine sulfate • HA: Hydroxylamine • FA: Ammonium fluoride • CAM: Ammonium decanoate (alkaline organic compound) • TMAH: Tetramethylammonium hydroxide • EDA: Ethylenediamine ( Polymer compound) • PVP: Polyethylene 1»Bilo bite • PVA: Polyvinyl alcohol • PA A : Polyacrylic acid (amino acid-containing carboxylic acid) AG : Arginine (organic solvent)

BuDO: 1,3-butanediol DPG: dipropylene glycol (acidic organic compound) AA: acetic acid CA: citric acid GA: glycolic acid GLA: gluconic acid 34 201207100 LA: lactic acid bismuth: malic acid ML A. maleic acid hydrazine: Malonic acid OA: oxalic acid PA: propionic acid SUA: succinic acid TA: tartaric acid DGA: oxydiacetic acid FOA: citric acid, residue removal [1] · Evaluation of residue removal on the surface ^ The first embodiment of the via window Metal corrosion around the hole [1]··对二果 a

Corrosion evaluation results TiN of the via hole at the bottom of the embodiment window. Si etching [1]: Evaluation of the first corrosion residue/check removal [2] · For the second Evaluation result of the surface of the periphery of the via hole of the embodiment, and the result of the evaluation of the metal corrosion (2): Evaluation result of the corrosion of the A1 of the via hole at the bottom of the second embodiment window • Si rot remaining [2] [Evaluation result of the corrosion of the enthalpy of the via hole in the second embodiment] Residue removal [3]: Evaluation result of the removal of the residue on the side surface and the upper surface of the wiring of the third embodiment 35 201207100 • Metal rot [3]: Evaluation results in the corrosion (groove) of A1 of the third embodiment. • Si rot [3]·· The evaluation results of the corrosion of the groove of the third embodiment are as shown in Table 1 above. It is understood that the cleaning composition (example) of the present invention prevents the corrosion of the metal member and the crucible of the semiconductor substrate in the manufacture of various types of semiconductor elements, and can sufficiently remove the plasma etching generated in the manufacturing steps thereof. Residue or ash residue. In particular, it exhibits an extremely excellent detergency and a metal corrosion preventing effect with respect to a composition which is acidic and does not contain a molecular compound (comparative example). A cleaning solution prepared by combining ammonium fluoride or hydroxylamine with polyvinylpyrrolidone (Comparative Example: equivalent to the example of the specification of the patent No. 3891768!, in the example (1), the metal or the stone has poor corrosion resistance. The composition which is neutral but does not use a polymer compound (reference example) has a high corrosion prevention effect of the metal (comparative reference composition 103 to composition 1〇5, composition sU, composition si2). The invention has been disclosed in the above preferred embodiments, but it is not intended to limit the invention, and the invention may be modified and modified without departing from the spirit and scope of the invention. The scope is defined by the scope of the appended patent application. [Simplified illustration of the drawings] Fig. 1 U) to Fig. 1 (d) are semiconductor elements for the implementation of the cleaning composition of the present invention. The steps of the manufacturing steps are partially explained in outline. Fig. 2 (a) to Fig. 2 (d) are explanatory diagrams schematically showing a part of the manufacturing steps of the semiconductor element of another embodiment in which the cleaning composition of the present invention is used in the 201207100. Fig. 3 (a) to Fig. 3 (d) are explanatory diagrams schematically showing a part of the manufacturing steps of the semiconductor element showing still another embodiment of the cleaning composition of the present invention. [Description of main components] 10: Semiconductor substrate 12: A1 alloy film 14, 26, 32: Titanium nitride film 16: Wiring 18: Cerium oxide film 20: via hole (via window pattern A) / (interlayer Window pattern B) 24: interlayer insulating film (yttria film) 28: titanium film 29: groove (groove between source and drain) . 30: A1 alloy film 34: wiring (wiring pattern) G: (plasma #刻 residue and ash residue) R: photoresist film 37

Claims (1)

201207100 VII. Patent application scope: 1. A cleaning composition 'substantially neutral, characterized by containing water, nitrogen-containing compound cleaner, test compound, 1-functional, bifunctional, trifunctional or 4-functional organic acid, polymer compound. 2. The cleaning composition according to claim 1, wherein the polymer compound is selected from the group consisting of polyethylene glycol, polyvinylpyrrolidine, polyethylene glycol, polyacrylic acid, and polyallylamine. At least one polymer compound of the group. 3. The cleaning composition according to claim 1 or 2, wherein the organic acid is selected from the group consisting of citric acid, lactic acid, acetic acid, propionic acid, malic acid, tartaric acid, malonic acid, oxalic acid , succinic acid, gluconic acid, glycolic acid, oxydiacetic acid, maleic acid, benzoic acid, o-dibenzoic acid, salicylic acid, lycopene phthalic acid and phthalhydroxamic acid At least one compound of the group formed. 4. The cleaning composition of claim 1 or 2, wherein the basic compound is an alkaline organic compound having a carbon number of 4 to 30. 5. The cleaning composition according to claim 1 or 2, wherein the basic compound is at least one compound selected from the group consisting of organic amines and quaternary ammonium hydroxides. 6. The cleansing composition 38 201207100, wherein the test compound is an organic amine having no hydroxyl group, as claimed in claim 1 or 2. 7. The cleaning composition as claimed in claim 1 or 2 wherein the basic compound is a tetraalkylammonium hydroxide. 8. The cleaning composition of claim 1 or 2, wherein the nitrogen-containing compound cleaning agent is a hydroxylamine compound or an amine phthalic acid compound. 9. The cleaning composition according to Item 1 or 2, wherein the nitrogen-containing compound cleaning agent is selected from the group consisting of hydroxylamine, hydroxylamine sulfate, hydroxylamine hydrochloride, hydroxylamine nitrate and hydroxylamine phosphate. At least one compound of the group formed. 10. The cleaning composition of claim 1 or 2, wherein the nitrogen-containing compound cleaner is hydroxylamine sulfate. 11. A cleaning composition as claimed in claim 1 or 2, which is used for removing plasma etching residues and/or ashing residues in a semiconductor component manufacturing step. Or the cleaning composition according to item 2, wherein the semiconductor substrate to be cleaned comprises an exposed layer or a copper layer. 13. A cleaning method characterized by: cleaning a plasma etching residue and/or an ash residue on a semiconductor substrate by a cleaning composition as described in claim 1 or 2 . 14. The method of cleaning according to claim 13 of the patent application, wherein 50. (The cleaning is performed at a temperature of ~9 ° C.' 15. A method of manufacturing a semiconductor device, comprising the steps of: 39 201207100: (a) (al) etching step to electrically charge the semiconductor substrate Slurry etching, and/or (a-2) ashing step, ashing the resist on the semiconductor substrate; and (b) washing step, as described in item j or item 2 of the patent application The β-cleaning composition' is washed away from the plasmon residue and/or the ash residue formed on the semiconductor substrate in the step of 彳 and/or the ashing step.