CN101412948B - Cleaning agent for plasma etching residue - Google Patents

Cleaning agent for plasma etching residue Download PDF

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Publication number
CN101412948B
CN101412948B CN2007100472657A CN200710047265A CN101412948B CN 101412948 B CN101412948 B CN 101412948B CN 2007100472657 A CN2007100472657 A CN 2007100472657A CN 200710047265 A CN200710047265 A CN 200710047265A CN 101412948 B CN101412948 B CN 101412948B
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acid
corrosion inhibitor
content
mass percent
clean
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CN101412948A (en
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刘兵
彭洪修
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Anji Microelectronics Shanghai Co Ltd
Anji Microelectronics Co Ltd
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Abstract

The invention discloses a plasma etching remainder detergent, which contains fluoride, water and a solvent, namely N-hydroxyethylpyrrolidone. The detergent has highly-efficient cleaning capability to plasma etching remainder, has lower etching speed to low dielectric materials (such as SiO2 and PETEOS), metal materials (such as Ti, Al and Cu) and other wafer base materials as well as low defect level, has the advantages of wide operation window, safety and environmental protection, and has excellent application prospect in semiconductor wafer cleaning and other micro-electronic fields.

Description

A kind of cleaning agent for plasma etching residue
Technical field
The present invention relates to the clean-out system in the semiconductor fabrication process, concrete relate to a kind of cleaning agent for plasma etching residue.
Background technology
In the semiconductor components and devices manufacturing processed, the coating of photoresist layer, exposure and imaging are necessary process steps to the pattern manufacturing of components and parts.Before last (promptly after coating, imaging, ion implantation and the etching at photoresist layer) of patterning carried out next process step, the residue of photoresist layer material need thoroughly be removed.At doping step intermediate ion bombardment meeting sclerosis photoresist layer polymkeric substance, therefore make photoresist layer become and be difficult for dissolving, thereby be difficult to remove.At present, the general two-step approach (dry ashing and wet etching) of using is removed this layer photoresistance tunic in semi-conductor industry.The first step utilizes dry ashing to remove the major part of photoresist layer (PR); Second step utilized composite corrosion inhibitor wet etching/cleaning to wash remaining photoresist layer.In the cleaning process in second step, composite corrosion inhibitor can only be removed residual polymkeric substance photoresist layer and inorganics, and can not damage metal level (like aluminium lamination).
Typical scavenging solution has following several kinds in the prior art: amine scavenging solution, semi-aqueous amido (non-azanol class) scavenging solution and fluorochemical based cleaning liquid.No matter be which kind of scavenging solution, all contain solvent.For example: US6,828,289 disclosed cleaning liquid compositions comprise: acidic buffer, organic polar solvent, fluorine-containing material and water.The use of solvent mainly is in order to remove the organism part in the plasma etching residues, if the dissolving cleansing power of solvent is not enough, two kinds of situation possibly occur: thus 1. needs improve the cleansing power that the service temperature of cleaning improves scavenging solution; But higher service temperature tends to bring higher material unaccounted-for (MUF) and less action pane, thereby might change the characteristic dimension of semiconducter device, influences the performance of semiconducter device; 2., remain on the semi-conductor, thereby influence the cleaning performance of semi-conductor chip even through improving the way of temperature, plasma etching residues is still removed unclean.Inappropriate solvent also has other problem.A large amount of fluorine-containing scavenging solutions that use glycols as solvent are disclosed like patent documentation US5698503.Because a large amount of ethylene glycol compounds that use, the viscosity of this scavenging solution and surface tension are all very big, influence its cleaning performance.So in the preparation process of semi-conductor industry ionic medium etching residual washing liquid, choice of Solvent is very important.
Summary of the invention
Technical problem to be solved by this invention be for the solvent that overcomes in the existing cleaning agent for plasma etching residue not enough to the organism cleansing power; Influence the cleaning performance of clean-out system, and the cleaning agent for plasma etching residue of the strong and safety and environmental protection of a kind of cleansing power is provided.
Cleaning agent for plasma etching residue of the present invention contains fluorochemical and water, also contains solvent N-hydroxyethyl-pyrrolidone.
Wherein, what the content of described N-hydroxyethyl-pyrrolidone was preferable is mass percent 10~80%, and better is mass percent 20~60%.
Wherein, described fluorochemical is preferable is in the salt that forms of hydrogen fluoride and/or hydrogen fluoride and alkali one or more, like HF, NH 4F, NH 4HF 2, N (CH 3) 4F or N (CH 2OH) 3HF etc.; What the content of described fluorochemical was preferable is mass percent 0.01~10%.
What wherein, the content of described water was preferable is mass percent 10~80%.
This plasma etching leftover cleaning agent also can further contain sequestrant, buffering in, corrosion inhibitor, tensio-active agent and the antifreezing agent one or more.
What wherein, the content of described sequestrant was preferable is mass percent 0~10%; What the content that described buffering is right was preferable is mass percent 0~20%. What the content of described corrosion inhibitor was preferable is mass percent 0~10%; What the content of described tensio-active agent was preferable is mass percent 0~10%; What the content of described antifreezing agent was preferable is mass percent 0~20%.
Among the present invention, described sequestrant is meant the material that contains two or more functional groups, is characterized in forming coordination or chelating with metal or MOX.As: contain 1 of phenolic hydroxyl group, 2-dihydroxyl phenol, pyrogallol and gallic acid etc.; The phthalic acid that contains carboxyl; Phosphonic acid based is as 1,3-(hydroxyethyl)-2,4,6-tri methylene phosphonic acid (HEDPA), ATMP (ATMP) or 2-phosphonic acids butane-1,2, one or more in the 4-tricarboxylic acid (PBTCA) etc.
Among the present invention, described buffering is to being meant the salt of organic acid and this organic acid and alkali formation, and like acetic acid and ammonium acetate, Hydrocerol A and ammonium citrate or lactic acid and DL-Lactic acid ammonium salt etc., what organic acid and the mol ratio of its corresponding salt were preferable is 10: 1~1: 10.
Among the present invention, described corrosion inhibitor can be a micromolecular inhibitor, can also be the polymer corrosion inhibitor, or both mixtures.Described small molecules corrosion inhibitor can be selected from one or more in following: phenols small molecules corrosion inhibitor, and like phenol, 1,2-dihydroxyl phenol, para hydroxybenzene phenol or pyrogallol etc.; Carboxylic-acid is like phenylformic acid, para-amino benzoic acid (PABA), phthalic acid (PA) or gallic acid (GA) etc.; Benzotriazole micromolecular corrosion inhibitor is like benzotriazole, methyl benzotriazazole or 4-carboxy benzotriazole etc.; Phosphonic acid based small molecules corrosion inhibitor, as 1,3-(hydroxyethyl)-2,4,6-tri methylene phosphonic acid (HEDPA), ATMP (ATMP) or 2-phosphonic acids butane-1,2,4-tricarboxylic acid (PBTCA) etc.Described polymer corrosion inhibitor is preferable is selected from hydroxyl polymer-containing and the carbonyl bearing polymer one or more.Wherein, described hydroxyl polymer-containing is preferable is homopolymer or multipolymer of hydroxyl polyethers or Z 150PH etc.; What described carbonyl bearing polymer was preferable is ammonium salt, sylvite or the sodium salt etc. that contain carboxyl polyethers, HPMA, ROHM, polymethyl acrylic acid, vinylformic acid and maleic acid, vinylbenzene and PEMULEN TR2 or above-claimed cpd.
Among the present invention, described tensio-active agent is preferable is in hydroxyl polyethers, Z 150PH (PVA), Vinylpyrrolidone polymer, T 46155 (POE), ZGK 5 (PSOA), fluoro Z 150PH, fluoro Vinylpyrrolidone polymer, fluoro T 46155, fluoro ZGK 5, silicate and the AS one or more.Wherein, be preferably the hydroxyl polyethers.
Among the present invention, described antifreezing agent is preferable is selected from polyvalent alcohol, like the terepthaloyl moietie in the divalent alcohol, Ucar 35; USP Kosher in the trivalent alcohol; Tetramethylolmethane in the tetravalent alcohol, preferable is Ucar 35.The use of antifreezing agent can make scavenging solution of the present invention under-18 ℃ condition, deposit not freeze in two months.
Scavenging solution of the present invention is simply mixed and can be used by mentioned component.This scavenging solution is applicable to the batch immersion type, use in multiple cleaning instrument such as the rotary or rotary treater of monolithic and the cleaning way in batches.And scavenging solution of the present invention can use in bigger TR, generally can in ℃ scope of room temperature~50, use.
Agents useful for same of the present invention and raw material are all commercially available to be got.
Positive progressive effect of the present invention is: it is solvent that plasma etching residual washing liquid of the present invention has adopted the N-hydroxyethyl-pyrrolidone, and it has the dissolving cleansing power of plasma etching residues efficiently, and Environmental Safety.Plasma etching residual washing liquid article on plasma etch residue of the present invention has cleansing power efficiently, to hanging down dielectric material (like SiO 2And PETEOS) and metallic substance wafer substrates such as (like Ti, Al and Cu) lower etch-rate is arranged, low defect level, and action pane is wide, safety and environmental protection has a good application prospect at microelectronics such as semiconductor wafer cleanings.
Description of drawings
Fig. 1 is for there being the electronic scanning Electronic Speculum figure of figure metal wafer before cleaning.
Fig. 2 is the electronic scanning Electronic Speculum figure that the figure metal wafer is arranged after adopting dipropylene glycol methyl ether (DPME) for contrast clean-out system 1 cleaning of solvent.
Fig. 3 is the electronic scanning Electronic Speculum figure that the figure metal wafer is arranged after adopting methyl-sulphoxide (DMSO) for contrast clean-out system 2 cleanings of solvent.
Fig. 4 is the electronic scanning Electronic Speculum figure that the figure metal wafer is arranged after adopting N-Methyl pyrrolidone (NMP) for contrast clean-out system 3 cleanings of solvent.
Fig. 5 is the electronic scanning Electronic Speculum figure that the figure metal wafer is arranged after adopting N-hydroxyethyl-pyrrolidone (HEP) for clean-out system of the present invention 1 cleaning of solvent.
Embodiment
Mode through embodiment further specifies the present invention below, but does not therefore limit the present invention among the described scope of embodiments.Among the following embodiment, per-cent is mass percent.
Embodiment 1
1%HF, 19%N-hydroxyethyl-pyrrolidone and 80% water.
Embodiment 2
10%NH 4F, 10%N-hydroxyethyl-pyrrolidone, 0.01%2-phosphonic acids butane-1,2,4-tricarboxylic acid and 79.99% water.
Embodiment 3
5%NH 4HF 2, the 40%N-hydroxyethyl-pyrrolidone, 20% acetic acid/ammonium acetate cushions (mol ratio 8: 1) and 35% water.
Embodiment 4
3%N (CH 3) 4F, 50%N-hydroxyethyl-pyrrolidone, 10% hydroxyl gather ethyl ether (molecular weight 1000) and 37% water.
Embodiment 5
0.01%N (CH 3) 4F, 80%N-hydroxyethyl-pyrrolidone, 0.98% para hydroxybenzene phenol, 0.01% polymethyl acrylic acid and 19% water.
Embodiment 6
3%N (CH 3) 4F, 67%N-hydroxyethyl-pyrrolidone, 20% terepthaloyl moietie and 10% water.
Embodiment 7
1%N (CH 2OH) 3HF, 77.7998%N-hydroxyethyl-pyrrolidone, 1% lactic acid/DL-Lactic acid ammonium salt cushion (mol ratio 10: 1), 0.0001% ROHM, 0.1% ammonium silicate, 0.1%1,2-dihydroxyl phenol, 0.0001% Ucar 35 and 20% water.
Embodiment 8
1%HF, 63%N-hydroxyethyl-pyrrolidone, 10% Hydrocerol A/Hydrocerol A tetramethyl-ammonium cushion (mol ratio 6: 1), 0.1% Z 150PH (molecular weight 2000), 0.1% HPMA (molecular weight 400), 1% USP Kosher, 1% phenylformic acid and 23.8% water.
Embodiment 9
5% fluoridizes tetramethyl-ammonium; 2%HF, 50%N-hydroxyethyl-pyrrolidone, 15% Hydrocerol A/Hydrocerol A Tetrylammonium cushion (mol ratio 5: 1); 0.05% Vinylpyrrolidone polymer (molecular weight 3000); 0.01% polymethyl acrylic acid (molecular weight 800), 2% tetramethylolmethane, 0.01% ATMP and 25.93% water.
Embodiment 10
0.01% fluoridizes tetraethyl ammonium, and 60%N-hydroxyethyl-pyrrolidone, 5% Hydrocerol A/Tripotassium Citrate cushion (mol ratio 4: 1); 5% T 46155 (molecular weight 1000), 0.01% vinylformic acid and maleic acid (molecular weight 1500), 0.01% Z 150PH and PEMULEN TR2 (molecular weight 800); 4.99% terepthaloyl moietie, 1% tetramethylolmethane, 0.02%1; 3-(hydroxyethyl)-2,4,6-tri methylene phosphonic acid and 23.96% water.
Embodiment 11
1% Neutral ammonium fluoride, 70%N-hydroxyethyl-pyrrolidone, 3% Hydrocerol A/Tripotassium Citrate cushion (mol ratio 2: 1); 1% pyrogallol; 0.01% ZGK 5 (molecular weight 800), 0.01% vinylbenzene and PEMULEN TR2 (molecular weight 1000), 0.01%2-phosphonic acids butane-1; 2,4-tricarboxylic acid, 2% tetramethylolmethane and 22.97% water.
Embodiment 12
5% fluoridizes tetraethyl ammonium; The 30%N-hydroxyethyl-pyrrolidone; 5% Hydrocerol A/Tripotassium Citrate cushions (mol ratio 1: 10), 0.01% fluoro Z 150PH (molecular weight 600), 0.01% polyacrylic acid potassium (molecular weight 800); 5% methyl benzotriazazole, 5% terepthaloyl moietie, 5% hydroxyl gather ethyl ether and 44.98% water.
Embodiment 13
7% fluoridizes tetraethyl ammonium; The 50%N-hydroxyethyl-pyrrolidone; 10% Hydrocerol A/Hydrocerol A Tetrylammonium cushions (mol ratio 1: 8); 0.01% fluoro Vinylpyrrolidone polymer (molecular weight 1500), 0.01% ZX-I (molecular weight 900), 1.98%4-carboxy benzotriazole, 1% tetramethylolmethane and 30% water.
Embodiment 14
10% fluoridizes tetraethyl ammonium; The 34.97%N-hydroxyethyl-pyrrolidone; 15% Hydrocerol A/Hydrocerol A Tetrylammonium cushions (mol ratio 1: 6), 0.01% fluoro T 46155 (molecular weight 800), 0.01% ammonium polyacrylate (molecular weight 600); 0.01% Z 150PH (molecular weight 800), 5% benzotriazole, 5% terepthaloyl moietie and 30% water.
30% water.
Embodiment 15
4% Neutral ammonium fluoride; 20%N-hydroxyethyl-pyrrolidone, 15% acetic acid/ammonium acetate cushion (mol ratio 1: 4), 0.01% fluoro ZGK 5 (molecular weight 1000); 1% hydroxyl gathers ethyl ether (molecular weight 800), 5% gallic acid, 5% terepthaloyl moietie and 49.99% water.
Embodiment 16
6% Neutral ammonium fluoride, 32.98%N-hydroxyethyl-pyrrolidone, 15% acetic acid/ammonium acetate cushion (mol ratio 1: 2), 0.01% sodium laurylsulfonate, 0.01% contains carboxyl gathers ethyl ether (molecular weight 1000), 1% USP Kosher, 5% phthalic acid and 40% water.
Embodiment 17
1% Neutral ammonium fluoride, 59%N-hydroxyethyl-pyrrolidone, 20% water, 10%1,2-dihydroxyl phenol and 10% benzotriazole.
Effect embodiment
Press each component of table 1 prescription uniform mixing, preparation contrast clean-out system 1~3 and clean-out system 1.
Table 1 contrast clean-out system 1~3 and clean-out system 1 and base material erosion rate thereof
Clean-out system Solvent and content wt% thereof Deionized water content wt% Ammonium acetate content wt% Acetic acid content wt% Neutral ammonium fluoride content wt% ROHM (molecular weight 1000) wt% Benzotriazole wt% Terepthaloyl moietie wt% The erosion rate of 35 ℃ of following solution (A/min)
Metal (aluminium) Nonmetal (tetraethoxysilane silicon-dioxide, PETEOS)
Contrast 1 Dipropylene glycol methyl ether (DPME), 60 27.36 8.51 2.13 1.0 ?0.2 0.3 0.5 3.79/3.20 3.19/3.59
Contrast 2 Methyl-sulphoxide (DMSO), 60 27.36 8.51 2.13 1.0 ?0.2 0.3 0.5 1.09/0.31 0.70/1.25
Contrast 3 N-Methyl pyrrolidone (NMP), 60 27.36 8.51 2.13 1.0 ?0.2 0.3 0.5 2.66/0.75 0.89/1.50
1 N-hydroxyethyl-pyrrolidone (HEP), 60 27.36 8.51 2.13 1.0 ?0.2 0.3 0.5 1.22/1.04 1.78/1.93
*The erosion rate value is the data of twice test.
The rate of metal corrosion testing method of solution:
(1) utilize Napson four-point probe appearance to test the resistance initial value (Rs1) of the blank silicon chip of 4*4cm aluminium;
(2) the blank silicon chip of this 4*4cm aluminium is immersed in advance in the solution of constant temperature to 35 ℃ 30 minutes;
(3) take out the blank silicon chip of this 4*4cm aluminium, use washed with de-ionized water, high pure nitrogen dries up, and utilizes the resistance value (Rs2) of the blank silicon chip of Napson four-point probe appearance test 4*4cm aluminium again;
(4) repeated for the second and the 3rd step and test once, resistance value is designated as Rs3;
(5) be input to suitable procedure to above-mentioned resistance value and soak time and can calculate its erosion rate.
The nonmetal erosion rate testing method of solution:
(1) utilize the Nanospec6100 thickness tester to test the thickness (T1) of 4*4cm PETEOS silicon chip;
(2) this 4*4cmPETEOS silicon chip is immersed in advance in the solution of constant temperature to 35 ℃ 30 minutes;
(3) take out this 4*4cmPETEOS silicon chip, use washed with de-ionized water, high pure nitrogen dries up, and utilizes the thickness (T2) of Nanospec6100 thickness tester test 4*4cmPETEOS silicon chip again;
(4) the second and the 3rd step of repetition tests a thickness again and is designated as T3;
(5) be input to suitable procedure to above-mentioned one-tenth-value thickness 1/10 and soak time and can calculate its erosion rate.
From table 1, can find out: select different solvents for use, even under the same condition of other components, the corrosion speed of its metallic aluminium and nonmetal PETEOS also is not quite similar.When wherein DPME was solvent, its erosion rate was greater than standard that industry requires (2A/min).In semi-conductor industry, scavenging solution is applicable to the batch immersion type, in batches in multiple cleaning instrument such as the rotary or rotary treater of monolithic and the cleaning way; The wafer type of cleaning has metal wire (pattem metal wafer) and passage (pattern via wafer) etc.The present invention has selected for use figure metal wafer (pattem metal wafer) to carry out immersion type and has cleaned (conclusion of the present invention is not limited thereto for example) when comparing cleansing power.(select for use with a kind of figure metal silicon chip (Fig. 1) arranged there being figure metal wafer (patternmetal wafer) plasma etching residues to clean with the clean-out system in the table 1; Same cleaning step); Its cleaning performance characterizes through the electronic scanning Electronic Speculum, sees Fig. 2~5, summarized in Table 2.
Table 2 contrast clean-out system 1~3 has figure metal silicon chip (pattern metal wafer) with 1 pair of clean-out system
The effect that plasma etching residues cleans
Clean-out system Solvent Assessment item Cleaning performance
Polymer residues Metallic corrosion Nonmetal corrosion
Contrast 1 Dipropylene glycol methyl ether (DPME) Small portion of residual Slight corrosion Do not have Bad
Contrast 2 Methyl-sulphoxide (DMSO) More remnants There is not corrosion Do not have Bad
Contrast 3 N-Methyl pyrrolidone (NMP) Small portion of residual There is not corrosion Do not have Bad
1 N-hydroxyethyl-pyrrolidone (HEP) Do not have remaining There is not corrosion Do not have Good

Claims (8)

1. a cleaning agent for plasma etching residue contains fluorochemical and water, it is characterized in that: it also contains solvent N-hydroxyethyl-pyrrolidone, and said fluorochemical is selected from and is HF, NH 4F, NH 4HF 2, N (CH 3) 4F and N (CH 2OH) 3Among the HF one or more,
Wherein, the content of described N-hydroxyethyl-pyrrolidone is mass percent 10~80%; The content of described fluorochemical is mass percent 0.01~10%; The content of described water is mass percent 10~80%.
2. clean-out system as claimed in claim 1 is characterized in that: the content of described N-hydroxyethyl-pyrrolidone is mass percent 20~60%.
3. clean-out system as claimed in claim 1 is characterized in that: described cleaning agent for plasma etching residue also contains sequestrant, buffering in, corrosion inhibitor, tensio-active agent and the antifreezing agent one or more.
4. clean-out system as claimed in claim 3 is characterized in that: the content of described sequestrant is mass percent 0~10%; The content that described buffering is right is mass percent 0~20%; The content of described corrosion inhibitor is mass percent 0~10%; The content of described tensio-active agent is mass percent 0~10%; The content of described antifreezing agent is mass percent 0~20%.
5. clean-out system as claimed in claim 3; It is characterized in that: described sequestrant is 1,2-dihydroxyl phenol, pyrogallol, gallic acid, phthalic acid, 1,3-(hydroxyethyl)-2; 4; 6-tri methylene phosphonic acid, ATMP and 2-phosphonic acids butane-1,2, one or more in the 4-tricarboxylic acid; Described buffering is to being the salt of organic acid and this organic acid and alkali formation; Described corrosion inhibitor is small molecules corrosion inhibitor and/or polymer corrosion inhibitor; Described tensio-active agent is one or more in hydroxyl polyethers, Z 150PH, Vinylpyrrolidone polymer, T 46155, ZGK 5, fluoro Z 150PH, fluoro Vinylpyrrolidone polymer, fluoro T 46155, fluoro ZGK 5, silicate and the AS; Described antifreezing agent is polyvalent alcohol, terepthaloyl moietie and/or Ucar 35.
6. clean-out system as claimed in claim 5 is characterized in that: described organic acid is acetic acid and ammonium acetate with the salt of this organic acid and alkali formation, Hydrocerol A and ammonium citrate, perhaps lactic acid and DL-Lactic acid ammonium salt; Described small molecules corrosion inhibitor is selected from one or more in phenols, carboxylic-acid, benzotriazole, the phosphonic acid based small molecules corrosion inhibitor; Described polymer corrosion inhibitor is selected from hydroxyl polymer-containing and/or carbonyl bearing polymer; Described polyvalent alcohol is USP Kosher and/or tetramethylolmethane.
7. clean-out system as claimed in claim 6 is characterized in that: described phenols small molecules corrosion inhibitor is a phenol, 1, one or more in 2-dihydroxyl phenol, para hydroxybenzene phenol and the pyrogallol; Described carboxylic-acid small molecules corrosion inhibitor is one or more in phenylformic acid, para-amino benzoic acid, phthalic acid and the gallic acid; Described benzotriazole micromolecular corrosion inhibitor is one or more in benzotriazole, methyl benzotriazazole and the 4-carboxy benzotriazole; Described phosphonic acid based small molecules corrosion inhibitor is 1,3-(hydroxyethyl)-2,4,6-tri methylene phosphonic acid, ATMP and 2-phosphonic acids butane-1,2, one or more in the 4-tricarboxylic acid; Described hydroxyl polymer-containing is one or more in hydroxyl polyethers, Z 150PH homopolymer and the polyvinyl alcohol copolymer; Described carbonyl bearing polymer is one or more in ammonium salt, sylvite and the sodium salt that contains carboxyl polyethers, HPMA, ROHM, polymethyl acrylic acid, vinylformic acid and maleic acid, vinylbenzene and PEMULEN TR2, above-claimed cpd.
8. clean-out system as claimed in claim 5 is characterized in that: described organic acid is 10: 1~1: 10 with the mol ratio of the salt of this organic acid and alkali formation.
CN2007100472657A 2007-10-19 2007-10-19 Cleaning agent for plasma etching residue Expired - Fee Related CN101412948B (en)

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