Summary of the invention
The invention provides a kind of cleaning constituent, can effectively remove and carry out the residue that produces after cmp processing procedure.
The present invention proposes a kind of cleaning constituent, comprises polyamines yl carboxylic acid salt (polyaminocarboxylic salt), acid and water.The content of polyamines yl carboxylic acid salt is 0.01 % by weight to 0.5 % by weight.The content of acid is 0.01 % by weight to 0.5 % by weight.Wherein, the remainder of cleaning constituent is water.
Described in one embodiment of the invention, in above-mentioned cleaning constituent, polyamines yl carboxylic acid salt is for being selected from ethylenediamine tetraacetic acid (EDTA) (ethylenediaminetetraacetic acid), diethylene triamine pentacetic acid (DTPA) (diethylenetriaminepentatacetic acid), three glycine nitrilotriacetic acid, N-hydroxyethyl-ethylenediamine nitrilotriacetic (N-(hydroxyethyl)-ethylenediaminetriacetic acid), at least one in an alkali metal salt of hydroxyethyl imido oxalic acid (hydroxyethyliminodiacetic acid) and ammonium salt (ammonium salt).
Described in one embodiment of the invention, in above-mentioned cleaning constituent, acid is at least one in phosphine carboxylic acid (phosphonic carboxylic acid) and carboxylic acid (carboxylic acid).
Described in one embodiment of the invention, in above-mentioned cleaning constituent, phosphine carboxylic acid is for being selected from 2-amido ethylphosphonic acid (2-aminoethylphosphonic acid, AEPN), dimethyl methyl phosphonate (Dimethyl methylphosphonate, DMMP), 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (1-HydroxyEthylidene-1, 1-Diphosphonic Acid, HEDP), amido three methylenephosphonic acids (Aminotris (methylene phosphonic acid), ATMP), ethylene diamine tetra methylene phosphonic acid (Ethylenediamine tetra (methylene phosphonic acid), EDTMP), tetramethylenediamine four methylenephosphonic acids (Tetramethylenediamine tetra (methylene phosphonicacid), TDTMP), hexanediamine four methylenephosphonic acids (Hexamethylenediaminetetra (methylene phosphonic acid), HDTMP), diethylenetriamine five methylenephosphonic acids (Diethylenetriamine penta (methylene phosphonic acid), DTPMP), 2-phosphonic acid butane-1, 2, 4-tricarboxylic acid (2-phosphonobutane-1, 2, 4-tricarboxlic acid, PBTC), N-(phosphine carboxymerhyl) imido oxalic acid (N-(phosphonomethyl) iminodiacetic acid, PMIDA), 2-propyloic phosphonic acids (2-carboxyethyl phosphonic acid, CEPA) and 2-HPAA (2-Hydroxyphosphonocarboxylic acid, HPAA) at least one in.
Described in one embodiment of the invention, in above-mentioned cleaning constituent, carboxylic acid is for being selected from formic acid (formic acid), acetic acid (acetic acid), propionic acid (propionic acid), oxalic acid (oxalicacid), vinylformic acid (acrylic acid), phenylformic acid (benzoic acid), maleic acid (maleicacid), oxysuccinic acid (malic acid), pentanedioic acid (glutaric acid), propanedioic acid (malonic acid), hexanodioic acid (adipic acid), citric acid (citric acid), at least one in achilleic acid (aconitic acid).
Described in one embodiment of the invention, in above-mentioned cleaning constituent, clean constituent and also comprise interfacial agent.
Described in one embodiment of the invention, in above-mentioned cleaning constituent, interfacial agent is non-ionic surfactant (nonionic surfactant), teepol (anionicsurfactant) or its combination.
Described in one embodiment of the invention, in above-mentioned cleaning constituent, non-ionic surfactant is for being selected from least one in alkyl polyethylene oxide (alkyl poly (ethylene oxide)), alkylphenol polyethylene oxide (alkylphenol poly (ethylene oxide)) and alkyl poly glucoside (alkylpolyglucosides).
Described in one embodiment of the invention, in above-mentioned cleaning constituent, teepol is for being selected from least one in alkyl-sulphate (alkyl sulfate salt) and alkylbenzene sulfonate (alkylbenzene sulfonate).
Described in one embodiment of the invention, in above-mentioned cleaning constituent, alkyl-sulphate is for being selected from least one in Sodium Lauryl sulphate (sodium dodecyl sulfate), ammonium lauryl sulfate (ammoniumlauryl sulfate) and sodium lauryl tri(oxyethyl) sulfate (sodium laureth sulfate).
Described in one embodiment of the invention, in above-mentioned cleaning constituent, alkylbenzene sulfonate comprises Witco 1298 Soft Acid (dodecylbenzene sulfonic acid).
Described in one embodiment of the invention, in above-mentioned cleaning constituent, clean constituent and comprise ion toughener, its content is 0.01 % by weight to 0.5 % by weight.
Described in one embodiment of the invention, in above-mentioned cleaning constituent, ion toughener is for being selected from least one in amine salt, sylvite, sodium salt and the lithium salts of formic acid, acetic acid, propionic acid, oxalic acid, vinylformic acid, phenylformic acid, maleic acid, oxysuccinic acid, pentanedioic acid, propanedioic acid, hexanodioic acid, citric acid, achilleic acid, Whitfield's ointment (salicylic acid), tartrate (tartaric acid), oxyacetic acid (glycolic acid) and sulfonic acid (sulfonic acid).
Described in one embodiment of the invention, in above-mentioned cleaning constituent, cleaning constituent can the highly enriched cleaning constituent of simmer down to.
Described in one embodiment of the invention, in above-mentioned cleaning constituent, the cycles of concentration of highly enriched cleaning constituent is 20 times to 60 times.
Described in one embodiment of the invention, in above-mentioned cleaning constituent, the pH-value that cleans constituent is 8 to 12.
Based on above-mentioned, because cleaning constituent proposed by the invention has polyamines yl carboxylic acid salt, make to clean constituent alkalize, therefore can carry out cmp processing procedure after effectively wafer and grinding pad etc. is cleaned, and can not damage it.
In addition,, because the slurry that grinds using in cmp processing procedure is all alkalescence with cleaning constituent proposed by the invention, can avoid producing soda acid and impact (pH shock).On the other hand, under this alkaline environment, can make abrasive grain there is preferably electrokinetic potential (zeta potential), and can promote the cleansing power that cleans constituent.
For above-mentioned feature and advantage of the present invention can be become apparent, special embodiment below, and be described in detail below in conjunction with institute's accompanying drawing.
Embodiment
First, cleaning constituent of the present invention is described, it is applicable to carry out after cmp processing procedure, in the manufacturing process for cleaning for wafer and grinding pad etc.
The cleaning constituent of one embodiment of the invention comprises polyamines yl carboxylic acid salt, acid and water.
The content of polyamines yl carboxylic acid salt is 0.01 % by weight to 0.5 % by weight, can be alkalescence so that clean constituent.The pH-value that cleans constituent is for example 8 to 12.Polyamines yl carboxylic acid salt is to be for example selected from an alkali metal salt of ethylenediamine tetraacetic acid (EDTA), diethylene triamine pentacetic acid (DTPA), three glycines, N-hydroxyethyl-ethylenediamine nitrilotriacetic, hydroxyethyl imido oxalic acid and at least one in ammonium salt.
The content of acid is 0.01 % by weight to 0.5 % by weight.Acid is for example at least one in phosphine carboxylic acid and carboxylic acid (carboxylic acid).
Carboxylic acid is to be for example selected from least one in formic acid, acetic acid, propionic acid, oxalic acid, vinylformic acid, phenylformic acid, maleic acid, oxysuccinic acid, pentanedioic acid, propanedioic acid, hexanodioic acid, citric acid, achilleic acid.
Phosphine carboxylic acid is to be for example selected from 2-amido ethylphosphonic acid, dimethyl methyl phosphonate, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, amido three methylenephosphonic acids, ethylene diamine tetra methylene phosphonic acid, tetramethylenediamine four methylenephosphonic acids, hexanediamine four methylenephosphonic acids, diethylenetriamine five methylenephosphonic acids, 2-phosphonic acid butane-1; at least one in 2,4-tricarboxylic acid, N-(phosphine carboxymerhyl) imido oxalic acid, 2-propyloic phosphonic acids and 2-HPAA.
In addition, clean constituent and also can comprise interfacial agent, to increase the wetting ability of cleaning constituent.Interfacial agent is for example non-ionic surfactant, teepol or its combination.Wherein, non-ionic surfactant is to be for example selected from least one in alkyl polyethylene oxide, alkylphenol polyethylene oxide and alkyl poly glucoside.Teepol is to be for example selected from least one in alkyl-sulphate and alkylbenzene sulfonate.Alkyl-sulphate is to be for example selected from least one in Sodium Lauryl sulphate, ammonium lauryl sulfate and sodium lauryl tri(oxyethyl) sulfate.Alkylbenzene sulfonate is for example Witco 1298 Soft Acid.
In addition, clean constituent and also can comprise ion toughener, its content is 0.01 % by weight to 0.5 % by weight, can improve the etch capabilities of cleaning constituent.Ion toughener is for example at least one in amine salt, sylvite, sodium salt and the lithium salts that is selected from formic acid, acetic acid, propionic acid, oxalic acid, vinylformic acid, phenylformic acid, maleic acid, oxysuccinic acid, pentanedioic acid, propanedioic acid, hexanodioic acid, citric acid, achilleic acid, Whitfield's ointment, tartrate, oxyacetic acid and sulfonic acid.
In addition, the remainder of cleaning constituent is water.Water is for example deionized water.
It should be noted that based on commercial factors and consider, can will clean the highly enriched cleaning constituent of constituent simmer down to, can reduce the weight and the volume that clean constituent, to reduce significantly, clean the shipment and delivery cost of constituent and the required space of storing goods.The cycles of concentration of highly enriched cleaning constituent is for example 20 times to 60 times.
Based on above-mentioned, the cleaning constituent proposing due to the present embodiment has polyamines yl carboxylic acid salt, makes to clean constituent alkalize, so after carrying out cmp processing procedure, can effectively to wafer and grinding pad etc., clean, and can not damage wafer and grinding pad.
In addition,, because the slurry that grinds using in cmp processing procedure is all alkalescence with the cleaning constituent that the present embodiment proposes, therefore do not exist soda acid to impact (pH shock).On the other hand, under this alkaline environment, can make abrasive grain there is preferably electrokinetic potential (zeta potential) and can prevent that abrasive grain from assembling, and can promote for short grained cleansing power, also to thering is preferably solubleness as organic residues such as benzotriazoles.
Below, carry out actual experiment test.Wherein, formula 1 is the product after concentrated to formula 10, and the scavenging solution sample in order to cleaning in each experimental example is diluted sample, be referred to as " sample during use (point-of-use (POU) sample, hereinafter to be referred as: POU sample) ".
[experimental example one]
Formula 1 is as shown in table 1 below to moiety, ratio and the pH-value of the cleaning constituent of formula 6.Wherein, formula 1 to the remainder of the cleaning constituent of formula 6 is water.In experimental example one, the 1 POU sample to formula 6 of filling a prescription is the sample after diluting 40 times with deionized water.
Table 1
Note:
KDTPA: diethylene triamine pentacetic acid (DTPA) five sylvite (potassiumdiethylenetriaminepentaacetate)
PBTC:2-phosphonic acid butane-1,2,4-tricarboxylic acid (2-phosphonobutane-1,2,4-tricarboxlic acid)
(1) static rate of etch test
1. the wafer that used, measuring instrument and experimental technique are as follows:
Wafer: the copper of 200 millimeters covers wafer, and wherein copper thickness is 2000 dusts
Measuring instrument: X-light fluorescence analyser (X-ray Fluorescence Spectrometer, hereinafter to be referred as: XRF)
Experimental technique: first, with the deionized waters of 40 times, the 1 cleaning constituent to formula 6 of filling a prescription is diluted.Then, copper is covered to wafer and be soaked in formula 1 in the diluting soln of formula 6 cleaning constituent 240 minutes.Then, utilize XRF to measure the thickness of copper before and after etching, with calculate average static rate of etch (static etching rate, hereinafter to be referred as: SER).
2. the result that static rate of etch is tested: as shown in table 2 below.
Table 2
Sample |
SER (A/min) |
The POU sample of formula 1 |
4.6 |
The POU sample of formula 2 |
3.5 |
The POU sample of formula 3 |
3.45 |
The POU sample of formula 4 |
3.5 |
The POU sample of formula 5 |
2.5 |
The POU sample of formula 6 |
3.45 |
Please refer to table 2, formula 1 is all very low for the SER of the copper metal on wafer to the POU sample of formula 6, is all less than 5 A/min.Hence one can see that, and formula 1 to the POU sample of formula 6 can't cause to copper metal the erosion of over etching, and do not have undercut phenomenon (under cut) generation.Therefore, formula 1 to the POU sample of formula 6 is applicable in existing manufacture of semiconductor.
(2) moistening test (wetting test)
1. the wafer that used, measuring instrument and experimental technique are as follows:
Wafer: the copper of 200 millimeters covers wafer and MIT 854 patterned wafers
Grind slurry: SuperNova SN2000 copper grinds slurry and SuperNova 4500 barrier layers grind slurry
Measuring instrument: contact angle measurement instrument (contact angle meter)
Experimental technique: first, with the deionized waters of 40 times, the 1 cleaning constituent to formula 6 of filling a prescription is diluted.Then, utilize the contact angle measurement instrument measurement formula 1 POU sample to formula 6 to cover the contact angle on wafer in copper.
In addition, about MIT 854 patterned wafers, first utilize Applied Marterials Mirra grinder station with SuperNova SN2000 copper grind slurry and SuperNova 4500 barrier layers grind slurry MIT 854 patterned wafers are ground.Then, utilize formula 1 to the POU sample of formula 6 with the flow rate of 15 ml/min, MIT 854 patterned wafers to be cleaned.After MIT 854 patterned wafers are cleaned, utilize contact angle measurement instrument to measure the contact angle of deionized water on MIT 854 patterned wafers.
2. the result of moistening test: as shown in table 3 below.
Table 3
Please refer to table 3, the contact angle of the 1 POU sample to formula 6 on wafer of filling a prescription is all very little, therefore have preferably wetting capacity for wafer.In addition, the contact angle of deionized water on the wafer after the 1 POU sample to formula 6 of filling a prescription cleans is also all very little, and the ionized water of dieing has preferably wetting capacity for the wafer after the 1 POU sample to formula 6 of filling a prescription cleans.
From the above, when the POU sample that uses formula 1 to formula 6 cleans wafer, formula 1 to POU sample and the deionized water of formula 6 all has preferably wetting capacity for wafer, therefore can effectively to wafer, clean.
(3) roughness test after cleaning
1. the wafer that used, measuring instrument and experimental technique are as follows:
Wafer: MIT 854 patterned wafers
Grind slurry: SuperNova SN2000 copper grinds slurry and SuperNova 4500 barrier layers grind slurry
Measuring instrument: (Atomic Force Microscope is called for short: AFM) atomic force microscope
Experimental technique: first utilize Applied Marterials Mirra grinder station, with SuperNova SN2000 copper grind slurry and SuperNova 4500 barrier layers grind slurry MIT 854 patterned wafers are ground.Then, utilize formula 1 to the POU sample of formula 6 with the flow rate of 15 ml/min, MIT 854 patterned wafers to be cleaned.After MIT 854 patterned wafers are cleaned, utilize AFM to measure the roughness of crystal column surface before and after etching.
2. the result of roughness test: as shown in table 4 below.
Table 4
Please refer to table 4, formula 1 is all very low for the roughness of the copper metal on wafer to the POU sample of formula 6, and Ra is all less than desired 7 dusts of specification.Hence one can see that, utilizes formula 1 to the POU sample of formula 6 to clean and can have preferably surfaceness wafer.
[experimental example two]
Formula 7 is as shown in table 5 below to moiety, ratio and the pH-value of the cleaning constituent of formula 10.Wherein, formula 7 to the remainder of the cleaning constituent of formula 10 is water.Formula 7 is to filling a prescription 10 for the product after concentrated, and in experimental example two, the 7 POU samples to formula 10 of filling a prescription are the sample after diluting 40 times with deionized water.
Table 5
Below, utilize formula 7 to carry out SER test, roughness test, moistening test, the test of BTA solubleness and electrokinetic potential test to the POU sample of formula 10, the result of its test is as shown in table 6 below.
Table 6
The result of 1.SER test:
Please refer to table 6, formula 7 is all very low for the SER of the copper metal on wafer to the POU sample of formula 10, is all less than 3 A/min.Hence one can see that, and formula 7 to the POU sample of formula 10 can't cause over etching to copper metal.
2. the result of roughness test:
Please refer to table 6, formula 7 is all very low for the roughness of the copper metal on wafer to the POU sample of formula 10, is all less than desired 7 dusts of specification.
3. the result of moistening test:
Please refer to table 6, from the experimental result of formula 7 and formula 8 POU sample, owing to adding teepol in formula 8, therefore filling a prescription 8 has preferably wet characteristic compared to formula 7.
The test of 4.BTA solubleness:
Please refer to table 6, formula 7 to the POU sample of formula 10 has preferably BTA solubleness compared to deionization.In addition, the formula 9 of interpolation ammonium oxalate has preferably BTA solubleness with the formula 10 that adds ammonium citrate.Hence one can see that, in cleaning constituent, adds as the ion toughener of ammonium oxalate and ammonium citrate etc., contribute to dissolve the organic residues such as BTA, and SER, roughness and wet characteristic still can maintain good level.
5. electrokinetic potential test:
Please refer to table 6, with 7 SiO that clean to formula 10 POU sample that fill a prescription
2abrasive grain has quite high negative electrokinetic potential, can make abrasive grain and wafer between there is sizable repulsive force, so can prevent that abrasive grain from adhering on wafer, and then there is preferably cleansing power.
[experimental example three]
Experimental technique: two MIT 854 patterned wafers are provided, first utilize Mirra grinder station with SuperNova SN2000 copper grind slurry and SuperNova 4500 barrier layers grind slurry MIT 854 patterned wafers are ground.Then, utilize respectively the POU sample of deionized water and formula 7 to clean wafer.In experimental example three, the POU sample of formula 7 is the sample after diluting 40 times with deionized water.
Figure 1A and Figure 1B are the photo figure after wafer being cleaned with deionized water after cmp processing procedure of an experimental example of the present invention.
Fig. 2 A and Fig. 2 B are the photo figure after wafer being cleaned with 7 the POU sample of filling a prescription after cmp processing procedure of an experimental example of the present invention.
Referring to Figure 1A and Figure 1B, on the wafer that utilizes deionized water to clean, in the copper metal line region of Figure 1A and the copper metal line of Figure 1B and the intersection of silicon oxide dielectric layer all there is organic residue.Hence one can see that, and list cleans with deionized water and cannot effectively remove the organic residue on wafer.
Referring to Fig. 2 A and Fig. 2 B, on the wafer cleaning at the POU sample that utilizes formula 7, in the copper metal line region of Fig. 2 A and the copper metal line of Fig. 2 B and the intersection of silicon oxide dielectric layer all do not find organic residue.Hence one can see that, and the POU sample of utilization formula 7 cleans and can effectively remove the organic residue on wafer.
[experimental example four]
Metal ion residue analysis:
1. experimental technique: three MIT 854 patterned wafers are provided, first utilize Mirra (ProductName) grinder station to grind slurry and SuperNova 4500 barrier layers with SuperNova SN2000 copper and grind slurry MIT 854 patterned wafers are ground.Then, wherein a wafer is not used scavenging solution to clean, and other two wafer utilize respectively the POU sample of formula 5 and formula 7 to clean wafer.Afterwards, utilize full-reflection X photoluminescence spectrum method (total reflection X-ray fluorescence (TXRF) spectroscopy) to carry out the measurement of metal residue.In experimental example four, the POU sample of formula 5 and formula 7 is the sample after diluting 40 times with deionized water.
2. the result of metal ion residue analysis: as shown in table 7 below.
Table 7
Please refer to table 7, on the wafer that does not use scavenging solution to clean, can leave a large amount of metal ion residues.Yet, on the wafer that the POU sample of utilization formula 5 and formula 7 cleans, only leave micro-metal ion residue.Hence one can see that, utilizes the POU sample of formula 5 and formula 7 wafer to be cleaned to the metal ion residue that can effectively remove on wafer.
Although the present invention discloses as above with embodiment; but it is not in order to limit the present invention, any those skilled in the art, without departing from the spirit and scope of the present invention; can do suitably change and be equal to replacement, therefore protection scope of the present invention should be as the criterion with the scope that claims were defined.