CN101665748A - Protection solution for semi-conductor wafer metal substrate and using method thereof - Google Patents
Protection solution for semi-conductor wafer metal substrate and using method thereof Download PDFInfo
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- CN101665748A CN101665748A CN200810042566A CN200810042566A CN101665748A CN 101665748 A CN101665748 A CN 101665748A CN 200810042566 A CN200810042566 A CN 200810042566A CN 200810042566 A CN200810042566 A CN 200810042566A CN 101665748 A CN101665748 A CN 101665748A
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Abstract
The invention discloses a protection solution for a semi-conductor wafer metal substrate, which comprises a solvent and water. The solvent is a solvent which is conventionally used for rinsing with solvent in a cleaning process after plasma etching in the field. The invention also provides a method for using the protection solution, which is characterized in that: after residues which are subjected to plasma etching or plasma etching and ashing on a semiconductor wafer are removed by a cleaning solution, the semiconductor wafer is rinsed by the protection solution for the semiconductor wafer metal substrate, and is dried. The protection solution has environmental protection and low cost, and the method has simple and easy operation and can remarkably reduce corrosion velocity on aluminum to ensure that the corrosion velocity is less than 2A/Min.
Description
Technical field
The present invention relates to a kind of purging method and scavenging solution in the semi-conductor manufacturing cleaning, be specifically related to a kind of protection solution for semi-conductor wafer metal substrate and using method thereof.
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 plasma etching at photoresist layer) of patterning carried out next processing step, the residue of photoresist layer material need thoroughly be removed.Can sclerosis photoresist layer polymkeric substance in doping step intermediate ion bombardment, thus therefore making photoresist layer become to be difficult for dissolving more is difficult to remove.So far 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 plasma etching residual washing liquid to carry out cleaning, and to remove remaining photoresist layer, its step is generally earlier and cleans with plasma etching residual washing liquid, then with solvent or rinsed with deionized water, uses rinsed with deionized water at last again.Require in this process only to remove residual polymkeric substance photoresist layer and inorganics, and can not destroy metal level such as aluminium lamination.This cleaning complicated operation, and cost height.
Typical plasma etching residual washing liquid has following several in the prior art: amine scavenging solution, semi-aqueous amido (non-azanol class) scavenging solution and fluorochemical based cleaning liquid.Wherein preceding two based cleaning liquids since its in water during rinsing the erosion rate of metallic aluminium higher, after having cleaned the plasma etching residue, often adopt the solvent rinsing.Used solvent mainly contains Virahol and N-Methyl pyrrolidone.The former progressively is eliminated in some semi-conductor manufacturing companies because flash-point is lower, volatile; Though and latter's flash-point is than higher, not volatile, a lot of semi-conductor manufacturing companies are using always; But along with environmental consciousness strengthens and cost pressure strengthens, more and more company wish can be with the direct rinsing of deionized water, and do not cause corrosion of metal.And existing fluorochemical based cleaning liquid cleans under lower temperature, uses rinsed with deionized water then.But the direct rinsing of water can cause corrosion to aluminium usually, and the change procedure of its erosion rate as shown in Figure 1.
Because its erosion rate has a peak value in time, in order to reduce the corrosion that rinsing brings, often in the process of reality adopt a large amount of quick rinsings of water so that with fast speeds and short time by the bigger zone of erosion rate, to reduce corrosion of metal.And this often brings the too small problem of rinse cycle action pane.
Summary of the invention
Technical problem to be solved by this invention is in order to solve the metallic corrosion problem in the wet-cleaned rinse step; and provide a kind of lower rate of metal corrosion that has, environmentally friendly simultaneously, that cost is low and easy to use protection solution for semi-conductor wafer metal substrate and using method thereof.
Protection solution for semi-conductor wafer metal substrate of the present invention, it contains solvent and water.
Wherein, that the consumption of described solvent is preferable is 5-95%, and that better is 50-90%.That the consumption of water is preferable is 5-95%, and that better is 10-60%.Per-cent is mass percent.
Described solvent is in the cleaning behind the plasma etching of this area, the conventional solvent that uses during with the solvent rinsing.Preferred one or more in sulfoxide, sulfone, imidazolidone, pyrrolidone, imidazolone, the pure and mild ether of acid amides.Described sulfoxide is preferable is in dimethyl sulfoxide (DMSO), diethyl sulfoxide and the first and second basic sulfoxides one or more; Described sulfone is preferable is in methyl sulfone, ethyl sulfone and the tetramethylene sulfone one or more; What described imidazolidone was preferable is 2-imidazolidone, 1,3-dimethyl-2-imidazolidone and 1, one or more in 3-diethyl-2-imidazolidone; Described pyrrolidone is preferable is in N-Methyl pyrrolidone, N-ethyl pyrrolidone, N-cyclohexyl pyrrolidone and the N-hydroxyethyl-pyrrolidone one or more; What described imidazolone was preferable is 1,3-dimethyl-2-imidazolone; What described acid amides was preferable is dimethyl formamide and/or N,N-DIMETHYLACETAMIDE; Described ether is preferable is in ethylene glycol monoalkyl ether, Diethylene Glycol monoalky lether, propylene-glycol monoalky lether, dipropylene glycol monoalky lether and the tripropylene glycol monoalky lether one or more.
In the protection solution for semi-conductor wafer metal substrate of the present invention, can also contain other conventional additives of this area as required.
In the preferable example of the present invention, described protection solution for semi-conductor wafer metal substrate only is made up of solvent and water.
Among the present invention, described metal base especially refers to aluminium, as is applied to the aluminium alloys such as standard aluminum, Al-Si-Cu alloy or aluminum-copper alloy of semiconductor technology.
The present invention also provides the using method of described protection solution for semi-conductor wafer metal substrate: after the resistates after plasma etching or plasma etching and ashing on the scavenging solution removal semiconductor wafer; directly semiconductor wafer is cleaned with described protection solution for semi-conductor wafer metal substrate, dry afterwards.
Wherein, described semiconductor wafer preferable for containing the aluminum semiconductor wafer; After with protection solution for semi-conductor wafer metal substrate semiconductor wafer being cleaned, preferable water again cleans.What the time of using protection solution for semi-conductor wafer metal substrate of the present invention that semiconductor wafer is cleaned was preferable is no more than 15 minutes.Protection solution for semi-conductor wafer metal substrate of the present invention can be the cleaning way of semiconductor wafer: overflow infusion method, fast prompt drop liquid method or rotary spray method.
Described scavenging solution is the scavenging solution of this area routine, as azanol based cleaning liquid and fluorinated scavenging solution.
Reagent of the present invention is all commercially available to be got.
Positive progressive effect of the present invention is:
1) provide a kind of environmental protection, low price, operation is simple and easy and the rinsing metal protection liquid of obvious results semiconductor crystal wafer after cleaning.
2) in the scavenging solution wet clean process of two classes that contain azanol and fluorine, can significantly reduce erosion rate to aluminium, itself to the corrosion speed of aluminium less than 2A/Min.
Description of drawings
Fig. 1 is the graph of a relation of the Dilution ratio of metallic aluminium erosion rate and fluorinated scavenging solution and azanol based cleaning liquid and water.
Embodiment
Further specify the present invention with embodiment below, but the present invention is not limited.Among the following embodiment, per-cent is mass percent.
Embodiment 1～37
Table 1 has provided the prescription of protection solution for semi-conductor wafer metal substrate embodiment 1～37 of the present invention, presses listed component and content thereof in the table 1, simply mixes, and promptly makes each corrosion inhibitor for semiconductor chip metal substrate.
Table 1 protection solution for semi-conductor wafer metal substrate 1～37 of the present invention
| Embodiment | Deionized water content wt% | Solvent species | Solvent wt% |
| ??1 | ??50 | Dimethyl sulfoxide (DMSO) | ??50 |
| ??2 | ??40 | Dimethyl sulfoxide (DMSO) | ??60 |
| ??3 | ??30 | Dimethyl sulfoxide (DMSO) | ??70 |
| ??4 | ??20 | Dimethyl sulfoxide (DMSO) | ??80 |
| ??5 | ??10 | Dimethyl sulfoxide (DMSO) | ??90 |
| ??6 | ??50 | Dipropylene glycol monomethyl ether | ??50 |
| ??7 | ??40 | Dipropylene glycol monomethyl ether | ??60 |
| ??8 | ??30 | Dipropylene glycol monomethyl ether | ??70 |
| ??9 | ??20 | Dipropylene glycol monomethyl ether | ??80 |
| ??10 | ??10 | Dipropylene glycol monomethyl ether | ??90 |
| ??11 | ??50 | The methyl sulfone | ??50 |
| ??12 | ??30 | Ethyl sulfone | ??70 |
| ??13 | ??10 | Tetramethylene sulfone | ??90 |
| ??14 | ??50 | The 2-imidazolidone | ??50 |
| ??15 | ??30 | 1,3-dimethyl-2-imidazolidone | ??70 |
| ??16 | ??10 | 1,3-diethyl-2-imidazolidone | ??90 |
| ??17 | ??25+25 | Methyl sulfone+dimethyl sulfoxide (DMSO) | ??50 |
| ??18 | ??50 | N-Methyl pyrrolidone | ??50 |
| ??19 | ??30 | The N-ethyl pyrrolidone | ??70 |
| ??20 | ??10 | N-cyclohexyl pyrrolidone | ??90 |
| ??21 | ??20 | The N-hydroxyethyl-pyrrolidone | ??80 |
| ??22 | ??20 | 1,3-dimethyl-2-imidazolone | ??80 |
| ??23 | ??40 | Dimethyl formamide | ??60 |
| ??24 | ??40 | N,N-DIMETHYLACETAMIDE | ??60 |
| ??25 | ??20 | Ethylene Glycol Methyl ether | ??80 |
| ??26 | ??20 | The Diethylene Glycol methyl ether | ??80 |
| ??27 | ??20 | Methyl proxitol | ??80 |
| ??28 | ??40 | The dipropylene glycol ether | ??60 |
| ??29 | ??40 | The tripropylene glycol methyl ether | ??60 |
| ??30 | ??50 | Virahol | ??50 |
| ??31 | ??40 | Virahol | ??60 |
| ??32 | ??30 | Virahol | ??70 |
| ??33 | ??20 | Virahol | ??80 |
| ??34 | ??5 | Diethyl sulfoxide | ??95 |
| ??35 | ??60 | The methyl sulfone | ??40 |
| ??36 | ??80 | The first and second basic sulfoxides | ??20 |
| ??37 | ??95 | Dipropylene glycol monomethyl ether | ??5 |
Effect embodiment
For effect of the present invention is described, prepared the scavenging solution that contains the azanol class and the scavenging solution (seeing table 2 for details) of fluorinated according to disclosed patent with typical meaning, and the metallic aluminium erosion rate (see table 3) of the water of having tested the two and different ratios when diluting.
Metallic aluminium erosion rate testing method:
1) utilize Napson four-point probe instrument 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 instrument test 4*4cm aluminium again;
4) if necessary, repeated for the second and the 3rd step and test once, resistance value is designated as Rs3;
5) above-mentioned resistance value and soak time are input to suitable procedure and can calculate its erosion rate.
Scavenging solution that table 2 liang class is common and composition thereof
| The scavenging solution kind | Referenced patent | Concrete scavenging solution is formed |
| The azanol based cleaning liquid, F1 | ??US5672577 | 17.5% azanol, 17.5% deionized water, 50% thanomin, 15% pyrocatechol |
| The fluorinated scavenging solution, F2 | ??US6828289 | 57.5% N,N-DIMETHYLACETAMIDE, 12.8% deionized water, 12% acetic acid, 15.2% ammonium acetate, 2.5% Neutral ammonium fluoride (40%, aq.) |
Rate of metal corrosion (35 ℃) when the common scavenging solution of table 3 liang class dilutes in water
As can be seen from Table 3: the fluorinated scavenging solution is bigger to rate of metal corrosion when diluting in water.And there is from high to low a curve (Fig. 1) again from low to high in rate of metal corrosion.In order to reduce the corrosion of rinsing to metal base, semi-conductor industry circle a large amount of quick rinsing of water of normal employing in the process of reality at present, so that with fast speeds and short time by the bigger zone of erosion rate, with the minimizing corrosion of metal, and this often brings the too small problem of rinse cycle action pane.The present invention has reduced peak shape height shown in Figure 1, will help reducing corrosion of metal in the rinse cycle, brings bigger action pane simultaneously.
With metal base protection liquid embodiment 7 of the present invention is example, illustrates the effect of metal base protection liquid of the present invention, and testing method is the same, the results are shown in Table 4,5,6 and 7.
Rate of metal corrosion (45 ℃) when the common scavenging solution of table 4 liang class dilutes in embodiment 8
Rate of metal corrosion (45 ℃) when the common scavenging solution of table 5 liang class dilutes in embodiment 20
Rate of metal corrosion (45 ℃) when the common scavenging solution of table 6 liang class dilutes in embodiment 23
Rate of metal corrosion (45 ℃) when the common scavenging solution of table 7 liang class dilutes in embodiment 34
Wherein, 1
StWith 2
NdBe respectively to repeat twice experimental result according to described testing method.From table 4,5,6 and 7 as can be seen, embodiment 8,20,23 and 34 rinsing liquid prescription can effectively be controlled after the scavenging solution wet-cleaned erosion rate of metallic aluminium when rinsing, with the erosion rate of maximum by the pure water rinsing liquid＞100A/min is reduced to about 2A/min, can provide bigger action pane for rinsing.
Claims (12)
1, a kind of protection solution for semi-conductor wafer metal substrate, it contains solvent and water, and wherein said solvent is in the cleaning behind the plasma etching of this area, the conventional solvent that uses during with the solvent rinsing.
2, protection liquid as claimed in claim 1, it is characterized in that: described protection solution for semi-conductor wafer metal substrate is made up of solvent and water.
3, protection liquid as claimed in claim 1 is characterized in that: the consumption of described solvent is mass percent 5-95%.
4, protection liquid as claimed in claim 3 is characterized in that: the consumption of described solvent is mass percent 50-90%.
5, protection liquid as claimed in claim 1 is characterized in that: the consumption of described water is mass percent 5-95%.
6, protection liquid as claimed in claim 5 is characterized in that: the consumption of described water is mass percent 10-60%.
7, protection liquid as claimed in claim 1 is characterized in that: described solvent is one or more in sulfoxide, sulfone, imidazolidone, pyrrolidone, imidazolone, the pure and mild ether of acid amides.
8, protection liquid as claimed in claim 7 is characterized in that: described sulfoxide is one or more in dimethyl sulfoxide (DMSO), diethyl sulfoxide and the first and second basic sulfoxides; Described sulfone is one or more in methyl sulfone, ethyl sulfone and the tetramethylene sulfone; Described imidazolidone is a 2-imidazolidone, 1,3-dimethyl-2-imidazolidone and 1, one or more in 3-diethyl-2-imidazolidone; Described pyrrolidone is one or more in N-Methyl pyrrolidone, N-ethyl pyrrolidone, N-cyclohexyl pyrrolidone and the N-hydroxyethyl-pyrrolidone; Described imidazolone is 1,3-dimethyl-2-imidazolone; Described acid amides is dimethyl formamide and/or N,N-DIMETHYLACETAMIDE; Described ether is one or more in ethylene glycol monoalkyl ether, Diethylene Glycol monoalky lether, propylene-glycol monoalky lether, dipropylene glycol monoalky lether and the tripropylene glycol monoalky lether.
9, as the using method of each described protection liquid of claim 1～8; it is characterized in that: after the resistates after plasma etching or plasma etching and ashing on the scavenging solution removal semiconductor wafer; with described protection solution for semi-conductor wafer metal substrate rinsing, drying.
10, method as claimed in claim 9 is characterized in that: after with described protection solution for semi-conductor wafer metal substrate semiconductor wafer being cleaned, water cleans again.
11, method as claimed in claim 9 is characterized in that: the time of semiconductor wafer being cleaned with described protection solution for semi-conductor wafer metal substrate is no more than 15 minutes.
12, method as claimed in claim 9 is characterized in that: described protection solution for semi-conductor wafer metal substrate to the cleaning way of semiconductor wafer is: overflow infusion method, fast prompt drop liquid method or rotary spray method.
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| Application Number | Priority Date | Filing Date | Title |
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| CN200810042566A CN101665748A (en) | 2008-09-05 | 2008-09-05 | Protection solution for semi-conductor wafer metal substrate and using method thereof |
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| CN200810042566A CN101665748A (en) | 2008-09-05 | 2008-09-05 | Protection solution for semi-conductor wafer metal substrate and using method thereof |
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| CN101665748A true CN101665748A (en) | 2010-03-10 |
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| CN200810042566A Pending CN101665748A (en) | 2008-09-05 | 2008-09-05 | Protection solution for semi-conductor wafer metal substrate and using method thereof |
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Application publication date: 20100310 |