CN102513314A - Method for treating pollutant of workpiece provided with yttrium oxide coating layer - Google Patents

Method for treating pollutant of workpiece provided with yttrium oxide coating layer Download PDF

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Publication number
CN102513314A
CN102513314A CN2011104542405A CN201110454240A CN102513314A CN 102513314 A CN102513314 A CN 102513314A CN 2011104542405 A CN2011104542405 A CN 2011104542405A CN 201110454240 A CN201110454240 A CN 201110454240A CN 102513314 A CN102513314 A CN 102513314A
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deionized water
processing method
workpiece
solution
mass concentration
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CN102513314B (en
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贺小明
万磊
陈振军
倪图强
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Medium and Micro Semiconductor Equipment (Shanghai) Co., Ltd.
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Advanced Micro Fabrication Equipment Inc Shanghai
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Priority to TW101129591A priority patent/TWI580486B/en
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Abstract

The invention relates to a method for treating the pollutant of a workpiece which is provided with an yttrium oxide coating layer and is used for etching plasma, which comprises the steps of: at least adopting acid solution to wipe the workpiece, and then adopting deionized water to flush the workpiece. The treatment method can be used for leading the polluted workpiece such as a spray head, a focusing ring and the like to be used again.

Description

Processing method with workpiece pollution thing of yittrium oxide clad
Technical field
The present invention relates to field of semiconductor manufacture, relate in particular to a kind of processing method that is used for the workpiece pollution thing with yittrium oxide clad of plasma etching.
Background technology
In recent years; In field of semiconductor manufacture; Relate to plasma etching in a lot of processing procedures; The plasma etching that for example relates to silicon in the formation of TSV (Through Silicon Via) relates to the plasma etching of metal in the forming process of metal interconnecting wires, the formation of grid relates to the etching of dielectric layer in the transistor.Above-mentioned processing procedure generally carries out in that plasma chamber is indoor, is provided with various workpieces in this chamber, and for example focusing ring, spray are first-class.
With the spray head is example, and its matrix of existing spray head is generally aluminium, but aluminium is corroded under plasma ambient easily, causes the life-span of this spray head not long.To this problem, cover the strong aluminium oxide (Al of one deck anti-etching ability force rate aluminium through outer surface in the prior art at this matrix 2O 3), yet, because spray head its surface meeting and etching gas in use; Be generally fluoro-gas, react, generate the aluminum fluoride particle; This particle aggregation gets up, and drops easily on wafer to be etched, causes polluting; Thereby aluminium oxide is not the tectal preferred material of spray head, produced and the good silicon (pyroconductivity: 149Wm of heat dispersion by contamination-free gradually in the industry -1K -1) or carborundum (pyroconductivity: 150Wm -1K -1) cover layer replaces.Yet, silicon with or carborundum react easily with etching gas, cause the spray head to shorten service life, to the problems referred to above, the spray head that etch resistance can better the yittrium oxide covering has appearred again.
With above-mentioned in the anti-etching purpose of the spray head mentioned similar, other surface of the work that is used for plasma etching generally all is coated with the yittrium oxide clad.
Yet the inventor finds that after the workpiece with yittrium oxide clad used a period of time, its surface had some pollutants, and this pollutant is not handled, and piles up to get up to drop easily on wafer to be etched, causes polluting, and finally reduces wafer manufacture efficient.
In view of this, be necessary to propose a kind of workpiece pollution substance treating method that is used for plasma etching in fact, to avoid the problems referred to above with yittrium oxide clad.
Summary of the invention
The purpose that the present invention realizes is to propose a kind of workpiece pollution substance treating method with yittrium oxide clad that is used for plasma etching, makes contaminated workpiece be able to again use.
For realizing above-mentioned purpose, the present invention provides a kind of workpiece pollution substance treating method with yittrium oxide clad that is used for plasma etching, comprising:
At least adopt the said workpiece of acid solution wiping;
Adopt the said workpiece of deionized water rinsing afterwards again.
Alternatively, adopt ultrasonic oscillation in the said deionized water rinsing process.
Alternatively, adopt high pressure de-ionized water to clean in the said deionized water rinsing process.
Alternatively, adopt in the high pressure de-ionized water cleaning process, comprise particle in the said deionized water.
Alternatively, said particle comprises at least a in yittrium oxide, aluminium oxide, zirconia, the silica.
Alternatively, the size range of said particle is 10nm-1mm.
Alternatively, the mass concentration of said particle is less than 50%.
Alternatively, adopt in the high pressure de-ionized water cleaning process, the pressure of said deionized water is 0.5MP-50MP.
Alternatively, the pressure of said deionized water is 1MP-30MP.
Alternatively, the pressure of said deionized water is 2MP-20MP.
Alternatively, the temperature of deionized water is more than 50 ℃ in the said deionized water rinsing process.
Alternatively, be added with isopropyl alcohol in the deionized water in the said deionized water rinsing process.
Alternatively, the temperature range of deionized water is 70 ℃-120 ℃ in the said deionized water rinsing process, and the mass concentration of said isopropyl alcohol is less than 90%.
Alternatively, the scope of the mass concentration of said isopropyl alcohol is 1%-80%.
Alternatively, the scope of the mass concentration of said isopropyl alcohol is 1%-50%.
Alternatively, said acid solution is at least a in nitric acid, HF acid, the hydrochloric acid.
Alternatively, said acid solution is a hydrochloric acid, and the mass concentration of HCl in deionized water is less than 90% in the said hydrochloric acid.
Alternatively, the scope of the mass concentration of HCl in deionized water is 1%-15% in the said hydrochloric acid.
Alternatively, the scope of the mass concentration of HCl in deionized water is 3%-10% in the said hydrochloric acid.
Alternatively, adopt before or after the said workpiece of acid solution wiping, also use the step of the said workpiece of alkaline solution wiping, said alkaline solution is KOH solution, NaOH solution, NH 4At least a in the OH solution.
Alternatively, said alkaline solution is NH 4OH solution, said NH 4NH in the OH solution 4The mass concentration of OH in deionized water is less than 50%.
Alternatively, said NH 4NH in the OH solution 4The scope of the mass concentration of OH in deionized water is 1%-30%.
Alternatively, said NH 4NH in the OH solution 4The scope of the mass concentration of OH in deionized water is 1%-5%.
Alternatively, adopt the said spray head step of alkaline solution wiping also to adopt the said spray head step of deionized water rinsing afterwards.
Alternatively; Adopt in the said workpiece step of employing deionized water rinsing of also carrying out after the said workpiece step of alkaline solution wiping, the temperature that adopt that ultrasonic oscillation, high pressure de-ionized water are cleaned, is added with isopropyl alcohol, deionized water in the deionized water is at least a in more than 50 ℃.
Compared with prior art; The present invention has the following advantages: the workpiece with yittrium oxide clad can produce some pollutants using after a period of time on it, and the main component of this pollutant is the compound between fluorine, yttrium, aluminium, carbon and the oxygen; And other contains the pollutant of metallic element such as copper, titanium etc.; Through using acid solution can remove the relatively poor pollutant of most of adhesive force, adopt deionized water rinsing afterwards after, can make contaminated spray head be able to again use;
Further, for few stronger pollutant of part adhesive force, in using the deionized water rinsing process, adopt ultrasonic oscillation or adopt high pressure de-ionized water to remove;
Further, for the extremely strong pollutant of indivedual adhesive force, adopt the deionized water that comprises particle to clean;
Further,, be added with isopropyl alcohol in the deionized water in the deionized water rinsing process, can strengthen the wetting capacity of deionized water, be easy to make pollutant to be cleaned removal on the pollutant surface because the wellability of isopropyl alcohol is very strong;
Further,, increase the temperature of water in the deionized water rinsing process because aluminum fluoride is dissolved in hot water, can make aluminum fluoride be base pollutant with face that yittrium oxide contact on become flexible, be easy to make pollutant to be cleaned removal;
Further, because yittrium oxide is dissolved in acid, thereby when removing pollutant, for preventing to damage the performance of yittrium oxide, the concentration of acid in deionized water needs strict control.
Description of drawings
Fig. 1 is the SEM test result of pollutant;
Fig. 2 is the EDS test result figure in Q zone among Fig. 1;
Fig. 3 is the flow chart of the processing method of the pollutant that provides of the embodiment of the invention.
The specific embodiment
Described in background technology, the workpiece with yittrium oxide clad can produce some pollutants using after a period of time on it; The inventor has carried out SEM test and EDS analysis of spectrum to this pollutant; The result is respectively like Fig. 1 and shown in Figure 2, and its main component is that fluorine, yttrium are the compound of base, carries out the present invention to propose to use acid solution to remove the relatively poor pollutant of most of adhesive force; After adopting deionized water rinsing afterwards, can make contaminated workpiece be able to again use.
For make above-mentioned purpose of the present invention, feature and advantage can be more obviously understandable, does detailed explanation below in conjunction with the accompanying drawing specific embodiments of the invention.Since focus on explanation principle of the present invention, therefore, drawing not in scale.
Below be example with the spray head, the Pollutant Treatment method flow diagram of the spray head that provides for the embodiment of the invention shown in Figure 3 with yittrium oxide clad.Below in conjunction with Fig. 3, introduce the implementation process of this processing method in detail.
Execution in step S11 at first adopts isopropyl alcohol (IPA) wiping to have the pollutant on the spray head of yittrium oxide clad.
The composition of this pollutant is noted earlier, is mainly the reaction of fluorine-containing etching gas and yittrium oxide clad produces in the plasma etch process fluorine, the yttrium compound for base.
The wetting capacity of isopropyl alcohol is very strong, after isopropyl alcohol is dissolved in the deionized water of subsequent step S12, can strengthen the wetting capacity that deionized water gets into pollutant and the interface of yttrium oxide layer, is easy in subsequent step cleaning and removing except that this pollutant.
Then execution in step S12 adopts deionized water rinsing.Be to strengthen pollutant removal, can 1 in this step) use ultrasonic waves for cleaning, 2) also can add isopropyl alcohol, 3 in the deionized water) temperature of deionized water also can be controlled at more than 50 ℃, also can 4) adopt high pressure de-ionized water to clean.Above-mentioned four kinds of methods can be used simultaneously, also can select a use, decide according to removal effect.
For 1), the hyperacoustic concrete frequency and the power of employing are decided according to removal effect.
For 2) because isopropyl alcohol is volatile, thereby, in the washed with de-ionized water step; The addition of isopropyl alcohol is difficult for excessive, the inventor finds that the temperature range of deionized water is 70 ℃-120 ℃ in this step; The mass concentration of said isopropyl alcohol in deionized water can not influence the function of yittrium oxide and can effectively remove pollutant, preferably less than 90% o'clock; The mass concentration scope of isopropyl alcohol is 1%-80%, and more preferably, the mass concentration scope of said isopropyl alcohol is 1%-50%.
For 3) because aluminum fluoride is dissolved in hot water, increase the temperature of water in the deionized water rinsing process, can make aluminum fluoride be base pollutant with face that yittrium oxide contact on become flexible, be easy to make pollutant to be cleaned removal;
For 4), when adopting high pressure de-ionized water to clean, the inventor finds; When pressure is 0.5MP-50MP, obvious to pollutant removal, preferably; The pressure of deionized water is 1MP-30MP, and more preferably, the pressure of deionized water is 2MP-20MP; Under the prerequisite of removing pollutant, the degree of infringement yittrium oxide is minimum.
In addition, adopt in the high pressure de-ionized water cleaning process, the extremely strong pollutant of adhesive force for some said methods all can't be removed can adopt 5) in deionized water, add particle.This particle can increase this pollutant and be stripped from the probability that gets off.In the practical implementation process, this particle can comprise one or more in yittrium oxide, aluminium oxide, zirconia or the silica, and particle size range is 10nm-1mm.Can also control simultaneously the content of this particle, the inventor finds that the mass concentration of this particle in said deionized water can adopt 1 with some less than 50% o'clock)-4) pollutant removal that can't remove of method.
Execution in step S13 adopts the acid solution wiping then.Acid solution in this step can be hydrochloric acid, nitric acid or HF acid, owing to be dissolved in acid as tectal yittrium oxide, even wiping, also needing needs strict control to the concentration control of acid.Adopt hydrochloric acid in the present embodiment, the inventor finds that the mass concentration of HCl in deionized water was less than 90% o'clock in this hydrochloric acid; Suitably the control wiping time, can promptly not damage the clad yittrium oxide, can remove pollutant again; Preferably; The mass concentration scope of HCl is 1%-15% in the hydrochloric acid, and more preferably, the mass concentration scope of HCl is 3%-10% in the hydrochloric acid.
Execution in step S14 adopts deionized water rinsing then.This step is identical with the S12 step.But can be from 1)-5) select one or more schemes the scheme.Carry out this step, can strengthen the removing function of the pollutant of peeling off from yttria surfaces.
Execution in step S15 adopts the alkaline solution wiping afterwards.Alkaline solution in this step can be KOH solution, NaOH solution or NH 4OH solution.
Adopt NH in the present embodiment 4OH solution, said NH 4NH in the OH solution 4The mass concentration of OH in deionized water be less than 50%, the acid solution that does not wash before can neutralizing, and in addition, this alkaline solution also can react with pollutant, makes pollutant dissolve in alkaline solution and is removed.Preferably, said NH 4NH in the OH solution 4The mass concentration scope of OH in deionized water is 1%-30%.More preferably, said NH 4NH in the OH solution 4The mass concentration scope of OH in deionized water is 1%-5%.
Then execution in step S16 adopts deionized water rinsing.This step is identical with the S12 step.But can be from 1)-5) select one or more schemes the scheme.Carry out this step, can strengthen the removing function of the pollutant of peeling off from yttria surfaces.
Execution in step S17 checks the spray head surface through above-mentioned processing afterwards, judges whether pollutant removal meets the requirements, if meet instructions for use, then disposes, if undesirable, execution in step S13-S17 again then is up to meeting the requirements.
Need to prove, the step S11-S17 of foregoing description, each step is finished, and can adopt the deionized water rinsing in the common process, so that the pollutant of peeling off from yttria surfaces in this step is washed.
Adopt the said spray head of alkaline solution wiping in the S15 step in the present embodiment; Also can, step S13 carry out before adopting the said spray head of acid solution wiping; After the acid solution wiping carried out can neutralize in the alkaline solution wiping process that formerly carries out the alkaline solution that does not wash fully.
Foregoing description be the flow process of the thing that depollutes of a standard, be suitable for batch processing.In the practical implementation process, can select part steps, remove but need carry out acid solution at least, adopt two steps of washed with de-ionized water afterwards.
What more than describe is to the handling process of the pollutant of the spray head that coats yittrium oxide, is used for plasma etching industrial for other, has the workpiece of yittrium oxide clad, the pollutant on focusing ring surface for example, and its handling process is identical with above-mentioned flow process.
To sum up; The present invention has the following advantages: the workpiece with yittrium oxide clad can produce some pollutants being used for plasma etching after a period of time on it, and the main component of this pollutant is the compound between fluorine, yttrium, aluminium, carbon and the oxygen; And other contains the pollutant of metallic element such as copper, titanium etc.; Through using acid solution can remove the relatively poor pollutant of most of adhesive force, adopt deionized water rinsing afterwards after, can make contaminated spray head be able to again use.
For few stronger pollutant of part adhesive force; In using the deionized water rinsing process, adopt 1) the use ultrasonic oscillation; 2) also can add isopropyl alcohol in the deionized water; The wetting capacity of isopropyl alcohol is very strong, can strengthen the wetting capacity of this deionized water to the spray head surface contaminant, thereby can be fast with this pollutant removal; 3) temperature of deionized water also can be controlled at more than 50 ℃; The temperature of rising deionized water solution; Can strengthen the solvability of the aqueous solution to the aluminum fluoride pollutant, make aluminum fluoride be base pollutant with face that yittrium oxide contact on become flexible, be easy to make pollutant to be cleaned removal; Also can 4) adopt high pressure de-ionized water to clean, little to the Yttrium oxide thin film extent of damage, reach the ability of peeling off pollutant from yttria surfaces simultaneously.
For the extremely strong pollutant of indivedual adhesive force, adopting 5) deionized water that comprises particle cleans.
Because yittrium oxide is dissolved in acid solution easily, thereby the concentration of acid in deionized water needs strict control, and when for example being hydrochloric acid, the mass concentration of HCl in deionized water is less than 90%.
Alkaline solution also carries out the deionized water rinsing step after cleaning said spray head step, in this deionized water rinsing step, can adopt above-mentioned 1)-5) step, strengthen the removing function of the pollutant of peeling off from yttria surfaces.
Though the present invention with preferred embodiment openly as above; But it is not to be used for limiting the present invention; Any those skilled in the art are not breaking away from the spirit and scope of the present invention; Can utilize the method and the technology contents of above-mentioned announcement that technical scheme of the present invention is made possible change and modification, therefore, every content that does not break away from technical scheme of the present invention; To any simple modification, equivalent variations and modification that above embodiment did, all belong to the protection domain of technical scheme of the present invention according to technical spirit of the present invention.

Claims (25)

1. a processing method that is used for the workpiece pollution thing with yittrium oxide clad of plasma etching is characterized in that, comprising:
At least adopt the said workpiece of acid solution wiping;
Adopt the said workpiece of deionized water rinsing afterwards again.
2. processing method according to claim 1 is characterized in that, adopts ultrasonic oscillation in the said deionized water rinsing process or adopts high pressure de-ionized water to clean.
3. processing method according to claim 2 is characterized in that, adopts in the high pressure de-ionized water cleaning process, comprises particle in the said deionized water.
4. processing method according to claim 3 is characterized in that, said particle comprises at least a in yittrium oxide, aluminium oxide, zirconia, the silica.
5. according to claim 3 or 4 described processing methods, it is characterized in that the size range of said particle is 10nm-1mm.
6. processing method according to claim 3 is characterized in that the mass concentration of said particle is less than 50%.
7. processing method according to claim 2 is characterized in that, adopts in the high pressure de-ionized water cleaning process, and the pressure of said deionized water is 0.5MP-50MP.
8. processing method according to claim 7 is characterized in that, the pressure of said deionized water is 1MP-30MP.
9. processing method according to claim 8 is characterized in that, the pressure of said deionized water is 2MP-20MP.
10. processing method according to claim 1 is characterized in that, the temperature of deionized water is more than 50 ℃ in the said deionized water rinsing process.
11. processing method according to claim 1 is characterized in that, is added with isopropyl alcohol in the deionized water in the said deionized water rinsing process.
12. processing method according to claim 11 is characterized in that, the temperature range of deionized water is 70 ℃-120 ℃ in the said deionized water rinsing process, and the mass concentration of said isopropyl alcohol is less than 90%.
13. processing method according to claim 12 is characterized in that, the mass concentration scope of said isopropyl alcohol is 1%-80%.
14. processing method according to claim 13 is characterized in that, the mass concentration scope of said isopropyl alcohol is 1%-50%.
15. processing method according to claim 1 is characterized in that, said acid solution is at least a in nitric acid, hydrofluoric acid, the hydrochloric acid.
16. processing method according to claim 15 is characterized in that, said acid solution is a hydrochloric acid, and the mass concentration of HCl in deionized water is less than 90% in the said hydrochloric acid.
17. processing method according to claim 16 is characterized in that, the mass concentration scope of HCl in deionized water is 1%-15% in the said hydrochloric acid.
18. processing method according to claim 17 is characterized in that, the mass concentration scope of HCl in deionized water is 3%-10% in the said hydrochloric acid.
19. processing method according to claim 1 is characterized in that, adopts before or after the said workpiece of acid solution wiping, also uses the step of the said workpiece of alkaline solution wiping, said alkaline solution is KOH solution, NaOH solution, NH 4At least a in the OH solution.
20. processing method according to claim 19 is characterized in that, said alkaline solution is NH 4OH solution, said NH 4NH in the OH solution 4The mass concentration of OH in deionized water is less than 50%.
21. processing method according to claim 20 is characterized in that, said NH 4NH in the OH solution 4The mass concentration scope of OH in deionized water is 1%-30%.
22. processing method according to claim 21 is characterized in that, said NH 4NH in the OH solution 4The mass concentration scope of OH in deionized water is 1%-5%.
23. processing method according to claim 19 is characterized in that, adopts the said workpiece step of alkaline solution wiping also to adopt the said workpiece step of deionized water rinsing afterwards.
24. processing method according to claim 23; It is characterized in that; Adopt in the said workpiece step of employing deionized water rinsing of also carrying out after the said workpiece step of alkaline solution wiping, the temperature that adopt that ultrasonic oscillation, high pressure de-ionized water are cleaned, is added with isopropyl alcohol, deionized water in the deionized water is at least a in more than 50 ℃.
25. processing method according to claim 1 is characterized in that, said workpiece is spray head or focusing ring.
CN201110454240.5A 2011-12-29 2011-12-29 Method for treating pollutant of workpiece provided with yttrium oxide coating layer Active CN102513314B (en)

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TW101129591A TWI580486B (en) 2011-12-29 2012-08-15 Treatment of contaminants in workpieces with yttrium oxide coating

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CN103628079A (en) * 2012-08-24 2014-03-12 宁波江丰电子材料有限公司 Cleaning method for tantalum focus rings
CN103903948A (en) * 2012-12-27 2014-07-02 中微半导体设备(上海)有限公司 Focusing ring improving uniformity of wafer edge etching rate
CN104028503A (en) * 2014-05-30 2014-09-10 邢台晶龙电子材料有限公司 Cleaning method of silicon raw materials
CN104312774A (en) * 2014-09-18 2015-01-28 高建 Cleaning liquid for parts with yttrium oxide coating and cleaning method
CN108144906A (en) * 2017-12-24 2018-06-12 苏州佳亿达电器有限公司 A kind of surface impurity removal process of LED mouldings

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CN103628079A (en) * 2012-08-24 2014-03-12 宁波江丰电子材料有限公司 Cleaning method for tantalum focus rings
CN103903948A (en) * 2012-12-27 2014-07-02 中微半导体设备(上海)有限公司 Focusing ring improving uniformity of wafer edge etching rate
CN103903948B (en) * 2012-12-27 2017-06-13 中微半导体设备(上海)有限公司 Improve the focusing ring of Waffer edge etch-rate uniformity
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CN104312774A (en) * 2014-09-18 2015-01-28 高建 Cleaning liquid for parts with yttrium oxide coating and cleaning method
CN108144906A (en) * 2017-12-24 2018-06-12 苏州佳亿达电器有限公司 A kind of surface impurity removal process of LED mouldings

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