CN115807231A - Cleaning process based on supercritical water and ultrasonic coupling - Google Patents
Cleaning process based on supercritical water and ultrasonic coupling Download PDFInfo
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- CN115807231A CN115807231A CN202111080506.4A CN202111080506A CN115807231A CN 115807231 A CN115807231 A CN 115807231A CN 202111080506 A CN202111080506 A CN 202111080506A CN 115807231 A CN115807231 A CN 115807231A
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- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a cleaning process based on supercritical water and ultrasonic coupling, which comprises the following steps: placing a workpiece to be processed in a processing cavity; introducing supercritical water into the treatment cavity to enable the workpiece to be treated to be in contact with the supercritical water; and applying ultrasonic energy to the treatment cavity, and performing supercritical water dissociation to form active hydrogen and hydroxyl radicals, wherein the active hydrogen can perform acid etching cleaning on the workpiece, and the hydroxyl radicals can perform quick repair on the surface of the cleaned workpiece. The cleaning process provided by the invention is used for cleaning the semiconductor workpiece, and can improve the roughness of the workpiece body and the combination degree of the workpiece body and a corrosion-resistant coating of a subsequent process; the cleaning process provided by the invention is used for cleaning a failed semiconductor workpiece, and can quickly repair the corrosion-resistant coating on the surface of the workpiece body while cleaning efficiently, so that the semiconductor workpiece is recovered as new.
Description
Technical Field
The invention relates to the field of semiconductor device cleaning, in particular to a cleaning process based on supercritical water and ultrasonic coupling.
Background
Semiconductor devices often have a need for plasma corrosion resistance, and therefore, it is desirable to coat or deposit a corrosion-resistant coating, such as Y, on the body of the semiconductor device 2 O 3 And the like yttrium based coatings.
In general, Y 2 O 3 These yttrium based coatings are all applied or grown on aluminum substrates. The roughness of the aluminum substrate directly affects important parameters such as the thickness and the surface appearance of the coating. The conventional way to control the roughness of aluminum substrates is sand blasting, and the main problem of this process is that sand particles such as alumina, zirconia, are embedded in the softer aluminum matrix and are difficult to remove by cleaning.
Furthermore, in addition to the problems of work-cleaning of the substrate, cleaning of the corrosion-resistant coating is also improved. It has been found that the structure of the coating material of a plasma-resistant component provided with a corrosion-resistant coating is often altered by prolonged plasma etching after the component has failed in use. The traditional polishing technology only physically removes the damaged coating and cannot repair the changed material structure after chemical etching.
Disclosure of Invention
An object of the present invention is to solve the problem of deep cleaning of semiconductor device parts, particularly how to improve the degree of bonding of a workpiece body to a subsequent process corrosion-resistant coating.
In order to achieve the above object, the present invention provides a cleaning process based on supercritical water and ultrasonic coupling, comprising:
placing a workpiece to be processed in a processing cavity;
introducing supercritical water into the treatment cavity to enable the workpiece to be treated to be in contact with the supercritical water;
and applying ultrasonic energy to the treatment cavity, and performing supercritical water dissociation to form active hydrogen and hydroxyl radicals, wherein the active hydrogen can perform acid etching cleaning on the workpiece, and the hydroxyl radicals can perform quick repair on the surface of the cleaned workpiece.
Optionally, the process further comprises:
and introducing an oxidant into the treatment cavity to assist in accelerating the cleaning process.
Optionally, the oxidant is selected from any one or combination of oxygen, ozone or hydrogen peroxide.
Optionally, the workpiece to be treated comprises any one of aluminum or alloy workpiece thereof, stainless steel or alloy workpiece thereof.
Optionally, the flow rate of the supercritical water is 10-100 sccm. .
Optionally, the power of the ultrasonic wave is 20 to 50W.
The invention also aims to solve the problem of how to clean the failed workpiece to be treated, and repair and renovate the workpiece to be treated while effectively cleaning the workpiece.
The workpiece to be processed is a semiconductor device which fails due to long-term operation in a plasma etching environment, and the semiconductor device comprises: the corrosion-resistant workpiece comprises a workpiece body, a corrosion-resistant coating covering the workpiece body, and a fluoride layer formed on the surface of the corrosion-resistant coating.
Optionally, the corrosion-resistant coating is at least one of an oxide of a rare earth element, an oxyfluoride.
Optionally, the rare earth element comprises at least one of Y, la, ce, pr, nd, sm, eu, gd, tb, dy, ho, er, tm, yb, lu.
Optionally, the corrosion-resistant coating is a yttria coating.
Optionally, the fluorinated layer is a Y-O-F layer.
Optionally, the flow rate of the supercritical water is 100sccm to 500sccm.
Optionally, the workpiece to be processed is a component of an inductively coupled plasma processing apparatus, and the component includes: at least one of a ceramic plate, an inner liner, a gas nozzle, a gas distribution plate, a gas pipe flange, an electrostatic chuck assembly, a cover ring, an insulating ring, or a plasma confinement device.
Optionally, the workpiece to be processed is a component of a capacitively-coupled plasma processing apparatus, and the component includes: at least one of a showerhead, an upper ground ring, a moving ring, a gas distribution plate, a gas baffle plate, an electrostatic chuck assembly, a lower ground ring, a cover ring, an insulator ring, or a plasma confinement device.
The invention has the advantages of
1) The cleaning agent is used for cleaning a workpiece body which is not coated with the corrosion-resistant coating, and active hydrogen generated by supercritical water decomposition can corrode and eliminate a protruding part in the workpiece body, so that uniform corrosion pits appear on the surface of the workpiece body, and the effect of increasing the roughness is achieved; furthermore, hydroxyl free radicals generated by supercritical water decomposition can generate hydroxyl on the surface of the workpiece body to modify the surface of the workpiece body, so that the combination degree of the corrosion-resistant coating and the workpiece body in the subsequent process is increased.
2) The active hydrogen dissociated from the supercritical water can rapidly decompose C-F organic matters attached to the surface of the corrosion-resistant coating (such as an yttrium oxide coating) on the workpiece body, corrode and eliminate a fluoride layer. Under the action of ultrasonic waves, hydrogen peroxide and oxygen generated by supercritical water decomposition can quickly repair Y 2 O 3 Surface, avoiding the formation of oxygen defects.
3) Compared with hydrofluoric acid and hydrochloric acid which are commonly used at present, supercritical water is environment-friendly as a cleaning medium and has higher controllability.
4) Compared with polishing and sand blasting, the cleaning method of the invention has no substance remaining on the surface of the substrate or the coating, thereby causing secondary pollution.
5) Compared with laser polishing, the cleaning method can uniformly treat the substrate or coating to be cleaned, avoid local high-temperature treatment and have small influence on the whole part.
Drawings
Fig. 1 is a flow chart of a cleaning process based on supercritical water and ultrasonic coupling according to the present invention.
Fig. 2 is a schematic view of the cleaning process of example 1.
FIG. 3 is a scanning electron microscope image of the workpiece body before and after the cleaning treatment in example 1.
Fig. 4 is a schematic view of the cleaning process of example 2.
FIG. 5 is a scanning electron microscope and electron energy spectra of the yttrium oxide coating of example 2 before and after cleaning.
The attached drawings are as follows:
a processing chamber 1, a workpiece body 10, an yttrium oxide coating 20 and a pollution layer 30.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it is to be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it should be noted that the terms "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, which are merely for convenience of description and simplification of description, and do not indicate or imply that the device or element referred to must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present invention.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; may be a mechanical connection; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
Supercritical water is water in which the density of water expanded by high temperature and the density of water vapor compressed by high pressure are exactly the same when the gas pressure and temperature reach a certain value (374 ℃,22 MPa). At this time, the liquid and the gas of water are completely mixed without distinction, and become a new fluid in a high-pressure and high-temperature state. Supercritical water has two significant characteristics. One is strong reactivity. Substances to be treated are put into supercritical water and charged with oxygen and hydrogen peroxide, and the substances are oxidized and hydrolyzed. The other characteristic is that the oil-soluble polymer can be mixed with oil and the like, and has wider fusion capability.
According to the invention, the characteristics of the supercritical water are utilized, and the supercritical water is coupled with the ultrasound on the basis, as shown in the formula (1), the instantaneous high temperature and high pressure generated by the ultrasound can further promote the decomposition of the supercritical water and generate active species such as a superoxide radical, a hydroxyl radical and the like, so that the acid corrosion cleaning capability of the aluminum substrate or the yttrium oxide coating is improved.
In the present invention, ultrasound is necessary, which can initiate a number of free radical reactions, such as active hydrogen to work the aluminum substrate, to remove the Y-O-F coating; the hydroxyl radical can assist in the in situ generation of oxidizing species (hydrogen peroxide and oxygen) for Y 2 O 3 And repairing the coating.
As shown in fig. 1, the cleaning process based on supercritical water and ultrasonic coupling of the present invention comprises the following steps:
step 1 (S1), a workpiece to be processed is placed in a processing chamber.
The workpiece to be processed comprises: the corrosion-resistant workpiece comprises a workpiece body, a corrosion-resistant coating covering the workpiece body, and a fluoride layer formed on the surface of the corrosion-resistant coating.
Or the workpiece to be treated is a metal workpiece, wherein the metal workpiece comprises any one of aluminum or an alloy workpiece thereof and stainless steel or an alloy workpiece thereof.
The corrosion-resistant coating is at least one of oxide and oxyfluoride of rare earth elements, and the rare earth elements comprise at least one of Y, la, ce, pr, nd, sm, eu, gd, tb, dy, ho, er, tm, yb and Lu. In this example, the corrosion-resistant coating is a yttria coating. The fluoride layer is a pollutant thin layer formed in a long-term plasma etching environment, usually covers the surface of the corrosion-resistant coating of the workpiece, some of the pollutant thin layer even reacts with the corrosion-resistant coating, the combination is tight, and the pollutant thin layer is usually difficult to completely remove by a physical method under the condition of not damaging the corrosion-resistant coating. In this example, the fluorinated layer is mainly a Y-O-F layer.
And 2 (S2) introducing supercritical water into the treatment cavity, so that the workpiece to be treated is in contact with the supercritical water.
And 3 (S3) applying ultrasonic energy to the treatment cavity, and dissociating supercritical water to form active hydrogen and hydroxyl radicals, wherein the active hydrogen can carry out acid etching cleaning on the workpiece, and the hydroxyl radicals can carry out quick repair on the surface of the cleaned workpiece.
In order to further accelerate the cleaning process, the cleaning process further comprises:
and introducing an oxidizing agent selected from any one or combination of oxygen, ozone or hydrogen peroxide into the treatment cavity.
The invention utilizes supercritical water and ultrasonic coupling technology to clean semiconductor devices, such as an aluminum matrix to be processed, the flow rate of the introduced supercritical water is 10-100 sccm, active hydrogen generated by supercritical water decomposition can corrode and eliminate the protruding part in the aluminum matrix, so that uniform corrosion pits appear on the surface of the aluminum matrix to be processed, namely the ability of increasing roughness is achieved. Hydroxyl radicals generated by supercritical water decomposition can generate hydroxyl on the surface of the aluminum substrate, so that the bonding degree of the coating and the substrate in the subsequent process is increased. The following description is given with reference to the examples.
Example 1 cleaning of a gas shower head
As shown in fig. 2, a gas shower head, which is an aluminum-based workpiece body 10, is provided as a workpiece to be processed. Alternatively, the aluminum substrate workpiece body 10 is simply rinsed first.
An aluminum substrate workpiece body 10 is arranged in a closed treatment cavity 1, and supercritical water is introduced into the treatment cavity 1. The flow rate of supercritical water is about 100sccm. Supercritical water can be sprayed in through a plurality of injection pipelines, and one or a plurality of spray headers can also be adopted to spray the supercritical water.
In order to accelerate the dissociation of supercritical water, ultrasonic energy is also applied in this example, and the power of the ultrasonic wave is 50w. Supercritical water is rapidly dissociated into active hydrogen and hydroxyl radicals under the action of ultrasonic waves. The active hydrogen radicals can carry out acid etching cleaning on the aluminum substrate workpiece body 10, and the hydroxyl radicals can be deposited on the surface of the aluminum substrate workpiece body 10, so that the aluminum substrate workpiece body is more easily combined with a corrosion-resistant coating coated by a subsequent process, is more compact in combination, and is not easy to fall off and lose efficacy.
In this example, scanning electron micrographs of the workpiece body 10 before and after processing are shown in fig. 3 a and b, where a is the workpiece body before processing (showerhead body); b is the processed workpiece body (spray header body), the black circle is the spray header air hole, and therefore, the roughness around the processed spray header air hole is obviously increased, and no impurity is introduced.
The supercritical water and ultrasonic coupling technology can also be used for cleaning the surface of the yttria coating and can quickly decompose C-F organic matters attached to the surface. The flow rate of introducing supercritical water is 100-500 sccm. Active hydrogen dissociated from supercritical water can corrode and eliminate Y-O-F, and hydrogen peroxide and oxygen generated by supercritical water decomposition can rapidly repair Y under the action of ultrasonic waves 2 O 3 Surface, avoiding the formation of oxygen defects. The following examples are given.
Example 2 cleaning and refurbishing of yttria coatings using oxidant assistance
As shown in fig. 4, providing a workpiece to be treated, which is a workpiece that fails after being eroded by a prolonged plasma etching environment, comprises: an aluminum substrate workpiece body 10 is coated with a dense plasma erosion resistant yttria coating 20, the yttria coating 20 having a thin contamination layer 30, such as a YOF layer, deposited on the surface thereof. The YOF thin layer is cleaned by a conventional physical method, and even if the YOF thin layer can be completely removed, the O element in the yttrium oxide coating can be lost, so that the yttrium oxide coating loses compactness, loses the function of resisting plasma corrosion and fails.
The workpiece to be treated is placed in a closed treatment cavity 1, and supercritical water is introduced into the treatment cavity 1. Flow rate of supercritical water is 100sccm. Supercritical water can be sprayed in through a plurality of injection pipelines, and one or a plurality of spray headers can also be adopted to spray the supercritical water. In order to accelerate the dissociation of supercritical water, ultrasonic energy is also applied in this example. The power of the ultrasonic wave was 20W. To assist in accelerating the cleaning process, at least one oxidizing agent, such as oxygen, ozone, or hydrogen peroxide, is also introduced into the chamber. Supercritical water is rapidly dissociated into active hydrogen and hydroxyl radicals under the action of ultrasonic waves and an oxidant. The active hydrogen is reacted with fluorinated Y 2 O 3 The coating is subjected to acid etching cleaning, and H generated in a micro area 2 O 2 Can be used for cleaning Y 2 O 3 And (4) rapidly repairing the surface, and oxidizing the fluoride layer on the surface again. As shown in the scanning electron microscope and the electron energy spectrogram before and after cleaning of the yttria coating of fig. 5, the scanning electron microscope shows that the morphology of the coating before and after cleaning is not obviously changed, and the disappearance of the fluorine element peak after cleaning in the electron energy spectrogram shows that the fluorine content in the coating is obviously reduced until eliminated.
Example 3 cleaning and refurbishing of yttria coatings without the use of oxidizer
In this example, an auxiliary reaction is not performed using an oxidizing agent in order to increase safety during cleaning due to the reactivity of supercritical water.
As shown in fig. 4, providing a workpiece to be treated, which is a workpiece that fails after being eroded through a prolonged plasma etching environment, comprises: an aluminum substrate workpiece body 10 is coated with a dense plasma erosion resistant yttria coating 20, the yttria coating 20 having a thin contamination layer 30, such as a YOF layer, deposited on the surface thereof.
And (3) placing the invalid workpiece to be treated in a closed treatment cavity 1, and introducing supercritical water into the treatment cavity 1. The flow rate of supercritical water was 500sccm. Supercritical water can be sprayed in through a plurality of injection pipelines, and one or a plurality of spray headers can also be adopted to spray the supercritical water. In order to accelerate the dissociation of supercritical water, ultrasonic energy is also applied in this example. The power of the ultrasonic wave was 50W. Supercritical water is rapidly dissociated into active hydrogen and hydroxyl radicals under the action of ultrasonic waves. The active hydrogen is reacted with fluorinated Y 2 O 3 The coating is subjected to acid etching cleaning, and H generated in a micro area 2 O 2 Can be used for cleaning Y 2 O 3 And (4) rapidly repairing the surface, and oxidizing the fluoride layer on the surface again.
The cleaning method provided by the invention is also suitable for cleaning the parts of the inductively coupled plasma processing device, and the parts comprise: at least one of a ceramic plate, an inner liner, a gas nozzle, a gas distribution plate, a gas pipe flange, an electrostatic chuck assembly, a cover ring, an insulating ring, or a plasma confinement device.
The cleaning method provided by the invention is also suitable for cleaning the parts of the capacitive coupling plasma processing device, and the parts comprise: at least one of a showerhead, an upper ground ring, a moving ring, a gas distribution plate, a gas baffle plate, an electrostatic chuck assembly, a lower ground ring, a cover ring, an insulator ring, or a plasma confinement device.
In conclusion, the invention provides a method for cleaning a semiconductor workpiece by using supercritical water and ultrasonic coupling technology, which can be used for cleaning the semiconductor workpiece, and not only improves the roughness of the surface of the workpiece body without introducing impurities; the active hydroxyl free radicals formed by the supercritical water dissociation can also modify the workpiece body, and the combination degree of the corrosion-resistant coating and the workpiece body in the subsequent process is increased. The supercritical water and ultrasonic coupling technology can also be used for cleaning and renewing invalid semiconductor workpieces, can quickly corrode a polluted layer by acid to achieve the aim of thorough cleaning, and can quickly repair Y 2 O 3 Surface, avoiding the formation of oxygen defects.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. Various modifications and alterations to this invention will become apparent to those skilled in the art upon reading the foregoing description. Accordingly, the scope of the invention should be determined from the following claims.
Claims (14)
1. A cleaning process based on supercritical water and ultrasonic coupling is characterized by comprising the following steps:
placing a workpiece to be processed in a processing cavity;
introducing supercritical water into the treatment cavity to enable the workpiece to be treated to be in contact with the supercritical water;
and applying ultrasonic energy to the treatment cavity, and dissociating supercritical water to form active hydrogen and hydroxyl radicals, wherein the active hydrogen can carry out acid etching cleaning on the workpiece, and the hydroxyl radicals can carry out quick repair on the surface of the cleaned workpiece.
2. The supercritical water and ultrasonic coupling based cleaning process of claim 1 further comprising:
and introducing an oxidant into the treatment cavity to assist in accelerating the cleaning process.
3. The supercritical water and ultrasonic coupling based cleaning process of claim 2 wherein the oxidant is selected from any one or combination of oxygen, ozone or hydrogen peroxide.
4. The supercritical water and ultrasonic coupling based cleaning process of claim 1 wherein the workpiece to be treated comprises any one of aluminum or its alloy workpiece, stainless steel or its alloy workpiece.
5. The supercritical water and ultrasonic coupling based cleaning process of claim 4, wherein the supercritical water is introduced at a flow rate of 10-100 sccm.
6. The cleaning process based on supercritical water and ultrasonic coupling of claim 4, wherein the power of the ultrasonic wave is 20-50W.
7. The supercritical water and ultrasonic coupling based cleaning process of claim 1 wherein the workpiece to be treated comprises: the corrosion-resistant workpiece comprises a workpiece body, a corrosion-resistant coating covering the workpiece body, and a fluoride layer formed on the surface of the corrosion-resistant coating.
8. The supercritical water and ultrasonic coupling based cleaning process of claim 7 where the corrosion resistant coating is at least one of an oxide of a rare earth element, an oxyfluoride.
9. The supercritical water and ultrasonic coupling based cleaning process of claim 8 wherein the rare earth elements comprise at least one of Y, la, ce, pr, nd, sm, eu, gd, tb, dy, ho, er, tm, yb, lu.
10. The supercritical water and ultrasonic coupling based cleaning process of claim 9 where the corrosion resistant coating is a yttria coating.
11. The supercritical water and ultrasonic coupling based cleaning process of claim 7 wherein the fluorinated layer is a Y-O-F layer.
12. The supercritical water and ultrasonic coupling based cleaning process of claim 7, wherein the supercritical water is introduced at a flow rate of 100-500 sccm.
13. The supercritical water and ultrasonic coupling based cleaning process of claim 1 wherein the workpiece to be treated is a component of an inductively coupled plasma treatment device, the component comprising: at least one of a ceramic plate, an inner liner, a gas nozzle, a gas distribution plate, a gas pipe flange, an electrostatic chuck assembly, a cover ring, an insulating ring, or a plasma confinement device.
14. The supercritical water and ultrasonic coupling based cleaning process of claim 1 wherein the workpiece to be treated is a component of a capacitively coupled plasma treatment device, the component comprising: at least one of a showerhead, an upper ground ring, a moving ring, a gas distribution plate, a gas baffle plate, an electrostatic chuck assembly, a lower ground ring, a cover ring, an insulator ring, or a plasma confinement device.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111080506.4A CN115807231A (en) | 2021-09-15 | 2021-09-15 | Cleaning process based on supercritical water and ultrasonic coupling |
| TW111127084A TWI847190B (en) | 2021-09-15 | 2022-07-19 | Cleaning process based on coupling of supercritical water and ultrasound |
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| CN202111080506.4A CN115807231A (en) | 2021-09-15 | 2021-09-15 | Cleaning process based on supercritical water and ultrasonic coupling |
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| CN1779920A (en) * | 2003-12-16 | 2006-05-31 | 气体产品与化学公司 | Method of Processing semiconductor components with dense processing fluids and ultrasonic energy |
| US20070240740A1 (en) * | 2006-04-13 | 2007-10-18 | Mcdermott Wayne T | Cleaning of contaminated articles by aqueous supercritical oxidation |
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| US7238085B2 (en) * | 2003-06-06 | 2007-07-03 | P.C.T. Systems, Inc. | Method and apparatus to process substrates with megasonic energy |
| US8486199B2 (en) * | 2011-07-22 | 2013-07-16 | Lam Research Ag | Ultrasonic cleaning method and apparatus |
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| US20070240740A1 (en) * | 2006-04-13 | 2007-10-18 | Mcdermott Wayne T | Cleaning of contaminated articles by aqueous supercritical oxidation |
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