CN115274389A - Method for removing metal pollution in semiconductor reaction cavity - Google Patents

Method for removing metal pollution in semiconductor reaction cavity Download PDF

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Publication number
CN115274389A
CN115274389A CN202110479085.6A CN202110479085A CN115274389A CN 115274389 A CN115274389 A CN 115274389A CN 202110479085 A CN202110479085 A CN 202110479085A CN 115274389 A CN115274389 A CN 115274389A
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fluorocarbon
copper
gas
metal
cavity
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郭盛
陈星建
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Advanced Micro Fabrication Equipment Inc Shanghai
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Advanced Micro Fabrication Equipment Inc Shanghai
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32431—Constructional details of the reactor
    • H01J37/32798—Further details of plasma apparatus not provided for in groups H01J37/3244 - H01J37/32788; special provisions for cleaning or maintenance of the apparatus
    • H01J37/32853—Hygiene
    • H01J37/32862—In situ cleaning of vessels and/or internal parts
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/67005—Apparatus not specifically provided for elsewhere
    • H01L21/67011—Apparatus for manufacture or treatment
    • H01L21/67017—Apparatus for fluid treatment
    • H01L21/67063—Apparatus for fluid treatment for etching
    • H01L21/67069—Apparatus for fluid treatment for etching for drying etching

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Power Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Epidemiology (AREA)
  • Public Health (AREA)
  • Plasma & Fusion (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Drying Of Semiconductors (AREA)

Abstract

The invention discloses a method for removing metal pollution in a semiconductor reaction cavity, which comprises the following steps: the inner side wall of the reaction cavity is provided with metal pollutants, fluorocarbon gas is introduced into the reaction cavity, fluorocarbon polymer is formed on the inner side wall of the reaction cavity by the fluorocarbon gas, and the metal pollutants adsorb the fluorocarbon polymer; and after adsorbing the fluorocarbon polymer by the metal pollutants, introducing oxidizing gas, and carrying out chemical reaction on the fluorocarbon polymer, the oxidizing gas and the metal pollutants to form gaseous compounds. The method provided by the invention can greatly reduce the content of metal pollutants in the cavity and improve the yield of products; metal pollutants on the inner wall of the cavity are removed on the premise of not opening the semiconductor cavity, and after the metal pollutants are removed, the cavity can continue to work without preventive maintenance, so that the time interval between processing processes is shortened; compared with the wiping or cleaning by chemical solution, the method for removing the pollutants by adopting the mode of introducing gas can save the cost.

Description

Method for removing metal pollution in semiconductor reaction cavity
Technical Field
The invention relates to the field of plasma etching, in particular to a method for removing metal pollution in a semiconductor reaction cavity.
Background
The development of logic circuit manufacture puts higher requirements on the metal pollution content on the surface of the wafer, and the equipment environment needs to be strictly controlled in order to ensure the product yield. Metal contamination in the semiconductor reaction chamber may originate from the wafer itself; or cross contamination during the installation or cleaning process of the cavity, introduced from the outside; corrosion of the equipment in normal service also results in an increase in the metal contaminant content of the chamber. The metal pollutants such as copper element have higher diffusion coefficient, and are easily transferred to the wafer from the reaction cavity in the process, so that the circuit communication error is caused, and the chip is invalid.
In the prior art, in order to remove metal pollutants on the wall of the reaction chamber, after the wafer is moved out of the reaction chamber after the process treatment is completed, equipment needs to be opened to directly wipe the inner wall, or the chamber needs to be taken out and cleaned by acid solution, so that the maintenance cost is high. Furthermore, the opened chamber requires a period of preventive maintenance (preventive maintenance) to continue processing the wafer.
Disclosure of Invention
The invention aims to provide a method for removing metal pollution in a semiconductor reaction cavity, which reduces the content of the metal pollution on the inner wall of the cavity on the premise of not opening the cavity.
In order to achieve the above object, the present invention provides a method for removing metal contamination in a semiconductor reaction chamber, comprising:
the inner side wall of the reaction cavity is provided with metal pollutants, fluorocarbon gas is introduced into the reaction cavity, fluorocarbon polymer is formed on the inner side wall of the reaction cavity by the fluorocarbon gas, and the metal pollutants adsorb the fluorocarbon polymer;
and after adsorbing the fluorocarbon polymer by the metal pollutant, introducing oxidizing gas, and carrying out chemical reaction on the fluorocarbon polymer, the oxidizing gas and the metal pollutant to form a gaseous compound.
Optionally, the fluorocarbon gas is a single gas, and the fluorocarbon gas is CxHyFzWherein x, y and z represent the atomic ratio of C, H, F, x > 0,y ≧ 0,z > 0.
Optionally, the fluorocarbon gas comprises CF4、CHF3、CH2F2、CH3F or C2HF5To (3) is provided.
Optionally, the fluorocarbon gas is a mixed gas containing both carbon and fluorine, but one of the mixed gases may contain only hydrocarbon or only fluorocarbon.
Optionally, the metal contaminant is copper and the gaseous compound comprises carbon dioxide and a fluoride of copper.
Optionally, the copper atom physically adsorbs the fluorocarbon polymer, and when an oxidizing gas is introduced, the oxidizing gas, the fluorocarbon polymer, and the copper atom chemically react to form carbon dioxide and a fluoride of copper.
Optionally, after the copper atoms physically adsorb the fluorocarbon polymer, the copper atoms also chemically react with the fluorocarbon polymer to form a copper fluorocarbon compound; after the oxidizing gas is introduced, the oxidizing gas and the copper fluorocarbon compound react chemically to form carbon dioxide and copper fluoride.
Optionally, the oxidizing gas comprises at least one of oxygen, ozone, and carbon dioxide.
Optionally, a step of exciting the fluorocarbon gas into plasma is included.
Optionally, a step of exciting the oxidizing gas into a plasma is included.
Optionally, the pressure in the reaction chamber is 5mtorr-500mtorr, and the radio frequency power is 50w-1000w.
Optionally, an external air pump is provided to pump out the gaseous compound in the reaction chamber after the oxidizing gas is introduced.
Optionally, the method of removing the metal contaminants comprises a plurality of cyclic processes, each cyclic process comprising: deposition to form fluorocarbon polymers, metal adsorption of fluorocarbon polymers, and formation of gaseous compounds.
Compared with the prior art, the invention has the beneficial effects that:
according to the method for removing the metal pollution in the semiconductor reaction cavity, firstly, fluorocarbon gas is introduced into the reaction cavity, the fluorocarbon gas reacts to form a fluorocarbon polymer, the fluorocarbon polymer is adsorbed by the metal pollutant, then oxidizing gas is introduced, the oxidizing gas reacts with the fluorocarbon polymer and the metal pollutant to form a gaseous compound, and the gaseous compound is pumped out of the reaction cavity through a suction pump. Therefore, metal pollutants on the inner wall of the cavity are removed on the premise of not opening the semiconductor cavity, after the metal pollutants are removed, the cavity can continue to work without preventive maintenance, and the time interval between machining processes is shortened.
Drawings
FIG. 1 is a flow chart of a method for removing metal contamination in a semiconductor reaction chamber according to the present invention;
FIG. 2 is a schematic view of the fluorocarbon polymer physically adsorbed by the metal contaminant in step S12 of FIG. 1;
FIG. 3 is a flow chart of another method for removing metal contamination in a semiconductor reaction chamber according to the present invention;
FIG. 4 is a schematic view of the metal contaminant chemisorbed fluorocarbon polymer in step S22 of FIG. 3;
FIG. 5 is a schematic view of the step S23 of FIG. 3 for removing the fluorocarbon compound
FIG. 6 is a schematic diagram illustrating the results of removing copper contamination from a plasma etch chamber according to an embodiment of the present invention;
FIG. 7 is a schematic diagram illustrating the result of removing copper contamination from a plasma etch chamber according to an embodiment of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. 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 a semiconductor reaction chamber, metal contamination is inevitable, which may originate from the wafer itself; or cross contamination during installation or cleaning of the reaction chamber, introduced from the outside; the corrosion of the equipment in normal service can also lead to the increase of the content of metal pollutants in the reaction cavity.
The invention provides a method for removing metal pollutants on the inner wall of a cavity without opening the cavity. And (2) introducing fluorocarbon gas and oxidizing gas into the cavity in sequence, and pumping out the gas after Deposition, adsorption and removal to the outside of the cavity to form a DAC (digital-to-analog converter) process, wherein the DAC process can rapidly and greatly reduce the content of metal pollutants on the inner wall of the cavity after a plurality of cycles.
The method provided by the invention can be suitable for various semiconductor reaction cavities needing to clean metal pollution on the inner wall of the cavity. The following description will be made by taking a plasma etching reaction chamber as an example.
Example 1
As shown in fig. 1, taking the removal of the metal copper contaminant in the plasma etching chamber as an example, the method provided by the present invention comprises:
s11, deposition (Deposition): and introducing fluorocarbon gas into the reaction cavity, and depositing the fluorocarbon gas on the inner side wall of the etching cavity to form a layer of fluorocarbon polymer.
In some embodiments, the fluorocarbon gas is a single gas, CxHyFzWherein x, y and z represent the atomic ratio of C, H, F, x is more than 0,y and is more than or equal to 0,z and is more than 0; the fluorocarbon gas is CF4、CHF3、CH2F2、CH3F or C2HF5One of (1);
in some embodiments, the fluorocarbon gas is a mixed gas containing both carbon and fluorine, but one of the mixed gases may contain only carbon hydrogen or only fluorocarbon; for example, the mixed gas may be CH4And C2HF5Mixed, or CF4And C2H6Mixing;
the deposition step further comprises exciting the fluorocarbon gas into a plasma under the following conditions: the pressure in the reaction chamber is 5-500mtorr, and the radio frequency power is 50-1000w.
S12, adsorption (adsorption): the fluorocarbon polymer is adsorbed by the metal copper contaminant in the plasma etching chamber.
In this example, there is only physisorption, and fig. 2 shows the reaction mechanism of this physisorption process. The fluorocarbon polymer has certain viscosity, so that the metal copper atoms on the inner wall of the cavity can physically adsorb the fluorocarbon polymer.
S13, clear: and introducing oxidizing gas to form gaseous compounds.
The oxidizing gas contains at least one of oxygen, ozone, and carbon dioxide.
The purging step further comprises exciting the oxidizing gas into a plasma under conditions selected from the group consisting of: the pressure of the cavity is 5-500mtorr, and the radio frequency power is 50-1000w.
In one embodiment, an external pump may be provided to pump the carbon dioxide and gaseous copper fluoride out of the plasma etch chamber after the oxidizing gas is introduced.
Copper + fluorocarbon polymer + oxidizing gas → fluoride of copper ≈ CO2↑(1)
As shown in the formula (1), the oxidizing gas chemically reacts with the physical adsorbed fluorocarbon polymer and the metal copper to generate carbon dioxide and gaseous copper fluoride, so that the metal copper pollutant is separated from the wall of the plasma etching chamber and released into the space inside the chamber. And the fluorides of the copper which generates the carbon dioxide and the gaseous state are gaseous, and can be pumped out of the reaction cavity through the air pump under the condition of not opening the cavity, the cavity can continue to work without preventive maintenance, and the time interval between the processing processes is shortened. The method provided by the invention can greatly reduce the content of metal pollutants in the cavity and improve the yield of products; compared with the traditional chemical solution wiping or cleaning, the method for removing the pollutants by adopting the gas introduction mode can save the cost.
Example 2
As shown in fig. 3, taking the removal of the metal copper contaminant in the plasma etching chamber as an example, the method provided by the present invention includes:
s21, deposition (Deposition): and introducing fluorocarbon gas into the reaction cavity, and depositing the fluorocarbon gas on the inner side wall of the etching cavity to form a layer of fluorocarbon polymer.
In some embodiments, the fluorocarbon gas is a single gas, CxHyFzWherein x, y and z represent C, H, F atomic ratio, x > 0,y ≧ 0,z > 0; the fluorocarbon gas is CF4、CHF3、CH2F2、CH3F or C2HF5One of (1);
in some embodiments, the fluorocarbon gas is a mixed gas containing both carbon and fluorine, but one of the mixed gases may contain only carbon hydrogen or only fluorocarbon; for example, the mixed gas may be CH4And C2HF5Mixed, or CF4And C2H6Mixing;
the deposition step further comprises exciting the fluorocarbon gas into a plasma under the following conditions: the pressure in the reaction chamber is 5-500mtorr, and the radio frequency power is 50-1000w.
S22, adsorption (adsorption): the fluorocarbon polymer is adsorbed by the metal copper contaminant in the plasma etching chamber.
In this embodiment, the method further includes chemisorption, which is premised on physisorption. The fluorocarbon polymer has a certain viscosity so that the metal copper atoms on the inner wall of the cavity can firstly physically adsorb the fluorocarbon polymer. Then, as shown in the formula (2), part of the metal copper can also continuously adsorb the fluorocarbon polymer. Fig. 4 shows the reaction mechanism of this chemisorption process. Specifically, because the cavity is in a high-vacuum and high-energy environment, part of the carbon-fluorine bonds of the physically adsorbed fluorocarbon polymer are activated and broken, the fluorocarbon polymer is bonded with metal copper and fluorine atoms, and a chemical reaction is carried out to generate the fluorocarbon copper compound.
Copper + fluorocarbon Polymer → Carbone copper Compound (2)
S23, clear: and introducing oxidizing gas to form gaseous compounds.
The oxidizing gas contains at least one of oxygen, ozone, and carbon dioxide.
The purging step further comprises exciting the oxidizing gas into a plasma under conditions selected from the group consisting of: the pressure of the cavity is 5-500mtorr, and the radio frequency power is 50-1000w.
In one embodiment, an external pump may be provided to pump carbon dioxide and gaseous copper fluoride out of the plasma etch chamber after the oxidizing gas is introduced.
Fluorocarbon copper compound + oxidizing gas → fluoride ↓ + CO of copper2↑(3)
As shown in formula (3), the oxidizing gas and the fluorocarbon copper compound react chemically to generate carbon dioxide and gaseous copper fluoride, so that the metal copper pollutant is separated from the wall of the plasma etching chamber and released into the space inside the chamber. FIG. 5 shows the reaction mechanism of this scavenging process, in which CuFmRepresents the fluoride of copper, m represents the number of fluorine atoms, and m is more than 0. Besides the beneficial effects of shortening the processing time, improving the product yield, saving the cost and the like, the embodiment has the advantages that a large amount of fluorine atoms exist in the cavity, so that under the action of the oxidizing gas, metal copper pollutants and the fluorine atoms are bonded more easily to generate gaseous copper fluoride, and the metal copper is further promoted to be separated from the inner wall of the cavity. Carbon dioxide and gaseous copper fluoride can be pumped out of the reaction chamber by a suction pump.
The method for removing metal pollutants provided by the invention is adopted to carry out verification experiments as follows:
selecting a plasma etching cavity polluted by metal copper, respectively operating the production process (production recipe) for 50 hours and the DAC process (DAC recipe) provided by the invention for 50 hours, and testing the amount of the residual copper pollutants in the reaction cavity to verify the cleaning effect of the invention.
The above DAC process was cycled several times for 50 hours.
As shown in fig. 6, in the initial state, the content of copper atoms per square centimeter of the inner wall of the plasma etching chamber is 17.09E10, after 50 hours of the simulated operation production process on the wafer, the content of copper atoms per square centimeter is 20.34E10, the production process is continuously operated without opening the chamber, copper pollutants in the chamber always exist, and the copper pollutants are increased. After the DAC process is circularly operated for 50 hours, the copper atom content per square centimeter is 0.91E10, and the requirement of a normal working environment is met when the copper atom content per square centimeter of the inner wall of the reaction cavity is lower than 1E10, which shows that the DAC process provided by the invention has a good removing effect.
In addition, in the production process (production recipe), the copper pollutants in the reaction chamber are bombarded in the process of bombarding the wafer by the plasma, one part of the bombarded copper pollutants fall on the surface of the wafer, the other part of the bombarded copper pollutants are extracted out of the reaction chamber, and the amount of the extracted copper pollutants out of the reaction chamber is positively correlated with the amount of the copper pollutants falling on the wafer. In the DAC process, copper pollutants on the side wall of the reaction cavity are formed into gaseous copper fluoride, part of the copper fluoride is adsorbed on the surface of the wafer, part of the copper fluoride is extracted out of the reaction cavity, and the amount of the copper pollutants extracted out of the reaction cavity is positively correlated with the amount of the copper pollutants adsorbed on the wafer. Therefore, the removal effect of the copper pollution in the reaction cavity can be verified by the copper pollution amount taken away from the surface of each wafer. Before the production process and the DAC process are operated, a wafer is respectively placed on the base to receive copper pollutants released into the cavity from the inner wall of the cavity and then falling on the base. And after the operation is finished, the copper pollutant content on the two wafers is respectively detected. As shown in fig. 7, 2.93E10 copper atoms per square centimeter and 52.86E10 copper atoms per square centimeter are used for carrying by the wafer in the DAC process, which indicates that the amount of copper pollution discharged by the DAC process is large, and further indicates that the DAC process provided by the present invention can separate a large amount of copper pollutants from the inner wall of the cavity, and the efficiency of removing copper pollution is about 18 times that of the common production process.
In summary, the present invention provides a method for removing metal contaminants from the inner wall of a chamber without opening the chamber, wherein fluorocarbon gas is introduced to deposit on the inner wall of the chamber to form a fluorocarbon polymer layer, the fluorocarbon polymer adsorbs metal on the wall of the reaction chamber, and then oxidizing gas is introduced to generate gaseous compounds, so that the metal contaminants are separated from the inner wall of the chamber. The method provided by the invention does not need preventive maintenance, improves the production efficiency, and has low cost and good removal effect.
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 (13)

1. A method for removing metal contamination in a semiconductor reaction chamber, comprising:
the inner side wall of the reaction cavity is provided with metal pollutants, fluorocarbon gas is introduced into the reaction cavity, fluorocarbon polymer is formed on the inner side wall of the reaction cavity by the fluorocarbon gas, and the metal pollutants adsorb the fluorocarbon polymer;
and after adsorbing the fluorocarbon polymer by the metal pollutants, introducing oxidizing gas, and carrying out chemical reaction on the fluorocarbon polymer, the oxidizing gas and the metal pollutants to form gaseous compounds.
2. The method of claim 1, wherein the fluorocarbon gas is a single gas and the fluorocarbon gas is CxHyFzWherein x, y and z represent the atomic ratio of C, H, F, x > 0,y ≧ 0,z > 0.
3. The method of claim 2, wherein the fluorocarbon gas comprises CF4、CHF3、CH2F2、CH3F or C2HF5One kind of (1).
4. The method of claim 1, wherein the fluorocarbon gas is a mixed gas containing both carbon and fluorine, but one of the mixed gases may contain only hydrocarbon or only fluorocarbon.
5. The method of claim 1, wherein the metal contaminant is copper and the gaseous compound comprises carbon dioxide and a fluoride of copper.
6. The method of claim 5, wherein the copper atoms physically adsorb the fluorocarbon polymer, and wherein the oxidizing gas, the fluorocarbon polymer, and the copper atoms chemically react to form carbon dioxide and copper fluorides when the oxidizing gas is introduced.
7. The method of claim 5, wherein after the copper atom physically adsorbs the fluorocarbon polymer, the copper atom further chemically reacts with the fluorocarbon polymer to form a fluorocarbon copper compound; after the oxidizing gas is introduced, the oxidizing gas and the copper fluorocarbon compound react chemically to form carbon dioxide and copper fluoride.
8. The method of claim 1, wherein the oxidizing gas comprises at least one of oxygen, ozone, and carbon dioxide.
9. The method of claim 1, comprising the step of exciting the fluorocarbon gas into a plasma.
10. The method of claim 1, comprising the step of exciting the oxidizing gas into a plasma.
11. The method of claim 1, wherein the pressure in the reaction chamber is between 5mtorr and 500mtorr and the radio frequency power is between 50w and 1000w.
12. The method of claim 1, wherein an external pump is provided to pump out gaseous compounds from the reaction chamber after the oxidizing gas is introduced.
13. The method of claim 1, wherein the method of removing the metal contaminants comprises a multiple cycle process, each cycle process comprising: deposition to form fluorocarbon polymers, adsorption of metal contaminants to fluorocarbon polymers, and formation of gaseous compounds.
CN202110479085.6A 2021-04-30 2021-04-30 Method for removing metal pollution in semiconductor reaction cavity Pending CN115274389A (en)

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CN202110479085.6A CN115274389A (en) 2021-04-30 2021-04-30 Method for removing metal pollution in semiconductor reaction cavity

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CN115274389A true CN115274389A (en) 2022-11-01

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