CN113690130A - Wet cleaning process - Google Patents

Wet cleaning process Download PDF

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Publication number
CN113690130A
CN113690130A CN202111251459.5A CN202111251459A CN113690130A CN 113690130 A CN113690130 A CN 113690130A CN 202111251459 A CN202111251459 A CN 202111251459A CN 113690130 A CN113690130 A CN 113690130A
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Prior art keywords
substrate
cleaning process
cleaning
wet
ozone
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CN202111251459.5A
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Chinese (zh)
Inventor
唐斌
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Guangzhou Yuexin Semiconductor Technology Co Ltd
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Guangzhou Yuexin Semiconductor Technology Co Ltd
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Priority to CN202111251459.5A priority Critical patent/CN113690130A/en
Publication of CN113690130A publication Critical patent/CN113690130A/en
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    • 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
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02041—Cleaning
    • H01L21/02057—Cleaning during device manufacture
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B7/00—Cleaning by methods not provided for in a single other subclass or a single group in this subclass
    • 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
    • H01L21/67028—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like
    • H01L21/6704—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like for wet cleaning or washing

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Cleaning Or Drying Semiconductors (AREA)

Abstract

The invention provides a wet cleaning process, which comprises the following steps: providing a substrate, wherein the substrate is provided with a first surface and a second surface which are oppositely arranged; performing an SPM cleaning process for removing organics and part of metal ions on the first and second surfaces of the substrate; performing an SC1 cleaning process to remove particles and part of metal ions on the first surface and the second surface of the substrate; performing an SC2 cleaning process for removing remaining metal ions on the first and second surfaces of the substrate; performing at least one ozone oxidation process for removing residual particles on the first surface and the second surface of the substrate; an HF cleaning process is performed for removing the oxide layer on the first and second surfaces of the substrate. Ozone is introduced into the pure water tank before the HF cleaning process, other impurities or chemical liquid are not introduced into the wet cleaning process, the cleaning cost is low, and the method can be popularized in a large scale.

Description

Wet cleaning process
Technical Field
The invention relates to the technical field of semiconductors, in particular to a wet cleaning process.
Background
The substrate cleaning technology is one of the most important factors affecting the yield of the substrate product, the quality and the reliability of the device.
The main purpose of cleaning is to remove the surface contamination of the substrate, such as particles, organic matter and metal ions. Before the substrate enters the relevant process, the cleaning degree of the substrate is ensured, so that before the relevant process, chemical cleaning is required, and ultrapure water cleaning enables the surface of the substrate to reach the required cleanliness, so that the manufactured semiconductor device can have the designed electrical characteristics. However, in advanced integrated circuit fabrication, cleaning silicon surface particles is most difficult due to the size, environment, and process conditions required for the particles on the substrate surface.
One type of scrubber cleaning in the prior art is to remove particulate contamination by pressurizing pure water with a gas to render it fluid. However, during integrated circuit fabrication, it has often been found that certain particulate contaminants are difficult to remove by the above methods, particularly very fine (less than 0.16um diameter) particulate contaminants. As integrated circuit fabrication advances today, removal of particulate contamination is one of the most important factors in device quality and reliability. The silicon dioxide is diffused and grown on the surface of the substrate through a furnace tube, and then the silicon dioxide film on the surface is cleaned through a wet hydrofluoric acid aqueous solution (according to the volume ratio required by the process), so that particles on the surface of the substrate are removed.
In the prior art, RCA cleaning mainly comprises SPM, HF, APM and HPM cleaning liquids to remove organic contamination on the surface of a silicon wafer, and because organic substances cover part of the surface of the silicon wafer, an oxide film and the contamination related to the oxide film are difficult to remove; then dissolving the oxide film, and finally removing the contamination of particles, metals and the like.
In the RCA cleaning and the Scrubber cleaning using the conventional process, particles which do not clean the surface of the substrate are often encountered, resulting in abnormal substrate yield.
Disclosure of Invention
The invention aims to provide a wet cleaning process to solve the problem of abnormal substrate yield caused by particles which cannot be cleaned off from the surface of a substrate.
In order to solve the above technical problems, the present invention provides a wet cleaning process, comprising:
providing a substrate, wherein the substrate is provided with a first surface and a second surface which are oppositely arranged;
performing an SPM cleaning process for removing organics and part of metal ions on the first and second surfaces of the substrate;
performing an SC1 cleaning process for removing particles and a portion of metal ions on the first and second surfaces of the substrate;
performing an SC2 cleaning process for removing remaining metal ions on the first and second surfaces of the substrate;
performing at least one ozone oxidation process for removing residual particles on the first surface and the second surface of the substrate;
an HF cleaning process is performed for removing the oxide layer on the first and second surfaces of the substrate.
Optionally, the ozone aqueous solution in the ozone oxidation process is obtained by introducing ozone into an aqueous solution, and the concentration of the ozone aqueous solution is 1ng/L-1 g/L.
Optionally, the process time of the ozone oxidation process is 10 seconds to 1200 seconds.
Optionally, the process temperature of the ozone oxidation process is 20-27 ℃.
Optionally, the removing of the oxide layer on the first surface and the second surface of the substrate by the HF cleaning process includes a native oxide layer on the first surface and the second surface of the substrate, and further includes oxide layers generated in an SC1 cleaning process, an SC2 cleaning process, and an ozone oxidation process.
Optionally, the ratio of HF to water in the HF cleaning process is 1:1 to 1: 500.
Optionally, after the HF cleaning process, the substrate is subjected to a drying process.
Optionally, the drying process is an isopropanol drying process or a spin-drying process.
Optionally, the process temperature of the isopropanol drying process is 25-150 ℃, and the process temperature of the spin-drying process is 23-27 ℃.
Optionally, the wet cleaning process is performed after the ion implantation.
Compared with the prior art, the invention has the beneficial effects that:
in the wet cleaning process provided by the invention, ozone is introduced into a pure water tank before the HF cleaning process, a water solution containing a considerable amount of ozone oxidizes silicon on the surface of a substrate to change the silicon into silicon dioxide, the silicon dioxide on the surface of the substrate is removed by a hydrofluoric acid water solution, and the times of cleaning silicon and ozone are set to wash away particulate stains which cannot be removed by SC1 and SC 2. The wet cleaning process does not introduce other impurities or chemical liquid, has low cleaning cost and can be popularized in a large scale. Therefore, the problem of abnormal substrate yield caused by particles which cannot be cleaned on the surface of the substrate can be solved.
Drawings
FIG. 1 is a flow diagram of a wet clean process of an embodiment of the present invention;
FIGS. 2 to 4 are schematic diagrams illustrating the principle of ozone oxidation according to an embodiment of the present invention;
FIG. 5 is a schematic view of a wet cleaning apparatus according to an embodiment of the present invention;
in the figure, the position of the upper end of the main shaft,
10-a substrate; 11-an oxide layer; 12-microparticles; 20-a wet cleaning device; 21-SPM process tank; 22-a first pure water tank; 23-SC 1 cleaning the process tank; 24-a second pure water tank; 25-SC 2 cleaning the process tank; 26-an ozone oxidation process tank; 27-HF cleaning process tank; 28-a third pure water tank; 29-drying means.
Detailed Description
The wet cleaning process proposed by the present invention is further described in detail with reference to the accompanying drawings and specific examples. Advantages and features of the present invention will become apparent from the following description and from the claims. It is to be noted that the drawings are in a very simplified form and are not to precise scale, which is merely for the purpose of facilitating and distinctly claiming the embodiments of the present invention.
Specifically, referring to fig. 1, fig. 1 is a flow chart of a wet cleaning process according to an embodiment of the invention. As shown in fig. 1, the present embodiment provides a wet cleaning process for integrated circuit manufacturing, comprising:
step S10, providing a substrate, wherein the substrate is provided with a first surface and a second surface which are oppositely arranged;
step S20, performing an SPM cleaning process for removing organics and a portion of metal ions on the first and second surfaces of the substrate;
step S30, performing an SC1 cleaning process for removing particles and a part of metal ions on the first surface and the second surface of the substrate;
step S40, performing an SC2 cleaning process for removing the remaining metal ions on the first surface and the second surface of the substrate;
step S50, performing at least one ozone oxidation process for removing residual particles on the first surface and the second surface of the substrate;
step S60, an HF cleaning process is performed for removing the oxide layer on the first surface and the second surface of the substrate.
The wet cleaning process is performed after an ion implantation process, for example, an ion implantation process such as an N-Well (N Well) or a P-Well (P Well). The substrate has been subjected to an ion implantation process, so that a high temperature furnace process cannot be used, and thus a normal temperature ozone oxidation process is employed.
In step S10, the substrate may be a silicon substrate, a silicon germanium substrate, a silicon carbide substrate, or a silicon-on-insulator (SOI) substrate, and the present embodiment does not limit the material and structure of the substrate. In addition, a device structure (not shown) may be formed in the substrate, and the device structure may be a device structure formed in a front-end semiconductor process, such as a MOS transistor.
In step S20, the SPM cleaning process solution includes H2SO4And H2O2(ii) a The process temperature of the SPM cleaning process is, for example, 120 ℃ to 150 ℃; the SPM cleaning process has high oxidizing capacity, can oxidize metal and dissolve in cleaning liquid, and can oxidize organic matter to produce CO2And H2O。
Between the step S20 and the step S30, a step S21 is further included for performing a first pure water cleaning process, which must be performed before proceeding to the next chemical cleaning processAnd removing the chemical liquid remained on the substrate in the previous chemical cleaning process. That is, performing the first pure water cleaning process can remove H remaining on the substrate 102SO4And H2O2And (3) solution.
In step S30, the SC1 cleaning process is used to remove particles and a portion of metal ions on the first and second surfaces of the substrate. The solution in the SC1 cleaning process comprises NH4OH、H2O2And H2O; the process temperature of the SC1 cleaning process is, for example, 30-80 ℃, because of H2O2Has a natural oxide film (SiO) on the surface of the substrate2) The particles are hydrophilic, and the surface of the substrate and the particles can be soaked by the cleaning solution. Because the natural oxide layer on the surface of the substrate is NH with the Si on the surface of the substrate 4OH is corroded, so that particles attached to the surface of the substrate fall into the cleaning solution, and the purpose of removing the particles is achieved. At NH4OH etching the substrate surface while H2O2And a new oxide film is formed on the surface of the oxide substrate.
Between the step S30 and the step S40, a step S31 is further included for performing a second pure water cleaning process capable of removing residual NH on the surface of the substrate in the SC1 cleaning process4OH、H2O2And (3) solution.
In step S40, the SC2 cleaning process is used to remove the remaining metal ions on the first and second surfaces of the substrate. The solution of the SC2 cleaning process is HCl, H2O2And H2O; the SC2 cleaning process has a process temperature of 65-85 ℃ for example, and is used for removing metal contamination of sodium, iron, magnesium and the like on the surface of the substrate. The SC2 cleaning process removes Fe and Zn at room temperature.
In step S50, the ozone oxidation process has an aqueous ozone solution concentration of, for example, 1ng/L to 1 g/L. The process time of the ozone oxidation process is, for example, 1 second to 3600 seconds, and further, the process time of the ozone oxidation process is, for example, 10 seconds to 1200 seconds. The process temperature of the ozone oxidation process is, for example, 20 ℃ to 27 ℃. The ozone oxidation process may be performed once or multiple times by setting the number of silicon and ozone cleans to wash away particulate contaminants that cannot be removed by SC1 and SC 2.
FIGS. 2 to 4 are schematic diagrams illustrating the principle of ozone oxidation according to an embodiment of the present invention; the chemical reaction formula for removing the residual particles by the ozone oxidation process is as follows:
Figure DEST_PATH_IMAGE002
(1)
Figure DEST_PATH_IMAGE004
(2)
Figure DEST_PATH_IMAGE006
(3)
as shown in fig. 2, particles 12 are on the substrate 10, and the particles 12 are located above the substrate 10. As shown in fig. 3, silicon on the surface of the substrate 10 is oxidized into silicon dioxide in the substrate 10 in the ozone environment, and as shown in fig. 4, the silicon dioxide on the surface of the substrate is removed by the hydrofluoric acid aqueous solution, so that the particles 12 on the surface of the substrate 10 are removed. The method for removing the particles by adopting the ozone oxidation process can achieve excellent cleaning effect, and in addition to the conventional ozone for removing the particles in the whole process, other impurities or chemical liquid are not introduced, so that the cleaning cost is low, and the method can be popularized in a large scale.
In step S60, the HF cleaning process removes the oxide layer on the first and second surfaces of the substrate including a native oxide layer on the first and second surfaces of the substrate and the oxide layer generated in the SC1 cleaning process, the SC2 cleaning process, and the ozone oxidation process. The solution of the HF cleaning process includes HF and deionized water (DIW), the volume ratio of HF to DIW is, for example, 1:1 to 1:500, and the cleaning time of the HF cleaning process is, for example, 5 seconds to 600 seconds.
Step S61 is further included after step S60, and a third pure water cleaning process is performed, which can remove the HF solution remaining on the surface of the substrate in the HF cleaning process.
After the HF cleaning process, there is further included a step S52 of performing a drying process on the substrate.
In step S62, the drying process is an isopropyl alcohol drying process or a spin-drying process. The process temperature of the isopropanol drying process is 25-150 ℃, the process temperature of the spin-drying process is 23-27 ℃, and the gas adopted in the spin-drying process is nitrogen (N), for example2）。
FIG. 5 is a schematic view of a wet cleaning apparatus according to an embodiment of the present invention; as shown in fig. 5, the present embodiment further provides a wet cleaning apparatus 20, where the wet cleaning apparatus 20 includes a process tank and a pure water tank, the process tank includes an SPM process tank 21, an SC1 cleaning process tank 23, an SC2 cleaning process tank 25, the ozonation process tank 26, an HF cleaning process tank 27, and a drying apparatus 29, and the SPM process tank 21 is configured to remove organic matters and a part of metal ions on the first surface and the second surface of the substrate; the SC1 cleaning process tank 23 is used for executing an SC1 cleaning process to remove particles and partial metal ions on the first surface and the second surface of the substrate; the SC2 cleaning process tank 25 is used for performing an SC2 cleaning process to remove residual metal ions on the first surface and the second surface of the substrate; the ozone oxidation process tank 26 is used for performing an ozone oxidation process to remove particles on the first surface and the second surface of the substrate; the HF cleaning process tank 27 is used to perform an HF cleaning process to remove the oxide layer on the first and second surfaces of the substrate; the drying device 29 is used to dry the substrate 10. The pure water tanks include a first pure water tank 22, a second pure water tank 24 and a third pure water tank 28, the first pure water tank 22 is located between the SPM process tank 21 and the SC1 cleaning process tank 23, and the first pure water tank 22 is used for removing residual H on the substrate 102SO4And H2O2And (3) solution. The second pure water tank 24 is positioned between the SC1 cleaning process tank 23 and the SC2 cleaning process tank 25, and the second pure water tank 24 is used for removing residual NH on the surface of the substrate in the SC1 cleaning process4OH、H2O2And (3) solution. What is needed isThe third pure water tank 28 is located between the HF cleaning process tank 27 and the drying device 29, and the third pure water tank 28 is used for removing the HF solution remaining on the surface of the substrate in the HF cleaning process. The substrate 10 sequentially passes through the SPM process tank 21, the first pure water tank 22, the SC1 cleaning process tank 23, the second pure water tank 24, the SC2 cleaning process tank 25, the ozone oxidation process tank 26, the HF cleaning process tank 27, and the third pure water tank 28 to complete the substrate cleaning process, so as to remove organic substances, particles, and metal ions on the substrate 10, and finally, the substrate 10 is dried by the drying device 29.
The process tank of the wet cleaning apparatus 20 is further provided with a sensor (not shown in the figure) for detecting the concentration of the solution in the process tank to ensure the stability of the concentration of the solution in the process tank.
In summary, in the wet cleaning process provided by the embodiment of the present invention, ozone is introduced into the pure water tank before the HF cleaning process, the aqueous solution containing a considerable amount of ozone oxidizes silicon on the surface of the substrate to change it into silicon dioxide, the silicon dioxide on the surface of the substrate is removed by the aqueous solution of hydrofluoric acid, and the number of times of cleaning silicon and ozone is set to wash off the particulate contamination which cannot be removed by SC1 and SC 2. The wet cleaning process does not introduce other impurities or chemical liquid, has low cleaning cost and can be popularized in a large scale. Therefore, the problem of abnormal substrate yield caused by particles which cannot be cleaned on the surface of the substrate can be solved.
The above description is only for the purpose of describing the preferred embodiments of the present invention, and is not intended to limit the scope of the present invention, and any variations and modifications made by those skilled in the art based on the above disclosure are within the scope of the appended claims.

Claims (10)

1. A wet cleaning process, comprising:
providing a substrate, wherein the substrate is provided with a first surface and a second surface which are oppositely arranged;
performing an SPM cleaning process for removing organics and part of metal ions on the first and second surfaces of the substrate;
performing an SC1 cleaning process for removing particles and a portion of metal ions on the first and second surfaces of the substrate;
performing an SC2 cleaning process for removing remaining metal ions on the first and second surfaces of the substrate;
performing at least one ozone oxidation process for removing residual particles on the first surface and the second surface of the substrate;
an HF cleaning process is performed to remove the oxide layer on the first and second surfaces of the substrate.
2. The wet cleaning process according to claim 1, wherein the ozone oxidation process employs an aqueous ozone solution in which ozone is introduced, and the concentration of the aqueous ozone solution is 1ng/L to 1 g/L.
3. The wet cleaning process according to claim 1 or 2, wherein the process time of the ozone oxidation process is 10 seconds to 1200 seconds.
4. The wet cleaning process according to claim 1 or 2, wherein the process temperature of the ozone oxidation process is 20 ℃ to 27 ℃.
5. The wet cleaning process of claim 1, wherein the HF cleaning process removes the oxide layer on the first and second surfaces of the substrate including a native oxide layer on the first and second surfaces of the substrate, further comprising oxide layers generated in the SC1 cleaning process, the SC2 cleaning process, and the ozone oxidation process.
6. The wet cleaning process according to claim 1 or 5, wherein the ratio of HF to water in the HF cleaning process is from 1:1 to 1: 500.
7. The wet cleaning process of claim 1, wherein the substrate is subjected to a drying process after the HF cleaning process.
8. The wet cleaning process of claim 7, wherein the drying process is an isopropanol drying process or a spin drying process.
9. The wet cleaning process according to claim 8, wherein the process temperature of the isopropanol drying process is 25 ℃ to 150 ℃, and the process temperature of the spin-drying process is 23 ℃ to 27 ℃.
10. The wet clean process of claim 1, wherein the wet clean process is performed after ion implantation.
CN202111251459.5A 2021-10-27 2021-10-27 Wet cleaning process Pending CN113690130A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115707527A (en) * 2022-10-08 2023-02-21 杭州中欣晶圆半导体股份有限公司 DK furnace tube cleaning method

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001326209A (en) * 2000-05-16 2001-11-22 Mitsubishi Materials Silicon Corp Method for treating surface of silicon substrate
CN1338771A (en) * 2001-06-15 2002-03-06 旺宏电子股份有限公司 Method for cleaning semiconductor wafer
CN112928017A (en) * 2021-04-02 2021-06-08 杭州中欣晶圆半导体股份有限公司 Cleaning method for effectively removing metal on surface of silicon wafer

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001326209A (en) * 2000-05-16 2001-11-22 Mitsubishi Materials Silicon Corp Method for treating surface of silicon substrate
CN1338771A (en) * 2001-06-15 2002-03-06 旺宏电子股份有限公司 Method for cleaning semiconductor wafer
CN112928017A (en) * 2021-04-02 2021-06-08 杭州中欣晶圆半导体股份有限公司 Cleaning method for effectively removing metal on surface of silicon wafer

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115707527A (en) * 2022-10-08 2023-02-21 杭州中欣晶圆半导体股份有限公司 DK furnace tube cleaning method

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Application publication date: 20211123