CN106033711A - Cleaning method of substrate - Google Patents

Cleaning method of substrate Download PDF

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Publication number
CN106033711A
CN106033711A CN201510118726.XA CN201510118726A CN106033711A CN 106033711 A CN106033711 A CN 106033711A CN 201510118726 A CN201510118726 A CN 201510118726A CN 106033711 A CN106033711 A CN 106033711A
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CN
China
Prior art keywords
substrate
flushing liquor
less
carbonated water
clean method
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201510118726.XA
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Chinese (zh)
Inventor
林忠彦
许忠晖
张皓为
施承桦
郭仪君
邱政嘉
林春利
郑博伦
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United Microelectronics Corp
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United Microelectronics Corp
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Filing date
Publication date
Application filed by United Microelectronics Corp filed Critical United Microelectronics Corp
Priority to CN201510118726.XA priority Critical patent/CN106033711A/en
Publication of CN106033711A publication Critical patent/CN106033711A/en
Pending legal-status Critical Current

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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02041Cleaning
    • H01L21/02057Cleaning during device manufacture

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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 cleaning method of a substrate. The method comprises the following steps of providing the substrate, wherein the substrate possesses a surface; using a dilute hydrofluoric acid cleaning fluid to clean the surface and then using a second flushing fluid to wash the surface, wherein the second flushing fluid includes carbonated water; a PH value of the second flushing fluid is less than 5; and a contact angle between the second flushing fluid and the surface of the substrate is less than 30 degree.

Description

The clean method of substrate
[technical field]
The present invention is the method for cleaning surface about substrate, more particularly to avoiding the formation in substrate surface The clean method of washmarking.
[background technology]
Mostly the produced foreign particles such as each step of manufacture of semiconductor such as deposition, etching and grinding are system The physically or chemically material using in journey or producing, if the most effectively removing, has bad for product yield Impact, for example, impurity or particle can occupy electric current conducting space, lowers properties of product, or causes Air spots is equal, and then affects the integrity of subsequent step, in some instances it may even be possible to cause semiconductor element to manufacture Failure.
If the impurity of residual or particle spill into board, it is also possible to cause board or the destruction of board element to add The coefficient of losses of speed board, the wafer that therefore can carry out tradition or standard washes down step to remove the removal of impurity or grain Son.But after traditional cleaning step, crystal column surface often remains the dirts such as washmarking (water mark) Dye thing, it is therefore necessary to propose a kind of new wafer cleaning mode without disadvantages mentioned above to replace traditional side Formula.
[summary of the invention]
According to a preferred embodiment of the invention, the present invention provides the clean method of a kind of substrate, comprises head First providing a substrate, this substrate has a surface, then rinses surface with the first flushing liquor, then with dilute After the hydrofluoric acid clean liquid released cleans surface, rinse surface, aforementioned second flushing liquor with the second flushing liquor Comprise carbonated water, and the pH value of the second flushing liquor is less than 5, then clean surface with standard cleaning liquid, then Rinse surface with the 3rd flushing liquor, be finally dried substrate.
According to another preferred embodiment of the invention, the present invention provides the clean method of a kind of substrate, comprises Thering is provided a substrate, this substrate has a surface, then cleans surface with cleanout fluid, after cleaning surface, Surface is hydrophobicity, afterwards after surface is hydrophobicity, rinses surface with carbonated water, carbonated water PH value less than 5 and carbonated water resistance less than 0.05 megohm-centimetre, carbonated water is formed even on surface Continuous moisture film.
[accompanying drawing explanation]
The substrate that the clean method of the substrate utilizing the present invention that what Fig. 1 illustrated is is cleaned.
What Fig. 2 illustrated is the flow chart of the clean method of the substrate of the present invention.
What Fig. 3 illustrated is the contact angle schematic diagram between deionized water and substrate.
Fig. 4 is the deionized water top view in suprabasil distribution.
What Fig. 5 illustrated is the contact angle schematic diagram between the carbonated water of the present invention and substrate.
Fig. 6 is the carbonated water top view in suprabasil distribution.
[Main Reference Numerals explanation]
10 substrate 11 surfaces
20 deionized water 30 carbonated waters
40 gate pole oxidation layer 50 high dielectric material layers
100 step 200 steps
300 step 400 steps
500 step 600 steps
700 steps
[detailed description of the invention]
The point on various opportunity that the clean method of the substrate of the present invention is applicable to that substrate need to clean, such as, aoxidize step Cleaning before rapid, cleaning, the cleaning after etching step or the cleaning etc. after grinding steps before deposition step. The substrate that the clean method of the substrate utilizing the present invention that what Fig. 1 illustrated is is cleaned.
In the preferred embodiment of the present invention, the clean method of this substrate can be used for cleaning on a silicon substrate Native oxide, native oxide on fin structure or the native oxide on nano wire.Citing For, the method for the present invention can be used for the silicon base cleaning formed before gate pole oxidation layer, as it is shown in figure 1, First, after the clean method clean substrate 10 of the substrate of the present invention, gate pole oxidation layer 40 is formed in base On the surface 11 at the end 10, form high dielectric material layer 50 the most again on gate pole oxidation layer 40, at base The end 10 cleaned before or cleaned while, substrate 10 is not also cut.
What Fig. 2 illustrated is the flow chart of the clean method of the substrate of the present invention.What Fig. 3 illustrated is deionization Contact angle schematic diagram between water and substrate.Fig. 4 is the deionized water top view in suprabasil distribution. What Fig. 5 illustrated is the contact angle schematic diagram between the carbonated water of the present invention and substrate.Fig. 6 is that carbonated water exists The top view of suprabasil distribution.As shown in the step 100 of Fig. 2 and Fig. 1, first provide substrate 10, Substrate 10 can be at the bottom of wafer, silicon base, germanio, GaAs substrate, silicon-Germanium base, indium phosphide The end, nitridation gallio, silicon carbide substrate, silicon-coated insulated substrate or silicon cover substrate of glass, and substrate 10 is permissible Include active region, fin structure or nano wire etc., as described in step 200, use the first flushing Liquid rinses the surface 11 of substrate 10, and the first flushing liquor can be one of deionized water or carbonated water, front The carbonic acid water system stated utilizes carbon dioxide (CO2) be dissolved in deionized water and formed, the electricity of carbonated water Resistance is preferably smaller than 0.05 megohm-centimetre (M Ω-cm), and its pH value is less than 7, preferably carbonated water PH value less than 5.First flushing liquor is preferably maintained at 24 degree Celsius, but the most real according to other Executing example, the first flushing liquor can also be other temperature.
Then, as shown in the step 300 of Fig. 2, with the surface 11 of the hydrofluoric acid clean substrate 10 of dilution, Fluohydric acid. can remove the native oxide on the surface 11 of substrate 10, but clear at the Fluohydric acid. with dilution After washing, the surface 11 of substrate 10 can be in hydrophobicity.That is as it is shown on figure 3, dilution hydrogen fluorine After acid is cleaned, when continuing to rinse substrate 10 with pure deionized water 20, pure deionized water 20 He Angle theta between the surface 11 of substrate 10 can be more than 90 degree, if being in other words to continue with deionization When water 20 cleans substrate 10, deionized water 20 can easily form water droplet on the surface 11 of substrate 10, As shown in Figure 4, deionized water 20 can form discontinuous form on the surface 11 of substrate 10, This this discontinuous form is called discontinuous moisture film, and deionized water 20 just cannot be with continuously thus Moisture film rinse out the microgranule that the Fluohydric acid. of dilution is washed down, furthermore discontinuous moisture film is also in substrate The washmarking (water mark) being partially formed.
Referring once again to Fig. 2, the most in the present invention, the second flushing liquor is used the most in step 400 Afterflush substrate immediately followed by the Fluohydric acid. in dilution, say, that in the hydrofluoric acid clean substrate of dilution And second flushing liquor rinse between substrate, there is no other cleaning.Second flushing liquor is carbonated water, Aforesaid carbonic acid water system utilizes carbon dioxide (CO2) be dissolved in deionized water and formed, carbonated water Resistance value is preferably smaller than 0.05 megohm-centimetre (M Ω-cm), and its pH value is less than 7, preferably carbonic acid The pH value of water is less than 5, and the second flushing liquor is preferably maintained at 24 degree Celsius, but preferred according to other Embodiment, the second flushing liquor can also be other temperature.According to a preferred embodiment of the invention, the present invention Carbonated water do not contain any surfactant.According to another preferred embodiment of the invention, carbonated water is not Containing alkaline solution.It should be noted that: when carbonated water resistance value less than 0.05 megohm-centimetre (M Ω-cm), and when its pH value is less than 7, as it is shown in figure 5, carbonated water 30 and the table of substrate 10 The contact angle α in face 11 can be less than 30 degree, say, that carbonated water 30 is on the surface 11 of substrate 10 Having low surface tension, as shown in Figure 6, little contact angle α makes carbonated water 30 on substrate 10 surface 11 form continuous print form, and referred herein to this continuous print form is continuous print moisture film, consequently, it is possible to dilution Microgranule that Fluohydric acid. is washed down and the washmarking formed in the hydrofluoric acid clean step of dilution, so that it may To be rinsed along continuous print moisture film.Additionally, the carbonated water of the present invention does not contains any surfactant, It is entirely by carbonic acid to make contact angle α be less than 30 degree, and reaches the characteristic of low surface tension.It addition, It is found by the applicant that the pH value of carbonated water is the lowest, the contact angle on itself and surface can be the least, therefore carbonated water PH value can adjust depending on different demands.
Afterwards as shown in the step 500 of Fig. 2, use standard cleaning liquid, be also called SC1 cleanout fluid clear Washing substrate, standard cleaning liquid is for comprising the mixed of hydrogen peroxide and ammonium hydroxide (hydroxide ammonium) Close liquid, by hydrogen peroxide, substrate surface is aoxidized, simultaneously by the etching of Ammonia Acting on, the micropartical and the Organic substance that will attach to substrate surface remove from substrate surface, and by silicon base The machining damage on surface is removed.According to a preferred embodiment of the invention, standard cleaning liquid is preferably low Being carried out under temperature, temperature is about 24 degree Celsius, but according to other preferred embodiment, standard cleaning Liquid can also be other temperature.
Then, as shown in the step 600 of Fig. 2, after standard cleaning liquid cleans substrate, the 3rd flushing is utilized Liquid rushes at the bottom of liquid-based, and the 3rd flushing liquor punching can be one of deionized water or carbonated water, aforesaid carbonated water System utilizes carbon dioxide (CO2) be dissolved in ionized water and formed, the resistance value of carbonated water is preferably smaller than 0.05 megohm-centimetre (M Ω-cm), its pH value is less than 7, and the preferably pH value of carbonated water is less than 5, 3rd flushing liquor is preferably maintained at 24 degree Celsius, but according to other preferred embodiment, the 3rd rinses Liquid can also be other temperature.Owing to, after standard cleaning liquid cleans substrate, the surface of substrate also can be in dredging Aqueous, if using merely deionized water rinsing, similarly can form discontinuous moisture film at substrate surface, Cannot rinse completely, and use resistance value to be less than 0.05 megohm-centimetre (M Ω-cm), and its PH value be less than 7, the carbonated water of preferably smaller than 5 rinses, then utilize have between carbonated water and substrate little The characteristic of contact angle so that carbonated water forms continuous print moisture film, is removed by microgranule.Step such as Fig. 2 Shown in 700, being dried substrate after the 3rd flushing liquor rinses substrate, its drying mode can be by by substrate High-speed rotary transfers to be reached.In substrate, form gate pole oxidation layer after drying, be subsequently formed high dielectric material After the elements such as material, gate, interlayer dielectric layer, metal interconnecting, begin to carry out the cutting of substrate.
According to a preferred embodiment of the invention, the first flushing liquor, the second flushing liquor and the 3rd flushing liquor are all Use carbonated water can reach preferable cleaning effect.Additionally, the first flushing liquor, the second flushing liquor and the 3rd In flushing liquor, the concentration of carbon dioxide can be different, it is preferable that the gas concentration lwevel in the second flushing liquor The gas concentration lwevel in the first flushing liquor, and the gas concentration lwevel meeting in the second flushing liquor can be more than More than the gas concentration lwevel in the 3rd flushing liquor.It addition, the first flushing liquor, the second flushing liquor and the 3rd Flushing liquor is when rinsing, and wafer can optionally rotate.
The present invention use carbonated water rinse substrate, aforementioned carbonated water resistance value less than 0.05 megohm-li Rice (M Ω-cm), and its pH value is less than 7, and this carbonated water advantage is have low surface tension, energy Little contact angle is formed, especially to institute's shape after hydrofluoric acid clean with having hydrophobic substrate surface Little contact angle is had, so utilizing carbonated water to rinse substrate table between the hydrophobic substrate surface become During face, continuous print moisture film can be formed at substrate surface, therefore can effectively microgranule and washmarking be removed.
The foregoing is only the preferred embodiments of the present invention, all done according to claims of the present invention scope Equal change and modification, all should belong to the covering scope of the present invention.

Claims (10)

1. a clean method for substrate, comprises:
Thering is provided a substrate, this substrate has a surface;
This surface is rinsed with the first flushing liquor;
This surface is cleaned with the hydrofluoric acid clean liquid of dilution;
Rinsing this surface with the second flushing liquor, this second flushing liquor comprises carbonated water, and this second flushing liquor PH value less than 7;
This surface is cleaned with standard cleaning liquid;
This surface is rinsed with the 3rd flushing liquor;And
It is dried this substrate.
2. the clean method of substrate as claimed in claim 1, wherein this first flushing liquor comprises carbonic acid Water, the pH value of this first flushing liquor less than 7 and resistance value less than 0.05 megohm-centimetre.
3. the clean method of substrate as claimed in claim 1, wherein the 3rd flushing liquor comprises carbonic acid Water, the pH value of the 3rd flushing liquor less than 7 and resistance value less than 0.05 megohm-centimetre.
4. the clean method of substrate as claimed in claim 1, wherein the resistance value of this second flushing liquor is little In 0.05 megohm-centimetre.
5. the clean method of substrate as claimed in claim 1, wherein in the hydrofluoric acid clean with this dilution After liquid cleans this surface, this surface has hydrophobicity.
6. the clean method of substrate as claimed in claim 5, wherein this second flushing liquor and this surface it Between contact angle less than 30 degree.
7. the clean method of substrate as claimed in claim 1, wherein rinses this base at this first flushing liquor , formation one high dielectric material is additionally comprised in this substrate at the end.
8. the clean method of substrate as claimed in claim 1, wherein this standard cleaning liquid comprises peroxide Change the mixed liquor of hydrogen and ammonium hydroxide (hydroxide ammonium).
9. a clean method for substrate, comprises:
Thering is provided a substrate, this substrate has a surface;
Cleaning this surface with cleanout fluid, after cleaning this surface, this surface is hydrophobicity;And
After this surface is hydrophobicity, rinsing this surface with carbonated water, the pH value of this carbonated water is less than 7 And the resistance of this carbonated water less than 0.05 megohm-centimetre, this carbonated water this surface formed continuous print water Film.
10. the clean method of substrate as claimed in claim 9, wherein between this carbonated water and this surface Contact angle less than 30.
CN201510118726.XA 2015-03-18 2015-03-18 Cleaning method of substrate Pending CN106033711A (en)

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Application Number Priority Date Filing Date Title
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107978511A (en) * 2017-11-20 2018-05-01 武汉新芯集成电路制造有限公司 The forming method of oxide layer and semiconductor devices
CN115338181A (en) * 2022-07-26 2022-11-15 泸州龙芯微科技有限公司 Surface cleaning device behind chip scribing
US20230154742A1 (en) * 2020-04-28 2023-05-18 Shin-Etsu Handotai Co., Ltd. Method for cleaning semiconductor wafer

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6090217A (en) * 1998-12-09 2000-07-18 Kittle; Paul A. Surface treatment of semiconductor substrates
US20060054181A1 (en) * 2000-06-26 2006-03-16 Applied Materials, Inc. Cleaning method and solution for cleaning a wafer in a single wafer process
US20080166872A1 (en) * 2005-08-10 2008-07-10 Fujitsu Limited Method of producing semiconductor device
CN103210476A (en) * 2010-11-15 2013-07-17 栗田工业株式会社 Method for cleaning silicon wafer and apparatus for cleaning silicon wafer

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6090217A (en) * 1998-12-09 2000-07-18 Kittle; Paul A. Surface treatment of semiconductor substrates
US20060054181A1 (en) * 2000-06-26 2006-03-16 Applied Materials, Inc. Cleaning method and solution for cleaning a wafer in a single wafer process
US20080166872A1 (en) * 2005-08-10 2008-07-10 Fujitsu Limited Method of producing semiconductor device
CN103210476A (en) * 2010-11-15 2013-07-17 栗田工业株式会社 Method for cleaning silicon wafer and apparatus for cleaning silicon wafer

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107978511A (en) * 2017-11-20 2018-05-01 武汉新芯集成电路制造有限公司 The forming method of oxide layer and semiconductor devices
US20230154742A1 (en) * 2020-04-28 2023-05-18 Shin-Etsu Handotai Co., Ltd. Method for cleaning semiconductor wafer
US11862456B2 (en) * 2020-04-28 2024-01-02 Shin-Etsu Handotai Co., Ltd. Method for cleaning semiconductor wafer
CN115338181A (en) * 2022-07-26 2022-11-15 泸州龙芯微科技有限公司 Surface cleaning device behind chip scribing

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