CN109388036A - A kind of minimizing technology for removing liquid and photoresist of photoresist - Google Patents

A kind of minimizing technology for removing liquid and photoresist of photoresist Download PDF

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Publication number
CN109388036A
CN109388036A CN201710657370.6A CN201710657370A CN109388036A CN 109388036 A CN109388036 A CN 109388036A CN 201710657370 A CN201710657370 A CN 201710657370A CN 109388036 A CN109388036 A CN 109388036A
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CN
China
Prior art keywords
photoresist
ammonia
removal
removal liquid
organic solvent
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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.)
Withdrawn
Application number
CN201710657370.6A
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Chinese (zh)
Inventor
温子瑛
孙富成
王致凯
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Wuxi Huaying Microelectronics Technology Co Ltd
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Wuxi Huaying Microelectronics Technology Co Ltd
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Priority to CN201710657370.6A priority Critical patent/CN109388036A/en
Priority to US16/633,159 priority patent/US11448966B2/en
Priority to PCT/CN2018/098332 priority patent/WO2019024892A1/en
Priority to EP18840852.0A priority patent/EP3663857A4/en
Publication of CN109388036A publication Critical patent/CN109388036A/en
Withdrawn legal-status Critical Current

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • G03F7/422—Stripping or agents therefor using liquids only
    • G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
  • Cleaning Or Drying Semiconductors (AREA)

Abstract

The invention discloses a kind of removal liquid of photoresist and the methods for carrying out photoresist removal using the removal liquid, the removal liquid includes ammonia and organic solvent, the ammonia is the mixture of ammonia, liquefied ammonia or ammonia and water, the organic solvent is organic solvent at least with an electron attractive functional group, the minimizing technology, which can be, generates above-mentioned removal liquid by online gas-liquid mixed, it is applied directly to the crystal column surface with photoresist, carries out the removal and crystal column surface cleaning of photoresist.The present invention using corrosive organic solvent low/no to substrate material/substrate metal and ammonia property, improve wet process remove photoresist the removal effect to photoresist and polymer while, reduce the corrosion to wafer substrate.Technique yields can be improved, and provide effective solution scheme for the development of smaller technology feature size.

Description

A kind of minimizing technology for removing liquid and photoresist of photoresist
Technical field
The present invention relates to a kind of removal liquid of photoresist, especially one kind low substrate and structure erosion and quickly to remove The removal liquid of photoresist and the method for removing glue using the removal liquid.
Background technique
Photoetching is an important step in semiconductor fabrication process, and the step is using exposure and imaging on photoresist layer Portray figure, then by etching technics by the pattern transfer on photomask on a semiconductor wafer.Above-mentioned steps are completed Afterwards, so that it may the technical process such as etching or the ion implanting of selectivity be carried out to wafer, dissolved photoresist will not protect quilt The crystal column surface of covering is not changed during these.After above-mentioned technical process, need to remove photoresist, wafer table Face cleaning, just can be carried out other steps of semiconductor devices manufacture.In general, will do it in semiconductor devices manufacture whole process Photolithographic procedures many times.Producing may need to carry out up to tens step photoetching in the technical process of complicated integrated circuit.
The removal of photoresist is broadly divided into that dry method is removed photoresist and wet process is removed photoresist two classes.The substance for needing to remove is predominantly remaining Photoresist and due to technical process generate polymer.It is one kind mainly by removing photoetching using gas ions that dry method, which is removed photoresist, The method of glue and polymer, it is a kind of side that photoresist and polymer are mainly removed by the effect of chemical solution that wet process, which is removed photoresist, Method.Dry method is removed photoresist advantageous on removal ability, but is gone between the substrate for needing the photoresist removed and needs to retain Except selection ratio is difficult to improve.Wet process, which is removed photoresist, can obtain very high removal selection ratio, but will receive chemistry on removal ability The limitation of solution.
After device feature size enters 65nm or less process node, with the reduction of junction depth and film thickness, to going Except the requirement of selection ratio reaches a new height.This, which makes dry method remove photoresist, can not continue to meet the requirement of removal selection ratio.Traditional is wet Method degumming process formula removal selection than and the removal of remained on surface polymer in terms of also by unprecedented challenge.
In terms of wet process degumming process, mainstream technology is gone using the organic solvents such as dioxysulfate water and NMP or EKC Glue work.
Traditional dioxysulfate water degumming process needs impregnate ten minutes or more ability under conditions of 120 degrees centigrade Reach effect.And since this solution has highly acid and strong oxidizing property, the metal layer under meeting heavy corrosion photoresist, certain The silicon materials that silicon wafer surface is aoxidized in degree cause the loss of substrate.Exist simultaneously personnel safety problem in use process and Safety dumping problem after use.
Using the technique that the organic solvents such as NMP or EKC remove photoresist be also required to 40 degrees Celsius or more at a temperature of carry out, and need 20 minutes or more time is wanted to can be only achieved satisfactory removal effect.This kind of chemicals are considered as carcinogenic substance Matter faces the challenge of contact personnel health and safety dumping.
Above problem makes industry there is an urgent need to the wet process degumming process that one kind more meets ESH requirement, can be effectively removed Photoresist and polymer improve removal selection ratio, while reducing the safety and health risk and to the maximum extent to contact personnel Reduce the negative effect to environment.
Summary of the invention
The purpose of the present invention is:
Exploitation can remove the chemical formulation and process of photoresist and polymer, the chemical formulation and process With shorter process time, lower reaction temperature (or even room temperature) and higher photoresist/polymer and substrate material Between removal ratio.
The technical solution of the present invention is as follows: a kind of removal liquid of photoresist, including ammonia and organic solvent, the ammonia be ammonia, The mixture of liquefied ammonia or ammonia and water, the organic solvent are organic solvent at least with an electron attractive functional group.
It further, include but is not limited to following functional group: hydroxyl in the electron attractive functional group that the organic solvent has (- OH), carbonyl (- CO-), aldehyde radical (- CHO), carboxyl (- COOH), amino (- NH2), oximido (- C=NOH).
Specifically, the organic solvent includes but is not limited to: ethyl alcohol, normal propyl alcohol, isopropanol, acetone, ethyl acetate, second Acid, trifluoroacetic acid, N-Methyl pyrrolidone, acetaldehyde, methacrylaldehyde, acrylic acid,.
Further, the removal liquid further includes that at least one organic matter contains at least one function in following functional group Group: hydroxyl (- OH), carbonyl (- CO-), aldehyde radical (- CHO), carboxyl (- COOH), amino (- NH2), oximido (- C=NOH).Specifically , above-mentioned organic matter includes but is not limited to: phenol, benzophenone, benzoic acid, paratolunitrile, o-trifluoromethyl aniline, 2- trifluoro Picoline, 3,5- diamido-benzotrifluoride, paranitroanilinum, acetaldoxime, acetoxime, cyclohexanone oxime, dimethylamino benzophenone ketoxime, second Glycol, glycerine, hydroquinone, phloroglucin, glyoxal, 2,4- pentanedione, benzoquinones, ethanedioic acid, malonic acid, maleic two Acid, phthalic acid, 3,5- bis- (trifluoromethyl) aniline, 2,4,6- trinitroaniline, dimethylglyoxime, two (fourth of methyl ethylene Ketoxime base) silane, phenyl tributanoximo silane, four butanone oximino silanes, parahydroxyben-zaldehyde, P-hydroxybenzoic acid, chloroethene Acid, fluoroacetic acid, para orientation nitration, o-nitrophenol, 4- chloro-acetophenone oxime, chloro oximide acetic acid ethyl ester, the bromo- 5- fluoroform of 3- Yl benzoic acid.In addition, above-mentioned organic matter is dissolved in other solvents first, it is also feasible for then mixing with ammonia.
Further, the removal liquid further includes water, and by mass percentage, including content is 10-85wt.% to component Organic solvent/acetone, content be 5-24wt.% ammonia, content be 0-60wt.% water.
The present invention also provides a kind of methods of removal that photoresist is carried out using above-mentioned removal liquid:
It is removed by way of by removal liquid spray to photoresist surface.
Further, after the removal liquid with gas by being sufficiently mixed, gas-liquid mixed state is formed, then sprays light again The mode on photoresist surface is removed.
Further, the gas is one or more mixing of ammonia, oxygen, nitrogen, air or ozone.
Further, the gas is that air or oxygen is occurred before the gas is mixed with the removal liquid by ozone Device is partly or entirely converted into ozone.
Minimizing technology of the invention can also be using formation solution or gas after being sufficiently mixed ammonia and the organic solvent Liquid mixed state, then directly spray arrives photoresist surface.
By adopting the above technical scheme, the present invention has following technical effect that
1, improve wet process remove photoresist the removal effect to photoresist and polymer while, reduce corrosion to wafer substrate. Technique yields can be improved, and provide effective solution scheme for the development of smaller technology feature size.
2, it even can reach satisfactory effect of removing photoresist at room temperature in lower temperature, solve or alleviate tradition and remove photoresist Temperature control equipment bring hidden danger in technique.
3, mitigate environmental pressure, reduce the influence to personnel health, save use cost.
4, under chemical formulation of the invention and process collective effect, it can be reached with the shorter process time and be met It is required that effect of removing photoresist.
5, process of the present invention is mixed in real time by gas-liquid, generates treatment fluid online, is improved to chemical substance Treatment effeciency and cleanliness.
6, above-mentioned chemical formulation and process, the removal in addition to can be applied to photoresist, can also be applied to wafer table Face cleaning.
Detailed description of the invention
Fig. 1 is the SEM figure of test wafer A of the invention before testing；
Fig. 2 is the sectional view of Fig. 1；
Fig. 3 is Fig. 1 same position, in the formula using embodiment 11, SEM figure of the spray after 1 minute.
Specific embodiment
Below by several embodiments, the present invention is described further, following embodiments only illustrate the present invention and , the present invention is not limited to the following examples.In following embodiments, the chemical liquids used are electron level, wherein The mass concentration of ammonium hydroxide is 25~28%, and for the convenience of calculating, in following each embodiments, the mass concentration of ammonium hydroxide is according to 28% It calculates.In following embodiments, for test removal effect test wafer the preparation method comprises the following steps: using rotation or carriage exist 1 micron thick current in the positive photoresist used (model AZ701, An Zhi electronic material group is coated in wafer entire surface (AZ Electronics Materials)), front baking is carried out at a temperature of substantially 150 DEG C or so using hot plate or oven, later Different wafers are exposed using the photomask of different graphic respectively, it is developed, dry, rear to dry, it then carries out plasma and bangs It hits, finally obtains test wafer；The square that wafer is about 1.5cm at length and width according to different pattern-cuts will be tested, taken The wafer for being wherein mainly coarse scale structures is test wafer A, and the wafer of long slice structure is test wafer B, short and thick structure Wafer be test wafer C, be removed measure of merit respectively.
Acetone is mixed with ammonium hydroxide according to the mass ratio of table 1, several groups removal liquid (embodiment 1-14, specific proportion are obtained It is shown in Table 1).
Acetone-ammonium hydroxide of 1. different proportion of table mixing removes liquid
Embodiment Acetone (wt.%) Ammonium hydroxide (wt.%) Ammonia (wt.%)
1 100 0 0
2 98.21 1.79 0.50
3 96.43 3.57 1.00
4 94.64 5.36 1.50
5 91.07 8.93 2.50
6 87.50 12.5 3.50
7 85.00 15 4.20
8 82.14 17.86 5.00
9 64.29 35.71 10.00
10 46.43 53.57 15.00
11 28.57 71.43 20.00
12 21.40 78.6 22.00
13 13.90 86.1 24.10
14 0.00 100 28.00
It is tested respectively by removal effect of several techniques to the obtained removal liquid of above-described embodiment 1-14.It (is going Except in the test table of effect: being assessed from remaining area angle, ×-indicates almost without removal effect (residual > 95%)； △-expression is effective but does not remove completely；Zero-indicates under 160 power microscopes without visible residual photoresist)
Method particularly includes:
Method is 1.: taking 14 pieces of test wafer A, test wafer B, test wafer C respectively, is immersed in above-described embodiment under room temperature In the removal liquid of 1-14, and weak vibrations, it takes out, is dried with nitrogen after 1 minute, by naked eyes and micro- sem observation, finally go Except effect is shown in Table 2.
The removal effect of 2. infusion method of table
Embodiment Test wafer A Test wafer B Test wafer C
1 × × ×
2 × × ×
3 × × ×
4 × × ×
5 × × ×
6 △ △ △
7 △ △ △
8 △ △ △
9 △ △ △
10 △ △ △
11 △ △ △
12 △ △ △
13 △ △ △
14 × × ×
As can be seen from Table 2,1. above-mentioned removal liquid, method do not remove photoresist clean.In fact, wherein embodiment 9,10,11 and 12 effect is best, the photoetching glue residua of only a small amount of (< 5%), and the removal liquid of embodiment 3 and 4 is only only capable of making The photoresist layer for obtaining test wafer generates slight crack and slight thinned (revolution mark > 99%).
If extend soaking time, when the removal liquid soaking time of the removal liquid using embodiment 8-12 reach 3 minutes it Afterwards, photoresist can be completely removed.
Method is 2.: after the removal liquid that embodiment 1-14 is prepared is mixed with oxygen by mixing arrangement, at normal temperature, spray Onto test wafer A, test wafer B, test wafer C, stop after 1 minute, be dried with nitrogen, by naked eyes and micro- sem observation, Final removal effect is shown in Table 3.In this experiment, the oxygen pressure used removes liquid fluid pressure 7psi for 10psi, and adopts It is sprayed with 1/16 inch pipe.
Above-mentioned mixing arrangement and its mixed method can be with another patent application (WO/2016/ of application reference people 023414) description as described in Liqiud-gas mixing device in.
The removal effect of 3. spray process of table (1 minute)
Embodiment Test wafer A Test wafer B Test wafer C
1 ○ △ △
2 ○ △ △
3 ○ △ △
4 ○ △ △
5 ○ △ △
6 ○ △ △
7 ○ △ △
8 ○ ○ ○
9 ○ ○ ○
10 ○ ○ ○
11 ○ ○ ○
12 ○ ○ ○
13 ○ ○ ○
14 △ △ △
As can be seen from Table 3, using spray process can the test wafer A to predominantly coarse scale structures play it is relatively good Removal effect, but test wafer B and test wafer C for thin strip structure, too low ammonia mass concentration (embodiment 1-7) or the removal effect that can make of too low content of acetone (embodiment 14) is deteriorated.In embodiment 14, the blocky photoresist in part Be detached from crystal column surface after, be re-attached on original photoresist in other positions, show remove liquid in individually amino molecule or Ammonium hydroxide has peeling effect to photoresist but there is no solute effects.
We by method 2. in aerosolization be air or nitrogen when, removal effect and oxygen are without significant difference. But it is (direct after line prepares ozone by the ozone generator of 5g/L using oxygen as raw material when replacing oxygen using ozone Using), using the removal liquid of embodiment 7, test wafer B and test wafer C do not observe photoetching glue residua, illustrate ozone It is added, hence it is evident that help to improve the removal effect of removal liquid.
The spray time of method 2. is foreshortened to 35s by the formula for taking embodiment 8-13 therein, and the result is shown in tables 4.
The removal effect of 4. spray process of table (35s)
Embodiment Test wafer A Test wafer B Test wafer C
8 ○ △ △
9 ○ △ △
10 ○ △ △
11 ○ △ ○
12 ○ ○ ○
13 ○ △ △
From table 4, it can be seen that after shortening the time, removal liquid (acetone 21.40wt.%, the ammonium hydroxide of embodiment 12 Removal effect 78.60wt.%) is best.In embodiment 12, by conversion, it can be found that the mass ratio of acetone and ammonia is about 1:1。
Further directly the removal liquid stream of embodiment 12 is dropped down and (but is not sprayed directly with oxygen or other gas mixings Leaching) surface of arriving test wafer, it is dried with nitrogen after 35s, through microscope it has been observed that test wafer A (i.e. big figure) and surveying Examination wafer C (short and thick item) can remove photoresist well, not observe residual, and test wafer B (long slice) then has pole A small amount of residual.
In order to further explain water to influence of the invention, provide herein several groups comparative example (comparative example 1-8, specifically 5) proportion is shown in Table.
5 acetone of table-ammonium hydroxide-water mixing removal liquid
Comparative example Acetone (wt.%) Ammonia (wt.%) Water (wt.%)
1 21.4 5 73.6
2 21.4 15 63.6
3 5 5 90
4 15 15 70
5 26.2 5 68.8
6 23.4 15 61.6
7 5 22 73
8 15 22 63
In upper table, the mass percent of ammonia is calculated for the mass percent of ammonium hydroxide multiplied by 28%, and the quality of water Percentage is then the mass percent that the mass percent of ammonium hydroxide adds the water being individually added into multiplied by 72%.
By the removal liquid in above-mentioned comparative example, the surface to test wafer A, after continuing 1 minute, nitrogen are 2. sprayed using method Air-blowing is dry, and observes under the microscope.The removal liquid of all comparative examples fails to remove effectively photoresist, wherein comparative example 3,4,7,8 do not observe significant change, comparative example 1 has almost no change, only observe a small amount of slight crack (revolution mark > 99%), the photoresist in comparative example 5 has a more thinning phenomenon, comparative example 6 then have most removal it is clean (revolution mark < 60%), remainder is thinned, and comparative example 2 and the removal of 6 similar portions of comparative example are clean, and remainder has occurred thinned.It can See, under this experiment condition, be added after excessive water, just reduce the mass concentration of acetone or ammonia, so that removal liquid Removal effect glide.
The optimum condition of the optimal proportion of each ingredient and process can be because of the ingredient and knot of glue in the chemical formulation Structure and the manufacturing process passed through and be varied.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art Scholar cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention.It is all according to the present invention Equivalent change or modification made by Spirit Essence, should be covered by the protection scope of the present invention.

Claims (10)

1. a kind of removal liquid of photoresist, it is characterised in that: including ammonia and organic solvent, the ammonia is ammonia, liquefied ammonia or ammonia With the mixture of water, the organic solvent is organic solvent at least with an electron attractive functional group.
2. the removal liquid of photoresist according to claim 1, it is characterised in that: the organic solvent has following functional group At least one of: hydroxyl, carbonyl, aldehyde radical, carboxyl, amino, oximido.
3. the removal liquid of photoresist according to claim 1 or 2, which is characterized in that the photoresist removes liquid and further includes At least one organic matter, the organic matter contain at least one of following functional group: hydroxyl, carbonyl, aldehyde radical, carboxyl, amino, Oximido.
4. the removal liquid of photoresist according to claim 2, which is characterized in that the organic solvent is isopropanol or third Ketone.
5. the removal liquid of photoresist according to claim 4, which is characterized in that the removal liquid further includes water, component By mass percentage, the organic solvent/acetone for being 10-85wt.% including content, content are the ammonia of 5-24wt.%, content For the water of 0-60wt.%.
6. a kind of minimizing technology of photoresist, which is characterized in that carry out photoresist using removal liquid described in claim 1-5 Removal.
7. the minimizing technology of photoresist according to claim 6, it is characterised in that: by spraying the removal liquid to light The mode on photoresist surface is removed.
8. the minimizing technology of photoresist according to claim 7, it is characterised in that: the removal liquid passes through abundant with gas After mixing, gas-liquid mixed state is formed, the mode for then spraying photoresist surface again is removed.
9. the minimizing technology of photoresist according to claim 8, it is characterised in that: the gas is ammonia, oxygen, nitrogen One or more mixing of gas, air or ozone.
10. the minimizing technology of photoresist according to claim 8, it is characterised in that: the gas is air or oxygen, institute It states before gas mixes with the removal liquid, by ozone generating-device, is partly or entirely converted into ozone.
CN201710657370.6A 2017-08-03 2017-08-03 A kind of minimizing technology for removing liquid and photoresist of photoresist Withdrawn CN109388036A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN201710657370.6A CN109388036A (en) 2017-08-03 2017-08-03 A kind of minimizing technology for removing liquid and photoresist of photoresist
US16/633,159 US11448966B2 (en) 2017-08-03 2018-08-02 Photoresist-removing liquid and photoresist-removing method
PCT/CN2018/098332 WO2019024892A1 (en) 2017-08-03 2018-08-02 Photoresist stripping solution and method of stripping photoresist
EP18840852.0A EP3663857A4 (en) 2017-08-03 2018-08-02 Photoresist stripping solution and method of stripping photoresist

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Application Number Priority Date Filing Date Title
CN201710657370.6A CN109388036A (en) 2017-08-03 2017-08-03 A kind of minimizing technology for removing liquid and photoresist of photoresist

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113275323A (en) * 2021-05-14 2021-08-20 云谷（固安）科技有限公司 Liquid colloid separation method and liquid colloid separation system
CN113394081A (en) * 2021-05-31 2021-09-14 上海华力集成电路制造有限公司 Photoresist removing method
CN114560644A (en) * 2022-03-26 2022-05-31 中建西部建设北方有限公司 Modified micro-nano bubble water, preparation method thereof and concrete

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS52100234A (en) * 1976-02-19 1977-08-23 Sony Corp Stripping solution of photosolubilizable light sensitive resin
US20030125225A1 (en) * 2001-12-31 2003-07-03 Chongying Xu Supercritical fluid cleaning of semiconductor substrates
CN1811603A (en) * 2001-05-14 2006-08-02 株式会社东芝 Alkaline solution and manufacturing method, and alkaline solution application, solution applying device and application thereof
CN101354542A (en) * 2007-07-27 2009-01-28 中芯国际集成电路制造(上海)有限公司 Method for removing photoresist
CN105467783A (en) * 2016-01-04 2016-04-06 仲恺农业工程学院 Alkaline photopolymerizing development secretion cleaning agent and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS52100234A (en) * 1976-02-19 1977-08-23 Sony Corp Stripping solution of photosolubilizable light sensitive resin
CN1811603A (en) * 2001-05-14 2006-08-02 株式会社东芝 Alkaline solution and manufacturing method, and alkaline solution application, solution applying device and application thereof
US20030125225A1 (en) * 2001-12-31 2003-07-03 Chongying Xu Supercritical fluid cleaning of semiconductor substrates
CN101354542A (en) * 2007-07-27 2009-01-28 中芯国际集成电路制造(上海)有限公司 Method for removing photoresist
CN105467783A (en) * 2016-01-04 2016-04-06 仲恺农业工程学院 Alkaline photopolymerizing development secretion cleaning agent and preparation method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113275323A (en) * 2021-05-14 2021-08-20 云谷（固安）科技有限公司 Liquid colloid separation method and liquid colloid separation system
CN113275323B (en) * 2021-05-14 2022-06-24 云谷（固安）科技有限公司 Liquid colloid separation method and liquid colloid separation system
CN113394081A (en) * 2021-05-31 2021-09-14 上海华力集成电路制造有限公司 Photoresist removing method
CN114560644A (en) * 2022-03-26 2022-05-31 中建西部建设北方有限公司 Modified micro-nano bubble water, preparation method thereof and concrete

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