CN102082089A - Method for removing photoresist - Google Patents

Method for removing photoresist Download PDF

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Publication number
CN102082089A
CN102082089A CN 200910241611 CN200910241611A CN102082089A CN 102082089 A CN102082089 A CN 102082089A CN 200910241611 CN200910241611 CN 200910241611 CN 200910241611 A CN200910241611 A CN 200910241611A CN 102082089 A CN102082089 A CN 102082089A
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Prior art keywords
photoresist
wafer
cineration technics
removal method
described wafer
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CN 200910241611
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CN102082089B (en
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杨峰
谭宗良
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Beijing North Microelectronics Co Ltd
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Beijing North Microelectronics Co Ltd
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Abstract

The invention discloses a method for removing a photoresist, which relates to the field of manufacturing of an integrated circuit element and is invented to solve the problems of long operating period for removing the photoresist and easy damage to a chip in a photoresist removing process. The method for removing the photoresist comprises the following steps of: removing residual photoresist from a plasma-etched chip by adopting an ashing process; cleaning the chip with a hydrofluoric acid solution; flushing the chip with ultrapure water or deionized water; and soaking the chip in an isopropanol solution. The method is suitable for removing photoresist produced in a semiconductor chip manufacturing process.

Description

The removal method of photoresist
Technical field
The present invention relates to integrated circuit component and make the field, relate in particular to the removal method of the photoresist that produces in a kind of semiconductor wafer manufacturing.
Background technology
In the making technology of semiconductor wafer (generally being silicon chip), in order to guarantee technological effect, wafer must be that cleaning is agranular.And in the making technology of wafer, be very frequent and important step to the pattern sheet etching that has photoresist (Photo resist) pattern, after to the plasma etching that has the photoresist wafer, understand a lot of accessory substances that form, as Si-Cl 2-O/Si-Br 2-O/CF xDeng material.These materials mainly exist with the residual form of photoresist, can become the passivation of wafer patterned surface even sidewall, wafer is formed pollution, and then influence the carrying out of next step technology, even cause the final defective of device, make described device can not reach designed device property, can't operate as normal.
So the effective removal to photoresist residual after the wafer engraving seems very important, and when guaranteeing these residual photoresists of removal in full force and effect, also to guarantee zero damage of wafer substrates or figure, increase cleaning efficiency, reduce defective.
Remove in the process of residual pollutants such as photoresist in clean wafers, traditional cleaning method is the RCA wet-chemical cleaning that directly adopts standard.In the RCA of standard wet-chemical cleaning technology, normally adopt following chemical liquids to clean respectively and remove respective substance:
A) 120 ℃ SPM (H 2SO 4/ H 2O 2, 4: 1) and removal metal impurities organic substance and photoresist;
B) about 20 ℃ DHF (HF/H 2O, 1: 100) removal natural oxide and metal impurities;
C) 70-90 ℃ APM (NH 4OH/H 2O 2/ UPW, 1: 1: 5) removal particle and organic pollutants;
D) 70-90 ℃ HPM (HCl/H 2O 2/ UPW, 1: 1: 6) the removal inorganic metal ion.
The RCA wet-chemical cleaning of standard, cleaning step is many, and the cycle of cleaning is long, and the cleaning process of monolithic needs about about 50 minutes time just can finish.In addition, the RCA wet-chemical cleaning of standard needs to use a large amount of strong acid, highly basic and strong oxidizers to operate, and so just the safety to operating personnel causes a hidden trouble.
In order to improve cleaning efficiency, occur first employing resist remover cineration technics in the prior art and removed residual photoresist, adopted the method for above-mentioned RCA wet-chemical cleaning to remove not removing completely photoresist and removing other residuals that produce in the photoresist process of wafer surface again.Resist remover is that oxygen atom and photoresist react in plasma environment and remove photoresist, because the main component of photoresist is a hydrocarbon, so, very fast the reacting with photoresist of oxygen atom generates carbon monoxide, carbon dioxide and the steam etc. of volatilization, taken away by vacuum system then.In the resist remover cineration technics removes photoresist, the removal of adopting duration control method to come the photoresist and the residuals on control wafer surface to resist remover.
In realizing process of the present invention, after the inventor finds to adopt the resist remover cineration technics to remove photoresist, adopt the RCA wet-chemical cleaning again, though can improve cleaning efficiency, but in RCA wet-chemical cleaning process, the use of a large amount of strong acid, highly basic and strong oxidizer also can cause a hidden trouble to operating personnel's safety, and may cause the damage to wafer itself.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of semiconductor wafer cleaning method, can reach the damage of cleaning purpose, in the time of reducing to remove photoresist again wafer itself being produced.
For solving the problems of the technologies described above, the technical scheme that semiconductor wafer cleaning method of the present invention adopts is:
A kind of removal method of photoresist comprises:
With the wafer behind the plasma etching, the employing cineration technics is removed the residual photoresist on the described wafer;
With weak acid solution described wafer is cleaned;
With ultra-pure water or deionized water described wafer is washed;
With organic solution described wafer is carried out immersion treatment.
The removal method of photoresist provided by the invention, the residual photoresist that adopts cineration technics to remove on the wafer is combined with the simple wet-cleaned that adopts organic solution to soak, can shorten the processing cycle of removing photoresist, improve cleaning efficiency, from adopting cineration technics to remove residual photoresist to adopting organic solution that described wafer is carried out immersion treatment, the time of whole cleaning process only needed about tens minutes.
In addition, after the residual photoresist on adopting cineration technics removal wafer, at first described wafer is cleaned with weak acid solution, with ultra-pure water or deionized water described wafer is washed again, carry out immersion treatment with organic solution afterwards, avoided the use of a large amount of strong acid, highly basic and strong oxidizer, the damage that when having reduced to remove photoresist wafer itself has been produced has reduced the safety that operating personnel are caused and has made hidden danger.
Description of drawings
Fig. 1 is the flow chart of removal method one embodiment of photoresist of the present invention;
Fig. 2 is the time dependent tendency chart of the intensity of spectral line of oxygen plasma among the removal method embodiment of photoresist of the present invention;
Fig. 3 is for carrying out the wafer slice sample drawing of oxygen gas plasma stripping among the removal method embodiment of photoresist of the present invention;
Fig. 4 is the flow chart of another embodiment of removal method of photoresist of the present invention;
Fig. 5 is the flow chart of the another embodiment of removal method of photoresist of the present invention;
Fig. 6 is among the removal method embodiment of photoresist of the present invention, is after the hydrofluoric acid solution of 1-10% cleans 5-60 time second and drying, to soak also sample after cleaning figure with 20-45 ℃ aqueous isopropanol with wafer concentration.
Embodiment
The present invention aims to provide a kind of removal method of photoresist of the damage that can improve cleaning efficiency, when reducing to remove photoresist again wafer itself be produced, and below in conjunction with drawings and Examples the present invention is elaborated.
With reference to shown in Figure 1, the removal method of embodiment of the invention photoresist comprises step:
S10, with the wafer behind the plasma etching, adopt cineration technics to remove residual photoresist on the described wafer;
Wherein, the main process of described cineration technics is: decompose oxygen molecule by radio frequency (RF) energy and produce oxygen atom, and the main product such as carbon monoxide, carbon dioxide and water that oxygen atom and residual photoresist react and generate volatilization, reaction equation is as follows:
e+O 2→2O+e
R *+O *→COorCO 2
These products are taken away by vacuum system with gaseous form.
S20, described wafer is cleaned with hydrofluoric acid solution;
In embodiments of the present invention, S20 employing concentration is that the hydrofluoric acid solution of 1-10% cleans 5-60 time second with described wafer, can remove like this when carrying out S10, at the natural oxidizing layer and the partial polymer of wafer surface generation.
S30, described wafer is washed with ultra-pure water or deionized water;
With ultra-pure water or deionized water described wafer is washed, the dilution of hydrofluoric acid residual solution, removal can be reduced the damage to wafer itself, and avoid residual hydrofluoric acid solution that follow-up aqueous isopropanol is polluted.Preferably, adopting water quality requirement to reach 10M Ω .cm above ultra-pure water or deionized water washes described wafer.
S40, described wafer is carried out immersion treatment with aqueous isopropanol.
With aqueous isopropanol described wafer is carried out immersion treatment, can dissolve the organic residual of wafer surface, improve wafer with the reacted hydrophobic character of hydrofluoric acid, effectively reduce granule foreign absorption.In order to reach cleaning performance preferably, preferably adopt 20-45 ℃ aqueous isopropanol to soak described wafer.
The removal method of photoresist of the present invention, the residual photoresist that adopts cineration technics to remove on the wafer is combined with the simple wet-cleaned that adopts aqueous isopropanol to soak, can shorten the processing cycle of removing photoresist, improve cleaning efficiency, from adopting cineration technics to remove residual photoresist to adopting aqueous isopropanol that described wafer is carried out immersion treatment, the time of whole cleaning process only needed about tens minutes.
In addition, after the residual photoresist on adopting cineration technics removal wafer, at first described wafer is cleaned with hydrofluoric acid solution, with ultra-pure water or deionized water described wafer is washed again, carry out immersion treatment with aqueous isopropanol afterwards, avoided the use of a large amount of strong acid, highly basic and strong oxidizer, the damage that when having reduced to remove photoresist wafer itself has been produced has reduced the safety that operating personnel are caused and has made hidden danger.
In the above-mentioned steps S10 of the embodiment of the invention, adopt the resist remover cineration technics to remove photoresist.
Control to the cineration technics of resist remover can be adopted traditional duration control method, preferred employing comes the cineration technics of resist remover is controlled according to the intensity of spectral line of predetermined substance in the present embodiment, controls the purpose that residual photoresist is removed more exactly to reach.
In the process of cineration technics, the residual photoresist on wafer more for a long time, predetermined substance with it fully the reaction, it is relatively low that the content of predetermined substance will become, correspondingly, the intensity of spectral line of predetermined substance is also relatively low; Otherwise, the residual photoresist on wafer more after a little while, it is less that predetermined substance is reacted with it, the content of predetermined substance will be higher relatively, correspondingly, the intensity of spectral line of predetermined substance is also higher relatively.
Further, the embodiment of the invention is to adopt atomic emission spectrometry, and the oxygen plasma in the cineration technics process is detected, and obtains the spectral line of described oxygen plasma, and, control of the removal of described cineration technics to described residual photoresist by monitoring the intensity of spectral line of described oxygen plasma.
Specifically, be that wavelength to the oxygen plasma in the cineration technics process is that the spectral line of 615nm and/or 777.2nm detects.The wavelength of selecting the article on plasma body for use is that the purpose that the spectral line of 615nm and/or 777.2nm detects is: be to detect by the wavelength of article on plasma body on the one hand, can reach very high accuracy; The wavelength that is plasma on the other hand is that the time dependent trend of intensity of spectral line of 615nm and 777.2nm is obvious, is convenient to observe.Fig. 2 is for carrying out the time dependent tendency chart of the intensity of spectral line of plasma in the present embodiment.Fig. 3 is for carrying out the wafer slice sample drawing of removing of photoresist by plasma in the present embodiment.
Should be understood that the embodiment of the invention is that to be that example is carried out illustrated so that the oxygen plasma in the cineration technics process is detected, but the present invention is not limited to this, also can detect hydrogen ion in the cineration technics process or carbon ion etc.
With reference to shown in Figure 4, another embodiment of the present invention is on the basis of the foregoing description, described with ultra-pure water or deionized water described wafer is washed after, also comprise step before with aqueous isopropanol described wafer being carried out immersion treatment:
S35, described wafer is purged with nitrogen.
After described wafer being washed with ultra-pure water or deionized water, with nitrogen the benefit that described wafer purges is: on the one hand described wafer is carried out drying, can remove the hydrofluoric acid residual solution of wafer surface more effectively, reduce the damage of hydrofluoric acid, avoid residual hydrofluoric acid solution that follow-up aqueous isopropanol is polluted wafer itself.Also can reduce consumption on the other hand to ultra-pure water or deionized water.
Referring to shown in Figure 5, further embodiment of this invention is on the basis of the foregoing description, also comprises step after with aqueous isopropanol described wafer being carried out immersion treatment:
S50, described wafer is washed with ultra-pure water or deionized water;
With ultra-pure water or deionized water described wafer is washed in this step, can remove the particle contamination in the cleaning operation, simultaneously also can be with the dilution of isopropyl alcohol residual solution, removal.
S60, a large amount of nitrogen of employing purge described wafer, make the wafer finish-drying.
After described wafer being carried out immersion treatment, with ultra-pure water or deionized water described wafer is washed, and described wafer is purged, so that wafer is carried out subsequent treatment with a large amount of nitrogen with aqueous isopropanol.
Figure 6 shows that in the embodiment of the invention, is after the hydrofluoric acid solution of 1-10% cleans 5-60 time second and drying, to soak and sample after cleaning figure with 20-45 ℃ aqueous isopropanol with wafer concentration.
Need to prove, in the embodiment of the invention, be not limited to above-mentioned two kinds of uses that chemical solution is hydrofluoric acid solution and aqueous isopropanol, also can use acetone or other and the similar chemical substance of isopropyl alcohol chemical characteristic to reach the technical program purpose.In addition, the concentration of hydrofluoric acid solution and aqueous isopropanol, temperature and time are decided according to the wafer actual conditions, the scope that includes but not limited in the literary composition to be put down in writing.
The above; only be the specific embodiment of the present invention, but protection scope of the present invention is not limited thereto, anyly is familiar with those skilled in the art in the technical scope that the present invention discloses; can expect easily changing or replacing, all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion by described protection range with claim.

Claims (10)

1. the removal method of a photoresist is characterized in that, may further comprise the steps:
With the wafer behind the plasma etching, the employing cineration technics is removed the residual photoresist on the described wafer;
With weak acid solution described wafer is cleaned;
With ultra-pure water or deionized water described wafer is washed;
(are other organic solvents passable with organic? can use acetone to replace isopropyl alcohol) solution carries out immersion treatment to described wafer.
2. the removal method of photoresist according to claim 1 is characterized in that, described weak acid solution is a hydrofluoric acid solution.
3. the removal method of photoresist according to claim 1 is characterized in that, described organic solution is a kind of in acetone or the isopropyl alcohol or both mixed solutions.
4. the removal method of photoresist according to claim 1 is characterized in that, in the process of described cineration technics, according to the intensity of spectral line of predetermined substance, controls the removal of described cineration technics to described residual photoresist.
5. the removal method of photoresist according to claim 4 is characterized in that, described the intensity of spectral line according to predetermined substance is controlled described cineration technics the removal of described residual photoresist is specially:
Adopt atomic emission spectrometry, the predetermined substance in the cineration technics process is detected, obtain the spectral line of described predetermined substance, and, control of the removal of described cineration technics described residual photoresist by monitoring the intensity of spectral line of described predetermined substance.
6. the removal method of photoresist according to claim 5 is characterized in that, described employing atomic emission spectrometry detects the predetermined substance in the cineration technics process and to be specially:
Adopt atomic emission spectrometry, the oxygen plasma in the cineration technics process, hydrogen plasma or carbon plasma are detected.
7. the removal method of photoresist according to claim 6 is characterized in that, described oxygen plasma in the cineration technics process is detected is specially:
To cineration technics process ionic medium body medium wavelength is that the spectral line of 615nm and/or 777.2nm detects.
8. the removal method of photoresist according to claim 2 is characterized in that, described hydrofluoric acid solution cleans described wafer and is specially:
Hydrofluoric acid solution with concentration 1-10% cleans 5 seconds-60 second time with described wafer.
9. the removal method of photoresist according to claim 1 is characterized in that, after described wafer being washed, described wafer is carried out also comprising before the immersion treatment with organic solution with ultra-pure water or deionized water:
With nitrogen described wafer is purged.
10. the removal method of photoresist according to claim 1 is characterized in that, described wafer is carried out also comprising after the immersion treatment with organic solution described:
With ultra-pure water or deionized water described wafer is washed;
With nitrogen described wafer is purged.
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Cited By (12)

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Publication number Priority date Publication date Assignee Title
CN102698983A (en) * 2012-05-08 2012-10-03 常州天合光能有限公司 Cleaning method for solar energy level silicon slice
CN104992898A (en) * 2015-05-28 2015-10-21 北京七星华创电子股份有限公司 Method for improving DHF corrosion uniformity and controlling corrosion rate
CN105448657A (en) * 2014-09-02 2016-03-30 无锡华润上华半导体有限公司 Method for improving threshold voltage uniformity of high-voltage device
CN106960778A (en) * 2016-01-11 2017-07-18 北大方正集团有限公司 A kind of method and system for removing photoetching residual
CN107808822A (en) * 2017-09-29 2018-03-16 上海华虹宏力半导体制造有限公司 The lithographic method of contact hole
CN105931949B (en) * 2016-06-20 2019-02-19 黄山博蓝特半导体科技有限公司 A kind of one chip cleaning method of graphical sapphire substrate rework wafers
CN110723909A (en) * 2019-10-29 2020-01-24 维达力实业(深圳)有限公司 Method for processing decorative pattern and microscopic texture on surface of base material
CN110993485A (en) * 2019-11-27 2020-04-10 江苏富乐德半导体科技有限公司 Surface passivation method of silicon nitride ceramic copper-clad substrate
CN111063828A (en) * 2019-12-31 2020-04-24 安徽熙泰智能科技有限公司 Silicon-based Micro OLED Micro-display anode and preparation method thereof
CN111487844A (en) * 2019-01-29 2020-08-04 山东浪潮华光光电子股份有限公司 Photoetching plate surface damage repairing solution and application thereof
CN113031409A (en) * 2021-03-03 2021-06-25 苏州子山半导体科技有限公司 Polyimide photoresist removing method in vanadium oxide thermal imaging chip manufacturing
CN114405908A (en) * 2021-12-31 2022-04-29 至微半导体(上海)有限公司 Cleaning method suitable for etched wafer chemicals

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CN104637791A (en) * 2013-11-14 2015-05-20 北大方正集团有限公司 Method and device for increasing wafer reworking satisfaction rates

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US6951823B2 (en) * 2001-05-14 2005-10-04 Axcelis Technologies, Inc. Plasma ashing process

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102698983A (en) * 2012-05-08 2012-10-03 常州天合光能有限公司 Cleaning method for solar energy level silicon slice
CN105448657A (en) * 2014-09-02 2016-03-30 无锡华润上华半导体有限公司 Method for improving threshold voltage uniformity of high-voltage device
CN104992898A (en) * 2015-05-28 2015-10-21 北京七星华创电子股份有限公司 Method for improving DHF corrosion uniformity and controlling corrosion rate
CN104992898B (en) * 2015-05-28 2017-12-08 北京七星华创电子股份有限公司 A kind of method of improvement DHF erosion uniformities and control corrosion rate speed
CN106960778A (en) * 2016-01-11 2017-07-18 北大方正集团有限公司 A kind of method and system for removing photoetching residual
CN105931949B (en) * 2016-06-20 2019-02-19 黄山博蓝特半导体科技有限公司 A kind of one chip cleaning method of graphical sapphire substrate rework wafers
CN107808822A (en) * 2017-09-29 2018-03-16 上海华虹宏力半导体制造有限公司 The lithographic method of contact hole
CN111487844A (en) * 2019-01-29 2020-08-04 山东浪潮华光光电子股份有限公司 Photoetching plate surface damage repairing solution and application thereof
CN110723909A (en) * 2019-10-29 2020-01-24 维达力实业(深圳)有限公司 Method for processing decorative pattern and microscopic texture on surface of base material
CN110993485A (en) * 2019-11-27 2020-04-10 江苏富乐德半导体科技有限公司 Surface passivation method of silicon nitride ceramic copper-clad substrate
CN111063828A (en) * 2019-12-31 2020-04-24 安徽熙泰智能科技有限公司 Silicon-based Micro OLED Micro-display anode and preparation method thereof
CN113031409A (en) * 2021-03-03 2021-06-25 苏州子山半导体科技有限公司 Polyimide photoresist removing method in vanadium oxide thermal imaging chip manufacturing
CN114405908A (en) * 2021-12-31 2022-04-29 至微半导体(上海)有限公司 Cleaning method suitable for etched wafer chemicals
CN114405908B (en) * 2021-12-31 2023-07-25 至微半导体(上海)有限公司 Cleaning method suitable for wafer chemicals after etching

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