CN102581484B - Method for preparing silicon-based surface light trapping structure by utilizing ultrashort pulse laser - Google Patents
Method for preparing silicon-based surface light trapping structure by utilizing ultrashort pulse laser Download PDFInfo
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- CN102581484B CN102581484B CN201210052373.4A CN201210052373A CN102581484B CN 102581484 B CN102581484 B CN 102581484B CN 201210052373 A CN201210052373 A CN 201210052373A CN 102581484 B CN102581484 B CN 102581484B
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- 238000000034 method Methods 0.000 title claims abstract description 36
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 32
- 239000010703 silicon Substances 0.000 title claims abstract description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 50
- 239000000377 silicon dioxide Substances 0.000 claims description 25
- 239000000758 substrate Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 229920002521 macromolecule Polymers 0.000 claims description 6
- 229920002799 BoPET Polymers 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 claims description 2
- 239000006260 foam Substances 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 4
- 229910021419 crystalline silicon Inorganic materials 0.000 abstract description 2
- 239000010409 thin film Substances 0.000 abstract description 2
- 239000007888 film coating Substances 0.000 abstract 1
- 238000009501 film coating Methods 0.000 abstract 1
- 230000006698 induction Effects 0.000 abstract 1
- 239000002210 silicon-based material Substances 0.000 abstract 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000010408 film Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- 239000002585 base Substances 0.000 description 2
- 229910021418 black silicon Inorganic materials 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000609 electron-beam lithography Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001020 plasma etching Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000002048 anodisation reaction Methods 0.000 description 1
- 230000003667 anti-reflective effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000001451 molecular beam epitaxy Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229910021426 porous silicon Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Laser Beam Processing (AREA)
Abstract
The invention relates to a silicon-based surface light trapping structure, in particular to a method for preparing the silicon-based surface light trapping structure under the induction of visible/near infrared ultrashort pulse laser. The method is applicable to a silicon-based material such as crystalline silicon, thin film silicon and the like. The method for preparing the silicon-based surface light trapping structure by utilizing the ultrashort pulse laser aims to overcome the shortcomings of the prior art. The silicon-based surface light trapping structure is formed by a surface film coating method without a gas or liquid as an ambient medium.
Description
Technical field
The present invention relates to silicon substrate surface light trapping structure, refer in particular to a kind of method of utilizing visible/near infrared induced by ultrashort pulse laser to prepare silicon substrate surface light trapping structure, applicable to silica-base materials such as crystalline silicon and thin film silicon.
Background technology
In solar battery structure, introducing light trapping structure is in order to improve the absorption of solar cell to light, thereby improves short circuit current and the conversion efficiency of solar cell; Light trapping structure, by reflection, refraction and scattering, is distributed to all angles by incident ray, thereby increases the light path of light in solar cell, and light absorption is increased; At present, silica-based solar cell due to raw material sources extensively, cost is compared with low and in occupation of the leading position in solar cell market, it is significant that therefore the new method of silicon substrate surface light trapping structure is prepared in research and development.
The conventional method of preparing silicon substrate surface light trapping structure mainly contains: the preparation table face suede structures such as (1) acid/alkali wet etching, reactive ion etching, photon/electron beam lithography, mechanical carving groove, induced with laser; (2) chemical vapour deposition technique or sputtering method etc. are prepared antireflective film; (3) the surperficial porous silicon layer of the preparation such as anodization method; (4) the special nanometer light trapping structure of the preparation such as electron beam lithography, plasma etching method, especially periodically sub-wavelength grate structure; (5) physical vaporous deposition, chemical vapour deposition technique, molecular beam epitaxy etc. are prepared the sunken photosphere of quantum dot; Formerly in technology, adopt induced with laser legal system conventionally to have two kinds of methods for silicon substrate surface light trapping structure: a kind of is " black silicon " preparation method who is proposed and developed by the Mazur of Harvard University professor seminar of report the earliest in 1998, utilize pulse laser at gas necessarily (as SF
6, H
2s, SiH
4, H
2deng, SF
6middle effect is best) irradiate the peak structure that silicon chip produces micron dimension under environment; originally be that local naked eyes that the glossiness silicon face of grey is crossed in etching are looked and become black completely (referring to document: [1] T. H. Her; R. J. Finlay; C. Wu; S. Deliwala, and E. Mazur. Applied Physics Letters 73 (1998) 1673 ~ 1675; [2] Michael A. Sheehy, Luke Winston, James E. Carey, Cynthia M. Friend, and Eric Mazur. Chemical Materials 17 (2005) 3582 ~ 3586), they have also inquired at SF
6in gas, adopt optics and the electric property of this " black silicon " prepared by nanosecond or femtosecond pulse, result shows that it has very strong low band gaps absorptivity and photogenerated current (referring to document: [3] C. H. Crouch, J. E. Carey, J. M. Warrender, M. J. Aziz, E. Mazurb and F. Y. G é nin. Applied Physics Letters 84 (2004) 1850 ~ 1852); Another kind is the method that the silicon chip that is placed in liquid (as distilled water, sulfuric acid solution etc.) by laser irradiation is prepared silicon substrate surface micro-nano structure, as the sea of gates employing near-infrared Gold Films Irradiated by Femtosecond Laser such as is rather immersed in the n type single crystal silicon sheet in sulfuric acid solution, after irradiation, silicon face is the column type structure that diameter is 5～8 μ m, height 15 μ m, fluorescence spectrum shows that there is very strong fluorescent emission in the region after laser scanning (referring to document: [4] sea of gates is peaceful near 700 nm, Cheng Guanghua, Sun Chuandong. light laser and the particle beams 18 (2006) 1081 ~ 1084).But these two kinds of methods all have the shortcomings such as complicated operation, environmental condition be restive and SF
6poisonous, sulfuric acid corrosion resistance is strong, easy contaminated environment and cause danger.
Summary of the invention
The object of the invention is to overcome formerly technical deficiency, a kind of method of utilizing induced by ultrashort pulse laser to prepare silicon substrate surface light trapping structure is provided, without gas or liquid, as surrounding medium, by surface label embrane method, realize silicon substrate surface structure formation.
The technical solution of the surface label embrane method that the present invention proposes is as follows:
Utilize induced by ultrashort pulse laser to prepare a method for silicon substrate surface light trapping structure, it is characterized in that: the method comprises the following steps:
1. select ultrashort pulse laser, require its pulse width to be less than 20 ns, wavelength at 400 ~ 1000 nm.
2. select the transparent pad pasting of macromolecule, resistance to temperature≤50 of the transparent pad pasting of macromolecule ℃, light rate≤90%, thick degree≤1 mm thoroughly.
3. silica-based sample being carried out to early stage cleans.
4. transparent pad pasting is close on the silica-based sample surfaces being placed on sample stage, adjust the position of sample stage, make laser beam that above-mentioned laser instrument the sends focus after lens focus be positioned at 100 ~ 500 μ m places below silica-based sample surfaces, silica-based sample surfaces is positioned at front 100 ~ 500 μ m places of laser Jiao.
5. adjust the output of laser instrument, controlling laser energy is 10 ~ 500 μ J, and sweep speed is 0.1 ~ 5 mm/s.
6. according to the laser energy of selecting, determine the line width of laser beam, the scanning pattern of setting laser bundle, is specially: laser beam is done unidirectional by line sweep accordingly, by setting distance between centers of tracks
lcontrol adjacent two lines mutually overlapping,
lbe greater than 0 and be less than laser scanning live width
d,each line multiple scanning number of times is 1 ~ 5 time; According to the laser beam flying path of having set, control laser beam motion, laser beam is scanned perpendicular to silica-based sample surfaces.
7. take off silica-based sample, it is carried out to later stage cleaning after throwing off surperficial transparent pad pasting.
A kind of described method of utilizing induced by ultrashort pulse laser to prepare silicon substrate surface light trapping structure, is characterized in that: the transparent pad pasting of described macromolecule is PET film, PC film, PMMA film or ETFE film.
A kind of described method of utilizing induced by ultrashort pulse laser to prepare silicon substrate surface light trapping structure, it is characterized in that: the method that clean early stage is: be first placed in deionized water for ultrasonic and clean 10 minutes, 25 ℃ of temperature, power 80 W, take out again with deionized water rinsing and dry, then being placed in mass fraction and being 5% hydrofluoric acid soaks 15 minutes, take out again subsequently with deionized water rinsing and dry, finally with absolute ethyl alcohol or acetone, cleaning to receive and do.
A kind of described method of utilizing induced by ultrashort pulse laser to prepare silicon substrate surface light trapping structure, it is characterized in that: the method that the later stage cleans is: first employing is blown ear ball and blown away the broken foam that splashes producing when prepared by micro-structural, being placed in mass fraction again and being 5% hydrofluoric acid soaks 5 minutes, take out subsequently by deionized water and repeatedly rinse and dry, finally with absolute ethyl alcohol or acetone, clean to receive and do.
The surface label embrane method that the present invention proposes has the following advantages:
1) simple to operate, requirement for environmental conditions is low; Only need to paste transparent pad pasting at silica-based sample surfaces and can realize light trapping structure processing, not need to introduce the harsh environmental condition such as special background gas or liquid medium.
2) pollution-free, without potential safety hazard; Do not adopt any poisonous or mordant medium, farthest eliminated environmental pollution and personal safety hidden danger.
Accompanying drawing explanation
Fig. 1 utilizes the schematic diagram of the silica-based sample surfaces of visible/near infrared ultra-short pulsed laser beam scanning pad pasting;
SEM and the reflective light intensity test result thereof of the silicon substrate surface light trapping structure of preparation in Fig. 2 embodiment 1;
SEM and the reflective light intensity test result thereof of the silicon substrate surface light trapping structure of preparation in Fig. 3 embodiment 2;
1, laser beam; 2, focus lamp; 3, transparent pad pasting; 4, silica-based sample.
The specific embodiment
Fig. 1 is the schematic diagram that utilizes the silica-based sample surfaces of visible/near infrared ultra-short pulsed laser beam scanning pad pasting in the present invention, wherein figure (a) is that silica-based sample levels is placed, the situation of laser beam horizontal direction scanning, figure (b) is that silica-based samples vertical is placed, the situation of laser beam vertical scan direction, and in figure, arrow all represents scanning direction; Laser beam 1 sees through transparent pad pasting 3 and is irradiated on the surface of silica-based sample 4 after focus lamp 2 focuses on, the focus of laser beam 1 is positioned at below the surface of silica-based sample 4, by laser beam, moved unidirectional by line sweep, by overlapping between adjacent two lines and then realize large-area scanning.
The monocrystalline silicon sheet surface that PET film is pasted in the laser scanning of take is below described further as the method that example proposes the present invention.
embodiment 1:the silica-based light trapping structure of the present embodiment is that to adopt pulsewidth be that 130 fs, wavelength are that 800 nm, mean power are that 2.5 W, repetition rate are prepared by the monocrystalline silicon sheet surface that PET film (approximately 60 ℃ of heatproofs, light transmittance reach more than 95%, thickness is 0.125 mm) is posted in the femtosecond laser scanning of 1 KHz; Its method is: the position of adjusting sample stage makes the finished surface of monocrystalline silicon piece be positioned at the front 100 μ m places of laser spot; Controlling laser energy is 200 μ J, and sweep speed is 1 mm/s; According to laser energy, determine that the line width of laser beam is 100 μ m, setting accordingly distance between centers of tracks is 50 μ m, and setting each line multiple scanning number of times is 2 times; The motion of control laser beam, makes laser beam make large-area scanning perpendicular to silica-based sample surfaces; Fig. 2 is 45 ° of observations of SEM(inclination of the silicon substrate surface light trapping structure of preparation) and reflective light intensity test result, from left side SEM, schemed, by induced with laser, on monocrystalline silicon sheet surface, formed intensive conoid protuberance structure, top taper, bottom is wider, highly be about 2 ~ 8 μ m, bottom width is about 3 ~ 6 μ m; The reflective light intensity correlation curve demonstration on the right, after scanning, the reflective light intensity of monocrystalline silicon sheet surface is all stabilized in low value at 200 ~ 1000 nm wave bands, before scanning, has significantly and reduces, and shows that it has extraordinary absorbing properties.
embodiment 2:the silica-based light trapping structure of the present embodiment is that to adopt pulsewidth be that 1 ~ 2 ns, wavelength are that 532 nm, mean power are that 0.9 W, repetition rate are prepared by the monocrystalline silicon sheet surface that PET film (approximately 60 ℃ of heatproofs, light transmittance reach more than 95%, thickness is 0.125 mm) is posted in the nanosecond laser scanning of 1 KHz; Its method is: the position of adjusting sample stage makes the finished surface of monocrystalline silicon piece be positioned at the front 200 μ m places of laser spot; Controlling laser energy is 500 μ J, and sweep speed is 0.2 mm/s; According to laser energy, determine that the line width of laser beam is 120 μ m, setting accordingly distance between centers of tracks is 100 μ m, and setting each line multiple scanning number of times is 1 time; The motion of control laser beam, makes laser beam make large-area scanning perpendicular to silica-based sample surfaces; Fig. 3 is the SEM(waist-level viewing of the silicon substrate surface light trapping structure of preparation) and reflective light intensity test result, from left side SEM, schemed, by induced with laser, on monocrystalline silicon sheet surface, formed the structure that more sparse hole and strumae are alternate, yardstick is inhomogeneous, the base diameter of strumae is about 6 ~ 20 μ m, and small part strumae damages because energy is bigger; The reflective light intensity correlation curve demonstration on the right, after scanning, the reflective light intensity of monocrystalline silicon sheet surface scans front decrease to some degree, shows that it has good absorbing properties.
Embodiment proposed by the invention only describes technical scheme, and does not limit.
Claims (4)
1. utilize induced by ultrashort pulse laser to prepare a method for silicon substrate surface light trapping structure, it is characterized in that: the method comprises the following steps:
1. select ultrashort pulse laser, requiring its pulse width is that 130 fs or 1 ~ 2 ns, wavelength are at 400 ~ 1000 nm;
2. select the transparent pad pasting of macromolecule, resistance to temperature≤50 of the transparent pad pasting of macromolecule ℃, light rate≤90%, thick degree≤1 mm thoroughly;
3. silica-based sample being carried out to early stage cleans;
4. transparent pad pasting is close on the silica-based sample surfaces being placed on sample stage, adjust the position of sample stage, make laser beam that above-mentioned laser instrument the sends focus after lens focus be positioned at 100 ~ 500 μ m places below silica-based sample surfaces, silica-based sample surfaces is positioned at front 100 ~ 500 μ m places of laser Jiao;
5. adjust the output of laser instrument, controlling laser energy is 10 ~ 500 μ J, and sweep speed is 0.1 ~ 5 mm/s;
6. according to the laser energy of selecting, determine the line width of laser beam, the scanning pattern of setting laser bundle, is specially: laser beam is done unidirectional by line sweep accordingly, by setting distance between centers of tracks
lcontrol adjacent two lines mutually overlapping,
lbe greater than 0 and be less than laser scanning live width
d,each line multiple scanning number of times is 1 ~ 5 time; According to the laser beam flying path of having set, control laser beam motion, laser beam is scanned perpendicular to silica-based sample surfaces;
7. take off silica-based sample, it is carried out to later stage cleaning after throwing off surperficial transparent pad pasting.
2. a kind of method of utilizing induced by ultrashort pulse laser to prepare silicon substrate surface light trapping structure as claimed in claim 1, is characterized in that: the transparent pad pasting of described macromolecule is PET film, PC film, PMMA film or ETFE film.
3. a kind of method of utilizing induced by ultrashort pulse laser to prepare silicon substrate surface light trapping structure as claimed in claim 1, it is characterized in that: the method that clean early stage is: be first placed in deionized water for ultrasonic and clean 10 minutes, 25 ℃ of temperature, power 80 W, take out again with deionized water rinsing and dry, then being placed in mass fraction and being 5% hydrofluoric acid soaks 15 minutes, take out again subsequently with deionized water rinsing and dry, finally with absolute ethyl alcohol or acetone, cleaning to receive and do.
4. a kind of method of utilizing induced by ultrashort pulse laser to prepare silicon substrate surface light trapping structure as claimed in claim 1, it is characterized in that: the method that the later stage cleans is: first employing is blown ear ball and blown away the broken foam that splashes producing when prepared by micro-structural, being placed in mass fraction again and being 5% hydrofluoric acid soaks 5 minutes, take out subsequently by deionized water and repeatedly rinse and dry, finally with absolute ethyl alcohol or acetone, clean to receive and do.
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| CN104009128A (en) * | 2014-06-12 | 2014-08-27 | 电子科技大学 | Preparing method of amorphous silicon membrane light trapping structure for solar cell |
| CN104178742B (en) * | 2014-08-05 | 2016-08-24 | 江苏大学 | A kind of preparation method of embedded type metal/transparent conductive film |
| CN107116216B (en) * | 2016-02-24 | 2019-05-21 | 哈尔滨福沃德多维智能装备有限公司 | A kind of 3D printing Laser Scanning |
| CN106524834A (en) * | 2016-12-19 | 2017-03-22 | 兰州空间技术物理研究所 | Infrared stealth light trapping structure of moving target and infrared stealth method |
| CN106624348B (en) * | 2016-12-22 | 2018-10-09 | 江苏大学 | The method that a kind of one step of FTO film surfaces selectivity prepares ripple struction |
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| CN107498183B (en) * | 2017-07-17 | 2019-11-08 | 西安交通大学 | A method of preparation large area periodic structure is induced with linear light spot |
| CN110116273A (en) * | 2019-06-05 | 2019-08-13 | 北京理工大学 | The method that femtosecond laser synergistic oxidation reaction prepares broad band anti-reflection structure |
| CN112025098B (en) * | 2020-08-25 | 2022-10-04 | 湖北工业大学 | Preparation method of titanium alloy surface with low reflectivity to visible light |
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| JP4214233B2 (en) * | 2003-03-26 | 2009-01-28 | 独立行政法人産業技術総合研究所 | Fine processing method and fine structure of transparent material |
| CN1654516A (en) * | 2005-01-20 | 2005-08-17 | 中国科学院上海光学精密机械研究所 | Method for preparing conductive polymer periodic microstructure |
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Inventor after: Li Baojia Inventor after: Zhou Ming Inventor after: Huang Lijing Inventor after: Zhang Wei Inventor after: Tang Wanyi Inventor after: Ma Ming Inventor after: Cai Lan Inventor before: Zhou Ming Inventor before: Li Baojia Inventor before: Zhang Wei Inventor before: Tang Wanyi Inventor before: Ma Ming Inventor before: Cai Lan |
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Effective date of registration: 20210312 Address after: Room 1002, Huali building, No.6 Gongnong Road, Chongchuan District, Nantong City, Jiangsu Province, 226000 Patentee after: Nantong Ningjing Information Technology Co.,Ltd. Address before: Zhenjiang City, Jiangsu Province, 212013 Jingkou District Road No. 301 Patentee before: JIANGSU University Effective date of registration: 20210312 Address after: 226600 no.428, Zhennan Road, Hai'an street, Hai'an City, Nantong City, Jiangsu Province Patentee after: Nantong Tongmai Automation Technology Co.,Ltd. Address before: Room 1002, Huali building, No.6 Gongnong Road, Chongchuan District, Nantong City, Jiangsu Province, 226000 Patentee before: Nantong Ningjing Information Technology Co.,Ltd. |
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Effective date of registration: 20220323 Address after: 226600 No.288, Changjiang West Road, Huji street, Hai'an City, Nantong City, Jiangsu Province Patentee after: Jiangsu chaozhihe New Material Co.,Ltd. Address before: 226600 no.428, Zhennan Road, Hai'an street, Hai'an City, Nantong City, Jiangsu Province Patentee before: Nantong Tongmai Automation Technology Co.,Ltd. |
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Granted publication date: 20141203 |