CN106104755A - 包括通过离子注入掺杂和沉积向外扩散阻挡物的用于制备太阳能电池的方法 - Google Patents
包括通过离子注入掺杂和沉积向外扩散阻挡物的用于制备太阳能电池的方法 Download PDFInfo
- Publication number
- CN106104755A CN106104755A CN201480058077.2A CN201480058077A CN106104755A CN 106104755 A CN106104755 A CN 106104755A CN 201480058077 A CN201480058077 A CN 201480058077A CN 106104755 A CN106104755 A CN 106104755A
- Authority
- CN
- China
- Prior art keywords
- layer
- adulterant
- cover layer
- aforementioned
- doped region
- Prior art date
- 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
Links
- 238000000034 method Methods 0.000 title claims abstract description 53
- 238000009792 diffusion process Methods 0.000 title claims abstract description 15
- 230000004888 barrier function Effects 0.000 title claims abstract description 5
- 238000005468 ion implantation Methods 0.000 title description 2
- 238000000137 annealing Methods 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 16
- 239000004065 semiconductor Substances 0.000 claims abstract description 15
- 239000013078 crystal Substances 0.000 claims abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 22
- 229910052698 phosphorus Inorganic materials 0.000 claims description 22
- 239000011574 phosphorus Substances 0.000 claims description 22
- 230000002441 reversible effect Effects 0.000 claims description 21
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 20
- 229910052796 boron Inorganic materials 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 230000035876 healing Effects 0.000 claims description 13
- 229910052710 silicon Inorganic materials 0.000 claims description 13
- 239000010703 silicon Substances 0.000 claims description 13
- 238000002161 passivation Methods 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 150000002500 ions Chemical class 0.000 claims description 7
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 7
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 6
- 230000036961 partial effect Effects 0.000 claims description 6
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 6
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 2
- 238000005530 etching Methods 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims 1
- 230000008569 process Effects 0.000 description 16
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 230000004913 activation Effects 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- 238000001465 metallisation Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 238000001505 atmospheric-pressure chemical vapour deposition Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000011435 rock Substances 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000000637 aluminium metallisation Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000002146 bilateral effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic Table
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/26—Bombardment with radiation
- H01L21/263—Bombardment with radiation with high-energy radiation
- H01L21/265—Bombardment with radiation with high-energy radiation producing ion implantation
- H01L21/26506—Bombardment with radiation with high-energy radiation producing ion implantation in group IV semiconductors
- H01L21/26513—Bombardment with radiation with high-energy radiation producing ion implantation in group IV semiconductors of electrically active species
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/028—Inorganic materials including, apart from doping material or other impurities, only elements of Group IV of the Periodic Table
- H01L31/0288—Inorganic materials including, apart from doping material or other impurities, only elements of Group IV of the Periodic Table characterised by the doping material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
- H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
- H01L31/068—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
- H01L31/1864—Annealing
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/547—Monocrystalline silicon PV cells
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Electromagnetism (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- High Energy & Nuclear Physics (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Sustainable Energy (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Inorganic Chemistry (AREA)
- Photovoltaic Devices (AREA)
Abstract
本发明涉及由晶体半导体材料制备太阳能电池(1)的方法，其中在半导体基材(3)的第一表面(3a)中通过离子注入(S2)第一掺杂剂形成第一掺杂区域(5)，并且在半导体基材的第二表面(3b)中通过离子注入(S3)或向内热扩散第二掺杂剂形成第二掺杂区域(7)，其中在掺杂第二表面之后在其上施加充当第二掺杂剂的向外扩散阻挡物的覆盖层(9b)，然后进行退火步骤(S4)。
Description
本发明涉及由晶体半导体材料制备太阳能电池的方法，其中在半导体基材的第一表面中通过离子注入第一掺杂剂形成第一掺杂区域，并且在半导体基材的第二表面中通过离子注入或向内热扩散第二掺杂剂形成第二掺杂区域。
背景技术
尽管新型太阳能电池(例如薄层太阳能电池和有机太阳能电池)已经被开发和推出市场，基于单晶或多晶半导体材料(特别是硅)的太能能电池产生绝大部分通过光电能量转换获得的电能。近年来在晶体硅太阳能电池中也存在重要的新型开发，其中包括上述类型的太阳能电池(特别是所谓的n-PERT太阳能电池)。
为了提高工业太阳能电池的效率，目前日益推进具有磷掺杂区域和硼掺杂区域的太阳能电池的开发。一个杰出示例为双面n型太阳能电池，其中在电池的正面上存在硼掺杂的发射体而在电池的反面上存在磷掺杂的背面场(BSF)。
发明内容
特别地，当掺杂区域与丝网印刷金属化结构接触时，希望的是调节两种掺杂剂的不同的掺杂轮廓。硼轮廓应当相对较深并且具有较低的表面浓度，而磷轮廓应当较浅并且具有更高的表面浓度。这取决于市售金属化糊剂的不同的接触行为。
最佳途径在于使用先进的掺杂技术，例如离子注入。所述方法允许在半导体基材中单面引入掺杂剂或者在半导体基材的两个主表面中引入不同掺杂剂。图1中显示了制备双面掺杂的太阳能电池的流程图。由于所述图是自解释的，在此无需进行更详细地描述。在此，在步骤S2和S3中的离子注入之后进行退火步骤或愈合步骤S4，在所述退火步骤或愈合步骤S4中在晶片表面上额外生长薄的氧化物层。所述氧化物层连同之后在步骤S5或S6中沉积的SiN覆盖层形成钝化叠层。
在本发明人的试验中证明，将所述途径转化成实践是成问题的。用所述方法制备的太阳能电池的效率显著低于用更复杂流程制备的太阳能电池。
这特别归因于如下效应：注入的硼发射体的愈合需要在极高温度(>1000℃)下在惰性气氛中的退火步骤。这些条件对于磷背面场(BSF)的愈合来说是不理想的。磷由于高温而扩散至基材中极深的位置。这造成升高的自由载流子吸收，这降低电池的量子效率。此外还发生表面磷的蒸发。这又由于掺杂剂的损失造成电池反面上的接触电阻的升高，并且可能由于所谓的自掺杂造成发射体和BSF之间的短路。
通过本发明提供具有权利要求1的特征的方法。本发明构思的有利的改进方案为从属权利要求的主题。
本发明包括的考虑是，在进行退火步骤(高温愈合步骤)之前采取预防措施从而至少限制和/或抵消磷掺杂区域上的所述不利效应。特别提出的是，在半导体基材的第二表面上施加充当第二掺杂剂的向外扩散阻挡物的覆盖层(盖)。
在本发明中，通过在注入BSF之后和在愈合步骤之前在太阳能电池的反面上沉积盖从而解决上述问题。盖阻止磷向外扩散。此外在一个实施方式中可以使用不透过氧气的覆盖层，所述覆盖层在电池反面上阻止所谓的氧化物增强的扩散(由于氧化物而加速的扩散，OED)。通过这些措施产生BSF轮廓，所述BSF轮廓不具有上述缺点。同样可以通过合适的掩膜阻止自掺杂。在另一个变体形式中可以沉积这样的层，所述层在退火步骤的过程中在硅中注入缺陷(空穴)。所述缺陷造成磷扩散的进一步变慢。这可以通过处于张应力下的覆盖层和/或亚化学计量的覆盖层而进行。
在从该观点来看优选的实施方案中，施加在第二表面上的覆盖层作为太阳能电池的防反射层/钝化层或其一部分保留在第二表面上。因此不产生额外的过程复杂性。其可行性在一定程度上是出人意料的，因为通常的假设是在此所讨论类型的一个层(特别是通过PECVD形成的层)在之后的高温步骤的过程中其钝化性能劣化，因此大部分不能用作钝化层。在一个替代性实施方案中提出，施加在第二表面上的覆盖层在退火步骤之后进行反蚀刻。在反蚀刻之后，在该实施方案中重新施加特定的钝化层。
如上所述，在另一个实施方案中，施加在第二表面上的覆盖层通过PECVD方法沉积。替代性地，可以使用PVD或APCVD或相似方法用于形成覆盖层。本领域技术人员通过考虑第二掺杂剂的掺杂参数可以由具体层的材料参数和后续热步骤的参数得出详细的方法实施方案，而无需详细解释。
下文进一步给出实施例的细节。
在材料方面从目前的角度来看优选的实施方案中，施加在第二表面上的覆盖层包括氧化硅层和/或氮化硅层和/或氮氧化硅层。覆盖层还可以被设计成包括多个局部层，所述局部层的至少一个以氮化硅层的形式形成。
根据上文，本发明从目前的角度来看对于如下太阳能电池是特别有价值的：其中使用硅作为半导体材料，并且使用选自硼、铟、镓、铝，特别是硼的元素作为第一掺杂剂，并且使用选自磷、砷、锑，特别是磷的元素作为第二掺杂剂。更特别的是如下太阳能电池：其中第一掺杂区域作为n硅基材的正面表面中的发射体区域形成，而第二掺杂区域作为n硅基材的反面表面中的背面场形成。
特别在这种材料/掺杂剂构造中提出，退火步骤包括在850℃和1100℃之间的温度下在中性或氧化大气中的愈合步骤。根据本发明基本上有利的是覆盖层以及预先作为扩散步骤设计的热过程步骤连同其它过程大气(以及含掺杂剂的大气)。
附图说明
下文借助于实施例参考示意性附图更详细地解释本发明。其中：
图1显示了制备晶体太阳能电池的已知方法的示意性流程图，
图2A和2B显示了根据本发明的方法的两个实施方式的示意性流程图，和
图3A至3E显示了在一个示例性实施方式的不同制备步骤中的硅基材或由其形成的太阳能电池的横截面图。
具体实施方式
图2A示意性地显示了根据本发明的方法的一个实施方式的制备晶体太阳能电池的主要步骤的流程图，其中该图也基本上是自解释的。相比于图1中显示的常规流程，在基材反面中注入磷的步骤(S2)和在基材正面中注入硼的步骤(S3)之后进行通过PECVD在反面上形成覆盖层的步骤(步骤S3+)，其中如标准流程一样，进行与基材表面的氧化结合的退火(退火；步骤S4)。在步骤S3+中形成的覆盖层作为防反射层/钝化层保留在基材上，因此在此省掉了标准流程的步骤S6。
与此不同，图2B中描绘的流程虽然同样设计在步骤S3+中在基材反面上形成覆盖层，但是在退火步骤S4之后在额外步骤S4+中重新除去覆盖层，并且如标准流程一样在步骤S6中通过PECVD在基材反面上重新施加防反射层/钝化层。此外，修改在基材正面上形成功能相似的层的步骤(S5')，从而在基材正面上施加氧化铝/氮化硅层结构代替SiN层。
在图3A至3E中以示意性横截面图显示了通过根据本发明的方法制备的太阳能电池的结构及其主要制备阶段，其中图3E显示了(关于在此感兴趣的流程)完成的太阳能电池1。
图3E以横截面图示意性显示了太阳能电池1，所述太阳能电池1具有n型晶体硅基材3和各自以金字塔形式结构化的第一(正面)表面3a和第二(反面)表面3b。在第一表面3a中通过硼扩散形成第一掺杂区域(发射体区域)5，并且在第二表面中通过磷注入和之后的愈合/活化形成作为第二掺杂区域的浅背面场7。在愈合/活化步骤(退火步骤)中在正面上形成热氧化硅层8。
在第一和第二表面3a、3b上分别沉积作为防反射层的厚氮化硅层9a或9b。防反射层可以补充由氧化物(例如氧化硅)组成的额外局部层，所述额外局部层改进层的钝化性能，但是在图中未示出。在太阳能电池正面(第一表面)3a上施加正面金属化结构11a，并且在太阳能电池反面(第二表面)3b上施加反面金属化结构11b。
图3A示意性显示了方法步骤S1之后的双面结构化和清洗的n硅基材1'；图3B显示了方法步骤S3之后的具有正面(初始)硼注入区域5'和反面磷注入区域7'的结构化的太阳能电池基材1'；图3C显示了在步骤S3+中沉积反面覆盖层9b之后的状态；并且图3D显示了在退火步骤(退火)S4之后的状态，其中两个掺杂区域5、7在深度方向上变大并且在正面表面上生长热氧化物8。
针对主要方法步骤的以上简要描述，下文补充修改形式或变体形式的评论和说明。
S1：结构化/清洗
在所述方法步骤中可以进行工业上常见的结构化和之后的清洗。任选可以使晶片反面平面化。用于该目的的多种方法属于现有技术并且与本发明不相关。
S2：硼注入
在电池正面中注入硼，(例如剂量在0.5和5e15 1/cm2之间，能量为1-40keV，优选1.5-3e15 1/cm2，3-10keV)。在愈合之后，硼层的层电阻为30-300欧姆/平方，优选60-100欧姆/平方。在另一个实施方式中，可以选择性地进行注入，使得金属化区域下方的剂量更高。
也可以在沉积反面盖之后(在S3+和S4之间)进行硼注入。这可以例如有利于避免注入区域在盖沉积时的机械损坏。
S3：磷注入
在此，在电池反面中注入磷(例如剂量在0.5和5e15 1/cm2之间，能量为1-40keV，优选2.5-4e15 1/cm2，10keV)。在愈合之后，磷层的层电阻为10-300欧姆/平方，优选30-120欧姆/平方。在另一个实施方式中，可以选择性地进行注入，使得金属化区域下方的剂量更高。
S3+：反面覆盖层
反面盖阻止磷向外扩散并且任选阻止氧气向内扩散。在根据图2A的实施变体中，盖保留在电池上并且用作反面钝化层。
在最简单的实施方案中，使用纯SiO2(n＝1.4-1.6，优选n＝1.46)或纯SiN层(n＝1.8-2.2，优选1.9-2)作为盖。任选地，还有可能使用SiON(n＝1.46-2.2)从而通过氧含量和氮含量的变化调节钝化作用和氧气透过性之间的最佳。所述层的厚度在1nm和250nm之间，优选30-80nm。
通常地，通过PECVD过程使用由一种或多种选自SiH4、N2O/O2/CO2、NH3、N2、Ar的气体组成的过程化学试剂沉积盖层。取决于沉积过程，所述层具有<15％的氢含量，所述氢含量通过退火(5)除去。替代性地，可以使用其它方法(例如APCVD或PVD)施加盖层。
为了优化所有要求，也可以使用叠层，例如SiO2/SiN2叠层或由两个具有不同折射率的SiN层组成的层。过程成功与否基本上取决于反面盖的操作进行。
在沉积盖之后可以进行任选的清洗步骤从而除去颗粒和可能存在的污染。这可以在水基浴中以湿式化学的方式使用一种或多种工艺化学制剂HF、HCl、H2O2进行。
S4：退火
热后处理步骤愈合注入损伤，活化注入的掺杂剂并且使硼和磷扩散进入晶片，用以实现希望的发射体深度和BSF深度。退火过程取决于硼的比磷更为苛刻的活化要求，硼的活化通常需要在高温(900-1100℃)下在惰性气氛(N2、Ar)中进行。在时间上的部分时期中可以导入氧气用以在晶片表面上生长氧化物层并且通过OED效应加快硼的扩散。退火时间在5和300min之间，优选在15和60min之间。在退火过程中生长的氧化物层用于之后的钝化并且厚度可以在1nm和150nm之间，优选5-25nm。扩散区域的深度在30nm和2500nm之间，优选400-1000nm。
替代性地，也可想到使用迅速热退火(RTA)步骤，其中在极短时间内将电池加热至极高温度(>1000℃)。
S5：正面钝化
在最简单的实施方案中，通过SiO/SiN叠层进行太阳能电池的正面钝化。在此利用来自步骤S4的热生长的氧化硅(SiO2)。通过PECVD过程沉积SiN。所述变体形式由于较低的工艺成本而是特别引人注意的。SiN通常具有在1.98和2.15之间(优选2.05)的折射率，并且以在10和150nm之间(优选60-90nm)的厚度沉积。
替代性地，对于正面钝化可以使用Al2O3/SiN叠层。为此必须选择性地除去正面上的SiO2。这可以例如通过使用HF的湿蚀刻步骤进行。
S7：金属化
金属化可以使用工业上常见的方法进行并且对本发明来说是不重要的。正面金属化通常使用银网栅进行，反面金属化同样使用银网栅进行或者使用例如通过激光烧蚀和PVD制备的具有局部触点的全面铝金属化进行。
本领域技术人员能够想到本文仅示例性描述的方法和装置的其它实施方案和实施方式。在此应当说明的是，本发明也可用于具有硼注入和磷注入的其它太阳能电池概念，例如MWT-nPERT电池，p型PERT电池等。
Claims (11)
1.由晶体半导体材料制备太阳能电池(1)的方法，其中在半导体基材(3)的第一表面(3a)中通过离子注入(S2)第一掺杂剂形成第一掺杂区域(5)，并且在半导体基材的第二表面(3b)中通过离子注入(S3)或向内热扩散第二掺杂剂形成第二掺杂区域(7)，其中在掺杂第二表面之后在第二表面上施加充当第二掺杂剂的向外扩散阻挡物的覆盖层(9b)，然后进行退火步骤(S4)。
2.根据权利要求1所述的方法，其中施加在第二表面(3b)上的覆盖层(9b)以这样方式形成，使得由于其组成、性质和厚度而不透过氧气。
3.根据权利要求1或2所述的方法，其中施加在第二表面(3b)上的覆盖层(9b)作为太阳能电池(1)的防反射层/钝化层或其一部分保留在第二表面上。
4.根据权利要求1或2所述的方法，其中施加在第二表面(3b)上的覆盖层(9b)在退火步骤(S4)之后反蚀刻。
5.根据前述权利要求任一项所述的方法，其中施加在第二表面(3b)上的覆盖层(9b)通过PECVD方法(S4)沉积。
6.根据前述权利要求任一项所述的方法，其中施加在第二表面(3b)上的覆盖层(9b)包括氧化硅层和/或氮化硅层和/或氮氧化硅层。
7.根据权利要求6所述的方法，其中覆盖层(9b)包括多个局部层，所述局部层的至少一个以氮化硅层的形式形成。
8.根据前述权利要求任一项所述的方法，其中在第一表面(3a)中离子注入第一掺杂剂之前形成覆盖层(9b)。
9.根据前述权利要求任一项所述的方法，其中使用硅作为半导体材料，并且使用选自硼、铟、镓、铝，特别是硼的元素作为第一掺杂剂，并且使用选自磷、砷、锑，特别是磷的元素作为第二掺杂剂。
10.根据前述权利要求任一项所述的方法，其中第一掺杂区域(5)作为n-硅基材(3)的正面表面(3a)中的发射区域形成，而第二掺杂区域作为n-硅基材的反面表面(3b)中的背面场(7)形成。
11.根据前述权利要求任一项所述的方法，其中退火步骤(S4)包括在850℃和1100℃之间的温度下在中性或氧化气氛中的愈合步骤。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102013218351.8A DE102013218351A1 (de) | 2013-09-13 | 2013-09-13 | Verfahren zur Herstellung einer Solarzelle |
| DE102013218351.8 | 2013-09-13 | ||
| PCT/EP2014/066856 WO2015036181A1 (de) | 2013-09-13 | 2014-08-05 | Verfahren zur herstellung einer solarzelle umfassend eine dotierung durch ionenimplantation und abscheiden einer ausdiffusionsbarriere |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106104755A true CN106104755A (zh) | 2016-11-09 |
Family
ID=51383707
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201480058077.2A Pending CN106104755A (zh) | 2013-09-13 | 2014-08-05 | 包括通过离子注入掺杂和沉积向外扩散阻挡物的用于制备太阳能电池的方法 |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US10263135B2 (zh) |
| EP (1) | EP3044813A1 (zh) |
| JP (1) | JP2016535457A (zh) |
| KR (1) | KR20160071373A (zh) |
| CN (1) | CN106104755A (zh) |
| DE (1) | DE102013218351A1 (zh) |
| MY (1) | MY173528A (zh) |
| WO (1) | WO2015036181A1 (zh) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107425086A (zh) * | 2017-05-18 | 2017-12-01 | 阳光中科（福建）能源股份有限公司 | 一种离子注入法制作n型pert双面太阳电池的制备工艺 |
| CN108231557A (zh) * | 2016-12-22 | 2018-06-29 | 英飞凌科技奥地利有限公司 | 在半导体器件中形成复合中心 |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101680036B1 (ko) * | 2015-07-07 | 2016-12-12 | 엘지전자 주식회사 | 태양 전지 및 이의 제조 방법 |
| JP6900370B2 (ja) | 2015-10-25 | 2021-07-07 | ソルアラウンド リミテッド | 両面セルを製造する方法 |
| DE102019104249A1 (de) * | 2019-02-20 | 2020-08-20 | Hanwha Q Cells Gmbh | Verfahren zur Herstellung einer PERC-Solarzelle und PERC-Solarzelle |
| CN111640804A (zh) * | 2020-06-01 | 2020-09-08 | 国家电投集团西安太阳能电力有限公司 | 一种氧化硅/氮化硅叠层膜的n-pert双面电池结构 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040112426A1 (en) * | 2002-12-11 | 2004-06-17 | Sharp Kabushiki Kaisha | Solar cell and method of manufacturing the same |
| CN101124681A (zh) * | 2004-02-05 | 2008-02-13 | 日出能源公司 | 发射极环绕型背触点硅太阳能电池的触点制备 |
| TW201234484A (en) * | 2011-02-03 | 2012-08-16 | Imec | Method for fabricating photovoltaic cells |
| CN102822988A (zh) * | 2010-04-09 | 2012-12-12 | 罗伯特·博世有限公司 | 用于制造太阳能的电池的方法 |
| CN103515477A (zh) * | 2012-06-22 | 2014-01-15 | Lg电子株式会社 | 制造太阳能电池及其掺杂层的方法 |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5363993A (en) * | 1976-11-19 | 1978-06-07 | Matsushita Electric Ind Co Ltd | Production of semiconductor device |
| DE3340874A1 (de) * | 1983-11-11 | 1985-05-23 | Telefunken electronic GmbH, 7100 Heilbronn | Verfahren zum herstellen einer solarzelle |
| JP2003152205A (ja) * | 2001-11-12 | 2003-05-23 | Sharp Corp | 光電変換素子及びその製造方法 |
| JP4632672B2 (ja) * | 2004-02-04 | 2011-02-16 | シャープ株式会社 | 太陽電池の製造方法 |
| US20060060238A1 (en) * | 2004-02-05 | 2006-03-23 | Advent Solar, Inc. | Process and fabrication methods for emitter wrap through back contact solar cells |
| US7144751B2 (en) * | 2004-02-05 | 2006-12-05 | Advent Solar, Inc. | Back-contact solar cells and methods for fabrication |
| JP4849786B2 (ja) * | 2004-08-30 | 2012-01-11 | シャープ株式会社 | 多接合型化合物太陽電池およびその製造方法 |
| JP2006310389A (ja) * | 2005-04-26 | 2006-11-09 | Sharp Corp | 太陽電池の製造方法 |
| US9318644B2 (en) * | 2009-05-05 | 2016-04-19 | Solexel, Inc. | Ion implantation and annealing for thin film crystalline solar cells |
| US20150007881A1 (en) | 2012-01-16 | 2015-01-08 | Heraeus Precious Metals North America Conshohocken Llc | Aluminum conductor paste for back surface passivated cells with locally opened vias |
| JP2013165160A (ja) * | 2012-02-10 | 2013-08-22 | Shin Etsu Chem Co Ltd | 太陽電池の製造方法及び太陽電池 |
| US9330917B2 (en) * | 2012-02-24 | 2016-05-03 | Varian Semiconductor Equipment Associates, Inc. | Passivation layer for workpieces formed from a polymer |
| CN102856436A (zh) * | 2012-09-05 | 2013-01-02 | 友达光电股份有限公司 | 太阳能电池及其制作方法 |
| DE102012217078B4 (de) * | 2012-09-21 | 2015-03-05 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Verfahren zum Herstellen einer photovoltaischen Solarzelle |
| US9515217B2 (en) * | 2012-11-05 | 2016-12-06 | Solexel, Inc. | Monolithically isled back contact back junction solar cells |
| US20140261666A1 (en) * | 2013-03-13 | 2014-09-18 | Applied Materials, Inc. | Methods of manufacturing a low cost solar cell device |
-
2013
- 2013-09-13 DE DE102013218351.8A patent/DE102013218351A1/de not_active Withdrawn
-
2014
- 2014-08-05 EP EP14753037.2A patent/EP3044813A1/de not_active Withdrawn
- 2014-08-05 JP JP2016541855A patent/JP2016535457A/ja active Pending
- 2014-08-05 WO PCT/EP2014/066856 patent/WO2015036181A1/de active Application Filing
- 2014-08-05 US US15/021,077 patent/US10263135B2/en active Active
- 2014-08-05 CN CN201480058077.2A patent/CN106104755A/zh active Pending
- 2014-08-05 MY MYPI2016700869A patent/MY173528A/en unknown
- 2014-08-05 KR KR1020167008592A patent/KR20160071373A/ko not_active Application Discontinuation
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040112426A1 (en) * | 2002-12-11 | 2004-06-17 | Sharp Kabushiki Kaisha | Solar cell and method of manufacturing the same |
| CN101124681A (zh) * | 2004-02-05 | 2008-02-13 | 日出能源公司 | 发射极环绕型背触点硅太阳能电池的触点制备 |
| CN102822988A (zh) * | 2010-04-09 | 2012-12-12 | 罗伯特·博世有限公司 | 用于制造太阳能的电池的方法 |
| TW201234484A (en) * | 2011-02-03 | 2012-08-16 | Imec | Method for fabricating photovoltaic cells |
| CN103515477A (zh) * | 2012-06-22 | 2014-01-15 | Lg电子株式会社 | 制造太阳能电池及其掺杂层的方法 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108231557A (zh) * | 2016-12-22 | 2018-06-29 | 英飞凌科技奥地利有限公司 | 在半导体器件中形成复合中心 |
| CN108231557B (zh) * | 2016-12-22 | 2022-02-11 | 英飞凌科技奥地利有限公司 | 在半导体器件中形成复合中心 |
| CN107425086A (zh) * | 2017-05-18 | 2017-12-01 | 阳光中科（福建）能源股份有限公司 | 一种离子注入法制作n型pert双面太阳电池的制备工艺 |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2015036181A1 (de) | 2015-03-19 |
| US10263135B2 (en) | 2019-04-16 |
| DE102013218351A1 (de) | 2015-03-19 |
| US20160233372A1 (en) | 2016-08-11 |
| JP2016535457A (ja) | 2016-11-10 |
| MY173528A (en) | 2020-01-31 |
| KR20160071373A (ko) | 2016-06-21 |
| EP3044813A1 (de) | 2016-07-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106104755A (zh) | 包括通过离子注入掺杂和沉积向外扩散阻挡物的用于制备太阳能电池的方法 | |
| US8138070B2 (en) | Methods of using a set of silicon nanoparticle fluids to control in situ a set of dopant diffusion profiles | |
| CN110299422A (zh) | 一种激光硼掺杂选择性发射极TOPCon结构电池及其制备方法 | |
| WO2011157422A3 (de) | Verfahren zur herstellung einer photovoltaischen solarzelle | |
| CN105895738A (zh) | 一种钝化接触n型太阳能电池及制备方法和组件、系统 | |
| CN101421851A (zh) | 太阳电池及其制造方法 | |
| WO2012027000A3 (en) | Back junction solar cell with selective front surface field | |
| US20120325291A1 (en) | Method for producing back electrode type, solar cell, back electrode type solar cell and back electrode type solar cell module | |
| TW201021232A (en) | Rapid thermal oxide passivated solar cell with improved junction | |
| CN102586884B (zh) | 一种多晶硅硅片两次扩散的制造方法 | |
| JP2017135386A (ja) | 太陽電池の製造方法 | |
| Lozac'h et al. | Role of silicon surface, polished< 100> and< 111> or textured, on the efficiency of double‐sided TOPCon solar cells | |
| CN103985780B (zh) | 太阳能电池的制作方法 | |
| CN102544215A (zh) | 利用激光掺杂加刻蚀制备选择性发射结太阳电池的方法 | |
| US20100210060A1 (en) | Double anneal process for an improved rapid thermal oxide passivated solar cell | |
| Ryu et al. | High efficiency screen-printed n-type silicon solar cell using co-diffusion of APCVD boron emitter and POCl3 back surface field | |
| CN102881772B (zh) | 一种选择性发射极太阳能电池的制备方法 | |
| CN111133589A (zh) | 掺杂剂增强的太阳能电池及其制造方法 | |
| CN111509054A (zh) | 一种topcon钝化结构及其制备方法 | |
| JP2013004889A (ja) | 裏面電極型太陽電池の製造方法 | |
| US20160240724A1 (en) | Method for producing a solar cell | |
| TW201701492A (zh) | 太陽能電池的製造方法 | |
| CN210778615U (zh) | 一种topcon钝化结构 | |
| CN111149217A (zh) | 界面特性得到提升的钝化发射极背面接触（perc）太阳能电池制造方法以及制造装置 | |
| CN102157626B (zh) | 一种降低太阳能电池发射极和埋栅电极间接触电阻的方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20161109 |