CN105731544B - A kind of preparation method of the one-dimensional dilute magnetic semiconductor material of Uniform Doped - Google Patents
A kind of preparation method of the one-dimensional dilute magnetic semiconductor material of Uniform Doped Download PDFInfo
- Publication number
- CN105731544B CN105731544B CN201610053385.7A CN201610053385A CN105731544B CN 105731544 B CN105731544 B CN 105731544B CN 201610053385 A CN201610053385 A CN 201610053385A CN 105731544 B CN105731544 B CN 105731544B
- Authority
- CN
- China
- Prior art keywords
- zinc powder
- oxide
- powder
- tube
- passed
- 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.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/42—Magnetic properties
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a kind of preparation method of the one-dimensional dilute magnetic semiconductor material of Uniform Doped, including following preparation process：Mol ratio is referred to as 9：1~19：1 zinc powder and metal oxide, is put into quartzy bottom of the tube；The rate of heat addition of zinc powder and metal oxide is set respectively, seals tube furnace, and full of quartz ampoule is heated after protective gas, start to be passed through reacting gas after temperature reaches 520 DEG C；Under protective gas protection, with 10 DEG C/min heating rate heated quarty tube to 600~800 DEG C, oxygen is passed through, its flow velocity is 20~40Sccm, until reaction terminates；Finally cool under vacuum atmosphere, to room temperature is cooled to, takes out sample and directly characterized.The present invention realizes the Uniform Doped of the element such as manganese, cobalt in ZnO nano-wire, moreover, not producing dephasign in parent after doping.Method described by patent of the present invention is applied to be doped Multimetal oxide, to zinc oxide, manganese oxide, cobalt oxide etc. and the more Yuans metal oxides such as cobalt acid nickel, mangaic acid nickel.
Description
Technical field
The present invention relates to metal oxide nano-material preparing technical field, specifically a kind of one-dimensional dilute magnetic of Uniform Doped half
The preparation method of conductor material.
Background technology
Today's society is the society that information is dominated, the processing of information, transmission and the unprecedented scale and speed of memory requirement.Electricity
The electric charge attribute and spin attribute of son play important role in information processing and transmission, but people for electron charge with
The research of spin attribute is parallel development.The electric charge of dilute magnetic semiconductor set electron and spin, utilize dilute magnetic semiconductor
Self-spining device made of nanostructured has the advantages that Stability Analysis of Structures, low in energy consumption, pollution-free, fast response time.Metal-doped oxygen
It is the very important research direction in one, dilute magnetic semiconductor material field to change zinc.
The current method for preparing high-quality ZnO dilute magnetic semiconductor mainly has following two：(1) with zinc powder and other metals
Compound is raw material, and the ZnO nano-structure of magnesium-yttrium-transition metal doping is prepared using chemical vapour deposition technique；(2) by high-purity
Zinc powder and other metal sheetings simultaneously sinter target into, and laser beam focus is made to heated point of the material of target material surface on the surface of target
Separate out and, the metal-doped ZnO nano-structure of race is crossed with oxygen reaction generation.In (1) kind method, due in preparation process
In employ plurality of raw materials, the molten boiling point of different material is different, is difficult to realize the uniformity of doping.Especially doping concentration is higher
When, it is very easy to dephasign occur.In (2) kind method, although the doping of higher concentration can be realized, the sample of preparation
Mostly thin-film material, the pattern of nanostructured are not easily controlled very much.
The content of the invention
Goal of the invention：In order to overcome the deficiencies in the prior art, the present invention provides a kind of one-dimensional dilute magnetic of Uniform Doped
The preparation method of semi-conducting material.
Technical scheme：In order to solve the above technical problems, a kind of one-dimensional dilute magnetic semiconductor material of Uniform Doped of the present invention
Preparation method, including following preparation process：
Step 1：Mol ratio is weighed as 9：1~19：1 zinc powder and metal oxide, is put into quartzy bottom of the tube；
Step 2：The rate of heat addition of zinc powder and metal oxide is set respectively, seals tube furnace, and full of after protective gas
Quartz ampoule is heated, starts to be passed through reacting gas after temperature reaches 520 DEG C；
Step 3：Under protective gas protection, with 10 DEG C/min heating rate heated quarty tube to 600~800 DEG C, lead to
Enter oxygen, its flow velocity is 20~40Sccm, until reaction terminates；
Step 4：Finally cool under vacuum atmosphere, until being cooled to room temperature, take out sample and directly characterized.
Preferably, the purity of zinc powder is 99.99% in the step 1, and the purity of metal oxide is 99.9%.
Preferably, the mol ratio of zinc powder and metal oxide is 19 in the step 1：1.
Preferably, the mol ratio of zinc powder and metal oxide is 9 in the step 1：1.
Preferably, zinc powder is placed in same root test tube or is respectively put into two test tubes with metal oxide powder.
Preferably, the protection gas in the step 2 is argon gas, and reacting gas is oxygen.
Preferably, zinc powder is respectively put into two quartz ampoules or is put into same stone with metal oxide in the step 1
English bottom of the tube.
Preferably, zinc powder is respectively put into two quartzy bottom of the tube with metal oxide in the step 1, in each quartz ampoule
Oral area set silicon base, the carrier as sample grown.
Preferably, the metal oxide is chlorination manganese powder or chlorination cobalt powder or manganese dioxide powder.
Beneficial effect：A kind of preparation method of the one-dimensional dilute magnetic semiconductor material of Uniform Doped of the present invention, is realized in ZnO
The Uniform Doped of the element such as manganese, cobalt in nano wire, moreover, not producing dephasign in parent after doping.Side described by patent of the present invention
Method is applied to be doped Multimetal oxide.Such as to zinc oxide, manganese oxide, cobalt oxide and cobalt acid nickel, mangaic acid nickel
Etc. more Yuans metal oxides.Multi-temperature zone chemical gaseous phase depositing process described in the invention has relatively low manufacture and is produced into
This, preparation technology is simple, and parameter is easily controlled, and sample purity and crystallinity are very high, has to the uniformity of dilute magnetic semiconductor doping
Large increase, and performance is greatly improved, the well-regulated geometrical morphology of one-dimension zinc oxide based diluted magnetic semiconductor prepared
Higher doping concentration, and there is room-temperature ferromagnetic.
Brief description of the drawings
Fig. 1 is the general profile chart of dual temperature area chemical vapor deposition unit；
Fig. 2 is horizontal quartz plate in growth room, the schematic diagram of quartz ampoule modes of emplacement；
The pattern for the additive Mn nano structure of zinc oxide that Fig. 3 is prepared using manganese dioxide as doped raw material single temperature zone method
Figure；
The shape appearance figure for the additive Mn nano structure of zinc oxide that Fig. 4 is prepared using manganese chloride as doped raw material single temperature zone method；
Fig. 5 is the shape appearance figure of the additive Mn zinc oxide nano rod prepared using manganese chloride as doped raw material dual temperature area method；
Fig. 6 is the XRD for the additive Mn zinc oxide nano rod that doping concentration is 2.8%；
Fig. 7 is the ESEM shape of the Co-doped ZnO nanometer rods prepared using cobalt chloride as doped raw material dual temperature area method
Looks figure.
Embodiment
The present invention is further described with embodiment below in conjunction with the accompanying drawings.
Embodiment 1
(1) mol ratio is weighed as 19 with electronic balance：Zinc powder and purity that 1 purity is 99.99% are the two of 99.9%
Manganese powder is aoxidized, the two is uniformly put into the bottom of a quartz ampoule after mixing using agate mortar, as shown in figure 1, by quartz ampoule
It is placed on horizontal long quartz glass plate, quartz plate is finally sent to suitable position in horizontal pipe furnace, and with stainless steel method
Orchid seals tube furnace；
(2) tube furnace is evacuated using mechanical pump, starts to heat quartz ampoule after 30 minutes, 10 DEG C of heating rate/
min.In heating process, it is passed through argon gas and is set as 100Sccm as protection gas, rate of flow of fluid.
(3) when zinc powder is after being warming up to 520 DEG C, oxygen, flow rate set 30Sccm are passed through.When zinc powder and manganese dioxide powder
After reaching 800 DEG C, constant temperature 60min is kept.
(4) cool after end to be heated under vacuum atmosphere, until room temperature, takes out sample and directly characterized.
(5) Fig. 2 is the shape appearance figure of additive Mn nano structure of zinc oxide prepared by single temperature zone method, in figure, quartz plate length
Three quartz ampoules can be fixed on quartz plate by 20cm, wide 4cm, the quartz plate, and test tube neck high 8cm, half circular diameter 9cm mix
Miscellaneous raw material is manganese dioxide powder.From figure 3, it can be seen that most of additive Mn nano structure of zinc oxide is bar-shaped for the hexagonal of rule
Profile, there is the block nanostructured in part to occur at the top of nanometer rods, nanowire diameter 300-500nm.
Embodiment 2
(1) mol ratio is weighed as 9 with electronic balance：The chlorination that the zinc powder and purity that 1 purity is 99.99% are 99.9%
Manganese powder, the different quartzy bottom of the tube of length is put it into respectively, is placed on two quartz ampoules on horizontal long quartz plate afterwards, will
Silicon base is lain in a horizontal plane at the quartzy mouth of pipe, and quartz plate finally is sent into suitable position in tube furnace, will with steel flange
Tube furnace seals.
(2) tube furnace is evacuated using mechanical pump, chlorination manganese powder and zinc powder are warming up to 800 DEG C and 550 after 80min
DEG C, oxygen is passed through afterwards, and manganese chloride keeps constant temperature, and zinc powder keeps constant temperature, constant temperature time 30min after reaching 650 DEG C.Adding
In thermal process, argon gas is passed through as protection gas, flow rate set 100Sccm.
(3) reaction cools after terminating under vacuum atmosphere, until room temperature, takes out sample and directly characterized.
(4) Fig. 4 is the shape appearance figure of additive Mn nano structure of zinc oxide prepared by dual temperature area method.It can be seen that, received by Fig. 4
The pattern of rice structure is very irregular, most of to be made up of block structure, a diameter of 1-2 μm of nanometer blocks.
Embodiment 3
(1) mol ratio is weighed as 9 with electronic balance：The chlorination that the zinc powder and purity that 1 purity is 99.99% are 99.9%
Manganese powder, the different quartzy bottom of the tube of length is put it into respectively.Two quartz ampoules are placed on horizontal long quartz plate afterwards such as
Shown in Fig. 2, silicon base is lain in a horizontal plane at the quartzy mouth of pipe.Quartz plate is finally sent to suitable position in tube furnace, with not
Rust steel flange seals tube furnace.
(2) tube furnace is evacuated using mechanical pump, chlorination manganese powder and zinc powder are warming up to 800 DEG C respectively after 80min
With 550 DEG C, be passed through oxygen afterwards, manganese chloride keeps constant temperature, and zinc powder keeps constant temperature after reaching 650 DEG C, and constant temperature time is
30min.In heating process, argon gas is passed through as protection gas, flow rate set 100Sccm.
(3) reaction cools after terminating under vacuum atmosphere, until room temperature, takes out sample and directly characterized.
(4) Fig. 5 is the shape appearance figure of additive Mn nano structure of zinc oxide prepared by dual temperature area method.By Fig. 5 it can be seen that, it is double
Warm area method prepare additive Mn nano structure of zinc oxide by rule the bar-shaped structure composition of hexagonal, nanometer rods it is a diameter of
150-200nm。
(5) Fig. 6 is the XRD for the additive Mn zinc oxide nano rod that doping concentration is 2.8%.Diffraction maximum and hexagonal wurtzite
Structure zinc oxide meets very well.And without the diffraction maximum for finding other impurities, illustrate that sample adulteration is very uniform.
Embodiment 4
(1) mol ratio is weighed as 19 with electronic balance：The zinc powder and purity that 1 purity is 99.99% are 99.9% chlorination
Cobalt powder, the two is put into the quartzy bottom of the tube of length different length, after guarantee is put into tube furnace, the two is in different warm areas.
(2) tube furnace is evacuated using mechanical pump, chlorination cobalt powder and zinc powder are warming up to 400 DEG C respectively after 60min
With 550 DEG C, keep constant temperature after zinc powder reaches 650 DEG C.In heating process, it is passed through argon gas and is set as protection gas, gas flow rate
It is set to 100Sccm.
(3) when zinc powder is after being warming up to 550 DEG C, oxygen, flow rate set 30Sccm are passed through.
(4) reaction cools after terminating under vacuum atmosphere, until room temperature, takes out sample and directly characterized.
(5) Fig. 7 is the shape appearance figure of Co-doped ZnO nanostructured prepared by dual temperature area method.By Fig. 7 it can be seen that, cobalt
Doping zinc-oxide has fairly regular geometrical morphology, has fraction of particle to occur in nanometer rods, nanometer rods it is a diameter of
150-500nm。
The testing result of the comparative example 1 of embodiment 2 can be seen that the Zinc oxide-base prepared using two-step method from table 1
Dilute magnetic semiconductor material has more regular geometrical morphology, and doping concentration can reach 3% even more high, and doping is first in sample
Element is evenly distributed, and dephasign does not occur.And the Zinc oxide based rare magnetic semiconductor material prepared using two-step method all has stronger
The intensity of magnetization, Curie temperature is more than room temperature.
The detection device of above example is by X-ray diffractometer (D8/Advance), SEM SEM
(Hitachi S4800), superconducting quantum interference device (SQUID) (MPMS-XL7Quantum Design, Inc.) etc. carry out observation analysis.
Table 1 is the comparison of magnetic property of zinc oxide nanowire in different embodiments
| Embodiment | Actual doping depth | Saturation magnetization | Curie temperature | Coercive field |
| Actual example 1 | 0.4% | 0.87μB/Mn | 313K | 43Oe |
| Actual example 2 | 3.4% | Paramagnetism | - | - |
| Embodiment 3 | 2.8% | 0.48μB/Mn | 297K | 67Oe |
| Actual example 4 | 5.6% | 0.27μB/Co | 304K | 52Oe |
Described above is only the preferred embodiment of the present invention, it should be pointed out that：For the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (1)
1. a kind of preparation method of the one-dimensional dilute magnetic semiconductor material of Uniform Doped, it is characterised in that including following preparation process：Step
Rapid one：Mol ratio is weighed as 9 with electronic balance：The chlorination manganese powder that the zinc powder and purity that 1 purity is 99.99% are 99.9%, point
The different quartzy bottom of the tube of length is not put it into；Two quartz ampoules are placed on horizontal long quartz plate afterwards, by silicon base
Lie in a horizontal plane at the quartzy mouth of pipe；Quartz plate is finally sent to suitable position in tube furnace, with steel flange by tube furnace
Sealing；
Step 2：Tube furnace is evacuated using mechanical pump, chlorination manganese powder and zinc powder are warming up to 800 DEG C respectively after 80 min
With 550 DEG C, be passed through oxygen afterwards, manganese chloride keeps constant temperature, and zinc powder keeps constant temperature, constant temperature time 30 after reaching 650 DEG C
min；In heating process, argon gas is passed through as protection gas, flow rate set is 100 sccm；
Step 3：Reaction cools after terminating under vacuum atmosphere, until room temperature, takes out sample and directly characterized.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610053385.7A CN105731544B (en) | 2016-01-26 | 2016-01-26 | A kind of preparation method of the one-dimensional dilute magnetic semiconductor material of Uniform Doped |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610053385.7A CN105731544B (en) | 2016-01-26 | 2016-01-26 | A kind of preparation method of the one-dimensional dilute magnetic semiconductor material of Uniform Doped |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105731544A CN105731544A (en) | 2016-07-06 |
| CN105731544B true CN105731544B (en) | 2017-12-22 |
Family
ID=56246659
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610053385.7A Expired - Fee Related CN105731544B (en) | 2016-01-26 | 2016-01-26 | A kind of preparation method of the one-dimensional dilute magnetic semiconductor material of Uniform Doped |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105731544B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111348936A (en) * | 2018-12-21 | 2020-06-30 | 汉能新材料科技有限公司 | Crucible oxidation device and oxidation method |
| CN112391609B (en) * | 2020-11-16 | 2023-03-28 | 连城凯克斯科技有限公司 | Multi-temperature-zone chemical vapor deposition device for organic semiconductor crystal |
| CN117205953B (en) * | 2023-09-08 | 2024-04-26 | 曲阜师范大学 | Nonmetal nitrogen-phosphorus co-doped porous carbon catalyst and preparation method and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100844894B1 (en) * | 2007-01-16 | 2008-07-09 | (주)레이저옵텍 | Ferromagnetic semiconductor thin layer and a fabrication method thereof |
| CN103400679B (en) * | 2013-07-22 | 2015-10-07 | 山东大学 | Highly doped ZnO:Co magnetic semiconductor film material and preparation method thereof |
| CN103578938B (en) * | 2013-11-20 | 2016-06-08 | 北京科技大学 | A kind of Sn mixed ZnO semiconductor material and preparation method and application thereof |
-
2016
- 2016-01-26 CN CN201610053385.7A patent/CN105731544B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN105731544A (en) | 2016-07-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Dai et al. | Fabrication and characterization of In2O3 nanowires | |
| CN105731544B (en) | A kind of preparation method of the one-dimensional dilute magnetic semiconductor material of Uniform Doped | |
| CN104671245B (en) | Preparation method of hafnium carbide nano-powder | |
| CN107140681A (en) | β‑Ga2O3The preparation method of micro belt | |
| CN110184654A (en) | A kind of Bi2O2Se crystal and preparation method thereof | |
| CN105543972B (en) | High-purity high-density MoO2The preparation method of lamellar nanostructured | |
| CN106830081B (en) | A kind of MoO2The preparation method of nanometer rods | |
| CN103160929B (en) | The preparation method of a kind of monocrystal AIN nano cone and nanometer sheet | |
| CN107021463B (en) | High-quality boron nitride nano-tube and preparation method thereof | |
| CN105314672A (en) | Method for preparing cobalt-doped zinc oxide nanorods through sol-gel | |
| CN110316752A (en) | A kind of ytterbium oxychloride nanometer sheet and its preparation method and application | |
| CN113373511B (en) | Large-size CrI 3 Method for producing single crystal | |
| CN105692694B (en) | Ti3O5/TiO2The preparation method of mixed crystal nanofiber | |
| Kuo et al. | Crystallization kinetics of lanthanum monoaluminate (LaAlO3) nanopowders prepared by co-precipitation process | |
| CN115240940A (en) | Rare earth alkali metal phosphate and preparation method and application thereof | |
| CN104477859B (en) | A kind of nanostructured fish spicule shape zinc selenide and preparation method thereof and device | |
| CN107934928B (en) | Preparation method of tungsten ditelluride nanotube | |
| CN107934927B (en) | Preparation method of molybdenum ditelluride nanotube | |
| CN102162135A (en) | Preparation method of ZnS/Si nuclear-shell nanowires or nanobelts and polycrystal Si tubes | |
| CN107267839B (en) | A kind of room temperature magnetic refrigerating alloy magneto-caloric material and the preparation method and application thereof | |
| JP4576607B2 (en) | Single crystal zinc sulfide nanotube and method for producing the same | |
| CN105428184B (en) | A kind of preparation method of the nano-particle modified SiC nanowires of Au | |
| CN111747386A (en) | Morphology-controllable boron nitride nanostructure-graphene composite material and preparation method thereof | |
| Li et al. | Molten salt solvent synthesis of La2Mo2O9 nano-wires by controlling the subsequent calcinations process | |
| CN105098055B (en) | A kind of doping cerium dioxide barrier layer and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20171222 Termination date: 20190126 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |