CN106400114B - A kind of non-polarized preferred orientation zno-based polycrystalline preparation of sections method - Google Patents
A kind of non-polarized preferred orientation zno-based polycrystalline preparation of sections method Download PDFInfo
- Publication number
- CN106400114B CN106400114B CN201610811260.6A CN201610811260A CN106400114B CN 106400114 B CN106400114 B CN 106400114B CN 201610811260 A CN201610811260 A CN 201610811260A CN 106400114 B CN106400114 B CN 106400114B
- Authority
- CN
- China
- Prior art keywords
- zno
- based polycrystalline
- preferred orientation
- bulk
- polarized
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B28/00—Production of homogeneous polycrystalline material with defined structure
- C30B28/02—Production of homogeneous polycrystalline material with defined structure directly from the solid state
Abstract
The invention discloses a kind of non-polarized preferred orientation zno-based polycrystalline preparation of sections methods of self-forming, belong to field of functional materials, and ZnO is mixed with the nanometer powder of blended metal oxide by required proportioning, ground by this method in the agate mortar；The mixed raw material after grinding is pressed into sheet bulk by tablet press machine；Raw material bulk is placed in corundum crucible and carries out high temperature sintering；After the completion of above-mentioned steps, you can spontaneously form height (10 between the isotropism zno-based polycrystalline bulk after high temperature sintering and corundum crucible0) preferentially, the zno-based polycrystalline thin slice of about 100 μm of thickness.The method of the invention method is simple, reproducible, of low cost.
Description
Technical field
The invention discloses a kind of non-polarized preferred orientation zno-based polycrystalline preparation of sections methods of self-forming, belong to function
Material Field.
Background technology
Hexagonal wurtzite structure ZnO is II-VI race's broad stopband direct band-gap semicondictor, and energy gap is at room temperature
3.37eV, exciton binding energy are up to 60meV, have good ultra-violet light-emitting characteristic and visible transparent, have been widely used
In the fields such as UV LED and electrically conducting transparent device.
(0001) face of ZnO has minimum surface free energy, it is made usually to select direction tachyauxesis along c-axis, and non-central
Symmetrical wurtzite structure makes ZnO that spontaneous polarization occur along c-axis direction, the built in field along c-axis direction is formed, in built in field
Under effect, the electron-hole pair in ZnO is spatially separating, and wave function amount over overlap is made to reduce, and is led to glow peak red shift, is shone
Efficiency declines, that is, quantum confined stark effect (Quantum-confined Stark effect) occurs.Therefore, it prepares non-
Polarization is preferentially（It is orientated perpendicular to c-axis）ZnO sills be improve its luminous efficiency effect approach.
Currently, non-polarized ZnO preferentially is mainly in thin-film material by regulating and controlling growth technique or substrate orientation and mispairing
Degree obtains.T. Coman et al. (Improving the uncommon (110) growing orientation of Al-
doped ZnO thin films through sequential pulsed laser deposition. Thin Solid
Films, 2014, 571:It is ZnO thin film doped 198-205.) to prepare Al on a glass substrate with pulsed laser deposition, finds logical
It crosses reduction growth of oxygen pressure or improving Al doping concentrations can be such that ZnO film is orientated from (0001) to (100) change, but it changes journey
It spends limited, and pulse laser is needed to bombard Zn and Al metallic targets regulation and control film composition respectively, deposition process is complicated.Y. T. Ho etc.
People (Epitaxy of m-plane ZnO on (112) LaAlO3 substrate. Physica Status Solidi
(RRL)-Rapid Research Letters, 2009, 3(4):109-111) it is orientated in (112) by pulsed laser deposition
LaAlO3(10 are prepared in single crystalline substrate0) ZnO film being orientated, but growth process need to carry out in ultrahigh vacuum, and
It will be to LaAlO3Substrate carries out chemical treatment and high annealing.M. C. Chou et al. (Epitaxial growth of
nonpolar m-plane ZnO (10-10) on large-size LiGaO2 (100) substrates. Thin
Solid Films, 2011, 519(11):3627-3631.) by chemical vapor deposition with the non-polarized crystal face mispairing of ZnO
The smaller LiGaO of degree2(100) (10 are grown on monocrystalline0) ZnO film being orientated, but its key problem in technology need to use lifting legal system
The LiGaO of standby large scale (diameter ~ 60mm, length ~ 140nn)2(100) monocrystalline, cost of material are expensive.
To sum up, the zno-based material of the non-polarized orientation of prior art preparation, process is complicated, expensive, and must rely on
Substrate makees physical support, can not independently form a film, and limits its application.
Invention content
In view of the above technical problems, the present invention provides a kind of non-polarized preferred orientation zno-based polycrystalline thin slices of self-forming
Preparation method, this method can be by traditional easy solid reaction processes, the isotropism zno-based polycrystalline bulk after high temperature sintering
(10 are spontaneously formed between corundum crucible0) the zno-based polycrystalline thin slice of preferred orientation.
Non-polarized preferred orientation zno-based polycrystalline preparation of sections method of the present invention, specifically includes following steps：
（1）By the mixed-powder that ZnO nano powder is uniformly mixed with metal oxide nano powder end be pressed into it is each to
Same sex zno-based bulk.
（2）By step（1）Obtained isotropism zno-based bulk, which is placed in corundum crucible, carries out high temperature sintering, sintering
Can be spontaneously formed between isotropic zno-based polycrystalline bulk and corundum crucible after the completion has (100) preferred orientation
Zno-based polycrystalline thin slice.
The technique of the high temperature sintering is to rise to 400-600 DEG C, 900-1100 DEG C successively by room temperature, keeps the temperature 0.5- respectively
2h, then 1350-1450 DEG C is risen to, it is sintered 10-20h, 900-1100 DEG C, 400-600 DEG C is down to successively later, keeps the temperature 0.5- respectively
2h, then it is down to room temperature；Wherein 3-7 DEG C of heating rate/min, 8-12 DEG C of rate of temperature fall/min, sintering atmosphere are air.
Preferably, blended metal oxide of the present invention is Al2O3、Fe2O3、Co3O4、Cu2O、Y2O3、MgO、In2O3、
AgO、SnO2In one kind, the molar ratio of wherein ZnO and doped metallic elements is (1 ﹣ x):The value of x, x are 0≤x≤0.05.
Preferably, the average grain diameter of ZnO and blended metal oxide of the present invention are 150 ~ 250 nm, and purity >=
99.9%。
Preferably, step of the present invention（1）In mixed process be in the agate mortar mixing, grinding >=2h.
Preferably, step of the present invention（1）The condition of middle compacting is 3 ~ 5MPa of uniaxial tension, 5 ~ 20min of dwell time.
Preferably, the thickness of isotropic zno-based polycrystalline bulk of the present invention is 2-7mm.
Preferably, step of the present invention（2）The aluminium oxide that the raw material of middle corundum crucible is 99%, firing temperature 1800 ~ 1900
DEG C, 35 ~ 45h of firing time.
The beneficial effects of the invention are as follows：The zno-based polycrystalline thin slice of non-polarized preferred orientation can be in isotropism polycrystalline bulk
It is spontaneously formed between corundum crucible, preparation process is simple, reproducible；Thin slice can be individually present, and be not necessarily to substrate support；Slice-shaped
Shape and size, can large area productions by the bottom shape and size Control of isotropism polycrystalline bulk；It is of low cost.
Description of the drawings
Fig. 1 is the photo of zno-based polycrystalline thin slice in embodiment 1.
Fig. 2 is the XRD diagram of zno-based polycrystalline thin slice in embodiment 1.
Fig. 3 is the SEM figures of zno-based polycrystalline thin slice in embodiment 1.
Specific implementation mode
With reference to embodiment, invention is further described in detail, but protection scope of the present invention be not limited to it is described
Content；Reagents or instruments used without specified manufacturer in embodiment is the conventional production that can be obtained by commercially available purchase
Product.
Embodiment 1
Non-polarized preferred orientation zno-based polycrystalline preparation of sections method, specifically includes following steps described in the present embodiment：
（1）The Al for being 200 nm with average grain diameter by the ZnO that average grain diameter is 200 nm2O3Nanometer powder presses Zn:Al rubs
You are than being 1:Then mixed raw material is 3MPa, pressurize in uniaxial tension by grinding >=2h in the agate mortar after 0 ratio mixing
The isotropism bulk that thickness is 4mm, diameter 20mm is pressed under conditions of time 10min.
（2）By step（1）Obtained isotropism bulk is placed on corundum crucible（1850 DEG C of firing temperature, firing time
40h, 99% aluminium oxide）Interior carry out high temperature sintering, can be spontaneous between each isotropism bulk and corundum crucible after the completion of sintering
Being formed has (100) the zno-based polycrystalline thin slice of preferred orientation is about 100 μm thick.
The technique of the high temperature sintering is to rise to 500 DEG C, 1000 DEG C successively by room temperature, keeps the temperature 0.5h respectively, then rise to
1400 DEG C, it is sintered 12h, 1000 DEG C, 500 DEG C is down to successively later, keeps the temperature 0.5h respectively, then be down to room temperature；Wherein heating rate 5
DEG C/min, 10 DEG C/min of rate of temperature fall, sintering atmosphere is air.
The zno-based polycrystalline thin slice that the present embodiment is prepared, macro morphology can be found in attached drawing 1；Gained ZnO polycrystalline thin slices
Crystalline quality is excellent, has significant non-polarized (100) preferred orientation, reference can be made to attached drawing 2；The grain size of gained ZnO thin slices
About 50 μm, microscopic appearance is regular and fine and close, reference can be made to attached drawing 3.
Embodiment 2
Non-polarized preferred orientation zno-based polycrystalline preparation of sections method, specifically includes following steps described in the present embodiment：
（1）The Al for being 150nm with average grain diameter by the ZnO that average grain diameter is 150nm2O3Nanometer powder presses Zn:Al moles
Than being 0.98:Then mixed raw material is by grinding >=2h in the agate mortar after 0.02 ratio mixing in uniaxial tension
The isotropism bulk that thickness is 7mm, diameter 20mm is pressed under conditions of 4MPa, dwell time 5min.
（2）By step（1）Obtained isotropism bulk is placed on corundum crucible（1800 DEG C of firing temperature, firing time
35h, 99% aluminium oxide）Interior carry out high temperature sintering, after the completion of sintering can between isotropism bulk and corundum crucible spontaneous shape
At with (100) the zno-based polycrystalline thin slice of preferred orientation is about 100 μm thick.
The technique of the high temperature sintering is to rise to 400 DEG C, 900 DEG C successively by room temperature, keeps the temperature 1h respectively, then rise to 1350
DEG C, it is sintered 20h, 900 DEG C, 400 DEG C is down to successively later, keeps the temperature 1h respectively, then be down to room temperature；Wherein 3 DEG C/min of heating rate,
8 DEG C/min of rate of temperature fall, sintering atmosphere are air.
The zno-based polycrystalline thin slice crystalline quality that the present embodiment is prepared is excellent, has significant non-polarized (100) it selects
Excellent orientation.
Embodiment 3
Non-polarized preferred orientation zno-based polycrystalline preparation of sections method, specifically includes following steps described in the present embodiment：
（1）The Al for being 250 nm with average grain diameter by the ZnO that average grain diameter is 250 nm2O3Nanometer powder presses Zn:Al rubs
You are than being 0.95:Then mixed raw material is by grinding >=2h in the agate mortar after 0.05 ratio mixing in uniaxial tension
The isotropism bulk that thickness is 2mm, diameter 20mm is pressed under conditions of 5MPa, dwell time 20min.
（2）By step（1）Obtained isotropism bulk is placed on corundum crucible（1900 DEG C of firing temperature, firing time
45h, 99% aluminium oxide）Interior carry out high temperature sintering, after the completion of sintering can between isotropism bulk and corundum crucible spontaneous shape
At with (100) the zno-based polycrystalline thin slice of preferred orientation is about 100 μm thick.
The technique of the high temperature sintering is to rise to 600 DEG C, 1100 DEG C successively by room temperature, keeps the temperature 2h respectively, then rise to 1450
DEG C, it is sintered 16h, 1100 DEG C, 600 DEG C is down to successively later, keeps the temperature 2h respectively, then be down to room temperature；Wherein 7 DEG C of heating rate/
Min, 12 DEG C/min of rate of temperature fall, sintering atmosphere is air.
The zno-based polycrystalline thin slice crystalline quality that the present embodiment is prepared is excellent, has significant non-polarized (100) it selects
Excellent orientation.
Embodiment 4
With embodiment 1, difference is blended metal oxide being changed to Fe respectively other conditions2O3、Co3O4、Cu2O、
Y2O3、MgO、In2O3、AgO、SnO2, wherein Zn:Fe molar ratios are 0.98:0.02, Zn:Co molar ratios are 0.98 0.02,
Zn:Cu molar ratios are 0.97 0.03, Zn:Y molar ratios are 0.96:0.04, Zn:Mg molar ratios are 0.95:0.05, Zn:
In molar ratios are 0.98:0.02, Zn:Ag molar ratios are 0.99:0.01, Zn:Sn molar ratios are 0.98: 0.02.
The zno-based polycrystalline thin slice crystalline quality that the present embodiment is prepared is excellent, has significant non-polarized (100) it selects
Excellent orientation.
Claims (7)
1. a kind of non-polarized preferred orientation zno-based polycrystalline preparation of sections method, which is characterized in that specifically include following steps：
（1）The mixed-powder that ZnO nano powder is uniformly mixed with metal oxide nano powder end is pressed into isotropism
Zno-based bulk；
（2）By step（1）Obtained isotropism zno-based bulk, which is placed in corundum crucible, carries out high temperature sintering, and sintering is completed
After can spontaneously form and have between isotropic zno-based polycrystalline bulk and corundum crucibleThe ZnO of preferred orientation
Quito crystalline substance thin slice；
The technique of the high temperature sintering is to rise to 400-600 DEG C, 900-1100 DEG C successively by room temperature, keeps the temperature 0.5-2h respectively, then
1350-1450 DEG C is risen to, 10-20h is sintered, is down to 900-1100 DEG C, 400-600 DEG C successively later, keeps the temperature 0.5-2h respectively, then
It is down to room temperature；Wherein 3-7 DEG C of heating rate/min, 8-12 DEG C of rate of temperature fall/min, sintering atmosphere are air.
2. non-polarized preferred orientation zno-based polycrystalline preparation of sections method according to claim 1, it is characterised in that：It is described
Blended metal oxide is Al2O3、Fe2O3、Co3O4、Cu2O、Y2O3、MgO、In2O3、AgO、SnO2In one kind, wherein ZnO with
The molar ratio of doped metallic elements is (1 ﹣ x):The value of x, x are 0≤x≤0.05.
3. non-polarized preferred orientation zno-based polycrystalline preparation of sections method according to claim 1 or claim 2, it is characterised in that：Institute
The average grain diameter for stating ZnO and blended metal oxide is 150 ~ 250nm, purity >=99.9%.
4. non-polarized preferred orientation zno-based polycrystalline preparation of sections method according to claim 1, it is characterised in that：Step
（1）In mixed process be in the agate mortar mixing, grinding >=2h.
5. non-polarized preferred orientation zno-based polycrystalline preparation of sections method according to claim 1, it is characterised in that：Step
（1）The condition of middle compacting is 3 ~ 5MPa of uniaxial tension, 5 ~ 20min of dwell time.
6. non-polarized preferred orientation zno-based polycrystalline preparation of sections method according to claim 1, it is characterised in that：Respectively to
The thickness of the zno-based polycrystalline bulk of the same sex is 2-7mm.
7. preferentially zno-based polycrystalline preparation of sections method, feature exist a kind of self-forming height according to claim 1
In：Step（2）The aluminium oxide that the raw material of middle corundum crucible is 99%, 1800 ~ 1900 DEG C of firing temperature, 35 ~ 45h of firing time.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610811260.6A CN106400114B (en) | 2016-09-09 | 2016-09-09 | A kind of non-polarized preferred orientation zno-based polycrystalline preparation of sections method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610811260.6A CN106400114B (en) | 2016-09-09 | 2016-09-09 | A kind of non-polarized preferred orientation zno-based polycrystalline preparation of sections method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106400114A CN106400114A (en) | 2017-02-15 |
| CN106400114B true CN106400114B (en) | 2018-10-23 |
Family
ID=57998892
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610811260.6A Active CN106400114B (en) | 2016-09-09 | 2016-09-09 | A kind of non-polarized preferred orientation zno-based polycrystalline preparation of sections method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106400114B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101235536A (en) * | 2007-11-09 | 2008-08-06 | 浙江大学 | Method for growing Na doping p type ZnO crystal thin film |
| CN101481817A (en) * | 2008-12-31 | 2009-07-15 | 浙江大学 | Growth method of nonpolar ZnO crystal film |
| CN101603199A (en) * | 2009-06-11 | 2009-12-16 | 浙江大学 | The method of Li, Na growing p-type ZnO crystal film by codoping |
| CN101831701A (en) * | 2010-04-13 | 2010-09-15 | 浙江大学 | Method for growing n-type transparent conducting ZnO crystal thin film by F doping |
| CN103710675A (en) * | 2013-12-18 | 2014-04-09 | 浙江大学 | ZnO-based film and preparation method thereof |
| CN105002555A (en) * | 2015-08-11 | 2015-10-28 | 武汉大学 | Growing method of ZnO single-crystal nanosheet |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003104792A (en) * | 2001-09-28 | 2003-04-09 | Sharp Corp | Method of controlling doping concentration for semiconductor thin film and semiconductor device |
| JP3826755B2 (en) * | 2001-09-28 | 2006-09-27 | 株式会社村田製作所 | ZnO film, method for producing the same, and light emitting device |
| JP4108962B2 (en) * | 2001-11-07 | 2008-06-25 | 東京電波株式会社 | Zinc oxide raw material preparation method |
-
2016
- 2016-09-09 CN CN201610811260.6A patent/CN106400114B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101235536A (en) * | 2007-11-09 | 2008-08-06 | 浙江大学 | Method for growing Na doping p type ZnO crystal thin film |
| CN101481817A (en) * | 2008-12-31 | 2009-07-15 | 浙江大学 | Growth method of nonpolar ZnO crystal film |
| CN101603199A (en) * | 2009-06-11 | 2009-12-16 | 浙江大学 | The method of Li, Na growing p-type ZnO crystal film by codoping |
| CN101831701A (en) * | 2010-04-13 | 2010-09-15 | 浙江大学 | Method for growing n-type transparent conducting ZnO crystal thin film by F doping |
| CN103710675A (en) * | 2013-12-18 | 2014-04-09 | 浙江大学 | ZnO-based film and preparation method thereof |
| CN105002555A (en) * | 2015-08-11 | 2015-10-28 | 武汉大学 | Growing method of ZnO single-crystal nanosheet |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106400114A (en) | 2017-02-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Photoluminescence of ZnO films prepared by rf sputtering on different substrates | |
| Sreedhar et al. | Enhanced photoluminescence properties of Cu-doped ZnO thin films deposited by simultaneous RF and DC magnetron sputtering | |
| Cui et al. | Effect of annealing temperature and annealing atmosphere on the structure and optical properties of ZnO thin films on sapphire (0 0 0 1) substrates by magnetron sputtering | |
| El Mir et al. | Preparation and characterization of n-type conductive (Al, Co) co-doped ZnO thin films deposited by sputtering from aerogel nanopowders | |
| Zhang et al. | Modulation of microstructure and optical properties of Mo-doped ZnO thin films by substrate temperature | |
| KR102414621B1 (en) | Doped gallium oxide crystalline material and its manufacturing method and application | |
| Cui et al. | Effects of annealing temperature on the structure and photoluminescence properties of ZnO films | |
| Guo et al. | Preparation and optical properties of Mg-doped ZnO nanorods | |
| Suo et al. | Effects of oxygen/argon pressure ratio on the structural and optical properties of Mn-doped ZnO thin films prepared by magnetron pulsed co-sputtering | |
| Chen et al. | Enhanced mechanism investigation on violet-blue emission of ZnO films by incorporating Al and Zn to form ZnO-Al-Zn films | |
| Seo et al. | Growth of ZnO/sapphire heteroepitaxial thin films by radio-frequency sputtering with a raw powder target | |
| Chou et al. | Preparation and characterization of solid-state sintered aluminum-doped zinc oxide with different alumina contents | |
| CN113956022A (en) | Zinc-doped indium oxide powder, sputtering target material and preparation method thereof | |
| Reddy et al. | Growth and physical behaviour of Zn1− xMgxO films | |
| Kim et al. | Improvement in crystallinity and optical properties of ZnO epitaxial layers by thermal annealed ZnO buffer layers with oxygen plasma | |
| Chen et al. | Preparation and photoluminescence studies of high-quality AZO thin films grown on Zno buffered Si substrate | |
| Sharma et al. | Diameter and density controlled growth of yttrium functionalized zinc oxide (YZO) nanorod arrays by hydrothermal | |
| CN106400114B (en) | A kind of non-polarized preferred orientation zno-based polycrystalline preparation of sections method | |
| Yoo et al. | Structural, optical and chemical analysis of zinc sulfide thin film deposited by RF-mganetron sputtering and post deposition annealing | |
| Huang et al. | The influence of magnesium and hydrogen introduction in sputtered zinc oxide thin films | |
| Tanigaki et al. | A new preparation method of ZnO cubic phase particle and its IR spectrum | |
| CN101359705A (en) | Multi-element alloy oxide film material with forbidden bandwidth continuously adjustable and preparation thereof | |
| CN1303650C (en) | p-Zn1-XMgXO crystal film and method for making same | |
| Guo et al. | Substrate effects on ZnO nanostructure growth via nanoparticle-assisted pulsed-laser deposition | |
| CN115537923A (en) | Highly textured delafossite structure CuMO 2 Method for producing polycrystalline block |
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 |