CN109678361A - A kind of preparation method of the alkali silicate glass of containing transition metal - Google Patents
A kind of preparation method of the alkali silicate glass of containing transition metal Download PDFInfo
- Publication number
- CN109678361A CN109678361A CN201910039916.0A CN201910039916A CN109678361A CN 109678361 A CN109678361 A CN 109678361A CN 201910039916 A CN201910039916 A CN 201910039916A CN 109678361 A CN109678361 A CN 109678361A
- Authority
- CN
- China
- Prior art keywords
- silicate glass
- alkali silicate
- transition metal
- ion
- preparation
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
- C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
- C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/06—Surface treatment of glass, not in the form of fibres or filaments, by coating with metals
- C03C17/09—Surface treatment of glass, not in the form of fibres or filaments, by coating with metals by deposition from the vapour phase
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/15—Deposition methods from the vapour phase
- C03C2218/151—Deposition methods from the vapour phase by vacuum evaporation
Abstract
The invention discloses a kind of preparation methods of the alkali silicate glass of containing transition metal, comprising the following steps: (1) alkali silicate glass is carried out ion-exchange treatment, rear cooling, cleaning, drying；(2) the alkali silicate glass after drying is placed in vacuum coating system, transition metal is deposited to by physical gas-phase deposite method by the alkali silicate glass surface, realize doping of the transition metal to alkali silicate glass.Wherein doping depth is regulated and controled by ion-exchange temperature and time, different physical gas-phase deposite methods and deposition parameter.This method can quickly, efficiently, controllably realize doping of the transition metal to alkali silicate glass.
Description
Technical field
The present invention relates to a kind of preparation method of glass doping more particularly to a kind of alkali silicate glass of containing transition metal
The preparation method of glass.
Background technique
With the fast development of communications industry, the demand to high transmission rates in the communications field and broadband component also constantly increases
By force.Glass has high uniformity, translucency and the distinguishing features such as low in cost, is not only as a kind of good optical material
Basis material important in preferred material and integrated optics in conventional optical systems design.The silicate of containing transition metal
Glass has unique optical property, is widely used in the passive or active optical waveguide device and laser system as communications industry
Equal optoelectronic areas.
It was verified that ion exchange is to control the maximally efficient general technology of glass material surface region index distribution.
In ion-exchange treatment, glass material is dipped into containing in Doped ions fuse salt, due to chemical potential gradient Doped ions into
Enter glass grid and replace basic ion, basic ion is discharged into melt, realizes the doping of glass material surface region.For many years, it adopts
A variety of geometries (plane, channel type and burial type) optical waveguide has been produced in silicate glass with ion-exchange.
It is mainly completed in fuse salt by ion-exchange currently, passive optical waveguide device is manufactured.And for
Active optical waveguide device developmental research is relatively rare, mainly with Ag+-Na+Or K+-Na+Exchange obtains, wherein active ions
Usually rare earth element.But in fact, directly carrying out ion exchange from containing transition metal ions or rare earth ion fuse salt
It is to be difficult successfully, to be primarily due to that these ions mobility ratio in glass grid is lower, and the glass of only particular components just has
It can be able to achieve doping, usually used glass is to be unsuitable for making active optical waveguide device.
Electric field-assisted solid liposome nanoparticle (FASSIE) is using external electrical field across the glass for being deposited with doping metals thin layer
Glass substrate body, under gradient of electrochemical potential driving, film and glass interface generate metal ion and are diffused into glass matrix
Realize doping.Currently, using electric field-assisted solid liposome nanoparticle (FASSIE) to monovalention as silver ion or copper ion are to glass
Glass is doped production planar optical waveguide and has many places report.Meanwhile FASSIE is for doping bivalent or trivalent metal ion glass
Glass waveguide is also a kind of effective technology.However, using field assisted ion-exchange method containing transition metal ion there is also
More problem: when 1, using electric field-assisted containing transition metal ion, needing high temperature high voltage, not easy to operate, consumes a large amount of energy
Source；2, under electric field action, ion in transition metal ions and glass matrix migrates simultaneously and diffusion, cause glass matrix by
Equilibrium state changes to nonequilibrium condition, and electric field is stronger, draws further away from equilibrium state when encountering under high temperature and unfavorable environment
It plays doped-glass to be changed from nonequilibrium condition to equilibrium state, doped-glass failure.
Summary of the invention
Goal of the invention: the object of the present invention is to provide a kind of quick, efficient, controllably containing transition metal alkali silicates
The preparation method of glass.
Technical solution: the preparation method of the alkali silicate glass of containing transition metal of the invention, comprising the following steps:
(1) alkali silicate glass is subjected to ion-exchange treatment, rear cooling, cleaning, drying；
(2) the alkali silicate glass after drying is placed in vacuum coating system, was incited somebody to action by physical gas-phase deposite method
Metal deposit is crossed to the alkali silicate glass surface, realizes doping of the transition metal to alkali silicate glass.
Preferably, Na will be contained+Or Li+Alkali silicate glass immersion contain K+Or Ag+Alkali metal fusion salt in carry out
Exchange, the alkali metal fusion salt are pure potassium nitrate or silver nitrate.
Preferably, the ion-exchange treatment temperature is 300~480 DEG C, and the time is 20min~96h.
Preferably, after the alkali silicate glass merging vacuum coating system, heated, the heating temperature
100~350 DEG C, 10~40min of heating time.
Preferably, the physical gas-phase deposite method includes in vacuum evaporation, sputtering sedimentation and ion-plating deposition method
It is a kind of.
It preferably, further include ion beam assisted depositing in the vacuum evaporation and sputter deposition.
Further, ion beam assisted depositing is carried out before or while transition metal deposition.
Preferably, the ion beam assisted depositing the following steps are included: the ion source into vacuum coating system be passed through it is auxiliary
Gas is helped, the auxiliary gas is inert gas, and the inert gas issues ion beam through ion source and acts on the alkali silicon
Silicate glass surface.
Preferably, the doping depth is 0.1~2.4 μm.
Technical principle: Na will be contained first+Or Li+Alkali silicate glass immersion contain K+Or Ag+Alkali metal fusion salt
In, the fuse salt of preferably pure potassium nitrate or silver nitrate carries out ion-exchange treatment, is determined according to the component of alkali silicate glass
Ion-exchange temperature and ion-exchange time, preferably ion-exchange treatment temperature be 300~480 DEG C, the time be 20min~
96h.Alkali silicate glass surface area is set to form higher bearing stress after ion exchange.It will after cooling, cleaning, drying
Alkali silicate glass is placed in vacuum coating system, is heated to it, the alkali silicate after improving ion-exchange treatment
The thermal vibration of molecule in glass substrate；After reaching certain vacuum degree and temperature, using physical gas-phase deposite method, by transition gold
Belong to and deposit to the alkali silicate glass substrate surface, the transition metal ions with energy enters surface region, in charge
To inside glass fast transferring and diffusion under balanced action, to realize the doping to the alkali silicate glass.It is using
It is more preferable in order to make to adulterate effect when vacuum evaporation and sputter deposition, before transition metal deposition or while deposition,
Ion source into vacuum coating system is passed through auxiliary gas to generate inert gas ion beam, bombards glass substrate,
Acceleration causes the glass substrate surface ionic bond to be broken, while under the action of surface region high pressure stress, exchange area
Interior exchange ion occurs to make surface region relaxation, doping metals are easier to enter exchange area, thus more to external migration and diffusion
It is advantageously implemented the doping to the alkali silicate glass.
The utility model has the advantages that 1, using physical gas-phase deposite method coupled ion exchange handle, can, quickly, efficiently, controllably
Realize doping of the transition metal to alkali silicate glass；2, the alkali silicate chemical durability of glass of obtained containing transition metal
More preferably；3, it by temperature and time when control ion exchange, using different physical gas-phase deposite methods and preferably assists
Deposition method regulates and controls doping depth, to realize transition metal to the controllability of alkali silicate glass doping preparation.
Detailed description of the invention
Fig. 1 is schematic device used in 1 preparation method of the embodiment of the present invention；
Fig. 2 is that 1 electron probe of the embodiment of the present invention (EPMA, JXA-8230) line scans alkali silicate glass doping section
Depth profile.
Specific embodiment
Present invention is further described in detail With reference to embodiment.
Embodiment 1
(1) commercial soda lime glass is cut into the glass substrate that size is 100 × 50 × 0.7mm, then carried out
Bevelling, chamfering, polishing, deionized water washing and drying treatment, wherein mass percent: 72%SiO2, 13.5%Na2O, 1%
K2O, 8%CaO, 4%MgO, 1.2%Al2O3With it is other.
(2) ion-exchange treatment: in automation annealing furnace, the glass substrate immersion purity that working process is crossed is greater than etc.
In 99.9% pure potassium nitrate fused salt, temperature is adjusted to 450 DEG C, ion exchange 8h.By K+-Na+Glass base after ion exchange
Piece carries out acetone and ethanol solution ultrasonic cleaning, and last wind drenches drying.
(3) doping treatment: the glass substrate after drying is placed in ZZSX-800F vacuum coating system, as shown in Figure 1,
Wherein 1 glass substrate；2 vacuum pumps；3 electron guns；4 evaporation sources；5 vacuum chambers；6 hall ion sources, being added in evaporation source will
The purity of doping is more than or equal to 99.99% chromium powder, and vacuum pump extracts vacuum, glass substrate is heated, to EH1000 Hall ion
Source is passed through argon gas and generates ar-ion beam, bombards glass substrate, makes surface region relaxation, then uses vacuum vapour deposition by crome metal
Glass substrate surface is deposited to, realizes doping of the crome metal to soda lime glass.Technological parameter is as follows: vacuum pressure:
3.84×10-3Pa；Operating pressure: 1.0 × 10-2Pa；Glass substrate heating temperature: 180 DEG C；Heating time: 30min；It imports suddenly
The argon flow of your ion source: 10sccm；Ar-ion beam average energy: 100eV；Ar-ion beam bombardment time: 10min.
Depth test is carried out using doping section of the electron probe line scanning technology to obtained alkali silicate glass.
Embodiment 2
(1) commercial soda lime glass is cut into the glass substrate that size is 80 × 40 × 0.8mm, is then fallen
Side, chamfering, polishing, deionized water washing and drying treatment, wherein mass percent: 69%SiO2, 15%Na2O, 1.14%
K2O, 6.53%CaO, 5.05%MgO, 1.73%Al2O3With it is other.
(2) ion-exchange treatment: in automation annealing furnace, the glass substrate immersion purity that working process is crossed is greater than etc.
In 99.9% pure potassium nitrate fused salt, temperature is adjusted to 480 DEG C, ion exchange 20min；By K+-Na+Glass after ion exchange
Glass substrate carries out acetone and ethanol solution ultrasonic cleaning, and last wind drenches drying.
(3) doping treatment: being placed in CCZK-ION multi-arc ion coating membranous system for the glass substrate after drying, adds in plating target
The purity that entering will adulterate is more than or equal to 99.99% gold particle, and vacuum pump extracts vacuum, glass substrate is heated, to EH1000
Hall ion source is passed through argon gas and generates ar-ion beam, bombards glass substrate, while gold is deposited to glass using ion electroplating method
Substrate surface realizes doping of the gold to soda lime glass.Technological parameter is as follows: vacuum pressure: 4.60 × 10-4Pa；Work
Pressure: 5.5 × 10-1Pa；Glass substrate heating temperature: 100 DEG C；Heating time: 40min；Import the argon gas stream of hall ion source
Amount: 20sccm；Back bias voltage: -350V；Gold target electric current: 70A.
Depth test is doped using doping section of the electron probe line scanning technology to obtained alkali silicate glass.
Embodiment 3
(1) commercial soda lime glass is cut into the glass substrate that size is 100 × 50 × 0.8mm, then carried out
Bevelling, chamfering, polishing, deionized water washing and drying treatment, 72%SiO2, 13.5%Na2O, 1%K2O, 8%CaO, 4%
MgO, 1.2%Al2O3With it is other.
(2) ion-exchange treatment: in automation annealing furnace, the glass substrate immersion purity that working process is crossed is greater than etc.
In 99.9% pure potassium nitrate fused salt, temperature is adjusted to 360 DEG C, ion exchange 50h；By K+-Na+Glass after ion exchange
Substrate carries out acetone soln ultrasonic cleaning, and last wind drenches drying.
(3) doping treatment: being placed in the multi-functional sputter coating system of FJL560D2 ion beam for the glass substrate after drying,
The chromium target that purity is more than or equal to 99.99% is added in sputtering target, vacuum pump extracts vacuum, heats glass substrate, use ion beam
Chromium metal deposit to glass substrate surface is then passed to Krypton and generates krypton ion beam bombardment glass substrate, realized by sputtering method
Doping of the crome metal to soda lime glass.Technological parameter is as follows: vacuum pressure: 2.0 × 10-4Pa；Operating pressure: 0.5 ×
100Pa；Glass substrate heating temperature: 200 DEG C；Heating time: 25min；Import the Krypton flow of hall ion source: 15sccm；
RF source power: 210W.
Depth test is doped using doping section of the electron probe line scanning technology to obtained alkali silicate glass.
Embodiment 4
(1) by the glass-cutting of lithium potassium silicate at size be 100 × 50 × 0.8mm glass substrate, then carry out bevelling,
Chamfering, polishing, deionized water washing and drying treatment, wherein mass percent: 70.8%SiO2, 19.14%K2O and 10.06%
Li2O。
(2) ion-exchange treatment: in automation annealing furnace, the glass substrate immersion purity that working process is crossed is greater than etc.
In 99.9% pure potassium nitrate fused salt, temperature is adjusted to 300 DEG C, ion exchange 96h；By K+-Li+Glass after ion exchange
Substrate carries out ethanol solution ultrasonic cleaning, and last wind drenches drying.
(3) doping treatment: the glass substrate after drying is placed in JGP450 magnetron sputtering coating system, is added in sputtering target
Enter purity more than or equal to 99.99% copper target, sputtering working gas is that purity is 99.999% argon gas, and vacuum pump extracts vacuum, adds
Metallic copper is deposited to glass substrate surface using magnetically controlled sputter method, realizes metallic copper to lithium potassium silicate by hot glass substrate
The doping of glass.Technological parameter is as follows: vacuum pressure: 2.5 × 10-4Pa；Argon flow: 18sccm；Operating pressure: 4.0 × 10-1Pa；Glass substrate heating temperature: 350 DEG C；Heating time: 10min；Sputtering power: 110W.
Depth test is doped using doping section of the electron probe line scanning technology to obtained alkali silicate glass.
The doping depth test data for the alkali silicate glass doping section that Examples 1 to 4 obtains is as shown in table 1:
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Doping depth | 2.4μm | 1.8μm | 1.1μm | 0.1μm |
| Coating film thickness | 0.2μm | 0.15μm | 0.09μm | 0.008μm |
Claims (10)
1. a kind of preparation method of the alkali silicate glass of containing transition metal, which comprises the following steps:
(1) alkali silicate glass is subjected to ion-exchange treatment, rear cooling, cleaning, drying；
(2) the alkali silicate glass after drying is placed in vacuum coating system, it is by physical gas-phase deposite method that transition is golden
Belong to and deposit to the alkali silicate glass surface, realizes doping of the transition metal to alkali silicate glass.
2. the preparation method of the alkali silicate glass of containing transition metal according to claim 1, which is characterized in that described
Ion-exchange treatment will be the following steps are included: will contain Na+Or Li+Alkali silicate glass immersion contain K+Or Ag+Alkali metal it is molten
Melt in salt and swap, the alkali metal fusion salt is pure potassium nitrate or silver nitrate.
3. the preparation method of the alkali silicate glass of containing transition metal according to claim 1, which is characterized in that described
Ion-exchange treatment temperature is 300~480 DEG C, and the time is 20min~96h.
4. the preparation method of the alkali silicate glass of containing transition metal according to claim 1, which is characterized in that described
Alkali silicate glass merging vacuum coating system after, heated, the heating temperature is 100~350 DEG C, when heating
Between be 10~40min.
5. the preparation method of the alkali silicate glass of containing transition metal according to claim 1, which is characterized in that described
Physical gas-phase deposite method includes one of vacuum evaporation, sputtering sedimentation and ion-plating deposition method.
6. the preparation method of the alkali silicate glass of containing transition metal according to claim 1, which is characterized in that described
It further include ion beam assisted depositing in vacuum evaporation and sputter deposition.
7. the preparation method of the alkali silicate glass of containing transition metal according to claim 6, which is characterized in that transition
Ion beam assisted depositing is carried out before or while metal deposit.
8. the preparation method of the alkali silicate glass of containing transition metal according to claim 6, which is characterized in that described
Ion beam assisted depositing is the following steps are included: the ion source into vacuum coating system is passed through auxiliary gas, the auxiliary gas
For inert gas, the inert gas issues ion beam through ion source and acts on the alkali silicate glass surface.
9. the preparation method of the alkali silicate glass of containing transition metal according to claim 1, which is characterized in that described
Doping depth is 0.1~2.4 μm.
10. the preparation method of the alkali silicate glass of containing transition metal according to claim 1, which is characterized in that institute
It states step (1) to be cleaned by ultrasonic using organic solution, the rear wind that carries out drenches drying, and the organic solvent is one of acetone, ethyl alcohol
Or two kinds.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910039916.0A CN109678361A (en) | 2019-01-16 | 2019-01-16 | A kind of preparation method of the alkali silicate glass of containing transition metal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910039916.0A CN109678361A (en) | 2019-01-16 | 2019-01-16 | A kind of preparation method of the alkali silicate glass of containing transition metal |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109678361A true CN109678361A (en) | 2019-04-26 |
Family
ID=66193430
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910039916.0A Pending CN109678361A (en) | 2019-01-16 | 2019-01-16 | A kind of preparation method of the alkali silicate glass of containing transition metal |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109678361A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1746707A (en) * | 2005-10-11 | 2006-03-15 | 浙江南方通信集团股份有限公司 | Production of ionic exchange glass light waveguide device |
| CN101079382A (en) * | 2007-05-24 | 2007-11-28 | 复旦大学 | Near-infrared high-transmission rate and multi-crystal transparent conductive oxide film and its making method |
| CN102809779A (en) * | 2012-08-06 | 2012-12-05 | 大连工业大学 | Method for preparing praseodymium-doped ion exchange aluminate and germanate glass waveguide |
| US20140093711A1 (en) * | 2012-10-03 | 2014-04-03 | Corning Incorporated | Physical vapor deposited layers for protection of glass surfaces |
| CN103745829A (en) * | 2013-12-30 | 2014-04-23 | 深圳市华星光电技术有限公司 | Preparation method of graphene composite electrode material |
-
2019
- 2019-01-16 CN CN201910039916.0A patent/CN109678361A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1746707A (en) * | 2005-10-11 | 2006-03-15 | 浙江南方通信集团股份有限公司 | Production of ionic exchange glass light waveguide device |
| CN101079382A (en) * | 2007-05-24 | 2007-11-28 | 复旦大学 | Near-infrared high-transmission rate and multi-crystal transparent conductive oxide film and its making method |
| CN102809779A (en) * | 2012-08-06 | 2012-12-05 | 大连工业大学 | Method for preparing praseodymium-doped ion exchange aluminate and germanate glass waveguide |
| US20140093711A1 (en) * | 2012-10-03 | 2014-04-03 | Corning Incorporated | Physical vapor deposited layers for protection of glass surfaces |
| CN103745829A (en) * | 2013-12-30 | 2014-04-23 | 深圳市华星光电技术有限公司 | Preparation method of graphene composite electrode material |
Non-Patent Citations (1)
| Title |
|---|
| WENJIE ZHANG等: "Surface modification of ion-exchanged float aluminosilicate glass during deposition of amorphous alumina coatings by e-beam evaporation", 《JOURNAL OF NON-CRYSTALLINE SOLIDS》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103388126B (en) | Low resistance height printing opacity ITO conducting film working method | |
| CN101476111A (en) | Transparent conductive film and preparation thereof | |
| CN110629186A (en) | Continuous deposition device for electrochromic functional thin film device | |
| CN113832430A (en) | Preparation method of diamond-based amorphous carbon-yttrium oxide gradient composite antireflection film | |
| CN106835012A (en) | A kind of preparation method of matte aluminum-doped zinc oxide films | |
| CN101497992A (en) | Method for preparing pile face zinc oxide transparent conductive film coating glass by plasma bombardment | |
| CN113636760B (en) | Antifog self-cleaning glass and preparation method thereof | |
| CN105842767A (en) | Equipment for preparing diffractive optical element by adopting microscopic pattern electrode thermal polarization and method thereof | |
| CN109678361A (en) | A kind of preparation method of the alkali silicate glass of containing transition metal | |
| CN102864578A (en) | Silicon-doped zinc oxide transparent conductive membrane and preparation method for same | |
| CN101806998B (en) | Manufacture method of substrate below silica-based electrowetting microdisplay device | |
| CN101736324B (en) | Microwave plasma preparation method of superhard titanium nitride thin film | |
| CN110983280A (en) | Preparation of W-doped ZrO by ion beam assisted deposition process2Method for making thin film | |
| CN1646418A (en) | Method for producing a product having a structured surface | |
| KR20120130468A (en) | Deposition method of anti-finger layer | |
| CN102051497A (en) | Preparation methods of gold and silver embedded target and film thereof | |
| CN102605334B (en) | Preparation method for Ge-Sb-Se amorphous film of all-optical device | |
| CN106222618B (en) | The preparation method of SnO2 doping ZnO sputtering target material | |
| CN102842643A (en) | Electric conductive glass and preparation method and application thereof | |
| CN110330237A (en) | One kind being based on chemcor glass substrate film deposition method | |
| CN110845156A (en) | Vacuum glass and manufacturing method thereof | |
| TW202030166A (en) | Tough glass composite and method | |
| CN110921612A (en) | Silicon nanopore structure with variable etching direction and preparation method thereof | |
| CN205275693U (en) | Focused ion beam physical vapor deposition device | |
| CN104233200B (en) | The preparation method of depolarization spectro-film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for 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: 20190426 |