CN105330336B - It is a kind of to seal the open technique of micropore - Google Patents

It is a kind of to seal the open technique of micropore Download PDF

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CN105330336B
CN105330336B CN201510687617.XA CN201510687617A CN105330336B CN 105330336 B CN105330336 B CN 105330336B CN 201510687617 A CN201510687617 A CN 201510687617A CN 105330336 B CN105330336 B CN 105330336B
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micropore
hole
substrate
nano
deposition
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CN105330336A (en
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王德强
赵越
陆文强
崔洪亮
杜春雷
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Chongqing Institute of Green and Intelligent Technology of CAS
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Chongqing Institute of Green and Intelligent Technology of CAS
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
    • C04B41/5049—Zinc or bismuth oxides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00008—Obtaining or using nanotechnology related materials

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  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
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Abstract

The open technique of micropore is sealed the invention discloses a kind of, assistant chemical vapor deposition growing technology is catalyzed using Au, in the Si with micron openings3N4ZnO nano-structure is prepared on substrate, the purpose of surface-sealing is realized.Central plane deposition of the sealing of hole process from hole wall to hole, the sedimentation rate of micropore surface is controlled by the temperature and time of deposition, zinc-oxide film is ultimately formed.The zinc-oxide film includes the zinc oxide nanowire layer being made up of zinc oxide nanowire, nanometer sheet or the nano-pillar of intersection growth, the nanometer material structure determination of formation, orderly, achievable high specific surface area.Si after sealing pores3N4Can be as carrying, wave transparent and thermally protective materials, available for semiconductor nano material technical field, polymorphic ZnO nano-structure easily etches and makes subsequent process processing more convenient.

Description

It is a kind of to seal the open technique of micropore
Technical field
It is more particularly to a kind of close using chemical vapor deposition ZnO nano layer the invention belongs to semiconductor process technique field Seal the open technique of micropore.
Background technology
ZnO is used as a kind of typical n-type, II-VI race's direct band gap, broad stopband (Eg about 3.37eV at room temperature) semiconductor material Material, it is adaptable to the application of shortwave shortwave photoelectric device, different from other wide bandgap semiconductors, its at room temperature exciton binding energy be up to 60meV, is 2.4 times of the hot ionization energy of room temperature (26meV), and exciton will not be by hot ionization at room temperature.ZnO micro-nanos material at room temperature Material due to good conduction, heat conductivility, unique piezoelectricity, thermoelectricity and photoelectric properties and excellent biocompatibility and Receive much concern.According to these characteristics, it is considered to be the ideal material of novel photoelectric subcomponent.At present, ZnO micro-nano materials are extensive Applied to light emitting diode (LED), photoelectric sensor, nano generator, ARC, film electroluminescence element, anti-purple Transition zone in outside material, laser material, DSSC etc..
Conventional deposition process has electrochemical deposition, sol-gel method, ald, electronics or ion auxiliary at present Deposition, sputtering, evaporation etc..It is published to be electrochemically-deposited in hole surface deposition Au and Pt [1] (Wei R S, Pedone as used D,Zurner A,et al.Fabrication of metallized nanopores in silicon nitride membranes for single-molecule sensing.Small,2010,6:1406-1414), ald is utilized (ALD) in hole surface depositing Al 2O3 [2] (Chen P, Mitsui T, Farmer D B, et al.Atomic layer deposition to fine-tune the surface properties and diameters of fabricated nanopores.Nano Lett,2004,4:1333-1337), electronics or ion assisted deposition make teos gas body Chemically reacted with vapor in silicon face, induce SiO2 be deposited on hole surface [3] (Danelon C, Santschi C, Brugger J,et al.Fabrication and functionalization of nanochannels by electron-beam-induced silicon oxide deposition.Langmuir,2006,22:10711–10715” or“Nilsson J,Lee J R I,Ratto T V,et al.Localized functionalization of single nanopores.Adv Mater,2006,18:427–431”).These methods are by hole wall both sides for the deposition process in hole Start to center deposition, the method for the planar depositions sealing of hole above hole has not been reported.And atomic layer deposition process is not Continuously, complicated surface chemical process and relatively low deposition velocity；Amount of liquid is big in gel in sol-gel process, dry in film Cracking and big contraction, the more difficult control of uniformity of film thickness are easily produced during dry；Organic solvent is toxic, to human body Harmful pollution environment；Process cycle is longer；The thickness of coating that sputtering is obtained is uneven, and device is excessively complicated, and sedimentation rate is low, fortune Row cost is higher.
The content of the invention
In view of this, the open technique of micropore is sealed it is an object of the invention to provide a kind of, one kind is based on chemical gaseous phase Deposit the new open micropore sealing technology of ZnO nano layer.ZnO nano material is prepared using Au catalysis auxiliary chemical vapor deposition methods Material is sealed to micron dimension opening, from the Si with micron dimension hole3N4Film is substrate, use carbothermic method with Graphite is above reaction source, sealing material tiling hole, vertically to cover bore region, rather than open from hole wall both sides with ZnO powder The deposition that begins develops to center, by controlling the temperature and time of deposition to control the sedimentation rate of micropore surface, ultimately forms oxygen Change zinc sealing of hole coating, reach that plane covers the purpose of micropore.
To reach above-mentioned purpose, the present invention provides following technical scheme：
It is a kind of to seal the open technique of micropore, auxiliary chemical vapor deposition method is catalyzed in the substrate containing micropore using Au ZnO nano coating is deposited, in Ar and O2Existence condition under, holding air pressure be 25-45KPa, temperature be 900~1000 DEG C progress Deposition.
Further, the substrate is Si3N4Substrate, SiO2Substrate or Hf2O5Substrate.
Further, the air pressure is 30KPa, and the temperature is 960 DEG C.
A kind of technique for sealing micropore opening, step is as follows：
1) by ZnO powder and carbon dust in mass ratio 1:1 is well mixed, and mixed-powder is placed in corundum boat；
2) appropriate Au is sputtered in the hole peripheral region containing microporous substrate, the substrate containing micropore is placed on container, and Make micropore open against mixed-powder, the container is corundum boat, quartz boat or crucible；
3) container is placed in the tube furnace center of chemical vapor depsotition equipment, air chamber is vacuumized, tube furnace heating speed Rate is 10-25 DEG C/min/min, when temperature rises to 600 DEG C, by carrier gas Ar and O2With 100sccm：1.5sccm ratio mixing Air chamber is passed through simultaneously, keeps growth air pressure stable in 30KPa, and temperature, which is warming up to after 960 DEG C, stops this condition that heats up and keep Deposited, sedimentation time is controlled according to hole size.
Further, the ZnO nano coating is by intersecting the zinc-oxide film, nano wire, nanometer sheet or the nano-pillar structure that grow Into.
The substrate of the open PROCESS FOR TREATMENT of the sealing micropore.
The substrate is used as carrying, the application of wave transparent and thermally protective materials.
The beneficial effects of the present invention are：
1st, above sealing material of the present invention tiling hole, bore region is vertically covered, rather than from hole wall both sides Start deposition to center to develop, by controlling the temperature and time of deposition to control the sedimentation rate of micropore surface, ultimately form Zinc oxide sealing of hole coating, reaches that plane covers the purpose of micropore.
2nd, the vertical oxidation zinc coating being covered in above hole has the film of even compact, intersects the zinc-oxide nano of growth The zinc oxide nanowire layer that line, nanometer sheet or nano-pillar are constituted, the thickness of nanometer layer, area and compactness extent are controllable, formation Nanometer material structure is determined, orderly, achievable high specific surface area.
3rd, addition Au, which makees catalyst, can make the obtained pattern for aoxidizing zinc coating rich and varied, can be according to different purposes To determine coating morphology.Si after sealing pores3N4Can as DNA sequencing, carrying, wave transparent, thermal protection and porous film material, Easily etch and make subsequent process processing more convenient, deposition obtains polymorphic ZnO nano-structure available for semiconductor nano material Technical field.
Brief description of the drawings
In order that the purpose of the present invention, technical scheme and beneficial effect are clearer, the present invention provides drawings described below and carried out Explanation：
Fig. 1 is that Au is catalyzed assistant chemical vapor deposition grower schematic diagram；
Fig. 2 is the SEM image that sealing of hole is carried out to a diameter of 5 μm of circular holes；
Fig. 3 is the SEM image that a length of 35 μm of square holes of opposite side carry out sealing of hole；
Fig. 4 is the SEM image that a length of 450 square hole of opposite side carries out sealing of hole；
Fig. 5 is bore region nano-deposit Cross Section Morphology；
Fig. 6 is the different-shape of bore region nano-deposit；
Fig. 7 is bore dia, the graph of a relation of Kong Houyu growth times.
Embodiment
Below in conjunction with accompanying drawing, the preferred embodiments of the present invention are described in detail.
CVD constructional devices of the present invention are as shown in figure 1, experimental facilities uses Anhui Bei Yike equipment Co., Ltd Double temperature-area tubular furnaces and flow control cabinet.
Embodiment 1
1) by ZnO powder and carbon dust in mass ratio 1:1 is mixed and grinds, and powder is placed in corundum boat；
2) in the Si containing a diameter of 5 μm of circular hole micropores3N4The hole peripheral region of substrate sputters appropriate Au, will contain micropore Si3N4 substrates be placed on corundum boat, and make micropore open against mixed-powder；
3) corundum boat is placed in the tube furnace center of chemical vapor depsotition equipment, air chamber is vacuumized, tube furnace heating Speed is 15 DEG C/min, when temperature rises to 600 DEG C, by carrier gas Ar and O2With 100sccm：1.5sccm ratio mixing is simultaneously Air chamber is passed through, keeps growth air pressure stable in 30KPa, temperature, which is warming up to after 960 DEG C, to be stopped heating up and keep this condition to carry out Deposit 20min.
Comparative example 1
Compared with operating procedure described in embodiment 1, not in Si3N4The hole peripheral region of substrate sputters appropriate Au as urging Agent.
Embodiment 1 is with the gained coating morphology figure of comparative example 1 as shown in Fig. 2 Si shown in a3N45 μm of diameter on film Circular port, in no Au as catalyst shown in b, complexion under the SEM after sedimentation time 20min, c show plating Au 40s, sunk The pattern of product time 20min.It can be seen that the coating complexion for not adding catalyst to obtain is single, and device to hole does not have sealing function.
Embodiment 2
1) by ZnO powder and carbon dust in mass ratio 1:1 is mixed and grinds, and powder is placed in corundum boat；
2) Si of the length of side for 35 μm of square opening micropore is being contained3N4The hole peripheral region of substrate sputters appropriate Au, will contain The Si of micropore3N4Substrate is placed on corundum boat, and makes micropore open against mixed-powder；
3) corundum boat is placed in the tube furnace center of chemical vapor depsotition equipment, air chamber is vacuumized, tube furnace heating Speed is 15 DEG C/min, when temperature rises to 600 DEG C, by carrier gas Ar and O2With 100sccm：1.5sccm ratio mixing is simultaneously Air chamber is passed through, keeps growth air pressure stable in 30KPa, temperature, which is warming up to after 900 DEG C, to be stopped heating up and keep this condition to carry out Deposit 20min, 30min, 40min.
Fig. 3 represents to carry out respectively in the SEM image of gained coating during deposition 20min, 30min, 40min, Fig. 3, shown in a Si3N4The square opening that a length of 35 μm of film top, b, c, d are respectively shown in the case where plating Au is as catalyst, sedimentation time 20min, 30min, 40min SEM complexions, the micro-variations situation of coating when depositing as can be seen from Figure.
Embodiment 3
1) by ZnO powder and carbon dust in mass ratio 1:1 is mixed and grinds, and powder is placed in corundum boat；
2) Si of the length of side for 450 μm of square opening micropore is being contained3N4The hole peripheral region of substrate sputters appropriate Au, will contain The Si3N4 substrates for having micropore are placed on corundum boat, and make micropore open against mixed-powder；
3) corundum boat is placed in the tube furnace center of chemical vapor depsotition equipment, air chamber is vacuumized, tube furnace heating Speed is 15 DEG C/min, when temperature rises to 600 DEG C, by carrier gas Ar and O2With 100sccm：1.5sccm ratio mixing is simultaneously Air chamber is passed through, keeps growth air pressure stable in 30KPa, temperature, which is warming up to after 1000 DEG C, to be stopped heating up and keep this condition to carry out Deposit 20min, 50min.
When Fig. 4 represents to deposit 20min, 50min respectively in the SEM image of gained coating, Fig. 4, Si shown in a3N4Film top A length of 450 μm of square opening, b, c, d are respectively shown in the case where plating Au is as catalyst, sedimentation time 20min, 50min and deposition The back side pattern in 50min holes.The micro-variations situation of coating when depositing as can be seen from Figure.
It is that the sample under 20min, 30min, 50min carries out section inspection to sedimentation time under in plating Au as catalyst Survey, it is found that coating is thick about 2 μm, 6 μm, 18 μm respectively, its microcosmic result is as shown in figure 5, when wherein a represents to start deposition, b, c, d It is the sample in cross section microgram under 20min, 30min, 50min to represent sedimentation time respectively.
Analysis is carried out to obtained ZnO nano coating to find, coating includes ZnO film, ZnO nano-wire, nano-pillar or received The film that rice piece interweaves, Fig. 6 represents the different-shape of bore region nano-deposit.
Data analysis is carried out to the pore size in embodiment, sedimentation time, thickness of coating, made as shown in Figure 7 Graph of a relation.
Finally illustrate, preferred embodiment above is merely illustrative of the technical solution of the present invention and unrestricted, although logical Cross above preferred embodiment the present invention is described in detail, it is to be understood by those skilled in the art that can be Various changes are made to it in form and in details, without departing from claims of the present invention limited range.

Claims (4)

1. a kind of seal the open technique of micropore, it is characterised in that is catalyzed auxiliary chemical vapor deposition method containing micro- using Au ZnO nano coating is deposited in the substrate in hole, step is as follows：
1）By ZnO powder and carbon dust in mass ratio 1:1 is well mixed, and mixed-powder is placed in corundum boat；
2）Appropriate Au is sputtered in the hole peripheral region containing microporous substrate, the substrate containing micropore is placed on container, and is made micro- Hole is open against mixed-powder, and the container is corundum boat, quartz boat or crucible；
3）Container is placed in the tube furnace center of chemical vapor depsotition equipment, air chamber is vacuumized, tube furnace heating rate is 10-25 DEG C/min, when temperature rises to 600 DEG C, by carrier gas Ar and O2With 100sccm：1.5sccm ratio mixing is led to simultaneously Air inlet chamber, keeps growth air pressure stable in 30KPa, and temperature, which is warming up to after 960 DEG C, to be stopped heating up and keep this condition to be sunk Product, sedimentation time is controlled according to hole size；
The substrate is the Si with micron dimension hole3N4Film.
2. a kind of according to claim 1 seal the open technique of micropore, it is characterised in that the ZnO nano coating is by handing over Zinc-oxide film, nano wire, nanometer sheet or the nano-pillar for pitching growth are constituted.
3. using the substrate of the open PROCESS FOR TREATMENT of sealing micropore described in claim 1.
4. substrate described in claim 3 is used as the application of carrying, wave transparent and thermally protective materials.
CN201510687617.XA 2015-10-21 2015-10-21 It is a kind of to seal the open technique of micropore Active CN105330336B (en)

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CN109813760A (en) * 2019-02-28 2019-05-28 江苏理工学院 A kind of zinc oxide nanowire gas sensor and preparation method thereof
CN113583156B (en) * 2021-06-30 2023-01-13 苏州大学 Preparation method of pore plate for high-flux sunlight open polymerization and high-flux sunlight open polymerization method

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