CN103288359A - Preparation method for oxide micro/nano-structured ordered porous array through oxygen-plasma irradiation - Google Patents
Preparation method for oxide micro/nano-structured ordered porous array through oxygen-plasma irradiation Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000001301 oxygen Substances 0.000 claims abstract description 23
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 23
- 239000004005 microsphere Substances 0.000 claims abstract description 22
- 239000013078 crystal Substances 0.000 claims abstract description 19
- 239000007789 gas Substances 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 32
- 239000000758 substrate Substances 0.000 claims description 27
- 239000004793 Polystyrene Substances 0.000 claims description 22
- 239000011521 glass Substances 0.000 claims description 22
- 229920002223 polystyrene Polymers 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 12
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 12
- 241000209094 Oryza Species 0.000 claims description 10
- 235000007164 Oryza sativa Nutrition 0.000 claims description 10
- 230000001678 irradiating effect Effects 0.000 claims description 10
- 235000009566 rice Nutrition 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 8
- 239000012702 metal oxide precursor Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- 238000007650 screen-printing Methods 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 3
- 238000002242 deionisation method Methods 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000001338 self-assembly Methods 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims description 2
- 229960003280 cupric chloride Drugs 0.000 claims description 2
- 229910001882 dioxygen Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 42
- 230000008569 process Effects 0.000 abstract description 5
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000004038 photonic crystal Substances 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 238000004140 cleaning Methods 0.000 abstract 1
- 230000004048 modification Effects 0.000 abstract 1
- 238000012986 modification Methods 0.000 abstract 1
- 238000012545 processing Methods 0.000 abstract 1
- 239000002356 single layer Substances 0.000 abstract 1
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 42
- 238000000137 annealing Methods 0.000 description 10
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 10
- 230000005855 radiation Effects 0.000 description 10
- 239000010409 thin film Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 6
- 208000037656 Respiratory Sounds Diseases 0.000 description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical group O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 4
- 229960004643 cupric oxide Drugs 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
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- 238000001816 cooling Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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- 238000003860 storage Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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Abstract
The invention discloses a preparation method for an oxide micro/nano-structured ordered porous array through oxygen-plasma irradiation. The preparation method includes a two-dimensional colloidal crystal template process and a plasma irradiation process and comprises the following concrete steps: synthesizing a single-layer two-dimensional colloidal crystal template by using a gas/liquid interfacial assembling method, wherein the two-dimensional colloidal crystal template is composed of a single microsphere with a diameter of 200 to 2000 nm; and in particular, transferring and floating the template onto the surface of a precursor solution with a concentration of 0.02 to 0.2 mol/L, taking out the template immersed in the solution, heating the template in a baking oven at a temperature of 80 to 120 DEG C for 15 to 30 min and subjecting the template to irradiation in a plasma cleaning machine in the atmosphere of oxygen for 10 to 60 min, wherein plasma power is 5.8 to 18 W. The method provided by the invention does not use any precious special apparatus and surface modification agent, has the advantages of simple and rapid preparation process, low cost, high efficiency, safety and environment friendliness and can be extensively used in fields like photonic crystals, micro/nano processing, catalysis, surface enhanced Raman scattering and sensing.
Description
Technical field
The present invention relates to the oxygen plasma irradiating preparation process of the structurally ordered porous array of oxide micro-nano rice, especially have the preparation method of the orderly hole film of less crackle.
Technical background
The micro ordered porous thin-film, contain the periodically hole of ordered arrangement, the aperture is micron, submicron-scale, and the hole wall in hole or the surface characteristic unit on the single hole (nano particle, nano wire) are nanoscale, and its structural unit (hole) evenly distributes on film.This film has important purposes in a lot of fields (as: photonic crystal, cell cultures, information storage, drug release etc.), and has favorable compatibility with semiconductor technology owing to the order of its height and high specific surface area.If as nano-device, not only the homogeneity of thickness can be guaranteed, homogeneity and the stability of film each several part character has also been guaranteed in the even distribution of structural unit on its film, and then has guaranteed the reliability and stability of device.Further, by specific surface area and the thickness of the easy change film of the big I of adjustment aperture, thereby be expected to realize the artificial regulatory of nano-device parameters.Wherein, this porous is little/micro-nano structure, the stability that not only has the micro-meter scale system, the high reactivity that simultaneously also has the nano material system, has more surfactivity site, adsorptivity to detected gas molecule is strong, be proved to be a kind of good gas sensitive, as a kind of " the multi-layer classification nanostructure ordered hole thin film type gas-sensitive sensor and preparation method thereof " that discloses among the disclosed Chinese invention patent Shen Qing Publication specification sheets CN 101435795AZ in May, 2009, it is intended to show based on this orderly hole film and can be used as the gas sensor material with superior performance.Thereby the micro ordered porous thin-film is one of candidate material of the tool potentiality of gas sensor of new generation.
Yet, above-mentioned synthesizing porous film generally is by following flow process, as " the binary ordered porous thin-film and preparation method thereof " that discloses among the disclosed Chinese invention patent Shen Qing Publication specification sheets CN 101435795AZ in March, 2010: with the colloidal spheres template transfer for preparing to precursor solution, the use substrate picks up, and places baking oven high temperature (300-400 ℃) annealing to form the film of oxide compound then.Because the difference between the thermal expansivity of film and substrate, (heat-cooling) in the treating processes when synthetic and cause that easily big crackle appears in film on substrate, influence the stability of electroconductibility and device, be unfavorable for the regulation and control of air-sensitive parameter, that namely synthesizes is repeated bad, is difficult to carry out practicability.
Summary of the invention
The technical problem to be solved in the present invention is the shortcoming part that overcomes prior art, and a kind of technology of preparing for preparing good, the easy ordered porous thin-film of universality is provided
The another one technical problem that the present invention will solve is that a kind of ordered porous thin-film for preparing flawless or have less crackle is provided.
For solving technical problem of the present invention, the technical scheme that adopts is:
The oxygen plasma irradiating preparation process of the structurally ordered porous array of oxide micro-nano rice may further comprise the steps:
(1) with simple glass difference ultrasonic cleaning 30-40min in acetone, ethanol, deionized water successively, and uses N
2Air-blowing is done, and uses the ozone ultraviolet to clean 20-30 minute, obtains super hydrophilic glass surface;
(2) simple glass that clean is crossed is positioned on the laboratory bench of level, removes ionized water and evenly drops on glass to form a layer thickness 0.2-0.3mm moisture film; Be that the polystyrene microsphere suspension of 2-3% disperses to obtain mixed solution with in the volume of ethanol after being uniformly dispersed with mass percent; Mixed solution is slowly injected along the glass edge that is covered with the deionization moisture film, finish until PS microballoon self-assembly on the gas/liquid interface; The temperature that controls environment is aided with weak gas flow to 30-40 ℃ and carries out drying, obtains the individual layer two-dimensional colloidal crystal template on glass substrate;
(3) the metal oxide precursor solution surface that the above-mentioned colloidal crystal template for preparing is shifted and is floated to, the time that keeps template to swim on the solution is 2-10 minute; Kept flat 5-6 minute after again template being picked up with substrate, place 80-120 ℃ of baking oven heating 15-30 minute then; Subsequently the sample of oven dry is placed in the plasma clean machine under the high purity oxygen gas atmosphere irradiation 10-60 minute and obtains the orderly hole of individual layer flawless array film;
(4) number of times of repeating step (2) obtains the orderly hole of two-layer flawless array film more than 0 time.
Ozone free air delivery demand is 100-120CFM in the described step (1), and ultraviolet wavelength is 254nm.
The contained microsphere diameter of polystyrene microsphere suspension is 200-2000nm in the described step (2), and dispersion liquid is deionized water.
Precursor solution is tin tetrachloride, iron(ic) chloride, cupric chloride, cupric nitrate or indium nitrate in the described step (3), and concentration is 0.02-0.2mol/L.
Substrate is the vitrified pipe of silicon chip, ito glass, connection Pt line or the plane comb electrode of silk screen printing in the described step (3), and it is shaped as plane or curved surface.
Described step (3) ionic medium body power is 5.8-18W, and oxygen flow is for being 10-50sccm.
The hole size of orderly hole array film is 200-2000nm in the described step (3), and thickness is 200-2000nm.
With respect to prior art, beneficial effect of the present invention: one, use scanning electron microscope and power spectrum and X-ray diffractometer thereof to characterize respectively to the product that makes, by the result as can be known, the product smooth surface, thickness is even, crackle is few, it is the orderly bowl-shape poroid metal oxide film that places on the substrate, and wherein the thickness of film is 200-2000nm, and the size in bowl-shape hole is 200-2000nm.Oxide compound is conductor oxidate, and it is stannic oxide, or cupric oxide or ferric oxide, or Indium sesquioxide.Substrate is silicon chip, ito glass, the vitrified pipe of connection Pt line, the plane comb electrode of silk screen printing.Being shaped as of substrate is plane, or the curved surface shape; Its two, synthetic position, orderly hole via-hole array is interconnected between the hole, is conducive to the diffusion circulation therein of gas or medicine, has expanded application prospect greatly; Its three, the preparation method has universality, and is synthetic applicable to the flawless of multiple metal oxide film, can be by adjusting composition, the concentration of precursor solution, composition, microstructure that can control punch; Its four, this method has easy and simple to handle, saves time, technology is simple, the advantage of safety non-pollution is suitable for the batch process in the semiconductor technology.
Further embodiment as useful result, the one, the preferred using plasma irradiation method of the film that synthesizes is synthetic, its film does not have crackle, can possess the more rare character of conventional crackle material, lead etc. as high electricity, by the synthetic film of this plasma process, has the surface property that the synthetic material of conventional annealing does not possess, hang key etc. as super hydrophilic, highdensity surface group and surface, the film than conventional annealing obtains is expected to obtain better properties; The preferred stannic oxide of the material of film, or cupric oxide or ferric oxide, or Indium sesquioxide, substrate is preferably monocrystalline silicon piece, ito glass, the vitrified pipe of connection Pt line, the plane comb electrode of silk screen printing., the shape of substrate is preferably plane, or the curved surface shape, and not only the source of material is abundanter, and the shape of substrate is also varied, can satisfy multiple Application Areas to the requirement of material; Synthetic film is owing to adopt high-quality colloidal spheres template, and each regional consistence of film is better, is conducive to the performance each several part unanimity of material, and the stability of the device of constructing and reproducibility.
Description of drawings
Fig. 1 is the stereoscan photograph that adopts the product of the inventive method plasma radiation method and annealing method (seeing " binary ordered porous thin-film and preparation method thereof " of disclosing among the Chinese invention patent Shen Qing Publication specification sheets CN 101435795AZ) acquisition respectively.Wherein, (a) film that obtains for the plasma radiation method, (b) film that obtains for annealing method.The colloidal spheres template that adopts is made of the polystyrene microsphere of 500nm, and 0.05M tin tetrachloride solution is precursor solution, and substrate is monocrystalline silicon piece.The illustration in the upper right corner is corresponding film contact angle test result, and the contact angle size is determined by the shape of water droplet.
Fig. 2 is the X ray diffracting spectrum that adopts the product of the inventive method plasma radiation method and annealing method (seeing " binary ordered porous thin-film and preparation method thereof " of disclosing among the Chinese invention patent Shen Qing Publication specification sheets CN 101435795AZ) acquisition respectively.Wherein, (a) film that obtains for the plasma radiation method, (b) film that obtains for annealing method.The colloidal spheres template that adopts is made of the polystyrene microsphere of 500nm, and 0.05M tin tetrachloride solution is precursor solution, and substrate is monocrystalline silicon piece.
Fig. 3 is the O1s spectrogram of the x-ray photoelectron power spectrum of the product that adopts the inventive method plasma radiation method and annealing method (seeing " binary ordered porous thin-film and preparation method thereof " of disclosing among the Chinese invention patent Shen Qing Publication specification sheets CN 101435795AZ) respectively and obtain.Wherein, (a) film that obtains for the plasma radiation method, (b) film that obtains for annealing method.The colloidal spheres template that adopts is made of the polystyrene microsphere of 500nm, and 0.05M tin tetrachloride solution is precursor solution, and substrate is monocrystalline silicon piece.
Fig. 4 is the scanning electron microscope picture of the product of employing the inventive method plasma radiation method acquisition.Wherein, the colloidal spheres template of employing is made of the polystyrene microsphere of 1000nm, and 0.1M tin tetrachloride solution is precursor solution, and substrate is monocrystalline silicon piece.Upper right corner illustration is its high magnification map picture among the figure.
Fig. 5 is the scanning electron microscope picture of the product of employing the inventive method plasma radiation method acquisition.Wherein, the colloidal spheres template of employing is made of the polystyrene microsphere of 200nm, and 0.02M tin tetrachloride solution is precursor solution, and substrate is monocrystalline silicon piece.Upper right corner illustration is its high magnification map picture among the figure.
Fig. 6 is the scanning electron microscope picture of the product of employing the inventive method plasma radiation method acquisition.Wherein, the colloidal spheres template of employing is made of the polystyrene microsphere of 500nm, and 0.05M tin tetrachloride solution is precursor solution, and substrate is curved vitrified pipe.(b) figure is the high magnification map picture of (a), (a) in upper right corner illustration be its fourier transformation image, show Kong Weiliu side's solid matter.
Fig. 7 is the scanning electron microscope picture of the product of employing the inventive method plasma radiation method acquisition.Wherein, the colloidal spheres template of employing is made of the polystyrene microsphere of 1000nm, and the 0.2M copper nitrate solution is precursor solution, and substrate is monocrystalline silicon piece, and the number of plies is 2 layers.
Embodiment
Embodiment 1
Synthesizing of individual layer two-dimensional colloidal crystal template:
(1) with simple glass difference ultrasonic cleaning 30-40min in acetone, ethanol, deionized water successively, and uses N
2Air-blowing is done, and uses the ozone ultraviolet to clean 30 minutes, obtains super hydrophilic glass surface;
(2) simple glass that clean is crossed is positioned on the laboratory bench of level, removes ionized water and evenly drops on glass to form a layer thickness 0.2mm moisture film; Be that 2.5% polystyrene microsphere suspension disperses with in the volume of ethanol with mass percent, obtain mixed solution after being uniformly dispersed; Mixed solution is slowly injected along the glass edge that is covered with the deionization moisture film, finish until PS microballoon self-assembly on the gas/liquid interface; The temperature that controls environment is aided with weak gas flow to 30-40 ℃ and carries out drying, obtains the individual layer two-dimensional colloidal crystal template on glass substrate.
Ozone free air delivery demand is 100-120CFM in the described step (1), and ultraviolet wavelength is 254nm.
The contained microsphere diameter of polystyrene microsphere suspension is 200-2000nm in the described step (2), and dispersion liquid is deionized water.
Embodiment 2
The colloidal crystal template that is constituted by the polystyrene microsphere of 500nm diameter according to the preparation of the method for embodiment 1;
The metal oxide precursor 0.05M tin tetrachloride solution surface that colloidal crystal template is shifted and is floated to kept flat 5 minutes after adopting monocrystalline silicon piece to pick up the template that is soaked with solution, placed 100 ° of C oven dry 15 minutes then; Subsequently the sample of oven dry was placed in the plasma clean machine in the oxygen atmosphere irradiation 40 minutes, power is 10W, and oxygen flow is 30sccm, obtains the orderly hole of the individual layer flawless array film shown in Fig. 1 (a).Than the method that annealing method obtains, the even flawless of film that present method is synthetic, and have better surperficial Superhydrophilic.By X-ray diffraction analysis, the thing of the film that the inventive method is synthetic is the tindioxide of rutile phase mutually, shown in Fig. 2 (a).Further, Fig. 3 shows that the synthetic film of the inventive method has more surface hydroxyl, has higher surfactivity.
The colloidal crystal template that is constituted by the polystyrene microsphere of 1000nm diameter according to the preparation of the method for embodiment 1;
The metal oxide precursor 0.1M tin tetrachloride solution surface that colloidal crystal template is shifted and is floated to kept flat 5 minutes after adopting monocrystalline silicon piece to pick up the template that is soaked with solution, placed 110 ° of C oven dry 20 minutes then; Subsequently the sample of oven dry was placed in the plasma clean machine in the oxygen atmosphere irradiation 50 minutes, power is 18W, and oxygen flow is 50sccm, obtains the orderly hole of individual layer flawless array film as shown in Figure 4.
Embodiment 4
The colloidal crystal template that is constituted by the polystyrene microsphere of 200nm diameter according to the preparation of the method for embodiment 1;
Metal oxide precursor 0.02M tin tetrachloride solution surface with colloidal crystal template shifts and is floated to adopts monocrystalline silicon piece to pick up and place 80 ° of C oven dry 20 minutes the template that is soaked with solution; Subsequently the sample of oven dry was placed in the plasma clean machine in the oxygen atmosphere irradiation 30 minutes, power is 5.8W, and oxygen flow is 10sccm, obtains the orderly hole of individual layer flawless array film as shown in Figure 5.
The colloidal crystal template that is constituted by the polystyrene microsphere of 500nm diameter according to the preparation of the method for embodiment 1;
Metal oxide precursor 0.05M tin tetrachloride solution surface with colloidal crystal template shifts and is floated to adopts substrate to pick up and place 100 ° of C oven dry 20 minutes the template that is soaked with solution; Subsequently the sample of oven dry was placed in the plasma clean machine in the oxygen atmosphere irradiation 30 minutes, power is 10W, and oxygen flow is 30sccm, obtains the orderly hole of individual layer flawless array film as shown in Figure 6, and substrate is vitrified pipe.
Embodiment 6
The colloidal crystal template that is constituted by the polystyrene microsphere of 500nm diameter according to the preparation of the method for embodiment 1;
The metal oxide precursor 0.2M copper nitrate solution surface that the colloidal crystal template that the polystyrene spheres by the 500nm diameter for preparing is in advance constituted shifts and is floated to adopts other substrates to pick up and place 100 ° of C oven dry 20 minutes the template that is soaked with solution; Subsequently the sample of oven dry was placed in the plasma clean machine in the oxygen atmosphere irradiation 40 minutes, power is 10W, and oxygen flow is 30sccm,
1 number of repeating step is 1 time, obtains double-deck cupric oxide hole array, as shown in Figure 7.Substrate is the vitrified pipe of curved surface.
Claims (7)
1. the oxygen plasma irradiating preparation process of the structurally ordered porous array of oxide micro-nano rice is characterized in that may further comprise the steps:
(1) with simple glass difference ultrasonic cleaning 30-40min in acetone, ethanol, deionized water successively,, and use N
2Air-blowing is done, and uses the ozone ultraviolet to clean 20-30 minute, obtains super hydrophilic glass surface;
(2) simple glass that clean is crossed is positioned on the laboratory bench of level, removes ionized water and evenly drops on glass to form a layer thickness 0.2-0.3mm moisture film; Be that the polystyrene microsphere suspension of 2-3% disperses to obtain mixed solution with in the volume of ethanol after being uniformly dispersed with mass percent; Mixed solution is slowly injected along the glass edge that is covered with the deionization moisture film, finish until PS microballoon self-assembly on the gas/liquid interface; The temperature that controls environment is aided with weak gas flow to 30-40 ℃ and carries out drying, obtains the individual layer two-dimensional colloidal crystal template on glass substrate;
(3) the metal oxide precursor solution surface that the above-mentioned colloidal crystal template for preparing is shifted and is floated to, the time that keeps template to swim on the solution is 2-10 minute; Kept flat 5-6 minute after again template being picked up with substrate, place 80-120 ℃ of baking oven heating 15-30 minute then; Subsequently the sample of oven dry is placed in the plasma clean machine under the high purity oxygen gas atmosphere irradiation 10-60 minute and obtains the orderly hole of individual layer flawless array film;
(4) number of times of repeating step (2) obtains the orderly hole of two-layer flawless array film more than 0 time.
2. according to the oxygen plasma irradiating preparation process of the structurally ordered porous array of claims 1 described oxide micro-nano rice, it is characterized in that ozone free air delivery demand is 100-120CFM in the described step (1), ultraviolet wavelength is 254nm.
3. according to the oxygen plasma irradiating preparation process of the structurally ordered porous array of claims 1 described oxide micro-nano rice, it is characterized in that, the contained microsphere diameter of polystyrene microsphere suspension is 200-2000nm in the described step (2), and dispersion liquid is deionized water.
4. according to the oxygen plasma irradiating preparation process of the structurally ordered porous array of claims 1 described oxide micro-nano rice, it is characterized in that, precursor solution is tin tetrachloride, iron(ic) chloride, cupric chloride, cupric nitrate or indium nitrate in the described step (3), and concentration is 0.02-0.2mol/L.
5. according to the oxygen plasma irradiating preparation process of the structurally ordered porous array of claims 1 described oxide micro-nano rice, it is characterized in that, substrate is the vitrified pipe of silicon chip, ito glass, connection Pt line or the plane comb electrode of silk screen printing in the described step (3), and it is shaped as plane or curved surface.
6. according to the oxygen plasma irradiating preparation process of the structurally ordered porous array of claims 1 described oxide micro-nano rice, it is characterized in that described step (3) ionic medium body power is 5.8-18W, oxygen flow is for being 10-50sccm.
7. according to the oxygen plasma irradiating preparation process of the structurally ordered porous array of claims 1 described oxide micro-nano rice, it is characterized in that the hole size of orderly hole array film is 200-2000nm in the described step (3), thickness is 200-2000nm.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104609362A (en) * | 2014-12-26 | 2015-05-13 | 上海维凯光电新材料有限公司 | Preparation method of polymer nanometer ring |
| CN105951166A (en) * | 2016-04-28 | 2016-09-21 | 河南大学 | Device for preparing two-dimensional colloidal crystals |
| CN106563472A (en) * | 2016-11-07 | 2017-04-19 | 中国科学院合肥物质科学研究院 | Gold-bismuth oxychloride nano composite material and preparation method thereof |
| CN109879247A (en) * | 2019-02-19 | 2019-06-14 | 中国科学院合肥物质科学研究院 | A kind of manufacturing method of the large area in any substrate, diversified organic formwork |
| CN114923961A (en) * | 2022-04-29 | 2022-08-19 | 安徽维纳物联科技有限公司 | SnO (stannic oxide) 2 Carbon monoxide gas sensor and preparation method thereof |
| CN115406944A (en) * | 2022-08-17 | 2022-11-29 | 安徽维纳物联科技有限公司 | Preparation method of carbon dioxide gas sensor and prepared gas sensor |
| CN116314851A (en) * | 2023-03-20 | 2023-06-23 | 安徽维纳物联科技有限公司 | Method for preparing lithium battery cathode porous current collector copper foil by template-stripping method, copper foil prepared by method and application of copper foil |
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Cited By (11)
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| CN104609362A (en) * | 2014-12-26 | 2015-05-13 | 上海维凯光电新材料有限公司 | Preparation method of polymer nanometer ring |
| CN105951166A (en) * | 2016-04-28 | 2016-09-21 | 河南大学 | Device for preparing two-dimensional colloidal crystals |
| CN105951166B (en) * | 2016-04-28 | 2019-03-29 | 河南大学 | The preparation facilities of two-dimensional colloidal crystal |
| CN106563472A (en) * | 2016-11-07 | 2017-04-19 | 中国科学院合肥物质科学研究院 | Gold-bismuth oxychloride nano composite material and preparation method thereof |
| CN106563472B (en) * | 2016-11-07 | 2019-01-11 | 中国科学院合肥物质科学研究院 | Gold-perite nanometer composite material and preparation method |
| CN109879247A (en) * | 2019-02-19 | 2019-06-14 | 中国科学院合肥物质科学研究院 | A kind of manufacturing method of the large area in any substrate, diversified organic formwork |
| CN114923961A (en) * | 2022-04-29 | 2022-08-19 | 安徽维纳物联科技有限公司 | SnO (stannic oxide) 2 Carbon monoxide gas sensor and preparation method thereof |
| CN115406944A (en) * | 2022-08-17 | 2022-11-29 | 安徽维纳物联科技有限公司 | Preparation method of carbon dioxide gas sensor and prepared gas sensor |
| CN115406944B (en) * | 2022-08-17 | 2024-07-02 | 安徽维纳物联科技有限公司 | Preparation method of carbon dioxide gas sensor and prepared gas sensor |
| CN116314851A (en) * | 2023-03-20 | 2023-06-23 | 安徽维纳物联科技有限公司 | Method for preparing lithium battery cathode porous current collector copper foil by template-stripping method, copper foil prepared by method and application of copper foil |
| CN116314851B (en) * | 2023-03-20 | 2024-04-02 | 安徽维纳物联科技有限公司 | Method for preparing lithium battery cathode porous current collector copper foil by template-stripping method, copper foil prepared by method and application of copper foil |
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