CN103160802A - Preparation method of nitrogen-doped titanium dioxide film - Google Patents
Preparation method of nitrogen-doped titanium dioxide film Download PDFInfo
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- CN103160802A CN103160802A CN2011104215507A CN201110421550A CN103160802A CN 103160802 A CN103160802 A CN 103160802A CN 2011104215507 A CN2011104215507 A CN 2011104215507A CN 201110421550 A CN201110421550 A CN 201110421550A CN 103160802 A CN103160802 A CN 103160802A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title abstract description 20
- 239000004408 titanium dioxide Substances 0.000 title abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 34
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 25
- 239000010936 titanium Substances 0.000 claims abstract description 25
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 20
- 239000007789 gas Substances 0.000 claims abstract description 19
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 6
- 230000008569 process Effects 0.000 claims abstract description 5
- 239000000758 substrate Substances 0.000 claims description 17
- 230000000802 nitrating effect Effects 0.000 claims description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000010703 silicon Substances 0.000 claims description 13
- 229910052710 silicon Inorganic materials 0.000 claims description 13
- 230000035484 reaction time Effects 0.000 claims description 9
- 230000002000 scavenging effect Effects 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000010306 acid treatment Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 4
- 239000010410 layer Substances 0.000 abstract 2
- 239000002356 single layer Substances 0.000 abstract 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 8
- 238000010586 diagram Methods 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910008332 Si-Ti Inorganic materials 0.000 description 1
- 229910006749 Si—Ti Inorganic materials 0.000 description 1
- 229910003077 Ti−O Inorganic materials 0.000 description 1
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010303 mechanochemical reaction Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000004549 pulsed laser deposition Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- -1 titanium alkoxide Chemical class 0.000 description 1
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Abstract
Discloses a preparation method of a nitrogen-doped titanium dioxide film, which comprises the steps of sequentially introducing titanium-containing source gases into a reaction chamber to form a silicon-titanium bond; introducing nitrogen and hydrogen into a reaction cavity of the atomic layer deposition equipment, carrying out plasma discharge, forming covalent bonds between partial nitrogen atoms and partial titanium atoms after nitrogen ionization, and forming bonds between non-bonded electrons of the nitrogen atoms and ionized hydrogen atoms; introducing an oxygen-containing source into a reaction cavity of the atomic layer deposition equipment to form a titanium-oxygen bond; growing the titanium dioxide film containing nitrogen atoms layer by layer. The invention provides a preparation method of a nitrogen-doped titanium dioxide film, which is characterized in that nitrogen doping is carried out on the titanium dioxide film by using plasma atomic layer deposition equipment. The method utilizes the characteristics of atomic layer deposition single-layer cycle growth and the characteristics of high chemical reaction activity of plasma to realize uniform growth in the process of titanium dioxide film growthThe whole film structure is doped with nitrogen atoms, so that the doped film structure is complete, the performance is obvious, and the TiO is effectively improved2Utilization ratio of visible light.
Description
Technical field
The present invention relates to the doping vario-property technical field of technique for atomic layer deposition and titanium dioxide, be specifically related to a kind of preparation method of nitrating titanium deoxid film.
Background technology
Conductor photocatalysis material is having broad application prospects aspect the solution energy and environmental problem.Semiconductor nano TiO
2Because its stable chemical nature, pollutent nontoxic and that can effectively remove in large G﹠W become the ideal material that solves the energy and environmental problem.Yet, TiO
2Energy gap large (Eg=3.2eV), light-catalyzed reaction could occur at wavelength under less than the UV-light of 387nm only, this means TiO
2Can only utilize a small amount of part in sunlight (approximately 5%), and the visible light that is in the great majority (approximately 45%) can't utilize in sunlight.Doping vario-property is to make TiO
2Have one of important means of visible light catalysis activity, although metal ion mixing can be realized visible light catalysis activity, because metal ion becomes the deathnium, the catalytic activity of UV-light wave band is reduced.The discovery nitrogen such as calendar year 2001 Asahi substitute a small amount of lattice oxygen can make TiO
2Band gap narrow down, make TiO in active under not reducing UV-light
2Has visible light activity.Present N doped Ti O
2The preparation method mainly contain sputtering method, pulsed laser deposition, precursor mixing calcining method, titanium alkoxide hydrolysis, sol-gel method, mechanochemical reaction and plasma processing method etc.Yet present N doped Ti O
2The preparation method in can not realize that all dopant states, component to N distributes and the accurate control of doping, to such an extent as to N doped Ti O
2Rear visible light-responded photo-quantum efficiency is low.
Summary of the invention
The object of the invention is to, provide a kind of and can realize the in-situ doped of nitrogen element in the synthesis of titanium dioxide film, can control accurately dopant states, component distribution and the doping of N, effectively improve TiO
2Preparation method to the nitrating titanium deoxid film of the utilization ratio of visible light.
Preparation method from an aspect a kind of nitrating titanium deoxid film provided by the invention comprises:
Silicon chip substrate is positioned in plasma body atomic layer deposition apparatus reaction chamber;
Pass into titaniferous source gas in the described plasma body atomic layer deposition apparatus reaction chamber, the titanium atom in the gas of described titaniferous source is adsorbed on described substrate;
Nitrogen buffer gas delivering hydrogen in the atomic layer deposition apparatus reaction chamber carries out plasma discharge simultaneously, and described nitrogen ionization rear section nitrogen-atoms and described partial-titanium atom formation covalent linkage, nitrogen-atoms be the electronics of Cheng Jian and the hydrogen atom Cheng Jian of ionization not;
Pass in the atomic layer deposition apparatus reaction chamber and contain oxygen source, with the titanium atom and the described Sauerstoffatom formation titanyl key that contains in oxygen source of described nitrogen-atoms reaction;
Successively the grow titanium deoxid film of nitrogen atom.
Further, described silicon chip substrate is positioned over plasma body atomic layer deposition apparatus reaction chamber before:
First with surface process reference liquid and the hydrofluoric acid treatment of described silicon chip substrate, form si-h bond on the surface of described silicon chip substrate.
Further, described titaniferous source gas is titanium tetrachloride.
Further, the flow of described nitrogen is 1sccm-100sccm, and inlet period is 0.1s-10s, and the reaction times is 1s-10s, and scavenging period is 5s-60s, and the basal disc temperature is 100 ℃-500 ℃.
Further, the flow of described nitrogen is 15sccm, and inlet period is 1s, and the reaction times is 5s, and scavenging period is 15s, and the basal disc temperature is 300 ℃.
Further, the flow of hydrogen is 1sccm-100sccm, and plasma discharge power is 1W-300W, and be 1s-10s discharge time.
Further, hydrogen flowing quantity is 10sccm, and plasma discharge power is 30W, and be 3s discharge time.
Further, the described oxygen source that contains is water.
The preparation method of a kind of nitrating titanium deoxid film provided by the invention, utilize the plasma body atomic layer deposition apparatus to carry out the nitrogen doping to titanium deoxid film, the method is simple, utilize the characteristics of ald individual layer cycling deposition and the characteristics of plasma height chemical reactivity, realize adulterating uniformly nitrogen-atoms in whole membrane structure in the process of titanium dioxide film growth, make the membrane structure after doping complete, performance is remarkable, effectively improves TiO
2Utilization ratio to visible light.
Description of drawings
In the preparation method of the nitrating titanium deoxid film that Fig. 1 provides for the embodiment of the present invention, treated silicon chip surface forms the schematic diagram of Si-H key;
Fig. 2 passes into the titanium tetrachloride gases schematic diagram after step shown in Figure 1 in cavity;
Fig. 3 is the chlorine in titanium tetrachloride and H-H reaction generation byproduct hydrogen chloride after step shown in Figure 2, and titanium is adsorbed on the substrate surface schematic diagram;
Fig. 4 passes into a small amount of hydrogen schematic diagram when passing into carrier gas nitrogen after step shown in Figure 3 in cavity;
Fig. 5 is nitrogen and hydrogen gas ionizes schematic diagram after step shown in Figure 4;
Fig. 6 is that after step shown in Figure 5, nitrogen-atoms partly deposits, and titanium forms the covalent linkage schematic diagram;
Fig. 7 passes into water after step shown in Figure 6, forms titanium-oxygen key schematic diagram with the non-reacted parts titanium atom;
Fig. 8 is after forming titanium-oxygen key after step shown in Figure 7, and the surface is all the schematic diagram of hydrogen atom.
Embodiment
In order to make purpose of the present invention, it is more clear that technical scheme and advantage are described, and is illustrated below in conjunction with specific embodiment and accompanying drawing.
Embodiment one:
The preparation method of a kind of nitrating titanium deoxid film provided by the invention comprises:
Step S1: surperficial by reference liquid and hydrofluoric acid treatment silicon chip substrate as shown in Figure 1, at silicon chip substrate surface formation si-h bond.The present embodiment adopts to such an extent that reference liquid is to be boiled according to the ratio of 5: 100 by sulfuric acid and hydrogen peroxide to form in 5 minutes.
Step S2: the silicon chip substrate that will carry out after hydrogen treatment is positioned in the atomic layer deposition apparatus reaction chamber.
Step S3: opening device, regulate working parameter, reach the required working conditions of experiment.In conjunction with Fig. 2, shown in Figure 3, pass into titaniferous source gas in the plasma body atomic layer deposition apparatus reaction chamber, the titanium atom in the gas of titaniferous source is adsorbed on described substrate.Wherein, titaniferous source gas is titanium tetrachloride, titanium tetrachloride gases and silicon chip substrate surface react Si-H+Ti-Cl → Si-Ti+HCl ↑, form silicon titanium key.
Step S4: in conjunction with Fig. 4, Fig. 5, shown in Figure 6, nitrogen buffer gas delivering hydrogen in the atomic layer deposition apparatus reaction chamber, react Ti-Cl+-H+-N-→ Ti-N-Ti+HCl ↑, carry out simultaneously plasma discharge, nitrogen ionization rear section nitrogen-atoms and described partial-titanium atom formation covalent linkage, nitrogen-atoms be the electronics of Cheng Jian and the hydrogen atom Cheng Jian of ionization not.Wherein, during delivering hydrogen, the flow of nitrogen is 1sccm-100sccm to nitrogen buffer gas in the atomic layer deposition apparatus reaction chamber, and inlet period is 0.1s-10s, and the reaction times is 1s-10s, and scavenging period is 5s-60s, and the basal disc temperature is 100 ℃-500 ℃.The flow preferred value of nitrogen is 15sccm, and the inlet period preferred value is 1s, and the reaction times preferred value is 5s, and the scavenging period preferred value is 15s, and basal disc temperature preferred value 300 is ℃.The flow of hydrogen is 1sccm-100sccm.Plasma discharge power is 1W-300W, and be 1s-10s discharge time.The hydrogen flowing quantity preferred value is 10sccm, and plasma discharge power preferred value is 30W, and discharge time, preferred value was 3s.
Step S5: as shown in Figure 8, pass in the atomic layer deposition apparatus reaction chamber and contain oxygen source, Ti-Cl+H reacts
2O → Ti-O+HCl ↑, titanium atom and the described Sauerstoffatom that contains in oxygen source with described nitrogen-atoms reaction do not form the titanyl key.Wherein containing oxygen source is water.
One all after dates, substrate surface are hydrogen atom entirely, can repeat above step S3-S5, the titanium deoxid film of the nitrogen atom of successively growing.Nitrogen-atoms is deposited on the different positions in every one deck, and quantity is less than the content of oxygen.
Embodiment two:
The difference of the present embodiment and embodiment one is, during delivering hydrogen, the flow of nitrogen is 1sccm to nitrogen buffer gas in the atomic layer deposition apparatus reaction chamber, and inlet period is 0.1s, and the reaction times is 1s, and scavenging period is 5s, and the basal disc temperature is 100 ℃.Hydrogen flowing quantity is 1sccm, and plasma discharge power is 1W, and be 1s discharge time.Elsewhere and embodiment one are in full accord.
Embodiment three:
The difference of the present embodiment and embodiment one is, during delivering hydrogen, the flow of nitrogen is 100sccm to nitrogen buffer gas in the atomic layer deposition apparatus reaction chamber, and inlet period is 10s, and the reaction times is 10s, and scavenging period is 60s, and the basal disc temperature is 500 ℃.Hydrogen flowing quantity is 100sccm, and plasma discharge power is 300W, and be 10s discharge time.Elsewhere and embodiment one are in full accord.
Embodiment four:
The difference of the present embodiment and embodiment one is, during delivering hydrogen, the flow of nitrogen is 50sccm to nitrogen buffer gas in the atomic layer deposition apparatus reaction chamber, and inlet period is 5s, and the reaction times is 6s, and scavenging period is 30s, and the basal disc temperature is 250 ℃.Hydrogen flowing quantity is 50sccm, and plasma discharge power is 100W, and be 5s discharge time.Elsewhere and embodiment one are in full accord.
The preparation method of a kind of nitrating titanium deoxid film provided by the invention, utilize the plasma body atomic layer deposition apparatus to carry out the nitrogen doping to titanium deoxid film, the method is simple, utilize the characteristics of ald individual layer cycling deposition and the characteristics of plasma height chemical reactivity, realize adulterating uniformly nitrogen-atoms in whole membrane structure in the process of titanium dioxide film growth, make the membrane structure after doping complete, performance is remarkable, effectively improves TiO
2Utilization ratio to visible light.
Above-described embodiment is the better embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, within being included in protection scope of the present invention.
Claims (8)
1. the preparation method of a nitrating titanium deoxid film, is characterized in that, comprising:
Silicon chip substrate is positioned in plasma body atomic layer deposition apparatus reaction chamber;
Pass into titaniferous source gas in the described plasma body atomic layer deposition apparatus reaction chamber, the titanium atom in the gas of described titaniferous source is adsorbed on described substrate;
Nitrogen buffer gas delivering hydrogen in the atomic layer deposition apparatus reaction chamber carries out plasma discharge simultaneously, and described nitrogen ionization rear section nitrogen-atoms and described partial-titanium atom formation covalent linkage, nitrogen-atoms be the electronics of Cheng Jian and the hydrogen atom Cheng Jian of ionization not;
Pass in the atomic layer deposition apparatus reaction chamber and contain oxygen source, with the titanium atom and the described Sauerstoffatom formation titanyl key that contains in oxygen source of described nitrogen-atoms reaction;
Successively the grow titanium deoxid film of nitrogen atom.
2. the preparation method of nitrating titanium deoxid film as claimed in claim 1, is characterized in that, described silicon chip substrate is positioned over plasma body atomic layer deposition apparatus reaction chamber before:
First with surface process reference liquid and the hydrofluoric acid treatment of described silicon chip substrate, form si-h bond on the surface of described silicon chip substrate.
3. the preparation method of nitrating titanium deoxid film as claimed in claim 1 is characterized in that:
Described titaniferous source gas is titanium tetrachloride.
4. the preparation method of nitrating titanium deoxid film as claimed in claim 1 is characterized in that:
The flow of described nitrogen is 1sccm-100sccm, and inlet period is 0.1s-10s, and the reaction times is 1s-10s, and scavenging period is 5s-60s, and the basal disc temperature is 100 ℃-500 ℃.
5. the preparation method of nitrating titanium deoxid film as claimed in claim 4 is characterized in that:
The flow of described nitrogen is 15sccm, and inlet period is 1s, and the reaction times is 5s, and scavenging period is 15s, and the basal disc temperature is 300 ℃.
6. the preparation method of nitrating titanium deoxid film as claimed in claim 1 is characterized in that:
The flow of hydrogen is 1sccm-100sccm, and plasma discharge power is 1W-300W, and be 1s-10s discharge time.
7. the preparation method of nitrating titanium deoxid film as claimed in claim 6 is characterized in that:
Hydrogen flowing quantity is 10sccm, and plasma discharge power is 30W, and be 3s discharge time.
8. the preparation method of nitrating titanium deoxid film as claimed in claim 6, it is characterized in that: the described oxygen source that contains is water.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103638915A (en) * | 2013-12-16 | 2014-03-19 | 复旦大学 | High-catalytic-property TiO2 nano powder/porous material as well as preparation method and application of high-catalytic-property TiO2 nano powder/porous material |
| CN103736508A (en) * | 2013-12-26 | 2014-04-23 | 大连大学 | Method for preparing F-doped TiO2 by using atmospheric pressure plasma body |
| CN104766546A (en) * | 2015-04-15 | 2015-07-08 | 京东方科技集团股份有限公司 | Display panel, manufacturing method thereof and display device |
| CN104888612A (en) * | 2015-05-25 | 2015-09-09 | 哈尔滨工业大学 | Method for carrying out compound photocatalyst modification on micro-filtration membrane by utilizing atomic layer deposition |
| CN104928653A (en) * | 2014-03-18 | 2015-09-23 | 长春理工大学 | Method for preparing p-type Cu2O thin film |
| CN105568229A (en) * | 2016-03-09 | 2016-05-11 | 无锡南理工科技发展有限公司 | Preparation method of nitrogen-doped titanium dioxide film |
| CN105944714A (en) * | 2016-05-24 | 2016-09-21 | 昆明理工大学 | Sulfur-resistant denitration catalyst preparation method |
| CN106471154A (en) * | 2014-04-17 | 2017-03-01 | Asm Ip控股有限公司 | Fluorine-containing conducting film |
| CN107159296A (en) * | 2017-06-19 | 2017-09-15 | 山西大同大学 | A kind of preparation method of nitrogen-doped anatase phase titanium dioxide nano ball |
| CN108371954A (en) * | 2018-03-30 | 2018-08-07 | 华南农业大学 | A kind of support type Ag-TiO2/Ti(NO2) film catalyst and its fruit storage in application |
| CN109395747A (en) * | 2018-11-15 | 2019-03-01 | 上海纳米技术及应用国家工程研究中心有限公司 | Flower-shape Ni-doped molybdenum disulfide/photocatalysis material of titanium dioxide preparation method and application |
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| CN103638915A (en) * | 2013-12-16 | 2014-03-19 | 复旦大学 | High-catalytic-property TiO2 nano powder/porous material as well as preparation method and application of high-catalytic-property TiO2 nano powder/porous material |
| CN103736508A (en) * | 2013-12-26 | 2014-04-23 | 大连大学 | Method for preparing F-doped TiO2 by using atmospheric pressure plasma body |
| CN104928653A (en) * | 2014-03-18 | 2015-09-23 | 长春理工大学 | Method for preparing p-type Cu2O thin film |
| CN106471154A (en) * | 2014-04-17 | 2017-03-01 | Asm Ip控股有限公司 | Fluorine-containing conducting film |
| CN106471154B (en) * | 2014-04-17 | 2019-06-28 | Asm Ip控股有限公司 | Fluorine-containing conductive film |
| CN104766546A (en) * | 2015-04-15 | 2015-07-08 | 京东方科技集团股份有限公司 | Display panel, manufacturing method thereof and display device |
| CN104888612A (en) * | 2015-05-25 | 2015-09-09 | 哈尔滨工业大学 | Method for carrying out compound photocatalyst modification on micro-filtration membrane by utilizing atomic layer deposition |
| CN104888612B (en) * | 2015-05-25 | 2017-06-20 | 哈尔滨工业大学 | It is a kind of that microfiltration membranes are carried out with the modified method of composite photo-catalyst using ald |
| CN105568229B (en) * | 2016-03-09 | 2018-10-30 | 无锡南理工科技发展有限公司 | A kind of preparation method of nitrogen doped titanium dioxide film |
| CN105568229A (en) * | 2016-03-09 | 2016-05-11 | 无锡南理工科技发展有限公司 | Preparation method of nitrogen-doped titanium dioxide film |
| CN105944714A (en) * | 2016-05-24 | 2016-09-21 | 昆明理工大学 | Sulfur-resistant denitration catalyst preparation method |
| CN107159296A (en) * | 2017-06-19 | 2017-09-15 | 山西大同大学 | A kind of preparation method of nitrogen-doped anatase phase titanium dioxide nano ball |
| CN108371954A (en) * | 2018-03-30 | 2018-08-07 | 华南农业大学 | A kind of support type Ag-TiO2/Ti(NO2) film catalyst and its fruit storage in application |
| CN109395747A (en) * | 2018-11-15 | 2019-03-01 | 上海纳米技术及应用国家工程研究中心有限公司 | Flower-shape Ni-doped molybdenum disulfide/photocatalysis material of titanium dioxide preparation method and application |
| CN109395747B (en) * | 2018-11-15 | 2021-07-20 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method and application of flower-shaped Ni-doped molybdenum disulfide/titanium dioxide photocatalytic material |
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