CN106384669A - Preparation method of photoelectric response carbon quantum dot modified zinc oxide photo anode - Google Patents
Preparation method of photoelectric response carbon quantum dot modified zinc oxide photo anode Download PDFInfo
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- CN106384669A CN106384669A CN201610950880.8A CN201610950880A CN106384669A CN 106384669 A CN106384669 A CN 106384669A CN 201610950880 A CN201610950880 A CN 201610950880A CN 106384669 A CN106384669 A CN 106384669A
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- carbon quantum
- quantum dot
- zinc oxide
- zno film
- electro
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- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- -1 carbon quantum dot modified zinc oxide Chemical class 0.000 title abstract 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 118
- 239000011787 zinc oxide Substances 0.000 claims abstract description 59
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000004070 electrodeposition Methods 0.000 claims abstract description 15
- 238000001179 sorption measurement Methods 0.000 claims abstract description 8
- 239000011521 glass Substances 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 12
- 230000004048 modification Effects 0.000 claims description 10
- 238000012986 modification Methods 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 8
- 238000010521 absorption reaction Methods 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 3
- VGHOIMZYOPHDCL-UHFFFAOYSA-N [F].O=[Sn]=O Chemical compound [F].O=[Sn]=O VGHOIMZYOPHDCL-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 3
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000010408 film Substances 0.000 claims 5
- 230000005611 electricity Effects 0.000 claims 1
- 239000010409 thin film Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 229910052772 Samarium Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000005622 photoelectricity Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001451 molecular beam epitaxy Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000004549 pulsed laser deposition Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/204—Light-sensitive devices comprising an oxide semiconductor electrode comprising zinc oxides, e.g. ZnO
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention discloses a preparation method of a carbon quantum dot modified zinc oxide photo anode. According to the method, carbon quantum dots are prepared by use of a hydrothermal method, a ZnO film is prepared by electro-deposition, a piece of conductive glass with the ZnO film deposited is soaked in carbon quantum dot solution, and heat treatment is performed after adsorption for a period of time to get a ZnO film with carbon quantum dots composited. The photocurrent can be increased obviously. As the method is implemented at room temperature, reaction is easy to control, and the adsorption effect is better.
Description
Technical field
The invention belongs to light anode modification technique field, particularly to a kind of photoelectric respone type carbon quantum dot modification zinc oxide
The preparation method of light anode.
Background technology
ZnO is a kind of new II-VI group direct band gap wide bandgap compound semiconductor material, and development prospect is very wide
Wealthy, for a long time, the research to ZnO film is concentrated mainly on piezoelectricity, transparent conductivity, photo electric, gas sensing property, pressure-sensitive etc.
Aspect.As a kind of direct band gap semiconductor material with wide forbidden band, the most potential application of ZnO is in field of photoelectric devices to ZnO.
The ZnO film of different application has different requirements to its crystalline orientation, roughness, piezoelectricity, optical property etc., this
A little differences are to be determined by different technologies of preparing and its technological parameter.In recent years, many advanced depositions and growing technology
It is used for the preparation of ZnO film, such as magnetron sputtering, molecular beam epitaxy, pulsed laser deposition, spray pyrolysis, so-gel, gold
Belong to the methods such as organic chemical vapor deposition, electrochemistry.Recent years, people prepare ZnO film to using electrochemical deposition method
Technology create keen interest.Because the method is simple to operate, with low cost, thickness and morphology controllable (only adjust electrification
Learn operating parameter), and it is suitable for complex-shaped substrate, and there is of a relatively high sedimentation rate, so just receiving once proposition
Widely pay attention to.
Because semi-conducting material ZnO can only absorb the ultraviolet light that photon energy is more than its band gap, it is led to be light anode
DSSC photoelectric transformation efficiency is low.Semiconductor is carried out element doping can effectively change material optics and
Electronic property, doping is a kind of change very effective means of characteristic of semiconductor.In doping ZnO can effectively improve ZnO photo-anode
The light capture intensity of battery, the IPCE especially in visible region significantly improves, and the doping of In simultaneously reduces electronics combined resistance,
Extend electron lifetime, improve battery efficiency.Hanhong Chen et al. rice metal organic chemical vapor deposition method prepares Ga doping
ZnO (GZO) film, the doping of Ga successfully improves the monochromatic light ray photoelectric transformation efficiency of material, the monochromatic light conversion effect of 530nm
Rate reaches 79%, however, GZO is orthotropic three-dimensional structure, absorbing dye amount is relatively low, and therefore total photoelectric transformation efficiency is only
For 0.77%.Sining Yun et al. uses Al atom to replace the Zn atom in ZnO lattice, prepares the ZnO photo-anode of Al doping, and
Improve light current density and the conversion efficiency of battery in terms of two.Researcher also finds that Sn doping ZnO can significantly improve battery
Chemical property, research find Sn doping change ZnO surface topography, after doping ZnO be spindle, doping improve further
The electric transmission of anode and electrolyte interface and collection efficiency, improve photoelectric properties.Lijuan Luo et al. is prepared for non-gold
Belong to the ZnO prismatic array of F doping, after doping, the electron lifetime of ZnO increases, electric transmission resistance reduces, photoelectric transformation efficiency increases
Greatly.Lanlan Lu et al. studies the impact to ZnO photoelectric properties for the series of rare earth element (La, Ce, Nd, Sm and Gd), finds dilute
Soil can be passivated the surface state of ZnO anode.The doping of Nd in these rare earth elements, Sm and Gd increased battery open-circuit voltage and
Fill factor, curve factor, the doping of La, Ce, Nd and Sm leads to the decline of photoelectric current, and the wherein doping of Gd successfully improves the light of battery
Photoelectric transformation efficiency.
It is, thus, sought for a kind of photoelectricity to improve zinc oxide for method of modification zinc oxide light anode simple to operation
Performance.
Content of the invention
Present invention aim at providing a kind of preparation method of photoelectric respone type carbon quantum dot modification zinc oxide light anode, carry
The photoelectric properties of the high ZnO film as light anode material.
For reaching above-mentioned purpose, the present invention adopts the following technical scheme that：
The method soaked under normal temperature, makes the ZnO film of electro-deposition adsorb carbon quantum dot solution, improves its photoelectric properties, including
Following steps：
Step 1) electro-deposition ZnO film working electrode extremely can using doping fluorine tin dioxide conductive glass (FTO),
It is platinum rod to electrode, reference electrode is Ag/AgCl electrode, with the aqueous solution of zinc nitrate as electrolyte, applied voltage, electro-deposition
ZnO film.
Step 2) Hydrothermal Synthesiss carbon quantum dot stirred in deionized water using ammonium citrate and ethylenediamine be placed in anti-
Answer in kettle, at 200 DEG C, react 5h, dialyse after filtration, be dried.
Step 3) electro-conductive glass of deposition ZnO film is immersed in carbon quantum dot solution, after absorption a period of time, through overheated
Process, obtain the ZnO film of compound carbon quantum dot.
Further, the concentration of the described zinc nitrate solution of electro-deposition ZnO film is 0.01～0.5mol/L.
Further, described adsorption time is 0.5～8h.
Further, described adsorption temp is normal temperature～80 degree.
Further, the ZnO film after absorption carbon quantum dot is heat-treated 1h at 90 DEG C.
Compared with prior art, the effect of the present invention and advantage are：
(1) adsorbed under normal temperature, obtained the composite membrane of ZnO/CQDs, the higher photoelectric current that improve ZnO film, operation letter
Just and reduce energy resource consumption；
(2) electrodeposition apparatus are simple, are easier to reach the scale of industrialized production and requirement；
(3) Hydrothermal Synthesiss carbon quantum dot method is simple, can stably preserve, and carbon quantum dot low price, and source is wide, energy
Substantially reduce production cost.
From above-mentioned advantage, the present invention is significant as the photoelectric properties of the ZnO film of light anode material to improving.
Brief description
In Fig. 1 embodiment 1, the scanning electron microscope (SEM) photograph of electro-deposition ZnO film.
In Fig. 2 embodiment 1, the fluorescence intensity (excitation wavelength is 364nm) of Hydrothermal Synthesiss carbon quantum dot.
In Fig. 3 fact Example 1, ZnO adsorbs the photoelectricity flow graph before and after carbon quantum dot.
Specific embodiment
It is described with reference to the accompanying drawings technology and the feature of the present invention below by way of specific embodiment, but these embodiments are not
In order to limit protection scope of the present invention.
The method soaked under normal temperature, makes the ZnO film of electro-deposition adsorb carbon quantum dot solution, improves its photoelectric properties, including
Following steps：
Step 1) electro-deposition ZnO film working electrode extremely can using doping fluorine tin dioxide conductive glass (FTO),
It is platinum rod to electrode, reference electrode is Ag/AgCl electrode, with the aqueous solution of zinc nitrate as electrolyte, applied voltage, electro-deposition
ZnO film.
Step 2) Hydrothermal Synthesiss carbon quantum dot stirred in deionized water using ammonium citrate and ethylenediamine be placed in anti-
Answer in kettle, at 200 DEG C, react 5h, dialyse after filtration, be dried.
Step 3) electro-conductive glass of deposition ZnO film is immersed in carbon quantum dot solution, after absorption a period of time, through overheated
Process, obtain the ZnO film of compound carbon quantum dot.
Further, the concentration of the described zinc nitrate solution of electro-deposition ZnO film is 0.1mol/L.
Further, described adsorption time is 2h.
Further, described adsorption temp is normal temperature.
Further, the ZnO film after absorption carbon quantum dot is heat-treated 1h at 90 DEG C.
Further, the test environment of photoelectrocatalysis is 0.1M Na2SO4,100mW/cm2.
Claims (5)
1. a kind of preparation method of photoelectric respone type carbon quantum dot modification zinc oxide light anode is it is characterised in that adopt under normal temperature
The method soaked, makes the ZnO film of electro-deposition adsorb carbon quantum dot solution, improves its photoelectric properties it is characterised in that including following
Step：
Step 1) electro-deposition ZnO film working electrode extremely can using doping fluorine tin dioxide conductive glass (FTO), to electricity
Extremely platinum rod, reference electrode is Ag/AgCl electrode, with the aqueous solution of zinc nitrate as electrolyte, applied voltage, electro-deposition ZnO is thin
Film.
Step 2) Hydrothermal Synthesiss carbon quantum dot stirred in deionized water using ammonium citrate and ethylenediamine and is placed in reactor
In, react 5h at 200 DEG C, dialyse after filtration, be dried.
Step 3) electro-conductive glass of deposition ZnO film is immersed in the carbon quantum dot aqueous solution, after absorption a period of time, through overheated place
Reason, obtains the ZnO film of compound carbon quantum dot.
2. carbon quantum dot modification zinc oxide light anode as claimed in claim 1 method it is characterised in that：Zinc nitrate solution
Concentration is 0.01～0.5mol/L.
3. carbon quantum dot modification zinc oxide light anode as claimed in claim 1 method it is characterised in that：Adsorption time 0.5
～8h.
4. the method for carbon quantum dot modification zinc oxide light anode as claimed in claim 1 it is characterised in that：Adsorption temp is
Normal temperature～80 degree.
5. carbon quantum dot modification zinc oxide light anode as claimed in claim 1 method it is characterised in that：Absorption carbon quantum dot
ZnO film afterwards is heat-treated 1h at 90 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610950880.8A CN106384669A (en) | 2016-10-27 | 2016-10-27 | Preparation method of photoelectric response carbon quantum dot modified zinc oxide photo anode |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610950880.8A CN106384669A (en) | 2016-10-27 | 2016-10-27 | Preparation method of photoelectric response carbon quantum dot modified zinc oxide photo anode |
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| CN201610950880.8A Pending CN106384669A (en) | 2016-10-27 | 2016-10-27 | Preparation method of photoelectric response carbon quantum dot modified zinc oxide photo anode |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107988615A (en) * | 2017-11-08 | 2018-05-04 | 常州大学 | A kind of preparation and application of carbonitride modification ZnO/CdS light anode materials |
| CN108120704A (en) * | 2017-12-11 | 2018-06-05 | 东莞理工学院 | A kind of fluorescence detection method of Acetamiprid |
| CN111490171A (en) * | 2019-05-08 | 2020-08-04 | 广东聚华印刷显示技术有限公司 | Zinc oxide nano material, preparation method thereof and luminescent device comprising zinc oxide nano material |
| CN112209635A (en) * | 2020-10-29 | 2021-01-12 | 华中科技大学 | Solid fluorescent carbon dot based on nano porous glass and preparation method thereof |
| CN112397314A (en) * | 2020-10-27 | 2021-02-23 | 南京邮电大学 | Semitransparent film electrode and preparation method thereof |
| CN114150338A (en) * | 2021-12-01 | 2022-03-08 | 湘潭大学 | Carbon quantum dot and nitrogen-doped carbon nitride co-modified zinc oxide photo-anode and preparation method thereof |
| CN114566392A (en) * | 2022-03-18 | 2022-05-31 | 南昌航空大学 | Oxygen-enriched defect epsilon-MnO2Preparation method of/carbon quantum dot composite film |
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| CN104928648A (en) * | 2015-07-10 | 2015-09-23 | 南开大学 | Zinc oxide photo-anode film and preparation method and application thereof |
| CN105845443A (en) * | 2016-05-16 | 2016-08-10 | 中国科学院兰州化学物理研究所 | Carbon quantum dot sensitized solar cell prepared in situ |
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| CN104928648A (en) * | 2015-07-10 | 2015-09-23 | 南开大学 | Zinc oxide photo-anode film and preparation method and application thereof |
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Non-Patent Citations (2)
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107988615A (en) * | 2017-11-08 | 2018-05-04 | 常州大学 | A kind of preparation and application of carbonitride modification ZnO/CdS light anode materials |
| CN108120704A (en) * | 2017-12-11 | 2018-06-05 | 东莞理工学院 | A kind of fluorescence detection method of Acetamiprid |
| CN111490171A (en) * | 2019-05-08 | 2020-08-04 | 广东聚华印刷显示技术有限公司 | Zinc oxide nano material, preparation method thereof and luminescent device comprising zinc oxide nano material |
| CN111490171B (en) * | 2019-05-08 | 2022-12-06 | 广东聚华印刷显示技术有限公司 | Zinc oxide nano material, preparation method thereof and luminescent device comprising zinc oxide nano material |
| CN112397314A (en) * | 2020-10-27 | 2021-02-23 | 南京邮电大学 | Semitransparent film electrode and preparation method thereof |
| CN112209635A (en) * | 2020-10-29 | 2021-01-12 | 华中科技大学 | Solid fluorescent carbon dot based on nano porous glass and preparation method thereof |
| CN112209635B (en) * | 2020-10-29 | 2021-12-03 | 华中科技大学 | Solid fluorescent carbon dot based on nano porous glass and preparation method thereof |
| CN114150338A (en) * | 2021-12-01 | 2022-03-08 | 湘潭大学 | Carbon quantum dot and nitrogen-doped carbon nitride co-modified zinc oxide photo-anode and preparation method thereof |
| CN114150338B (en) * | 2021-12-01 | 2023-09-08 | 湘潭大学 | Zinc oxide photo-anode co-modified by carbon quantum dots and nitrogen-doped carbon nitride and preparation method thereof |
| CN114566392A (en) * | 2022-03-18 | 2022-05-31 | 南昌航空大学 | Oxygen-enriched defect epsilon-MnO2Preparation method of/carbon quantum dot composite film |
| CN114566392B (en) * | 2022-03-18 | 2023-04-11 | 南昌航空大学 | Oxygen-enriched defect epsilon-MnO 2 Preparation method of/carbon quantum dot composite film |
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Application publication date: 20170208 |