CN106158389A - Titanium deoxid film structure that cadmium sulfoselenide and zinc sulfur selenide are modified and preparation method - Google Patents
Titanium deoxid film structure that cadmium sulfoselenide and zinc sulfur selenide are modified and preparation method Download PDFInfo
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- CN106158389A CN106158389A CN201610567821.2A CN201610567821A CN106158389A CN 106158389 A CN106158389 A CN 106158389A CN 201610567821 A CN201610567821 A CN 201610567821A CN 106158389 A CN106158389 A CN 106158389A
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- PGWFQHBXMJMAPN-UHFFFAOYSA-N ctk4b5078 Chemical compound [Cd].OS(=O)(=O)[Se]S(O)(=O)=O PGWFQHBXMJMAPN-UHFFFAOYSA-N 0.000 title claims abstract description 42
- IPCGGVKCDVFDQU-UHFFFAOYSA-N [Zn].[Se]=S Chemical compound [Zn].[Se]=S IPCGGVKCDVFDQU-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 20
- 239000010936 titanium Substances 0.000 title claims abstract description 20
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000002096 quantum dot Substances 0.000 claims abstract description 51
- 238000010521 absorption reaction Methods 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 35
- 239000010409 thin film Substances 0.000 claims abstract description 30
- 239000010408 film Substances 0.000 claims abstract description 24
- 239000002245 particle Substances 0.000 claims abstract description 13
- 239000002105 nanoparticle Substances 0.000 claims abstract description 11
- 238000007650 screen-printing Methods 0.000 claims abstract description 8
- 238000010345 tape casting Methods 0.000 claims abstract description 8
- 239000012528 membrane Substances 0.000 claims abstract description 4
- 239000008367 deionised water Substances 0.000 claims description 32
- 229910021641 deionized water Inorganic materials 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 26
- 239000002002 slurry Substances 0.000 claims description 24
- 230000004087 circulation Effects 0.000 claims description 20
- 239000011521 glass Substances 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 16
- 238000002161 passivation Methods 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 14
- 239000011701 zinc Substances 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 10
- 239000001856 Ethyl cellulose Substances 0.000 claims description 8
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 8
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 8
- 238000000137 annealing Methods 0.000 claims description 8
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 8
- 229920001249 ethyl cellulose Polymers 0.000 claims description 8
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 229940116411 terpineol Drugs 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 238000005034 decoration Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- WGPCGCOKHWGKJJ-UHFFFAOYSA-N sulfanylidenezinc Chemical compound [Zn]=S WGPCGCOKHWGKJJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011669 selenium Substances 0.000 claims 4
- ZQRRBZZVXPVWRB-UHFFFAOYSA-N [S].[Se] Chemical group [S].[Se] ZQRRBZZVXPVWRB-UHFFFAOYSA-N 0.000 claims 3
- 229910052793 cadmium Inorganic materials 0.000 claims 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims 3
- 238000001179 sorption measurement Methods 0.000 abstract description 7
- 230000004048 modification Effects 0.000 abstract description 6
- 230000004044 response Effects 0.000 abstract description 6
- 239000010405 anode material Substances 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 4
- 230000003595 spectral effect Effects 0.000 abstract description 4
- 230000001699 photocatalysis Effects 0.000 abstract description 3
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 238000004886 process control Methods 0.000 abstract description 3
- 239000000956 alloy Substances 0.000 abstract description 2
- 229910045601 alloy Inorganic materials 0.000 abstract description 2
- 238000013461 design Methods 0.000 abstract description 2
- 238000002715 modification method Methods 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 229910002058 ternary alloy Inorganic materials 0.000 abstract description 2
- 239000004408 titanium dioxide Substances 0.000 description 6
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- -1 Zinc modified titanium Chemical class 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000007790 scraping Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- YBNMDCCMCLUHBL-UHFFFAOYSA-N (2,5-dioxopyrrolidin-1-yl) 4-pyren-1-ylbutanoate Chemical compound C=1C=C(C2=C34)C=CC3=CC=CC4=CC=C2C=1CCCC(=O)ON1C(=O)CCC1=O YBNMDCCMCLUHBL-UHFFFAOYSA-N 0.000 description 1
- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 0.000 description 1
- 229910020275 Na2Sx Inorganic materials 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000013016 learning Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003608 titanium Chemical class 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
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
-
- 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
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Hybrid Cells (AREA)
- Luminescent Compositions (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention relates to a kind of cadmium sulfoselenide and the titanium deoxid film structure of zinc sulfur selenide modification and preparation method, this membrane structure is TiO2Nano-particle is carrier, at TiO2Particle surface absorption CdSSe alloy quantum dot, absorption ZnSSe modifies quantum dot afterwards.Silk screen printing or knife coating is used to prepare TiO2Thin film, continuous ionic layer reciprocal adsorption method is at TiO2Particle surface absorption CdSSe and ZnSSe.The main purpose of this structure design is the ratio by regulating S Yu Se, and one-step method is prepared energy gap adjustable CdSSe ternary alloy quantum dot and realized the controllable precise to spectral response, utilizes ZnSSe to carry out quantum dot modifying its surface defect of reduction simultaneously.The preparation method of nano material that the present invention relates to has that method is simple and quick, with low cost, process control, the advantage such as reproducible, can operate with solar battery light anode material it can also be used to photocatalysis field.
Description
Technical field
The present invention relates to a kind of cadmium sulfoselenide and the titanium deoxid film structure of zinc sulfur selenide modification and preparation method, especially
Relate to the preparation of a kind of quantum dot sensitized solar battery light anode material.
Background technology
Quantum dot (quantum dots, QDs) is that three-dimensional dimension is less than or close to Exciton Bohr Radius, has quantum confinement
The quasi-zero-dimension nano particle of effect, can produce multiple excitons, the most multiple exciton effect by absorbing a photon energy
(multiple exciton generation, abbreviated as MEG), and then form multiple charge carrier pair, with more efficient land productivity
Use solar energy.The S-Q limit model proposed according to American Physical scholar Shockley and Queisser, semiconductor PN solar energy
The photoelectric transformation efficiency limit of battery is 31%, but the quantum dot sensitized solaode constructed for photosensitizer with QD
(Quantum dot sensitized solar cell is called for short QDSC), under MEG effect effect, then can break through the S-Q limit
Efficiency Model, has higher theoretical light photoelectric transformation efficiency.Further, QDSC manufacturing cost is far below silicon solar cell.Therefore,
QDSC is considered as the most potential a new generation solaode, one of focus studied in becoming world wide.
Compared with single CdS, CdSe, InP, PbSe QDs, CdS/CdSe sensitization system altogether obtains in QDSC
Higher energy conversion efficiency due to its by introduce CdS improve CdSe quantum dot adsorbance thus add light capture energy
Amount.But, in traditional preparation method, first with continuous ionic layer reciprocal adsorption method (SILAR) absorption CdS QDs and change
The method learning bath deposition absorption CdSe QDs prepares the time of light anode more than 5h.And utilize nucleocapsid structure prepared by method for externally
CdS/CdSe process needs to completely cut off air, and operating condition is harsh.
The present invention uses the synthetic method of continuous ionic layer reciprocal adsorption, is prepared by the ratio controlling S Yu Se
CdSxSe1-x/ZnSxSe1-xQDs modifying titanium dioxide film structure, this structure both can obtain the adjustable CdS of band gapxSe1-x
QDs realizes the regulation to spectral response range, can make again ZnSxSe1-xEffectively reduce CdSxSe1-xThe defect of QDs, minimizing electronics-
Hole-recombination.This experiment synthetic method uses same Na2SxSe1-xSolution synthesis ZnSxSe1-xWith CdSxSe1-xQDs, saves
Cost, simplify operation, control, in 1h, to highly shortened the response time by quantum dot adsorption time, improve efficiency.With
Time, the light anode of this structure is applied to quantum dot sensitized solaode can be effectively improved the conversion efficiency of solaode.This
The preparation method of nano material that relates to of invention has with low cost, process control, the advantage such as reproducible, can operate with solar energy
Battery light anode material is it can also be used to photocatalysis field.
Summary of the invention
It is an object of the invention to, it is provided that a kind of cadmium sulfoselenide and the titanium deoxid film structure of zinc sulfur selenide modification and system
Preparation Method, this membrane structure is TiO2Nano-particle is carrier, at TiO2Particle surface absorption CdSSe alloy quantum dot, inhales afterwards
Attached ZnSSe modifies quantum dot.Silk screen printing or knife coating is used to prepare TiO2Thin film, uses continuous ionic layer reciprocal adsorption
Method is at TiO2Particle surface absorption CdSSe and ZnSSe.The main purpose of this structure design is the ratio by regulating S Yu Se, one
Footwork is prepared energy gap adjustable CdSSe ternary alloy quantum dot and is realized the controllable precise to spectral response, utilizes simultaneously
Quantum dot is carried out modifying its surface defect of reduction by ZnSSe.The method of the invention has simple and quick, with low cost, process
The advantage such as controlled, reproducible, can operate with solar battery light anode material it can also be used to photocatalysis field.
The titanium deoxid film structure that a kind of cadmium sulfoselenide of the present invention and zinc sulfur selenide are modified, this membrane structure is
The TiO that cadmium sulfoselenide quantum dot is modified2Nano-particle, then modify formation cadmium sulfoselenide/zinc sulfur selenide hetero-junctions with zinc sulfur selenide,
Wherein TiO2Nano-particle is P25 or the TiO of the adjustable 20-400nm of particle diameter2Nano-particle, concrete operations follow these steps to into
OK:
A, prepare titania slurry: by the TiO of adjustable to P25 or particle diameter 20-400nm2, terpineol and ethyl cellulose press
Ratio according to 2:7:1 mixes, and adds 10mL dehydrated alcohol, after stirring 0.5h, uses Rotary Evaporators to remove dehydrated alcohol, prepares
TiO2Slurry；
B, transparent conducting glass is cleaned up, dry, use the TiO that silk screen printing or knife coating will prepare2Slurry
Scraping at transparent conductive glass surface, then temperature 500 DEG C annealing 30min, heating rate 5 DEG C/min in Muffle furnace, obtain
TiO2Thin film；
C, absorption cadmium sulfoselenide quantum dot: at the Na of 0.1M2S solution adds Se powder mix homogeneously, obtains Na2SSe is molten
Liquid；Prepare the Cd (NO of 0.01-0.1M again3)2Or Cd (CH3COO)2Solution；Use SILAR method absorption quantum dot: by TiO2Thin film
At Cd2+With deionized water rinsing after submergence 1min in solution, dry up, then immerse Na2SSe solution rushes with deionized water after 1min
Washing, dry up, this process is referred to as 1 circulation, repeats 4-12 circulation；
D, absorption zinc sulfur selenide passivation layer: the Zn (NO of preparation 0.01-0.1M3)2Or Zn (CH3COO)2Solution, will be adsorbed with
The TiO of cadmium sulfoselenide quantum dot2Thin film is at Zn2+With deionized water rinsing after submergence 1min in solution, dry up, then immerse step c
In Na2With deionized water rinsing after 1min in SSe solution, dry up, repeat 1-4 circulation, obtain cadmium sulfoselenide and sulfur selenizing
Zinc modified titanium deoxid film.
The preparation method of the titanium deoxid film structure that a kind of cadmium sulfoselenide and zinc sulfur selenide are modified, follow these steps to into
OK:
A, prepare titania slurry: by the TiO of adjustable to P25 or particle diameter 20-400nm2, terpineol and ethyl cellulose press
Ratio according to 2:7:1 mixes, and adds 10mL dehydrated alcohol, after stirring 0.5h, uses Rotary Evaporators to remove dehydrated alcohol, prepares
TiO2Slurry；
B, by clean for FTO glass cleaning, dry, use the TiO that silk screen printing or knife coating will prepare2Slurry is scraped
FTO glass surface, then temperature 500 DEG C annealing 30min, heating rate 5 DEG C/min in Muffle furnace, obtain TiO2Thin film；
C, absorption cadmium sulfoselenide quantum dot: at the Na of 0.1M2S solution adds Se powder mix homogeneously, obtains Na2SSe is molten
Liquid；Prepare the Cd (NO of 0.01-0.1M again3)2Or Cd (CH3COO)2Solution；Use SILAR method absorption quantum dot: by TiO2Thin film
At Cd2+With deionized water rinsing after submergence 1min in solution, dry up, then immerse Na2SSe solution rushes with deionized water after 1min
Washing, dry up, this process is referred to as 1 circulation, repeats 4-12 circulation；
D, absorption zinc sulfur selenide passivation layer: the Zn (NO of preparation 0.01-0.1M3)2Or Zn (CH3COO)2Solution, will be adsorbed with
The TiO of cadmium sulfoselenide quantum dot2Thin film is at Zn2+With deionized water rinsing after submergence 1min in solution, dry up, then immerse step c
In Na2With deionized water rinsing after 1min in SSe solution, dry up, repeat 1-4 circulation, obtain cadmium sulfoselenide and sulfur selenizing
Zinc modified titanium deoxid film.
In step c, the addition of Se powder is mol ratio 0.1-0.9 of Se and S.
In step d, the adsorbance of passivation layer is accurately controlled by cycle-index.
Titanium deoxid film structure that cadmium sulfoselenide of the present invention and zinc sulfur selenide are modified and preparation method, its advantage
And good effect: the present invention uses cadmium sulfoselenide and zinc sulfur selenide (CdSSe/ZnSSe) modifying titanium dioxide film structure to pass through
Controlling CdSSe/ZnSSe QDs modifying titanium dioxide film structure prepared by the ratio of S Yu Se, it is adjustable that this structure i.e. obtains band gap
CdSSe QDs realize regulation to spectral response range, make again ZnSSe effectively reduce the defect of CdSSe QDs, reduce electricity
Son-hole-recombination.The method of the invention uses same Na2SSe solution synthesis ZnSSe Yu CdSSe QDs, saved cost,
Simplify operation, control, in 1h, to highly shortened the response time by quantum dot adsorption time, improve efficiency.This thin film
The light anode of structure is applied to quantum dot sensitized solaode can be effectively improved the conversion efficiency of solaode.Use continuously
Sheath reciprocal adsorption method preparation technology is simple, with low cost, process control, the advantage such as reproducible.
The titanium deoxid film that the CdSSe/ZnSSe obtained by the method for the invention is modified, this material structure is
The TiO that CdSSe quantum dot is modified2Modify with ZnSSe after nano-particle and form CdSSe/ZnSSe, wherein TiO2Nano-particle is
P25 or the TiO of particle diameter adjustable (20～400nm)2Nanocrystalline, Quantum dots CdS Se Yu ZnSSe forms hetero-junctions.This structure can
It is applied to quantum dot sensitized solar battery light anode material.
Accompanying drawing explanation
Fig. 1 is that the present invention implements 2 I-V diagram being assembled into quantum dot sensitized solaode；
Fig. 2 is cadmium sulfoselenide of the present invention and the titanium deoxid film figure of zinc sulfur selenide modification, and wherein a is the result of example 1,
The cycle-index of absorption CdSSe quantum dot is 4, and the cycle-index of absorption ZnSSe is 1；B is the result of example 2, adsorbs CdSSe
The cycle-index of quantum dot is respectively 6, the cycle-index of absorption ZnSSe is 2；C is the result of example 3, adsorbs CdSSe quantum
The cycle-index of point is respectively 10, and the cycle-index of absorption ZnSSe is 3；D is the result of example 4, absorption CdSSe quantum dot
Cycle-index is respectively 12, and the cycle-index of absorption ZnSSe is 4；
The titanium deoxid film structure that Fig. 3 is the cadmium sulfoselenide that obtains of the embodiment of the present invention 2 and zinc sulfur selenide is modified saturating
Penetrate ultramicroscope (TEM) photo.
Detailed description of the invention
Embodiment 1
A, prepare titania slurry: by the TiO of P252, terpineol and ethyl cellulose mix according to the ratio of 2:7:1,
Add 10mL dehydrated alcohol, after stirring 0.5h, use Rotary Evaporators to remove dehydrated alcohol, prepare TiO2Slurry；
B, transparent conducting glass (FTO) is cleaned up, dries, use silk screen printing to scrape the slurry prepared transparent
Conductive glass surface, then temperature 500 DEG C annealing 30min, heating rate 5 DEG C/min in Muffle furnace, obtain TiO2Thin film；
C, absorption cadmium sulfoselenide (CdSSe) quantum dot: at the Na of 0.1M2S solution adds the mixing of 0.01moL Se powder all
Even, obtain Na2SSe solution；Prepare the Cd (NO of 0.01M again3)2Solution；Use SILAR method absorption quantum dot: by TiO2Thin film exists
Cd2+With deionized water rinsing after submergence 1min in solution, dry up, then immerse Na2SSe solution rushes with deionized water after 1min
Washing, dry up, this process is referred to as 1 circulation, repeats 4 cyclic processes；
D, absorption ZnSSe passivation layer: the Zn (NO of preparation 0.01M3)2Solution, will be adsorbed with cadmium sulfoselenide (CdSSe) quantum
The TiO of point2Thin film is at Zn2+With deionized water rinsing after submergence 1min in solution, dry up, then immerse the Na in step c2SSe is molten
With deionized water rinsing after 1min in liquid, dry up, repeat 1 circulation, obtain cadmium sulfoselenide and zinc sulfur selenide (CdSSe/ZnSSe)
The titanium deoxid film modified, the adsorbance of passivation layer is accurately controlled (Fig. 2 a) by cycle-index.
Embodiment 2
A, prepare titania slurry: by the TiO of adjustable for particle diameter 20nm2, terpineol and ethyl cellulose be according to 2:7:1's
Ratio mixes, and adds 10mL dehydrated alcohol, after stirring 0.5h, uses Rotary Evaporators to remove dehydrated alcohol, prepares TiO2Slurry；
B, by clean for transparent conducting glass (FTO) glass cleaning, dry, use the TiO that knife coating will prepare2Slurry is scraped
At transparent conductive glass surface, then temperature 500 DEG C annealing 30min, heating rate 5 DEG C/min in Muffle furnace, obtain TiO2
Thin film；
C, absorption cadmium sulfoselenide quantum dot: at the Na of 0.1M2S solution adds 0.03moL Se powder mix homogeneously, obtains
Na2SSe solution；Prepare the Cd (CH of 0.01M again3COO)2Solution；Use SILAR method absorption quantum dot: by TiO2Thin film is at Cd2+
With deionized water rinsing after submergence 1min in solution, dry up, then immerse Na2With deionized water rinsing after 1min in SSe solution, blow
Dry, this process is referred to as 1 circulation, repeats 6 cyclic processes；
D, absorption zinc sulfur selenide passivation layer: the Zn (CH of preparation 0.01M3COO)2Solution, will be adsorbed with cadmium sulfoselenide quantum dot
TiO2Thin film is at Zn2+With deionized water rinsing after submergence 1min in solution, dry up, then immerse the Na in step c2SSe solution
With deionized water rinsing after middle 1min, dry up, repeat 2 circulations, obtain cadmium sulfoselenide and zinc sulfur selenide (CdSSe/ZnSSe) is repaiied
The titanium deoxid film of decorations, the adsorbance of passivation layer is accurately controlled (Fig. 2 b) by cycle-index.
Embodiment 3
A, prepare titania slurry: the TiO of 400nm will be adjusted2, terpineol and ethyl cellulose be according to the ratio of 2:7:1
Mixing, adds 10mL dehydrated alcohol, after stirring 0.5h, uses Rotary Evaporators to remove dehydrated alcohol, prepares TiO2Slurry；
B, by clean for transparent conducting glass (FTO) glass cleaning, dry, use the TiO that silk screen printing will prepare2Slurry
Scraping at transparent conductive glass surface, then temperature 500 DEG C annealing 30min, heating rate 5 DEG C/min in Muffle furnace, obtain
TiO2Thin film；
C, absorption cadmium sulfoselenide quantum dot: at the Na of 0.1M2S solution adds 0.05moL Se powder mix homogeneously, obtains
Na2SSe solution；Prepare the Cd (NO of 0.01M again3)2Solution；Use SILAR method absorption quantum dot: by TiO2Thin film is at Cd2+Solution
With deionized water rinsing after middle submergence 1min, dry up, then immerse Na2With deionized water rinsing after 1min in SSe solution, dry up,
This process is referred to as 1 circulation, repeats 10 cyclic processes；
D, absorption zinc sulfur selenide passivation layer: the Zn (NO of preparation 0.01M3)2Solution, will be adsorbed with cadmium sulfoselenide quantum dot
TiO2Thin film is at Zn2+With deionized water rinsing after submergence 1min in solution, dry up, then immerse the Na in step c2In SSe solution
With deionized water rinsing after 1min, drying up, repeat 3 circulations, the titanium dioxide obtaining cadmium sulfoselenide and zinc sulfur selenide modification is thin
Film, the adsorbance of passivation layer is accurately controlled (Fig. 2 c) by cycle-index.
Embodiment 4
A, prepare titania slurry: by the TiO of adjustable for particle diameter 200nm2, terpineol and ethyl cellulose be according to 2:7:1
Ratio mixing, add 10mL dehydrated alcohol, stirring 0.5h after, use Rotary Evaporators remove dehydrated alcohol, prepare TiO2Slurry
Material；
B, by clean for transparent conducting glass (FTO) glass cleaning, dry, use the TiO that knife coating will prepare2Slurry is scraped
At transparent conductive glass surface, then temperature 500 DEG C annealing 30min, heating rate 5 DEG C/min in Muffle furnace, obtain TiO2
Thin film；
C, absorption cadmium sulfoselenide quantum dot: at the Na of 0.1M2S solution adds 0.09moL Se powder mix homogeneously, obtains
Na2SSe solution；Prepare the Cd (CH of 0.01M again3COO)2Solution；Use SILAR method absorption quantum dot: by TiO2Thin film is at Cd2+
With deionized water rinsing after submergence 1min in solution, dry up, then immerse Na2With deionized water rinsing after 1min in SSe solution, blow
Dry, this process is referred to as 1 circulation, repeats 12 cyclic processes；
D, absorption zinc sulfur selenide passivation layer: the Zn (CH of preparation 0.01M3COO)2Solution, will be adsorbed with cadmium sulfoselenide quantum dot
TiO2Thin film is at Zn2+With deionized water rinsing after submergence 1min in solution, dry up, then immerse the Na in step c2SSe solution
With deionized water rinsing after middle 1min, dry up, repeat 4 circulations, obtain cadmium sulfoselenide and the titanium dioxide of zinc sulfur selenide modification
Thin film, the adsorbance of passivation layer is accurately controlled (Fig. 2 d) by cycle-index.
Embodiment 5
The titanium deoxid film that any one cadmium sulfoselenide of embodiment 1-4 and zinc sulfur selenide (CdSSe/ZnSSe) are modified
Quantum dot sensitized solar cell test: the titanium dioxide that the cadmium sulfoselenide obtained and zinc sulfur selenide (CdSSe/ZnSSe) are modified
Titanium thin film, as light anode, uses Cu to electrode2S electrode, with polysulfide solution as electrolyte, is assembled into analog solar
Battery, uses AM 1.5 (100mW cm-2) analog solar light source battery test system to assemble battery carry out performance survey
Examination, wherein the effective area of battery testing is 0.2cm2。
Claims (4)
1. the titanium deoxid film structure that a cadmium sulfoselenide and zinc sulfur selenide are modified, it is characterised in that this membrane structure is sulfur selenium
The TiO that cadmium quantum dot is modified2Nano-particle, then modify formation cadmium sulfoselenide/zinc sulfur selenide hetero-junctions with zinc sulfur selenide, wherein
TiO2Nano-particle is P25 or the TiO of particle diameter adjustable 20-400 nm2Nano-particle, concrete operations follow these steps to carry out:
A, prepare titania slurry: by the TiO of adjustable to P25 or particle diameter 20-400 nm2, terpineol and ethyl cellulose be according to 2:
The ratio mixing of 7:1, adds 10 mL dehydrated alcohol, after stirring 0.5 h, uses Rotary Evaporators to remove dehydrated alcohol, prepares
TiO2Slurry；
B, transparent conducting glass is cleaned up, dry, use the TiO that silk screen printing or knife coating will prepare2Slurry is scraped thoroughly
Bright conductive glass surface, then temperature 500 DEG C annealing 30 min, heating rate 5 DEG C/min in Muffle furnace, obtain TiO2Thin
Film；
C, absorption cadmium sulfoselenide quantum dot: at the Na of 0.1 M2S solution adds Se powder mix homogeneously, obtains Na2SSe solution；Again
Cd (the NO of preparation 0.01-0.1 M3)2Or Cd (CH3COO)2Solution；Use SILAR method absorption quantum dot: by TiO2Thin film is at Cd2 +With deionized water rinsing after submergence 1 min in solution, dry up, then immerse Na2SSe solution is used after 1 min deionized water rinsing,
Drying up, this process is referred to as 1 circulation, repeats 4-12 circulation；
D, absorption zinc sulfur selenide passivation layer: the Zn (NO of preparation 0.01-0.1 M3)2Or Zn (CH3COO)2Solution, will be adsorbed with sulfur selenium
The TiO of cadmium quantum dot2Thin film is at Zn2+With deionized water rinsing after submergence 1 min in solution, dry up, then immerse in step c
Na2With deionized water rinsing after 1 min in SSe solution, dry up, repeat 1-4 circulation, obtain cadmium sulfoselenide and zinc sulfur selenide is repaiied
The titanium deoxid film of decorations.
2. the preparation method of the titanium deoxid film structure that a cadmium sulfoselenide and zinc sulfur selenide are modified, it is characterised in that by following
Step is carried out:
A, prepare titania slurry: by the TiO of adjustable to P25 or particle diameter 20-400 nm2, terpineol and ethyl cellulose be according to 2:
The ratio mixing of 7:1, adds 10 mL dehydrated alcohol, after stirring 0.5 h, uses Rotary Evaporators to remove dehydrated alcohol, prepares
TiO2Slurry；
B, transparent conducting glass is cleaned up, dry, use the TiO that silk screen printing or knife coating will prepare2Slurry is scraped thoroughly
Bright conductive glass surface, then temperature 500 DEG C annealing 30 min, heating rate 5 DEG C/min in Muffle furnace, obtain TiO2Thin
Film；
C, absorption cadmium sulfoselenide quantum dot: at the Na of 0.1 M2S solution adds Se powder mix homogeneously, obtains Na2SSe solution；Again
Cd (the NO of preparation 0.01-0.1 M3)2Or Cd (CH3COO)2Solution；Use SILAR method absorption quantum dot: by TiO2Thin film is at Cd2 +With deionized water rinsing after submergence 1 min in solution, dry up, then immerse Na2SSe solution is used after 1 min deionized water rinsing,
Drying up, this process is referred to as 1 circulation, repeats 4-12 circulation；
D, absorption zinc sulfur selenide passivation layer: the Zn (NO of preparation 0.01-0.1 M3)2Or Zn (CH3COO)2Solution, will be adsorbed with sulfur selenium
The TiO of cadmium quantum dot2Thin film is at Zn2+With deionized water rinsing after submergence 1 min in solution, dry up, then immerse in step c
Na2With deionized water rinsing after 1 min in SSe solution, dry up, repeat 1-4 circulation, obtain cadmium sulfoselenide and zinc sulfur selenide is repaiied
The titanium deoxid film of decorations.
The preparation side of the titanium deoxid film structure that a kind of cadmium sulfoselenide the most as claimed in claim 2 and zinc sulfur selenide are modified
Method, it is characterised in that in step c, the addition of Se powder is mol ratio 0.1-0.9 of Se and S.
The preparation side of the titanium deoxid film structure that a kind of cadmium sulfoselenide the most as claimed in claim 2 and zinc sulfur selenide are modified
Method, it is characterised in that in step d, the adsorbance of passivation layer is accurately controlled by cycle-index.
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| CN112563036A (en) * | 2019-11-28 | 2021-03-26 | 长江师范学院 | Preparation method of double-layer zinc sulfide passivated cadmium selenide quantum dot sensitized solar cell |
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