CN106158389B - Cadmium sulfoselenide and the titanium deoxid film structure and preparation method of zinc sulfur selenide modification - Google Patents
Cadmium sulfoselenide and the titanium deoxid film structure and preparation method of zinc sulfur selenide modification Download PDFInfo
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- CN106158389B CN106158389B CN201610567821.2A CN201610567821A CN106158389B CN 106158389 B CN106158389 B CN 106158389B CN 201610567821 A CN201610567821 A CN 201610567821A CN 106158389 B CN106158389 B CN 106158389B
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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
- 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
- 238000012986 modification Methods 0.000 title claims abstract description 19
- 230000004048 modification Effects 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 80
- 239000002096 quantum dot Substances 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 37
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 21
- 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
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 6
- 239000012528 membrane Substances 0.000 claims abstract description 4
- 239000010408 film Substances 0.000 claims description 49
- 239000008367 deionised water Substances 0.000 claims description 32
- 229910021641 deionized water Inorganic materials 0.000 claims description 32
- 239000002002 slurry Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 230000004087 circulation Effects 0.000 claims description 20
- 239000011521 glass Substances 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 16
- 238000002161 passivation Methods 0.000 claims description 14
- 239000011701 zinc Substances 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 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
- 238000000137 annealing Methods 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 125000005909 ethyl alcohol group Chemical group 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
- 238000002156 mixing Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- RBNWAMSGVWEHFP-UHFFFAOYSA-N trans-p-Menthane-1,8-diol Chemical compound CC(C)(O)C1CCC(C)(O)CC1 RBNWAMSGVWEHFP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- VPQBLCVGUWPDHV-UHFFFAOYSA-N sodium selenide Chemical compound [Na+].[Na+].[Se-2] VPQBLCVGUWPDHV-UHFFFAOYSA-N 0.000 claims description 4
- 238000005034 decoration Methods 0.000 claims description 3
- 238000009738 saturating Methods 0.000 claims description 3
- 239000010409 thin film Substances 0.000 claims description 3
- WGPCGCOKHWGKJJ-UHFFFAOYSA-N sulfanylidenezinc Chemical compound [Zn]=S WGPCGCOKHWGKJJ-UHFFFAOYSA-N 0.000 claims description 2
- 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
- 239000011669 selenium Substances 0.000 claims 2
- 238000001179 sorption measurement Methods 0.000 abstract description 7
- 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
- 230000004044 response 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
- 229910045601 alloy Inorganic materials 0.000 abstract description 2
- 239000000956 alloy Substances 0.000 abstract description 2
- 238000013461 design Methods 0.000 abstract description 2
- 239000002086 nanomaterial Substances 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
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- -1 Zinc modified titanium Chemical class 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000005215 recombination 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
- 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
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011258 core-shell material 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
- 238000004519 manufacturing process Methods 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
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000001235 sensitizing effect 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)
- Luminescent Compositions (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Hybrid Cells (AREA)
Abstract
The present invention relates to the titanium deoxid film structure and preparation method that a kind of cadmium sulfoselenide and zinc sulfur selenide are modified, the membrane structure is TiO2Nano particle is carrier, in TiO2Particle surface adsorbs CdSSe alloy quantum dots, adsorbs ZnSSe modification quantum dots afterwards.TiO is prepared using silk-screen printing or knife coating2Film, continuous ionic layer reciprocal adsorption method is in TiO2Particle surface adsorbs CdSSe and ZnSSe.The main purpose of the structure design is the ratio by adjusting S and Se, and one-step method prepares the adjustable CdSSe ternary alloy quantum dots of energy gap and realizes controllable precise to spectral response, while modification is carried out to quantum dot using ZnSSe reduces its surface defect.Preparation method of nano material of the present invention has the advantages that method is simple and quick, cost is cheap, process control, 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 the titanium deoxid film structure and preparation method that a kind of cadmium sulfoselenide and zinc sulfur selenide are modified, especially
It is related to a kind of preparation 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, multiple excitons, i.e., multiple exciton effect can be produced by absorbing a photon energy
(multiple exciton generation, abbreviated as MEG), and then multiple charge carrier pair is formed, with more efficient land productivity
Use solar energy.The S-Q limit models proposed according to American physicist Shockley and Queisser, semiconductor PN solar energy
The photoelectric transformation efficiency limit of battery is 31%, but the quantum dot sensitized solar cell constructed using QD as sensitising agent
(Quantum dot sensitized solar cell, abbreviation QDSC), under the effect of MEG effects, then it can break through the S-Q limit
Efficiency Model, there is higher theoretical light photoelectric transformation efficiency.Also, QDSC manufacturing costs are far below silicon solar cell.Therefore,
QDSC is considered as extremely potential solar cell of new generation, turns into one of focus of research in world wide.
Compared with single CdS, CdSe, InP, PbSe QDs, CdS/CdSe is sensitized system and is used in QDSC obtain altogether
Higher energy conversion efficiency captures energy because it improves the adsorbance of CdSe quantum dot by introducing CdS so as to add light
Amount.However, in traditional preparation method, CdS QDs and change are adsorbed first with continuous ionic layer reciprocal adsorption method (SILAR)
The time for learning bath deposition absorption CdSe QDs method preparation light anode is more than 5h.And the core shell structure for utilizing method for externally to prepare
CdS/CdSe processes need 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 controlling S and Se ratio
CdSxSe1-x/ZnSxSe1-xQDs modifying titanium dioxide film structures, the structure can both obtain the adjustable CdS of band gapxSe1-x
QDs realizes the regulation to spectral response range, can make ZnS againxSe1-xEffectively reduce CdSxSe1-xThe defects of QDs, reduction electronics-
Hole-recombination.This experiment synthetic method uses same Na2SxSe1-xSolution synthesizes ZnSxSe1-xWith CdSxSe1-xQDs, save
Cost, process is simplified, by the control of quantum dot adsorption time in 1h, highly shortened the reaction time, improve efficiency.Together
When, the light anode of the structure is applied to the conversion efficiency that quantum dot sensitized solar cell can effectively improve solar cell.This
Inventing the preparation method of nano material that is related to has the advantages that cheap cost, process control, reproducible, can operate with solar energy
Battery light anode material, it can also be used to photocatalysis field.
The content of the invention
It is an object of the present invention to provide the titanium deoxid film structure and system that a kind of cadmium sulfoselenide and zinc sulfur selenide are modified
Preparation Method, the membrane structure are TiO2Nano particle is carrier, in TiO2Particle surface adsorbs CdSSe alloy quantum dots, inhales afterwards
Attached ZnSSe modifies quantum dot.TiO is prepared using silk-screen printing or knife coating2Film, using continuous ionic layer reciprocal adsorption
Method is in TiO2Particle surface adsorbs CdSSe and ZnSSe.The main purpose of the structure design is the ratio by adjusting S and Se, one
Footwork prepares the adjustable CdSSe ternary alloy quantum dots realization of energy gap to the controllable precise of spectral response, utilizes simultaneously
ZnSSe, which carries out modification to quantum dot, reduces its surface defect.The method of the invention has that simple and quick, cost is cheap, process
The advantages that controllable, reproducible, it can operate with solar battery light anode material, it can also be used to photocatalysis field.
A kind of titanium deoxid film structure of cadmium sulfoselenide and zinc sulfur selenide modification of the present invention, the membrane structure are
The TiO of cadmium sulfoselenide quantum dot modification2Nano particle, then modify to form cadmium sulfoselenide/zinc sulfur selenide hetero-junctions with zinc sulfur selenide,
Wherein TiO2Nano particle is P25 or the adjustable 20-400nm of particle diameter TiO2Nano particle, concrete operations follow these steps into
OK：
A, titania slurry is prepared：By the P25 or adjustable 20-400nm of particle diameter TiO2, terpinol and ethyl cellulose press
According to 2:7:1 ratio mixing, adds 10mL absolute ethyl alcohols, after stirring 0.5h, removes absolute ethyl alcohol using Rotary Evaporators, is made
TiO2Slurry；
B, transparent conducting glass is cleaned up, dried, the TiO that will be prepared using silk-screen printing or knife coating2Slurry
Scrape in transparent conductive glass surface, then 500 DEG C of annealing 30min of temperature in Muffle furnace, 5 DEG C/min of heating rate, are obtained
TiO2Film；
C, cadmium sulfoselenide quantum dot is adsorbed：In 0.1M Na2Se powder is added in S solution to be well mixed, and obtains Na2SSe is molten
Liquid；0.01-0.1M Cd (NO are prepared again3)2Or Cd (CH3COO)2Solution；Quantum dot is adsorbed using SILAR methods：By TiO2Film
In Cd2+Deionized water rinsing is used after submerging 1min in solution, is dried up, then immerse Na2Rushed in SSe solution after 1min with deionized water
Wash, dry up, this process is referred to as 1 circulation, repeats 4-12 circulation；
D, zinc sulfur selenide passivation layer is adsorbed：Prepare 0.01-0.1M Zn (NO3)2Or Zn (CH3COO)2Solution, it will be adsorbed with
The TiO of cadmium sulfoselenide quantum dot2Film is in Zn2+Deionized water rinsing is used after submerging 1min in solution, is dried up, then immerse step c
In Na2Deionized water rinsing is used in SSe solution after 1min, is dried up, 1-4 circulation is repeated, obtains cadmium sulfoselenide and sulphur selenizing
Zinc modified titanium deoxid film.
A kind of preparation method of the titanium deoxid film structure of cadmium sulfoselenide and zinc sulfur selenide modification, follow these steps into
OK：
A, titania slurry is prepared：By the P25 or adjustable 20-400nm of particle diameter TiO2, terpinol and ethyl cellulose press
According to 2:7:1 ratio mixing, adds 10mL absolute ethyl alcohols, after stirring 0.5h, removes absolute ethyl alcohol using Rotary Evaporators, is made
TiO2Slurry；
B, it is FTO glass cleanings is clean, drying, the TiO that will be prepared using silk-screen printing or knife coating2Slurry is scraped
FTO glass surfaces, then 500 DEG C of annealing 30min of temperature in Muffle furnace, 5 DEG C/min of heating rate, obtain TiO2Film；
C, cadmium sulfoselenide quantum dot is adsorbed：In 0.1M Na2Se powder is added in S solution to be well mixed, and obtains Na2SSe is molten
Liquid；0.01-0.1M Cd (NO are prepared again3)2Or Cd (CH3COO)2Solution；Quantum dot is adsorbed using SILAR methods：By TiO2Film
In Cd2+Deionized water rinsing is used after submerging 1min in solution, is dried up, then immerse Na2Rushed in SSe solution after 1min with deionized water
Wash, dry up, this process is referred to as 1 circulation, repeats 4-12 circulation；
D, zinc sulfur selenide passivation layer is adsorbed：Prepare 0.01-0.1M Zn (NO3)2Or Zn (CH3COO)2Solution, it will be adsorbed with
The TiO of cadmium sulfoselenide quantum dot2Film is in Zn2+Deionized water rinsing is used after submerging 1min in solution, is dried up, then immerse step c
In Na2Deionized water rinsing is used in SSe solution after 1min, is dried up, 1-4 circulation is repeated, obtains cadmium sulfoselenide and sulphur selenizing
Zinc modified titanium deoxid film.
The addition of Se powder is Se and S mol ratio 0.1-0.9 in step c.
The adsorbance of passivation layer is accurately controlled by cycle-index in step d.
The titanium deoxid film structure and preparation method of cadmium sulfoselenide and zinc sulfur selenide modification of the present invention, its advantage
And good effect：The present invention is passed through using cadmium sulfoselenide and zinc sulfur selenide (CdSSe/ZnSSe) modifying titanium dioxide film structure
The CdSSe/ZnSSe QDs modifying titanium dioxide film structures for controlling S and Se ratio to prepare, it is adjustable that the structure obtains band gap
CdSSe QDs realize regulation to spectral response range, the defects of making ZnSSe effectively reduce CdSSe QDs again, reduce electricity
Son-hole-recombination.The method of the invention uses same Na2SSe solution synthesizes ZnSSe and CdSSe QDs, saved cost,
Process is simplified, by the control of quantum dot adsorption time in 1h, the reaction time is highly shortened, improves efficiency.The film
The light anode of structure is applied to the conversion efficiency that quantum dot sensitized solar cell can effectively improve solar cell.Using continuous
Sheath reciprocal adsorption method preparation technology is simple, cost is cheap, process control, it is reproducible the advantages that.
The titanium deoxid film that the CdSSe/ZnSSe obtained by the method for the invention is modified, the material structure are
The TiO of CdSSe quantum dots modification2Modified to form CdSSe/ZnSSe with ZnSSe after nano particle, wherein TiO2Nano particle is
P25 or particle diameter adjustable (20~400nm) TiO2Nanocrystalline, Quantum dots CdS Se and ZnSSe forms hetero-junctions.The structure can
Applied to quantum dot sensitized solar battery light anode material.
Brief description of the drawings
Fig. 1 is that the present invention implements 2 I-V diagrams for being assembled into quantum dot sensitized solar cell；
Fig. 2 is the titanium deoxid film figure that cadmium sulfoselenide of the present invention and zinc sulfur selenide are modified, and wherein a is the result of example 1,
The cycle-index for adsorbing CdSSe quantum dots is 4, and the cycle-index for adsorbing ZnSSe is 1；B is the result of example 2, adsorbs CdSSe
The cycle-index of quantum dot is respectively 6, the cycle-index for adsorbing 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 for adsorbing ZnSSe is 3；D is the result of example 4, absorption CdSSe quantum dots
Cycle-index is respectively 12, and the cycle-index for adsorbing ZnSSe is 4；
Fig. 3 is the saturating of the titanium deoxid film structure of the cadmium sulfoselenide that the embodiment of the present invention 2 obtains and zinc sulfur selenide modification
Penetrate electron microscope (TEM) photo.
Embodiment
Embodiment 1
A, titania slurry is prepared：By P25 TiO2, terpinol and ethyl cellulose be according to 2:7:1 ratio mixing,
10mL absolute ethyl alcohols are added, after stirring 0.5h, absolute ethyl alcohol is removed using Rotary Evaporators, TiO is made2Slurry；
B, transparent conducting glass (FTO) is cleaned up, dried, scraped the slurry prepared transparent using silk-screen printing
Conductive glass surface, then 500 DEG C of annealing 30min of temperature in Muffle furnace, 5 DEG C/min of heating rate, obtain TiO2Film；
C, cadmium sulfoselenide (CdSSe) quantum dot is adsorbed：In 0.1M Na2It is equal that the mixing of 0.01moL Se powder is added in S solution
It is even, obtain Na2SSe solution；0.01M Cd (NO are prepared again3)2Solution；Quantum dot is adsorbed using SILAR methods：By TiO2Film exists
Cd2+Deionized water rinsing is used after submerging 1min in solution, is dried up, then immerse Na2Rushed in SSe solution after 1min with deionized water
Wash, dry up, this process is referred to as 1 circulation, repeats 4 cyclic processes；
D, ZnSSe passivation layers are adsorbed：Prepare 0.01M Zn (NO3)2Solution, cadmium sulfoselenide (CdSSe) quantum will be adsorbed with
The TiO of point2Film is in Zn2+Deionized water rinsing is used after submerging 1min in solution, is dried up, then the Na immersed in step c2SSe is molten
Deionized water rinsing is used in liquid after 1min, is dried up, 1 circulation is repeated, obtains cadmium sulfoselenide and zinc sulfur selenide (CdSSe/ZnSSe)
The titanium deoxid film of modification, the adsorbance of passivation layer are accurately controlled (Fig. 2 a) by cycle-index.
Embodiment 2
A, titania slurry is prepared：By the adjustable 20nm of particle diameter TiO2, terpinol and ethyl cellulose be according to 2:7:1
Ratio mixes, and adds 10mL absolute ethyl alcohols, after stirring 0.5h, removes absolute ethyl alcohol using Rotary Evaporators, TiO is made2Slurry；
B, it is transparent conducting glass (FTO) glass cleaning is clean, drying, the TiO that will be prepared using knife coating2Slurry is scraped
In transparent conductive glass surface, then 500 DEG C of annealing 30min of temperature in Muffle furnace, 5 DEG C/min of heating rate, obtain TiO2
Film；
C, cadmium sulfoselenide quantum dot is adsorbed：In 0.1M Na20.03moL Se powder is added in S solution to be well mixed, and is obtained
Na2SSe solution；0.01M Cd (CH are prepared again3COO)2Solution；Quantum dot is adsorbed using SILAR methods：By TiO2Film is in Cd2+
Deionized water rinsing is used after submerging 1min in solution, is dried up, then immerse Na2Deionized water rinsing is used in SSe solution after 1min, is blown
Dry, this process is referred to as 1 circulation, repeats 6 cyclic processes；
D, zinc sulfur selenide passivation layer is adsorbed：Prepare 0.01M Zn (CH3COO)2Solution, cadmium sulfoselenide quantum dot will be adsorbed with
TiO2Film is in Zn2+Deionized water rinsing is used after submerging 1min in solution, is dried up, then the Na immersed in step c2SSe solution
Deionized water rinsing is used after middle 1min, is dried up, 2 circulations is repeated, obtains cadmium sulfoselenide and zinc sulfur selenide (CdSSe/ZnSSe) is repaiied
The titanium deoxid film of decorations, the adsorbance of passivation layer are accurately controlled (Fig. 2 b) by cycle-index.
Embodiment 3
A, titania slurry is prepared：400nm TiO will be adjusted2, terpinol and ethyl cellulose be according to 2:7:1 ratio
Mixing, 10mL absolute ethyl alcohols are added, after stirring 0.5h, remove absolute ethyl alcohol using Rotary Evaporators, TiO is made2Slurry；
B, it is transparent conducting glass (FTO) glass cleaning is clean, drying, the TiO that will be prepared using silk-screen printing2Slurry
Scrape in transparent conductive glass surface, then 500 DEG C of annealing 30min of temperature in Muffle furnace, 5 DEG C/min of heating rate, are obtained
TiO2Film；
C, cadmium sulfoselenide quantum dot is adsorbed：In 0.1M Na20.05moL Se powder is added in S solution to be well mixed, and is obtained
Na2SSe solution；0.01M Cd (NO are prepared again3)2Solution；Quantum dot is adsorbed using SILAR methods：By TiO2Film is in Cd2+Solution
Deionized water rinsing is used after middle submergence 1min, is dried up, then immerse Na2Deionized water rinsing is used in SSe solution after 1min, is dried up,
This process is referred to as 1 circulation, repeats 10 cyclic processes；
D, zinc sulfur selenide passivation layer is adsorbed：Prepare 0.01M Zn (NO3)2Solution, cadmium sulfoselenide quantum dot will be adsorbed with
TiO2Film is in Zn2+Deionized water rinsing is used after submerging 1min in solution, is dried up, then the Na immersed in step c2In SSe solution
Deionized water rinsing is used after 1min, is dried up, repeats 3 circulations, the titanium dioxide for obtaining cadmium sulfoselenide and zinc sulfur selenide modification is thin
Film, the adsorbance of passivation layer are accurately controlled (Fig. 2 c) by cycle-index.
Embodiment 4
A, titania slurry is prepared：By the adjustable 200nm of particle diameter TiO2, terpinol and ethyl cellulose be according to 2:7:1
Ratio mixing, add 10mL absolute ethyl alcohols, stir 0.5h after, use Rotary Evaporators remove absolute ethyl alcohol, be made TiO2Slurry
Material；
B, it is transparent conducting glass (FTO) glass cleaning is clean, drying, the TiO that will be prepared using knife coating2Slurry is scraped
In transparent conductive glass surface, then 500 DEG C of annealing 30min of temperature in Muffle furnace, 5 DEG C/min of heating rate, obtain TiO2
Film；
C, cadmium sulfoselenide quantum dot is adsorbed：In 0.1M Na20.09moL Se powder is added in S solution to be well mixed, and is obtained
Na2SSe solution；0.01M Cd (CH are prepared again3COO)2Solution；Quantum dot is adsorbed using SILAR methods：By TiO2Film is in Cd2+
Deionized water rinsing is used after submerging 1min in solution, is dried up, then immerse Na2Deionized water rinsing is used in SSe solution after 1min, is blown
Dry, this process is referred to as 1 circulation, repeats 12 cyclic processes；
D, zinc sulfur selenide passivation layer is adsorbed：Prepare 0.01M Zn (CH3COO)2Solution, cadmium sulfoselenide quantum dot will be adsorbed with
TiO2Film is in Zn2+Deionized water rinsing is used after submerging 1min in solution, is dried up, then the Na immersed in step c2SSe solution
Deionized water rinsing is used after middle 1min, is dried up, repeats 4 circulations, obtains cadmium sulfoselenide and the titanium dioxide of zinc sulfur selenide modification
Film, the adsorbance of passivation layer are 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 of acquisition and zinc sulfur selenide (CdSSe/ZnSSe) are modified
Titanium film uses Cu as light anode to electrode2S electrodes, using polysulfide solution as electrolyte, it is assembled into analog solar
Battery, using (the 100mW cm of AM 1.5-2) battery test system of analog solar light source carries out performance survey to the battery of assembling
Examination, wherein the effective area of battery testing is 0.2cm2。
Claims (4)
1. a kind of cadmium sulfoselenide and the titanium deoxid film structure of zinc sulfur selenide modification, it is characterised in that the membrane structure is sulphur selenium
The TiO of cadmium quantum dot modification2Nano particle, then modify to form cadmium sulfoselenide/zinc sulfur selenide hetero-junctions with zinc sulfur selenide, wherein
TiO2Nano particle is P25 or the adjustable 20-400 nm of particle diameter TiO2Nano particle, concrete operations follow these steps to carry out：
A, titania slurry is prepared：By the P25 or adjustable 20-400 nm of particle diameter TiO2, terpinol and ethyl cellulose be according to 2:
7:1 ratio mixing, adds 10 mL absolute ethyl alcohols, after stirring 0.5 h, removes absolute ethyl alcohol using Rotary Evaporators, is made
TiO2Slurry；
B, transparent conducting glass is cleaned up, dried, the TiO that will be prepared using silk-screen printing or knife coating2Slurry is scraped saturating
Bright conductive glass surface, then 500 DEG C of 30 min of annealing of temperature in Muffle furnace, 5 DEG C/min of heating rate, obtain TiO2It is thin
Film；
C, cadmium sulfoselenide quantum dot is adsorbed：In 0.1 M Na2Se powder is added in S solution to be well mixed, and obtains Na2SSe solution；Again
Prepare 0.01-0.1 M Cd (NO3)2Or Cd (CH3COO)2Solution；Quantum dot is adsorbed using SILAR methods：By TiO2Film is in Cd2 +Deionized water rinsing is used after 1 min is submerged in solution, is dried up, then immerse Na2Deionized water rinsing is used in SSe solution after 1 min,
Drying, this process are referred to as 1 circulation, repeat 4-12 circulation；
D, zinc sulfur selenide passivation layer is adsorbed：Prepare 0.01-0.1 M Zn (NO3)2Or Zn (CH3COO)2Solution, sulphur selenium will be adsorbed with
The TiO of cadmium quantum dot2Film is in Zn2+Deionized water rinsing is used after 1 min is submerged in solution, is dried up, then immerse in step c
Na2Deionized water rinsing is used in SSe solution after 1 min, is dried up, 1-4 circulation is repeated, obtains cadmium sulfoselenide and zinc sulfur selenide is repaiied
The titanium deoxid film of decorations.
2. the preparation method of a kind of cadmium sulfoselenide and the titanium deoxid film structure of zinc sulfur selenide modification, it is characterised in that by following
Step is carried out：
A, titania slurry is prepared：By the P25 or adjustable 20-400 nm of particle diameter TiO2, terpinol and ethyl cellulose be according to 2:
7:1 ratio mixing, adds 10 mL absolute ethyl alcohols, after stirring 0.5 h, removes absolute ethyl alcohol using Rotary Evaporators, is made
TiO2Slurry；
B, transparent conducting glass is cleaned up, dried, the TiO that will be prepared using silk-screen printing or knife coating2Slurry is scraped saturating
Bright conductive glass surface, then 500 DEG C of 30 min of annealing of temperature in Muffle furnace, 5 DEG C/min of heating rate, obtain TiO2It is thin
Film；
C, cadmium sulfoselenide quantum dot is adsorbed：In 0.1 M Na2Se powder is added in S solution to be well mixed, and obtains Na2SSe solution；Again
Prepare 0.01-0.1 M Cd (NO3)2Or Cd (CH3COO)2Solution；Quantum dot is adsorbed using SILAR methods：By TiO2Film is in Cd2 +Deionized water rinsing is used after 1 min is submerged in solution, is dried up, then immerse Na2Deionized water rinsing is used in SSe solution after 1 min,
Drying, this process are referred to as 1 circulation, repeat 4-12 circulation；
D, zinc sulfur selenide passivation layer is adsorbed：Prepare 0.01-0.1 M Zn (NO3)2Or Zn (CH3COO)2Solution, sulphur selenium will be adsorbed with
The TiO of cadmium quantum dot2Film is in Zn2+Deionized water rinsing is used after 1 min is submerged in solution, is dried up, then immerse in step c
Na2Deionized water rinsing is used in SSe solution after 1 min, is dried up, 1-4 circulation is repeated, obtains cadmium sulfoselenide and zinc sulfur selenide is repaiied
The titanium deoxid film of decorations.
A kind of 3. preparation side of the titanium deoxid film structure of cadmium sulfoselenide and zinc sulfur selenide modification as claimed in claim 2
Method, it is characterised in that the addition of Se powder is Se and S mol ratio 0.1-0.9 in step c.
A kind of 4. preparation side of the titanium deoxid film structure of cadmium sulfoselenide and zinc sulfur selenide modification as claimed in claim 2
Method, it is characterised in that the adsorbance of passivation layer is accurately controlled by cycle-index in step d.
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| WO2014088155A1 (en) * | 2012-12-07 | 2014-06-12 | 한양대학교 산학협력단 | Solar cell and method for manufacturing same |
| KR20140087383A (en) * | 2012-12-28 | 2014-07-09 | 포항공과대학교 산학협력단 | Manufacturing method of quantum dot solar cell |
| CN104282440A (en) * | 2014-10-08 | 2015-01-14 | 景德镇陶瓷学院 | Method for preparing sulfur group quantum dot sensitization oxide semiconductor photo-anode |
| CN104952627A (en) * | 2014-12-29 | 2015-09-30 | 中国科学院物理研究所 | Quantum dot sensitized solar battery and preparation method thereof |
| CN105225841A (en) * | 2015-10-09 | 2016-01-06 | 河南大学 | A kind of preparation method of DSSC NiO photocathode |
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| WO2014088155A1 (en) * | 2012-12-07 | 2014-06-12 | 한양대학교 산학협력단 | Solar cell and method for manufacturing same |
| KR20140087383A (en) * | 2012-12-28 | 2014-07-09 | 포항공과대학교 산학협력단 | Manufacturing method of quantum dot solar cell |
| CN104282440A (en) * | 2014-10-08 | 2015-01-14 | 景德镇陶瓷学院 | Method for preparing sulfur group quantum dot sensitization oxide semiconductor photo-anode |
| CN104952627A (en) * | 2014-12-29 | 2015-09-30 | 中国科学院物理研究所 | Quantum dot sensitized solar battery and preparation method thereof |
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