CN108666141A - II-type nuclear shell structure quantum point of one kind and its preparation method and application - Google Patents
II-type nuclear shell structure quantum point of one kind and its preparation method and application Download PDFInfo
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- CN108666141A CN108666141A CN201810385108.5A CN201810385108A CN108666141A CN 108666141 A CN108666141 A CN 108666141A CN 201810385108 A CN201810385108 A CN 201810385108A CN 108666141 A CN108666141 A CN 108666141A
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- 239000002096 quantum dot Substances 0.000 claims abstract description 161
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
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- 239000000843 powder Substances 0.000 description 4
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 4
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- 239000003381 stabilizer Substances 0.000 description 4
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
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- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 1
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
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- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
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- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 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
-
- 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)
- Hybrid Cells (AREA)
- Photovoltaic Devices (AREA)
Abstract
Application the invention discloses a kind of II type nuclear shell structure quantum point and preparation method thereof and in preparing quantum dot sensitized photoelectrodes, the II type nuclear shell structure quantum point includes shell and stratum nucleare, group is 0.15~1.8 as the molar ratio of CdZnTe CdS, the Elements C d and element Zn：1.The invention discloses a kind of novel nuclear shell structure quantum points, and II type nucleocapsid is obtained under the CdS shells of low thickness.The light capture ability of the quantum dot sensitized optoelectronic pole prepared with the quantum dot of the structure is significantly improved, and the injection efficiency of light induced electron is not affected, and is expected to have more excellent electricity conversion with the quantum dot sensitized solar cell that this is prepared.
Description
Technical field
The present invention relates to the technical fields of sensitization solar battery, and in particular to II-type quantum dot of one kind and its preparation side
Method and the application in preparing quantum dot sensitized photoelectrodes.
Background technology
Quantum dot sensitized solar cell is a research hotspot, and basic structure includes semiconductor photoelectrode, quantum dot
Sensitizer, electrolyte, electro-conductive glass, to electrode, wherein semiconductor optoelectronic extremely electron-transport provide access, while be also amount
The carrier of son point sensitizer attachment.But currently, compared with other types of solar cell, quantum dot sensitized solar cell
Electricity conversion is relatively low.Quantum dot sensitizer be influence quantum dot sensitization solar battery electricity conversion it is main because
Element.Ideal quantum dot sensitizer should have wider spectral response range, higher conduction level and low defect state close
Degree.Wherein, II type structure quantum point of nucleocapsid to detach on light induced electron and vacant spaces, is conducive to carrying for electron injection rate
High effective inhibition with Carrier recombination process.In addition, " space indirect transition band structure " can effectively widen quantum dot
Absorption spectrum, and then enhance quantum dot light capture ability.
The energy gap of cadmium telluride quantum dot (CdTe) is 1.5eV or so, has higher absorptivity, is a kind of outstanding
Light absorbing material.The synthetic method of CdTe quantum divides into Aqueous phase and oil phase method with reaction medium at present.Oil phase method with
High boiling organic solvent is reaction medium, completes reaction at relatively high temperatures, and product crystallinity is high, surface modificability is good,
It is preferred material synthesis method in prepared by photoelectric device.But in the deposition process of quantum dot, oil-soluble quantum dot need to pass through
Ligand exchange can be just anchored on optoelectronic pole, and the quantum dot of Aqueous phase synthesis can be used directly, easy to operate.
However, in more sulphur electrolyte, the stability of CdTe is poor, is formed by coating cadmium sulfide (CdS) on its surface
CdTe/CdS core-shell quanta dots then avoid degradation of the quantum dot in more sulphur electrolyte.But due to the conduction band energy of CdTe and CdS
Grade is close, and the CdTe/CdS nucleocapsids of formation are unfavorable for the transmission of photo-generated carrier based on I type level structure.
The Amway people etc. (the Amway people, Zeng Qinghui, Zhao family dragon et al, CdTe/CdS quantum dots I-II type structure transformation with it is glimmering
Light property, Chemical Journal of Chinese Universities) it is prepared for the CdTe/CdS core-shell quanta dots that shell thickness can accurately control, and profit
CdS shell thicknesses are analyzed to the fluorescence quantum yield of CdTe quantum and the affecting laws of spectral composition, hair with multiple technologies
It is existing：With the increase of CdS shell thicknesses, CdTe is gradually transitions II type nucleocapsid from I type structure.This is because due to
CdTe is close with CdS conduction levels, and needing thicker CdS shells just can make CdTe CdS core shell quantum dots form II type energy level knot
Structure.But when shell is blocked up, it is applied to the elimination that quantum dot sensitized solar cell will be unfavorable for hole.
In view of the above-mentioned problems, the present invention introduces Zn elements in CdTe, prepare ternary quantum dots, by the regulation and control of component with
CdS forms II type nuclear shell structure quantum point, avoids the blocked up problem of CdS shells.
Invention content
The invention discloses a kind of novel nuclear shell structure quantum points, and II type core is obtained under the CdS shells of low thickness
Shell structure.The light capture ability of the quantum dot sensitized optoelectronic pole prepared with the quantum dot of the structure is significantly improved, and photoproduction
The injection efficiency of electronics is not affected, and is expected to have more excellent light with the quantum dot sensitized solar cell that this is prepared
Electrotransformation efficiency.
Specific technical solution is as follows：
A kind of II-type nuclear shell structure quantum point, including shell and stratum nucleare, group become CdZnTe CdS, the Elements C d with
The molar ratio of element Zn is 0.15~1.8：1.
The present invention looks for another way, and is regulated and controled with content by the composition to kernel, realizes the CdS shells in low thickness
II type nucleocapsid of lower acquisition avoids when preparing CdTe/CdS core-shell quanta dots in the prior art, or by will be in CdTe
The size controlling of core obtains II type nucleocapsid at 2nm, or by increasing the thickness (being not less than 1nm) of CdS shells.System
It is standby simple for process, and the injection efficiency of light induced electron will not be had an impact.
Cubic sphalerite structure is belonged to as the more first quantum dots of the CdZnTe of kernel, CdTe and ZnTe in the present invention, and
The lattice constant of CdTe, ZnTe are respectively 0.648,0.610, are easily formed alloy cpd.And further experiments verify that, lead to
The more first quantum dots of CdZnTe of required size can be obtained by crossing the regulation and control of time.
It is found through experiment, with the raising of element Zn contents, the conduction level of the more first quantum dots of CdZnTe also accordingly improves,
But its valence-band level also accordingly improves, so that the potential barrier of hole transport improves, hole is constantly accumulated in stratum nucleare so that stratum nucleare
The probability that Carrier recombination occurs increases.Preferably, the molar ratio of the Elements C d and element Zn is 0.5~1.8：1.
Due to the presence of " bowing effect ", the energy gaps of CdZnTe ternary quantum dots is as there are one for the raisings of Zn contents
A minimum, further preferably, the molar ratio of the Elements C d and element Zn is 1.8：1.
Preferably, the grain size of the stratum nucleare CdZnTe of the II-type nuclear shell structure quantum point is 2~4nm, the thickness of shell CdS
Degree is 0.5~1nm.
Further preferably, the molar ratio of the Elements C d and element Zn is 1.8：The grain size of 1, the stratum nucleare CdZnTe be 3.0 ±
The thickness of 0.1nm, shell CdS are 0.9 ± 0.1nm.
It is found that II-type nuclear shell structure quantum point disclosed by the invention, the requirement to kernel particle size and shell thickness is all more
It is loose.Using new inventive concept, the difficulty of preparation process is not only greatly reduced, while avoiding the note to light induced electron
Enter efficiency to have an impact.
The invention discloses the preparation methods of the II-type nuclear shell structure quantum point, including：
(1) Aqueous phase is used to prepare the more first quantum dots of CdZnTe；
(2) CdS is coated in the more first quantum dot surfaces of the CdZnTe by successive ionic layer adsorption and reaction method (SILAR)
Shell.
The invention also discloses a kind of quantum dot sensitized optoelectronic pole, including wide-band gap semiconductor thin film and it is deposited on described thin
Quantum dot sensitizer on film, using the II-type nuclear shell structure quantum point as quantum dot sensitizer.
It is found through experiment that II-type nuclear shell structure quantum point disclosed by the invention to divide on light induced electron and vacant spaces
From being conducive to the raising of electron injection rate and effective inhibition of Carrier recombination process；On the other hand, " space indirect transition
Band structure " can effectively widen the absorption light of the quantum dot sensitized optoelectronic pole prepared by the II-type nuclear shell structure quantum point
Spectrum, and then enhance the light capture ability of quantum dot.
The preparation method of the quantum dot sensitized optoelectronic pole can be used and directly be anchored on II-type nuclear shell structure quantum point
The two-step method on wide-band gap semiconductor thin film surface；
Can also use and the more first quantum dots of CdZnTe are first anchored on wide-band gap semiconductor thin film surface, then by continuously from
Sublayer adsorbs the three-step approach for coating CdS shells in the more first quantum dot surfaces of CdZnTe with reaction method.
The two-step method, specially：
Step 1: wide-band gap semiconductor thin film is prepared on transparent conductive substrate surface, then using bridging agent to the broadband
Gap semiconductor film is handled；
Step 2: preparing the more first quantum dots of CdZnTe using Aqueous phase, then existed by successive ionic layer adsorption and reaction method
The CdZnTe is more, and first quantum dot surface coats CdS shells, obtains II-type nuclear shell structure quantum point, finally uses chemical baths
II-type the nuclear shell structure quantum point is anchored on step 1 treated wide-band gap semiconductor thin film surface.
The three-step approach, specially：
Step 1: wide-band gap semiconductor thin film is prepared on transparent conductive substrate surface, then using bridging agent to the broadband
Gap semiconductor film is handled；
Step 2: preparing the more first quantum dots of CdZnTe using Aqueous phase, then use chemical baths by the more members of the CdZnTe
Quantum dot is anchored on step 1 treated wide-band gap semiconductor thin film surface；
Step 3: coating CdS shells in the more first quantum dot surfaces of the CdZnTe by successive ionic layer adsorption and reaction method
Layer, is prepared quantum dot sensitized optoelectronic pole.
In order to further increase the adhesion amount of quantum dot sensitizer, it is preferred to use the preparation process of three-step approach.
Preferably, in step 1, the wide-band gap semiconductor thin film is selected from titanium deoxid film, zinc-oxide film, dioxy
Change tin thin film and/or tungstic acid；A variety of existing preparation processes, such as silk screen print method may be used in its preparation.Further preferably,
The wide-band gap semiconductor thin film is selected from titanium deoxid film.
In step 1, the bridging agent is containing organic molecule bifunctional, and effect is for by broad-band gap
The more first quantum dots of CdZnTe that semiconductive thin film is prepared with Aqueous phase are connected.Preferably, the difunctional organic molecule,
It is chosen in particular from mercaptopropionic acid, thioacetic acid or L-cysteine.
The invention also discloses a kind of quantum dot sensitized solar cells, using the quantum dot sensitized photoelectricity of above-mentioned preparation
Pole.
Compared with prior art, the invention has the advantages that：
The present invention is regulated and controled by the composition to kernel with content on the basis of CdTe CdS core shell quantum dots, real
Show and obtained II type nucleocapsid under the CdS shells of low thickness, has both been not necessarily to by kernel particle size control at 2nm, without general
The thickness control of CdS shells is in 1nm or more.
The present invention, in conjunction with successive ionic layer adsorption and reaction method, realizes II-type nucleocapsid quantum using Aqueous phase
The preparation of point, preparation process are simple, controllable.
Using the quantum dot sensitized optoelectronic pole that the II-type nuclear shell structure quantum point is prepared as quantum dot sensitizer, light
Capture ability is significantly improved, and the injection efficiency of light induced electron is not affected, with its preparation it is quantum dot sensitized too
Positive energy battery is expected to obtain more excellent electricity conversion.
Description of the drawings
Fig. 1 is pure titinium dioxide electrode (a), Cd prepared by embodiment 10.64Zn0.36Te quantum dots (b) with
Cd0.64Zn0.36The HRTEM of Te@CdS II-type nuclear shell structure quantum points (c) schemes；
Fig. 2 is pure titinium dioxide electrode prepared by embodiment 1, Cd0.64Zn0.36The quantum dot sensitized titanium dioxide electrodes of Te with
Cd0.64Zn0.36The absorption spectrum of Te@CdS II-type nuclear shell structure quantum point sensitized titanium dioxide electrodes, and provide CdTe@CdS with
CdS quantum dot sensitized titanium dioxide electrode is as a comparison；
Fig. 3 is Cd prepared by embodiment 10.64Zn0.36Te quantum dots and Cd0.64Zn0.36Te@CdS II-type nucleocapsid amounts
The fluorescence decay analysis of son point, and provide the fluorescence decay analysis of CdTe@CdS quantum dots as a comparison；
Fig. 4 is Cd prepared by embodiment 10.64Zn0.36The quantum dot sensitized titanium dioxide electrodes of Te and Cd0.64Zn0.36Te@CdS
The fluorescence decay of II-type nuclear shell structure quantum point sensitized titanium dioxide electrode is analyzed, and provides CdTe@CdS core shell structure quantum
The fluorescence decay analysis of point sensitized titanium dioxide electrode is as a comparison；
Fig. 5 is Cd prepared by comparative example0.70Zn0.30The quantum dot sensitized titanium dioxide electrodes of Te and Cd0.70Zn0.30Te@CdS
The absorption spectrum of nuclear shell structure quantum point sensitized titanium dioxide electrode；
Fig. 6 is Cd prepared by comparative example0.70Zn0.30Te quantum dots and Cd0.70Zn0.30Te@CdS core core-shell structure quantum dots
Fluorescence decay is analyzed；
Fig. 7 is Cd prepared by comparative example0.70Zn0.30The quantum dot sensitized titanium dioxide electrodes of Te and Cd0.70Zn0.30Te@CdS
The fluorescence decay of nuclear shell structure quantum point sensitized titanium dioxide electrode is analyzed；
Fig. 8 is Cd prepared by embodiment 20.37Zn0.63The quantum dot sensitized titanium dioxide electrodes of Te and Cd0.37Zn0.63Te@CdS
The absorption spectrum of nuclear shell structure quantum point sensitized titanium dioxide electrode；
Fig. 9 is Cd prepared by embodiment 20.37Zn0.63Te quantum dots and Cd0.37Zn0.63Te@CdS core core-shell structure quantum dots
Fluorescence decay is analyzed；
Figure 10 is Cd prepared by embodiment 20.37Zn0.63The quantum dot sensitized titanium dioxide electrodes of Te and Cd0.37Zn0.63Te@
The fluorescence decay of CdS core core-shell structure quantum dots sensitized titanium dioxide electrode is analyzed.
Figure 11 is Cd prepared by embodiment 30.14Zn0.86The quantum dot sensitized titanium dioxide electrodes of Te and Cd0.14Zn0.86Te@
The absorption spectrum of CdS core core-shell structure quantum dots sensitized titanium dioxide electrode；
Figure 12 is Cd prepared by embodiment 30.14Zn0.86Te quantum dots and Cd0.14Zn0.86Te@CdS core core-shell structure quantum dots
Fluorescence decay analysis；
Figure 13 is Cd prepared by embodiment 30.14Zn0.86The quantum dot sensitized titanium dioxide electrodes of Te and Cd0.14Zn0.86Te@
The fluorescence decay of CdS core core-shell structure quantum dots sensitized titanium dioxide electrode is analyzed.
Specific implementation mode
With reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Embodiment 1
(1) preparation of titanium dioxide dense layer：
By silk screen print method by TiO2Slurry (P25) is uniformly layered on silk screen, and gently feeding is quickly scratched with scraper.So
The conducting surface of electro-conductive glass is placed in the underface of silk screen plate afterwards, firmly quickly scratches TiO2Slurry makes it be printed onto electro-conductive glass
On.By TiO2Film is placed in the seal box for having a small amount of ethyl alcohol, is stood 3min and is waited for TiO under alcohol vapour atmosphere2Film flows naturally
It is flat, it is transferred in baking oven, is dried at 125 DEG C.
(2) Aqueous phase prepares Cd0.64Zn0.36Te (rate of charge Cd/Zn=1/1) quantum dot：
Using sodium borohydride, tellurium powder as raw material, using deionized water as solvent, in nitrogen atmosphere, 30 DEG C of reaction 2-3h are formed
Transparent sodium hydrogen telluride solution.With CdCl2、ZnCl2For raw material, mercaptopropionic acid is stabilizer, in molar ratio CdCl2:ZnCl2:Sulfydryl
Propionic acid=1:1:4 mixing are dissolved in deionized water, and 1M sodium hydroxide solutions are slowly added dropwise while stirring, and adjust pH=6, will
Solution is transferred in 250ml three neck round bottom flask, in nitrogen atmosphere, 80 DEG C of stirring 30min.Brand-new sodium hydrogen telluride solution is fast
Speed is injected into three neck round bottom flask, and in a nitrogen atmosphere, 100 DEG C of condensing reflux reactions are for 24 hours.In clear obtained by the reaction
In solution, the isopropanol of same volume is added, centrifugation obtains Cd0.64Zn0.36Te powder samples, in the sample, Elements C d and element Zn
Practical molar ratio be 1.8:1.
(3) organic molecule assisted deposition is combined to prepare Cd with SILAR method0.64Zn0.36Te@CdS
Nuclear shell structure quantum point sensitized titanium dioxide electrode：
By TiO2Electrode is placed in 1h in the alkaline solution of mercaptopropionic acid, and the Cd of a concentration of 4mM of 2.4ml is added0.64Zn0.36Te
Quantum dot aqueous solution stands for 24 hours, is dried at 60 DEG C, be denoted as Cd0.64Zn0.36The quantum dot sensitized electrodes of Te.It is respectively configured 0.5M's
Caddy aqueous solution and sodium sulfide solution, by above-mentioned Cd0.64Zn0.36The quantum dot sensitized electrodes of Te are immersed in cadmium chloride solution
1min, taking-up are rinsed well, then are immersed in 1min in sodium sulfide solution, and taking-up is rinsed well, and cycle for several times, is denoted as
Cd0.64Zn0.36Te@CdS II-type nuclear shell structure quantum point sensitized titanium dioxide electrodes.
(a) figure is the HRTEM figures of pure titinium dioxide electrode prepared by the present embodiment step (1) in Fig. 1, and (b) figure is this reality
Apply the Cd of a step (3) preparation0.64Zn0.36Te quantum dots HRTEM figures, (c) figure is that the present embodiment is finally prepared
Cd0.64Zn0.36The HRTEM of Te@CdS II-type nuclear shell structure quantum points schemes, it can be found that nano-TiO after observation2Size be
20nm or so, and Cd0.64Zn0.36The grain size of Te quantum dots (QD) is 3.0nm or so；Cd0.64Zn0.36Te quantum dot surfaces coat
The thickness of CdS shells be 0.9nm or so.
Fig. 2 is pure titinium dioxide electrode manufactured in the present embodiment, Cd0.64Zn0.36The quantum dot sensitized titanium dioxide electrodes of Tee
With Cd0.64Zn0.36The absorption spectrum of Te@CdS II-type nuclear shell structure quantum point sensitized titanium dioxide electrodes, and provide CdTe@CdS
As a comparison with CdS quantum dot sensitized titanium dioxide electrode.
The preparation process of above-mentioned CdTe@CdS quantum dots sensitized titanium dioxide electrode is as follows：
By TiO2Electrode is placed in 1h in the alkaline solution of mercaptopropionic acid, and the CdTe quantum water of a concentration of 4mM of 2.4ml is added
Solution stands for 24 hours, is dried at 60 DEG C, is denoted as CdTe quantum sensitization electrode.The caddy aqueous solution and sulphur of 0.5M is respectively configured
Change sodium water solution, above-mentioned CdTe quantum sensitization electrode is immersed in 1min in cadmium chloride solution, taking-up is rinsed well, then is impregnated
The 1min in sodium sulfide solution, taking-up are rinsed well, and cycle for several times, is denoted as CdTe CdS core core-shell structure quantum dots sensitization titanium dioxide
Ti electrode.
The preparation process of above-mentioned CdS quantum dot sensitized titanium dioxide electrode is as follows：
By TiO2Electrode is immersed in 1min in cadmium chloride solution, and taking-up is rinsed well, then is immersed in sodium sulfide solution
1min, taking-up are rinsed well, and is denoted as CdS quantum dot sensitized titanium dioxide electrode to cycle for several times.
It can be seen that Cd0.64Zn0.36Te@CdS II-type nuclear shell structure quantum points are sensitized the light capture ability of electrode compared with CdS
Quantum dot sensitized titanium dioxide electrodes, Cd0.64Zn0.36The quantum dot sensitized titanium dioxide electrodes of Te and CdTe@CdS core shell structure amounts
There is significant improve in son point sensitized titanium dioxide electrode.
Fig. 3 is Cd manufactured in the present embodiment0.64Zn0.36Te quantum dots and Cd0.64Zn0.36Te@CdS II-type nucleocapsid amounts
The fluorescence decay analysis of son point, and provide the fluorescence decay analysis of CdTe@CdS quantum dots as a comparison, it can be seen that CdTe@
CdS quantum dot and Cd0.64Zn0.36The average life span that the light of Te quantum dots swashs carrier is respectively 10.26ns and 24.07ns.Therewith
It compares, Cd0.64Zn0.36The light of II type quantum dot of Te@CdS cores shell swashs carrier average life span and dramatically increases, and is 39.80ns.Explanation
The recombination process of quantum dot photo-generated carrier is inhibited.
Fig. 4 is Cd manufactured in the present embodiment0.64Zn0.36The quantum dot sensitized titanium dioxide electrodes of Te and Cd0.64Zn0.36Te@
The fluorescence decay of CdS II-type nuclear shell structure quantum point sensitized titanium dioxide electrodes is analyzed, and provides CdTe@CdS core shell structure amounts
The fluorescence decay analysis of son point sensitized titanium dioxide electrode is as a comparison.CdTe@CdS core core-shell structure quantum dots sensitized titanium dioxides
The fluorescence lifetime of electrode is higher, illustrates that the injection process of quantum dot light induced electron receives the inhibition of CdS barrier layers.With
Cd0.64Zn0.36The quantum dot sensitized titanium dioxide electrodes of Te are compared, Cd0.64Zn0.36II type nuclear shell structure quantum points of Te@CdS are sensitized
The fluorescence lifetime of titanium dioxide electrodes has no significant change, illustrates that the injection efficiency of quantum dot light induced electron is not affected.
Comparative example
(1) preparation of titanium dioxide dense layer：
By silk screen print method by TiO2Slurry (P25) is uniformly layered on silk screen, and gently feeding is quickly scratched with scraper.So
The conducting surface of electro-conductive glass is placed in the underface of silk screen plate afterwards, firmly quickly scratches TiO2Slurry makes it be printed onto electro-conductive glass
On.By TiO2Film is placed in the seal box for having a small amount of ethyl alcohol, is stood 3min and is waited for TiO under alcohol vapour atmosphere2Film flows naturally
It is flat, it is transferred in baking oven, is dried at 125 DEG C.
(2) Aqueous phase prepares Cd0.70Zn0.30Te (rate of charge Cd/Zn=3/1) quantum dot：
Using sodium borohydride, tellurium powder as raw material, using deionized water as solvent, in nitrogen atmosphere, 30 DEG C of reaction 2-3h are formed
Transparent sodium hydrogen telluride solution.With CdCl2、ZnCl2For raw material, mercaptopropionic acid is stabilizer, in molar ratio CdCl2:ZnCl2:Sulfydryl
Propionic acid=3:1:8 mixing are dissolved in deionized water, and 1M sodium hydroxide solutions are slowly added dropwise while stirring, and adjust pH=6, will
Solution is transferred in 250ml three neck round bottom flask, in nitrogen atmosphere, 80 DEG C of stirring 30min.Brand-new sodium hydrogen telluride solution is fast
Speed is injected into three neck round bottom flask, and in a nitrogen atmosphere, 100 DEG C of condensing reflux reactions are for 24 hours.In clear obtained by the reaction
In solution, the isopropanol of same volume is added, centrifugation obtains Cd0.70Zn0.30Te powder samples, in the sample, Elements C d and element Zn
Practical molar ratio be 2.3:1.
(3) organic molecule assisted deposition is combined to prepare Cd with SILAR method0.70Zn0.30Te@CdS
Nuclear shell structure quantum point sensitized titanium dioxide electrode：
By TiO2Electrode is placed in 1h in the alkaline solution of mercaptopropionic acid, and the Cd of a concentration of 4mM of 2.4ml is added0.70Zn0.30Te
Quantum dot aqueous solution stands for 24 hours, is dried at 60 DEG C, be denoted as Cd0.70Zn0.30The quantum dot sensitized electrodes of Te.It is respectively configured 0.5M's
Caddy aqueous solution and sodium sulfide solution, by above-mentioned Cd0.70Zn0.30The quantum dot sensitized electrodes of Te are immersed in cadmium chloride solution
1min, taking-up are rinsed well, then are immersed in 1min in sodium sulfide solution, and taking-up is rinsed well, and cycle for several times, is denoted as
Cd0.70Zn0.30Te@CdS core core-shell structure quantum dots sensitized titanium dioxide electrodes.
Fig. 5 is pure titinium dioxide electrode prepared by this comparative example, Cd0.70Zn0.30The quantum dot sensitized titanium dioxide electrodes of Te with
Cd0.70Zn0.30The absorption spectrum of Te@CdS core core-shell structure quantum dots sensitized titanium dioxide electrodes.
It can be seen that with Cd0.70Zn0.30The quantum dot sensitized titanium dioxide electrodes of Te are compared, Cd0.70Zn0.30Te@CdS core shells
Apparent Red Shift Phenomena does not occur for the absorption spectrum of structure quantum point sensitization electrode, shows Cd0.70Zn0.30The energy level knot of Te@CdS
Structure is I-type.
Fig. 6 is Cd prepared by this comparative example0.70Zn0.30Te quantum dots and Cd0.70Zn0.30Te@CdS core core-shell structure quantum dots
Fluorescence decay analysis, it can be seen that it is close that the two light swashs carrier average life span, with Cd0.70Zn0.30Te@CdS core shell structures
The level structure of quantum dot is that I-type is consistent.
Fig. 7 is Cd prepared by this comparative example0.70Zn0.30The quantum dot sensitized titanium dioxide electrodes of Te and Cd0.70Zn0.30Te@
The fluorescence decay of CdS core core-shell structure quantum dots sensitized titanium dioxide electrode is analyzed.With Cd0.70Zn0.30The quantum dot sensitized titanium dioxides of Te
Ti electrode is compared, Cd0.70Zn0.30The fluorescence lifetime of Te@CdS core core-shell structure quantum dots sensitized titanium dioxide electrodes has no apparent change
Change, shows Cd0.70Zn0.30Te is close with the conduction level of CdS.
Embodiment 2
(1) preparation of titanium dioxide dense layer：
By silk screen print method by TiO2Slurry (P25) is uniformly layered on silk screen, and gently feeding is quickly scratched with scraper.So
The conducting surface of electro-conductive glass is placed in the underface of silk screen plate afterwards, firmly quickly scratches TiO2Slurry makes it be printed onto electro-conductive glass
On.By TiO2Film is placed in the seal box for having a small amount of ethyl alcohol, is stood 3min and is waited for TiO under alcohol vapour atmosphere2Film flows naturally
It is flat, it is transferred in baking oven, is dried at 125 DEG C.
(2) Aqueous phase prepares Cd0.37Zn0.63Te (rate of charge Cd/Zn=1/3) quantum dot：
Using sodium borohydride, tellurium powder as raw material, using deionized water as solvent, in nitrogen atmosphere, 30 DEG C of reaction 2-3h are formed
Transparent sodium hydrogen telluride solution.With CdCl2、ZnCl2For raw material, mercaptopropionic acid is stabilizer, in molar ratio CdCl2:ZnCl2:Sulfydryl
Propionic acid=1:3:8 mixing are dissolved in deionized water, and 1M sodium hydroxide solutions are slowly added dropwise while stirring, and adjust pH=6, will
Solution is transferred in 250ml three neck round bottom flask, in nitrogen atmosphere, 80 DEG C of stirring 30min.Brand-new sodium hydrogen telluride solution is fast
Speed is injected into three neck round bottom flask, and in a nitrogen atmosphere, 100 DEG C of condensing reflux reactions are for 24 hours.In clear obtained by the reaction
In solution, the isopropanol of same volume is added, centrifugation obtains Cd0.37Zn0.63Te powder samples, in the sample, Elements C d and element Zn
Practical molar ratio be 1:1.7.
(3) organic molecule assisted deposition is combined to prepare Cd with SILAR method0.37Zn0.63Te@CdS
Nuclear shell structure quantum point sensitized titanium dioxide electrode：
By TiO2Electrode is placed in 1h in the alkaline solution of mercaptopropionic acid, and the Cd of a concentration of 4mM of 2.4ml is added0.37Zn0.63Te
Quantum dot aqueous solution stands for 24 hours, is dried at 60 DEG C, be denoted as Cd0.37Zn0.63The quantum dot sensitized electrodes of Te.It is respectively configured 0.5M's
Caddy aqueous solution and sodium sulfide solution, by above-mentioned Cd0.37Zn0.63The quantum dot sensitized electrodes of Te are immersed in cadmium chloride solution
1min, taking-up are rinsed well, then are immersed in 1min in sodium sulfide solution, and taking-up is rinsed well, and cycle for several times, is denoted as
Cd0.37Zn0.63Te@CdS core core-shell structure quantum dots sensitized titanium dioxide electrodes.
Fig. 8 is pure titinium dioxide electrode manufactured in the present embodiment, Cd0.37Zn0.63The quantum dot sensitized titanium dioxide electrodes of Te with
Cd0.37Zn0.63The absorption spectrum of Te@CdS core core-shell structure quantum dots sensitized titanium dioxide electrodes.
It can be seen that with Cd0.37Zn0.63The quantum dot sensitized titanium dioxide electrodes of Te are compared, Cd0.37Zn0.63Te@CdS core shells
Apparent Red Shift Phenomena occurs for the absorption spectrum that structure quantum point is sensitized electrode, shows Cd0.37Zn0.63The level structure of Te@CdS is
II-type.
Fig. 9 is Cd manufactured in the present embodiment0.37Zn0.63Te quantum dots and Cd0.37Zn0.63Te@CdS core core-shell structure quantum dots
Fluorescence decay analysis, it can be seen that Cd0.37Zn0.63The light of Te@CdS core core-shell structure quantum dots swashs carrier average life span substantially
Increase, with Cd0.37Zn0.63The level structure of Te@CdS core core-shell structure quantum dots is that II-type is consistent.
Figure 10 is Cd manufactured in the present embodiment0.37Zn0.63The quantum dot sensitized titanium dioxide electrodes of Te and Cd0.37Zn0.63Te@
The fluorescence decay of CdS core core-shell structure quantum dots sensitized titanium dioxide electrode is analyzed.With Cd0.37Zn0.63The quantum dot sensitized titanium dioxides of Te
Ti electrode is compared, Cd0.37Zn0.63The fluorescence lifetime of Te@CdS core core-shell structure quantum dots sensitized titanium dioxide electrodes is increased slightly.Table
The bright separation with photo-generated carrier, there are inhibiting effect for the further transmission of the accumulation in stratum nucleare hole to electronics.
Embodiment 3
(1) preparation of titanium dioxide dense layer：
By silk screen print method by TiO2Slurry (P25) is uniformly layered on silk screen, and gently feeding is quickly scratched with scraper.So
The conducting surface of electro-conductive glass is placed in the underface of silk screen plate afterwards, firmly quickly scratches TiO2Slurry makes it be printed onto electro-conductive glass
On.By TiO2Film is placed in the seal box for having a small amount of ethyl alcohol, is stood 3min and is waited for TiO under alcohol vapour atmosphere2Film flows naturally
It is flat, it is transferred in baking oven, is dried at 125 DEG C.
(2) Aqueous phase prepares Cd0.14Zn0.86Te (rate of charge Cd/Zn=1/7) quantum dot：
Using sodium borohydride, tellurium powder as raw material, using deionized water as solvent, in nitrogen atmosphere, 30 DEG C of reaction 2-3h are formed
Transparent sodium hydrogen telluride solution.With CdCl2、ZnCl2For raw material, mercaptopropionic acid is stabilizer, in molar ratio CdCl2:ZnCl2:Sulfydryl
Propionic acid=1:7:16 mixing are dissolved in deionized water, and 1M sodium hydroxide solutions are slowly added dropwise while stirring, and adjust pH=6,
Solution is transferred in 250ml three neck round bottom flask, in nitrogen atmosphere, 80 DEG C of stirring 30min.By brand-new sodium hydrogen telluride solution
It is rapidly injected in three neck round bottom flask, in a nitrogen atmosphere, 100 DEG C of condensing reflux reactions are for 24 hours.It is saturating in clarification obtained by the reaction
In bright solution, the isopropanol of same volume is added, centrifugation obtains Cd0.14Zn0.86Te powder samples, in the sample, Elements C d and element
The practical molar ratio of Zn is 1:6.4.
(3) organic molecule assisted deposition is combined to prepare Cd with SILAR method0.14Zn0.86Te@CdS
Nuclear shell structure quantum point sensitized titanium dioxide electrode：
By TiO2Electrode is placed in 1h in the alkaline solution of mercaptopropionic acid, and the Cd of a concentration of 4mM of 2.4ml is added0.14Zn0.86Te
Quantum dot aqueous solution stands for 24 hours, is dried at 60 DEG C, be denoted as Cd0.14Zn0.86The quantum dot sensitized electrodes of Te.It is respectively configured 0.5M's
Caddy aqueous solution and sodium sulfide solution, by above-mentioned Cd0.14Zn0.86The quantum dot sensitized electrodes of Te are immersed in cadmium chloride solution
1min, taking-up are rinsed well, then are immersed in 1min in sodium sulfide solution, and taking-up is rinsed well, and cycle for several times, is denoted as
Cd0.14Zn0.86Te@CdS core core-shell structure quantum dots sensitized titanium dioxide electrodes.
Fig. 8 is pure titinium dioxide electrode manufactured in the present embodiment, Cd0.14Zn0.86The quantum dot sensitized titanium dioxide electrodes of Te with
Cd0.14Zn0.86The absorption spectrum of Te@CdS core core-shell structure quantum dots sensitized titanium dioxide electrodes.
It can be seen that with Cd0.14Zn0.86The quantum dot sensitized titanium dioxide electrodes of Te are compared, Cd0.14Zn0.86Te@CdS core shells
Apparent Red Shift Phenomena occurs for the absorption spectrum that structure quantum point is sensitized electrode, shows Cd0.88Zn0.12The level structure of Te@CdS is
II-type.
Fig. 9 is Cd manufactured in the present embodiment0.14Zn0.86Te quantum dots and Cd0.14Zn0.86Te@CdS core core-shell structure quantum dots
Fluorescence decay analysis, it can be seen that Cd0.14Zn0.86The light of Te@CdS core core-shell structure quantum dots swashs carrier average life span substantially
Increase, with Cd0.14Zn0.86The level structure of Te@CdS core core-shell structure quantum dots is that II-type is consistent.
Figure 10 is Cd manufactured in the present embodiment0.14Zn0.86The quantum dot sensitized titanium dioxide electrodes of Te and Cd0.14Zn0.86Te@
The fluorescence decay of CdS core core-shell structure quantum dots sensitized titanium dioxide electrode is analyzed.With Cd0.14Zn0.86The quantum dot sensitized titanium dioxides of Te
Ti electrode is compared, Cd0.14Zn0.86The fluorescence lifetime of Te@CdS core core-shell structure quantum dots sensitized titanium dioxide electrodes is increased slightly, table
The bright separation with photo-generated carrier, there are inhibiting effect for the further transmission of the accumulation in stratum nucleare hole to electronics.
By comparative example 1~3 it can be found that when Cd/Zn molar ratios are less than 1.8, with the increase of Zn contents, one
Aspect, CdyZn1-yThe energy gap of Te quantum dots broadens so that and the light capture ability of quantum dot declines, on the other hand, CdyZn1- yThe valence-band level of Te quantum dots also improves therewith so that the potential barrier of hole transport improves, hole by sunken domain in stratum nucleare, with
The separation of photo-generated carrier, hole is accumulated in stratum nucleare, is unfavorable for the further transmission of light induced electron.
Claims (10)
1. one kind II-type nuclear shell structure quantum point, including shell and stratum nucleare, which is characterized in that group becomes CdZnTe CdS, described
The molar ratio of Elements C d and element Zn is 0.15~1.8：1.
2. II-type nuclear shell structure quantum point according to claim 1, which is characterized in that the Elements C d and element Zn's
Molar ratio is 0.5~1.8：1.
3. II-type nuclear shell structure quantum point according to claim 1, which is characterized in that the grain size of stratum nucleare CdZnTe be 2~
The thickness of 4nm, shell CdS are 0.5~1nm.
4. a kind of preparation method of II-type nuclear shell structure quantum point according to claims 1 to 3 any claim,
It is characterized in that, including：
(1) Aqueous phase is used to prepare the more first quantum dots of CdZnTe；
(2) CdS shells are coated in the more first quantum dot surfaces of the CdZnTe by successive ionic layer adsorption and reaction method.
5. a kind of quantum dot sensitized optoelectronic pole, including wide-band gap semiconductor thin film and deposition on the membrane quantum dot sensitized
Agent, which is characterized in that using the II-type nuclear shell structure quantum point as described in claims 1 to 3 any claim as quantum
Point sensitizer.
6. a kind of preparation method of quantum dot sensitized optoelectronic pole according to claim 5, which is characterized in that including：
Step 1: wide-band gap semiconductor thin film is prepared on transparent conductive substrate surface, then using bridging agent to the broad-band gap half
Conductor thin film is handled；
Step 2: preparing the more first quantum dots of CdZnTe using Aqueous phase, then use chemical baths by the more first quantum of the CdZnTe
Point is anchored on step 1 treated wide-band gap semiconductor thin film surface；
Step 3: coating CdS shells, system in the more first quantum dot surfaces of the CdZnTe by successive ionic layer adsorption and reaction method
It is standby to obtain quantum dot sensitized optoelectronic pole.
7. the preparation method of quantum dot sensitized optoelectronic pole according to claim 6, which is characterized in that described in step 1
Wide-band gap semiconductor thin film is selected from titanium deoxid film, zinc-oxide film, tin dioxide thin film and/or WO 3 film.
8. the preparation method of quantum dot sensitized optoelectronic pole according to claim 6, which is characterized in that described in step 1
Bridging agent is difunctional organic molecule.
9. the preparation method of quantum dot sensitized optoelectronic pole according to claim 8, which is characterized in that the difunctional has
Machine small molecule is selected from least one of thioacetic acid, mercaptopropionic acid, L-cysteine.
10. a kind of quantum dot sensitized solar cell, which is characterized in that including quantum dot sensitized light as claimed in claim 5
Electrode.
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