CN106548873B - A kind of quantum dot sensitized nano-TiOs of ZnSe2The preparation method of film - Google Patents
A kind of quantum dot sensitized nano-TiOs of ZnSe2The preparation method of film Download PDFInfo
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- CN106548873B CN106548873B CN201610916642.5A CN201610916642A CN106548873B CN 106548873 B CN106548873 B CN 106548873B CN 201610916642 A CN201610916642 A CN 201610916642A CN 106548873 B CN106548873 B CN 106548873B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
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- Y02E10/542—Dye sensitized solar cells
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Abstract
A kind of quantum dot sensitized nano-TiOs of ZnSe2The preparation method of film, it mainly includes the following steps：(1) by TiO2Slurry drips to conductive glass surface, scratches one layer of TiO2Pulp layer, 500 DEG C of calcining 0.5h, the 1st coating is obtained after cooling after drying；Continue to prepare the 2nd, 3 or 4 layer as stated above, one or more layers TiO is made2Film；(2) deionized water is added sodium borohydride and selenium powder, and magnetic agitation under nitrogen obtains Se precursor solutions；(3) ligand L Cys and zinc acetate is added in deionized water, adjusts PH to 11 with NaOH solution, obtains Zn precursor solutions；(4) by volume 1:1 mixes Se precursor liquids and Zn precursor liquids, by TiO2Film tilts about 30 ° and is dipped in mixed liquor, is taken out after being protected from light in 25 80 DEG C and stand 1.5 7h, is rinsed with deionized water, dry to be placed in vacuum drying chamber and dry, the quantum dot sensitized TiO of ZnSe are made2Film.Reaction condition of the present invention is mild, low for equipment requirements, energy loss is small, more environmentally protective.
Description
Technical field
The invention belongs to solar battery photoanode field of material technology, more particularly to a kind of semiconductor-quantum-point is sensitized TiO2
The preparation method of film.
Background technology
In recent years, quantum dot sensitized light anode technology is a new generation after traditional silicon wafer and dye-sensitized solar cells
Solar cell technology of preparing.The theoretical light photoelectric transformation efficiency of quantum dot solar cell reaches as high as 66%, is far above traditional silicon
Brilliant and dye-sensitized solar cells transfer limits.Currently, the conversion ratio of the quantum dot sensitized solar cell of practical study is managed away from it
There is larger gap by transformation efficiency.According to the literature, research mostly uses the quantum dots such as CdTe, CdS or CdSe as light at present
Quick dose, using TiO2The thin-film material of nanometer rods or nano-tube array as light anode substrate；Wherein most contain Cd or its
His heavy metal element, be easy to cause environmental pollution.The preparation method of quantum dot sensitized light anode mainly include direct absorption method and
Two kinds of chemical bath deposition method.Later approach there is currently main problem include：Quantum dot deposition and optical property have
Effect regulation and control and the raising of actual light photoelectric transformation efficiency.
Invention content
That the purpose of the present invention is to provide a kind of reaction conditions is mild, low for equipment requirements, energy loss is small, more green
Environmental protection, the quantum dot sensitized nano-TiOs of ZnSe with high light photoelectric transformation efficiency2The preparation method of film.
The preparation method of the present invention is as follows：
(1)TiO2The making of film
TiO is prepared using knife coating23-4 drops TiO is added dropwise with dropper in film2Slurry is fast with blade to conductive glass surface
Speed blade coating, it is 2 μm of uniform TiO to obtain a layer thickness2Pulp layer；After drying, the TiO coated will be scraped2It is dry that film is placed in vacuum
This film, is then heat-treated, to improve TiO by 60 DEG C of drying 2h in Muffle furnace in dry case2Between film and FTO substrates
Binding force, 500 DEG C calcining 0.5h, taken out after being cooled to room temperature, thus obtain the 1st coating；Exist by above-mentioned same method
Continue to prepare the 2nd, the 3rd or the 4th layer of TiO on the basis of a upper coating2Film, one or more layers finally obtained TiO2Film；
(2) preparation of Se precursor solutions
The ratio of 0.145g sodium borohydrides and 0.099g selenium powders, i.e. sodium borohydride and selenium are added in every 10 ml deionized water
The molar ratio of powder is 3:1, deionized water is added to the container, N is led to215min removes oxygen, sodium borohydride is then added
(NaBH4), it is added selenium powder until completely dissolved, magnetic agitation under nitrogen, reaction is completely disappeared to black selenium powder, and there is no bubbles
Until generation, the Se precursor solutions of water white transparency are obtained at this time, solution are sealed spare；
(3) preparation of Zn precursor solutions
The ratio of 0.06g ligand L-Cys and 0.073g zinc acetates, i.e. ligand L-Cys are added in every 10 ml deionized water
Molar ratio with zinc acetate is 3:2, it is added ligand L-Cys and zinc acetate into deionized water successively, it is anti-under the conditions of magnetic agitation
0.5h is answered, PH to 11 is adjusted with the NaOH solution of 2mol//L, which is transferred in four-hole boiling flask and leads to nitrogen about 30min, is removed
Remove O2To get to Zn precursor solutions；
(4) preparation of quantum dot sensitized film
By volume 1:Se precursor liquids made from step (2) and step (3) and Zn precursor liquids are mixed, will be walked by 1 ratio
Suddenly the TiO that prepared by (1)2Film tilts about 30 ° and is dipped in above-mentioned mixed liquor, and it is quiet to be protected from light condition in 25-80 DEG C (80 DEG C of embodiment)
It takes out after setting 1.5-7h, is rinsed with deionized water, to wash away the excess ions for being attached to film surface；After being dried in air,
60 DEG C of drying 2h are placed in vacuum drying chamber to get to the quantum dot sensitized TiO of ZnSe2Film.
The present invention has following advantage compared with prior art：
(1) it uses and prepares ZnSe quantum dots under normal temperature condition as sensitizer, reaction condition is mild, to equipment requirement
It is low, energy loss is reduced, it is more environmentally protective.
(2) the quantum dot sensitized TiO of ZnSe prepared under different condition2Film has stable state and the transient state surface of different characteristics
Photovoltaic property has regulatable photoelectronic property.
(3) TiO after being sensitized2Film surface photovoltaic response range increases to 300-800nm by original 300-380nm, i.e.,
Photovoltaic response range increases 420nm.
(4) TiO after being sensitized2The film transient state photovoltaic response maximum value corresponding time is by original 4.9x10-7S is extended to
1.9x10-4s。
Description of the drawings
Fig. 1 is TiO prepared by the embodiment of the present invention 12The steady state surface photovoltage spectrogram of film and powder.
Fig. 2 is TiO prepared by the embodiment of the present invention 12The transient state photocurrent spectrogram of film.
Fig. 3 is the quantum dot sensitized nano-TiOs of ZnSe prepared by the embodiment of the present invention 12Film：(a) surface photovoltage spectrogram；
(b) transient state photocurrent spectrogram.
Fig. 4 is the quantum dot sensitized nano-TiOs of ZnSe prepared by the embodiment of the present invention 22Film：(a) surface photovoltage spectrogram；
(b) transient state photocurrent spectrogram.
Fig. 5 is the quantum dot sensitized nano-TiOs of ZnSe prepared by the embodiment of the present invention 32Film：(a) surface photovoltage spectrogram；
(b) transient state photocurrent spectrogram.
Fig. 6 is the quantum dot sensitized nano-TiOs of ZnSe prepared by the embodiment of the present invention 42Film：(a) surface photovoltage spectrogram；
(b) transient state photocurrent spectrogram.
Fig. 7 is the quantum dot sensitized nano-TiOs of ZnSe prepared by the embodiment of the present invention 52Film：(a) surface photovoltage spectrogram；
(b) transient state photocurrent spectrogram.
Fig. 8 is the quantum dot sensitized nano-TiOs of ZnSe prepared by the embodiment of the present invention 62Film：(a) surface photovoltage spectrogram；
(b) transient state photocurrent spectrogram.
Fig. 9 is the quantum dot sensitized nano-TiOs of ZnSe prepared by the embodiment of the present invention 72Film：(a) surface photovoltage spectrogram；
(b) transient state photocurrent spectrogram.
Figure 10 is the quantum dot sensitized nano-TiOs of ZnSe prepared by the embodiment of the present invention 82Film：(a) surface photovoltaic spectroscopy
Figure；(b) transient state photocurrent spectrogram.
Figure 11 is the quantum dot sensitized nano-TiOs of ZnSe prepared by real embodiment 9 of the invention2Film：(a) surface photovoltaic spectroscopy
Figure；(b) transient state photocurrent spectrogram.
Figure 12 is the quantum dot sensitized nano-TiOs of ZnSe prepared by the embodiment of the present invention 102Film：(a) surface photovoltaic spectroscopy
Figure；(b) transient state photocurrent spectrogram.
Specific implementation mode：
Embodiment 1
(1)TiO2The making of film
3 drop TiO are added dropwise with disposable dropper2Slurry is in scratch area, using blade in the electro-conductive glass that slurry has been added dropwise
Surface is scratched rapidly, and the uniform TiO that a layer thickness is 2 μm is obtained2Pulp layer will scrape the TiO coated after drying2Film
60 DEG C of drying 2h in vacuum drying chamber are placed in, are then heat-treated this film in Muffle furnace, 0.5h are calcined through 500 DEG C,
It is taken out after being cooled to room temperature, the TiO of 1 coating is made2Film；
(2) preparation of Se precursor solutions
It takes 20ml deionized waters to be added in conical flask, leads to N2About 15min, the oxygen in removing system.0.29g is then added
Sodium borohydride (NaBH4), 0.198g selenium powders are added until completely dissolved, magnetic agitation under nitrogen, reaction is complete to black selenium powder
It disappears, until being generated there is no bubble, obtains the Se precursor solutions of water white transparency at this time, solution is sealed spare；
(3) preparation of Zn precursor solutions
It takes 75ml deionized waters in beaker, under magnetic agitation, sequentially adds 0.45g ligand L-Cys and 0.55g acetic acid
Zinc reacts 0.5h under the conditions of magnetic agitation, adjusts PH to 11 with the NaOH solution of 2mol//L, which is transferred to four mouthfuls of burnings
Lead to nitrogen about 30min in bottle, removes O2To get to Zn precursor solutions；
(4) preparation of quantum dot sensitized film
Take volume ratio 1:1 Se precursor liquids and Zn precursor liquids is mixed in culture dish, the TiO that will be prepared2Film tilts
About 30 ° are dipped in the above mixed liquor, after 25 DEG C are protected from light condition standing 1.5h, take out and are rinsed with a large amount of deionized waters, removal is attached
The excess ions in film surface, after being dried in air, are placed in vacuum drying chamber 60 DEG C of drying 2h to get to ZnSe amounts
Son point sensitization TiO2Film.
As shown in Figure 1, the TiO made2Film and TiO2The same surface photovoltaic spectroscopy of powder is in 300-400 nano wave lengths
With stronger positive surface photovoltage response in range；
As shown in Fig. 2, the TiO made2It is 4.9 × 10 that the positive transient state photocurrent of film, which composes positive photovoltaic response from the time,-7s
The recombination velocity for starting photo-generated carrier is more than its formation speed.
As shown in Fig. 3 (a), quantum dot sensitized (after 25 DEG C the are protected from light condition standing 1.5h) TiO of ZnSe2The table of film (single layer)
There is negative surface photovoltage response in 380-550 nanometer ranges in face photovoltaic spectrum, occurs in 550-750 nanometer ranges relatively strong
Positive surface photovoltage response.As shown in Fig. 3 (b), quantum dot sensitized (after 25 DEG C the are protected from light condition standing 1.5h) TiO of ZnSe2It is thin
The positive transient state photovoltaic response of film (single layer) is in 4.4x10-6The recombination velocity that s starts photo-generated carrier is much larger than its formation speed.
Embodiment 2
(1)TiO2The making of film
3 drop TiO are added dropwise with disposable dropper2Slurry is in scratch area, using blade in the electro-conductive glass that slurry has been added dropwise
Surface is scratched rapidly, and the uniform TiO that a layer thickness is 2 μm is obtained2Pulp layer will scrape the TiO coated after drying2Film
60 DEG C of drying 2h in vacuum drying chamber are placed in, are then heat-treated this film in Muffle furnace, 0.5h are calcined through 500 DEG C,
It is taken out after being cooled to room temperature, thus obtains the 1st coating；Continue preparation on the basis of a upper coating by above-mentioned same method
2 layers of TiO2The TiO of 2 coatings is made in film2Film；
(2) preparation of Se precursor solutions
It takes 20ml deionized waters to be added in conical flask, leads to N2About 15min, the oxygen in removing system.0.29g is then added
Sodium borohydride (NaBH4), 0.198g selenium powders are added until completely dissolved, magnetic agitation under nitrogen, reaction is complete to black selenium powder
It disappears, until being generated there is no bubble, obtains the Se precursor solutions of water white transparency at this time, solution is sealed spare；
(3) preparation of Zn precursor solutions
It takes 75ml deionized waters in beaker, under magnetic agitation, sequentially adds 0.45g ligand L-Cys and 0.55g acetic acid
Zinc reacts 0.5h under the conditions of magnetic agitation, adjusts PH to 11 with the NaOH solution of 2mol//L, which is transferred to four mouthfuls of burnings
Lead to nitrogen about 30min in bottle, removes O2To get to Zn precursor solutions；
(4) preparation of quantum dot sensitized film
Take volume ratio 1:1 Se precursor liquids and Zn precursor liquids is mixed in culture dish, the TiO that will be prepared2Film tilts
About 30 ° are dipped in the above mixed liquor, after 25 DEG C are protected from light condition standing 1.5h, take out and are rinsed with a large amount of deionized waters, removal is attached
The excess ions in film surface, after being dried in air, are placed in vacuum drying chamber 60 DEG C of drying 2h to get to ZnSe amounts
Son point sensitization TiO2Film.
As shown in Fig. 4 (a), quantum dot sensitized (after 25 DEG C the are protected from light condition standing 1.5h) TiO of ZnSe2The table of film (bilayer)
There is negative surface photovoltage response in 375-575 nanometer ranges in face photovoltaic spectrum, occurs in 575-750 nanometer ranges relatively strong
Positive surface photovoltage response.As shown in Fig. 3 (b), quantum dot sensitized (after 25 DEG C the are protected from light condition standing 1.5h) TiO of ZnSe2It is thin
The positive transient state photovoltaic response of film (bilayer) is from 7.6x10-5The recombination velocity that s starts photo-generated carrier is more than its formation speed.
Embodiment 3
(1)TiO2The making of film
3 drop TiO are added dropwise with disposable dropper2Slurry is in scratch area, using blade in the electro-conductive glass that slurry has been added dropwise
Surface is scratched rapidly, and the uniform TiO that a layer thickness is 2 μm is obtained2Pulp layer will scrape the TiO coated after drying2Film
60 DEG C of drying 2h in vacuum drying chamber are placed in, are then heat-treated this film in Muffle furnace, 0.5h are calcined through 500 DEG C,
It is taken out after being cooled to room temperature, thus obtains the 1st coating；It is prepared by above-mentioned same method and continues to make on the basis of first coating
Standby 2nd and 3 layer of TiO2The TiO of 3 coatings is made in film2Film；
(2) preparation of Se precursor solutions
It takes 20ml deionized waters to be added in conical flask, leads to N2About 15min, the oxygen in removing system.0.29g is then added
Sodium borohydride (NaBH4), 0.198g selenium powders are added until completely dissolved, magnetic agitation under nitrogen, reaction is complete to black selenium powder
It disappears, until being generated there is no bubble, obtains the Se precursor solutions of water white transparency at this time, solution is sealed spare；
(3) preparation of Zn precursor solutions
It takes 75ml deionized waters in beaker, under magnetic agitation, sequentially adds 0.45g ligand L-Cys and 0.55g acetic acid
Zinc reacts 0.5h under the conditions of magnetic agitation, adjusts PH to 11 with the NaOH solution of 2mol//L, which is transferred to four mouthfuls of burnings
Lead to nitrogen about 30min in bottle, removes O2To get to Zn precursor solutions；
(4) preparation of quantum dot sensitized film
Take volume ratio 1:1 Se precursor liquids and Zn precursor liquids is mixed in culture dish, the TiO that will be prepared2Film tilts
About 30 ° are dipped in the above mixed liquor, after 25 DEG C are protected from light condition standing 1.5h, take out and are rinsed with a large amount of deionized waters, removal is attached
The excess ions in film surface, after being dried in air, are placed in vacuum drying chamber 60 DEG C of drying 2h to get to ZnSe amounts
Son point sensitization TiO2Film.
As shown in Fig. 5 (a), quantum dot sensitized (after 25 DEG C the are protected from light condition standing 1.5h) TiO of ZnSe2The table of film (three layers)
There is negative surface photovoltage response in 371-575 nanometer ranges in face photovoltaic spectrum, occurs in 575-780 nanometer ranges relatively strong
Positive surface photovoltage response.As shown in Fig. 5 (b), quantum dot sensitized (after 25 DEG C the are protected from light condition standing 1.5h) TiO of ZnSe2It is thin
The positive transient state photovoltaic response of film (three layers) is from 3.1x10-5The recombination velocity that s starts photo-generated carrier is more than its formation speed.
Embodiment 4
(1)TiO2The making of film
4 drop TiO are added dropwise with disposable dropper2Slurry is in scratch area, using blade in the electro-conductive glass that slurry has been added dropwise
Surface is scratched rapidly, and the uniform TiO that a layer thickness is 2 μm is obtained2Pulp layer will scrape the TiO coated after drying2Film
60 DEG C of drying 2h in vacuum drying chamber are placed in, are then heat-treated this film in Muffle furnace, 0.5h are calcined through 500 DEG C,
Taken out after being cooled to room temperature, thus obtain 1 coating, by above-mentioned same method continue on the basis of first coating prepare the 2nd,
3 and 4 layers of TiO2The TiO of 4 coatings is finally made in film2Film.
(2) preparation of Se precursor solutions
It takes 20ml deionized waters to be added in conical flask, leads to N2About 15min, the oxygen in removing system.0.29g is then added
Sodium borohydride (NaBH4), 0.198g selenium powders are added until completely dissolved, magnetic agitation under nitrogen, reaction is complete to black selenium powder
It disappears, until being generated there is no bubble, obtains the Se precursor solutions of water white transparency at this time, solution is sealed spare；
(3) preparation of Zn precursor solutions
It takes 75ml deionized waters in beaker, under magnetic agitation, sequentially adds 0.45g ligand L-Cys and 0.55g acetic acid
Zinc reacts 0.5h under the conditions of magnetic agitation, adjusts PH to 11 with the NaOH solution of 2mol//L, which is transferred to four mouthfuls of burnings
Lead to nitrogen about 30min in bottle, removes O2To get to Zn precursor solutions；
(4) preparation of quantum dot sensitized film
Take volume ratio 1:1 Se precursor liquids and Zn precursor liquids is mixed in culture dish, the TiO that will be prepared2Film tilts
About 30 ° are dipped in the above mixed liquor, after 25 DEG C are protected from light condition standing 1.5h, take out and are rinsed with a large amount of deionized waters, removal is attached
The excess ions in film surface, after being dried in air, are placed in vacuum drying chamber 60 DEG C of drying 2h to get to ZnSe amounts
Son point sensitization TiO2Film.
As shown in Fig. 6 (a), quantum dot sensitized (after 25 DEG C the are protected from light condition standing 1.5h) TiO of ZnSe2The table of film (four layers)
There is positive surface photovoltage response in 400-500 nanometer ranges in face photovoltaic spectrum, occurs in 500-700 nanometer ranges relatively strong
Negative surface photovoltage response.As shown in Fig. 6 (b), quantum dot sensitized (after 25 DEG C the are protected from light condition standing 1.5h) TiO of ZnSe2It is thin
The positive transient state photovoltaic response of film (four layers) is from 3.02x10-7The recombination velocity that s starts photo-generated carrier is more than its formation speed.
Embodiment 5
(1)TiO2The making of film
4 drop TiO are added dropwise with disposable dropper2Slurry is in scratch area, using blade in the electro-conductive glass that slurry has been added dropwise
Surface is scratched rapidly, and the uniform TiO that a layer thickness is 2 μm is obtained2Pulp layer will scrape the TiO coated after drying2Film
60 DEG C of drying 2h in vacuum drying chamber are placed in, are then heat-treated this film in Muffle furnace, 0.5h are calcined through 500 DEG C,
It is taken out after being cooled to room temperature, thus obtains the 1st coating, continue preparation on the basis of first coating by above-mentioned same method
2,3 layers of TiO2The TiO of 3 coatings is finally made in film2Film.
(2) preparation of Se precursor solutions
It takes 20ml deionized waters to be added in conical flask, leads to N2About 15min, the oxygen in removing system.0.29g is then added
Sodium borohydride (NaBH4), 0.198g selenium powders are added until completely dissolved, magnetic agitation under nitrogen, reaction is complete to black selenium powder
It disappears, until being generated there is no bubble, obtains the Se precursor solutions of water white transparency at this time, solution is sealed spare.
(3) preparation of Zn precursor solutions
It takes 75ml deionized waters in beaker, under magnetic agitation, sequentially adds 0.45g ligand L-Cys and 0.55g acetic acid
Zinc reacts 0.5h under the conditions of magnetic agitation, adjusts PH to 11 with the NaOH solution of 2mol//L, which is transferred to four mouthfuls of burnings
Lead to nitrogen about 30min in bottle, removes O2To get to Zn precursor solutions；
(4) preparation of quantum dot sensitized film
Take volume ratio 1:1 Se precursor liquids and Zn precursor liquids is mixed in culture dish, the TiO that will be prepared2Film tilts
About 30 ° are dipped in the above mixed liquor, after 40 DEG C are protected from light condition standing 1.5h, take out and are rinsed with a large amount of deionized waters, removal is attached
The excess ions in film surface, after being dried in air, are placed in vacuum drying chamber 60 DEG C of drying 2h to get to ZnSe amounts
Son point sensitization TiO2Film.
As shown in Fig. 7 (a), quantum dot sensitized (after 40 DEG C the are protected from light condition standing 1.5h) TiO of ZnSe2The table of film (three layers)
There is strong negative surface photovoltage response in 355-555 nanometer ranges in face photovoltaic spectrum, occurs in 555-700 nanometer ranges
Stronger positive surface photovoltage response.As shown in Fig. 7 (b), ZnSe quantum dot sensitized (after 40 DEG C are protected from light condition standing 1.5h)
TiO2The positive transient state photovoltaic response of film (three layers) is from 2.4x10-5The recombination velocity that s starts photo-generated carrier is more than its generation speed
Degree.
Embodiment 6
(1)TiO2The making of film
4 drop TiO are added dropwise with disposable dropper2Slurry is in scratch area, using blade in the electro-conductive glass that slurry has been added dropwise
Surface is scratched rapidly, and the uniform TiO that a layer thickness is 2 μm is obtained2Pulp layer will scrape the TiO coated after drying2Film
60 DEG C of drying 2h in vacuum drying chamber are placed in, are then heat-treated this film in Muffle furnace, 0.5h are calcined through 500 DEG C,
It is taken out after being cooled to room temperature, thus obtains the 1st coating, continue preparation on the basis of first coating by above-mentioned same method
2,3 layers of TiO2The TiO of 3 coatings is finally made in film2Film；
(2) preparation of Se precursor solutions
It takes 20ml deionized waters to be added in conical flask, leads to N2About 15min, the oxygen in removing system.0.29g is then added
Sodium borohydride (NaBH4), 0.197g selenium powders are added until completely dissolved, magnetic agitation under nitrogen, reaction is complete to black selenium powder
It disappears, until being generated there is no bubble, obtains the Se precursor solutions of water white transparency at this time, solution is sealed spare.
(3) preparation of Zn precursor solutions
It takes 75ml deionized waters in beaker, under magnetic agitation, sequentially adds 0.45g ligand L-Cys and 0.55g acetic acid
Zinc reacts 0.5h under the conditions of magnetic agitation, adjusts PH to 11 with the NaOH solution of 2mol//L, which is transferred to four mouthfuls of burnings
Lead to nitrogen about 30min in bottle, removes O2To get to Zn precursor solutions；
(4) preparation of quantum dot sensitized film
Take volume ratio 1:1 Se precursor liquids and Zn precursor liquids is mixed in culture dish, the TiO that will be prepared2Film tilts
About 30 ° are dipped in the above mixed liquor, after 60 DEG C are protected from light condition standing 1.5h, take out and are rinsed with a large amount of deionized waters, removal is attached
The excess ions in film surface, after being dried in air, are placed in vacuum drying chamber 60 DEG C of drying 2h to get to ZnSe amounts
Son point sensitization TiO2Film.
As shown in Fig. 8 (a), quantum dot sensitized (after 60 DEG C the are protected from light condition standing 1.5h) TiO of ZnSe2The table of film (three layers)
There is strong positive surface photovoltage response in 300-755 nanometer ranges in face photovoltaic spectrum.As shown in Fig. 8 (b), ZnSe quantum dots
Sensitization (after 60 DEG C are protected from light condition standing 1.5h) TiO2The positive transient state photovoltaic response of film (three layers) is from 8.2x10-7S starts photoproduction
The recombination velocity of carrier is more than its formation speed.
Embodiment 7
(1)TiO2The making of film
4 drop TiO are added dropwise with disposable dropper2Slurry is in scratch area, using blade in the electro-conductive glass that slurry has been added dropwise
Surface is scratched rapidly, and the uniform TiO that a layer thickness is 2 μm is obtained2Pulp layer will scrape the TiO coated after drying2Film
60 DEG C of drying 2h in vacuum drying chamber are placed in, are then heat-treated this film in Muffle furnace, 0.5h are calcined through 500 DEG C,
It is taken out after being cooled to room temperature, thus obtains the 1st coating, continue preparation on the basis of first coating by above-mentioned same method
2,3 layers of TiO2Film.Finally obtained 3 layers of TiO2Film is through 500 DEG C of calcining 0.5h；Heat treatment, which finishes, is cooled to room temperature taking-up
Afterwards, that is, TiO is completed2The making of film, as shown in Figure 1.
(2) preparation of Se precursor solutions
It takes 20ml deionized waters to be added in conical flask, leads to N2About 15min, the oxygen in removing system.0.29g is then added
Sodium borohydride (NaBH4), 0.197g selenium powders are added until completely dissolved, magnetic agitation under nitrogen, reaction is complete to black selenium powder
It disappears, until being generated there is no bubble.The Se precursor solutions of water white transparency are obtained at this time.Solution is sealed spare.
(3) preparation of Zn precursor solutions
It takes 75ml deionized waters in beaker, under magnetic agitation, sequentially adds 0.45g ligand L-Cys and 0.55g acetic acid
Zinc reacts 0.5h under the conditions of magnetic agitation, adjusts PH to 11 with the NaOH solution of 2mol//L, which is transferred to four mouthfuls of burnings
Lead to nitrogen about 30min, the O in removing system in bottle2To get to Zn precursor solutions.
(4) preparation of quantum dot sensitized film
Take volume ratio 1:1 Se precursor liquids and Zn precursor liquids is mixed in culture dish, the mesoporous TiO that will be prepared2Film
It tilts about 30 ° to be dipped in the above mixed liquor, after 80 DEG C are protected from light condition standing 1.5h, take out and rinsed with a large amount of deionized waters, with
Wash away the excess ions for being attached to film surface.After being dried in air, be placed in vacuum drying chamber 60 DEG C of drying 2h to get to
The quantum dot sensitized TiO of ZnSe2Film
As shown in Fig. 9 (a), quantum dot sensitized (after 80 DEG C the are protected from light condition standing 1.5h) TiO of ZnSe2The table of film (three layers)
There is strong negative surface photovoltage response in 300-550 nanometer ranges in face photovoltaic spectrum；Occur in 550-800 nanometer ranges strong
Positive surface photovoltage response.As shown in Fig. 9 (b), quantum dot sensitized (after 80 DEG C the are protected from light condition standing 1.5h) TiO of ZnSe2It is thin
The negative transient state photovoltaic responses of (three layers) of film are from 1.9x10-5The recombination velocity that s starts photo-generated carrier is more than its formation speed.
Embodiment 8
(1)TiO2The making of film
TiO is prepared using knife coating2Film.Concrete operation step is as follows：3 drop TiO are added dropwise with disposable dropper2Slurry in
Scratch area is scratched rapidly in the conductive glass surface that slurry has been added dropwise using blade, obtains the equal of about 2 μm of a layer thickness
Even TiO2Pulp layer.The TiO coated will be scraped after drying2Film is placed in vacuum drying chamber and dries 2h for 60 DEG C, then that this is thin
Film is heat-treated in Muffle furnace, to improve TiO2Thus binding force between film and FTO substrates obtains the 1st coating.
Continue to prepare the 2nd, 3 layer of TiO on the basis of first coating by above-mentioned same method2The TiO of 3 coatings is finally made in film2
Film.
(2) preparation of Se precursor solutions
It takes 20ml deionized waters to be added in conical flask, leads to N2About 15min removes oxygen, 0.29g sodium borohydrides is then added
(NaBH4), 0.197g selenium powders are added until completely dissolved, magnetic agitation under nitrogen, reaction to black selenium powder completely disappears, no longer
Until having bubble generation, the Se precursor solutions of water white transparency are obtained at this time, solution are sealed spare；
(3) preparation of Zn precursor solutions
It takes 75ml deionized waters in beaker, under magnetic agitation, sequentially adds 0.45g ligand L-Cys and 0.55g acetic acid
Zinc reacts 0.5h under the conditions of magnetic agitation, adjusts PH to 11 with the NaOH solution of 2mol//L, which is transferred to four mouthfuls of burnings
Lead to nitrogen about 30min in bottle, removes O2To get to Zn precursor solutions；
(4) preparation of quantum dot sensitized film
Take volume ratio 1:1 Se precursor liquids and Zn precursor liquids is mixed in culture dish, the TiO that will be prepared2Film tilts
About 30 ° are dipped in the above mixed liquor, after 60 DEG C are protected from light condition standing 3h, take out and are rinsed with a large amount of deionized waters, removal attachment
In the excess ions of film surface, after being dried in air, 60 DEG C of drying 2h are placed in vacuum drying chamber to get to ZnSe quantum
Point sensitization TiO2Film.
As shown in Figure 10 (a), quantum dot sensitized (after 60 DEG C the are protected from light condition standing 3h) TiO of ZnSe2The table of film (three layers)
There is strong positive surface photovoltage response in 300-350 nanometer ranges in face photovoltaic spectrum；Occur in 350-500 nanometer ranges strong
Negative surface photovoltage response；Occurs strong positive surface photovoltage response in 500-770 nanometer ranges.As shown in Figure 10 (b),
Quantum dot sensitized (after 60 DEG C the are protected from light condition standing 3h) TiO of ZnSe2The positive transient state photovoltaic response of film (three layers) is from 2.7x10-6s
The recombination velocity for starting photo-generated carrier is more than its formation speed.
Embodiment 9
(1)TiO2The making of film
3 drop TiO are added dropwise with disposable dropper2Slurry is in scratch area, using blade in the electro-conductive glass that slurry has been added dropwise
Surface is scratched rapidly, and the uniform TiO that a layer thickness is 2 μm is obtained2Pulp layer will scrape the TiO coated after drying2Film
60 DEG C of drying 2h in vacuum drying chamber are placed in, are then heat-treated this film in Muffle furnace, 0.5h are calcined through 500 DEG C,
It is taken out after being cooled to room temperature, thus obtains the 1st coating, continue preparation on the basis of first coating by above-mentioned same method
2,3 layers of TiO2Film, the TiO of finally obtained 3 coatings2Film.
(2) preparation of Se precursor solutions
It takes 20ml deionized waters to be added in conical flask, leads to N2About 15min removes oxygen, 0.29g sodium borohydrides is then added
(NaBH4), 0.197g selenium powders are added until completely dissolved, magnetic agitation under nitrogen, reaction to black selenium powder completely disappears, no longer
Until having bubble generation, the Se precursor solutions of water white transparency are obtained at this time, solution are sealed spare；
(3) preparation of Zn precursor solutions
It takes 75ml deionized waters in beaker, under magnetic agitation, sequentially adds 0.45g ligand L-Cys and 0.55g acetic acid
Zinc reacts 0.5h under the conditions of magnetic agitation, adjusts PH to 11 with the NaOH solution of 2mol//L, which is transferred to four mouthfuls of burnings
Lead to nitrogen about 30min in bottle, removes O2To get to Zn precursor solutions；
(4) preparation of quantum dot sensitized film
Take volume ratio 1:1 Se precursor liquids and Zn precursor liquids is mixed in culture dish, the TiO that will be prepared2Film tilts
About 30 ° are dipped in the above mixed liquor, after 60 DEG C are protected from light condition standing 5h, take out and are rinsed with a large amount of deionized waters, removal attachment
In the excess ions of film surface, after being dried in air, 60 DEG C of drying 2h are placed in vacuum drying chamber to get to ZnSe quantum
Point sensitization TiO2Film.
As shown in Figure 11 (a), quantum dot sensitized (after 60 DEG C the are protected from light condition standing 5h) TiO of ZnSe2The table of film (three layers)
There is strong negative surface photovoltage response in 350-550 nanometer ranges in face photovoltaic spectrum；Occur in 550-750 nanometer ranges strong
Positive surface photovoltage response.As shown in Figure 11 (b), quantum dot sensitized (after 60 DEG C the are protected from light condition standing 5h) TiO of ZnSe2It is thin
The positive transient state photovoltaic response of film (three layers) is from 1.9x10-4The recombination velocity that s starts photo-generated carrier is more than its formation speed.
Embodiment 10
(1)TiO2The making of film
3 drop TiO are added dropwise with disposable dropper2Slurry is in scratch area, using blade in the electro-conductive glass that slurry has been added dropwise
Surface is scratched rapidly, and the uniform TiO that a layer thickness is 2 μm is obtained2Pulp layer will scrape the TiO coated after drying2Film
60 DEG C of drying 2h in vacuum drying chamber are placed in, are then heat-treated this film in Muffle furnace, 0.5h are calcined through 500 DEG C,
It is taken out after being cooled to room temperature, thus obtains the 1st coating, continue preparation on the basis of first coating by above-mentioned same method
2,3 layers of TiO2The TiO of 3 coatings is finally made in film2Film.
(2) preparation of Se precursor solutions
It takes 20ml deionized waters to be added in conical flask, leads to N2About 15min removes oxygen.0.29g sodium borohydrides are then added
(NaBH4), 0.198g selenium powders are added until completely dissolved, magnetic agitation under nitrogen, reaction to black selenium powder completely disappears, no longer
Until having bubble generation, the Se precursor solutions of water white transparency are obtained at this time, solution are sealed spare；
(3) preparation of Zn precursor solutions
It takes 75ml deionized waters in beaker, under magnetic agitation, sequentially adds 0.45g ligand L-Cys and 0.55g acetic acid
Zinc reacts 0.5h under the conditions of magnetic agitation, adjusts PH to 11 with the NaOH solution of 2mol//L, which is transferred to four mouthfuls of burnings
Lead to nitrogen about 30min in bottle, removes O2To get to Zn precursor solutions；
(4) preparation of quantum dot sensitized film
Take volume ratio 1:1 Se precursor liquids and Zn precursor liquids is mixed in culture dish, the TiO that will be prepared2Film tilts
About 30 ° are dipped in the above mixed liquor, after 60 DEG C are protected from light condition standing 7h, take out and are rinsed with a large amount of deionized waters, removal attachment
In the excess ions of film surface, after being dried in air, 60 DEG C of drying 2h are placed in vacuum drying chamber to get to ZnSe quantum
Point sensitization TiO2Film.
As shown in Figure 12 (a), quantum dot sensitized (after 60 DEG C the are protected from light condition standing 7h) TiO of ZnSe2The table of film (three layers)
There is strong positive surface photovoltage response in 0-350 nanometer ranges in face photovoltaic spectrum；Occur strong in 350-800 nanometer ranges
Negative surface photovoltage response.As shown in Figure 12 (b), quantum dot sensitized (after 60 DEG C the are protected from light condition standing 7h) TiO of ZnSe2Film
(three layers) negative transient state photovoltaic responses are from 7.5x10-5The recombination velocity that s starts photo-generated carrier is more than its formation speed.
Claims (1)
1. a kind of quantum dot sensitized nano-TiOs of ZnSe2The preparation method of film, it is characterised in that：It includes the following steps：
(1)TiO2The making of film
TiO is prepared using knife coating23-4 drops TiO is added dropwise with dropper in film2Slurry is scraped rapidly to conductive glass surface, with blade
It applies, it is 2 μm of uniform TiO to obtain a layer thickness2Pulp layer；After drying, the TiO coated will be scraped2Film is placed in vacuum drying chamber
In 60 DEG C drying 2h, then this film is heat-treated in Muffle furnace, to improve TiO2Knot between film and FTO substrates
With joint efforts, 500 DEG C of calcining 0.5h, take out after being cooled to room temperature, thus obtain the 1st coating；By above-mentioned same method upper one
Continue to prepare the 2nd, the 3rd or the 4th layer of TiO on the basis of coating2Film, one or more layers finally obtained TiO2Film；
(2) preparation of Se precursor solutions
The ratio of 0.145g sodium borohydrides and 0.099g selenium powders, i.e. sodium borohydride and selenium powder are added in every 10 ml deionized water
Molar ratio is 3:1, deionized water is added to the container, N is led to215min removes oxygen, and sodium borohydride (NaBH is then added4),
It is added selenium powder until completely dissolved, magnetic agitation under nitrogen, reaction is completely disappeared to black selenium powder, and there is no bubbles to be produced as
Only, the Se precursor solutions for obtaining water white transparency at this time, solution are sealed spare；
(3) preparation of Zn precursor solutions
The ratio of 0.06g ligand L-Cys and 0.073g zinc acetates, i.e. ligand L-Cys and vinegar are added in every 10 ml deionized water
The molar ratio of sour zinc is 3:2, ligand L-Cys and zinc acetate is added into deionized water successively, is reacted under the conditions of magnetic agitation
0.5h adjusts PH to 11 with the NaOH solution of 2mol/L, which is transferred in four-hole boiling flask and leads to nitrogen about 30min, is removed
O2To get to Zn precursor solutions；
(4) preparation of quantum dot sensitized film
By volume 1:1 ratio mixes Se precursor liquids made from step (2) and step (3) and Zn precursor liquids, by step
(1) TiO prepared2Film tilts about 30 ° and is dipped in above-mentioned mixed liquor, is protected from light after condition stands 1.5-7h and takes out in 25-80 DEG C,
It is rinsed with deionized water, to wash away the excess ions for being attached to film surface；After being dried in air, it is placed in vacuum drying chamber
60 DEG C of drying 2h are to get to the quantum dot sensitized TiO of ZnSe2Film.
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| CN101393938A (en) * | 2007-12-28 | 2009-03-25 | 北京大学 | Wide forbidden region semi-conductor nano tube/linear array film, preparation and photoelectric pole thereof |
| CN102013331A (en) * | 2009-09-04 | 2011-04-13 | 北京大学 | Method for preparing photo-electrode |
| CN102543461A (en) * | 2010-10-12 | 2012-07-04 | 霍尼韦尔国际公司 | Flexible quantum dot sensitized solar cells |
| CN103972611A (en) * | 2013-01-29 | 2014-08-06 | 三星电子株式会社 | Composite protective layer, photoelectrode structure, and photoelectrochemical cell |
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| CN101393938A (en) * | 2007-12-28 | 2009-03-25 | 北京大学 | Wide forbidden region semi-conductor nano tube/linear array film, preparation and photoelectric pole thereof |
| CN102013331A (en) * | 2009-09-04 | 2011-04-13 | 北京大学 | Method for preparing photo-electrode |
| CN102543461A (en) * | 2010-10-12 | 2012-07-04 | 霍尼韦尔国际公司 | Flexible quantum dot sensitized solar cells |
| CN103972611A (en) * | 2013-01-29 | 2014-08-06 | 三星电子株式会社 | Composite protective layer, photoelectrode structure, and photoelectrochemical cell |
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