CN102148098A - Method for preparing quantum dot sensitized oxide film with broad spectral response - Google Patents
Method for preparing quantum dot sensitized oxide film with broad spectral response Download PDFInfo
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- CN102148098A CN102148098A CN2010106094606A CN201010609460A CN102148098A CN 102148098 A CN102148098 A CN 102148098A CN 2010106094606 A CN2010106094606 A CN 2010106094606A CN 201010609460 A CN201010609460 A CN 201010609460A CN 102148098 A CN102148098 A CN 102148098A
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- quantum dot
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Abstract
The invention discloses a method for preparing a quantum dot sensitized oxide film with broad spectral response. The method comprises the following steps of: (1) depositing oxide on a transparent conductive substrate to obtain a first-layer porous oxide film by adopting electrophoretic deposition; (2) depositing a quantum dot sensitized material on the duct surface of the first-layer porous oxide film to obtain a first-layer quantum dot sensitized oxide film by adopting socking adsorption or electrophoretic deposition; (3) sequentially repeating the steps (1) and (2) on the first-layer quantum dot sensitized oxide film obtained in the step (2) to obtain a two-layer laminated quantum dot sensitized oxide film; and (4) sequentially repeating the steps (1) and (2) on the two-layer laminated quantum dot sensitized oxide film obtained in the step (3) to obtain a multi-layer laminated quantum dot sensitized oxide film, and repeating for a plurality of times to obtain the quantum dot sensitized oxide film with the broad spectral response. The quantum dot sensitized oxide film prepared by the invention mutually makes up the defect that respective absorption spectrum ranges are not wide enough, thus the range can be expanded to a near infrared region from an ultraviolet region after all the quantum dot spectrum absorption ranges are superimposed and the film has the broad spectral response.
Description
Technical field
The present invention relates to the sensitization solar battery technical field, specifically a kind of preparation method with quantum dot sensitized sull of wide spectral response.
Background technology
DSSC be a kind of be the electrooptical device of electric energy or electric energy and chemical energy with solar energy converting by optoelectronic pole.At present the most successful is Gr tzel type solar cell, promptly is the solar photocell of light anode with the dye-sensitized nano sull.The semi-conducting material that wherein is used to prepare the light anode has a lot, as TiO
2, ZnO, Nb
2O
5Deng, but the most frequently used be TiO
2TiO
2Be a kind of low price and widely used material, its preparation is simple, nontoxic, stable, and corrosion resistance is good.But because its energy gap big (band gap of rutile is 3 ev, and the band gap of anatase is 3.2 ev), therefore absorption region need carry out dye sensitization all in the ultra-violet (UV) band, could absorb the energy of visible region.
Sensitizer is the key factor that influences photoelectric conversion efficiency, and improves constantly the target that photoelectric conversion efficiency is the DSSC development, so DSSC is very high to the requirement of sensitizer.The most of organic dye molecule that is used for sensitization at present is visible light absorbing all, but it is narrow that it absorbs the territory, experience several thousand times so circulation up to ten thousand time after performance reduce greatly, can not satisfy the requirement that works long hours to thermal stability, therefore further raising photoelectric conversion efficiency is restricted.Along with the semiconductor-quantum-point Development of Preparation Technology, utilize the semiconductor-quantum-point sensitization TiO of low energy gap
2Electrode has become the focus of optoelectronic pole investigation of materials.That the advantage of semiconductor-quantum-point is is easy to prepare, cheap, extinction coefficient is high, band gap is adjustable, Heat stability is good etc.But as sensitizer, have only very near TiO with semiconductor-quantum-point
2The sensitizer on surface could successfully be injected into TiO to the electronics of excitation state
2In the conduction band, the existence of multilayer sensitizer can hinder the transportation of electronics on the contrary, causes conversion efficiency to descend, and therefore owing to can only adsorb one deck quantum dot, is subjected to the restriction of single quantum dot absorption spectrum ranges, and is still not high to the utilance of sunlight.
In order to improve the utilance to sunlight, the quantum dot of the same race that the someone proposes the different-grain diameter size that absorption spectrum ranges is different is adsorbed on individual layer TiO
2In the pipeline of nanotube, make the less quantum dot of particle diameter absorb the higher sunlight of energy, the quantum dot that particle diameter is bigger absorbs the lower sunlight of energy.But this method since the quantum dot of different-grain diameter size by TiO
2Do not have strict subregion in the nanotube adsorption process, when solar light irradiation, the quantum dot of every kind of particle diameter also can cause the loss of the sunlight of other energy ranges behind the sunlight that has adsorbed certain energy range, therefore to sunlight to utilize effect to improve not obvious.
Summary of the invention
The objective of the invention is at present quantum dot sensitized TiO
2The deficiency that the utilance of electrode pair sunlight is not high, photoelectric conversion efficiency is lower, stacked multilayer has the quantum dot sensitized sull of different spectral responses in the electrically conducting transparent substrate, and a kind of preparation method with quantum dot sensitized sull of wide spectral response is provided.
The concrete technical scheme that realizes the object of the invention is:
A kind of preparation method with quantum dot sensitized sull of wide spectral response is characterized in that this method comprises following concrete steps:
The first step is utilized electrophoretic deposition deposition oxide in the electrically conducting transparent substrate, obtains ground floor porous oxide film, and film is after cleaning, argon gas dry up, and is dry at low temperatures;
Second step utilized immersion absorption or electrophoretic deposition that quantum dot sensitized material is deposited on the surface, duct of ground floor porous oxide film, obtained the quantum dot sensitized sull of ground floor, and film is after cleaning, argon gas dry up, and is dry at low temperatures;
Repeat the first step and the operation of second step on the quantum dot sensitized sull that the 3rd step obtained successively in second step, obtain the quantum dot sensitized sull of two-layer laminate;
The 4th step went on foot the 3rd and repeats the first step and the operation of second step on the quantum dot sensitized sull of two-layer laminate that obtains successively, obtain multilayer laminated quantum dot sensitized sull, repeat for several times the quantum dot sensitized sull that obtains having wide spectral response with this;
Wherein:
Described electrically conducting transparent substrate is indium tin oxide electro-conductive glass or the SnO that mixes fluorine
2Electro-conductive glass;
Described oxide is TiO
2, ZnO, W
2O
3, Nb
2O
5Or A1
2O
3
The inorganic quantum dot that described quantum dot sensitized material is made up of II-VI family in the periodic table of chemical element or III-V family element.
In the described stacked quantum dot sensitized sull, the spectral absorption scope difference of every layer of employed quantum dot.The absorbing wavelength of employed quantum dot the shortest (or absorb energy the highest) in the ground floor sull wherein, taking second place in the second layer, taking second place again in the 3rd layer.By that analogy, after the spectral absorption scope stack of all quantum dots, can expand to the near infrared region from the ultra-violet (UV) band.
Described inorganic quantum dot is the big or small or variform quantum dot of kind, thereby can expand to the near infrared region from the ultra-violet (UV) band after the stack of their spectral absorption scope.
Described inorganic quantum dot has the functional groups that can combine with described metal oxide surface, as hydroxyl, carboxyl, sulfonic group etc.
The present invention has remedied the deficiencies in the prior art, takes multiple quantum dot cooperated-sensitization, improves the utilance to sunlight, strengthens photoelectric conversion efficiency, and a kind of preparation method with quantum dot sensitized sull of wide spectral response is provided.The quantum dot sensitized sull that utilizes electrophoretic deposition stacked multilayer in the electrically conducting transparent substrate to have different spectral responses, when solar irradiation is mapped on the film, the higher ultraviolet light of energy is at first absorbed by the quantum dot of ground floor band gap maximum or particle diameter minimum, the visible light that energy is low slightly passes the back by the quantum dot that band gap is slightly little or particle diameter the is big slightly absorption of layer after a while, the near infrared light that energy is very low continues across the back and is absorbed by the quantum dot of the band gap minimum of final layer or particle diameter maximum, like this because being used of various different quantum dots, remedied the wide inadequately shortcoming of absorption spectrum ranges separately mutually, can expand to the near infrared region from the ultra-violet (UV) band after making the spectral absorption scope stack of all quantum dots, thereby realize the quantum dot sensitized sull that preparation has wide spectral response.
Description of drawings
Fig. 1 is the schematic diagram of the quantum dot sensitized sull with wide spectral response of the present invention's preparation;
Fig. 2 is the ultraviolet-visible-near infrared light abosrption spectrogram of three kinds of quantum dots among the embodiment 4.
Embodiment
Further set forth the present invention by following specific embodiment:
Embodiment 1
(1) ITO electro-conductive glass and the zinc metal sheet with suitable dimension cleans up and dries up.
(2) take by weighing the P25 TiO of 0.1 g
2Powder is scattered in the 10 ml n-butanols, ultrasonic 30 min, and centrifugation is then got supernatant liquor and is promptly made stable TiO
2Suspension.
(3) with the ITO electro-conductive glass as anode, zinc metal sheet immerses above-mentioned TiO as negative electrode
2In the suspension, setting applied voltage is 15 V, and sedimentation time is 5 min, can obtain ground floor porous TiO on the ITO electro-conductive glass
2Film.Film is after cleaning, argon gas dry up, and is dry at low temperatures.
(4) get TGA (TGA) modified ZnS (TGA-ZnS) the quantum dot hydrosol 2.5 ml that the surface has negative electrical charge, add 0.5 ml, 5 mg/ml aqueous ascorbic acids, regulating its pH value with 0.1 M NaOH is 9.0.
(5) surface deposition in the step (3) there is porous TiO
2The ITO electro-conductive glass of film is as anode, and zinc metal sheet immerses in the above-mentioned TGA-ZnS quantum dot hydrosol as negative electrode, and setting applied voltage is 2.8 V, and sedimentation time is 5 min, can be at ground floor TiO
2Deposition one deck ZnS quantum dot on the duct inner surface of film.Take out the ITO electro-conductive glass, with drying up with argon gas again after the washed with de-ionized water.
(6) surface deposition in the step (5) there is ground floor TiO
2And the ITO electro-conductive glass that has adsorbed the ZnS quantum dot is as anode, and zinc metal sheet immerses TiO as negative electrode
2In the suspension, utilize electrophoretic deposition can deposit second layer porous TiO
2Film.Film is after cleaning, argon gas dry up, and is dry at low temperatures.
(7) get the CdS(TGA-CdS that TGA (TGA) that the surface has negative electrical charge is modified) the quantum dot hydrosol 2.5 ml, with surface deposition in the step (6) second layer porous TiO
2The ITO electro-conductive glass of film is immersed in wherein 10 h, can be at second layer TiO
2Absorption one deck CdS quantum dot on the duct inner surface of film.Take out the ITO electro-conductive glass, with drying up with argon gas again after the washed with de-ionized water.
(8) with the ITO electro-conductive glass in the step (7) as anode, zinc metal sheet is as negative electrode, immerses TiO
2In the suspension, utilize electrophoretic deposition can deposit the 3rd layer of porous TiO
2Film.Film is after cleaning, argon gas dry up, and is dry at low temperatures.
(9) get the PbS(TGA-PbS that TGA (TGA) that the surface has negative electrical charge is modified) the quantum dot hydrosol 2.5 ml, add 0.5 ml, 5 mg/ml aqueous ascorbic acids, regulating its pH value with 0.1 M NaOH is 10.0.
(10) with surface deposition in the step (8) the 3rd layer of porous TiO
2The ITO electro-conductive glass of film is as anode, and zinc metal sheet immerses in the above-mentioned TGA-PbS quantum dot hydrosol as negative electrode, and setting applied voltage is 2.8 V, and sedimentation time is 5 min, can be at the 3rd layer of TiO
2Deposition one deck PbS quantum dot on the duct inner surface of film.Take out the ITO electro-conductive glass, with drying up, preserve with argon gas again after the washed with de-ionized water.
Embodiment 2
Present embodiment is similar to embodiment 1 step, and different is to make ground floor porous TiO
2Absorption ZnSe quantum dot on the duct inner surface of film, second layer porous TiO
2Absorption CdSe quantum dot on the duct inner surface of film, the 3rd layer of porous TiO
2Absorption PbSe quantum dot on the duct inner surface of film.
Embodiment 3
Present embodiment is similar to embodiment 1 step, and different is to make ground floor porous TiO
2Absorption ZnTe quantum dot on the duct inner surface of film, second layer porous TiO
2Absorption CdTe quantum dot on the duct inner surface of film, the 3rd layer of porous TiO
2Absorption PbTe quantum dot on the duct inner surface of film.
Embodiment 4
Present embodiment is similar to embodiment 1 step, and different is to make ground floor porous TiO
2The absorption particle diameter is the CdTe quantum dot of 2.5 nm on the duct inner surface of film, second layer porous TiO
2The absorption particle diameter is the CdTe quantum dot of 5.8 nm on the duct inner surface of film, the 3rd layer of porous TiO
2The absorption particle diameter is the PbS quantum dot of 2.9 nm on the duct inner surface of film.
The above only is a preferred implementation of the present invention.Should be understood that; for those skilled in the art; according to know-why of the present invention and thought; can also make some changes and improvement; the quantum dot that for example will be used for the sensitization sull replaces to various organic dye molecules or Macrocyclic metal complex, and these changes and improvement also should be considered as protection scope of the present invention.
Claims (1)
1. preparation method with quantum dot sensitized sull of wide spectral response is characterized in that this method comprises following concrete steps:
The first step is utilized electrophoretic deposition deposition oxide in the electrically conducting transparent substrate, obtains ground floor porous oxide film, and film is after cleaning, argon gas dry up, and is dry at low temperatures;
Second step utilized immersion absorption or electrophoretic deposition that quantum dot sensitized material is deposited on the surface, duct of ground floor porous oxide film, obtained the quantum dot sensitized sull of ground floor, and film is after cleaning, argon gas dry up, and is dry at low temperatures;
Repeat the first step and the operation of second step on the quantum dot sensitized sull that the 3rd step obtained successively in second step, obtain the quantum dot sensitized sull of two-layer laminate;
The 4th step went on foot the 3rd and repeats the first step and the operation of second step on the quantum dot sensitized sull of two-layer laminate that obtains successively, obtain multilayer laminated quantum dot sensitized sull, repeat for several times the quantum dot sensitized sull that obtains having wide spectral response with this;
Wherein:
Described electrically conducting transparent substrate is indium tin oxide electro-conductive glass or the SnO that mixes fluorine
2Electro-conductive glass;
Described oxide is TiO
2, ZnO, W
2O
3, Nb
2O
5Or A1
2O
3
The inorganic quantum dot that described quantum dot sensitized material is made up of II-VI family in the periodic table of chemical element or III-V family element.
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Cited By (8)
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| CN103400698A (en) * | 2013-07-29 | 2013-11-20 | 奇瑞汽车股份有限公司 | Method of pulping through powder, photo-anode of dye-sensitized solar cell and dye-sensitized solar cell |
| CN103943366A (en) * | 2014-05-12 | 2014-07-23 | 天津师范大学 | Dye-sensitized solar cell of novel structure and preparation method thereof |
| CN106115603A (en) * | 2016-07-19 | 2016-11-16 | 中国科学院重庆绿色智能技术研究院 | A kind of porous/quantum dot composite construction infrared detector unit and preparation method |
| CN109935691A (en) * | 2017-12-15 | 2019-06-25 | Tcl集团股份有限公司 | Composite membrane and its preparation method and application |
| CN111354573A (en) * | 2020-02-14 | 2020-06-30 | 中山大学 | Quantum dot modified titanium dioxide-based photo-anode, solar cell and preparation method |
| CN111944190A (en) * | 2020-08-07 | 2020-11-17 | 武汉珈源同创科技有限公司 | Quantum dot fluorescent coding microsphere and preparation method thereof |
| CN113054054A (en) * | 2021-03-08 | 2021-06-29 | 深圳市华星光电半导体显示技术有限公司 | Quantum dot photoelectric detector and preparation method thereof |
| CN113698925A (en) * | 2021-08-03 | 2021-11-26 | 深圳市华星光电半导体显示技术有限公司 | Quantum dot film manufacturing method and quantum dot substrate |
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Cited By (14)
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| CN103400698A (en) * | 2013-07-29 | 2013-11-20 | 奇瑞汽车股份有限公司 | Method of pulping through powder, photo-anode of dye-sensitized solar cell and dye-sensitized solar cell |
| CN103943366A (en) * | 2014-05-12 | 2014-07-23 | 天津师范大学 | Dye-sensitized solar cell of novel structure and preparation method thereof |
| CN103943366B (en) * | 2014-05-12 | 2016-09-14 | 天津师范大学 | A kind of DSSC of new structure and preparation method thereof |
| CN106115603A (en) * | 2016-07-19 | 2016-11-16 | 中国科学院重庆绿色智能技术研究院 | A kind of porous/quantum dot composite construction infrared detector unit and preparation method |
| CN106115603B (en) * | 2016-07-19 | 2017-11-07 | 中国科学院重庆绿色智能技术研究院 | A kind of porous/quantum dot composite construction infrared detector unit and preparation method |
| CN109935691A (en) * | 2017-12-15 | 2019-06-25 | Tcl集团股份有限公司 | Composite membrane and its preparation method and application |
| CN111354573A (en) * | 2020-02-14 | 2020-06-30 | 中山大学 | Quantum dot modified titanium dioxide-based photo-anode, solar cell and preparation method |
| CN111354573B (en) * | 2020-02-14 | 2021-10-01 | 中山大学 | Quantum dot modified titanium dioxide-based photo-anode, solar cell and preparation method |
| CN111944190A (en) * | 2020-08-07 | 2020-11-17 | 武汉珈源同创科技有限公司 | Quantum dot fluorescent coding microsphere and preparation method thereof |
| CN111944190B (en) * | 2020-08-07 | 2022-12-02 | 武汉珈源同创科技有限公司 | Quantum dot fluorescence coding microsphere and preparation method thereof |
| CN113054054A (en) * | 2021-03-08 | 2021-06-29 | 深圳市华星光电半导体显示技术有限公司 | Quantum dot photoelectric detector and preparation method thereof |
| CN113054054B (en) * | 2021-03-08 | 2022-04-26 | 深圳市华星光电半导体显示技术有限公司 | Quantum dot photoelectric detector and preparation method thereof |
| CN113698925A (en) * | 2021-08-03 | 2021-11-26 | 深圳市华星光电半导体显示技术有限公司 | Quantum dot film manufacturing method and quantum dot substrate |
| CN113698925B (en) * | 2021-08-03 | 2024-02-09 | 深圳市华星光电半导体显示技术有限公司 | Quantum dot film manufacturing method and quantum dot substrate |
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Application publication date: 20110810 |