CN102637754A - Full-inorganic solar cell with schottky quantum dots and method for preparing full-inorganic solar cell - Google Patents
Full-inorganic solar cell with schottky quantum dots and method for preparing full-inorganic solar cell Download PDFInfo
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Abstract
Disclosed is a full-inorganic solar cell with schottky quantum dots. ITO (indium tin oxide) glass (In2O3 conducting glass doped with Sn) is used as a substrate, and an ITO anode, a PbS quantum dot layer and an aluminum cathode are sequentially stacked, so that the full-inorganic solar cell is formed. The thickness of the PbS quantum dot layer is 100nm, and the thickness of the aluminum cathode is 100nm. A method for preparing the full-inorganic solar cell includes sequentially rotationally coating PbS quantum dot chloroform liquor, mercaptopropionic acid methanol liquor and methanol liquor on the cleaned and dried substrate; realizing vacuum thermal annealing; and finally forming the aluminum electrode by means of vacuum thermal evaporation. The full-inorganic solar cell with the quantum dots has the advantages that absorption of the cell to sunlight can be changed by means of adjusting the particle sizes of the quantum dots, open-circuit voltage and short-circuit current of the cell can also be changed, a preparation process is simple, preparation time is short, and preparation cost is low.
Description
Technical field
The present invention relates to solar cell and preparation thereof, particularly a kind of full-inorganic solid Schottky quantum dot solar cell and preparation method thereof.
Background technology
Monocrystal material such as silicon and III-V compound semiconductor can reach the transformation efficiency of 20-41.4% on photovoltaic cell; So high transformation efficiency be since these devices to the absorption of light Spectral matching with sunlight arrival ground, and these semiconductors have good electron transport property.Simultaneously, low cost, the solar cell of low energy consumption (utilize solwution method synthetic with roll coating process film forming) also came into one's own in recent years, and organic polymer solar cell is exactly wherein a kind of, but its poor stability.
The colloid quantum dot synthesizes in solution and can pass through and floods, spin coating, and method of printing comprises the flexible substrates film forming in substrate, these have demonstrated potential using value on light-emitting diode.
Narrow gap semiconductor can absorb more light, big electric current is provided, but voltage is little, and wide bandgap material is because to absorb limited current little but voltage is big; At last; Behind balanced voltage and the electric current, best band gap is between 1.1ev-1.4ev, and it has the highest energy conversion efficiency in single junction cell.Body material Si, InP and CuInSe2 have only band gap, but body material PbS, LnAs and PbSe are not suitable for being applied on the photovoltaic, and a kind of method of regulating band gap is its formations of regulation and control.
The exciton Bohr radius of PbS is 18nm, can make its ABSORPTION EDGE adjustable from 3000nm to 600nm (M.A.Hines, G.D.Scholes, Adv through the size of when synthetic, controlling the PbS quantum point grain diameter.Mater。2003,15,1844), for unijunction solar cell, best band gap is 1.1ev, and corresponding PbS quantum point grain diameter approximately is 3.5nm.
In experiment, having observed PbS has many exciton effects and (sees Randy J.Ellingson, Matthew C.Beard, Justin C.Johnson; Nano Letters; 2005, Vol.5, No.5865-871); Promptly low energy gap quanta of energy point can produce a plurality of electron hole pairs through absorbing single high-energy photon, makes quantum efficiency greater than 100%.
PbS is a kind of P type semiconductor, is to use the metal electrode of low work function with the advantage of the Schottky photovoltaic cell of its preparation.In this device, band curvature only occurs in the quantum dot film, and there is a depletion layer centre, and internal electric field can make electronics and hole separate, and electron drift is to metal electrode, and hole transport is to one-level such as the ITO or the FTO of high work content.
Quantum dot solar cell becomes the third generation solar cell of tool potentiality because its preparation technology is simple, and cost is low.
Summary of the invention
It is poor to the objective of the invention is to overcome existing organic substance solar cell stability, and the shortcoming that the silicon solar cell cost is high provides a kind of full-inorganic Schottky quantum dot solar cell and preparation method thereof; Utilize the quantum limitation effect of quantum dot, the advantage of many exciton effects can make the absorption of light adjustable; Cover the infrared visible whole zone of arriving, the transformation efficiency of battery is high, and preparation technology is simple; Preparation time is short, and preparation cost is low.
Technical scheme of the present invention:
A kind of full-inorganic Schottky quantum dot solar cell (is mixed the In of Sn with ito glass
2O
3Electro-conductive glass) be substrate, being superposeed successively by ito anode, PbS quantum dot layer and aluminium negative electrode constitutes.
The thickness of said PbS quantum dot layer is 100nm, and the thickness of aluminium negative electrode is 100nm.
A kind of preparation method of said full-inorganic Schottky quantum dot solar cell, step is following:
1) the ito glass substrate is carried out ultrasonic cleaning with liquid detergent, deionized water, acetone, isopropyl alcohol, ethanol respectively successively, be placed on then in the vacuum tank 80 ℃ dry 1 hour down;
2) preparation PbS quantum dot chloroformic solution is as spin coating liquid;
3) the ito glass substrate after will handling is placed on the spin coater, on electro-conductive glass, drips above-mentioned spin coating liquid 0.4-0.6ml, stops 2 seconds; Rotating speed spin coating with 600rpm makes its film forming, air dry 10min, the methanol solution of a 0.4-0.6ml mercaptopropionic acid (MPA); Rotating speed spin coating with 3000rpm; Air dry 5min drips the 0.2-0.4ml methanol solution then, with the rotation of the rotating speed of 3000rpm to wash unnecessary MPA; The thickness that so is repeated to the PbS quantum dot layer is 100nm;
4) be 10 in vacuum degree
-2Annealed 30 minutes under pa, 110 ℃ of temperature;
5) last is 10 in vacuum degree on the film after the above-mentioned processing
-5The Al negative electrode that hot vapor deposition thickness is 100nm under the condition can make this solar cell.
The particle diameter of said PbS quantum dot is 3.3-4.0nm, and mol ratio plumbous and sulphur is 1: 0.3-0.8.
The concentration of said PbS quantum dot chloroformic solution is 10mg/ml.
The concentration of volume percent of said mercaptopropionic acid (MPA) methanol solution is 10%.
Preparating mechanism of the present invention:
In this solar cell preparation, the synthetic LSS method of using of PbS coats lead ion with oleic acid, can control the growth of PbS quantum dot on the one hand, can reduce the blemish of PbS quantum dot on the other hand, and then reduces the compound of charge carrier.Through changing the size that recently changes quantum dot of Pb and S, the mol ratio of plumbous sulphur is big more, and the diameter of particle is more little.Because the oleic acid chain has 2.6nm long, and insulate, it can stop the transmission of charge carrier, reduces the transformation efficiency of battery, so is necessary to replace it with short chain, and that the present invention uses is mercaptopropionic acid (MPA), the MPA chain can with Pb
2+In conjunction with to replace long oleic acid chain, heat treatment meeting subsequently makes MPA tighter with being connected of PbS, plays the effect of modification of surfaces defective, improves the transmission of charge carrier, and then improves the transformation efficiency of battery.After the PbS quantum dot absorbed photon, excited electron was collected the formation negative pole by the Al electrode after the transmission from the valence to the conduction band, and the hole is then collected by ITO and formed positive pole, between Al electrode and ITO, produces electrical potential difference.
Advantage of the present invention and good effect:
The invention provides a kind of quantum dot solar cell of full-inorganic; Can change the absorption of battery through the size of regulating quantum point grain diameter, also can change the open circuit voltage and the short circuit current of battery, and preparation technology be simple sunlight; Preparation time is short, and preparation cost is low.
Description of drawings
Fig. 1 is the transmission electron microscope picture of the PbS quantum dot of different plumbous sulphur ratios; A. plumbous sulphur is than the transmission electron microscope picture that is the PbS quantum dot of 1:0.3; B. plumbous sulphur is than the transmission electron microscope picture that is the PbS quantum dot of 1:0.5, and the plumbous sulphur of c. is than the transmission electron microscope picture that is the PbS quantum dot of 1:0.8.
Fig. 2 is this full-inorganic Schottky quantum dot solar battery structure sketch map.
Embodiment
A kind of full-inorganic Schottky quantum dot solar cell, as shown in Figure 2, (mix the In of Sn with ito glass
2O
3Electro-conductive glass) be substrate, being superposeed successively by ito anode, PbS quantum dot layer and aluminium negative electrode constitutes, and the thickness of PbS quantum dot layer is 100nm, and the thickness of aluminium negative electrode is 100nm.
Embodiment 1:
A kind of preparation method of said full-inorganic Schottky quantum dot solar cell, step is following:
1) the ito glass substrate is carried out ultrasonic cleaning with liquid detergent, deionized water, acetone, isopropyl alcohol, ethanol respectively successively, be placed on then in the vacuum tank 80 ℃ dry 1 hour down;
2) preparation PbS quantum dot chloroformic solution is as spin coating liquid:
Lead acetate water solution and the 20ml concentration of preparing 20ml concentration respectively and be 10mmol/L are the 3mmol/L sodium sulfide solution, and make its dissolving with ultrasonic Treatment; Under magnetic agitation, in lead acetate water solution, add the linoleic ethanolic solution of 10ml, wherein the volume ratio of linoleic acid and ethanol is 1: 5; Adding 50ml concentration then is the enuatrol ethanolic solution of 5g/l; In temperature is to stir 30min under 30 ℃ of conditions; Solution becomes clarification by milky, splashes into above-mentioned sodium sulfide solution with funnel again, and reaction is centrifugal behind the 30min, cleaning, drying; Make the PbS quantum dot, it is dispersed in the transmission electron microscope picture that records in the chloroform shown in Fig. 1 (a);
3) the ito glass substrate after will handling is placed on the spin coater, on electro-conductive glass, drips above-mentioned spin coating liquid 0.4ml, stops 2 seconds; Rotating speed spin coating with 600rpm makes its film forming, air dry 10min, the methanol solution of a 0.4ml mercaptopropionic acid (MPA); With the rotating speed spin coating of 3000rpm, air dry 5min drips the 0.2ml methanol solution then; Rotating speed with 3000rpm rotates to wash unnecessary MPA, and so repeating 5 thickness to the PbS quantum dot layer is 100nm;
4) be 10 in vacuum degree
-2Annealed 30 minutes under pa, 110 ℃ of temperature;
5) last is 10 in vacuum degree on the film after the above-mentioned processing
-5The Al negative electrode that hot vapor deposition thickness is 100nm under the condition can make this solar cell.
Embodiment 2:
A kind of preparation method of said full-inorganic Schottky quantum dot solar cell, step is following:
1) the ito glass substrate is carried out ultrasonic cleaning with liquid detergent, deionized water, acetone, isopropyl alcohol, ethanol respectively successively, be placed on then in the vacuum tank 80 ℃ dry 1 hour down;
2) preparation PbS quantum dot chloroformic solution is as spin coating liquid:
Lead acetate water solution and the 20ml concentration of preparing 20ml concentration respectively and be 10mmol/L are the 5mmol/L sodium sulfide solution, and make its dissolving with ultrasonic Treatment; Under magnetic agitation, in lead acetate water solution, add the linoleic ethanolic solution of 10ml, wherein the volume ratio of linoleic acid and ethanol is 1: 5; Add the ethanolic solution that 50ml concentration is the enuatrol of 5g/l then; In temperature is to stir 30min under 30 ℃ of conditions; Solution becomes clarification by milky, splashes into above-mentioned sodium sulfide solution with funnel again, and reaction is centrifugal behind the 30min, cleaning, drying; Make the PbS quantum dot, it is dispersed in the transmission electron microscope picture that records in the chloroform shown in Fig. 1 (b);
3) the ito glass substrate after will handling is placed on the spin coater, on electro-conductive glass, drips above-mentioned spin coating liquid 0.5ml, stops 2 seconds; Rotating speed spin coating with 600rpm makes its film forming, air dry 10min, the methanol solution of a 0.5ml mercaptopropionic acid (MPA); With the rotating speed spin coating of 3000rpm, air dry 5min drips the 0.3ml methanol solution then; Rotating speed with 3000rpm rotates to wash unnecessary MPA, and so repeating 5 thickness to the PbS quantum dot layer is 100nm;
4) be 10 in vacuum degree
-2Annealed 30 minutes under pa, 110 ℃ of temperature;
5) last is 10 in vacuum degree on the film after the above-mentioned processing
-5The Al negative electrode that hot vapor deposition thickness is 100nm under the condition can make this solar cell.
Embodiment 3:
A kind of preparation method of said full-inorganic Schottky quantum dot solar cell, step is following:
1) the ito glass substrate is carried out ultrasonic cleaning with liquid detergent, deionized water, acetone, isopropyl alcohol, ethanol respectively successively, be placed on then in the vacuum tank 80 ℃ dry 1 hour down;
2) preparation PbS quantum dot chloroformic solution is as spin coating liquid:
Lead acetate water solution and the 20ml concentration of preparing 20ml concentration respectively and be 10mmol/L are the 8mmol/L sodium sulfide solution, and make its dissolving with ultrasonic Treatment; Under magnetic agitation, in lead acetate water solution, add the linoleic ethanolic solution of 10ml, wherein the volume ratio of linoleic acid and ethanol is 1: 5; Add the ethanolic solution that 50ml concentration is the enuatrol of 5g/l then; In temperature is to stir 30min under 30 ℃ of conditions; Solution becomes clarification by milky, splashes into above-mentioned sodium sulfide solution with funnel again, and reaction is centrifugal behind the 30min, cleaning, drying; Make the PbS quantum dot, it is dispersed in the transmission electron microscope picture that records in the chloroform shown in Fig. 1 (c);
3) the ito glass substrate after will handling is placed on the spin coater, on electro-conductive glass, drips above-mentioned spin coating liquid 0.6ml, stops 2 seconds; Rotating speed spin coating with 600rpm makes its film forming, air dry 10min, the methanol solution of a 0.6ml mercaptopropionic acid (MPA); With the rotating speed spin coating of 3000rpm, air dry 5min drips the 0.4ml methanol solution then; Rotating speed with 3000rpm rotates to wash unnecessary MPA, and so repeating 5 thickness to the PbS quantum dot layer is 100nm;
4) be 10 in vacuum degree
-2Annealed 30 minutes under pa, 110 ℃ of temperature;
5) last is 10 in vacuum degree on the film after the above-mentioned processing
-5The Al negative electrode that hot vapor deposition thickness is 100nm under the condition can make this solar cell.
Claims (6)
1. a full-inorganic Schottky quantum dot solar cell is characterized in that: (mix the In of Sn with ito glass
2O
3Electro-conductive glass) be substrate, being superposeed successively by ito anode, PbS quantum dot layer and aluminium negative electrode constitutes.
2. according to the said full-inorganic Schottky of claim 1 quantum dot solar cell, it is characterized in that: the thickness of said PbS quantum dot layer is 100nm, and the thickness of aluminium negative electrode is 100nm.
3. preparation method of full-inorganic Schottky quantum dot solar cell according to claim 1 is characterized in that step is following:
1) the ito glass substrate is carried out ultrasonic cleaning with liquid detergent, deionized water, acetone, isopropyl alcohol, ethanol respectively successively, be placed on then in the vacuum tank 80 ℃ dry 1 hour down;
2) preparation PbS quantum dot chloroformic solution is as spin coating liquid;
3) the ito glass substrate after will handling is placed on the spin coater, on electro-conductive glass, drips above-mentioned spin coating liquid 0.4-0.6ml, stops 2 seconds; Rotating speed spin coating with 600rpm makes its film forming, air dry 10min, the methanol solution of a 0.4-0.6ml mercaptopropionic acid (MPA); Rotating speed spin coating with 3000rpm; Air dry 5min drips the 0.2-0.4ml methanol solution then, with the rotation of the rotating speed of 3000rpm to wash unnecessary MPA; The thickness that so is repeated to the PbS quantum dot layer is 100nm;
4) be 10 in vacuum degree
-2Annealed 30 minutes under pa, 110 ℃ of temperature;
5) last is 10 in vacuum degree on the film after the above-mentioned processing
-5The Al negative electrode that hot vapor deposition thickness is 100nm under the condition can make this solar cell.
4. according to the preparation method of the said full-inorganic Schottky of claim 3 quantum dot solar cell, it is characterized in that: the particle diameter of said PbS quantum dot is 3.3-4.0nm, and mol ratio plumbous and sulphur is 1: 0.3-0.8.
5. according to the preparation method of the said full-inorganic Schottky of claim 3 quantum dot solar cell, it is characterized in that: the concentration of said PbS quantum dot chloroformic solution is 10mg/ml.
6. according to the preparation method of the said full-inorganic Schottky of claim 3 quantum dot solar cell, it is characterized in that: the concentration of volume percent of said mercaptopropionic acid (MPA) methanol solution is 10%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107579138A (en) * | 2017-09-28 | 2018-01-12 | 武汉大学 | A kind of full-inorganic perovskite Schottky photodetector and preparation method thereof |
| US10236400B2 (en) | 2016-02-01 | 2019-03-19 | Heptagon Micro Optics Pte. Ltd. | Quantum dot film based demodulation structures |
| CN110556480A (en) * | 2019-09-12 | 2019-12-10 | 合肥工业大学 | All-solid-state solar cell based on synchronous deposition quantum dots and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102237202A (en) * | 2010-04-22 | 2011-11-09 | 财团法人工业技术研究院 | Thin film solar cell with quantum dots |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102237202A (en) * | 2010-04-22 | 2011-11-09 | 财团法人工业技术研究院 | Thin film solar cell with quantum dots |
Non-Patent Citations (3)
| Title |
|---|
| JASON P. CLIFFORD等: "Fast, sensitive and spectrally tuneable colloidalquantum-dot photodetectors", 《NATURE NANOTECHNOLOGY》, vol. 4, 31 January 2009 (2009-01-31), pages 40 - 44 * |
| JIANG TANG等: "Infrared Colloidal Quantum Dots for Photovoltaics: Fundamentals and Recent Progress", 《ADV. MATER.》, 14 September 2010 (2010-09-14), pages 12 - 29 * |
| JIANG TANG等: "Schottky Quantum Dot Solar Cells Stable in Air under Solar Illumination", 《ADV. MATER. 》, 7 January 2010 (2010-01-07), pages 1398 - 1402 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10236400B2 (en) | 2016-02-01 | 2019-03-19 | Heptagon Micro Optics Pte. Ltd. | Quantum dot film based demodulation structures |
| CN107579138A (en) * | 2017-09-28 | 2018-01-12 | 武汉大学 | A kind of full-inorganic perovskite Schottky photodetector and preparation method thereof |
| CN107579138B (en) * | 2017-09-28 | 2019-01-29 | 武汉大学 | A kind of full-inorganic perovskite Schottky photodetector and preparation method thereof |
| CN110556480A (en) * | 2019-09-12 | 2019-12-10 | 合肥工业大学 | All-solid-state solar cell based on synchronous deposition quantum dots and preparation method thereof |
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Application publication date: 20120815 |