CN101640133A - Polymer/inorganic nano-crystal hybrid solar cell and manufacture method thereof - Google Patents
Polymer/inorganic nano-crystal hybrid solar cell and manufacture method thereof Download PDFInfo
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- CN101640133A CN101640133A CN200910067426A CN200910067426A CN101640133A CN 101640133 A CN101640133 A CN 101640133A CN 200910067426 A CN200910067426 A CN 200910067426A CN 200910067426 A CN200910067426 A CN 200910067426A CN 101640133 A CN101640133 A CN 101640133A
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Abstract
The invention provides a polymer/inorganic nano-crystal hybrid solar cell and a manufacture method thereof. P type inorganic nano-crystal cuprous oxide is induced to be taken as a cavity-collecting layer. The cuprous oxide nano-crystal improves ITO surface work function, enhances open circuit voltage, and improves the energy conversion efficiency of the solar cell. Compared with the cell which takes the traditional poly (3, 4-ring dioxide ethylthiophene): polystyrene sulfonate as a cavity transportation layer, the cell which takes the cuprous oxide as the cavity-collecting layer improves the open circuit voltage by 32.5%, short-circuit current by 49% and energy conversion efficiency by 171%; and compared with the cell which not use the cavity transportation layer, the device which takes the cuprous oxide as the cavity-collecting layer improves the open circuit voltage by 55.9%, short-circuit current by 57.2% and energy conversion efficiency by 222%.
Description
Technical field
The present invention relates to a kind of polymer/inorganic nano-crystal hybrid solar cell and method for making thereof.
Background technology
Utilize conjugated polymer to combine processing of organic semiconducting materials solution and the high advantage of inorganic semiconductor carrier mobility, become the research focus in this field in recent years as electron donor, the nanocrystalline polymer/inorganic nano-crystal hybrid solar cell of inorganic semiconductor as electron acceptor.Zinc oxide (ZnO) is environment-friendly material, the electron mobility height, and the preparation method is simple, and these advantages make ZnO that wide application prospect be arranged in polymer/inorganic nano-crystal hybrid solar cell.J.Janssen adopted zinc oxide nano-particle and [2-methoxyl group-5-(3 for the first time in 2004,7-dimethyl octyloxy)-and right-styrene support] (MDMO-PPV) blend (Adv.Mater.2004,16,1009-1013) tectosome heterojunction hybrid solar cell is at 100mW/cm
2AM1.5 simulated solar optical condition under battery conversion efficiency be 1.6%.
Yet the energy conversion efficiency of present polymer-inorganic nano crystal thin-film solar cell is also lower, one of them subject matter is to compare with inorganic semiconductor is nanocrystalline, the carrier mobility of conjugated polymer is lower, limit effective collection of photo-generated carrier, therefore caused the energy conversion efficiency of battery lower.If solve the collection efficiency problem in hole in this type of battery, the energy conversion efficiency of battery is improved a lot.
Summary of the invention
In order to solve the low problem of energy conversion efficiency of the battery that prior art exists, the invention provides a kind of polymer/inorganic nano-crystal hybrid solar cell and method for making thereof.Improve the carrier collection efficient of battery as the collecting layer, hole by the p N-type semiconductor N cuprous nano crystalline substance of introducing high carrier mobility at indium tin oxide (ITO) anode surface.Cuprous oxide (Cu
2O) surface, collecting layer, nanocrystalline hole has coarse surface texture, has increased the contact area with conjugated polymer, thereby forms the collection efficiency that effective hole transport passage improves hole in the conjugated polymer, reduces the compound of charge carrier; And then short circuit current, open circuit voltage, fill factor, curve factor and the energy conversion efficiency of raising battery.
As shown in Figure 1, a kind of polymer/inorganic nano-crystal hybrid solar cell, its glass substrate 1 is connected with ito anode layer 2; The photosensitive layer 4 that the blend of conjugated polymer and zinc oxide constitutes is connected with negative electrode aluminium 5; It is characterized in that also having collecting layer, cuprous oxide hole 3, collecting layer, described cuprous oxide hole 3 is connected with the photosensitive layer 4 that the blend of ito anode layer 2 and conjugated polymer and zinc oxide constitutes respectively; The thickness of described indium tin oxide anode layer 2 is the 80-150 nanometer; Collecting layer, cuprous oxide hole 3 thickness are the 30-80 nanometer; The thickness of photosensitive layer 4 is the 100-200 nanometer; The thickness of negative electrode aluminium 5 is the 80-200 nanometer.
A kind of polymer/inorganic nano-crystal hybrid solar cell and preparation method thereof, its Step By Condition is as follows:
In inert-atmosphere glove box, to gather [2-methoxyl group-5-(2-ethyl hexyl oxy)-1,4-styrene support] (MEH-PPV) be dissolved in chlorobenzene with 1: 3.3 mass ratio with ZnO: the methyl alcohol volume ratio was in 95: 5 the mixed solvent, to obtain mixed solution, with mixed solution magnetic agitation 12 hours; The concentration of described MEH-PPV is 3.5 mg/ml; The particle diameter of ZnO is 5 nanometers, and the concentration of ZnO is 11.55 mg/ml;
Will be on glass substrate 1 thickness be that to be etched into width be 4 millimeters fine strip shape for the ito anode layer 2 of 80-150 nanometer, the ito glass of the good fine strip shape of etching is cleaned up, put into baking oven 120 ℃ of oven dry down, place it in again on the carriage of film applicator, by 0.45 micron filtering head cuprous oxide ethylene glycol dispersion liquid is evenly coated on the ito substrate, the particle diameter of cuprous nano crystalline substance is between the 20-100 nanometer, the concentration of this dispersion liquid is 7 mg/ml, rotation is one minute under 450-4000 rev/min rotating speed, forming a layer thickness on the ITO surface is the collecting layer, cuprous oxide hole 3 of 30-80 nanometer, the vacuum drying oven of putting into vacuum degree and be 0.1 Pascal vacuumizes removed ethylene glycol solvent in 1 hour, to scribble the substrate-transfer of collecting layer, hole 3 again in glove box, be placed on the carriage of film applicator, the filtering head of the MEH-PPV/ZnO mixed solution that stirs by 0.45 micron be evenly coated in collecting layer, cuprous oxide hole 3 above, with 900 rpms rotating speed spin-coating, obtaining thickness is the substrate of the photosensitive layer 4 of 100-200 nanometer;
The substrate that scribbles photosensitive layer 4 is taken out in glove box with shifting bottle, put into vacuum coating equipment and vacuumize, when vacuum degree reaches 4 * 10
-4During Pascal, the aluminium of evaporation 80-200 nanometer is as negative electrode 5; Making structure by above step is ITO (120nm)/Cu
2Polymer-inorganic nano-crystal hybrid hybrid solar cell of O (30-80nm)/MEH-PPV:ZnO (140nm)/Al (80nm).The effective area of this battery is 12 square millimeters.
In intensity is the performance of testing polymer/inorganic nano-crystal hybrid solar cell of the present invention under the AM 1.5G simulated solar irradiation of 100 milliwatt/square centimeters, comprises open circuit voltage, short circuit current, energy conversion efficiency and fill factor, curve factor.
Table 1 has been listed the performance parameter of Comparative Examples 1,2 and embodiment 1,2,3,4,5 polymer/inorganic nano-crystal hybrid solar cells.As can be seen from Table 1: short circuit current increases with cuprous oxide spin coating rotating speed, and when cuprous oxide spin coating rotating speed was 2000 rpms, short circuit current was 4.15 milliamperes/square centimeter to the maximum, and the ceiling capacity transformation efficiency is 2.22%.Short circuit current and energy conversion efficiency all reduce when cuprous oxide spin coating rotating speed continues to increase.And open circuit voltage increases variation not quite with cuprous oxide spin coating rotating speed.Compare with Comparative Examples 1, the open circuit voltage of embodiment 3 has improved 32.5%; Short circuit current has improved 49%; Energy conversion efficiency has improved 171%; Compare with Comparative Examples 2, the open circuit voltage of embodiment 3 has improved 55.9%; Short circuit current has improved 57.2%; Energy conversion efficiency has improved 222%.
Beneficial effect: the present invention relates to a kind of polymer/inorganic nano-crystal hybrid solar cell.Be specially by collecting layer, spin coating hole cuprous oxide on ito substrate, on the one hand improved the hole collection efficiency, thereby make and hole and electron mobility transmit more balance to have reduced charge carrier compound, improved the short circuit current of battery; Improve the ITO work content on the other hand, increased the too open circuit voltage of hydridization sun energy battery of polymer-inorganic nano-crystal, this two aspects effect has improved polymer inorganic nano-crystal hybrid solar cell energy conversion efficiency.With using poly-(3,4-vinyl dioxy thiophene): poly styrene sulfonate (PEDOT:PSS) is made the device of hole transmission layer and is compared, the series resistance of using cuprous oxide to make the battery of collecting layer, hole drops to 17 ohm of square centimeters by 165 ohm of square centimeters, has reduced 89.7%.Open circuit voltage is increased to 1.06 volts by 0.80 volt, has improved 32.5%.Short circuit current increases to 4.15 milliamperes/square centimeter by 2.78 milliamperes/square centimeter, has improved 49%, and energy conversion efficiency increases to 2.22% by 0.82%, has improved 171%.Compare with the device that does not use hole transmission layer, the series resistance of using cuprous oxide to make the battery of collecting layer, hole drops to 17 ohm of square centimeters by 283 ohm of square centimeters, reduced 94%, open circuit voltage is increased to 1.06 volts by 0.68 volt, improved 55.9%, short circuit current increases to 4.15 milliamperes/square centimeter by 2.64 milliamperes/square centimeter, has improved 57.2%, energy conversion efficiency increases to 2.22% by 0.69%, has improved 222%.
Description of drawings
Fig. 1 is the battery structure schematic diagram that Comparative Examples 1 and embodiment 1,2,3,4,5 adopt.Among the figure: 1 layer is glass substrate; 2 layers is the ito anode layer; 4 layers is the MEH-PPV:ZnO photosensitive layer; 5 layers is the aluminium cathode layer; 3 layers of Comparative Examples 1 is PEDOT:PSS, and embodiment 1,2,3,4 and 53 layers are Cu
2Collecting layer, O hole.
Fig. 2 is the battery structure schematic diagram of Comparative Examples 2.Wherein: 1 layer is glass substrate; 2 layers is the ito anode layer; 4 layers is the MEH-PPV:ZnO photosensitive layer; 5 layers is the aluminium cathode layer.
Fig. 3 is that Comparative Examples 1,2 and embodiment 1,2,3,4,5 are the current-voltage characteristic curve figure that tests under the AM 1.5G simulated solar irradiation of 100 milliwatt/square centimeters in intensity.
Wherein, curve A is that Comparative Examples 1 is the current-voltage characteristic curve figure that tests under the AM 1.5G simulated solar irradiation of 100 milliwatt/square centimeters in intensity.
Curve B is that Comparative Examples 2 is the current-voltage characteristic curve figure that tests under the AM 1.5G simulated solar irradiation of 100 milliwatt/square centimeters in intensity.
Curve C is that embodiment 1 is the current-voltage characteristic curve figure that tests under the AM 1.5G simulated solar irradiation of 100 milliwatt/square centimeters in intensity.
Curve D is that embodiment 2 is the current-voltage characteristic curve figure that tests under the AM 1.5G simulated solar irradiation of 100 milliwatt/square centimeters in intensity.
Curve E is that embodiment 3 is the current-voltage characteristic curve figure that tests under the AM 1.5G simulated solar irradiation of 100 milliwatt/square centimeters in intensity.
Curve F is that embodiment 4 is the current-voltage characteristic curve figure that tests under the AM 1.5G simulated solar irradiation of 100 milliwatt/square centimeters in intensity.
Curve G is that embodiment 5 is the current-voltage characteristic curve figure that tests under the AM 1.5G simulated solar irradiation of 100 milliwatt/square centimeters in intensity.
Embodiment
Comparative Examples 1
In inert-atmosphere glove box, to gather [2-methoxyl group-5-(2-ethyl hexyl oxy)-1,4-styrene support] (MEH-PPV) be dissolved in chlorobenzene with 1: 3.3 mass ratio with ZnO: the methyl alcohol volume ratio was in 95: 5 the mixed solvent, to obtain mixed solution, with mixed solution magnetic agitation 12 hours; The concentration of described MEH-PPV is 3.5 mg/ml; The particle diameter of ZnO is 5 nanometers, and the concentration of ZnO is 11.55 mg/ml;
Will be on glass substrate 1 thickness be that to be etched into width be 4 millimeters fine strip shape for the indium tin oxide anode layer 2 of 120 nanometers, the ito glass of the good fine strip shape of etching is cleaned up, put into baking oven, 120 ℃ of oven dry, again this workpiece is placed on the carriage of film applicator, filtering head by 0.45 micron, to gather (3,4-vinyl dioxy thiophene): the solution of poly styrene sulfonate (PEDOT:PSS) evenly is coated with completely whole slice, thin piece, with 3000 rpms rotating speed spin-coating film, form the film of one deck 40 nanometer thickness on the ITO surface, as anode modification layer 3, put into baking oven again, 120 ℃ were heated 30 minutes;
The workpiece that scribbles PEDOT:PSS is transferred in the glove box, treat to be placed on the spin coater carriage after the substrate cooling, the MEH-PPV/ZnO mixed solution that stirs is evenly coated in the surface of PEDOT:PSS by 0.45 micron filtering head, with 900 rpms speed rotations one minute, obtain the photosensitive layer of 140 nanometer thickness;
The sample that scribbles photosensitive layer 4 is taken out from glove box with shifting bottle, put into vacuum coating equipment, vacuumize, when vacuum degree reaches 4 * 10
-4During Pascal, the aluminium cathode layer 5 of evaporation 80 nanometer thickness.Transfer in the glove box having steamed aluminium electrode device afterwards, encapsulation is got up, and finishes the making of polymer-inorganic nano-crystal hybrid solar cell.Making structure is ITO (120nm)/PEDOT:PSS (40nm)/MEH-PPV:ZnO (140nm)/Al (80nm) polymer/inorganic nano-crystal hybrid solar cell.
Comparative Examples 2
Device architecture and preparation method are with Comparative Examples 1, different is the MEH-PPV/ZnO mixed solution that stirs in the direct spin coating in ito anode surface, and making structure is the polymer/inorganic nano-crystal hybrid solar cell of ITO (120nm)/MEH-PPV:ZnO (140nm)/Al (80nm).
In inert-atmosphere glove box, MEH-PPV and ZnO are dissolved in chlorobenzene with 1: 3.3 mass ratio: the methyl alcohol volume ratio was in 95: 5 mixed solvents, to obtain mixed solution, with mixed solution magnetic agitation 12 hours; The concentration of described MEH-PPV is 3.5 milligrams every milliliter; The particle diameter of ZnO is 5 nanometers, and the concentration of ZnO is 11.55 milligrams every milliliter;
Will be on glass substrate 1 thickness be that to be etched into width be 4 millimeters fine strip shape for the indium tin oxide anode layer 2 of 120nm, the ito glass of the good fine strip shape of etching is cleaned up, put into baking oven, 120 ℃ of oven dry, again this workpiece is placed on the carriage of film applicator, by 0.45 micron filtering head, with Cu
2The dispersion liquid of O evenly is coated with completely whole slice, thin piece, with 450 rpms rotating speed spin-coating film, forms the Cu that a layer thickness is 80 nanometers in this this work piece surface
2Collecting layer, O hole 3, the vacuum drying oven of putting into vacuum degree again and be 0.1 Pascal vacuumizes removed ethylene glycol solvent in 1 hour;
The preparation that baking is good has Cu
2The sample transfer of collecting layer, O hole 3 places it on the carriage of film applicator in glove box, and the MEH-PPV/ZnO mixed solution that the stirs filtering head by 0.45 micron is evenly coated in Cu
2Above the O hole transmission layer 3, spin-coating, rotating speed are that per minute 900 changes, and obtaining thickness is the photosensitive layer 4 of 140 nanometers;
The workpiece that scribbles photosensitive layer 4 is taken out from glove box with shifting bottle, put into vacuum coating equipment, vacuumize, when vacuum degree reaches 4 * 10
-4During Pascal, the aluminium cathode layer 5 of evaporation 80 nanometer thickness.Transfer in the glove box having steamed aluminium electrode device afterwards, encapsulation is got up, and finishes the making of polymer/inorganic nano-crystal solar cell.Device architecture is ITO (120nm)/Cu
2O (80nm)/MEH-PPV:ZnO (140nm)/Al (80nm).
Device architecture and preparation method are with embodiment 1, and that different is Cu
2O spin coating rotating speed is that per minute 1000 changes, and obtains the Cu that thickness is 50 nanometers
2Collecting layer, O hole.Device architecture is ITO (120nm)/Cu
2O (50nm)/MEH-PPV:ZnO (140nm)/Al (80nm).
Device architecture and preparation method are with embodiment 1, and that different is Cu
2O spin coating rotating speed is that per minute 2000 changes, and obtains the Cu that thickness is 40 nanometers
2Collecting layer, O hole.Device architecture is ITO (120nm)/Cu
2O (40nm)/MEH-PPV:ZnO (140nm)/Al (80nm).
Device architecture and preparation method are with embodiment 1, and that different is Cu
2O spin coating rotating speed is that per minute 3000 changes, and obtains the Cu that thickness is 35 nanometers
2Collecting layer, O hole.Device architecture is ITO (120nm)/Cu
2O (35nm)/MEH-PPV:ZnO (140nm)/Al (80nm).
Device architecture and preparation method are with embodiment 1, and that different is Cu
2O spin coating rotating speed is that per minute 4000 changes, and obtains the Cu that thickness is 30 nanometers
2Collecting layer, O hole.Device architecture is ITO (120nm)/Cu
2O (30nm)/MEH-PPV:ZnO (140nm)/Al (80nm).
Table 1
| Open circuit voltage (V) | Short circuit current (mA/cm 2) | Conversion efficiency (%) | Fill factor, curve factor | Series resistance (Ω .cm 2) | |
| Comparative Examples 1 | ??0.80 | ??2.78 | ??0.82 | ??0.37 | ??165 |
| Comparative Examples 2 | ??0.68 | ??2.64 | ??0.69 | ??0.39 | ??283 |
| |
??1.08 | ??3.04 | ??1.45 | ??0.44 | ??30 |
| |
??1.08 | ??3.58 | ??1.71 | ??0.44 | ??39 |
| |
??1.06 | ??4.15 | ??2.22 | ??0.50 | ??17 |
| |
??1.06 | ??4.05 | ??2.11 | ??0.49 | ??20 |
| |
??1.06 | ??3.83 | ??1.91 | ??0.47 | ??22 |
Table 1 is to be the device performance parameter comparison of Comparative Examples 1,2 and embodiment 1,2,3,4,5 under the AM 1.5G simulated solar irradiation of 100 milliwatt/square centimeters in intensity, comprising: open circuit voltage, short circuit current, fill factor, curve factor, energy conversion efficiency and series resistance.
Claims (2)
1. polymer/inorganic nano-crystal hybrid solar cell, it is characterized in that it is constructed as follows: glass substrate (1) is connected with indium tin oxide anode layer (2); The photosensitive layer (4) that the blend of conjugated polymer and zinc oxide constitutes is connected with negative electrode aluminium (5); It is characterized in that also having collecting layer, cuprous oxide hole (3), collecting layer, described cuprous oxide hole (3) is connected with the photosensitive layer (4) that the blend of ito anode layer (2) and conjugated polymer and zinc oxide constitutes respectively; The thickness of described indium tin oxide anode layer (2) is the 80-150 nanometer; Collecting layer, cuprous oxide hole (3) thickness is the 30-80 nanometer; The thickness of photosensitive layer (4) is the 100-200 nanometer; The thickness of negative electrode aluminium (5) is the 80-200 nanometer.
2. a kind of polymer/inorganic nano-crystal hybrid solar cell as claimed in claim and preparation method thereof, its Step By Condition is as follows:
In inert-atmosphere glove box, to gather [2-methoxyl group-5-(2-ethyl hexyl oxy)-1,4-styrene support] be dissolved in chlorobenzene with ZnO with 1: 3.3 mass ratio: the methyl alcohol volume ratio was in 95: 5 the mixed solvent, to obtain mixed solution, with mixed solution magnetic agitation 12 hours; The concentration of described poly-[2-methoxyl group-5-(2-ethyl hexyl oxy)-1, the support of 4-styrene] is 3.5 mg/ml; The particle diameter of ZnO is 5 nanometers, and the concentration of ZnO is 11.55 mg/ml;
Will be on glass substrate 1 thickness be that to be etched into width be 4 millimeters fine strip shape for the indium tin oxide anode layer 2 of 120 nanometers, the glass substrate of the indium tin oxide of the good fine strip shape of etching is cleaned up, put into baking oven 120 ℃ of oven dry down, place it in again on the carriage of film applicator, by 0.45 micron filtering head cuprous oxide ethylene glycol dispersion liquid is evenly coated on the glass substrate of indium tin oxide, the particle diameter of cuprous nano crystalline substance is between the 20-100 nanometer, the concentration of this dispersion liquid is 7 mg/ml, rotation is one minute under 450-4000 rev/min rotating speed, forming a layer thickness on the indium tin oxide surface is the collecting layer, cuprous oxide hole 3 of 30-80 nanometer, the vacuum drying oven of putting into vacuum degree and be 0.1 Pascal vacuumizes removed ethylene glycol solvent in 1 hour, to scribble the substrate-transfer of collecting layer, hole 3 again in glove box, be placed on the carriage of film applicator, the poly-[2-methoxyl group-5-(2-ethyl hexyl oxy)-1 that stirs, the filtering head of 4-styrene support/ZnO mixed solution by 0.45 micron be evenly coated in collecting layer, cuprous oxide hole 3 above, spin-coating obtains photosensitive layer 4;
The substrate that scribbles photosensitive layer 4 is taken out in glove box with shifting bottle, put into vacuum coating equipment and vacuumize, when vacuum degree reaches 4 * 10
-4During Pascal, AM aluminum metallization obtains the polymer/inorganic nano-crystal hybrid hybrid solar cell as negative electrode 5.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101969102A (en) * | 2010-08-09 | 2011-02-09 | 吉林大学 | Method for preparing all-water phase nanocrystal/conductive polymer hybrid solar cells |
| CN102214734A (en) * | 2011-06-07 | 2011-10-12 | 济南大学 | Method for manufacturing zinc oxide/cuprous oxide thin film solar cell |
| CN102569480A (en) * | 2012-01-01 | 2012-07-11 | 浙江大学 | Cuprous oxide-based PIN-junction solar battery of nano structure and preparation method thereof |
| CN102945693A (en) * | 2012-10-31 | 2013-02-27 | 清华大学 | Method for improving surface work function of ITO transparent conducting thin film and application of ITO transparent conducting thin film |
| WO2014047859A1 (en) * | 2012-09-28 | 2014-04-03 | 海洋王照明科技股份有限公司 | Polymer solar cell and preparation method thereof |
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2009
- 2009-08-24 CN CN2009100674268A patent/CN101640133B/en active Active
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101969102A (en) * | 2010-08-09 | 2011-02-09 | 吉林大学 | Method for preparing all-water phase nanocrystal/conductive polymer hybrid solar cells |
| CN101969102B (en) * | 2010-08-09 | 2012-05-23 | 吉林大学 | Method for preparing all-water phase nanocrystal/conductive polymer hybrid solar cells |
| CN102214734A (en) * | 2011-06-07 | 2011-10-12 | 济南大学 | Method for manufacturing zinc oxide/cuprous oxide thin film solar cell |
| CN102569480A (en) * | 2012-01-01 | 2012-07-11 | 浙江大学 | Cuprous oxide-based PIN-junction solar battery of nano structure and preparation method thereof |
| WO2014047859A1 (en) * | 2012-09-28 | 2014-04-03 | 海洋王照明科技股份有限公司 | Polymer solar cell and preparation method thereof |
| CN102945693A (en) * | 2012-10-31 | 2013-02-27 | 清华大学 | Method for improving surface work function of ITO transparent conducting thin film and application of ITO transparent conducting thin film |
| CN102945693B (en) * | 2012-10-31 | 2016-03-16 | 清华大学 | Improve method and the application thereof of ITO transparent conductive film surface work function |
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