CN101834275B - Intermediate electrode layer used in inversed laminated organic solar cell and preparation method - Google Patents
Intermediate electrode layer used in inversed laminated organic solar cell and preparation method Download PDFInfo
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- CN101834275B CN101834275B CN 201010184894 CN201010184894A CN101834275B CN 101834275 B CN101834275 B CN 101834275B CN 201010184894 CN201010184894 CN 201010184894 CN 201010184894 A CN201010184894 A CN 201010184894A CN 101834275 B CN101834275 B CN 101834275B
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Abstract
The invention discloses an intermediate electrode layer used in an inversed laminated organic solar cell and a preparation method. The electrode layer is sequentially deposited with a molybdenum trioxide layer, a metal silver or gold or platinum layer, a metal aluminum layer and a metal calcium or magnesium layer from bottom to top. The preparation method comprises the following steps of: scrubbing a glass substrate plated with indium tin oxid with a detergent, and then sequentially ultrasonically cleaning by using the detergent, deionized water, acetone and alcohol; placing the dried substrate in an ozone environment for plasma treatment, conveying the substrate to a high vacuum chamber with the vacuum degree of 9.0*10-5Pa through a glove box, evaporating metal calcium of 1 nm, and then transferring the substrate deposited with the calcium of 1 nm into the glove box for preparing a conjugated polymer light absorption layer; and conveying the conjugated polymer light absorption layer with a set thickness, which is deposited with the calcium of 1 nm, into the high vacuum chamber, and sequentially depositing the molybdenum trioxide layer, the metal silver or gold or platinum layer, the metal aluminum layer and the metal calcium or magnesium layer. The invention can effectively protect the prepared light absorption layer at the lower layer.
Description
Technical field
The present invention relates to a kind of intermediate electrode layer of inverted stack organic solar batteries, particularly a kind of intermediate electrode layer that is used for the inverted stack organic solar batteries and preparation method who adopts metal oxide layer and the combination of ultra-thin many metal nanos layer structural membrane.
Background technology
Solar energy is a kind of environmental protection, regenerative resource.Organic material possesses the advantage of certain uniqueness, such as low-cost, portable, flexible and be easy to large-scale production.This makes organic solar batteries become the technology that solar energy is changed into the tool potentiality of electric energy gradually.Yet the organic solar batteries of conventional structure receives the many restrictions of organic material itself, as:, exciton diffusion length narrow with respect to whole solar spectrum absorption region is lacked, the mobility of electric charge carrier is low, the life-span is short etc.In order to overcome these disadvantages, laminated construction is applied to organic solar batteries, promptly is made up of as sub-battery two or more light-absorption layers with spectrum complementation.Therefore, the intermediate electrode layer of connexon battery plays important role to the overall performance of device effectively.
Present intermediate electrode layer is mainly used in conventional laminated organic solar cell.Existing intermediate electrode layer mainly is prepared from vacuum vapour deposition and liquid film forming method, and combination wherein has: argent nanocluster, super thin metal gold; Metallic aluminium/tungsten oxide, tin indium oxide/3,4-vinyl dioxy thiophene polystyrene doped sulfonic acid; Aluminium/gold/3,4-vinyl dioxy thiophene polystyrene doped sulfonic acid, zinc oxide/3; 4-vinyl dioxy thiophene polystyrene doped sulfonic acid, titanium oxide/3,4-vinyl dioxy thiophene polystyrene doped sulfonic acid; Metallic aluminium/molybdenum trioxide, the titanium oxide of metallic aluminium/cesium doped/3,4-vinyl dioxy thiophene polystyrene doped sulfonic acid.Yet, be not useful on the intermediate electrode layer of inverted stack organic solar batteries so far as yet.This intermediate electrode layer be except having high light transmission rate and connexon battery effectively, also need play the effect that is not washed off of lower floor's light-absorption layer that protection prepared.
Summary of the invention
Technical problem to be solved by this invention is; Providing a kind of can be applied to have in the inverted stack battery of organic/conjugated polymer material as light-absorption layer of different absorption spectrum ranges; Can protect the lower floor's light-absorption layer that has prepared effectively, realize the intermediate electrode layer that is used for the inverted stack organic solar batteries and the preparation method of inverted stack organic solar batteries.
The technical scheme that the present invention adopted is: a kind of intermediate electrode layer and preparation method who is used for the inverted stack organic solar batteries; Wherein, the intermediate electrode layer that is used for the inverted stack organic solar batteries is to be arranged at down between straton battery and the last straton battery, is provided with by what the following supreme straton battery of straton battery deposited successively: the molybdenum trioxide layer; Argent or gold or platinum layer; Metal aluminium lamination and calcium metal or magnesium layer, the thickness of described molybdenum trioxide layer are 7～8 nanometers, and the thickness of argent or gold or platinum layer is 0.5～1.5 nanometer; The thickness of metal aluminium lamination is 0.5～1.5 nanometer, and the thickness of calcium metal or magnesium layer is 2.5～3.5 nanometers.
Be used for the preparation method of the intermediate electrode layer of inverted stack organic solar batteries, comprise the steps:
1) selection of substrate and processing:
The glass substrate that at first will be coated with tin indium oxide is cleaned with washing agent, uses washing agent, deionized water, acetone and alcohol ultrasonic cleaning subsequently successively again;
2) preparation of substrate modification:
With dried substrate, be put in and carry out Cement Composite Treated by Plasma in the ozone environment, through glove box, in the high vacuum chamber, the calcium metal of vapor deposition 1 nanometer, chamber vacuum degree are 9.0 * 10 with transfer substrates afterwards
-5Pa, the substrate-transfer that will deposit 1 nanometer calcium is again carried out the preparation of conjugated polymer light-absorption layer in glove box;
3) preparation of intermediate electrode layer:
Send in the high vacuum chamber with the sample of the conjugated polymer light-absorption layer of setting thickness depositing 1 nanometer calcium, deposit the molybdenum trioxide layer successively, argent or gold or platinum layer, metal aluminium lamination and calcium metal or magnesium layer.
The described molybdenum trioxide layer of step 3, argent or gold or platinum layer and calcium metal or magnesium layer all adopt the thermal evaporation vapor deposition, and described metal aluminium lamination adopts thermal evaporation or electron beam evaporation plating.
The deposition rate of the described molybdenum trioxide layer of step 3 is 0.02～0.05 nm/sec; The deposition rate of described argent or gold or platinum layer is 0.01～0.02 nm/sec; The deposition rate of described metal aluminium lamination is 0.02～0.05 nm/sec, and the deposition rate of described calcium metal or magnesium layer is 0.04～0.08 nm/sec.
Intermediate electrode layer and the preparation method who is used for the inverted stack organic solar batteries of the present invention has following characteristics.
1. only adopted the new combination of a series of metal and metal oxide to realize the purpose of connexon battery effectively.This scheme is easy to be used in various types of inverted stack organic solar batteries, thereby is that the performance that improves device provides safeguard.Its preparation method and flow process are simple, repeatability is strong.
2. optical characteristics of the present invention is a high permeability, has reduced the light loss that causes owing to sandwich construction.Its electrology characteristic is to make the electric charge carrier that comes from sub-battery to compound effectively in this layer, reaches the purpose of the open circuit voltage sum of corresponding inverted stack battery.Therefore, this invention helps being used for having the inverted stack organic solar batteries that the complementary light-absorption layer of spectrum is formed as sub-battery.
3. this invention can be protected the lower floor's light-absorption layer that has prepared effectively, realizes the inverted stack organic solar batteries.
Description of drawings
Fig. 1 is a structural representation of the present invention;
Fig. 2 is the light transmission rate collection of illustrative plates of the resulting intermediate electrode layer of the present invention;
Fig. 3 is resulting two contrasts of being inverted sub-battery and inverted stack organic solar batteries current density-voltage curve of the present invention.
Wherein:
1: following straton battery 2: molybdenum trioxide layer
3: argent or gold or platinum layer 4: metal aluminium lamination
5: calcium metal or magnesium layer 6: go up the straton battery
7: the incident sunlight
Embodiment
Provide specific embodiment below in conjunction with accompanying drawing, further specify intermediate electrode layer and the preparation method who is used for the inverted stack organic solar batteries of the present invention and how to realize.
As shown in Figure 1; The intermediate electrode layer that is used for the inverted stack organic solar batteries of the present invention; Be to be arranged at down between straton battery 1 and the last straton battery 6; Be provided with by what following straton battery 1 supreme straton battery 6 deposited successively: molybdenum trioxide layer 2, argent or gold or platinum layer 3, metal aluminium lamination 4 and calcium metal or magnesium layer 5.
The thickness of described molybdenum trioxide layer 2 is 7～8 nanometers, and the thickness of argent or gold or platinum layer 3 is 0.5～1.5 nanometer, and the thickness of metal aluminium lamination 4 is 0.5～1.5 nanometer, and the thickness of calcium metal or magnesium layer 5 is 2.5～3.5 nanometers.
Select for use in the embodiment of the invention: the thickness of molybdenum trioxide layer 2 is 7.5 nanometers, and the thickness of argent or gold or platinum layer 3 is 1 nanometer, and the thickness of metal aluminium lamination 4 is 1 nanometer, and the thickness of calcium metal or magnesium layer 5 is 3 nanometers.
The preparation method who is used for the intermediate electrode layer of inverted stack organic solar batteries of the present invention comprises the steps:
1) selection of substrate and processing:
The glass substrate that at first will be coated with tin indium oxide is cleaned with washing agent, uses washing agent, deionized water, acetone and alcohol ultrasonic cleaning subsequently successively again;
2) preparation of substrate modification:
With dried substrate, be put in and carry out Cement Composite Treated by Plasma in the ozone environment, through glove box, in the high vacuum chamber, the calcium metal of vapor deposition 1 nanometer, chamber vacuum degree are 9.0 * 10 with transfer substrates afterwards
-5Pa, the substrate-transfer that will deposit 1 nanometer calcium is again carried out the preparation of conjugated polymer light-absorption layer in glove box;
3) preparation of intermediate electrode layer:
Send in the high vacuum chamber with the sample of the conjugated polymer light-absorption layer of setting thickness depositing 1 nanometer calcium, deposit molybdenum trioxide layer 2 successively, argent or gold or platinum layer 3, metal aluminium lamination 4 and calcium metal or magnesium layer 5.
The thickness of the described molybdenum trioxide layer 2 of step 3 is 7～8 nanos, and the thickness of argent or gold or platinum layer 3 is 0.5～1.5 nanometer, and the thickness of metal aluminium lamination 4 is 0.5～1.5 nanometer, and the thickness of calcium metal or magnesium layer 5 is 2.5～3.5 nanometers.
Select for use in the embodiment of the invention: the thickness of molybdenum trioxide layer 2 is 7.5 nanometers, and the thickness of argent or gold or platinum layer 3 is 1 nanometer, and the thickness of metal aluminium lamination 4 is 1 nanometer, and the thickness of calcium metal or magnesium layer 5 is 3 nanometers.
The described molybdenum trioxide layer of step 32, argent or gold or platinum layer 3 and calcium metal or magnesium layer 5 all adopt the thermal evaporation vapor deposition, and described metal aluminium lamination 4 adopts thermal evaporation or electron beam evaporation platings.
The deposition rate of the described molybdenum trioxide layer 2 of step 3 is 0.02～0.05 nm/sec; The deposition rate of described argent or gold or platinum layer 3 is 0.01～0.02 nm/sec; The deposition rate of described metal aluminium lamination 4 is 0.02～0.05 nm/sec, and the deposition rate of described calcium metal or magnesium layer 5 is 0.04～0.08 nm/sec.
Select for use in the embodiment of the invention: the deposition rate of molybdenum trioxide layer 2 is 0.05 nm/sec; The deposition rate of argent or gold or platinum layer 3 is 0.01 nm/sec; The deposition rate of metal aluminium lamination 4 is 0.03 nm/sec, and the deposition rate of calcium metal or magnesium layer 5 is 0.06 nm/sec.
Fig. 2 is the light transmission rate collection of illustrative plates of the resulting intermediate electrode layer of the present invention; Fig. 3 is resulting two contrasts of being inverted sub-battery and inverted stack organic solar batteries current density-voltage curve of the present invention.
Resulting two performance comparison of being inverted sub-battery and inverted stack organic solar batteries of table 1 the present invention
Claims (4)
1. intermediate electrode layer that is used for the inverted stack organic solar batteries; Be arranged at down between straton battery (1) and the last straton battery (6), it is characterized in that, be provided with by what the following supreme straton battery of straton battery (1) (6) deposited successively: molybdenum trioxide layer (2); Argent or gold or platinum layer (3); Metal aluminium lamination (4) and calcium metal or magnesium layer (5), the thickness of described molybdenum trioxide layer (2) is 7～8 nanometers, the thickness of argent or gold or platinum layer (3) is 0.5～1.5 nanometer; The thickness of metal aluminium lamination (4) is 0.5～1.5 nanometer, and the thickness of calcium metal or magnesium layer (5) is 2.5～3.5 nanometers.
2. the described preparation method who is used for the intermediate electrode layer of inverted stack organic solar batteries of claim 1 is characterized in that, comprises the steps:
1) selection of substrate and processing:
The glass substrate that at first will be coated with tin indium oxide is cleaned with washing agent, uses washing agent, deionized water, acetone and alcohol ultrasonic cleaning subsequently successively again;
2) preparation of substrate modification:
With dried substrate, be put in and carry out Cement Composite Treated by Plasma in the ozone environment, through glove box, in the high vacuum chamber, the calcium metal of vapor deposition 1 nanometer, chamber vacuum degree are 9.0 * 10 with transfer substrates afterwards
-5Pa, the substrate-transfer that will deposit 1 nanometer calcium is again carried out the preparation of conjugated polymer light-absorption layer in glove box;
3) preparation of intermediate electrode layer:
Send in the high vacuum chamber with the sample of the conjugated polymer light-absorption layer of setting thickness depositing 1 nanometer calcium, deposit molybdenum trioxide layer (2) successively, argent or gold or platinum layer (3), metal aluminium lamination (4) and calcium metal or magnesium layer (5).
3. the preparation method who is used for the intermediate electrode layer of inverted stack organic solar batteries according to claim 2; It is characterized in that; The described molybdenum trioxide layer of step 3 (2), argent or gold or platinum layer (3) and calcium metal or magnesium layer (5) all adopt the thermal evaporation vapor deposition, and described metal aluminium lamination (4) adopts thermal evaporation or electron beam evaporation plating.
4. the preparation method who is used for the intermediate electrode layer of inverted stack organic solar batteries according to claim 2; It is characterized in that; The deposition rate of the described molybdenum trioxide layer of step 3 (2) is 0.02～0.05 nm/sec; The deposition rate of described argent or gold or platinum layer (3) is 0.01～0.02 nm/sec, and the deposition rate of described metal aluminium lamination (4) is 0.02～0.05 nm/sec, and the deposition rate of described calcium metal or magnesium layer (5) is 0.04～0.08 nm/sec.
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| CN109545869A (en) * | 2018-10-24 | 2019-03-29 | 四川大学 | A kind of flexible cadmium telluride solar cell of two-sided three terminal |
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| CN101179115A (en) * | 2007-12-17 | 2008-05-14 | 中国科学院长春应用化学研究所 | White light organic electroluminescent device and method for fabricating the same based on fluorochrome |
| JP2010103460A (en) * | 2008-03-26 | 2010-05-06 | Toppan Printing Co Ltd | Organic electroluminescence element, method for manufacturing organic electroluminescence element, and display unit |
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| CN101179115A (en) * | 2007-12-17 | 2008-05-14 | 中国科学院长春应用化学研究所 | White light organic electroluminescent device and method for fabricating the same based on fluorochrome |
| JP2010103460A (en) * | 2008-03-26 | 2010-05-06 | Toppan Printing Co Ltd | Organic electroluminescence element, method for manufacturing organic electroluminescence element, and display unit |
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