CN102074654A - Preparation method for improving efficiency of polymer solar battery - Google Patents
Preparation method for improving efficiency of polymer solar battery Download PDFInfo
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Abstract
一种提高聚合物太阳电池效率的制备方法，电极采用电子束蒸发技术制备，制备方法包括如下步骤：在glass层上制作ITO层，作为太阳电池的阳极；采用光刻的方法，将ITO层一侧刻蚀掉，刻蚀深度到glass层的表面，防止ITO与电池的阴极连通；在暴露的glass层的上面及ITO层制备一层PEDOT:PSS层，作为太阳电池的空穴传输层；将ITO层一侧上面的PEDOT:PSS层擦除掉，擦除深度到ITO层的表面，使暴露的ITO层形成台面，该台面为阳极，与外电路连接；在PEDOT:PSS层上制备聚合物/富勒烯衍生物共混薄膜；在聚合物/富勒烯衍生物共混薄膜上制备Al薄膜；在Al薄膜上制备Al电极，该Al电极为阴极；退火，将制备完成的聚合物太阳电池退火，完成电极的制备。
A preparation method for improving the efficiency of a polymer solar cell. The electrode is prepared by electron beam evaporation technology. The preparation method includes the following steps: making an ITO layer on the glass layer as the anode of the solar cell; The side is etched away, and the etching depth reaches the surface of the glass layer to prevent the ITO from being connected to the cathode of the battery; prepare a layer of PEDOT:PSS layer on the exposed glass layer and the ITO layer as the hole transport layer of the solar cell; The PEDOT:PSS layer on one side of the ITO layer is erased, and the depth of the erase is to the surface of the ITO layer, so that the exposed ITO layer forms a mesa, which is an anode and is connected to the external circuit; polymer is prepared on the PEDOT:PSS layer / fullerene derivative blend film; Al film is prepared on the polymer/fullerene derivative blend film; Al electrode is prepared on the Al film, and the Al electrode is the cathode; annealing, the prepared polymer solar The battery is annealed to complete the electrode preparation.
Description
Technical field
The present invention relates to the solar-photovoltaic technology field, particularly a kind of preparation method who improves the polymer efficiency of solar cell.
Background technology
The organic polymer solar cell has that cost is low, in light weight, preparation technology is simple, can be prepared into outstanding advantage such as flexible device.Therefore, the research of this class solar cell associated materials and device technology in recent years becomes the forward position and the focus of domestic and international research.In the organic polymer solar cell based on polythiophene (P3HT) and fullerene derivate (PCBM) blend film, preparation good conductivity, stable fine and close metallic aluminium (Al) electrode are to obtain high efficiency key as cell cathode.Traditionally, often adopt thermal evaporation techniques at room temperature to deposit the negative electrode of the Al of preparation 100-200nm, then entire device is carried out the efficient that thermal annealing improves solar cell as the polymer solar cell.Yet thermal evaporation techniques prepares metal electrode and has that poor controllability, utilization rate of raw materials are low, poor stability, be subject to shortcomings such as resistive heater pollution, is difficult to realize the suitability for industrialized production requirement of controlled large-area preparation solar cell metal electrode.Electron beam evaporation is the good metallic film depositing technics of a kind of cleaning, utilization rate of raw materials height, controllability and stable type, can be applied in the metal electrode preparation of large tracts of land polymer solar cell.Yet the example that utilizes electron beam evaporation technique to prepare the metal A l electrode of polymer solar cell is not reported as yet.And, if the direct Al electrode of deposited by electron beam evaporation deposition techniques one deck desired thickness at room temperature on organic film, electrode is chapping easily through low temperature (normally 150 ℃) annealing back, the conductivity of electrode is reduced greatly, and its efficient will be lower than the battery that utilizes conventional thermal evaporation techniques to prepare electrode.Consult Figure 1B prepares the polymer solar cell of electrode for conventional thermal evaporation techniques structural representation.
Summary of the invention
The objective of the invention is to, a kind of preparation method who improves the polymer efficiency of solar cell is provided, wherein be to adopt efficient cheap electron beam evaporation technique to prepare the negative electrode Al electrode of polymer solar cell, and, have characteristics such as cost is low, simple to operate, widely applicable, practical by the efficient that the preparation technology of control electrode improves solar cell.
The invention provides a kind of preparation method who improves the polymer efficiency of solar cell, electrode adopts the electron beam evaporation technique preparation, and the preparation method comprises the steps:
Step 1: on the glass layer, make the ITO layer, as the anode of solar cell;
Step 2: adopt the method for photoetching, ITO layer one side etched away, etching depth prevents that to the surface of glass layer ITO is communicated with the negative electrode of battery;
Step 3: on the glass layer that exposes and the ITO layer prepare one deck PEDOT:PSS layer, as the hole transmission layer of solar cell;
Step 4: the PEDOT:PSS layer above ITO layer one side is wiped, wiped the surface of the degree of depth to the ITO layer, make the ITO layer of exposure form table top, this table top is an anode, is connected with external circuit;
Step 5: on the PEDOT:PSS layer, prepare polymer/fullerene derivate blend film;
Step 6: preparation Al film on polymer/fullerene derivate blend film;
Step 7: preparation Al electrode on the Al film, this Al electrode is a negative electrode;
Step 8: annealing, with the polymer solar cell annealing that preparation is finished, finish the preparation of electrode.
Wherein annealing is to carry out thermal annealing in being full of the glove box of high pure nitrogen, and the water in the glove box and the content of oxygen are lower than 1ppm, and annealing temperature is 120-160 ℃, and annealing time is 5-15 minute.
The background vacuum pressure that wherein prepares the used electron beam evaporation system of Al film and Al electrode is 1-3 * 10
-4Pa, the line of electron gun are 80-120mA, and operating voltage is 8500-9500V.When wherein preparing the Al film, preparation temperature is 20-25 ℃, and deposition rate is
/ second.
Wherein the thickness of Al film is 50-120nm.
When wherein preparing the Al electrode, preparation temperature is 70-90 ℃, and deposition rate is
/ second.
Wherein the thickness of Al electrode is 80-150nm.
The present invention also provides a kind of preparation method who improves the polymer efficiency of solar cell, and electrode adopts the electron beam evaporation technique preparation, and the preparation method comprises the steps:
Step 1: on the glass layer, make the ITO layer, as the anode of solar cell;
Step 2: adopt the method for photoetching, ITO layer one side etched away, etching depth prevents that to the surface of glass layer ITO is communicated with the negative electrode of battery;
Step 3: on the glass layer that exposes and the ITO layer prepare one deck PEDOT:PSS layer, as the hole transmission layer of solar cell;
Step 4: the PEDOT:PSS layer above ITO layer one side is wiped, wiped the surface of the degree of depth to the ITO layer, make the ITO layer of exposure form table top, this table top is an anode, is connected with external circuit;
Step 5: on the PEDOT:PSS layer, prepare polymer/fullerene derivate blend film;
Step 6: preparation Al electrode on polymer/fullerene derivate blend film, this Al electrode is a negative electrode;
Step 7: annealing, with the polymer solar cell annealing that preparation is finished, finish the preparation of electrode.
Wherein annealing is to carry out thermal annealing in being full of the glove box of high pure nitrogen, and the water in the glove box and the content of oxygen are lower than 1ppm, and annealing temperature is 120-160 ℃, and annealing time is 5-15 minute.
The background vacuum pressure that wherein prepares the used electron beam evaporation system of Al electrode is 1-3 * 10
-4Pa, the line of electron gun are 80-120mA, and operating voltage is 8500-9500V.
When wherein preparing the Al electrode, preparation temperature is 70-90 ℃, and deposition rate is
/ second.
Wherein the thickness of Al electrode is 80-150nm.
Description of drawings
For further specifying feature of the present invention and technical scheme, below in conjunction with application example the present invention is explained in detail, wherein:
Figure 1A is the structural representation of polymer solar cell of the present invention.
Figure 1B prepares the structural representation of the polymer solar cell of electrode for conventional thermal evaporation techniques.
Fig. 2 is according to the density of photocurrent-photovoltage curve of polymer solar cell in the embodiment of the invention under the big sunlight of standard (AM1.5G).
Embodiment
See also Figure 1A, the invention provides a kind of preparation method who improves the polymer efficiency of solar cell, electrode adopts the electron beam evaporation technique preparation, and the preparation method comprises the steps:
Step 1: make ITO layer 20 on glass layer 10, as the anode of polymer solar cell, the square resistance of ITO layer 20 is the 7-15 ohms/square;
Step 2: adopt the method for photoetching, ITO layer 20 1 side are etched away, etching depth prevents that to the surface of glass layer 10 ITO is communicated with the negative electrode of battery;
Step 3: on the glass layer 10 that exposes and ITO layer 20 preparation one deck PEDOT:PSS layer 30, as the hole transmission layer of polymer solar cell, the thickness of PEDOT:PSS layer 30 is 20～40 nanometers;
Step 4: the PEDOT:PSS layer 30 above ITO layer 20 1 side is wiped, wiped the surface of the degree of depth to ITO layer 20, make the ITO layer 20 of exposure form table top 21, this table top is the anode of polymer solar cell, is used for being connected with external circuit;
Step 5: on PEDOT:PSS layer 30, prepare semi-conductive polymer/fullerene derivate blend film 40, as the photosensitive layer of battery;
Step 6: preparation Al film 50 on semi-conductive polymer/fullerene derivate blend film 40, when wherein preparing Al film 50, preparation temperature is 20-25 ℃, deposition rate is
/ second, the thickness of this Al film 50 is 50-120nm;
Step 7: preparation Al electrode 60 on Al film 50, this Al electrode 60 is the negative electrode of polymer solar cell, and when wherein preparing Al electrode 60, preparation temperature is 70-90 ℃, and deposition rate is
/ second, the thickness of this Al electrode 60 is 80-150nm;
The background vacuum pressure that wherein prepares the used electron beam evaporation system of Al film 50 and Al electrode 60 is 2 * 10
-4Pa, the line of electron gun are 80-120mA, and operating voltage is 8500-9500V;
Step 8: annealing, with the polymer solar cell annealing that preparation is finished, finish the preparation of electrode, described annealing is to carry out thermal annealing in being full of the glove box of high pure nitrogen, the water in the glove box and the content of oxygen are lower than 1ppm, and annealing temperature is 120-160 ℃, and annealing time is 5-15 minute.
Specific embodiment
Example 1: consult shown in Figure 1A, make ITO layer 20 on glass layer 10, the square resistance of ITO layer 20 is 15 ohms/square.Adopt the method for photoetching, ITO layer 20 1 side are etched away, etching depth is to the surface of glass layer 10.On the glass layer 10 that exposes and ITO layer 20 preparation one deck PEDOT:PSS layer 30, the thickness of PEDOT:PSS layer 30 is 30 nanometers.PEDOT:PSS layer 30 above ITO layer 20 1 side is wiped, wiped the surface of the degree of depth, make the ITO layer 20 of exposure form table top 21 to ITO layer 20.Spin coating P3HT/PCBM blend film 40 on PEDOT:PSS layer 30, the mass ratio of P3HT and PCBM is 1: 1, thickness is 100 nanometers.Adopt electron beam evaporation system depositing Al film 50 on P3HT/PCBM blend film 40, the background vacuum pressure of electron beam evaporation system is 2 * 10
-4Pa, the line of electron gun are 100mA, and operating voltage is 9000V, underlayer temperature T
1Be 25 ℃, deposition rate is
/ second, the thickness of Al film 50 is 50nm.Adopt electron beam evaporation system depositing Al electrode 60 on Al membrane electrode 50 then, the background vacuum pressure of electron beam evaporation system is 2 * 10
-4Pa, the line of electron gun are 100mA, and operating voltage is 9000V, and underlayer temperature is 80 ℃, and deposition rate is for being
/ second, the thickness of Al film 60 is 100nm.Be full of high-purity N
2Glove box in, battery is carried out thermal annealing, annealing temperature is 150 ℃, annealing time is 10 minutes.At the big sunlight of standard (AM 1.5G, a 100mW/cm
2) following open circuit voltage 0.68V, the short-circuit current density 8.97mA/cm that records battery of irradiation
2, fill factor, curve factor 0.45, energy conversion efficiency be 2.7%.
Example 2: consult shown in Figure 1B, make ITO layer 20 on glass layer 10, the square resistance of ITO layer 20 is 15 ohms/square.Adopt the method for photoetching, ITO layer 20 1 side are etched away, etching depth is to the surface of glass layer 10.On the glass layer 10 that exposes and ITO layer 20 preparation one deck PEDOT:PSS layer 30, the thickness of PEDOT:PSS layer 30 is 30 nanometers.PEDOT:PSS layer 30 above ITO layer 20 1 side is wiped, wiped the surface of the degree of depth, make the ITO layer 20 of exposure form table top 21 to ITO layer 20.Spin coating P3HT/PCBM blend film 40 on PEDOT:PSS layer 30, the mass ratio of P3HT and PCBM is 1: 1, thickness is 100 nanometers.Adopt thermal evaporation system depositing Al electrode 50 ' on P3HT/PCBM blend film 40, the background vacuum pressure of thermal evaporation system is 2 * 10
-4Pa, underlayer temperature T are 25 ℃, and deposition rate V is
/ second, the thickness d of Al electrode 50 ' is 150 nanometers.In the glove box that is full of high-purity N 2, battery is carried out thermal annealing, annealing temperature is 150 ℃, annealing time is 10 minutes.At the big sunlight of standard (AM 1.5G, a 100mW/cm
2) following open circuit voltage 0.66V, the short-circuit current density 6.62mA/cm that records battery of irradiation
2, fill factor, curve factor 0.56, energy conversion efficiency be 2.5%.
Wherein the difference of first embodiment and second embodiment is, this second embodiment only lacks one deck Al film 50 of growing than first embodiment.
Growth result
As shown in Figure 2, adopt method of the present invention, adopt electron beam evaporation technique to prepare the negative electrode Al electrode of polymers of excellent properties solar cell, promptly earlier at 25 ℃ of Al films that deposit 50nm, then at the Al of 80 ℃ of deposit 100nm electrode, annealing is after 10 minutes down at 150 ℃ for battery, and the efficient of polymer solar cell brings up to 2.77% than the efficient height of the battery of routine techniques preparation from 2.46%.
Invention is compared the significative results that is had with background technology
Utilize electron beam evaporation technique, adopt the two-step method depositing operation, successfully prepared the negative electrode Al electrode of polymers of excellent properties solar cell.The Al film of deposition and the good adhesion of organic film can not chap behind high annealing.In addition, utilize electron beam evaporation to adopt the two-step method depositing operation to prepare the cathode electrode of polymer battery, the efficient of battery will be higher than the battery of conventional thermal evaporation prepared.Therefore, cleaning, utilization rate of raw materials height, controllability and the good electron beam evaporation process of stable type can be applied in the metal electrode preparation of large tracts of land polymer solar cell, for the industrialization that realizes cheap organic photovoltaic is laid a good foundation.
The above; only be the embodiment among the present invention, but protection scope of the present invention is not limited thereto, anyly is familiar with the people of this technology in the disclosed technical scope of the present invention; the conversion that can expect easily or replacement all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection range of claims.
Claims (12)
1. preparation method who improves the polymer efficiency of solar cell, electrode adopts the electron beam evaporation technique preparation, and the preparation method comprises the steps:
Step 1: on the glass layer, make the ITO layer, as the anode of solar cell;
Step 2: adopt the method for photoetching, ITO layer one side etched away, etching depth prevents that to the surface of glass layer ITO is communicated with the negative electrode of battery;
Step 3: on the glass layer that exposes and the ITO layer prepare one deck PEDOT:PSS layer, as the hole transmission layer of solar cell;
Step 4: the PEDOT:PSS layer above ITO layer one side is wiped, wiped the surface of the degree of depth to the ITO layer, make the ITO layer of exposure form table top, this table top is an anode, is connected with external circuit;
Step 5: on the PEDOT:PSS layer, prepare polymer/fullerene derivate blend film;
Step 6: preparation Al film on polymer/fullerene derivate blend film;
Step 7: preparation Al electrode on the Al film, this Al electrode is a negative electrode;
Step 8: annealing, with the polymer solar cell annealing that preparation is finished, finish the preparation of electrode.
2. the preparation method of raising polymer efficiency of solar cell according to claim 1, wherein annealing is to carry out thermal annealing in being full of the glove box of high pure nitrogen, the water in the glove box and the content of oxygen are lower than 1ppm, and annealing temperature is 120-160 ℃, and annealing time is 5-15 minute.
3. the preparation method of raising polymer efficiency of solar cell according to claim 1, the background vacuum pressure that wherein prepares the used electron beam evaporation system of Al film and Al electrode is 1-3 * 10
-4Pa, the line of electron gun are 80-120mA, and operating voltage is 8500-9500V.
4. the preparation method of raising polymer efficiency of solar cell according to claim 1, when wherein preparing the Al film, preparation temperature is 20-25 ℃, deposition rate is
/ second.
5. according to the preparation method of claim 1 or 4 described raising polymer efficiency of solar cell, wherein the thickness of Al film is 50-120nm.
6. the preparation method of raising polymer efficiency of solar cell according to claim 1, when wherein preparing the Al electrode, preparation temperature is 70-90 ℃, deposition rate is
/ second.
7. according to the preparation method of claim 1 or 6 described raising polymer efficiency of solar cell, wherein the thickness of Al electrode is 80-150nm.
8. preparation method who improves the polymer efficiency of solar cell, electrode adopts the electron beam evaporation technique preparation, and the preparation method comprises the steps:
Step 1: on the glass layer, make the ITO layer, as the anode of solar cell;
Step 2: adopt the method for photoetching, ITO layer one side etched away, etching depth prevents that to the surface of glass layer ITO is communicated with the negative electrode of battery;
Step 3: on the glass layer that exposes and the ITO layer prepare one deck PEDOT:PSS layer, as the hole transmission layer of solar cell;
Step 4: the PEDOT:PSS layer above ITO layer one side is wiped, wiped the surface of the degree of depth to the ITO layer, make the ITO layer of exposure form table top, this table top is an anode, is connected with external circuit;
Step 5: on the PEDOT:PSS layer, prepare polymer/fullerene derivate blend film;
Step 6: preparation Al electrode on polymer/fullerene derivate blend film, this Al electrode is a negative electrode;
Step 7: annealing, with the polymer solar cell annealing that preparation is finished, finish the preparation of electrode.
9. the preparation method of raising polymer efficiency of solar cell according to claim 8, wherein annealing is to carry out thermal annealing in being full of the glove box of high pure nitrogen, the water in the glove box and the content of oxygen are lower than 1ppm, and annealing temperature is 120-160 ℃, and annealing time is 5-15 minute.
10. the preparation method of raising polymer efficiency of solar cell according to claim 8, the background vacuum pressure that wherein prepares the used electron beam evaporation system of Al electrode is 1-3 * 10
-4Pa, the line of electron gun are 80-120mA, and operating voltage is 8500-9500V.
11. the preparation method of raising polymer efficiency of solar cell according to claim 8, when wherein preparing the Al electrode, preparation temperature is 70-90 ℃, and deposition rate is
/ second.
12. according to Claim 8 or the preparation method of 11 described raising polymer efficiency of solar cell, wherein the thickness of Al electrode is 80-150nm.
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| CN106893984A (en) * | 2017-02-04 | 2017-06-27 | 上海理工大学 | The preparation method of the tin-doped indium oxide based coextruded film of enhancing visible light wave range transmission |
| RU2709069C1 (en) * | 2019-06-03 | 2019-12-13 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Томский государственный университет систем управления и радиоэлектроники" | Method for electron-beam application of hardening coating on articles made from polymer materials |
| CN111020521A (en) * | 2019-11-26 | 2020-04-17 | 浙江长宇新材料有限公司 | Preparation method of metal-plated film for battery |
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