CN103715356B - A kind of based on MoO3organic solar batteries of/Ag anode and preparation method thereof - Google Patents

A kind of based on MoO3organic solar batteries of/Ag anode and preparation method thereof Download PDF

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CN103715356B
CN103715356B CN201310729340.3A CN201310729340A CN103715356B CN 103715356 B CN103715356 B CN 103715356B CN 201310729340 A CN201310729340 A CN 201310729340A CN 103715356 B CN103715356 B CN 103715356B
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layer
moo
p3ht
pcbm
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CN103715356A (en
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张春福
王之哲
陈大正
陆小力
郝跃
魏炜
高汭
孙丽
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Xidian University
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/81—Electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/60—Forming conductive regions or layers, e.g. electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

The invention discloses a kind of based on MoO3Organic solar batteries of/Ag anode and preparation method thereof, described organic solar batteries based on MoO3/Ag anode includes the glass substrate that thickness is 1mm the most successively, thickness is the MoO3 intermediate layer of 2 10nm and Ag layer that thickness is 7 13nm, and thickness is the MoO of 10nm3Hole transmission layer, thickness is that P3HT: PCBM of 80 100nm have active layer, and thickness is the Al cathode layer of 100nm.The present invention based on MoO3The organic solar batteries of/Ag anode takes full advantage of pliability and the high conductivity of Ag intrinsic so that electrode can be suitably used for flexible substrate, and then is applied in organic solar batteries volume to volume large-scale production；MoO simultaneously3The introducing in intermediate layer, it is possible to promote the cross growth of Ag film and reduce the thickness of required Ag layer, reducing electrode cost further.

Description

A kind of based on MoO3Organic solar batteries of/Ag anode and preparation method thereof
Technical field
The invention belongs to microelectronics technology, relate to the preparation method of organic solar batteries, particularly a kind of based on MoO3Organic solar batteries of/Ag anode and preparation method thereof.
Technical background
Sharply increasing and paying attention to the continuous of environmental conservation along with energy demand, people are increasing for the demand of clean energy resource.Solar energy is inexhaustible, nexhaustible, the most pollution-free, is the energy that can freely be used of the mankind, and solaode is the effective means utilizing solar energy.But the high cost of prevailing silica-based solar cell hinders its development and universal significantly.And organic material has the advantages such as low cost, the absorption coefficient of light is high, quality is light, pliability good, manufacturing process is simple so that it is application in solar cells causes the extensive concern of people.Organic solar batteries has become one of most promising solar battery technology of future generation, the focus in solar energy research field, the Ye Shi world.
The major parameter of organic solar batteries such as fill factor, curve factor and short-circuit current density are heavily dependent on series resistance and the light transmission of transparency electrode.In organic solar batteries, most widely used transparent electrode material general, that technology is the most ripe is indium tin oxide (ITO) at present, and the many achievements in research before obtained are all based on ito transparent electrode.But the comparision contents of indium is low on the earth；And on substrate, to form ITO electrode commonly use preparation technology (such as sputtering, thermal evaporation, pulsed laser deposition etc.) equipment is had certain requirement, cost is the most costly；Thus the cost of ito transparent electrode is difficult to reduce, it is unfavorable for the large-scale production of organic solar batteries.The following commercialization trend of organic solar batteries is mainly large area and flexibility (the most collapsible).And the fragility of ito transparent electrode and the unstability under acidity, pressure condition also allow it cannot adapt to the commercialization trend of organic solar batteries.So people start actively to find the substitution material of ITO, and do a lot of trial.Transparent conductive oxide (such as sowing doping zinc-oxide (GZO) and aluminium-doped zinc oxide (AZO)), nano silver wire, Graphene and CNT without indium are the most successfully used as the transparent anode of organic solar batteries to substitute ITO.
These methods also have the defect of their own.Although the cost of GZO and AZO ITO to be less than, but both electrodes still need high temperature sputtering technology when being deposited on substrate, it is impossible to be applied in flexible substrate.And the preparation technology of nano silver wire, Graphene and CNT is the most complicated, be not suitable for the application in terms of extensive device.
Summary of the invention
It is an object of the invention to the shortcoming overcoming ITO electrode cannot be applied to flexible substrate, it is provided that a kind of based on MoO3The preparation method of the organic solar batteries of/Ag anode, can also be effectively applicable to volume to volume large-scale production process while being substantially reduced battery cost.
Realize the object of the invention key problem in technology as follows:
A kind of based on MoO3The organic solar batteries of/Ag anode, includes the glass substrate that thickness is 1mm the most successively, and thickness is the MoO of 2-10nm3Intermediate layer and the Ag layer that thickness is 7-13nm, thickness is the MoO of 10nm3Hole transmission layer, thickness is that P3HT: PCBM of 80-100nm has active layer, and thickness is the Al cathode layer of 100nm；The pliability of Ag itself and high conductivity ensure that this MoO3/ Ag anode can substitute ITO and be applicable to the preparation of organic solar batteries based on flexible substrate；MoO3The introducing in intermediate layer then can effectively reduce required Ag layer thickness, reduces cost further.
A kind of based on MoO3The preparation method of the organic solar batteries of/Ag anode, comprises the steps:
(1) glass substrate is carried out；
(2) sample is put into the metallic room of integrated multi-source multicell coating system, be the MoO of 2-10nm with the mode of thermal evaporation evaporation thickness in described glass substrate3Intermediate layer, the vacuum of metallic room is 5 × 10-4Pa；
(3) by the mode of thermal evaporation at described MoO3On intermediate layer, evaporation thickness is the Ag layer of 7-13nm, and the vacuum of metallic room is 5 × 10-4Pa；
(4) it is the MoO of 10nm with the mode of thermal evaporation evaporation thickness on described Ag layer3Hole transmission layer, the vacuum of metallic room is 5 × 10-4Pa；
(5) polymer (P3HT) of 3-hexyl thiophene and the derivant (PCBM) of fullerene being dissolved in 1 respectively, forming concentration in 2-chlorobenzene is the solution of 18mg/ml, then is configured to mixed liquor at 1: 0.8 by volume；
(6) sample is moved on the whirl coating platform in glove box, at described MoO by the way of above-mentioned P3HT: the PCBM mixed liquor of whirl coating spin coating3It is 1200rpms that obtain on hole transmission layer that thickness is 80-100nm P3HT: PCBM has active layer, the rotating speed of whirl coating platform, and the time is 60s；
(7) sample being retracted in the metallic room of integrated multi-source multicell coating system from glove box, the mode of deposited by electron beam evaporation is at described P3HT: the PCBM Al cathode layer having evaporation thickness in active layer to be 100nm, and the vacuum of metallic room is 5 × 10-4Pa；
(8) sample is moved to glove box (nitrogen atmosphere) from metallic room, carry out annealing operation.Annealing temperature is 140-150 DEG C, and the time is 10-15min.
Present invention have the advantage that
1. due to MoO3Preparation with Ag layer all uses thermal evaporation process, and integrated artistic temperature is the highest, so when being deposited in flexible substrate, substrate will not be produced damage.
2. due to pliability and the high conductivity of Ag itself so that this MoO3/ Ag anode has good electric conductivity and can be suitably used for flexible substrate.
3. due to MoO3The introducing in intermediate layer, makes required Ag layer thickness greatly reduce, reduce further the cost of electrode.
Accompanying drawing explanation
Fig. 1 be the present invention with MoO3/ Ag is organic solar batteries each layer position relationship schematic diagram of anode；
Fig. 2 be the present invention with MoO3/ Ag is the organic solar batteries growth flow chart of anode.
Detailed description of the invention
Embodiment 1:
As it is shown in figure 1, one is based on MoO3The organic solar batteries of/Ag anode, it be the most successively thickness be the glass substrate of 1mm, thickness is the MoO of 2nm3Intermediate layer and the Ag layer (i.e. the anode of battery) that thickness is 9nm, thickness is the MoO of 10nm3Hole transmission layer, thickness is that P3HT: PCBM of 80nm has active layer, and thickness is the Al cathode layer of 100nm.
As in figure 2 it is shown, the present invention to realize step as follows:
Step 1, is carried out substrate.
Glass is sequentially placed in detergent, deionized water, acetone and ethanol and carries out ultrasonic cleaning, each ultrasonic 15min.
Step 2, prepares the MoO that thickness is 2nm3Intermediate layer.
Above-mentioned glass nitrogen gun is dried up, puts into the metallic room of integrated multi-source multicell coating system, be the MoO of 2nm with the mode of thermal evaporation evaporation thickness in described glass substrate3Intermediate layer, the vacuum of metallic room is 5 × 10-4Pa。
Step 3, prepares the Ag layer that thickness is 9nm.
By the mode of thermal evaporation at described MoO3On intermediate layer, evaporation thickness is the Ag layer of 9nm, and the vacuum of metallic room is 5 × 10-4Pa。
Step 4, prepares the MoO that thickness is 10nm3Hole transmission layer.
It is the MoO of 10nm with the mode of thermal evaporation evaporation thickness on described Ag layer3Hole transmission layer, the vacuum of metallic room is 5 × 10-4Pa
Step 5, configures P3HT: PCBM mixed liquor.
P3HT and PCBM being dissolved in respectively 1, forming concentration in 2-chlorobenzene is the solution of 18mg/ml, then is configured to mixed liquor at 1: 0.8 by volume.
Step 6, prepare that thickness is 80nm P3HT: PCBM has active layer.
Sample is moved on the whirl coating platform in glove box, at described MoO by the way of above-mentioned P3HT: the PCBM mixed liquor of whirl coating spin coating3It is 1200rpms that obtain on hole transmission layer that thickness is 80nm P3HT: PCBM has active layer, the rotating speed of whirl coating platform, and the time is 60s.
Step 7, prepares the Al cathode layer that thickness is 100nm.
Sample is moved in the metallic room of integrated multi-source multicell coating system from glove box, and the mode of deposited by electron beam evaporation is at described P3HT: the PCBM A1 cathode layer having evaporation thickness in active layer to be 100nm, and the vacuum of metallic room is 5 × 10-4Pa。
Step 8, makes annealing treatment sample.
Sample is moved to glove box (nitrogen atmosphere) from metallic room, carry out annealing operation.Annealing temperature is 140 DEG C, and the time is 10min.
Embodiment 2:
As it is shown in figure 1, one is based on MoO3The organic solar batteries of/Ag anode, it be the most successively thickness be the glass substrate of 1mm, thickness is the MoO of 10nm3Intermediate layer and the Ag layer (i.e. the anode of battery) that thickness is 9nm, thickness is the MoO of 10nm3Hole transmission layer, thickness is that P3HT: PCBM of 100nm has active layer, and thickness is the Al cathode layer of 100nm.
As in figure 2 it is shown, the present invention to realize step as follows:
Step 1, is carried out substrate.
Glass is sequentially placed in detergent, deionized water, acetone and ethanol and carries out ultrasonic cleaning, each ultrasonic 15min.
Step 2, prepares the MoO that thickness is 10nm3Intermediate layer.
Above-mentioned glass nitrogen gun is dried up, puts into the metallic room of integrated multi-source multicell coating system, be the MoO of 10nm with the mode of thermal evaporation evaporation thickness in described glass substrate3Intermediate layer, the vacuum of metallic room is 5 × 10-4Pa。
Step 3, prepares the Ag layer that thickness is 9nm.
By the mode of thermal evaporation at described MoO3On intermediate layer, evaporation thickness is the Ag layer of 9nm, and the vacuum of metallic room is 5 × 10-4Pa。
Step 4, prepares the MoO that thickness is 10nm3Hole transmission layer.
It is the MoO of 10nm with the mode of thermal evaporation evaporation thickness on described Ag layer3Hole transmission layer, the vacuum of metallic room is 5 × 10-4Pa
Step 5, configures P3HT: PCBM mixed liquor.
P3HT and PCBM being dissolved in respectively 1, forming concentration in 2-chlorobenzene is the solution of 18mg/ml, then is configured to mixed liquor at 1: 0.8 by volume.
Step 6, prepare that thickness is 100nm P3HT: PCBM has active layer.
Sample is moved on the whirl coating platform in glove box, at described MoO by the way of above-mentioned P3HT: the PCBM mixed liquor of whirl coating spin coating3It is 1200rpms that obtain on hole transmission layer that thickness is 100nm P3HT: PCBM has active layer, the rotating speed of whirl coating platform, and the time is 60s.
Step 7, prepares the Al cathode layer that thickness is 100nT.
Sample is moved in the metallic room of integrated multi-source multicell coating system from glove box, and the mode of deposited by electron beam evaporation is at described P3HT: the PCBM Al cathode layer having evaporation thickness in active layer to be 100nm, and the vacuum of metallic room is 5 × 10-4Pa。
Step 8, makes annealing treatment sample.
Sample is moved to glove box (nitrogen atmosphere) from metallic room, carry out annealing operation.Annealing temperature is 150 DEG C, and the time is 15min.
Embodiment 3:
As it is shown in figure 1, one is based on MoO3The organic solar batteries of/Ag anode, it be the most successively thickness be the glass substrate of 1mm, thickness is the MoO of 5nm3Intermediate layer and the Ag layer (i.e. the anode of battery) that thickness is 11nm, thickness is the MoO of 10nm3Hole transmission layer, thickness is that P3HT: PCBM of 80nm has active layer, and thickness is the Al cathode layer of 100nm.
As in figure 2 it is shown, the present invention to realize step as follows:
Step 1, is carried out substrate.
Glass is sequentially placed in detergent, deionized water, acetone and ethanol and carries out ultrasonic cleaning, each ultrasonic 15min.
Step 2, prepares the MoO that thickness is 5nm3Intermediate layer.
Above-mentioned glass nitrogen gun is dried up, puts into the metallic room of integrated multi-source multicell coating system, be the MoO of 5nm with the mode of thermal evaporation evaporation thickness in described glass substrate3Intermediate layer, the vacuum of metallic room is 5 × 10-4Pa。
Step 3, prepares the Ag layer that thickness is 11nm.
By the mode of thermal evaporation at described MoO3On intermediate layer, evaporation thickness is the Ag layer of 11nm, and the vacuum of metallic room is 5 × 10-4Pa。
Step 4, prepares the MoO that thickness is 10nm3Hole transmission layer.
It is the MoO of 10nm with the mode of thermal evaporation evaporation thickness on described Ag layer3Hole transmission layer, the vacuum of metallic room is 5 × 10-4Pa
Step 5, configures P3HT: PCBM mixed liquor.
P3HT and PCBM being dissolved in respectively 1, forming concentration in 2-chlorobenzene is the solution of 18mg/ml, then is configured to mixed liquor at 1: 0.8 by volume.
Step 6, prepare that thickness is 80nm P3HT: PCBM has active layer.
Sample is moved on the whirl coating platform in glove box, at described MoO by the way of above-mentioned P3HT: the PCBM mixed liquor of whirl coating spin coating3It is 1200rpms that obtain on hole transmission layer that thickness is 80nm P3HT: PCBM has active layer, the rotating speed of whirl coating platform, and the time is 60s.
Step 7, prepares the Al cathode layer that thickness is 100nm.
Sample is moved in the metallic room of integrated multi-source multicell coating system from glove box, and the mode of deposited by electron beam evaporation is at described P3HT: the PCBM A1 cathode layer having evaporation thickness in active layer to be 100nm, and the vacuum of metallic room is 5 × 10-4Pa。
Step 8, makes annealing treatment sample.
Sample is moved to glove box (nitrogen atmosphere) from metallic room, carry out annealing operation.Annealing temperature is 150 DEG C, and the time is 10min.
For those skilled in the art; after understanding present invention and principle; can be in the case of without departing substantially from the principle and scope of the present invention; the method according to the invention carries out the various corrections in form and details and change, but these corrections based on the present invention and change are still within the claims of the present invention.

Claims (2)

1. one kind based on MoO3The organic solar batteries of/Ag anode, it is characterised in that: include that thickness is the most successively The glass substrate of 1mm, thickness is the MoO of 2-10nm3Intermediate layer and the Ag layer that thickness is 7-13nm, thickness is 10nm MoO3Hole transmission layer, thickness is that the P3HT:PCBM of 80-100nm has active layer, and thickness is the Al cathode layer of 100nm.
One the most according to claim 1 is based on MoO3The preparation method of the organic solar batteries of/Ag anode, it is special Levy and be: comprise the steps:
(1) glass substrate is carried out；
(2) sample is put into the metallic room of integrated multi-source multicell coating system, by the mode of thermal evaporation in described glass substrate Upper evaporation thickness is the MoO of 2-10nm3Intermediate layer, the vacuum of metallic room is 5 × 10-4Pa；
(3) by the mode of thermal evaporation at described MoO3On intermediate layer, evaporation thickness is the Ag layer of 7-13nm, metallic room true Reciprocal of duty cycle is 5 × 10-4Pa；
(4) it is the MoO of 10nm with the mode of thermal evaporation evaporation thickness on described Ag layer3Hole transmission layer, metallic room Vacuum is 5 × 10-4Pa；
(5) P3HT and PCBM being dissolved in respectively 1, forming concentration in 2-chlorobenzene is the solution of 18mg/ml, more by volume Be configured to mixed liquor at 1: 0.8；
(6) sample is moved on the whirl coating platform in glove box, by the way of whirl coating spin coating above-mentioned P3HT:PCBM mixed liquor Described MoO3Obtaining the P3HT:PCBM that thickness is 80-100nm on hole transmission layer has active layer, the rotating speed of whirl coating platform to be 1200 Rpms, the time is 60s；
(7) sample being retracted in the metallic room of integrated multi-source multicell coating system from glove box, the mode of deposited by electron beam evaporation exists The Al cathode layer that described P3HT:PCBM has evaporation thickness in active layer to be 100nm, the vacuum of metallic room is 5 × 10-4Pa；
(8) sample being moved to from metallic room, the glove box of nitrogen atmosphere, carry out annealing operation, annealing temperature is 140-150 DEG C, Time is 10-15min.
CN201310729340.3A 2013-12-20 2013-12-20 A kind of based on MoO3organic solar batteries of/Ag anode and preparation method thereof Expired - Fee Related CN103715356B (en)

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CN104051625A (en) * 2014-06-13 2014-09-17 西安电子科技大学 Polymer solar cell based on AZO/ZnO cathode and manufacturing method of polymer solar cell
US10930809B2 (en) 2016-06-04 2021-02-23 International Business Machines Corporation Photovoltaic devices with increased efficiency and methods for making the same
CN111129311A (en) * 2019-12-23 2020-05-08 太原理工大学 Flexible organic photomultiplier detector based on ultrathin silver film anode and manufacturing method

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CN103227287A (en) * 2013-04-23 2013-07-31 吉林大学 Three-terminal parallel polymer solar cell based on metal nanoparticle doping and preparation method of solar cell

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