CN109980089A - A kind of organic solar batteries and preparation method thereof - Google Patents
A kind of organic solar batteries and preparation method thereof Download PDFInfo
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- CN109980089A CN109980089A CN201910174495.2A CN201910174495A CN109980089A CN 109980089 A CN109980089 A CN 109980089A CN 201910174495 A CN201910174495 A CN 201910174495A CN 109980089 A CN109980089 A CN 109980089A
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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
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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
- H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/731—Liquid crystalline materials
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- 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
Abstract
The invention discloses a kind of organic solar batteries and preparation method thereof, which is inverted structure, from top to bottom successively includes substrate, transparent conductive cathode, cathode buffer layer, photoactive layer, anode buffer layer and metal anode；Cathode buffer layer is modified through liquid crystal material；Liquid crystal material structural formula are as follows:Wherein, R1Selected from the alkyl with 1-8 carbon atom；R2、R3It is respectively and independently selected from the alkyl with 1-5 carbon atom；M, n is respectively and independently selected from any integer in 0-4.In the above manner, organic solar batteries of the present invention modify cathodic modification layer by using specific liquid crystal material, it can induce the dispersion on the material formation scale of cathode buffer layer, it is passivated the defect on cathode cushioning layer material surface simultaneously, improve the generation and transmission of electronics, hole, increase short circuit current and energy conversion efficiency, so that the device performance of organic solar batteries be greatly improved；And used liquid crystal material is easy to get and at low cost.
Description
Technical field
The present invention relates to photovoltaic device technical fields, and in particular to a kind of organic solar batteries and preparation method thereof.
Background technique
With the development of human society, the demand to the energy is higher and higher, and limited fossil energy is unable to satisfy and nothing
The regeneration of method short time, therefore, it is extremely urgent that the sustainable energy is cleaned in exploitation.Wherein solar energy is used as one kind is inexhaustible to use it
A kind of inexhaustible energy, receives the extensive concern of countries in the world.Compared with other energy, solar energy has cleanliness without any pollution,
The advantages that storage utilizes on the spot.So being that the present future world energy problem of solution is most promising to making full use of for solar energy
One of method.Organic solar batteries light weight, stabilization are suitble to large area production, also achieve and are sprayed on flexible substrates
Ink printing and the production technologies such as silk-screen printing, actually solve the high cost investment commercially producing photovoltaic device and facing, it is low at
The problem of this output.Research workers use efficient new material by design synthesis, design new device structure, living to light
Property layer and interface buffer layer carry out the methods of modification, the performance of organic solar batteries is continuously improved.
Compared with inorganic silicon solar cell, the efficiency of organic solar batteries is still to be improved.According to organic sun
The principle of energy battery, cathode interface buffer layer can play the role of adjusting cathode work function number, while between cathode and active layer
Interface dipole square is formed, separated electrons and holes are compound for inhibition, promote the transmission and collection of electric charge carrier, raising has
The photoelectric conversion efficiency of machine solar energy, therefore the performance for promoting cathode interface buffer layer is urgent problem.
Summary of the invention
In order to solve the above technical problem, the present invention provides a kind of organic solar batteries and preparation method thereof.
The technical scheme adopted by the invention is that: a kind of organic solar batteries, the organic solar batteries are to be inverted
Structure successively includes substrate, transparent conductive cathode, cathode buffer layer, photoactive layer, anode buffer layer and metal sun from top to bottom
Pole；The cathode buffer layer is modified through liquid crystal material, the liquid crystal material structural formula are as follows:Wherein,
R1Selected from the alkyl with 1-8 carbon atom, concretely linear or branched alkyl group；R2、R3It is respectively and independently selected from 1-5
The alkyl of carbon atom, concretely linear or branched alkyl group；M, n is respectively and independently selected from any integer in 0-4, when m is 2,3,4
In any value when, each R2It can be identical or different；When n is any value in 2,3,4, each R3It can be identical or different.
Preferably, the liquid crystal material includes at least one of 7CB, 5CB, 8CB and its derivative.
Wherein, the chemical structural formula of liquid crystal material 7CB are as follows:
The specific structure of liquid crystal material 7CB derivative can are as follows:Wherein, R1Selected from having
The alkyl of 1-8 carbon atom；R2、R3It is respectively and independently selected from the alkyl with 1-5 carbon atom；M, n is respectively and independently selected from 0-4
Any integer；
The chemical structural formula of liquid crystal material 5CB are as follows:
The chemical structural formula of liquid crystal material 8CB are as follows:
Derivative of the derivative species of liquid crystal material 5CB and 8CB like liquid crystal material 7CB.
In addition, the liquid crystal material requirement that can be used for modifying cathode buffer layer is more stringent, and not all liquid crystal material is suitable
It closes, such as liquid crystal material of cholesteric phase is not suitable for modification cathode buffer layer；Specifically, by existing experimental verification, following liquid crystal is not
It is suitble to modification cathode buffer layer: liquid crystal monomer HCM006, HCM008, HCM020, HCM021, E7 and positivity liquid crystal S811, bears
Property liquid crystal S1011.
Preferably, to modify cathode buffer layer in material of the liquid crystal material by being doped in the cathode buffer layer.
Preferably, the material of the cathode buffer layer includes TiOx, at least one of LiF, ZnO.It is further preferred that
The thickness range of cathode buffer layer is 25~30nm.
Preferably, the photoactive layer is mixed by electron donor and electron acceptor, the electron donor and electronics by
The mass ratio of body is (0.5~1.2): (0.8~1.6).
Preferably, the material of the electron donor includes at least one of PCE-10, PBDB-T；The electron acceptor
Material includes PC71At least one of BM, ITTC.
Preferably, the material of the anode buffer layer includes PEDOT:PSS, MoO3、V2O5, at least one of NiO.Into
Preferably, the thickness range of the anode buffer layer is 8~10nm to one step.
Preferably, the material of the metal anode includes at least one of Al, Ag；The material of the substrate includes transparent
At least one of glass, transparent flexible polymer P ET.The material of transparent conductive cathode is preferably ITO.The thickness of metal anode
Generally 80~150nm.And whole organic solar device removes substrate thickness, overall thickness is usually no more than 250nm, thickness
It is relatively thin.
The present invention also provides a kind of preparation methods of above-mentioned organic solar batteries, comprising the following steps:
The substrate that S1, cleaning are made of substrate and transparent conductive cathode, is then dried；
S2, cathode buffer layer is prepared on the surface of the transparent conductive cathode；
S3, photoactive layer is prepared on the cathode buffer layer；
S4, anode buffer layer is prepared on the photoactive layer；
S5, the evaporation metal anode on the anode buffer layer.
Step S1 specifically can be by being cleaned by ultrasonic the substrate being made of substrate and transparent conductive cathode, and cleaning agent successively uses
Acetone, ITO cleaning solution, deionized water, dehydrated alcohol are cleaned by ultrasonic 15~20mim respectively, are then placed in 70~90 DEG C of baking ovens
Drying.
Preferably, step S2 is specifically included: the precursor solution of the cathode buffer layer is first prepared, then by liquid crystal material
It is dissolved in the precursor solution, stirs evenly, the precursor solution of liquid crystal material doping is made；The liquid crystal material is adulterated again
Precursor solution be spun on the surface of the transparent conductive cathode, form film layer, then carry out thermal anneal process, cathode be made
Buffer layer.Wherein, the doping dosage of liquid crystal material preferably accounts for 0.2~0.5wt% of precursor solution；The temperature of thermal anneal process
Preferably 180~220 DEG C, the time is 1~2h.
Step S3 specifically can prepare photoactive layer by being spin-coated on cathode buffer layer；Preferably, spin coating revolving speed is 1200
~2500rpm, the time is 30~60s, with a thickness of 100~150nm.
Specifically MoO can be deposited by vapour deposition method in step S43Prepare anode buffer layer；Preferably, evaporation rate be 0.1~
10A0/s.In step S5, the preferred 1A of evaporation rate0/s。
The method have the benefit that: the present invention provides a kind of organic solar batteries and preparation method thereof, this has
Machine solar battery modifies cathodic modification layer by using specific liquid crystal material, to can induce the material shape of cathode buffer layer
At the dispersion on scale, while it being passivated the defect on cathode cushioning layer material surface, improve the generation and transmission of electronics, hole, increased
Big short circuit current and energy conversion efficiency, so that the device performance of organic solar batteries is greatly improved, and performance is stablized；Separately
Outside, liquid crystal material used has realized mass production and inexpensive, can directly buy use, and raw material is easy to get and at low cost.
Detailed description of the invention
For the clearer technical solution illustrated in the embodiment of the present invention, will make below to required in embodiment description
Attached drawing briefly describes.
Fig. 1 is the structural schematic diagram of obtained organic solar batteries in the embodiment of the present invention 1；
Fig. 2 be in embodiment 1 organic solar batteries in AM1.5 (intensity 100mW/cm2) irradiation under current density-
Voltage characteristic curve；
Fig. 3 be in comparative example 1 organic solar batteries in AM1.5 (intensity 100mW/cm2) irradiation under current density-
Voltage characteristic curve.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Embodiment 1
A kind of organic solar batteries, preparation method include: to by transparent substrate and transparent conductive cathode ITO institute group
At base-plate cleaning after dry it is stand-by；The mixing that 1g zinc acetate is dissolved in the ethylene glycol monomethyl ether of 10ml and the ethanol amine of 288ul is molten
In liquid, with the revolving speed of 2000r/min under the conditions of 60 DEG C heating stirring 1h, be made ZnO precursor solution；Again by liquid crystal material
7CB takes 3mg to be dissolved in the precursor solution of ZnO with the weight ratio of 0.3wt%, with the revolving speed of 2000r/min in 60 DEG C of conditions
The ZnO precursor solution of liquid crystal 7CB doping is made in lower heating stirring 1h；Pass through collosol and gel on the surface transparent conductive cathode ITO
The ZnO precursor solution of method spin coating liquid crystal 7CB doping prepares cathode buffer layer, wherein spin coating revolving speed is 2500rpm, and the time is
30s, spin coating is with a thickness of 30nm；Thermal anneal process then is carried out to the film of formation, thermal annealing temperatures are 200 DEG C, handle the time
For 1h；It is moved on in the glove box full of nitrogen again, the spin coating photoactive layer PBDB-T:ITIC on cathode buffer layer, wherein
The mass percent of PBDB-T and ITIC be 50%:50%, spin coating revolving speed be 2300rmp, time 60s, spin coating with a thickness of
120nm；It is moved back in vapor deposition case in 160 DEG C of thermal annealings, anode buffer layer MoO is deposited on photoactive layer3, wherein vapor deposition speed
Degree is 10A0/ s, with a thickness of 10nm；Organic sun is made with a thickness of 80nm in the evaporation metal anode A l on anode buffer layer again
It can battery.
As shown in Figure 1, obtained organic solar batteries are inverted structure, include successively from top to bottom substrate 1, transparent leads
Electric cathode 2, cathode buffer layer 3, photoactive layer 4, anode buffer layer 5 and metal anode 6, wherein cathode buffer layer 3 is through liquid crystal
7CB modification.
Comparative example
A kind of organic solar batteries, preparation method include: to by transparent substrate and transparent conductive cathode ITO institute group
At base-plate cleaning after dry it is stand-by；The mixing that 1g zinc acetate is dissolved in the ethylene glycol monomethyl ether of 10ml and the ethanol amine of 288ul is molten
In liquid, with the revolving speed of 2000r/min under the conditions of 60 DEG C heating stirring 1h, be made ZnO precursor solution；In transparent conductive cathode
The surface ITO prepares cathode buffer layer by sol-gal process spin coating ZnO precursor solution, wherein and spin coating revolving speed is 2500rpm,
Time is 30s, and spin coating is with a thickness of 30nm；Thermal anneal process then is carried out to the film of formation, thermal annealing temperatures are 200 DEG C, place
The reason time is 1h；It is moved on in the glove box full of nitrogen again, the spin coating photoactive layer PBDB-T:ITIC on cathode buffer layer,
In, the mass percent of PBDB-T and ITIC is 50%:50%, and spin coating revolving speed is 2300rmp, time 60s, spin coating with a thickness of
100nm；It is moved back in vapor deposition case in 160 DEG C of thermal annealings, anode buffer layer MoO is deposited on photoactive layer3, wherein vapor deposition speed
Degree is 10A0/ s, with a thickness of 10nm；Organic sun is made with a thickness of 80nm in the evaporation metal anode A l on anode buffer layer again
It can battery.
It is in place of this comparative example and the main difference of the organic solar batteries in embodiment 1, the yin in this comparative example
The unmodified liquid crystal material of pole buffer layer.
In standard conditions AM1.5 (intensity 100mW/cm2) under irradiation respectively to organic obtained by embodiment 1 and comparative example
Solar battery is tested for the property, after tested: organic solar batteries open-circuit voltage Voc=obtained by embodiment 1
0.86V, short-circuit current density Jsc=18.22mA/cm2, fill factor FF=65.42%, energy conversion efficiency PCE=
10.25%, Current density-voltage performance diagram is as shown in Figure 2；Organic solar batteries open-circuit voltage obtained by comparative example
Voc=0.86V, short-circuit current density Jsc=16.07mA/cm2, fill factor FF=63.11%, energy conversion efficiency PCE=
8.72%, Current density-voltage performance diagram is as shown in Figure 3.The above test result and Fig. 2, Fig. 3 are compared it is found that reality
It applies cathodic modification layer in the organic solar batteries of example 1 to modify by using liquid crystal, so that product organic solar batteries have
Bigger short circuit current and fill factor, smaller series resistance and bigger parallel resistance, bigger energy conversion efficiency are said
Bright liquid crystal 7CB modification cathodic modification layer can greatly improve the performance of device.
In addition, liquid crystal 5CB, 8CB can also be used for modification inverted structure organic solar by the similar above experimental verification
The cathodic modification layer of battery can induce the dispersion that the ZnO nano particle in cathode buffer layer is formed on scale, be passivated simultaneously
The defect of ZnO nano particle surface improves the generation and transmission of electronics, hole, increases short circuit current and energy conversion efficiency,
Greatly improve the device performance of organic solar batteries.
Although specifically showing and describing the present invention in conjunction with preferred embodiment, those skilled in the art should be bright
It is white, it is not departing from the spirit and scope of the present invention defined by described claims, it in the form and details can be right
The present invention makes a variety of changes, and is protection scope of the present invention.
Claims (10)
1. a kind of organic solar batteries, which is characterized in that the organic solar batteries are inverted structure, from top to bottom successively
Including substrate, transparent conductive cathode, cathode buffer layer, photoactive layer, anode buffer layer and metal anode；The cathode buffer layer
It is modified through liquid crystal material；The structural formula of the liquid crystal material are as follows:
Wherein, R1Selected from the alkyl with 1-8 carbon atom；R2、R3It is respectively and independently selected from 1-
The alkyl of 5 carbon atoms；M, n is respectively and independently selected from any integer in 0-4.
2. organic solar batteries according to claim 1, which is characterized in that the liquid crystal material include 7CB, 5CB,
At least one of 8CB and its derivative.
3. organic solar batteries according to claim 1, it is characterised in that the liquid crystal material is described by being doped in
To modify cathode buffer layer in the material of cathode buffer layer.
4. organic solar batteries according to claim 2, which is characterized in that the material of the cathode buffer layer includes
TiOx, at least one of LiF, ZnO.
5. organic solar batteries according to claim 1, which is characterized in that the photoactive layer is by electron donor and electricity
Sub- receptor is mixed, and the mass ratio of the electron donor and electron acceptor is (0.5~1.2): (0.8~1.6).
6. organic solar batteries according to claim 4, which is characterized in that the material of the electron donor includes PCE-
10, at least one of PBDB-T；The material of the electron acceptor includes PC71At least one of BM, ITTC.
7. organic solar batteries according to claim 1, which is characterized in that the material of the anode buffer layer includes
PEDOT:PSS、MoO3、V2O5, at least one of NiO.
8. organic solar batteries according to claim 1, which is characterized in that the material of the metal anode include Al,
At least one of Ag；The material of the substrate includes at least one of transparent glass, transparent flexible polymer P ET.
9. the preparation method of organic solar batteries of any of claims 1-8, which is characterized in that including following step
It is rapid:
The substrate that S1, cleaning are made of substrate and transparent conductive cathode, is then dried；
S2, cathode buffer layer is prepared on the surface of the transparent conductive cathode；
S3, photoactive layer is prepared on the cathode buffer layer；
S4, anode buffer layer is prepared on the photoactive layer；
S5, the evaporation metal anode on the anode buffer layer.
10. the preparation method of organic solar batteries according to claim 9, which is characterized in that step S2 includes: first to match
The precursor solution of the cathode buffer layer is made, then liquid crystal material is dissolved in the precursor solution, is stirred evenly, liquid is made
Brilliant material doped precursor solution；The precursor solution that the liquid crystal material adulterates is spun on the transparent conductive cathode again
Surface, form film layer, then carry out thermal anneal process, cathode buffer layer is made.
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