CN110283185A - A kind of quinoxaline derivant acceptor material and the preparation method and application thereof - Google Patents
A kind of quinoxaline derivant acceptor material and the preparation method and application thereof Download PDFInfo
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Abstract
Quinoxaline derivant shown in Formulas I and its preparing the purposes in organic solar batteries.Quinoxaline derivant shown in Formulas I shows low optical band gap (1.35eV) in the film.By being matched with middle width strip gap polymeric donor PBDB-TF polymeric donor, the device of preparation PCE with higher, and the E of the devicelossIt is significantly reduced.Quinoxaline derivant shown in Formulas I dissolves in a variety of organic solvents, therefore easily prepared various organic photovoltaic materials.It is had broad application prospects using organic solar batteries prepared by quinoxaline derivant.
Description
Technical field
The invention belongs to organic photovoltaic technical field of material, and in particular to a kind of quinoxaline derivant acceptor material and
Preparation method and application.
Background technique
Organic photovoltaic material (OPVs) is because it is inexpensive, can be manufactured or be used to prepare flexible and translucent device with large area
And it is concerned.However, OPVs shows low optical-electronic transfer efficiency compared with inorganic and perovskite solar battery, this master
If because the low dielectric constant of organic material itself will lead to relatively large energy loss (Eloss=Eg-eVoc, wherein EgIt is light
The optical band gap of active layer, and VocIt is the open-circuit voltage of photovoltaic device).For application fullerene derivate as electron acceptor
Traditional bulk heterojunction OPVs, ElossS is usually above 0.6eV, this makes photoelectric conversion efficiency (PCEs) lower than 12%.With condensed ring
Electron acceptor, the especially development containing a receptor (A)-donor (D)-receptor (A) arrangement condensed ring electron acceptor, non-fowler
The PCEs of alkene OPVs is rapidly more than 12%, it might even be possible to reach 16% within the very short time, wherein only a few materials
ElossS is lower than 0.6eV.
Although this is normal, E for inorganic or perovskite solar batterylossS is lower than the high-performance of 0.5eV
OPVs is more rare so far, it means that ElossIt is still the key factor for limiting OPV technology photovoltaic efficiency.Although such as
This, in the past few years, people make great efforts Eloss0.5Ev is decreased below, to improve the efficiency of OPVs.Pertinent literature report
The big band gap polymerization of the 1,3,4- thiadiazoles part of benzo [1,2-b:4,5-b '] Dithiophene and electron deficient based on electron rich
Object donor PBDTS-TDZ.It is combined with representative non-fullerene acceptor ITIC, the equipment of PBDTS-TDZ base has most
High reachable 12.8% PCE and low Eloss(0.48eV).Pertinent literature also reported due to introducing a high rich electronic core
Heart DTPC, electron acceptor DTPC-DFIC show to absorb in 1021nm in the film, this corresponds to the optical band gap of 1.21eV.
Use narrow band gap PTB7-Th polymer as electron donor, the PCE of the device based on DTPC-DFICmaxIt is 10.21%, has
Extremely low Eloss(0.45eV)。
In work in our prior, we are opened by introducing weak electron receptor benzo [1,2-d:4,5-d '] double thiazole
A kind of big band gap polymeric donor BBTA is sent out.By matching low band gaps electron acceptor ZITI-Br, 11.08% is realized
PCEmax, and ElossOnly 0.50eV.Recently, there is document to disclose a kind of effective electron acceptor Y6, be shown in 931nm
Place starts to absorb, the optical band gap with 1.33eV.Device based on Y6 shows very high PCEmax(15.7%) and it is low
Eloss(0.50eV)。
High PCE and low E in order to obtainlossOPVs, above-mentioned electron acceptor material structure remains to be further improved.
Summary of the invention
To improve above-mentioned technical problem, present invention firstly provides the quinoxaline derivant as shown in following formula I,
Wherein, R1、R2、R3、R4、R5、R6It is identical or different, it is independently from each other H, unsubstituted or optionally by one, two
The following group that a or more Rs replaces: alkyl, naphthenic base, heterocycle；
X1、X2、X3、X4It is identical or different, it is independently from each other halogen or halogenated alkyl；
Z1、Z2It is identical or different, it is independently from each other O or S；
Rs is selected from halogen, hydroxyl, sulfydryl, cyano, nitro, alkyl, naphthenic base, heterocycle.
According to an embodiment of the invention, the R1、R2、R3、R4、R5、R6It is identical or different, it is independently from each other H, nothing
The C for replacing or optionally being replaced by one, two or more Rs1-12Alkyl；
X1、X2、X3、X4It is identical or different, it is independently from each other fluorine or chlorine；
Z1、Z2Selected from O；
Rs is selected from halogen or C1-12Alkyl.
As example, quinoxaline derivant shown in Formulas I is selected from following compound:
Wherein, EH=2- ethylhexyl.
The present invention also provides the preparation methods of quinoxaline derivant shown in Formulas I as described above, comprising:
Compound I-A reacts to obtain compound I with compound I-B, compound I-C；
R1、R2、R3、R4、R5、R6、X1、X2、X3、X4、Z1、Z2With definitions as described above.
According to an embodiment of the invention, the reaction is Knoevenagel condensation reaction.
According to an embodiment of the invention, the reaction carries out in the presence of organic base, such as in the presence of pyridine
It carries out.
The present invention also provides quinoxaline derivants shown in Formulas I as described above to prepare the purposes in organic solar batteries.
The present invention also provides compound I-A as described above, with structure as follows:
Wherein, R1、R2、R3、R4、R5、R6It is identical or different, it is independently from each other H, unsubstituted or optionally by one, two
The following group that a or more Rs replaces: alkyl, naphthenic base, heterocycle；
Rs is selected from halogen, hydroxyl, sulfydryl, cyano, nitro, alkyl, naphthenic base, heterocycle.
According to an embodiment of the invention, the R1、R2、R3、R4、R5、R6It is identical or different, it is independently from each other H, nothing
The C for replacing or optionally being replaced by one, two or more Rs1-12Alkyl.
As example, compound I-A is selected from following compound:
Wherein, EH=2- ethylhexyl.
The present invention also provides the preparation methods of compound I-A, include the following steps:
Compound I-A6 reacts to obtain compound I-A with LDA and DMF,
R1、R2、R3、R4、R5、R6With definitions as described above.
According to an embodiment of the invention, compound I-A6 is prepared with the following method:
Compound I-A1 and compound I-A2, compound I-A2 ' occur coupling reaction and compound I-A3 are prepared；Chemical combination
Object I-A3 occurs azido reaction and compound I-A4 is prepared；Compound I-A4 occurs ring closure reaction and compound I- is prepared
A5；Compound I-A5 and compound R3-L1And compound R4-L2Substitution reaction occurs and obtains compound I-A6,
R1、R2、R3、R4、R5、R6With definitions as described above；L1With L2It is identical or different, it is independently from each other and leaves away
Group, such as halogen.
The present invention also provides purposes of the compound I-A in prepare compound I.
The present invention also provides a kind of organic solar batteries comprising quinoxaline derivant shown in Formulas I as described above.
According to an embodiment of the invention, the organic solar batteries include active layer, it include Formulas I in the active layer
Shown quinoxaline derivant.
According to an embodiment of the invention, further including PBDB-TF polymer in the active layer of the organic solar batteries
Donor, with structure as follows,
Wherein, EH=2- ethylhexyl.
According to an embodiment of the invention, quinoxaline derivant shown in Formulas I and PBDB-TF polymer in the active layer
The mass ratio of donor is 1:(0.8~1.2), for example, 1:1.
According to an embodiment of the invention, the organic solar batteries include: tin indium oxide (ITO), poly- (3,4- Asia second
Base dioxy thiophene): poly- (styrene sulfonate) (PEDOT:PSS), active layer, PDINO and Al.
According to an embodiment of the invention, the organic solar batteries successively include: substrate, tin indium oxide (ITO) layer,
Poly- (3,4- ethyldioxythiophene): poly- (styrene sulfonate) layer (PEDOT:PSS layers), active layer, PDINO layers and Al layers.
According to an embodiment of the invention, in the organic solar batteries PEDOT:PSS layers with a thickness of 25~35nm,
Such as 30nm.
According to an embodiment of the invention, the active layer with a thickness of 80~140nm, preferably 90~135nm.
According to an embodiment of the invention, in the organic solar batteries aluminium (Al) with a thickness of 80~120nm, preferably
90~100nm.
The present invention also provides the preparation methods of organic solar batteries as described above, include the following steps:
S1) ultrasonic cleaning is coated with the glass substrate of ITO and carries out oxygen plasma treatment；
S2) the spin coating PEDOT:PSS on the ito glass substrate of step S1) preparation, is toasted after the completion of spin coating；
S3) the spin coating active layer on the material of step S2) preparation, optionally carries out thermal anneal process after the completion；
S4) the spin coating PDINO on the active layer of step S3) preparation；
S5 aluminothermy) is evaporated to step S4) preparation substrate on.
According to an embodiment of the invention, step S2) baking temperature be 130~170 DEG C.
According to an embodiment of the invention, step S3) operation carried out in atmosphere of inert gases.
According to an embodiment of the invention, step S3) in active layer preparation process are as follows: quinoxaline shown in Formulas I is spread out
Biology and PBDB-TF polymeric donor be dissolved in chloroformic solution, step S2 is spin-coated on after mixing) preparation material on, then adjust
Save the active layer of revolving speed preparation required thickness.
Preferred embodiment according to the present invention, step S3) in active layer preparation process are as follows: by quinoline shown in Formulas I
Quinoline derivant and PBDB-TF polymeric donor are dissolved in chloroformic solution, are added 1- chloronaphthalene (1-CN), are spin-coated on step after mixing
S2) on the material prepared, the active layer of revolving speed preparation required thickness is then adjusted.As example, the additive amount of the 1- chloronaphthalene
For 0.1~0.5v/v% of chloroformic solution, such as 0.25v/v%.
Preferred embodiment according to the present invention, step S3) in carry out thermal anneal process.
According to an embodiment of the invention, step S3) in annealing operation in 70~130 DEG C of processing 1min~for 24 hours.
The present invention also provides the organic solar batteries that method as described above is prepared.
Beneficial effect
Quinoxaline derivant prepared by the present invention shows low optical band gap (1.35eV) in the film.By with middle width
The matching of band gap polymeric donor PBDB-TF polymeric donor, the device of preparation PCE with higher, and the device
ElossIt is significantly reduced.In addition, the compound of the present invention dissolves in a variety of organic solvents, therefore easily prepared various organic light
Lie prostrate material.The present invention is had broad application prospects using organic solar batteries prepared by quinoxaline derivant.
Term explanation and illustration
Unless otherwise indicated, group and the term definition recorded in present specification and claims, including its work
For the definition of example, illustrative definition, preferably definition, the definition recorded in table, particular compound determines in embodiment
Justice etc., can any combination and combination each other.Group definition and compound structure after such combination and combination, should
Belong to the range of the application record.
It " optionally " indicates to can according to need progress or without subsequent step in the application.
" halogen " that the present invention uses refers to fluorine, chlorine, bromine and iodine.
" optionally ... replacing " is substituted or unsubstituted by any substituent group.
The present invention is used alone or " alkyl " as suffix or prefix means branch and linear saturation aliphatic hydrocarbyl, preferably
Including having the branch and straight chain of 1 to 30 carbon atom (if or provide the specific number of carbon atom, refer to the specific number)
Radical of saturated aliphatic alkyl.For example, the alkyl can be C1-10The alkyl, " C1-12Alkyl " indicate have 1,2,3,4,5,6,7,
8, the alkyl of 9,10,11 and 12 carbon atoms.The example of alkyl include but is not limited to methyl, ethyl, propyl, butyl, amyl, oneself
Base, isopropyl, isobutyl group, sec-butyl, tert-butyl, isopentyl, 2- methyl butyl, 1- methyl butyl, 1- ethyl propyl, 1,2- bis-
Methyl-propyl, neopentyl, 1,1- dimethyl propyl, 4- methyl amyl, 3- methyl amyl, 2- methyl amyl, 1- methyl amyl, 2-
Ethyl-butyl, 1- ethyl-butyl, 3,3- dimethylbutyl, 2,2- dimethylbutyl, 1,1- dimethylbutyl, 2,3- dimethyl butyrate
Base, 1,3- dimethylbutyl, 1,2- dimethylbutyl, 2- ethylhexyl, 3- ethylhexyl, 2- hexyl decyl etc. and above-mentioned
Whole isomeric forms of group.
Terminology used in the present invention " naphthenic base " means the hydrocarbon ring of saturation, may include condensed or bridge joint multi-loop system.
Naphthenic base preferably has 3 to 40 carbon atoms in its ring structure.Preferably, naphthenic base has 3,4,5 or 6 in its ring structure
A carbon atom.For example, " C3-6The group of naphthenic base " expression such as cyclopropyl, cyclobutyl, cyclopenta or cyclohexyl.
Terminology used in the present invention " heterocycle " refers to the list of the saturation comprising 3 to 20 atoms, insatiable hunger and/or fractional saturation
Ring, two rings or tricyclic (unless otherwise indicated), wherein 1,2,3,4 or 5 annular atom is selected from nitrogen, sulphur or oxygen, unless otherwise indicated,
It can be connected by carbon or nitrogen, wherein-CH2Group is optionally replaced by-C (O)-；And wherein unless otherwise indicated, ring
Nitrogen-atoms or ring sulfur atom are optionally oxidized to form N- oxide or S- oxide or theheterocyclic nitrogen atom and optionally be quaternized；Wherein
- NH in ring is optionally replaced by acetyl group, formoxyl, methyl or mesyl；And ring is optionally replaced by one or more halogens.
It should be understood that these hetero atoms are not adjacent to each other when the sum of S atom in heterocycle and O atom is more than 1.If described
Heterocycle is two rings or tricyclic, then at least one ring may optionally be heteroaromatic rings or aromatic ring, and condition is at least one ring right and wrong
Heteroaromatic.It is not centainly aromatics if the heterocycle is monocycle.The example of heterocycle includes but is not limited to piperidines
Base, N- acetylpiperidinyl, N- methyl piperidine base, N- formyl piperazine base, N- mesylpiperazinyl, high piperazine base, piperazine
Base, azetidinyl, oxetanyl, morpholinyl, tetrahydro isoquinolyl, tetrahydric quinoline group, indolinyl, tetrahydro pyrrole
It mutters base, dihydro -2H- pyranose, tetrahydrofuran base, tetrahydro thiapyran base, tetrahydric thiapyran -1- oxide, tetrahydric thiapyran -1,1- dioxy
Compound, 1H- pyridin-2-ones and 2,5- dioxoimidazolidin alkyl.
Detailed description of the invention
Fig. 1 is the TGA testing result of compound AQx；
(a) is the UV-vis-NIR absorption spectrum of AQx and PBDT-TF in Fig. 2；(b) it is used for OPV device active layers different
The energy diagram of material；(c) in AM1.5G (100mW cm-2) radiate lower AQx base OPV device feature J-V curve；(d) phase
The EQE curve answered；(e) E is detectedlossMethod；(f) PCE reported in the literaturemaxMore than 9% and ElossBinary lower than 0.6eV
OPV。
A is the density of photocurrent (J of four kinds of different components in Fig. 3ph) and effective voltage (Veff) variation；B is four kinds of devices
Exciton fission probability graph.
Fig. 4 is illustrative AQx, PBDT-TF film and reference Fc (ferrocene) in CH3Cyclic voltammetric in CN solution
Figure, sweep speed are 100mV s-1。
Fig. 5 a is in AM1.5G (100mW cm-2) radiate lower AQx-2 base OPV device feature J-V curve；Fig. 5 b is to change
Close the wavelength and-incident optical light quanta transformation efficiency testing result of object AQx-2.
Specific embodiment
Further detailed description is done to technical solution of the present invention below in conjunction with specific embodiment.It should be appreciated that
The following example is merely illustrative the ground description and interpretation present invention, and is not necessarily to be construed as limiting the scope of the invention.
In the range of all technologies realized based on above content of the present invention are encompassed by the present invention is directed to protect.
Unless otherwise indicated, raw materials and reagents used in following examples are commercial goods, or can pass through this
The preparation of method known to the technical staff of field.
In following examples, nucleus magnetic hydrogen spectrum is obtained using the test of 300 spectrometer of Bruker Avance.In following examples
MALDI data are measured with MALDI-TOF MS Bruker Autoflex III.UV- is recorded with Jasco V-570 spectrometer
vis.Cyclic voltammetry (CV) test is carried out with CHI620D potentiostat.All current potentials use Fc/Fc+Correction.Use Shimadzu
60 instrument of DTG is under 30 to 550 DEG C, nitrogen atmosphere with 40 DEG C of min-1The rate of heat addition measure thermogravimetric analysis (TGA).
In following examples, the film is by the way that compound such as AQx or PBDB-TF polymeric donor to be dissolved in right amount
In chloroformic solution, it is spun on silicon wafer and is prepared with refiner.
Preparation example 1: the preparation of compound 1
1 bibliography Org Lett 2011 of compound；Method in 13:5484-5487, preparation process are as follows: compound
A1 and compound A2 occurs coupling reaction and compound A-13 is prepared, and compound A-13 occurs azido reaction and compound is prepared
A4, compound A4 occur ring closure reaction and compound A-45 are prepared, and compound A-45 occurs substitution reaction with 2- bromomethyl octane and obtains
To compound 1-1.Then, N2Under environment, compound 1-1 (95mg, 0.098mmol) is dissolved in tetrahydrofuran (20ml), be placed in-
In 78 DEG C of environment.N-BuLi (0.49mmol) is added dropwise in above-mentioned solution system, is reacted 1.5 hours.By DMF
(0.98mmol) is added in above-mentioned mixed system, system is placed in room temperature environment after half an hour, saturated ammonium chloride is quenched, dichloromethane
Alkane extracts organic phase three times, merges organic phase, anhydrous MgSO4It is dry.Column chromatography for separation purification.Product is obtained through column chromatography for separation
83mg (yield 83%), MS (MALDI-TOF): 1048.7 [M]+。
Preparation example 2: the preparation of compound 2
With reference to the preparation process of preparation example 1, compound 2 is prepared.
Embodiment 1: the preparation and performance test of compound AQx
Wherein, EH=2- ethylhexyl.
Compound 1 (140mg, 0.13mmol) is dissolved in chloroform (20mL).INCN-2F is added into said mixture
(5,6- bis- fluoro- 3- (dicyano methylene) indigo ketone) (153mg, 0.67mmol) and a few drop pyridines, above-mentioned system add at 60 DEG C
Thermal response 14 hours.It uses chloroform as eluant, eluent after the reaction was completed, mixture is purified using silica gel column chromatography, is obtained
100mg compound AQx, for black solid (yield 51%).1H NMR(300MHz,CDCl3):δ9.12(s,2H),8.52(m,
2H),7.70(t,3J=7.5Hz, 2H), 4.79 (d,3J=7.5Hz, 4H), 3.25 (t,3J=7.2Hz, 4H), 2.88 (s, 6H),
2.15(m,2H),1.88(m,4H),1.50-0.50(m,66H)；MS(MALDI-TOF):1473.7[M]+.
The TGA testing result of compound AQx is as shown in Figure 1.Compound AQx only has Fig. 1 at 347 DEG C of high temperature as the result is shown
5% weightlessness shows compound AQx thermal stability with higher.
In chloroformic solution, (concentration is 1 × 10 to compound AQx-5Mg/mL) and the absorption spectrum of film Plays, and
The testing result of PBDB-TF polymeric donor in the film is as shown in Figure 2 a.Compound AQx has most at 749nm in chloroform
Big absorption peak has 1.93 × 105M-1cm-1High molar absorption coefficient.The significant red shift of maximum absorption band is extremely in the film for it
820nm.In addition, observing broader absorption at 500 to 950nm, this is well matched with PBDB-TF polymeric donor, and
And be conducive to solar energy collecting.According to the wavelength (918nm) started when absorbing in film, the optical band gap for calculating AQx is
1.35eV。
Also use cyclic voltammetry to assess the energy level of frontier orbital of AQx simultaneously, testing result is as shown in Figure 2 b.Compound
The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy level of AQx is respectively -5.58 and -3.85eV.
HOMO between PBDB-TF polymeric donor and AQx deviates very little (0.08eV), this is usually only observed in non-fullerene OPVs
It arrives, and lesser energy loss can be brought.
Embodiment 2: the preparation and performance test of compound AQx-2
Raw material compound 1 is replaced with compound 2 by reference implementation example 1, and compound AQx-2 (yield 93%) is prepared
.1H NMR(300MHz,CDCl3):d 9.18(s,2H),8.98(s,2H),8.57(m,2H),7.71(t,3J=7.5Hz, 2H)
4.81(d,3J=7.5Hz, 4H), 3.26 (t,3J=7.5Hz, 4H), 2.12 (m, 2H), 1.89 (m, 4H), 1.50-0.64 (m,
66H)。
Test shows AQx-2 also thermal stability with higher.
Embodiment 3: the photovoltaic performance test comprising compound AQx device
The present embodiment is prepared for the device of the AQx containing compound: tin indium oxide (ITO)/poly- (3,4- ethyldioxythiophene):
Poly- (styrene sulfonate) (PEDOT:PSS)/active layer/PDINO/Al, wherein compound AQx and PBDB-TF polymeric donor
It is used separately as electron acceptor and donor material in active layer.
The specific preparation process of device are as follows: 1) be coated with the glass substrate (15 Ω sq-1) of ITO using deionized water, acetone and
Isopropanol is cleaned by ultrasonic 20 minutes, then carries out 20 minutes oxygen plasma treatments.It is being prepared first with the frequency of 3000rpm
Ito glass substrate on spin coating about 30nm thickness PEDOT:PSS (Bayer Baytron 4083) layer, and toasted at 150 DEG C
15 minutes.It transfers it in the glove box full of nitrogen, by active layer with chloroformic solution (by compound AQx and PBDB-
TF polymeric donor is dissolved in chloroformic solution) spin coating, PBDB-TF polymeric donor in chloroformic solution: AQx receptor (D/A) quality
Than for 1:1, solution total concentration is 17mg/mL.
2) alcoholic solution of PDINO is spin-coated on the active layer of step 1) preparation with the frequency of 3000rpm.Finally in Gao Zhen
It will be in aluminium (100nm) thermal evaporation to substrate under sky.The effective coverage of device is defined as 0.05cm by shadow mask2.It will be prepared into
As-cast is named as to device.
Also, 80 DEG C/10min of device, 100 DEG C/10min of device, device 120 are also prepared for reference to the preparation of as-cast
DEG C/10min, device 1-CN, device 3000rpm, device 3500rpm and device 2500rpm, in which:
The preparation of 80 DEG C/10min of device and as-cast the difference is that, after step 1) is using active layer spin coating also
Thermal anneal process is carried out, the condition of processing is 80 DEG C/10min.
The treatment process of 100 DEG C/10min of device (being also denoted as device TA) and 80 DEG C/10min of device is the difference is that heat
Annealing conditions are 100 DEG C/10min.
The treatment process of 120 DEG C/10min of device and 80 DEG C/10min of device is the difference is that hot annealing conditions are 120
℃/10min。
Device 1-CN and device as-cast is the difference is that also use 0.25v/v%1- chloronaphthalene (1- in preparation process
CN) the additive as solvent chloroform when preparing active layer.
The preparation of device 3000rpm (being also denoted as device 1-CN+TA) are as follows: identical using above-mentioned 100 DEG C/10min of device
Preparation method, the difference is that 0.25v/v%1- chloronaphthalene (1-CN) is also used to add as solvent chloroform when preparing active layer
The spin speed for adding agent, and controlling active layer is 3000rpm, and the film thickness for obtaining active layer is 110nm.
The preparation of device 3500rpm are as follows: using the identical preparation method of above-mentioned 100 DEG C/10min of device, difference exists
In also using additive of the 0.25v/v%1- chloronaphthalene (1-CN) as solvent chloroform when preparing active layer, and control active layer
Spin speed is 3500rpm, and the film thickness of active layer is 95nm.
The preparation of device 2500rpm are as follows: using the identical preparation method of above-mentioned 100 DEG C/10min of device, difference exists
In also using additive of the 0.25v/v%1- chloronaphthalene (1-CN) as solvent chloroform when preparing active layer, and control active layer
Spin speed is 2500rpm, and the film thickness of active layer is 130nm.
Using 2400 source instrument of Keithley in AM1.5G (100mW cm-2) irradiation under measure Current density-voltage (J-
V) curve.The certified IPCE equipment of external quantum efficiency (EQE) use (Zolix Instruments, Inc,
SolarCellScan100 it) tests.
With ITO/PEDOT:PSS/PBDB-TF:AQx/MnO3The device of/Al hole device and only electronic equipment
Test space charge-limited current in ITO/ZnO/PBDB-TF:AQx/Al.Hole and electron mobility calculate as follows:Wherein J is electric current, μ0It is null field mobility, ε0It is the dielectric constant of free space, εrIt is in material
Under relative dielectric constant, V is effective voltage, and L is the thickness of active layer.
The photovoltaic parameter testing result of the different components of preparation is as shown in the table.
Photovoltaic parameter of the table 1. based on the device that PBDB-TF:AQx is active layer under different thermal annealing temperatures
Table 2. has photovoltaic parameter when different activities tunic thickness based on the device that PBDB-TF:AQx is active layer
As shown in the result of table 1 and 2, each device obtains excellent photovoltaic performance.Wherein, device 3000rpm, which is shown, mentions
The short circuit current (Jsc) risen, current values are 20.06 to 22.18mA cm-2, fill factor (FF) is 59.34% to arrive
67.14%, open-circuit voltage Voc are 0.893V, and energy conversion efficiency PCE reaches as high as 13.31%.
Photovoltaic parameter of the table 3. based on AQx devicea
aEvery group of data are the average value of 15 equipment detection.
Corresponding Current density-voltage (J-V) and external quantum efficiency (EQE) curve be as illustrated in figures 2 c and 2d in table 3.It is based on
The device of AQx shows wide and high EQE response, the absorption spectrum one of this and corresponding photoactive component at 300 to 900nm
It causes.At different conditions according to the calculated J of EQE spectrum integralscThe s and J obtained according to J-V curvescS, which has, well may be used
Than property, error is less than 2%~3%.
We are according to equation Eloss=Eg-eVocCalculate the E of the device based on AQxlossS (table 3), wherein EgBased on EQE
Spectrum determines (Fig. 2 e).All E of the mixed film handled at different conditionslossS is below 0.47eV, and minimum reaches
0.45eV。
According to the charge transmission analysis of space charge limited current method detection, improved FF and JscIt is attributable to higher
Charge carrier mobility (μh:1.50vs 2.06cm2V-1s-1,μe:1.84vs 2.10cm2V-1s-1) and the μ that more balancesh/μe
Close to 1.We measure density of photocurrent (Jph) and effective voltage (Veff) variation) check exciton fission and extract property
Efficiency.
We measure density of photocurrent (Jph) and effective voltage (Veff) variation, to examine exciton fission and extractability
The efficiency of matter.Testing result is as shown in Figure 3a, JphIn the high V of 2VeffUnder reach saturation.The J of four kinds of devicesph/JsatRatio point
It Wei 90.66%, 93.94%, 94.58% and 95.52%.
The exciton fission probability of four kinds of devices in table 3 is tested, this is consistent with its optimal photovoltaic performance.We pass through survey
Measure JscWith Plight(luminous intensity) further studies charge recombination process, and testing result is as shown in Figure 3b.α is by Jsc∝Plight α's
Formula estimation.For as cast condition and after-treatment device, the α value of four kinds of devices is similar, and range is 0.95-0.96, it means that these
Device processing does not influence regrouping process, and shows insignificant bimolecular recombination.
The configuration of surface of PBDB-TF:AQx blend film in four kinds of devices in table 3 is studied by atomic force microscope (AFM).
The blend film r.m.s. roughness (RMS) of device as-cast is 0.77nm, the blend film r.m.s. roughness (RMS) of device TA
For 0.94nm, the blend film r.m.s. roughness (RMS) of device 1-CN is 0.98nm, the blend film root mean square of device 1-CN+TA
Roughness (RMS) reaches 1.44nm, this is conducive to charge transmission.In addition, we study using transmission electron microscope (TEM)
Bulk & form, it can be observed that the separation of biggish phase, the blend film of device 1-CN+TA show nanoscale in as cast condition active layer
Fiber interpenetrating networks, this is conducive to charge dissociation and transmission.
Compound AQx, PBDT-TF and Fc are dissolved in diluted CH3(concentration is 10 to CN solution-3Mol/L it is carried out in)
Cyclic voltammetry, sweep speed are 100mV s-1, testing result is as shown in figure 4, the HOMO of AQx as shown in Figure 4, lumo energy
Respectively -5.58 and -3.85eV, the HOMO of PBDT-TF, lumo energy are respectively -5.50 and -3.36eV, receptor AQx and donor
PBDT-TF has the energy level to match.
Embodiment 4: the photovoltaic performance test comprising compound AQx-2 device
The preparation method of device 3000rpm in reference implementation example 3 is prepared the difference is that AQx is replaced with AQx-2
Device based on AQx-2, and tested using the test method of embodiment 3, as a result as shown in the table:
Table 4: the photovoltaic parameter based on AQx-2 deviceb
bEvery group of data are the average value of 15 equipment detection.
In AM1.5G (100mW cm-2) radiate the feature J-V curve of the OPV device of AQx-2 base as shown in Figure 5 a, chemical combination
The wavelength of object AQx-2 shows with-incident optical light quanta transformation efficiency testing result such as Fig. 5 b.
It is above-mentioned the experimental results showed that, AQx-2 have superior photovoltaic performance.
More than, embodiments of the present invention are illustrated.But the present invention is not limited to above embodiment.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in guarantor of the invention
Within the scope of shield.
Claims (10)
1. the quinoxaline derivant as shown in following formula I,
Wherein, R1、R2、R3、R4、R5、R6It is identical or different, be independently from each other H, it is unsubstituted or optionally by one, two or
The following group that more Rs replace: alkyl, naphthenic base, heterocycle；
X1、X2、X3、X4It is identical or different, it is independently from each other halogen or halogenated alkyl；
Z1、Z2It is identical or different, it is independently from each other O or S；
Rs is selected from halogen, hydroxyl, sulfydryl, cyano, nitro, alkyl, naphthenic base, heterocycle.
2. quinoxaline derivant according to claim 1, which is characterized in that the R1、R2、R3、R4、R5、R6It is identical or not
Together, H, C that is unsubstituted or optionally being replaced by one, two or more Rs are independently from each other1-12Alkyl；
X1、X2、X3、X4It is identical or different, it is independently from each other fluorine or chlorine；
Z1、Z2Selected from O；
Rs is selected from halogen or C1-12Alkyl.
3. quinoxaline derivant according to claim 1, which is characterized in that quinoxaline derivant shown in Formulas I is selected from such as
Lower compound:
Wherein, EH=2- ethylhexyl.
4. the preparation method of any one of the claim 1-3 quinoxaline derivant characterized by comprising
Compound I-A reacts to obtain compound I with compound I-B, compound I-C；
R1、R2、R3、R4、R5、R6、X1、X2、X3、X4、Z1、Z2With the described in any item definition of claim 1-3.
5. the described in any item quinoxaline derivants of claim 1-3 are preparing the purposes in organic solar batteries.
6. a kind of organic solar batteries comprising the described in any item quinoxaline derivants of claim 1-3.
7. organic solar batteries according to claim 6, which is characterized in that the active layer of the organic solar batteries
In include any one of the claim 1-3 quinoxaline derivant；
Preferably, further include PBDB-TF polymeric donor in the active layer of the organic solar batteries, have as follows
Structure,
Wherein, EH=2- ethylhexyl；
Preferably, the mass ratio of quinoxaline derivant shown in Formulas I and PBDB-TF polymeric donor is 1:(0.8 in the active layer
~1.2)；
Preferably, the organic solar batteries include: tin indium oxide (ITO), poly- (3,4- ethyldioxythiophene): poly- (benzene
Vinyl sulfonate) (PEDOT:PSS), active layer, PDINO and Al；
Preferably, in the organic solar batteries PEDOT:PSS with a thickness of 25~35nm；
Preferably, the active layer with a thickness of 80~140nm；
Preferably, in the organic solar batteries aluminium with a thickness of 80~120nm.
8. the preparation method of the organic solar batteries of claim 6 or 7, which comprises the steps of:
S1) ultrasonic cleaning is coated with the glass substrate of ITO and carries out oxygen plasma treatment；
S2) on the ito glass substrate of step S1) preparation spin coating PEDOT:PSS, toasted after the completion of spin coating；
S3) the spin coating active layer on the material of step S2) preparation, optionally carries out thermal anneal process after the completion；
S4) the spin coating PDINO on the active layer of step S3) preparation；
S5 aluminothermy) is evaporated to step S4) preparation substrate on.
9. such as following formula I-A compound represented,
Wherein, R1、R2、R3、R4、R5、R6It is identical or different, be independently from each other H, it is unsubstituted or optionally by one, two or
The following group that more Rs replace: alkyl, naphthenic base, heterocycle；
Rs is selected from halogen, hydroxyl, sulfydryl, cyano, nitro, alkyl, naphthenic base, heterocycle.
10. purposes of the compound I-A described in claim 9 in any one of the preparation claim 1-3 quinoxaline derivant.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111499840A (en) * | 2020-04-30 | 2020-08-07 | 深圳睿迅有机光电有限公司 | Conjugated polymer, preparation method thereof, donor-acceptor material and photoelectric device |
| CN113583019A (en) * | 2021-08-03 | 2021-11-02 | 中国科学院长春应用化学研究所 | ADA' DA type full condensed ring micromolecule and preparation method and application thereof |
| CN114181229A (en) * | 2021-12-20 | 2022-03-15 | 国家纳米科学中心 | Organic small-molecule photovoltaic material based on benzopyrazine donor nucleus and preparation method and application thereof |
| WO2023035401A1 (en) * | 2021-09-09 | 2023-03-16 | 苏州大学 | Non-fullerene acceptor having cooperative assembly performance, and preparation method therefor and application thereof |
| CN116514835A (en) * | 2022-01-19 | 2023-08-01 | 南开大学 | Organic photoelectric compound, preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104448251A (en) * | 2013-09-24 | 2015-03-25 | 海洋王照明科技股份有限公司 | Quinoxalinyl-containing polymer, preparation method thereof and solar cell device |
| WO2018095940A1 (en) * | 2016-11-25 | 2018-05-31 | Merck Patent Gmbh | Bisbenzofuran-fused indeno[1,2-b]fluorene derivatives and related compounds as materials for organic electroluminescent devices (oled) |
-
2019
- 2019-07-01 CN CN201910586691.0A patent/CN110283185B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104448251A (en) * | 2013-09-24 | 2015-03-25 | 海洋王照明科技股份有限公司 | Quinoxalinyl-containing polymer, preparation method thereof and solar cell device |
| WO2018095940A1 (en) * | 2016-11-25 | 2018-05-31 | Merck Patent Gmbh | Bisbenzofuran-fused indeno[1,2-b]fluorene derivatives and related compounds as materials for organic electroluminescent devices (oled) |
Non-Patent Citations (1)
| Title |
|---|
| M.L. KESHTOV ET AL.: "Synthesis and photophysical properties of semiconductor molecules D1-A-D2-A-D1-type structure based on derivatives of quinoxaline and dithienosilole for organics solar cells", 《ORGANIC ELECTRONICS》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111499840A (en) * | 2020-04-30 | 2020-08-07 | 深圳睿迅有机光电有限公司 | Conjugated polymer, preparation method thereof, donor-acceptor material and photoelectric device |
| CN111499840B (en) * | 2020-04-30 | 2023-04-11 | 深圳睿迅有机光电有限公司 | Conjugated polymer, preparation method thereof, donor-acceptor material and photoelectric device |
| CN113583019A (en) * | 2021-08-03 | 2021-11-02 | 中国科学院长春应用化学研究所 | ADA' DA type full condensed ring micromolecule and preparation method and application thereof |
| WO2023035401A1 (en) * | 2021-09-09 | 2023-03-16 | 苏州大学 | Non-fullerene acceptor having cooperative assembly performance, and preparation method therefor and application thereof |
| CN114181229A (en) * | 2021-12-20 | 2022-03-15 | 国家纳米科学中心 | Organic small-molecule photovoltaic material based on benzopyrazine donor nucleus and preparation method and application thereof |
| CN114181229B (en) * | 2021-12-20 | 2023-11-03 | 嘉兴禾浦光电科技有限公司 | Organic micromolecular photovoltaic material based on benzopyrazine donor cores, and preparation method and application thereof |
| CN116514835A (en) * | 2022-01-19 | 2023-08-01 | 南开大学 | Organic photoelectric compound, preparation method and application thereof |
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