CN107141449A - Cross-linking solar cell interface material of one class based on azido derivant - Google Patents
Cross-linking solar cell interface material of one class based on azido derivant Download PDFInfo
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Abstract
The invention belongs to organic polymer field of functional materials, it is related to cross-linking solar cell interface material of the class based on azido derivant, using indeno fluorene derivative fragment as fat-soluble unit, fluorene derivative fragment is the affine unit in interface, the Suzuki couplings being catalyzed by Pd are made, the interlayer materials for organic solar battery forward or backwards.The polymer can be effectively improved the electric charge transmission between active layer and metal oxide layer, so as to lift the short circuit current flow of polymer photovoltaic cell due to introducing the molten fragment of Dual-arm ester and the affine unit in interface on main chain.Compared with now widely used boundary material PFN, such polymer can effectively lift solar cell short circuit current flow JSCAnd fill factor, curve factor, further improve the electricity conversion of solar cell.
Description
Technical field
The invention belongs to filed of functional, and in particular to a class solar cell interface material.
Background technology
Research and most widely used solar cell are mainly monocrystalline silicon, polysilicon and non-crystalline silicon series battery at present, so
And such battery has the shortcomings that cost of material height, complex manufacturing, manufacturing process cost height, high energy consumption, limits it and enter
One step industrialization.As third generation solar cell, organic solar batteries have inexpensive, flexible, easy preparation etc. significantly
Advantage, the organic solar batteries that new high conversion is developed by adjusting material structure are that one kind can effectively improve the sun
The research method of the performance of energy battery.At present there are some researches show in organic solar batteries, between metal oxide and activity
Boundary layer between layer, can effectively change metal oxide surface pattern and have certain regulation to the longitudinal pattern of active layer
Effect.Boundary layer is to the energy conversion efficiency important of whole battery, the solar-electricity to developing new high conversion
Pond tool is of great significance.
In recent years, scientific research personnel's design has synthesized a series of copolymers for being based on 9,9- bis- (alkylamine) fluorenes fragment, can
It is efficiently modified active layer and the interface performance of transport layer.The PFN of Cao Yong et al. synthesis is now widely used interlayer materials,
The material can effectively improve the V of deviceoc, Jsc, and FF [Appl.Phys.Lett.2009,95,043301；
J.Mater.Chem.,2010,20,2617–2622；Adv.Mater.2011,23,4636–4643；
Adv.Funct.Mater.2012,22,2846–2854；Organic Electronics,2014,15,758–774].For this
Class material and the weaker shortcoming of interfacial interaction, Huang Fei et al. passes through introduces alkene [Adv.Energy in fat-soluble fragment
Mater.2016,1502563], the mode such as oxygen fourth ring [J.Am.Chem.Soc., 2013,135 (41), 15326-15329],
The stability for crosslinking to improve such material under heating or illumination condition and the firm interaction with interface.Fang Junfeng
Et al. report the small molecule interlayer materials [Adv.Energy Mater.2014,1400359] based on PFN amino fragments, can
By PTB7/PC71BM brings up to 8.93% for the solar battery efficiency of active layer.Peng Qiang et al. is also reported based on triphenylamine knot
The small molecule receptor material [Adv.Funct.Mater.2016, adfm.201504734] of structure, such material can be by PTB7/
PC71BM brings up to 10.1% for the solar battery efficiency of active layer.
Influence of the boundary layer to battery performance in view of the above, introduces prepared by azido derivant on boundary layer main chain
Novel crosslinkable solar cell interface material is expected to further improve metal oxide surface pattern, the longitudinal shape of regulation active layer
Looks are distributed, and lift charge transport ability, so as to improve device photovoltaic performance, but yet there are no the preparation about such material so far
Report of the method and its application in photovoltaic cell.
The content of the invention
In order to overcome the shortcomings of that prior art is present and defect, the present invention provides a class based on the cross-linking of azido derivant
Solar cell interface material：With the crosslinkable high molecular polymer based on fluorenes, indeno fluorene skeleton of nitrine, alcohol-soluble is good,
Heat endurance is good, can illumination or heat cross-linking.
Azido group is incorporated into polymer alkyl chain end, because nitrine functional group can under heating or ultraviolet lighting
The characteristic of crosslinking, while polar segment modifying metallic oxide surface, influence active layer longitudinal direction topographic profile, passes through polymerization
Thing interchain linkage effectively enough lifts boundary layer stability, further boost device photoelectric conversion performance；Such material can be carried effectively
Device performance is risen, is shown than now widely used boundary material PFN more preferably photoelectric conversion performances.
The nitrine crosslinkable polymer of the present invention has following architectural feature (formula I~VI)：
In formula I~VI, x, y, z is molal quantity ratio between each monomer, meets x=y+z, y=x+z, or z=x+y
One of feature；N is the degree of polymerization, is the natural number between 0~1,000,000；
Interface is affine, and unit PG is selected from one of following structures：
The class formation includes amino with its nitrogen oxides, with alkyl halide quaternary ammonium of the carbon number for 1 to 8 straight or branched
Quaternary ammonium salt obtained by changing, with all kinds of acid (including but is not limited to nitrate anion, acetate, sulfate radical, phosphate radical, perchlorate etc.)
The salt formed, or each analog derivative that the form such as nitrogen oxides is present.
Fat-soluble unit LG is selected from one of following structures：
In said structure：A1For C, Si or Ge atoms；A2For N, P, or As atom；A3For O, S, or Se atom；
Alk is the alkyl for the straight or branched that carbon number is 1-20；R1It is hydrogen atom, fluorine atom, carbon number is 1 to 20 straight chain
Or the alkyl of side chain, or the carbon number that end is azido be 1-20 straight or branched alkyl；R2It is hydrogen atom, carbon
Atomicity is the alkyl of 1 to 10 straight or branched；R3It is hydrogen atom, fluorine atom, carbon number is 1 to 20 straight or branched
Alkyl, or the carbon number that end is amino and its alkyl derivative be 1-20 straight or branched alkyl；R4For carbon
Atomicity is the alkyl of 1-20 straight or branched；R5It is hydrogen atom, fluorine atom, carbon number is 1 to 20 straight or branched
Alkyl, carbon number for 1 to 20 straight or branched alkoxy, carbon number for 1 to 20 straight or branched neighbour,
Between, contraposition alkyl phenyl, carbon number for 1 to 20 straight or branched it is o-, m-, contraposition alkoxyl phenyl.
The present invention provides the cross-linking solar cell interface material for being preferably based on azido derivant, and its structural formula is such as
Any one in lower compound A-E：
Structural formula A
Structural formula B
Structural formula C
Structural formula D
Structural formula E
The preparation method of the present invention comprises the following steps：The reaction is carried out under nitrogen protection, be bromine by x mol ends,
A kind of polar segment PG, the y mol ends of functional group are a kind of official in bromine, boric acid or borate in boric acid or borate
The azido derivant that can be rolled into a ball, z mol ends are a kind of fat-soluble fragment LG of functional group in bromine, boric acid or borate according to x
A kind of ratio is added in two mouthfuls of dry flasks in=y+z, y=x+z, or z=x+y, toluene/tetrahydrofuran/chloroform/second
One or more of solvents dissolving in ether, monomer concentration is controlled in 0.1mol/L or so, and 0.02 is added after logical inert gas 0.5h
The Pd catalyst of times mole, adds or is added without basic additive tetraethylamine hydroxide/potassium carbonate/sodium carbonate/hydroxide
One or more in sodium.Begun to warm up after continuing ventilation 0.5h, after 24~48h of back flow reaction, stop reaction.System is cooled to
Room temperature, reaction solution is instilled in methanol and settled, filtering, 50 DEG C of the polymer vacuum drying oven baking 12h of collection, successively with methanol, just
Hexane, chloroform carry out soxhlet extraction, concentrate chloroform extracted solution, are settled again with methanol, filter, and obtain containing shown in formula I
The conjugated polymer of indeno fluorene derivative.
By in one or more of solvents of the polymer in tetrahydrofuran/methanol/acetone, the hydrogen peroxide of 10 equivalents is added
Oxidation obtains corresponding nitrogen oxides.
By in one or more of solvents of the polymer in tetrahydrofuran/methanol/acetone, the R of 10 equivalents is added2X enters
Row is quaternized to obtain corresponding quaternary ammonium compound.
By in one or more of solvents of the polymer in tetrahydrofuran/methanol/acetone, the Bronsted acid of 10 equivalents is added
(including but is not limited to nitric acid, acetic acid, sulfuric acid, phosphoric acid, perchloric acid etc.) obtains corresponding amide.
The present invention can be effectively improved the charge transport properties between electrode and active layer, reduce electrode surface work function；
Boundary layer stability can further improve by ultraviolet lighting or heating post-crosslinking；Can be as modifying interface material in solar-electricity
Applied in the fields such as pond.
Main advantages of the present invention are：
1. the cross-linking solar cell interface material based on azido derivant of synthesis can be processed by orthogonal solution, easily
It is dissolved in methanol, ethanol, water polar solvent；
2. the cross-linking solar cell interface material heat endurance based on azido derivant of synthesis is good, temperature is decomposed in fact
Degree is more than 300 DEG C；
3. the cross-linking solar cell interface material based on azido derivant of synthesis, can be effectively improved electrode and work
Property layer between charge transport properties, reduce electrode surface work function, be adapted to do boundary material；
4. the cross-linking solar cell interface material based on azido derivant of synthesis, can pass through ultraviolet lighting or heating
Post-crosslinking can further improve boundary layer stability；
5. the cross-linking solar cell interface material based on azido derivant of synthesis is as boundary layer in solar-electricity
The electricity conversion lifting of highly significant is illustrated in pond, better than now widely used boundary material PFN.
It is with low cost, excellent performance, steady 6. the cross-linking solar cell interface material based on azido derivant prepared
Qualitative height, is adapted to large area preparation and uses.
Brief description of the drawings
Fig. 1 is the C-V figures of some conjugated polymer in A~E.
Fig. 2 is the C-V figures of some conjugated polymer in A~E.
Fig. 3 is the C-V figures of some conjugated polymer in A~E.
Fig. 4 is the structural representation of the polymer interface layer photovoltaic cell of the present invention.
Fig. 5 is ZnO, PFN or when structural formula is that some conjugated polymer is boundary layer in A~E, uses fullerene acceptor
Material PC71The J-V curves of photovoltaic cell during BM.
Embodiment
The synthetic method to polymer, polymeric precursors is described in detail separately below, and given example is not intended to limit this specially
Sharp protection domain, is intended merely to more fully understand the present invention.Nitrine of the present invention is characterized with elementary analysis, nuclear magnetic resonance, mass spectrum etc.
The chemical constitution of crosslinkable polymer, with analysis and characterization its heat endurance is keen to, its electrochemical properties is characterized with cyclic voltammetry,
Its photophysical property is studied with ultra-violet absorption spectrum.
Embodiment 1：The synthesis of fat-soluble unit
(1) preparation of n-octyl indenes [1,2-b] fluorenes (5) of 6,6,12,12- tetra-
2.54g compounds 4 (10mmol) are a certain or several molten in 100mL tetrahydrofurans/ether/methyl tertiary butyl ether(MTBE)
In agent, Ar is protected, and n-BuLi (2.5M, 30mmol, 12mL) is added dropwise at -20 DEG C and is slowly increased to after room temperature stir 1.5h, again
It is cooled to after adding n-Octyl Bromide (30mmol) at -20 DEG C and is warmed to room temperature lower stirring 4h.Again add 30mmol n-BuLi and
30mmol n-Octyl Bromides are stayed overnight after reaction at room temperature and put plate detection reaction.Extraction, is spin-dried for adding petroleum ether precipitation after solvent
Solid, column chromatography receives white solid 8.7g, yield 95%.1H NMR(500MHz,CDCl3),δ(ppm):7.78 (dd, J=2.0,
7.0Hz, 2H), 7.56 (s, 2H), 7.37 (dd, J=3.0,13.5Hz, 4H), 7.34-7.27 (m, 2H), 2.08-2.04 (m,
8H), 1.21-1.08 (m, 40H), 0.83 (t, J=7.0Hz, 12H), 0.71-0.69 (m, 8H)13C NMR(125MHz,
CDCl3),δ(ppm):151.1,150.0,141.5,140.5,126.6,122.8,119.3,113.8,54.7,40.7,31.8,
30.0,29.2,29.2,23.7,22.6,14.0.MS:702.6.
(2) preparation of bromo- n-octyl indenes [1,2-b] fluorenes (6) of 6,6,12,12- tetra- of 2,8- bis-
In one or more of solvents of the 1.9g compounds 5 (27mmol) in 30mL benzene/carbon tetrachloride/DMF/DMSO, plus
Enter Br2/CuBr/CuBr2In one or more as bromine source, be heated to react 24h under specified temp.Filtering, is spin-dried for filtrate and obtains
To pale solid, cross post and purify to obtain 2.1g white solids, yield 90%.1H NMR(500MHz,CDCl3),δ(ppm):7.59
(dd, J=2.0,7.0Hz, 2H), 7.55 (s, 2H), 7.47-7.45 (m, 4H), 1.98 (t, J=7.5Hz, 8H), 1.18-1.03
(m, 40H), 0.79 (t, J=7.0Hz, 12H), 0.63-0.61 (m, 8H)13C NMR(125MHz,CDCl3),δ(ppm):
153.4,150.0,140.3,140.0,129.8,126.1,120.9,120.8,114.0,55.1,40.5,31.8,29.9,
29.2,29.2,23.7,22.6,14.1.MS:1011.2.
(3) it is coupled the preparation of precursor compound 7
10mmol polymeric precursors 6 are dissolved in 50mL tetrahydrofurans/ether/methyl tertiary butyl ether(MTBE) under inert gas shielding
In the mixing of a certain solvent or certain several solvent, 4 eq. n-BuLis are added at low temperature after reacting 1h under low temperature, then
Risen to after the 2- isopropoxy -4,4,5,5- tetramethyl -1,3,2- di (hetero) oxygen pentaboranes or trimethyltin chloride that add 3 equivalents
24h is reacted at room temperature.Cross post purifying and obtain white solid polymeric precursors for needed for.By compound 6 ' exemplified by, its characterize data tool
There is following feature：1H NMR(500MHz,CDCl3),δ(ppm):7.81 (d, J=7.5Hz, 2H), 7.74 (dd, J=4.5,
7.0Hz, 4H), 7.63 (s, 2H), 2.06-1.99 (m, 8H), 1.40 (s, 24H), 1.16-1.05 (m, 40H), 0.77 (t, J=
7.0Hz,12H),0.62-0.60(m,8H).13C NMR(125MHz,CDCl3),δ(ppm):150.6,150.4,144.5,
140.9,133.7,128.8,118.8,114.4,83.7,54.8,40.5,31.8,30.0,29.2,29.2,25.0,23.7,
22.6,14.1.MS:955.1.
Embodiment 2：The synthesis of interface is affine unit
(1) preparation of the bromo- 9,9- bis- of 2,7- bis- (6- dimethylaminos hexyl) fluorenes (12)
1,6- dibromo-hexane (40mL, 256mmol), 40mL KOH (50%) solution and TBAB (TBAB,
1.436g, 4.3mmol) sequentially add in reaction bulb, it is warming up at 75 DEG C and adds compound 11 (5g, 15.4mmol) continuation reaction
15min, is cooled to and (30mLx3) is extracted with chloroform at room temperature, and organic phase is washed with 1M HCl, and saturated common salt washing, anhydrous magnesium sulfate is done
It is dry, remove vacuum distillation after DCM and remove 1,6- dibromo-hexanes, crude product purified by silica gel post purifying (PE).
Above-mentioned product is dissolved in 50mL tetrahydrofurans/ether/methyl tertiary butyl ether(MTBE) a certain solvent or certain is several molten
In the mixing of agent, required compound is obtained after the dimethylamine agueous solution lucifuge reaction 24h for adding 20 equivalents, post purifying is crossed and obtains white
Color solid.1H NMR(500MHz,CDCl3),δ(ppm):7.55 (d, J=9.0Hz, 2H), 7.47-7.45 (m, 4H), 2.81
(dd, J=8.5,11.0Hz, 4H), 2.68 (s, 12H), 1.94-1.91 (m, 4H), 1.60-1.57 (m, 4H), 1.16-1.11
(m,4H),0.61-0.58(m,4H).13C NMR(125MHz,CDCl3),δ(ppm):152.1,139.0,130.4,126.1,
121.5,121.4,58.2,55.5,43.4,39.7,34.8,29.0,26.1,24.6,23.2.MS:578.5.
(2) 2,7- bis- (4,4,5,5- tetramethyl -1,3,2- di (hetero) oxygen pentaboranes base) -9,9- two (6- dimethylaminos hexyl)
The preparation of fluorenes (13)
10mmol compounds 12 are dissolved in certain in 50mL tetrahydrofurans/ether/methyl tertiary butyl ether(MTBE) under inert gas shielding
In the mixing of a kind of solvent or certain several solvent, 4 eq. n-BuLis are added at low temperature after reacting 1h under low temperature, then add
Lower reaction 24h is warmed to room temperature after the 2- isopropoxy -4,4,5,5- tetramethyl -1,3,2- di (hetero) oxygen pentaboranes for entering 3 equivalents.Cross post
Purifying obtains white solid polymeric precursors for needed for.1H NMR(500MHz,CDCl3),δ(ppm):7.82 (d, J=7.5Hz,
2H), 7.76 (d, J=7.5Hz, 2H), 2.84 (dd, J=8.5,11.0Hz, 4H), 2.68 (s, 12H), 1.94-1.91 (m,
4H),1.60-1.57(m,4H),1.42(s,24H),1.16-1.11(m,4H),0.61-0.58(m,4H).13C NMR
(125MHz,CDCl3),δ(ppm):150.1,138.0,130.7,126.9,121.6,121.5,83.7,58.8,55.1,
43.2,39.5,34.1,29.4,26.6,25.2,24.2,23.4.MS:672.6.
Embodiment 3：Coupling precursor synthesis containing nitrine functional group
X is one kind in bromine, boric acid, borate.
15.4mmol compounds 1 are in the DMSO that 150mL is newly opened, N2The lower addition sodium azide of protection (3eq.,
46.2mmol, 3g) and be warming up at 70 DEG C and react 12h, poured into after TLC detections reaction completely in 500mL frozen water, chloroform extraction three
It is secondary, merge organic phase, anhydrous magnesium sulfate is dried.It is spin-dried for obtaining required compound.HPLC>99%.By taking X=Br as an example：1H NMR
(500MHz,CDCl3),δ(ppm):7.52 (d, J=8.0Hz, 2H), 7.47-7.43 (m, 2H), 7.26 (s, 2H), 3.15 (t, J
=7.0Hz, 4H), 1.94-1.91 (m, 4H), 1.44-1.38 (m, 4H), 1.17-1.05 (m, 8H), 0.62-0.60 (m, 4H)
Embodiment 4：By taking synthesis of the structural formula for A conjugated polymer as an example
X1、X2、X3It is bromine or the derivative of boron when three is different for one kind in bromine, boric acid, borate.
Under argon gas protection, by 1.0mmol both arms indenos fluorene derivative 1,0.8mmol interfaces are affine unit 2 and 0.2mmol
Azido derivant 3 is added in two mouthfuls of dry flasks, with the one or more in 10mL toluene/tetrahydrofuran/chloroform/ether
The Pd catalyst of 0.02 equivalent is added after dissolving, logical argon gas 0.5h, add or be added without basic additive tetraethylamine hydroxide/
One or more in potassium carbonate/sodium carbonate/sodium hydroxide, continue the 0.5h that ventilates, are then heated to reflux 24~48h.Stop anti-
Should.System is cooled to room temperature, adds 20mL water quenchings and goes out reaction, is extracted with chloroform (20mL × 3), merging organic phase and in anhydrous sulphur
Sour sodium is dried.It is spin-dried for adding a small amount of chloroform dissolving after solvent, is instilled in methanol and settled, filtering, the polymer vacuum of collection
50 DEG C of baking 12h of baking oven, soxhlet extraction is carried out with methanol, n-hexane, chloroform, chloroform extracted solution is concentrated, is sunk again with methanol successively
Drop, filtering, obtains polymer A.
Embodiment 5：By taking synthesis of the structural formula for B conjugated polymer as an example
X1、X2、X3It is bromine or the derivative of boron when three is different for one kind in bromine, boric acid, borate.
Under argon gas protection, by 1.0mmol both arms indenos fluorene derivative 1,0.9mmol interfaces are affine unit 2 and 0.1mmol
Azido derivant 3 is added in two mouthfuls of dry flasks, with the one or more in 10mL toluene/tetrahydrofuran/chloroform/ether
The Pd catalyst of 0.02 equivalent is added after dissolving, logical argon gas 0.5h, add or be added without basic additive tetraethylamine hydroxide/
One or more in potassium carbonate/sodium carbonate/sodium hydroxide, continue the 0.5h that ventilates, are then heated to reflux 24~48h.Stop anti-
Should.System is cooled to room temperature, adds 20mL water quenchings and goes out reaction, is extracted with chloroform (20mL × 3), merging organic phase and in anhydrous sulphur
Sour sodium is dried.It is spin-dried for adding a small amount of chloroform dissolving after solvent, is instilled in methanol and settled, filtering, the polymer vacuum of collection
50 DEG C of baking 12h of baking oven, soxhlet extraction is carried out with methanol, n-hexane, chloroform, chloroform extracted solution is concentrated, is sunk again with methanol successively
Drop, filtering, obtains polymer B.
Embodiment 6：By taking synthesis of the structural formula for C conjugated polymer as an example
X1、X2、X3It is bromine or the derivative of boron when three is different for one kind in bromine, boric acid, borate.
Under argon gas protection, by 1.0mmol both arms indenos fluorene derivative 1,0.95mmol interfaces the are affine and of unit 2
0.05mmol azido derivants 3 are added in two mouthfuls of dry flasks, with one in 10mL toluene/tetrahydrofuran/chloroform/ether
Plant or several dissolvings, the Pd catalyst of 0.02 equivalent is added after logical argon gas 0.5h, basic additive hydrogen-oxygen is added or be added without
Change the one or more in triethylammonium tetrakis/potassium carbonate/sodium carbonate/sodium hydroxide, continue the 0.5h that ventilates, then it is heated to reflux 24~
48h.Stop reaction.System is cooled to room temperature, adds 20mL water quenchings and goes out reaction, is extracted with chloroform (20mL × 3), merging organic phase
And in anhydrous sodium sulfate drying.It is spin-dried for adding a small amount of chloroform dissolving after solvent, is instilled in methanol and settled, filtering, collection
50 DEG C of baking 12h of polymer vacuum drying oven, soxhlet extraction is carried out with methanol, n-hexane, chloroform, chloroform extracted solution is concentrated, used successively
Methanol is settled again, filtering, obtains polymer C.
Embodiment 7：By taking synthesis of the structural formula for D conjugated polymer as an example
Polymer A (100mg) is dissolved in one or more of solvents in tetrahydrofuran/methanol/acetone, adds 0.8mL
Lucifuge reacts 24h after bromoethane, is spin-dried for solvent and obtains required polymer D.
Embodiment 8：By taking synthesis of the structural formula for E conjugated polymer as an example
X1、X2、X3It is bromine or the derivative of boron when three is different for one kind in bromine, boric acid, borate.
Under argon gas protection, by 0.9mmol both arms indenos fluorene derivative 1,1.0mmol interfaces are affine unit 2 and 0.1mmol
Azido derivant 3 is added in two mouthfuls of dry flasks, with the one or more in 10mL toluene/tetrahydrofuran/chloroform/ether
The Pd catalyst of 0.02 equivalent is added after dissolving, logical argon gas 0.5h, add or be added without basic additive tetraethylamine hydroxide/
One or more in potassium carbonate/sodium carbonate/sodium hydroxide, continue the 0.5h that ventilates, are then heated to reflux 24~48h.Stop anti-
Should.System is cooled to room temperature, adds 20mL water quenchings and goes out reaction, is extracted with chloroform (20mL × 3), merging organic phase and in anhydrous sulphur
Sour sodium is dried.It is spin-dried for adding a small amount of chloroform dissolving after solvent, is instilled in methanol and settled, filtering, the polymer vacuum of collection
50 DEG C of baking 12h of baking oven, soxhlet extraction is carried out with methanol, n-hexane, chloroform, chloroform extracted solution is concentrated, is sunk again with methanol successively
Drop, filtering, obtains polymer E.
Embodiment 9：The electro-chemical test of above-mentioned boundary material
With CHI660D type electrochemical workstations, glass carbon is used for working electrode, and platinum electrode is to electrode, Ag/Ag+ electricity
Extremely reference electrode, Bu4N·PF6Make electrolyte, in acetonitrile/methanol=1：In 5 solvent, respectively it polymerize through cyclic voltammetry
The HOMO and lumo energy of thing.
Embodiment 10：Application of the above-mentioned boundary material in photovoltaic device
Using sandwich type battery structure as shown in Figure 3, by polymer A-E by finite concentration be dissolved in methanol/acetic acid/
In one or several kinds of solution of toluene/tetrahydrofuran, ZnO surfaces are spun on according to certain thickness；Active layer uses PTB7-Th
Active layer, effective area 0.16cm is made according to certain weight ratio with small molecule receptor2, in Newport Thermal
Current-voltage test is carried out under the simulated solar light sources of Oriel 69911, is gathered using the source tables of Keithley 2400.Part interface
The device of material the results are shown in Table 1, and accompanying drawing 4 is seen using PFN as the I-V curve of boundary layer and EQE, the part I- by boundary layer of A~P
V curves and EQE are shown in accompanying drawing 5.Compared with PFN, polymer A~P can not change open-circuit voltage (V when being boundary layeroc=0.98V)
On the premise of effectively improve short circuit current flow (Jsc=12.37mA/cm2,0.26mA/ is improved compared to PFN for the device of boundary layer
Cm2), fill factor, curve factor FF also increases.Comprehensive device performance can effectively improve 0.2%~1.0%.
Under table 1 is different components structure, different thickness, ZnO, PFN or structural formula are some conjugated polymer in A~E
For boundary layer, fullerene acceptor material PC is used71Photovoltaic battery performance during BM.
Table 1
Solvent:Chlorobenzene+paradiiodobenzene (97.5:2.5)；
Device architecture:ITO/ZnO/active layer(90±0nm)/MoO3(10nm)/Al(100nm)；
Active layer:PTB7:PC71BM=1:1.5 10mg/ml；
Device area 0.16cm2。
Claims (2)
1. cross-linking solar cell interface material of the class based on azido derivant, it is characterised in that structural formula is formula I~VI
In one kind：
In formula I~VI, x, y, z is molal quantity ratio between each monomer, meet x=y+z, y=x+z or z=x+y feature it
One；N is the degree of polymerization, is the natural number between 0~1,000,000；
Interface is affine, and unit PG is selected from one of following structures：
Fat-soluble unit LG is selected from one of following structures：
In said structure, A1For C, Si or Ge atom；A2For N, P or As atom；A3For O, S or Se atom；Alk is carbon number
For 1-20 alkyl；R1It is hydrogen atom, fluorine atom, the alkyl that carbon number is 1 to 20 or carbon number that end is azido
1-20 alkyl；R2It is the alkyl that hydrogen atom or carbon number are 1 to 10；R3Be hydrogen atom, fluorine atom, carbon number be 1 to 20
Alkyl or carbon number 1-20 that end is amino and its alkyl derivative alkyl；R4The alkane for being 1-20 for carbon number
Base；R5It is hydrogen atom, fluorine atom, carbon number is 1 to 20 alkyl, carbon number is 1 to 20 alkoxy, and carbon number is
1 to 20 o-, m- or p- position alkyl phenyl, or the o-, m- or p- position alkoxyl phenyl that carbon number is 1 to 20.
2. the cross-linking solar cell interface material as claimed in claim 1 based on azido derivant, it is characterised in that should
Boundary material is applied to polymer photovoltaic cell.
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