CN105541694A - A series of unsymmetric squarine micromolecules and their preparation method and use - Google Patents
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Abstract
The invention provides a series of novel unsymmetric squarine micromolecules and their preparation method and use. Two different electron-rich aromatic units as donors and a high-electron affinity 1, 3-squaric acid unit as an acceptor introduced into a conjugated system form a donor-acceptor-donor-type unsymmetric squarine micromolecule. The preparation method can prepare a low-band gap micromolecule material. The absorption spectrum of the novel unsymmetric squarine micromolecule can cover the visible light zone and a near infrared zone of 450-800nm. The novel unsymmetric squarine micromolecules have good dissolvability and film forming ability and can be used for preparation of excellent-performance organic solar energy cells.
Description
The application is the divisional application that " a series of asymmetric side's acid cyanines small molecules and preparation method and application " apply for, the applying date of original application is on 04 03rd, 2013, application number is 2013101140279, and denomination of invention is " a series of asymmetric side's acid cyanines small molecules and preparation method and application ".
One, technical field
The present invention relates to a series of asymmetric side's acid cyanines small molecules and preparation method, and the utilization of the sour cyanines small molecules of such side in organic solar batteries.
Two, background technology
At present, energy dilemma and environmental problem increasingly serious, sun power obtains everybody attention as a kind of never exhausted clean energy.Organic solar batteries (OPV) has the remarkable advantages such as cost is low, lightweight, snappiness is good compared with inorganic solar cell.In recent years, compared to polymer solar battery, small molecules organic solar batteries, owing to having the advantages such as the molecular structure determined, the molecular mass determined and easy purification, thus receives and pays close attention to widely and study.For advancing its practicalization, research and develop more have in visible and near-infrared region strong absorption, easily preparation micromolecular compound donor material significant for the efficiency improving photovoltaic device.
Indolenium squaraine cyanine dye is because of its excellent photochemistry and optical physics stability, and in strong absorption that is visible and near-infrared region, the application in organic solar batteries field causes the interest of people gradually.2008, Paganietal first time reported the symmetric form side's acid cyanines small molecules organic solar batteries based on solution processing, and its electricity conversion (PCE) is 1.24%(J.Am.Chem.Soc.2008,130,17640-17641.).Up to now, PCE based on the micromolecular body heterojunction organic solar batteries of symmetric form side's acid cyanines of solution processing reaches 5.50%(Adv.Energy.Mater.2011,1,184-187.), the PCE of its double-deck organic solar batteries is up to 6.30%(NanoLett.2011 simultaneously, 11,4261-4264.), the sour cyanines material in the side of showing is rich in application prospect in this field.Than 1,3-symmetric form side's acid cyanines photovoltaic material of current excellent property, the performance of asymmetric side's acid cyanines is relatively low, and applicant only retrieves four sections of application of asymmetric side's acid cyanine compound in OPV (Angew.Chem., Int.Ed.2009,48,8776-8779; Sol.EnergyMater.Sol.Cells2012,98,224-232; ACSNano2012,6,972-978; J.Mater.Chem.2012,22,6704-6710), the material property reported in ACSNano is best, but optical energy gap is about 2.0eV, relatively high, not good with mating of solar spectrum.
The sour cyanine compound in side is formed with electron rich aromatic ring or heterocyclic condensation by square acid, can form 1,3-and replace (structure is shown in down), identical or not identical according to X, Y, is divided into again symmetrical and asymmetric two types.Generally speaking, asymmetric side's acid cyanines have better solvability, the most important thing is that there is abundanter adjustability of structure, in photosensitive application aspect such as dye-sensitized solar cells, xerox, near infrared sensitizing, there is the performance more excellent compared with symmetric form side's acid compound.Thus design, synthesizing new asymmetric side's acid cyanines photovoltaic material, significant to the new and effective photovoltaic material of structure.
Three, summary of the invention
An object of the present invention is to provide series of new asymmetric side's acid cyanines small molecules.
The invention provides asymmetric side's acid cyanines small molecules with following formula I, A, B represent different richness electricity aromatic nucleus unit,
Its constitutional features is:
Described A is any one in following group 1 or 2, wherein R
1for the alkoxyphenyl radical of the cycloalkyl of hydrogen atom or fluorine atom or cyano group or phenyl or phenoxy group or carbonatoms to be the alkyl of the straight or branched of 1-20 or carbonatoms be 3-10 or carbonatoms to be the alkoxyl group of the straight or branched of 1-20 or carbonatoms the be straight or branched of 1-20, R
2for the alkoxyphenyl radical that the cycloalkyl of carbonatoms to be the alkyl of the straight or branched of 1-20 or carbonatoms be 3-10 or phenyl or carbonatoms are the straight or branched of 1-20.
Group 1:
Group 2:
Described B is any one in following group 3 to 5,
Group 3:
In group 3, R
1and R
2be hydroxyl or R
1for hydroxyl and R
2for hydrogen atom, R
3and R
4for the alkoxyphenyl radical that the cycloalkyl of identical or not identical carbonatoms to be the alkyl of the straight or branched of 1-20 or carbonatoms be 3-10 or phenyl or carbonatoms are the straight or branched of 1-20.
Group 4:
In group 4, R
1and R
2for identical or not identical hydrogen atom or hydroxyl, R
3, R
4, R
5and R
6for the alkyl that identical or not identical hydrogen atom or carbonatoms are the straight or branched of 1-20.
Group 5:
In group 5, R
1and R
2for identical or not identical hydrogen atom or hydroxyl, R
3, R
4, R
5and R
6for the alkoxyphenyl radical of the cycloalkyl of identical or not identical hydrogen atom or carbonatoms to be the alkyl of the straight or branched of 1-20 or carbonatoms be 3-10 or carbonatoms to be the alkoxyl group of the straight or branched of 1-20 or phenyl or carbonatoms the be straight or branched of 1-20.
Two of object of the present invention is to provide arbitrary asymmetric side's acid cyanines of the present invention micromolecular preparation method; it is characterized in that step and reaction conditions are: under high-purity argon gas protection; add two reaction substrates of equimolar amount proportioning successively; using toluene: propyl carbinol=1:1(volume ratio) mixing solutions as solvent; heating point water back flow reaction 13h; react complete; evaporating solvent is to dry; the resistates obtained is carried out column chromatography for separation; collect respective components; recrystallization, synthetic route is as follows:
Wherein, the compound of Ar corresponding to the 3-5 of group described in claim 1, its structure is:
Compound 3:
Compound 4:
Compound 5:
Three of object of the present invention is to provide the micromolecular purposes of asymmetric side's acid cyanines in the present invention, the utilization particularly on organic solar batteries.
As shown in Figure 5, a is body heterojunction device architecture, wherein MoO to this organic solar batteries device architecture
3thickness be the thickness of 6-10nm or PEDOT:PSS be 30-40nm; The blend film of asymmetric side's acid cyanines small molecules and PCBM is photoactive layer, and thickness is 20-400nm; The thickness of LiF is 0.5-0.8nm; The thickness of Al or Ag electrode is 60-200nm.B is bi-layer devices structure, wherein MoO
3thickness be the thickness of 6-16nm or PEDOT:PSS be 30-40nm; Asymmetric side's acid cyanines small molecules is as the P-type semiconductor material of photoactive layer, and film thickness is 4-80nm; C
60or C
70as the N-type semiconductor material of photoactive layer, the degree of film is 20-80nm; The thickness of BCP (chemical structure is shown in figure) is 5-20nm; The thickness of Al or Ag electrode is 60-200nm.
Beneficial effect: asymmetric side's acid cyanines small molecule material provided by the invention, as the photoactive layer of organic solar batteries, its beneficial effect is:
(1) good solubility is had.As follows relative to symmetric form side's acid cyanines small molecule photovoltaic material SQ(chemical structural formula of classics) for, asymmetric side's acid cyanines small molecule material provided by the invention is at common organic solvents (as: chloroform, tetrahydrofuran (THF), chlorobenzene, orthodichlorobenzene etc.) in there is better solvability (dissolubility data list in table 1,6a is asymmetric side's acid cyanines small molecules in embodiment 1), also have good film-forming properties, these are all very beneficial for the organic solar batteries adopting the solution of low cost processing processability excellent simultaneously.
Table 1: side's micromolecular solubility data of sour cyanines (mg/mL) (15 DEG C)
Note: a represents insoluble
(2) wider absorption spectrum is had.Relative to ACSNano2012,6, the asymmetric side's acid cyanines small molecules reported in 972-978., the spectral response range wider (450-800nm) of asymmetric side's acid cyanines small molecule material provided by the invention, more mate with solar spectrum, this improves the absorption to sunlight by being conducive to, and improves the electricity conversion of photovoltaic device.
The asymmetric side's acid small molecules prepared is that the organic solar batteries device performance of donor material is respectively: white light 1.5G(100mw/cm
2) under irradiation, open circuit voltage (Voc)=0.70-1.20V, short-circuit current (Jsc)=4.76-12.10mA/cm
2, packing factor (FF)=0.30-0.70, electricity conversion (PCE)=1.03-5.05%.
Four, accompanying drawing explanation
Fig. 1 is that in embodiment 1, asymmetric side acid 6a in chloroformic solution and the ultraviolet-visible absorption spectroscopy of solid film, is also Figure of abstract simultaneously.
Fig. 2 be in embodiment 3 asymmetric side acid 6c in chloroformic solution and the ultraviolet-visible absorption spectroscopy of solid film.
Fig. 3 is the current-voltage curve of the body heterojunction organic solar batteries device of asymmetric side's acid 6e in asymmetric side acid 6a and embodiment 5 in embodiment 1.
Fig. 4 is the external quantum efficiency figure of the body heterojunction organic solar batteries device of asymmetric side's acid 6e in asymmetric side acid 6a and embodiment 5 in embodiment 1.
Fig. 5 is the structural representation of organic solar batteries device.
Five, embodiment
Embodiment 1: the preparation of asymmetric side's acid 6a
(1) 3-((3-butyl-1,1-dimethyl-1H benzo [e] indoles-2 (3H)-subunit) methyl) preparation of-4-ethoxy basic ring fourth-3-alkene-1,2-diketone 3a
2a5.00g (12.7mmol) (synthetic method is shown in Eur.J.Org.Chem.2008,12,2107 – 2117.) adds 120mL mixed solvent (triethylamine: ethanol=1:8, v/v), reflux 30min.Be cooled to room temperature, add 11.83g (12.7mmol) (synthetic method is shown in J.Am.Chem.Soc.2007,129,10320-10321.), back flow reaction 30min, decompression steams solvent, column chromatography (PE:EA=8:1), ethyl alcohol recrystallization obtains orange-yellow crystal 2.04g, productive rate 68%.m.p.187-188℃;
1HNMR(CDCl
3,400MHz,ppm)δ:8.11(d,J=8.4Hz,1H),7.89(d,J=8.4Hz,1H),7.85(d,J=8.4Hz,1H),7.54(t,J=7.6Hz,1H),7.38(t,J=7.6Hz,1H),7.23(d,J=8.8Hz,1H),5.46(s,1H),4.96(q,J=7.2Hz,2H),3.94(t,J=7.2Hz,2H),1.90(s,6H),1.83-1.75(m,2H),1.58(t,J=7.2Hz,3H),1.50-1.43(m,2H),1.01(t,J=7.2Hz,3H)。
(2) 3-((3-butyl-1,1-dimethyl-1H-benzo [e] indoles-2 (3H)-subunit) methyl) preparation of-4-hydroxyl ring fourth-3-alkene-1,2-diketone 4a
3a2.04g (5.2mmol) adds 40mL dehydrated alcohol, adds 3mL40%NaOH under reflux state, reaction 30min, decompression is revolved and is desolventized, and resistates is dissolved in 20mL water, drips saturated citric acid to PH=3 ~ 4, yellow mercury oxide is separated out, and filters to obtain yellow powder 1.32g, productive rate 70%.
1HNMR(DMSO-d
6,400MHz,ppm)δ:8.06(d,J=8.8Hz,1H),7.85(d,J=8.0Hz,1H),7.81(d,J=8.8Hz,1H),7.45(t,J=7.6Hz,1H),7.34(d,J=8.8Hz,1H),7.23(t,J=7.6Hz,1H),5.45(s,1H),3.83(t,J=7.2Hz,2H),1.83(s,6H),1.68-1.61(m,2H),1.43-1.34(m,2H),0.93(t,J=7.6Hz,3H)。
(3) 5-(diisobutylamine) preparation of benzene-1,3-diphenol 5a
Under argon shield; Phloroglucinol 10.00g (79.3mmol); diisobutylamine 20.50g (158.6mmol) adds in 280mL mixed solvent (propyl carbinol: toluene=1:3); divide water backflow 6h; decompression steams solvent; column chromatography (sherwood oil: acetone=4:1) obtains brown-red solid, productive rate 24%.
1HNMR(CDCl
3,400MHz,ppm)δ:10.96(s,2H),5.80(s,2H),5.64(s,1H),3.24(d,J=7.4Hz,4H),2.12(m,2H),0.92(d,J=6.6Hz,12H)。
(4) preparation of asymmetric side's acid 6a
4a0.6250g (1.7mmol), 5a0.4035g (1.7mmol), 80mL mixed solvent (toluene: propyl carbinol=1:1, v/v), point water backflow 13h, decompression steams solvent, column chromatography (CH
2cl
2: CH
3oH=50:1), recrystallization (methylene chloride/methanol) obtains bright yellow solid 0.80g, productive rate 23%.m.p.198-199℃，
1HNMR(CDCl
3,400MHz,ppm)δ:12.41(s,2H),8.20(d,J=8.5Hz,1H),7.91(dd,J=7.7,8.4Hz,2H),7.59(t,J=7.4Hz,1H),7.46(t,J=7.7Hz,1H),7.32(d,J=8.8Hz,1H),5.85(s,1H),5.80(s,2H),4.13(t,J=7.4Hz,2H),3.22(d,J=7.4Hz,4H),2.20-2.10(m,2H),2.01(s,6H),1.88-1.81(m,2H),1.54-1.44(m,2H),1.01(t,J=7.3Hz,3H),0.92(d,J=6.8Hz,12H)。
Embodiment 2: the preparation of asymmetric side's acid 6b
(1) preparation of compound 4a is with embodiment 1.
(2) preparation of asymmetric side's acid 6b
4a1.00g (2.8mmol), 5b0.68g (2.8mmol) (synthetic method is shown in DyesandPigments.2003.59,63-69.), 80mL mixed solvent (toluene: propyl carbinol=1:1, v/v), point water backflow 13h, decompression steams solvent, column chromatography (CH
2cl
2: CH
3oH=50:1), recrystallization (methylene chloride/methanol) obtains bright green crystal 6b0.88g, productive rate 54%.
1HNMR(CDCl
3,400MHz,ppm)δ:12.48(s,2H),8.19(d,J=8.4Hz,1H),8.04(s,1H),7.92(dd,J=9.2,9.2Hz,2H),7.60(t,J=7.6Hz,1H),7.45(t,J=7.2Hz,1H),7.32(d,J=8.8Hz,1H),5.98(s,1H),4.13(s,2H),3.30(br,4H),2.04(s,6H),1.88-1.81(m,2H),1.77-1.71(m,4H),1.54-1.45(m,2H),1.48(s,6H),1.31(s,6H),1.02(t,J=7.2Hz,3H)。
Embodiment 3: the preparation of asymmetric side's acid 6c
(1) preparation of compound 4a is with embodiment 1.
(2) preparation of 5-9H-carbazole-9-phenyl-1,3-glycol 5c
Carbazole 5.00g (30mmol), 3,5-dimethoxy bromobenzene 7.80g (36mmol), the Pd (OAc) of 3% molar weight
2, the P (t-Bu) of 6% molar weight
3 .bF
4, the sodium tert-butoxide of 1.5 times of molar weights adds in 200mL toluene, 110 DEG C of heating 12h, filter, filtrate decompression is revolved and is desolventized, column chromatography (PE:EA), sherwood oil recrystallization obtains white needle-like crystals 9-(3,5-dimethoxy-phenylf)-9H-carbazole 6.60g, productive rate 73%.
1HNMR(CDCl
3,400MHz,ppm)δ:8.13(d,J=8.0Hz,2H),7.48(d,J=7.6Hz,2H),7.41(t,J=7.6Hz,2H),7.29(t,J=7.6Hz,2H),6.72(s，2H),6.56(s,1H),3.84(s,6H)。
9-(3,5-dimethoxy-phenylf)-9H-carbazole 1.00g (3.30mmol) adds 40mL anhydrous methylene chloride, the anhydrous methylene chloride solution of 34mL containing boron tribromide 8.26g (33.00mmol) is slowly dripped under ice bath, after dropwising, naturally be warming up to room temperature, stir 36h.In reaction solution impouring 150mL frozen water, with dichloromethane extraction, water washing, saturated sodium carbonate washs, dry, and concentrated, column chromatography obtains white powder 0.80g, productive rate 88%.
1HNMR(CDCl
3,400MHz,ppm)δ：8.12(d,J=8.0Hz,2H),7.49(t,J=7.6Hz,2H),7.40(t,J=8.0Hz,2H),7.25(t,J=7.6Hz,2H),6.63(s,2H),6.44(s,1H)。
(3) preparation of asymmetric side's acid 6c
4a1.00g (2.8mmol), 5c0.77g (2.8mmol), 80mL mixed solvent (toluene: propyl carbinol=1:1, v/v), divide water backflow 13h, decompression steams solvent, column chromatography (PE:EA=6:1), recrystallization (methylene chloride/methanol) obtains glassy yellow crystal 0.35g, productive rate 20%.
1HNMR(DMSO-d
6,400MHz,ppm)δ:12.20(s,2H),8.44(d,J=8.4Hz,1H),8.24(d,J=7.6Hz,2H),8.23(d,J=9.2Hz,1H),8.17(d,J=8.0Hz,1H),8.08(d,J=9.4Hz,1H),7.78-7.73(m,
3J=7.2Hz,
4J=0.8Hz,1H),7.68(t,J=7.2Hz,1H),7.60(d,J=8.4Hz,2H),7.51-7.46(m,
3J=7.2Hz,
4J=0.8Hz,2H),7.34-7.30(m,
3J=7.2Hz,
4J=0.4Hz,2H),6.55(s,2H),6.42(s,1H),4.66(t,J=7.2Hz,2H),2.02(s,6H),1.91-1.83(m,2H),1.52-1.43(m,2H),0.97(t,J=7.2Hz,3H)。
Embodiment 4: the preparation of asymmetric side's acid 6d
(1) preparation of compound 1 is with embodiment 1.
(2) 3-oxyethyl group-4-((3-ethyl naphtho-[2,1-d] thiazole-2 (3H)-subunit) methyl) preparation of ring fourth-3-alkene-1,2-diketone 3b
2b2.52g (7.06mmol) (synthetic method is shown in J.Org.Chem.1995,60,2391-2395.) adds 20mL mixed solvent (triethylamine: ethanol=1:8, v/v), reflux 30min.Drip 11.20g (7.06mmol), back flow reaction 15min, decompression steams solvent, column chromatography (PE:EA=8:1), and ethyl alcohol recrystallization obtains orange-yellow crystal 1.98g, productive rate 80%.
1HNMR(CDCl
3,400MHz,ppm)δ:8.17(d,J=8.4Hz,1H),7.90(d,J=8.4Hz,1H),7.85(d,J=8.4Hz,1H),7.76(t,J=7.6Hz,1H),7.43(t,J=7.6Hz,1H),7.29(d,J=8.8Hz,1H),5.38(s,1H),4.96(q,J=7.2Hz,2H),3.83(q,J=7.2Hz,2H),1.49(t,J=7.2Hz,3H),1.93(t,J=7.2Hz,3H)。
(3) 3-((3-ethyl naphtho-[2,1-d] thiazole-2 (3H)-subunit) methyl) preparation of-4-hydroxyl ring fourth-3-alkene-1,2-diketone 4b
3b1.84g (5.24mmol) adds 40mL dehydrated alcohol, adds 3mL40%NaOH under reflux state, reaction 30min, decompression is revolved and is desolventized, and resistates is dissolved in 20mL water, drips saturated citric acid to PH=3 ~ 4, yellow mercury oxide is separated out, and filters to obtain yellow powder 1.02g, productive rate 60%.
1HNMR(DMSO-d
6,400MHz,ppm)δ:8.21(d,J=8.8Hz,1H),8.01(d,J=8.4Hz,1H),7.79(d,J=8.4Hz,1H),7.45(t,J=7.6Hz,1H),7.25(d,J=8.8Hz,1H),7.14(t,J=7.6Hz,1H),5.38(s,1H),4.57(q,J=7.2Hz,2H),1.84(t,J=7.2Hz,3H)。
(4) preparation of compound 5a is with embodiment 1.
(5) preparation of asymmetric side's acid 6d
4b0.5694g (1.73mmol), 5a0.4106g (1.73mmol), 80mL mixed solvent (toluene: propyl carbinol=1:1, v/v), point water backflow 13h, decompression steams solvent, column chromatography (CH
2cl
2: CH
3oH), recrystallization (methylene chloride/methanol) must have metalluster solid 0.32g, productive rate 34%.
1HNMR(CDCl
3,400MHz,ppm)δ:12.20(s,2H),8.21(d,J=8.8Hz,1H),7.91(dd,J=7.6,8.4Hz,2H),7.64(t,J=7.4Hz,1H),7.46(t,J=7.6Hz,1H),7.23(d,J=8.8Hz,1H),5.79(s,1H),5.72(s,2H),4.13(q,J=7.2Hz,2H),3.22(d,J=7.2Hz,4H),2.21-2.13(m,2H),1.90(t,J=7.6Hz,3H),0.92(d,J=6.8Hz,12H)。
Embodiment 5: the preparation of asymmetric side's acid 6e
(1) preparation of compound 4b is with embodiment 4.
(2) preparation of compound 5b is with embodiment 2.
(3) preparation of asymmetric side's acid 6e
4b0.9054 (2.8mmol), 5b0.6870g (2.8mmol), 80mL mixed solvent (toluene: propyl carbinol=1:1, v/v), point water backflow 13h, decompression steams solvent, column chromatography (CH
2cl
2: CH
3oH=50:1), recrystallization (methylene chloride/methanol) obtains bright yellow solid 0.74g, productive rate 48%.
1HNMR(CDCl
3,400MHz,ppm)δ:12.27(s,2H),8.19(d,J=8.4Hz,1H),7.90(s,1H),7.83(dd,J=9.2,9.2Hz,2H),7.75(t,J=7.6Hz,1H),7.54(t,J=7.2Hz,1H),7.30(d,J=8.8Hz,1H),5.45(s,1H),4.57(q,J=7.2Hz,2H),3.30(br,4H),2.04(t,J=7.2Hz,3H),1.79-1.70(m,4H),1.37(s,6H),1.28(s,6H)。
Embodiment 6: the preparation of asymmetric side's acid 6f
(1) preparation of compound 4b is with embodiment 4.
(2) preparation of compound 5c is with embodiment 3.
(3) preparation of asymmetric side's acid 6f
4b0.9054g (2.8mmol), 5c0.7708g (2.8mmol), 80mL mixed solvent (toluene: propyl carbinol=1:1, v/v), divide water backflow 13h, decompression steams solvent, column chromatography (PE:EA=6:1), recrystallization (methylene chloride/methanol) obtains green crystal 0.44g, productive rate 27%.
1HNMR(DMSO-d
6,400MHz,ppm)δ:12.20(s,2H),8.34(d,J=8.4Hz,1H),8.14(d,J=7.6Hz,2H),8.05(d,J=8.8Hz,1H),7.99(d,J=8.0Hz,1H),7.91(d,J=9.4Hz,1H),7.87(t,J=7.6Hz,1H),7.68(t,J=7.2Hz,1H),7.63(d,J=8.4Hz,2H),7.51(t,J=7.2Hz,2H),7.34-7.30(t,J=7.2Hz,2H),6.68(s,2H),6.35(s,1H),4.54(q,J=7.2Hz,2H),1.91(t,J=7.2Hz,3H)。
Embodiment 7: the preparation of asymmetric side's acid 6a organic solar batteries device
(1) device architecture 3mg6a and 17mgPCBM mixing as shown in Figure 5 a, adds 1mL chloroform and dissolves, by spin coating mode through MoO
3the ito glass substrate of modified prepares film, and then vacuum evaporation LiF and Al prepares negative electrode.White light 1.5G(100mW/cm
2) under irradiation, device photoelectric transformation efficiency (PCE) is 2.24%.
(2) the 6a chloroformic solution of device architecture 1mg/mL is as shown in Figure 5 b spin-coated on through MoO
3on the ito glass substrate of modified, then vacuum evaporation C successively
60layer, BCP layer and Al electrode layer.White light 1.5G(100mW/cm
2) under irradiation, device photoelectric transformation efficiency (PCE) is 4.23%.
Embodiment 8: the preparation of asymmetric side's acid 6c organic solar batteries device
(1) device architecture 3mg6c and 17mgPCBM mixing as shown in Figure 5 a, adds 1mL chloroform and dissolves, by spin coating mode through MoO
3the ito glass substrate of modified prepares film, and then vacuum evaporation LiF and Al prepares negative electrode.White light 1.5G(100mW/cm
2) under irradiation, device open circuit voltage (Voc)=1.09V, electricity conversion (PCE) is 2.20%.
(2) device architecture is as shown in Figure 5 b through MoO
3vacuum evaporation 6c thin film layer, C successively on the ito glass substrate of modified
60layer, BCP layer and Al electrode layer.White light 1.5G(100mW/cm
2) under irradiation, device photoelectric transformation efficiency (PCE) is 4.58%.
Embodiment 9: the preparation of asymmetric side's acid 6e organic solar batteries device
(1) device architecture 4mg6e and 16mgPCBM mixing as shown in Figure 5 a, adds 1mL chloroform and dissolves, by spin coating mode through MoO
3the ito glass substrate of modified prepares film, and then vacuum evaporation LiF and Al prepares negative electrode.White light 1.5G(100mW/cm
2) under irradiation, device photoelectric transformation efficiency (PCE)=1.72%.
(2) the 6e chloroformic solution of device architecture 1mg/mL is as shown in Figure 5 b spin-coated on through MoO
3on the ito glass substrate of modified, then vacuum evaporation C successively
60layer, BCP layer and Al electrode layer.White light 1.5G(100mW/cm
2) under irradiation, device photoelectric transformation efficiency (PCE) is 3.97%.
Table 2: the device photoelectric transformation efficiency PCE (%) of the sour cyanines small molecules 6a-6f in side
| The sour cyanines small molecules in side | 6a | 6b | 6c | 6d | 6e | 6f |
| Bulk heteroj junction device | 2.24 | 2.08 | 2.20 | 2.59 | 1.72 | 2.93 |
| Bi-layer devices | 4.23 | 3.40 | 4.58 | 3.15 | 3.97 | 4.07 |
Claims (3)
1. a series of asymmetric side's acid cyanines small molecules with formula I structure, A, B represent different rich electric aromatic nucleus unit,
Its constitutional features is:
Described A is following group 1, wherein R
1for the alkoxyl group that the cycloalkyl of hydrogen atom or fluorine atom or cyano group or phenyl or phenoxy group or carbonatoms to be the alkyl of the straight or branched of 1-20 or carbonatoms be 3-10 or carbonatoms are the straight or branched of 1-20, R
2for cycloalkyl or the phenyl of carbonatoms to be the alkyl of the straight or branched of 1-20 or carbonatoms be 3-10.
Group 1:
Described B is any one in following group 2 to 4,
Group 2:
In group 2, R
1and R
2be hydroxyl or R
1for hydroxyl and R
2for hydrogen atom, R
3and R
4for cycloalkyl or the phenyl of identical or not identical carbonatoms to be the alkyl of the straight or branched of 1-20 or carbonatoms be 3-10.
Group 3:
In group 3, R
1and R
2for identical or not identical hydrogen atom or hydroxyl, R
3, R
4, R
5and R
6for the alkyl that identical or not identical hydrogen atom or carbonatoms are the straight or branched of 1-20.
Group 4:
In group 4, R
1and R
2for identical or not identical hydrogen atom or hydroxyl, R
3, R
4, R
5and R
6for alkoxyl group or phenyl that the cycloalkyl of identical or not identical hydrogen atom or carbonatoms to be the alkyl of the straight or branched of 1-20 or carbonatoms be 3-10 or carbonatoms are the straight or branched of 1-20.
2. the micromolecular preparation method of arbitrary asymmetric side acid cyanines as claimed in claim 1; it is characterized in that step and reaction conditions are: under high-purity argon gas protection; add two reaction substrates of equimolar amount proportioning successively, using toluene: the volume ratio of propyl carbinol be the mixing solutions of 1:1 as solvent, a heating point water back flow reaction 13h; react complete; the resistates obtained, to dry, is carried out column chromatography for separation by evaporating solvent, collects respective components; recrystallization, synthetic route is as follows:
Wherein, the compound of Ar corresponding to the 2-4 of group described in claim 1, its structure is:
Compound 2:
Compound 3:
Compound 4:
。
3. the application of arbitrary asymmetric side's acid cyanines small molecules in organic solar batteries as claimed in claim 1.
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