阅读说明：本技术 聚合物和包含其的有机太阳能电池 (Polymer and organic solar batteries comprising it ) 是由 李志永 崔斗焕 林潽圭 金志勋 于 2019-02-26 设计创作，主要内容包括：本说明书涉及包含化学式1的第一单元、化学式2的第二单元和化学式3或4的第三单元的聚合物以及包含其的有机太阳能电池。(This specification is related to the first unit comprising chemical formula 1, the polymer of the third unit of the second unit of chemical formula 2 and chemical formula 3 or 4 and the organic solar batteries comprising it.)

1. a kind of polymer, includes:

The first unit indicated by following formula 1；

The second unit indicated by following formula 2；With

The third unit indicated by following formula 3 or 4:

[chemical formula 1]

[chemical formula 2]

[chemical formula 3]

[chemical formula 4]

In chemical formula 1 to 4,

X1 to X6 is same or different to each other, and is each independently CRR ', NR, O, SiRR ', PR, S, GeRR ', Se or Te；

A1 to A4 is same or different to each other, and is each independently halogen group；

Cy1 to Cy3 is same or different to each other, and is each independently the heterocycle for being substituted or being unsubstituted；

Q1 and Q2 are same or different to each other, and are each independently O or S；

R, R ', R " and R1 to R8 are same or different to each other, and are each independently hydrogen；Deuterium；Halogen group；Hydroxyl；It is substituted Or the alkyl being unsubstituted；The naphthenic base for being substituted or being unsubstituted；The alkoxy for being substituted or being unsubstituted；It is substituted or not The aryloxy group being substituted；The alkyl sulfenyl for being substituted or being unsubstituted；The artyl sulfo for being substituted or being unsubstituted；Be substituted or The alkyl sulphonyl being unsubstituted；The aryl sulfonyl for being substituted or being unsubstituted；The alkenyl for being substituted or being unsubstituted；Through taking Generation or the amido being unsubstituted；The aryl for being substituted or being unsubstituted；Or the heterocycle for being substituted or being unsubstituted；And

R11 and R12 are same or different to each other, and are each independently the alkyl for being substituted or being unsubstituted；It is substituted or not The alkoxy being substituted；Or the alkyl sulfenyl for being substituted or being unsubstituted.

2. polymer according to claim 1, wherein the first unit is indicated by following formula 1-1:

[chemical formula 1-1]

In chemical formula 1-1,

R1, R2, R11, R12, X1, X2, A1 and A2 have and identical restriction in chemical formula 1；And

X7 and X8 are same or different to each other, and are each independently NR, O, SiRR ', PR, S, GeRR ', Se or Te.

3. polymer according to claim 1, wherein the first unit is indicated by following formula 1-2:

[chemical formula 1-2]

In chemical formula 1-2,

R11, R12, A1 and A2 have and identical restriction in chemical formula 1.

4. polymer according to claim 1, wherein the second unit is indicated by following formula 2-1:

[chemical formula 2-1]

In chemical formula 2-1,

R3 to R6, A3 and A4 have and identical restriction in chemical formula 2.

5. polymer according to claim 1, wherein any of the third unit by following formula 3-1 into 3-3 Person indicates:

[chemical formula 3-1]

[chemical formula 3-2]

[chemical formula 3-3]

In chemical formula 3-1 into 3-3,

R7, R8, Q1 and Q2 have and identical restriction in chemical formula 3 and 4；

X9 is CRR ', NR, O, SiRR ', PR, S, GeRR ', Se or Te；

Y1 to Y4 is same or different to each other, and is each independently CR ", N, SiR ", P or GeR "；And

R, R ', R ", R9, R10 and R19 are same or different to each other, and are each independently hydrogen；The alkane for being substituted or being unsubstituted Base；The alkoxy for being substituted or being unsubstituted；The alkyl sulfenyl for being substituted or being unsubstituted；The fragrant oxygen for being substituted or being unsubstituted Base；The artyl sulfo for being substituted or being unsubstituted；The aryl for being substituted or being unsubstituted；Or it is substituted or is unsubstituted and is miscellaneous Ring group.

6. polymer according to claim 5, wherein any of the third unit by following formula 3-4 into 3-9 Person indicates:

[chemical formula 3-4]

[chemical formula 3-5]

[chemical formula 3-6]

[chemical formula 3-7]

[chemical formula 3-8]

[chemical formula 3-9]

In chemical formula 3-4 into 3-9,

R7 to R10 and R19 has the identical restriction into 3-3 with chemical formula 3-1.

7. polymer according to claim 1 includes the unit indicated by following formula 5:

[chemical formula 5]

In chemical formula 5,

L is the real number of 0 < l < 1 as molar fraction；

M is the real number of 0 < m < 1 as molar fraction；

L+m=1；

A is the first unit indicated by chemical formula 1；

B is the second unit indicated by chemical formula 2；

C and C ' are same or different to each other, and the third unit to be indicated by chemical formula 3 or chemical formula 4 each independently； And

Repeat number of the n as unit is 1 to 10,000 integer.

8. polymer according to claim 7 includes the unit by following formula 5-1 or 5-2 expression:

[chemical formula 5-1]

[chemical formula 5-2]

In chemical formula 5-1 and 5-2,

X1 is to X6, A1 to A4, Cy1 to Cy3, Q1, Q2, R, R ', R ", R1 to R8, R11 and R12 has and phase in chemical formula 1 to 4 Same restriction；

L, m and n has and identical restriction in chemical formula 5；

X15 and X16 are same or different to each other, and are each independently CRR ', NR, O, SiRR ', PR, S, GeRR ', Se or Te；

Cy13 is the heterocycle for being substituted or being unsubstituted；

Q11 and Q12 are same or different to each other, and are each independently O or S；And

R17 and R18 are same or different to each other, and are each independently hydrogen；Deuterium；Halogen group；Hydroxyl；It is substituted or without taking The alkyl in generation；The naphthenic base for being substituted or being unsubstituted；The alkoxy for being substituted or being unsubstituted；It is substituted or is unsubstituted Aryloxy group；The alkyl sulfenyl for being substituted or being unsubstituted；The artyl sulfo for being substituted or being unsubstituted；It is substituted or is unsubstituted Alkyl sulphonyl；The aryl sulfonyl for being substituted or being unsubstituted；The alkenyl for being substituted or being unsubstituted；Be substituted or without Substituted amido；The aryl for being substituted or being unsubstituted；Or the heterocycle for being substituted or being unsubstituted.

9. it is following formula 5-3 any one of to 5-9 polymer according to claim 1:

[chemical formula 5-3]

[chemical formula 5-4]

[chemical formula 5-5]

[chemical formula 5-6]

[chemical formula 5-7]

[chemical formula 5-8]

[chemical formula 5-9]

In chemical formula 5-3 into 5-9,

A1, A2, R11 and R12 have with identical restriction in chemical formula 1,

R107 and R108 are same or different to each other, and respectively hydrogen；The alkyl for being substituted or being unsubstituted；Be substituted or without Substituted alkoxy or halogen group and R109, R110 and R119 are same or different to each other, and respectively hydrogen；Or warp The alkyl for replacing or being unsubstituted；

L is the real number of 0 < l < 1 as molar fraction；

M is the real number of 0 < m < 1 as molar fraction；

L+m=1；And

Repeat number of the n as unit is 1 to 10,000 integer.

10. it is following formula 6-1 any one of to 6-30 polymer according to claim 1:

[chemical formula 6-1]

[chemical formula 6-2]

[chemical formula 6-3]

[chemical formula 6-4]

[chemical formula 6-5]

[chemical formula 6-6]

[chemical formula 6-7]

[chemical formula 6-8]

[chemical formula 6-9]

[chemical formula 6-10]

[chemical formula 6-11]

[chemical formula 6-12]

[chemical formula 6-13]

[chemical formula 6-14]

[chemical formula 6-15]

[chemical formula 6-16]

[chemical formula 6-17]

[chemical formula 6-18]

[chemical formula 6-19]

[chemical formula 6-20]

[chemical formula 6-21]

[chemical formula 6-22]

[chemical formula 6-23]

[chemical formula 6-24]

[chemical formula 6-25]

[chemical formula 6-26]

[chemical formula 6-27]

[chemical formula 6-28]

[chemical formula 6-29]

[chemical formula 6-30]

In chemical formula 6-1 into 6-30,

L is the real number of 0 < l < 1 as molar fraction；

M is the real number of 0 < m < 1 as molar fraction；

L+m=1；And

Repeat number of the n as unit is 1 to 10,000 integer.

11. a kind of organic solar batteries, comprising:

First electrode；

It is arranged to the second electrode opposite with the first electrode；And

One or more organic material layers between the first electrode and the second electrode are set, and described organic Material layer includes photoactive layer,

Wherein the photoactive layer includes polymer according to any one of claim 1 to 10.

12. organic solar batteries according to claim 11, wherein the photoactive layer includes electron donor and electronics Receptor, and the electron donor includes the polymer.

13. organic solar batteries according to claim 12, wherein the electron acceptor includes non-fullerene chemical combination Object.

14. organic solar batteries according to claim 13, wherein the non-lipid Le vinyl compound is by following chemistry Formula A is indicated:

[chemical formula A]

In chemical formula A,

Ra to Rf is same or different to each other, and is each independently hydrogen；Or the alkyl for being substituted or being unsubstituted；

La to Ld is same or different to each other, and is each independently the arlydene for being substituted or being unsubstituted；Or it is substituted Or the divalent heterocycle being unsubstituted；

Ma and Mb are same or different to each other, and are each independently halogen group；Or the alkyl for being substituted or being unsubstituted；

P and q are same or different to each other, and are each independently 0 to 2 integer；And

When p or q is 2, the structure in bracket is mutually the same.

15. organic solar batteries according to claim 12, wherein the electron acceptor is following below formula A-1 to A- Any one of 6:

[chemical formula A-1]

[chemical formula A-2]

[chemical formula A-3]

[chemical formula A-4]

[chemical formula A-5]

[chemical formula A-6]

16. organic solar batteries according to claim 12, wherein the matter of the electron donor and the electron acceptor Amount is than being 2:1 to 1:5.

Technical field

This application claims the South Korea patent application 10-2018- submitted on March 12nd, 2018 to Korean Intellectual Property Office No. 0028525 priority and right, entire contents are incorporated herein by reference.

This specification is related to polymer and the organic solar batteries comprising it.

Background technique

Organic solar batteries are the devices that solar energy can be directly changed into electric energy by application photovoltaic effect.According to The material of film is formed, solar battery is divided into inorganic solar cell and organic solar batteries, and due to existing Inorganic solar cell is restricted in terms of economic feasibility and material supply, therefore is easily worked, is cheap and have The organic solar batteries of multiple functions are as long-term alternative energy source by favor.

For solar battery, it is important that improve efficiency to export electric energy as much as possible by solar energy, in order to mention High efficiency generates exciton as much as possible in semiconductor and is important, however, generated charge is taken to external without damaging Mistake is also important.The reason of loss of charge first is that generated electrons and holes are lost due to recombining.It has mentioned A variety of methods for generated electronics or hole to be delivered to electrode without loss are gone out, however, most methods all need Additional process is wanted, and therefore manufacturing cost can increase.

Summary of the invention

Technical problem

This specification is intended to provide polymer and the organic solar batteries comprising it.

Technical solution

One embodiment of this specification provides polymer, it includes: the first list indicated by following formula 1 Member；The second unit indicated by following formula 2；With the third unit indicated by following formula 3 or 4.

[chemical formula 1]

[chemical formula 2]

[chemical formula 3]

[chemical formula 4]

In chemical formula 1 to 4,

X1 to X6 is same or different to each other, and is each independently CRR ', NR, O, SiRR ', PR, S, GeRR ', Se or Te,

A1 to A4 is same or different to each other, and is each independently halogen group,

Cy1 to Cy3 is same or different to each other, and is each independently the heterocycle for being substituted or being unsubstituted,

Q1 and Q2 are same or different to each other, and are each independently O or S,

R, R ', R " and R1 to R8 are same or different to each other, and are each independently hydrogen；Deuterium；Halogen group；Hydroxyl；Through The alkyl for replacing or being unsubstituted；The naphthenic base for being substituted or being unsubstituted；The alkoxy for being substituted or being unsubstituted；It is substituted Or the aryloxy group being unsubstituted；The alkyl sulfenyl for being substituted or being unsubstituted；The artyl sulfo for being substituted or being unsubstituted；Through taking Generation or the alkyl sulphonyl being unsubstituted；The aryl sulfonyl for being substituted or being unsubstituted；The alkenyl for being substituted or being unsubstituted； The amido for being substituted or being unsubstituted；The aryl for being substituted or being unsubstituted；Or the heterocycle for being substituted or being unsubstituted, with And

R11 and R12 are same or different to each other, and are each independently the alkyl for being substituted or being unsubstituted；It is substituted Or the alkoxy being unsubstituted；Or the alkyl sulfenyl for being substituted or being unsubstituted.

This specification another embodiment provides organic solar batteries comprising: first electrode；Be arranged to The opposite second electrode of first electrode；And one or more organic materials between first electrode and second electrode are set Layer, and the organic material layer includes photoactive layer, wherein the photoactive layer includes the polymer.

Beneficial effect

Polymer according to this specification embodiment is conductive material, and has thermal stability, excellent Dissolubility and high electron mobility.Therefore, when being used for organic solar batteries, excellent power conversion efficiency can be obtained.

In addition, high HOMO energy level is had according to the polymer of this specification embodiment, it is living as light comprising it Property layer electron donor organic solar batteries have excellent open circuit voltage characteristic.

Detailed description of the invention

Fig. 1 is to show the figure of the organic solar batteries of an embodiment according to this specification.

Fig. 2 is the figure for presenting the NMR spectra of the chemical formula K synthesized in preparation example.

Fig. 3 is the figure for presenting the NMR spectra of the chemical formula K-1 synthesized in preparation example.

[appended drawing reference]

101: first electrode

102: electron transfer layer

103: photoactive layer

104: hole transmission layer

105: second electrode

Specific embodiment

Hereinafter, this specification will be explained in more detail.

In the present specification, " unit " be polymer monomer in include repetitive structure, and mean that wherein monomer is logical Cross the structure that polymerization is bonded in the polymer.

In the present specification, the meaning of " including unit " is intended to be included in the main chain in polymer.

In the present specification, the description of certain a part of certain ingredient of " comprising " means can also to include other compositions, and Except non-specifically conversely bright, it is otherwise not excluded for other compositions.

In the present specification, it not only includes the adjacent another structure of a component that a component, which is placed in the description of another component "upper", The case where part, but also it is included in the case where there are another components between the two components.

In the present specification, energy level means energy size.Therefore, even if when to be indicated from negative (-) direction of vacuum level When energy level, energy level is also interpreted to mean the absolute value of corresponding energy value.For example, HOMO energy level means from vacuum level to most The distance of high occupied molecular orbital.In addition, lumo energy means the distance from vacuum level to lowest unoccupied molecular orbital.

One embodiment of this specification provides polymer, it includes: the first list indicated by following formula 1 Member；The second unit indicated by following formula 2；With the third unit indicated by following formula 3 or 4.

Specifically, the first unit indicated by chemical formula 1 can replace through halogen group (preferably fluorine), and it reduce HOMO energy level leads to the effect for improving open-circuit voltage.

In the present specification, the example of substituent group is described herein below, however, substituent group is without being limited thereto.

The position that term " substitution " means to become another substituent group with the hydrogen atom of the carbon atom bonding of compound, and replaces Set that there is no limit as long as it is the substituted position of hydrogen atom (that is, position that substituent group can replace), and when two Or more substituent group replace when, two or more substituent groups can be the same or different from each other.

In the present specification, term " be substituted or be unsubstituted " means through one or more substitutions selected from the following Base replaces: deuterium；Halogen group；Itrile group；Nitro；Hydroxyl；The alkyl for being substituted or being unsubstituted；The ring for being substituted or being unsubstituted Alkyl；The alkoxy for being substituted or being unsubstituted；The alkyl sulfenyl for being substituted or being unsubstituted；The virtue for being substituted or being unsubstituted Oxygroup；The alkenyl for being substituted or being unsubstituted；The aryl for being substituted or being unsubstituted；And the heterocycle for being substituted or being unsubstituted Base, the substituent group being perhaps connected through two or more substituent groups in substituent group illustrated above replace or do not have Substituted base.For example, " substituent group that two or more substituent groups are connected " may include xenyl.In other words, xenyl It can be aryl, or be construed to the substituent group that two phenyl are connected.

In the present specification, the example of halogen group may include fluorine, chlorine, bromine or iodine.

In the present specification, alkyl can be linear or branching, although and be not particularly limited to this, carbon atom number Preferably 1 to 50.Its specific example may include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, normal-butyl, isobutyl Base, tert-butyl, sec-butyl, 1- methyl-butvl, 1- Ethyl-butyl, amyl, n-pentyl, isopentyl, neopentyl, tertiary pentyl, oneself Base, n-hexyl, 1- methyl amyl, 2- methyl amyl, 4- methyl -2- amyl, 3,3- dimethylbutyl, 2- ethyl-butyl, heptyl, N-heptyl, 1- methylhexyl, cyclopentyl-methyl, cyclohexyl methyl, octyl, n-octyl, t-octyl, 1- methylheptyl, 2- ethyl Hexyl, 2- propylpentyl, n-nonyl, 2,2- dimethyl heptyl, 1- Ethyl-propyl, 1,1- Dimethyl-propyl, isohesyl, 2- first Base hexyl, 4- methylhexyl, 5- methylhexyl etc., but not limited to this.

In the present specification, naphthenic base is not particularly limited, it is preferred that having 3 to 60 carbon atoms.Its specific example It may include cyclopropyl, cyclobutyl, cyclopenta, 3- methylcyclopentyl, 2,3- dimethylcyclopentyl, cyclohexyl, 3- methyl cyclohexane Base, 4- methylcyclohexyl, 2,3- Dimethylcyclohexyl, 3,4,5- trimethylcyclohexyl, 4- tert-butylcyclohexyl, suberyl, ring Octyl etc., but not limited to this.

In the present specification, when aryl is monocyclic aryl, carbon atom number is not particularly limited, it is preferred that being 6 to 25. The specific example of monocyclic aryl may include phenyl, xenyl, terphenyl etc., but not limited to this.

In the present specification, when aryl be polyaromatic when, carbon atom number is not particularly limited, it is preferred that for 10 to 24.The specific example of polyaromatic may include naphthalene, anthryl, phenanthryl, pyrenyl, base,Base, fluorenyl etc., but be not limited to This.

In the present specification, fluorenyl can be substituted, and adjacent substituents can bond together to form ring.

In the present specification, arlydene means the aryl for having there are two binding site, i.e. bivalent group.Pair provided above The description of aryl can be applied to arlydene, the difference is that these are respectively divalent.

In the present specification, alkoxy can be linear, branching or cricoid.The carbon atom number of alkoxy does not limit especially System, it is preferred that being 1 to 20.Its specific example may include methoxyl group, ethyoxyl, positive propoxy, isopropoxy, isopropyl oxygen Base, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyl oxygen, isoamoxy, positive hexyloxy, 3, 3- dimethyl butyrate oxygroup, 2- ethyl-butoxy, n-octyloxy, positive nonyl epoxide, n-decyloxy etc., but not limited to this.

In the present specification, alkyl sulfenyl means the substituent group indicated by-S-R (R is alkyl), and can for it is linear, Branching is cricoid.The carbon atom number of alkyl sulfenyl is not particularly limited, it is preferred that being 1 to 20.Its specific example can wrap Include methylsulfany, ethylsulfanyl, n-propyl sulfenyl, isopropylsulfanyl (isopropylthio), isopropylsulfanyl (i- Propylthio), n-butylthio, i-butylthio, tert. butyl-sulphenyl, s-butylthio, n-pentyl sulfenyl, neopentyl sulphur Base, isopentyl sulfenyl, n-hexyl sulfenyl, 3,3- dimethylbutyl sulfenyl, 2- ethyl-butyl sulfenyl, n-octyl sulfenyl, n-nonyl Sulfenyl, positive decyl sulfenyl, benzyl sulfenyl, to methylbenzylthio etc., but not limited to this.

In the present specification, the aryl in aryloxy group, artyl sulfo and aryl sulfonyl is identical as the example of above-mentioned aryl. The specific example of aryloxy group may include phenoxy group, to toloxyl, toloxyl, 3,5- Dimehtyl-phenoxy, 2,4,6- Trimethylbenzene oxygroup, to tert-butyl benzene oxygroup, 3- biphenylyloxy, 4- biphenylyloxy, 1- naphthoxy, 2- naphthoxy, 4- methyl-1- Naphthoxy, 5- methyl -2- naphthoxy, 1- anthracene oxygroup, 2- anthracene oxygroup, 9- anthracene oxygroup, 1- phenanthrene oxygroup, 3- phenanthrene oxygroup, 9- phenanthrene oxygroup, Benzyloxy, to methylbenzyloxy etc., the example of artyl sulfo may include phenylsulfartyl, 2- aminomethyl phenyl sulfenyl, 4- tert-butyl Phenylsulfartyl etc., the example of aryl sulfonyl may include benzenesulfonyl, p-toluenesulfonyl etc., however, aryloxy group, aryl sulphur Base and aryl sulfonyl are without being limited thereto.

In the present specification, the alkyl in alkyl sulfenyl and alkyl sulphonyl is identical as the example of abovementioned alkyl.Alkyl sulphur The specific example of acyl group may include methyl sulphonyl, ethylsulfonyl, sulfonyl propyl base, butyl sulfonyl etc., but be not limited to This.

In the present specification, alkenyl can be linear or branching, although and be not particularly limited to this, carbon atom number Preferably 2 to 40.Its specific example may include vinyl, 1- acrylic, isopropenyl, 1- cyclobutenyl, 2- cyclobutenyl, 3- fourth Alkenyl, 1- pentenyl, 2- pentenyl, 3- pentenyl, 3-methyl-1-butene base, 1,3- butadienyl, allyl, 1- phenyl second Alkenyl -1- base, 2- phenyl vinyl -1- base, 2,2- diphenylacetylene -1- base, 2- phenyl -2- (naphthalene -1- base) vinyl - 1- base, 2,2- bis- (diphenyl -1- base) vinyl -1- base, Stilbene base, styryls etc., but not limited to this.

In the present specification, the carbon atom number of amido is not particularly limited, it is preferred that being 1 to 30.In amido, N is former Son can replace through aryl, alkyl, aryl alkyl, heterocycle etc., and the specific example of amido may include methylamino, two Methylamino, ethyl amido, diethyl amido, phenyl amido, naphthalene amido, benzidion, anthryl amido, 9- methyl-anthryl Amido, diphenyl amido, phenyl napthyl amido, xylyl amido, phenyltoluene base amido, triphenyl amido etc., but it is unlimited In this.

In the present specification, heterocycle is the group comprising one or more non-carbon (that is, hetero atom), and is had Body, hetero atom may include one or more atoms in O, N, Se, S etc..The carbon atom number of heterocycle is without spy It does not limit, it is preferred that being 2 to 60.The example of heterocycle may include thienyl, furyl, pyrrole radicals, imidazole radicals, thiazole Base,Oxazolyl,Di azoly, triazolyl, pyridyl group, bipyridyl, pyrimidine radicals, triazine radical, triazolyl, acridinyl, pyridazine Base, pyrazinyl, quinolyl, quinazolyl, quinoxalinyl, isoquinolyl, indyl, carbazyl, benzoOxazolyl, benzo miaow Oxazolyl, benzothiazolyl, benzo click+base, benzothienyl, dibenzothiophene, benzofuranyl, phenanthroline, thiazolyl, It is differentOxazolyl,Di azoly, thiadiazolyl group, phenothiazinyl, dibenzofuran group, selenium di azoly (selenadiazolyl) etc., But not limited to this.

In an embodiment of this specification, X1 to X5 is respectively S.

In an embodiment of this specification, X6 NR, and R is the alkyl with 1 to 20 carbon atom.

In an embodiment of this specification, X6 NR, and R is ethylhexyl.

In an embodiment of this specification, X6 NR, and R is 2- ethylhexyl.

In an embodiment of this specification, A1 to A4 is respectively fluorine.

In an embodiment of this specification, Cy1 and Cy2 are respectively the heterocycle with 2 to 10 carbon atoms.

In an embodiment of this specification, Cy1 and Cy2 are respectively thienyl.

In an embodiment of this specification, Cy3 is heterocycle.

In an embodiment of this specification, Cy3 is the heterocycle replaced through alkyl or aryl.

In an embodiment of this specification, Cy3 is comprising S, Se and/or N as heteroatomic heterocycle.

In an embodiment of this specification, Cy3 is pyrazinyl.

In an embodiment of this specification, Cy3 is the pyrazinyl replaced through alkyl or aryl.

In an embodiment of this specification, Cy3 is selenium di azoly.

In an embodiment of this specification, Cy3 1,2,5- selenium di azoly.

In an embodiment of this specification, Cy3 is thiadiazolyl group.

In an embodiment of this specification, Cy3 1,2,5- thiadiazolyl group.

In an embodiment of this specification, Cy3 is triazolyl.

In an embodiment of this specification, Cy3 is the triazolyl replaced through alkyl or aryl.

In an embodiment of this specification, Q1 and Q2 are respectively O.

In an embodiment of this specification, Q1 and Q2 are respectively S.

In an embodiment of this specification, R1 to R6 is respectively hydrogen.

In an embodiment of this specification, R7 and R8 are respectively the alkoxy for being substituted or being unsubstituted.

In an embodiment of this specification, R7 and R8 are respectively the alkoxy with 1 to 20 carbon atom.

In an embodiment of this specification, R7 and R8 are respectively dodecyloxy.

In an embodiment of this specification, R7 and R8 are respectively (ethylhexyl) oxygroup.

In an embodiment of this specification, R7 and R8 are respectively (2- ethylhexyl) oxygroup.

In an embodiment of this specification, R7 and R8 are respectively halogen group.

In an embodiment of this specification, R7 and R8 are respectively fluorine.

In an embodiment of this specification, R7 and R8 are respectively hydrogen.

In an embodiment of this specification, R11 and R12 are respectively the alkyl with 1 to 20 carbon atom.

In an embodiment of this specification, R11 and R12 are respectively the alkyl with 5 to 15 carbon atoms.

In an embodiment of this specification, R11 and R12 are respectively hexyl.

In an embodiment of this specification, R11 and R12 are respectively ethylhexyl.

In an embodiment of this specification, R11 and R12 are respectively 2- ethylhexyl.

In an embodiment of this specification, R11 and R12 are respectively butyl hexyl.

In an embodiment of this specification, R11 and R12 are respectively 2- butyl hexyl.At one of this specification In embodiment, first unit can be indicated by following formula 1-1.

[chemical formula 1-1]

In chemical formula 1-1,

R1, R2, R11, R12, X1, X2, A1 and A2 have with identical restriction in chemical formula 1, and

X7 and X8 are same or different to each other, and are each independently NR, O, SiRR ', PR, S, GeRR ', Se or Te.

In an embodiment of this specification, X7 and X8 are respectively S.

In an embodiment of this specification, first unit can be indicated by following formula 1-2.

[chemical formula 1-2]

In chemical formula 1-2,

R11, R12, A1 and A2 have and identical restriction in chemical formula 1.

In an embodiment of this specification, in chemical formula 1-2, A1 and A2 are respectively fluorine.

In an embodiment of this specification, in chemical formula 1-2, A1 and A2 are respectively chlorine.

In an embodiment of this specification, first unit can be indicated by following formula 1-2-1 or 1-2-2.

[chemical formula 1-2-1]

[chemical formula 1-2-2]

In an embodiment of this specification, second unit can be indicated by following formula 2-1.

[chemical formula 2-1]

In chemical formula 2-1,

R3 to R6, A3 and A4 have and identical restriction in chemical formula 2.

In an embodiment of this specification, third unit can be by any one of following formula 3-1 to 3-3 It indicates.

[chemical formula 3-1]

[chemical formula 3-2]

[chemical formula 3-3]

In chemical formula 3-1 into 3-3,

R7, R8, Q1 and Q2 have with identical restriction in chemical formula 3 and 4,

X9 is CRR ', NR, O, SiRR ', PR, S, GeRR ', Se or Te,

Y1 to Y4 is same or different to each other, and is each independently CR ", N, SiR ", P or GeR ", and

R, R ', R ", R9, R10 and R19 are same or different to each other, and are each independently hydrogen；It is substituted or is unsubstituted Alkyl；The alkoxy for being substituted or being unsubstituted；The alkyl sulfenyl for being substituted or being unsubstituted；It is substituted or is unsubstituted Aryloxy group；The artyl sulfo for being substituted or being unsubstituted；The aryl for being substituted or being unsubstituted；Or it is substituted or is unsubstituted Heterocycle.

In an embodiment of this specification, X9 S.

In an embodiment of this specification, X9 Se.

In an embodiment of this specification, X9 NR, and R is the alkyl for being substituted or being unsubstituted.

In an embodiment of this specification, X9 NR, and R is the alkyl with 1 to 20 carbon atom.

In an embodiment of this specification, X9 NR, and R is ethylhexyl.

In an embodiment of this specification, X9 NR, and R is 2- ethylhexyl.

In an embodiment of this specification, Y1 to Y4 is respectively N.

In an embodiment of this specification, R19 is the alkyl for being substituted or being unsubstituted.

In an embodiment of this specification, R19 is the alkyl with 1 to 30 carbon atom.

In an embodiment of this specification, R19 is the alkyl with 1 to 15 carbon atom.

In an embodiment of this specification, R19 is ethylhexyl.

In an embodiment of this specification, R19 is 2- ethylhexyl.

In an embodiment of this specification, R9 and R10 are respectively the aryloxy group for being substituted or being unsubstituted.

In an embodiment of this specification, R9 and R10 are respectively (octyloxy) benzene for being substituted or being unsubstituted Base.

In an embodiment of this specification, R9 and R10 are respectively the alkyl with 1 to 20 carbon atom.

In an embodiment of this specification, R9 and R10 are respectively the alkyl with 5 to 15 carbon atoms.

In an embodiment of this specification, R9 and R10 are respectively octyl.

In an embodiment of this specification, third unit can be by any one of following formula 3-4 to 3-9 It indicates.

[chemical formula 3-4]

[chemical formula 3-5]

[chemical formula 3-6]

[chemical formula 3-7]

[chemical formula 3-8]

[chemical formula 3-9]

In chemical formula 3-4 into 3-9,

R7 to R10 and R19 has the identical restriction into 3-3 with chemical formula 3-1.

In an embodiment of this specification, polymer may include the unit indicated by following formula 5.

[chemical formula 5]

In chemical formula 5,

L is the real number of 0 < l < 1 as molar fraction,

M is the real number of 0 < m < 1 as molar fraction,

L+m=1,

A is the first unit indicated by chemical formula 1,

B is the second unit indicated by chemical formula 2,

C and C ' are same or different to each other, and the third unit to be indicated by chemical formula 3 or chemical formula 4 each independently； And

Repeat number of the n as unit is 1 to 10,000 integer.

In an embodiment of this specification, polymer may include the list by following formula 5-1 or 5-2 expression Member.

[chemical formula 5-1]

[chemical formula 5-2]

In chemical formula 5-1 and 5-2,

X1 is to X6, A1 to A4, Cy1 to Cy3, Q1, Q2, R, R ', R ", R1 to R8, R11 and R12 has and chemical formula 1 to 4 In identical restriction,

L, m and n have with identical restriction in chemical formula 5,

X15 and X16 are same or different to each other, and are each independently CRR ', NR, O, SiRR ', PR, S, GeRR ', Se Or Te,

Cy13 is the heterocycle for being substituted or being unsubstituted,

Q11 and Q12 are same or different to each other, and are each independently O or S；And

R17 and R18 are same or different to each other, and are each independently hydrogen；Deuterium；Halogen group；Hydroxyl；It is substituted or not The alkyl being substituted；The naphthenic base for being substituted or being unsubstituted；The alkoxy for being substituted or being unsubstituted；It is substituted or without taking The aryloxy group in generation；The alkyl sulfenyl for being substituted or being unsubstituted；The artyl sulfo for being substituted or being unsubstituted；Be substituted or without Substituted alkyl sulphonyl；The aryl sulfonyl for being substituted or being unsubstituted；The alkenyl for being substituted or being unsubstituted；Be substituted or The amido being unsubstituted；The aryl for being substituted or being unsubstituted；Or the heterocycle for being substituted or being unsubstituted.

In an embodiment of this specification, Q11 and Q12 are respectively O.

In an embodiment of this specification, Q11 and Q12 are respectively S.

In an embodiment of this specification, R17 and R18 are respectively the alkoxy for being substituted or being unsubstituted.

In an embodiment of this specification, R17 and R18 are respectively the alkoxy with 1 to 20 carbon atom.

In an embodiment of this specification, R17 and R18 are respectively dodecyloxy.

In an embodiment of this specification, R17 and R18 are respectively (ethylhexyl) oxygroup.

In an embodiment of this specification, R17 and R18 are respectively (2- ethylhexyl) oxygroup.

In an embodiment of this specification, R17 and R18 are respectively halogen group.

In an embodiment of this specification, R17 and R18 are respectively fluorine.

In an embodiment of this specification, R17 and R18 are respectively hydrogen.

In an embodiment of this specification, Cy13 is heterocycle.

In an embodiment of this specification, Cy13 is the heterocycle replaced through alkyl or aryl.

In an embodiment of this specification, Cy13 is comprising S, Se and/or N as heteroatomic heterocycle.

In an embodiment of this specification, Cy13 is pyrazinyl.

In an embodiment of this specification, Cy13 is the pyrazinyl replaced through alkyl or aryl.

In an embodiment of this specification, Cy13 is selenium di azoly.

In an embodiment of this specification, Cy13 1,2,5- selenium di azoly.

In an embodiment of this specification, Cy13 is thiadiazolyl group.

In an embodiment of this specification, Cy13 1,2,5- thiadiazolyl group.

In an embodiment of this specification, Cy13 is triazolyl.

In an embodiment of this specification, Cy13 is the triazolyl replaced through alkyl or aryl.

In an embodiment of this specification, X15 S.

In an embodiment of this specification, X16 NR, and R is the alkyl with 1 to 20 carbon atom.

In an embodiment of this specification, X16 NR, and R is ethylhexyl.

In an embodiment of this specification, X16 NR, and R is 2- ethylhexyl.

In an embodiment of this specification, polymer is any one of following formula 5-3 to 5-9.

[chemical formula 5-3]

[chemical formula 5-4]

[chemical formula 5-5]

[chemical formula 5-6]

[chemical formula 5-7]

[chemical formula 5-8]

[chemical formula 5-9]

In chemical formula 5-3 into 5-9,

A1, A2, R11 and R12 have with identical restriction in chemical formula 1,

R107 and R108 are same or different to each other, and respectively hydrogen；The alkyl for being substituted or being unsubstituted；Be substituted or The alkoxy or halogen group being unsubstituted, R109, R110 and R119 are same or different to each other, and respectively hydrogen；Or warp The alkyl for replacing or being unsubstituted,

L is the real number of 0 < l < 1 as molar fraction,

M is the real number of 0 < m < 1 as molar fraction,

L+m=1, and

Repeat number of the n as unit is 1 to 10,000 integer.

In an embodiment of this specification, A1 and A2 are respectively fluorine or chlorine.

In an embodiment of this specification, R107 and R108 are respectively the alkyl with 1 to 30 carbon atom.

In an embodiment of this specification, R107 and R108 are respectively the alkyl with 5 to 15 carbon atoms.

In an embodiment of this specification, R107 and R108 are respectively dodecyl.

In an embodiment of this specification, R107 and R108 are respectively octyl.

In an embodiment of this specification, R107 and R108 are respectively ethylhexyl.

In an embodiment of this specification, R107 and R108 are respectively 2- ethylhexyl.

In an embodiment of this specification, R107 and R108 are respectively the alkoxy with 1 to 30 carbon atom.

In an embodiment of this specification, R107 and R108 are respectively the alkoxy with 5 to 15 carbon atoms.

In an embodiment of this specification, R107 and R108 are respectively (dodecyl) oxygroup.

In an embodiment of this specification, R107 and R108 are respectively (octyl) oxygroup.

In an embodiment of this specification, R107 and R108 are respectively (ethylhexyl) oxygroup.

In an embodiment of this specification, R107 and R108 are respectively (2- ethylhexyl) oxygroup.

In an embodiment of this specification, R107 and R108 are respectively fluorine.

In an embodiment of this specification, R107 and R108 are respectively hydrogen.

In an embodiment of this specification, R109 and R110 are respectively the alkyl with 1 to 30 carbon atom.

In an embodiment of this specification, R109 and R110 are respectively the alkyl with 5 to 15 carbon atoms.

In an embodiment of this specification, R109 and R110 are respectively octyl.

In an embodiment of this specification, R119 is the alkyl with 1 to 30 carbon atom.

In an embodiment of this specification, R119 is the alkyl with 1 to 15 carbon atom.

In an embodiment of this specification, R119 is ethylhexyl.

In an embodiment of this specification, R119 is 2- ethylhexyl.

In an embodiment of this specification, polymer can be any one of following formula 6-1 to 6-30.

[chemical formula 6-1]

[chemical formula 6-2]

[chemical formula 6-3]

[chemical formula 6-4]

[chemical formula 6-5]

[chemical formula 6-6]

[chemical formula 6-7]

[chemical formula 6-8]

[chemical formula 6-9]

[chemical formula 6-10]

[chemical formula 6-11]

[chemical formula 6-12]

[chemical formula 6-13]

[chemical formula 6-14]

[chemical formula 6-15]

[chemical formula 6-16]

[chemical formula 6-17]

[chemical formula 6-18]

[chemical formula 6-19]

[chemical formula 6-20]

[chemical formula 6-21]

[chemical formula 6-22]

[chemical formula 6-23]

[chemical formula 6-24]

[chemical formula 6-25]

[chemical formula 6-26]

[chemical formula 6-27]

[chemical formula 6-28]

[chemical formula 6-29]

[chemical formula 6-30]

In chemical formula 6-1 into 6-30,

L is the real number of 0 < l < 1 as molar fraction,

M is the real number of 0 < m < 1 as molar fraction,

L+m=1, and

Repeat number of the n as unit is 1 to 10,000 integer.

In an embodiment of this specification, l and m are respectively 0.5.

One embodiment of this specification provides organic solar batteries comprising: first electrode；It is arranged to and the The opposite second electrode of one electrode；And one or more organic materials between first electrode and second electrode are set Layer, and the organic material layer includes photoactive layer, wherein the photoactive layer includes the polymer.

In an embodiment of this specification, photoactive layer includes electron donor and electron acceptor, and electronics supplies Body includes the polymer.

In an embodiment of this specification, electron acceptor includes non-fullerene compound.

In an embodiment of this specification, non-fullerene compound can be indicated by following below formula A.

[chemical formula A]

In chemical formula A,

Ra to Rf is same or different to each other, and is each independently hydrogen；Or the alkyl for being substituted or being unsubstituted,

La to Ld is same or different to each other, and is each independently the arlydene for being substituted or being unsubstituted；Or warp The divalent heterocycle for replacing or being unsubstituted,

Ma and Mb are same or different to each other, and are each independently halogen group；Or be substituted or be unsubstituted Alkyl,

P and q are same or different to each other, and are each independently 0 to 2 integer, and

When p or q is 2, the structure in bracket is mutually the same.

In an embodiment of this specification, Ra to Rd is respectively alkyl.

In an embodiment of this specification, Ra to Rd is respectively the alkyl with 1 to 30 carbon atom.

In an embodiment of this specification, Ra to Rd is respectively the alkyl with 1 to 10 carbon atom.

In an embodiment of this specification, Ra to Rd is respectively hexyl.

In an embodiment of this specification, Re and Rf are respectively hydrogen.

In an embodiment of this specification, La to Ld is respectively arlydene.

In an embodiment of this specification, La to Ld is respectively the arlydene with 6 to 25 carbon atoms.

In an embodiment of this specification, La to Ld is respectively phenylene.

In an embodiment of this specification, Ma and Mb are respectively hydrogen.

In an embodiment of this specification, Ma and Mb are respectively alkyl.

In an embodiment of this specification, Ma and Mb are respectively the alkyl with 1 to 10 carbon atom.

In an embodiment of this specification, Ma and Mb are respectively methyl.

In an embodiment of this specification, Ma and Mb are respectively halogen group.

In an embodiment of this specification, Ma and Mb are respectively fluorine.

In an embodiment of this specification, p and q are respectively 0.

In an embodiment of this specification, p and q are respectively 1.

In an embodiment of this specification, p and q are respectively 2.

In an embodiment of this specification, electron acceptor can be any of following below formula A-1 into A-6 Person.

[chemical formula A-1]

[chemical formula A-2]

[chemical formula A-3]

[chemical formula A-4]

[chemical formula A-5]

[chemical formula A-6]

In an embodiment of this specification, non-fullerene compound has more compared with fullerene compound High thermal stability.

In an embodiment of this specification, electron donor is the unit comprising being indicated by chemical formula 5-1 or 5-2 Polymer, electron acceptor are the compounds indicated by chemical formula A.

In an embodiment of this specification, the mass ratio of electron donor and electron acceptor is 2:1 to 1:5.Quality Than being preferably 1:1 to 1:5, and more preferably 1:1 to 1:3.

In an embodiment of this specification, electron donor and electron acceptor can form body heterojunction (BHJ). Body heterojunction means the electron donor material and electron acceptor material mixed in photoactive layer.

In an embodiment of this specification, electron donor can be p-type organic material layer, and electron acceptor can be N-shaped organic material layer.

In an embodiment of this specification, polymer is atactic polymer.In addition, atactic polymer has enhancing Dissolubility, this is cost-effective in terms of time and cost in device fabrication.

In an embodiment of this specification, the end group of polymer is heterocycle or aryl.

In an embodiment of this specification, the end group of polymer is 4- (trifluoromethyl) phenyl.

In an embodiment of this specification, the end group of polymer is bromothiophene base.

In an embodiment of this specification, the end group of polymer is trifluorophenyl.

In an embodiment of this specification, the end group of polymer can be without sealing end.

In an embodiment of this specification, polymer preferably has 5 a, 000g/mol to 1,000,000g/mol Number-average molecular weight.Number-average molecular weight is preferably 100,000g/mol or smaller, so as to certain level or higher solubility, This is advantageous in using solution coating process.

In an embodiment of this specification, polymer can have 1 to 10 molecular weight distribution.Preferably, gather Close the molecular weight distribution that object has 1 to 3.When molecular weight distribution reduces and number-average molecular weight increases, advantageous electricity is obtained Characteristic and mechanical property.

In an embodiment of this specification, molecular weight distribution means weight average molecular weight (Mw) divided by the equal molecule of number It measures (Mn), i.e. weight average molecular weight (Mw)/number-average molecular weight (Mn) number, and weight average molecular weight (Mw) and number-average molecular weight (Mn) Chlorobenzene is used as solvent by gel permeation chromatography (GPC) to measure.

Polymer can by using chlorobenzene as solvent by the monomer and Pd of each unit₂(dba)₃With P (o-tolyl)₃ It is concomitantly introduced into and prepares gains polymerization using microwave reactor.

Multi-step chemical reaction can be used according to the polymer of this specification to prepare.By alkylated reaction, After Grignard reaction, Suzuki coupling reaction, Stille coupling reaction etc. prepare monomer, it can be coupled by carbon-to-carbon anti- Final polymer should be prepared such as Stille coupling reaction.When substituent group to be introduced is boric acid or boric acid ester compound, Suzuki coupling reaction can be used, and when substituent group to be introduced is tributyl tin or tin trimethyl compound, it can make With Stille coupling reaction, however, method is without being limited thereto.

Fig. 1 is to show the figure of the organic solar batteries of an embodiment according to this specification, is had wherein Electron transfer layer 102, photoactive layer 103, hole transmission layer 104 and second electrode 105 are laminated in succession in first electrode 101 Structure, however, the structure of the organic solar batteries of this specification is without being limited thereto.

In an embodiment of this specification, organic solar batteries can also include other organic material layer. Organic solar batteries can reduce the quantity of organic material layer by using having the organic material of multiple functions simultaneously.

In an embodiment of this specification, first electrode is anode, and second electrode is cathode.In another implementation In scheme, first electrode is cathode, and second electrode is anode.

In another embodiment, organic solar batteries can have its Anodic, hole transmission layer, photolytic activity Layer, electron transfer layer and cathode press the structure of consecutive order arrangement, or can have wherein cathode, electron transfer layer, light and live Property layer, hole transmission layer and anode press consecutive order arrangement structure, however, structure is without being limited thereto.

In an embodiment of this specification, organic solar batteries have normal configuration.In normal configuration, base Bottom, first electrode, hole transmission layer, the organic material layer including photoactive layer, electron transfer layer and second electrode can be by these Sequential laminating.

In an embodiment of this specification, organic solar batteries have inverted structure.In inverted structure, base Bottom, first electrode, electron transfer layer, the organic material layer including photoactive layer, hole transmission layer and second electrode can be by these Sequential laminating.

In an embodiment of this specification, organic solar batteries have cascaded structure.In this case, have Machine solar battery may include two or more photoactive layers.According to organic sun of this specification embodiment Energy battery can have one layer, two or more layers photoactive layer.

It can have one layer, two or more layers light according to the organic solar batteries of this specification embodiment Active layer.

It in another embodiment, can be between photoactive layer and hole transmission layer or in photoactive layer and electronics Buffer layer is set between transport layer.Herein, hole injection layer can also be set between anode and hole transmission layer.In addition, Electron injecting layer can also be set between cathode and electron transfer layer.

In an embodiment of this specification, substrate may include have excellent transparency, surface flatness, easily Operability and water resistance substrate of glass or transparent plastic substrate, but not limited to this, and can be used commonly used in it is organic too Substrate in positive energy battery is without limiting.Its specific example includes glass, polyethylene terephthalate (PET), poly- naphthalene Naphthalate (PEN), polypropylene (PP), polyimides (PI), triacetyl cellulose (TAC) etc., but not limited to this.

The material of first electrode may include material transparent and with excellent electric conductivity, but not limited to this.First electricity The example of pole material includes: metal, such as vanadium, chromium, copper, zinc or gold or its alloy；Metal oxide, such as zinc oxide, oxidation Indium, tin indium oxide (ITO) or indium zinc oxide (IZO)；The combination of metal and oxide, such as ZnO:Al or SnO₂:Sb；Conduction is poly- Close object, such as poly- (3 methyl thiophene), poly- [3,4- (bis- oxygroup of ethylidene -1,2-) thiophene] (PEDOT), polypyrrole and polyaniline Deng, but not limited to this.

Formed first electrode method be not particularly limited, however, it is, for example, possible to use sputtering, electron beam, heat deposition, The method of spin coating, silk-screen printing, ink jet printing, blade coating or intaglio printing.

When first electrode is formed on the substrate, the cleaning of gains experience can be made, moisture is removed and be modified as hydrophilic Process.

For example, carrying out cleaning it to patterning ITO substrate by consecutive order cleaning agent, acetone and isopropanol (IPA) Afterwards, ITO substrate is 1 minute to 30 minutes dry at 100 DEG C to 150 DEG C on hot plate, it is 10 points dry preferably at 120 DEG C Substrate surface is modified as hydrophilic by clock to remove moisture, and when substrate is thoroughly cleaned.

Modified by such as above-mentioned surface, engagement surface potential may remain in the surface potential for being suitable for photoactive layer Level.In addition, thin polymer film, and the product of film can be readily formed on the first electrode when surface is modified Matter can be improved.

The preconditioning technique of first electrode include a) using parallel-plate discharge surface oxidation method, b) by under vacuum by The ozone that UV line generates makes the method for surface oxidation and c) using the oxidizing process etc. of the oxygen radical generated by plasma.

One of above method can be selected according to the state of first electrode or substrate.However, regardless of which kind of is used Method, it is usually preferred that prevent the oxygen on the surface of first electrode or substrate from leaving and inhibit moisture as much as possible and have Machine substance residual.In this case, pretreated actual effect can maximize.

As a specific example, the method for making surface oxidation by the ozone generated by UV line can be used.Herein, After ultrasonic cleaning, it can be toasted by will be patterned into ITO substrate on hot plate sufficiently dry to make to pattern ITO substrate It is dry, and will be patterned into ITO substrate and be introduced into room, it may then pass through by using UV lamp to generate oxygen smelly with UV light reaction Oxygen is cleaned.

However, the surface modifying method of the patterning ITO substrate in this specification is not particularly limited, and can be used Make any method of base oxidation.

Second electrode may include the metal with small work function, but not limited to this.Its specific example may include: gold Belong to, such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminium, silver, tin and lead or its alloy；Or sandwich, such as LiF/Al、LiO₂/Al、LiF/Fe、Al:Li、Al:BaF₂And Al:BaF₂: Ba, but not limited to this.

Second electrode can be by having 5 × 10^-7It deposits and is formed in the heat deposition equipment of support or smaller vacuum degree, This method is not limited to however, being formed.

Hole transmission layer and/or electron transport layer materials play the electrons and holes that will be separated in photoactive layer effectively It is transmitted to the effect of electrode, and material is not particularly limited.

Hole transport layer material may include poly- (the 3,4- ethene-dioxythiophene) doped with poly- (styrene sulfonic acid) (PEDOT:PSS), molybdenum oxide (MoO_x), barium oxide (V₂O₅), nickel oxide (NiO), tungsten oxide (WO_x) etc., but it is unlimited In this.

Electron transport layer materials may include bathocuproine (BCP) or electron extraction metal oxide, and can be specifically It include: bathocuproine (BCP)；The metal complex of 8-hydroxyquinoline；Include Alq₃Complex；Metal complex comprising Liq； LiF；Ca；Titanium oxide (TiO_x)；Zinc oxide (ZnO)；Cesium carbonate (Cs₂CO₃) etc., but not limited to this.

In an embodiment of this specification, vacuum deposition method can be used or solution coating process is used as and is used to form The method of photoactive layer, solution coating process mean for light active material such as electron donor and/or electron acceptor to be dissolved in organic molten In agent, the method for then using the method coating solution of such as spin coating, dip-coating, silk-screen printing, spraying, blade coating and brushing, however, Method is without being limited thereto.

It can be used according to the compound of this specification embodiment and will be described below preparation method to prepare. Representative example, which is described in, will be described below in preparation method, however, when necessary, substituent group can be added or remove, and The position of substituent group can change.In addition, being based on techniques known in the art, raw material, reaction material, reaction condition etc. can be with Variation.

In addition, will be described in detail this specification to specifically describe this specification referring to embodiment.However, according to this The embodiment of specification can be modified to various other forms, and the range of this specification should not be construed as limited by following retouch The embodiment stated.The embodiment of this specification is provided so that this specification is more fully described to those of ordinary skill in the art.

<Preparation example: the synthesis of polymer 1 to 8>

The synthesis of 1. polymer 1 of preparation example

(1) synthesis of chemical formula K

Toluene is introduced into two kinds of raw material, and in the tetrakis triphenylphosphine palladium (0) for adding 0.05 equivalent thereto (Pd(PPh₃)₄) after, gains are stirred 15 hours at 80 DEG C, reaction solution gradually becomes black.To its carry out after Reason, it is dry with magnesium sulfate, and recrystallize to obtain chemical formula K (white powder, 4.3g).

The NMR spectra of the chemical formula K of synthesis is shown in Figure 2.

(2) synthesis of chemical formula K-1

The chemical formula K of preparation is dissolved in tetrahydrofuran (THF), and after cooling the temperature to -78 DEG C, thereto The n-BuLi (n-BuLi) of 2.1 equivalents is added, and gains are stirred 30 minutes.Later, by gains at room temperature into When one step stirs 1 hour, solution is turned yellow.Temperature is down to -78 DEG C again, and is adding the three of 2.1 equivalents thereto After methyl chloride tin, gains are stirred 12 hours while temperature is slowly increased to room temperature.After 12 hours, solution Become yellow ocher, gains are post-processed and are then recrystallized, to obtain the chemical formula K- in the form of glossiness sheet yellow solid 1。

The NMR spectra of the chemical formula K-1 of synthesis is shown in Figure 3.

(3) synthesis of chemical formula L

Based on JOURNAL OF POLYMER SCIENCE PART A:POLYMER CHEMISTRY 2011,49,4387- The compound of 4397 4389 synthesis chemical formula L.

(4) synthesis of chemical formula M

10.0g 2- (2- ethylhexyl) -3- fluorine thiophene is being added and is being dissolved in it in 5500mL tetrahydrofuran (THF) Afterwards, -78 DEG C are cooled the temperature to.At such a temperature, it is slowly added the 2.5M n-BuLi of 24.0mL dissolution in hexane thereto (n-BuLi), it and by gains stirs 30 minutes.Later, temperature is risen to 0 DEG C, gains is stirred at such a temperature 1 hour, And 3.3g 4 is disposably being introduced thereto, after 8- dehydrogenation benzo [1,2-b:4,5-b '] Dithiophene -4,8- diketone, by institute Object is obtained to stir 3 hours at 50 DEG C.After being cooled to room temperature the solution, stannic chloride (II) dihydrate is introduced thereto (26g) and 1M HCl (56ml), and gains are futher stirred 3 hours.Ice is poured into the solution, by gains ether It is extracted twice, is washed twice with water, and use magnesium sulfate (MgSO₄) remove remaining water.Remaining solution is vacuumized to remove Solvent is removed, and by silica column, obtains the chemical formula M of yellow dense liquids form.(yield: 40%)

(5) synthesis of chemical formula M-1

After adding and being dissolved in 100mL tetrahydrofuran (THF) by the compound of 3g chemical formula M, 0 is cooled the temperature to ℃.At such a temperature, it is slowly added the 1.6M n-BuLi (n-BuLi) of the dissolution of 2.1 equivalents in hexane thereto, and will Gains are stirred at room temperature 1 hour.The 1M trimethyl ammonia chloride of 3 equivalents being dissolved in THF is disposably introduced into the solution Tin, and gains are stirred 2 hours.Water is poured into the solution, gains are extracted twice with ether, are washed twice with water, And use magnesium sulfate (MgSO₄) remove remaining water.Remaining solution is vacuumized to remove solvent, and with ethyl alcohol recrystallization with Obtain the chemical formula M-1 of pale yellow crystals form.(yield: 60%)

(6) synthesis of polymer 1

Use chlorobenzene as solvent by the monomer and Pd of chemical formula K-1, L and M-1 for synthesizing above₂(dba)₃With P (adjacent first Phenyl)₃It is concomitantly introduced into, and is polymerize using microwave reactor to prepare following polymer 1.Passing through gel permeation chromatography (GPC) when the polymer 1 of analysis preparation, number-average molecular weight (Mn) is 59,800g/mol, and weight average molecular weight (Mw) is 70,330g/ Mol, HOMO and lumo energy are respectively 5.3 and 3.45, and the edge UV is 670nm.

[polymer 1]

The synthesis of 2. polymer 2 of preparation example

Polymer 2 is prepared in a manner of identical with preparation example 1, the difference is that using following compound as preparation Reactant in (4) of example 1.In the polymer 2 prepared by gpc analysis, number-average molecular weight (Mn) is 49,200g/mol, Weight average molecular weight (Mw) is 65,980g/mol, HOMO and lumo energy is respectively 5.31 and 3.46, and the edge UV is 671nm.

[polymer 2]

The synthesis of 3. polymer 3 of preparation example

Polymer 3 is prepared in a manner of identical with preparation example 2, the difference is that using C₈H₁₇Br replaces preparation example 2 (3) in C₁₂H₂₅Br.In the polymer 3 prepared by gpc analysis, number-average molecular weight (Mn) is 54,670g/mol, weight Average molecular weight (Mw) is 68,990g/mol, HOMO and lumo energy is respectively 5.31 and 3.46, and the edge UV is 670nm.

[polymer 3]

The synthesis of 4. polymer 4 of preparation example

Polymer 4 is prepared in a manner of identical with preparation example 1, the difference is that usingInstead of preparation C in (3) of example 1₁₂H₂₅Br, and use following compound as the reactant in (4) of preparation example 1.Passing through GPC points When analysing the polymer 4 of preparation, number-average molecular weight (Mn) is 59,800g/mol, and weight average molecular weight (Mw) is 70,330g/mol, HOMO and lumo energy are respectively 5.3 and 3.45, and the edge UV is 670nm.

[polymer 4]

The synthesis of 5. polymer 5 of preparation example

Polymer 5 is prepared in a manner of identical with preparation example 1, the difference is that usingInstead of preparation C in (3) of example 1₁₂H₂₅Br.In the polymer 5 prepared by gpc analysis, number-average molecular weight (Mn) is 46,240g/mol, Weight average molecular weight (Mw) is 62,380g/mol, HOMO and lumo energy is respectively 5.32 and 3.46, and the edge UV is 667nm.

[polymer 5]

The synthesis of 6. polymer 6 of preparation example

(1) synthesis of chemical formula N

Based on Polymer Bulletin, volume 2017,74, the 7th phase, the change of the synthesis chemical formula N of page 2755 to 2766 Close object.

Polymer 6 is prepared in a manner of identical with preparation example 1, the difference is that replacing chemical formula using chemical formula N L.In the polymer 6 prepared by gpc analysis, number-average molecular weight (Mn) is 38,290g/mol, and weight average molecular weight (Mw) is 55,240g/mol, HOMO and lumo energy are respectively 5.3 and 3.45, and the edge UV is 670nm.

[polymer 6]

The synthesis of 7. polymer 7 of preparation example

Based on J.Am.Chem.Soc.2011,133, the compound of the synthesis chemical formula M of page 4625 to 4631.

Polymer 7 is prepared in a manner of identical with preparation example 1, the difference is that replacing chemical formula using chemical formula M L.In the polymer 7 prepared by gpc analysis, number-average molecular weight (Mn) is 35,960g/mol, and weight average molecular weight (Mw) is 44,510g/mol, HOMO and lumo energy are respectively 5.29 and 3.42, and the edge UV is 663nm.

[polymer 7]

The synthesis of 8. polymer 8 of preparation example

It usesInstead of in preparation example 1To prepare following polymer 8.Passing through gpc analysis When the polymer 8 of preparation, number-average molecular weight (Mn) is 28,850g/mol, and weight average molecular weight (Mw) is that 51,350g/mol, PDI is 1.78, HOMO and lumo energy be respectively 5.31 and 3.46, the edge UV is 672nm.

<embodiment: the manufacture of organic solar batteries>