阅读说明：本技术 用于电子和光子应用的垂直苯并二噻吩基给体-受体聚合物 (The vertical benzene thiophene base donor-receiver polymer applied for electronics and photon ) 是由 颜河 陈尚尚 于 2018-04-25 设计创作，主要内容包括：本文提供了给体-受体共轭的垂直苯并二噻吩基聚合物、它们的制备方法和其中使用的中间体、含有这样的聚合物的制剂用于制备有机电子器件例如有机光伏器件和有机场效应晶体管器件中的半导体的用途以及由这些制剂制成的OE器件和OPV器件。(The purposes for being used to prepare the semiconductor in organic electronic device such as organic photovoltaic devices and organic field effect tube device there is provided herein vertical benzene thiophene based polyalcohol, their preparation method and the intermediate used in it of donor-receiver conjugation, the preparation containing such polymer and OE device and OPV device made of these preparations.)

1. a kind of donor-receiver conjugated polymer, it includes one or more repetitive units, the repetitive unit includes formula 1 Repetitive unit:

Wherein R₁Selected from by H, F, Cl, Br, I or CN, (C₁-C₄₀) straight chained alkyl, (C₃-C₄₀) branched alkyl and (C₃-C₄₀) naphthenic base The group of composition, wherein one or more non-conterminous C atoms are optionally by-O- ,-S- ,-C (O)-,-C (O)-O- ,-O-C (O)-、-O-C(O)-O-、-CR⁰=CR⁰⁰Or-C ≡ C- displacement, wherein R⁰And R⁰⁰Be independently straight chained alkyl, branched alkyl or Naphthenic base, and wherein one or more H atoms are optionally replaced by F, Cl, Br, I or CN；Or R₁It is aryl, heteroaryl, virtue Oxygroup, heteroaryloxy, aryl carbonyl, Heteroarylcarbonyl, aryl carbonyl epoxide, Heteroarylcarbonyl oxygroup, aryloxycarbonyl or miscellaneous Aryloxy carbonyl has 5 to 30 annular atoms；And

R₂It is-CH₂CH(R₃)(R₄), wherein R₃And R₄It is independently C₁-C₂₀Alkyl.

2. donor-receiver conjugated polymer according to claim 1, wherein R₂It is selected from:

3. donor-receiver conjugated polymer according to claim 1, wherein R₁It is H, F, Cl, Br, I, CN, (C₁-C₄₀) straight Alkyl group, (C₃-C₄₀) branched alkyl and (C₃-C₄₀) naphthenic base, aryl or heteroaryl.

4. donor-receiver conjugated polymer according to claim 1, wherein R₁It is H, aryl or heteroaryl.

5. donor-receiver conjugated polymer according to claim 1, wherein repetition of the repetitive unit of the formula 1 by formula 2 Unit indicates:

Wherein Ar is selected from the group being made of the following terms:

Wherein each R is independently selected from by (C₁-C₄₀) straight chained alkyl, (C₃-C₄₀) branched alkyl and (C₃-C₄₀) naphthenic base composition Group, wherein one or more non-conterminous C atoms are optionally by-O- ,-S- ,-C (O)-,-C (O)-O- ,-O-C (O)-,-O-C (O)-O-、-CR⁰=CR⁰⁰Or-C ≡ C- displacement, wherein R⁰And R⁰⁰It is independently straight chained alkyl, branched alkyl or naphthenic base, and And wherein one or more H atoms are optionally replaced by F, Cl, Br, I or CN；Or R is aryl, heteroaryl, aryloxy group, heteroaryl oxygen Base, aryl carbonyl, Heteroarylcarbonyl, aryl carbonyl epoxide, Heteroarylcarbonyl oxygroup, aryloxycarbonyl or heteroaryl oxygen carbonyl, With 4 to 30 annular atoms；And

R₂Selected from the group being made of the following terms:

6. donor-receiver conjugated polymer according to claim 5, wherein R₁It is H, aryl or heteroaryl.

7. donor-receiver conjugated polymer according to claim 6, wherein the conjugation donor-receiver polymer is flat Average molecular weight is in about 10,000kDa to the range of about 100,000kDa.

8. donor-receiver conjugated polymer according to claim 7, wherein the donor-receiver conjugated polymer is molten The peak optical absorption spectrum that liquid shows under membrane stage red shift at least 80nm compared with the solution state.

9. donor-receiver conjugated polymer according to claim 7, it is further characterized in that the donor-receiver is total Conjugated polymer has 2.05eV or lower optical band gap.

10. donor-receiver conjugated polymer according to claim 6, wherein the donor-receiver conjugated polymer is selected from The group being made of the following terms:

Wherein m is the integer selected from 5 to 100.

11. a kind of composition, it includes at least one of fullerene acceptors and non-fullerene acceptor；According to claim 1 The donor-receiver conjugated polymer.

12. composition according to claim 11, wherein the fullerene acceptor is selected from the group being made of the following terms:

Wherein

Each n is 1,2,4,5 or 6；

Each Ar independently selected from by monocyclic aryl, bicyclic aryl, polyaromatic and bicyclic heteroaryl, bicyclic heteroaryl and The group of polyheteroaromatic composition, wherein each Ar can contain 1 to 5 aryl or heteroaryl, wherein each institute Stating aryl or heteroaryl can condense or connect；

Each R^xIndependently selected from by Ar, (C₁-C₄₀) straight chained alkyl, (C₃-C₄₀) branched alkyl and (C₃-C₄₀) naphthenic base composition Group, wherein one or more non-conterminous C atoms are optionally by-O- ,-S- ,-C (O)-,-C (O-)-O- ,-O-C (O)-,-O- C(O)-O-、-CR⁰=CR⁰⁰Or-C ≡ C- displacement, wherein R⁰And R⁰⁰It is independently straight chained alkyl, branched alkyl or naphthenic base, and And wherein one or more H atoms are optionally replaced by F, Cl, Br, I or CN；Or R^xIt is aryl, heteroaryl, aryloxy group, heteroaryl Oxygroup, aryl carbonyl, Heteroarylcarbonyl, aryl-carbonyl oxygen, Heteroarylcarbonyl oxygroup, aryloxycarbonyl or heteroaryl oxygen carbonyl, With 4 to 30 annular atoms；

Each R¹Selected from by (C₁-C₄₀) straight chained alkyl, (C₃-C₄₀) branched alkyl and (C₃-C₄₀) naphthenic base composition group, wherein One or more non-conterminous C atoms optionally by-O- ,-S- ,-C (O)-,-C (O)-O- ,-O-C (O)-,-O-C (O)-O- ,- CR⁰=CR⁰⁰Or-C ≡ C- displacement, and wherein one or more H atoms are optionally replaced by F, Cl, Br, I or CN；Or R¹It is Aryl, heteroaryl, aryloxy group, heteroaryloxy, aryl carbonyl, Heteroarylcarbonyl, aryl-carbonyl oxygen, Heteroarylcarbonyl oxygroup, virtue Epoxide carbonyl or heteroaryl oxygen carbonyl have 4 to 30 annular atoms, unsubstituted or taken by one or more nonaromatics Generation, wherein R¹The carbon number contained is greater than 1, wherein R⁰And R⁰⁰It is independently straight chained alkyl, branched alkyl or naphthenic base；

Each Ar¹Independently selected from the group being made of bicyclic heteroaryl, bicyclic heteroaryl and polyheteroaromatic, wherein each Ar¹1 to 5 heteroaryl can be contained, wherein each described heteroaryl can be condensed or be connected；

Each Ar²Independently selected from the aryl contained more than 6 atoms in addition to H；And the fullerene ball expression is selected from By C₆₀Fullerene, C₇₀Fullerene and C₈₄The fullerene of the group of fullerene composition.

13. composition according to claim 11, wherein the non-lipid alkene receptor of strangling is selected from the group being made of the following terms:

Each R₅Independently selected from by Ar, (C₁-C₄₀) straight chained alkyl, (C₃-C₄₀) branched alkyl and (C₃-C₄₀) naphthenic base composition Group, wherein one or more non-conterminous C atoms are optionally by-O- ,-S- ,-C (O)-,-C (O)-O- ,-O-C (O)-,-O-C (O)-O-、-CR⁰=CR⁰⁰Or-C ≡ C- displacement, wherein one or more H atoms are optionally replaced by F, Cl, Br, I or CN, and And wherein R⁰And R⁰⁰It is independently straight chained alkyl, branched alkyl or naphthenic base；Or each R₅Be independently aryl, heteroaryl, Aryloxy group, heteroaryloxy, aryl carbonyl, Heteroarylcarbonyl, aryl-carbonyl oxygen, Heteroarylcarbonyl oxygroup, aryloxycarbonyl or miscellaneous Aryloxy carbonyl has 4 to 30 annular atoms.

14. composition according to claim 11, wherein there is the composition power of about 5.9% to about 12% to convert Efficiency.

15. composition according to claim 11, wherein the non-lipid alkene receptor of strangling is selected from the group being made of the following terms:

Wherein each R₆It is (C₁-C₁₄) alkyl；

R₇It is-CH₂CH(R₉)(R₁₀), wherein R₉And R₁₀It is independently (C₁-C₂₀) alkyl；And

R₈It is (C₁-C₁₄) alkyl.

16. composition according to claim 15, wherein R₁It is H, F, Cl, Br, I, CN, (C₁-C₄₀) straight chained alkyl, (C₃- C₄₀) branched alkyl, (C₃-C₄₀) naphthenic base, aryl or heteroaryl.

17. composition according to claim 11, wherein the donor-receiver conjugated polymer is selected from by the following terms group At group:

And

The non-fullerene acceptor is selected from the group being made of the following terms:

Wherein m is the integer selected from 5 to 100.

18. a kind of organic electronic (OE) device, it includes compositions according to claim 11.

19. OE device according to claim 18, it is characterised in that the OE device is organic field effect tube (OFET) device or organic photovoltaic (OPV) device.

20. OE device according to claim 19, wherein the OPV device has the power of about 5.9% to about 11.2% Transfer efficiency.

Technical field

This disclosure relates to donor-receiver conjugated polymer, their preparation method and intermediate used in it, contain this The composition of a little polymer is used to prepare organic electronic (OE) device, such as organic photovoltaic (OPV) device and organic effect crystalline substance The purposes of semiconductor in body pipe (OFET) device and OE device and OPV device made of these preparations.

Background technique

In recent years, to will include that the organic semiconductor of conjugated polymer is used for various electronic application devices and has increasingly closed Note.

The field of one special attention is the development of organic photovoltaic devices (OPV).Organic semiconductor (OSC) can be used for OPV In, this is because they allow to manufacture device such as spin coating and printing by solution processing technology.With for manufacturing inorganic thin film The evaporation technique of device is compared, and solution processing can be economically and in more extensive upper progress.

Be usually used in polymer in polymer solar battery usually by electron comonomer unit (donor or D) and by Electronics comonomer unit (receptor or A) composition.It is convenient to use such D-A alternate copolymer strategy is had The polymer of low optical band gap, this is because highest occupied molecular orbital (HOMO) energy level of the polymer is normally at donor On unit and lowest unoccupied molecular orbital (LUMO) energy level is normally in receptor unit.By generally connecing for the exploitations such as Brabec The model received shows the HOMO energy level carefully selected and the basic demand that lumo energy is high-performance polymer solar battery, This is because open-circuit voltage (the V of polymer solar battery_oc) be by polymer HOMO energy level and receptor lumo energy it Between difference determine.HOMO/HOMO or LUMO/LUMO offset between donor and receptor, which should be small enough to, makes V_ocLoss subtracts To bottom line.By modifying donor monomer with electron donating group or electron-withdrawing group, D-A polymer can be effectively adjusted HOMO energy level, while it is also possible that doing to adjust lumo energy by modified receptor unit.

In order to realize higher V_OCAnd reduce energy loss, it is important that it is novel to construct to probe into new building block Conjugated polymer.In the design of donor polymer, benzene thiophene (BDT) unit is common building block, and By developing a series of BDT units being wherein incorporated to different substituent groups.In general, the position α via thiophene connects BDT unit Into main polymer chain.It is also possible to BDT unit is connected in main polymer chain via the vacancy on phenyl, such as so-called Vertical BDT unit (vBDT).However, such thiophene-vBDT- thienyl donor polymer may show bad performance. Therefore, it is necessary to develop the new donor polymer containing vBDT with improved characteristic.

Summary of the invention

There is provided herein the donor-receiver conjugated polymers with significantly improved performance.The donor-receiver conjugation is poly- The repetitive unit that object includes the thiophene of-vBDT- containing thiophene is closed, strong temperature dependency aggregation properties, relatively wide light are shown Band gap is learned, and can realize the advantageous form with high charge mobility in the OSC of formation.

In the first aspect, there is provided herein a kind of donor-receiver conjugated polymers, repeat list it includes one or more Member, the repetitive unit include the repetitive unit of formula 1:

Wherein R₁Selected from by H, F, Cl, Br, I or CN, (C₁-C₄₀) straight chained alkyl, (C₃-C₄₀) branched alkyl and (C₃-C₄₀) The group of naphthenic base composition, wherein one or more non-conterminous C atoms are optionally by-O- ,-S- ,-C (O)-,-C (O)-O- ,-O- C(O)-、-O-C(O)-O-、-CR⁰=CR⁰⁰Or-C ≡ C- displacement, wherein R⁰And R⁰⁰Be independently straight chained alkyl, branched alkyl or Naphthenic base, and wherein one or more H atoms are optionally replaced by F, Cl, Br, I or CN；Or R₁It is aryl, heteroaryl, virtue Oxygroup, heteroaryloxy, aryl carbonyl, Heteroarylcarbonyl, aryl carbonyl epoxide, Heteroarylcarbonyl oxygroup, aryloxycarbonyl or miscellaneous Aryloxy carbonyl has 5 to 30 annular atoms；And

R₂It is-CH₂CH(R₃)(R₄), wherein R₃And R₄It is independently C₁-C₂₀Alkyl.

In first embodiment in the first aspect, there is provided herein the donor-receiver conjugated polymers of first aspect Object, wherein R₂It is selected from:

In the second embodiment in the first aspect, there is provided herein the donor-receiver conjugated polymers of first aspect Object, wherein R₁It is H, F, Cl, Br, I, CN, (C₁-C₄₀) straight chained alkyl, (C₃-C₄₀) branched alkyl and (C₃-C₄₀) naphthenic base, aryl Or heteroaryl.

In third embodiment in the first aspect, there is provided herein the donor-receiver conjugated polymers of first aspect Object, wherein R₁It is H, aryl or heteroaryl.

In the 4th embodiment in the first aspect, there is provided herein the donor-receiver conjugated polymers of first aspect Object, wherein the repetitive unit of formula 1 is indicated by the repetitive unit of formula 2:

Wherein Ar is selected from the group being made of the following terms:

Wherein each R is independently selected from by (C₁-C₄₀) straight chained alkyl, (C₃-C₄₀) branched alkyl and (C₃-C₄₀) naphthenic base The group of composition, wherein one or more non-conterminous C atoms are optionally by-O- ,-S- ,-C (O)-,-C (O)-O- ,-O-C (O)-、-O-C(O)-O-、-CR⁰=CR⁰⁰Or-C ≡ C- displacement, wherein R⁰And R⁰⁰Be independently straight chained alkyl, branched alkyl or Naphthenic base, and wherein one or more H atoms are optionally replaced by F, Cl, Br, I or CN；Or R is aryl, heteroaryl, fragrant oxygen Base, heteroaryloxy, aryl carbonyl, Heteroarylcarbonyl, aryl carbonyl epoxide, Heteroarylcarbonyl oxygroup, aryloxycarbonyl or heteroaryl Oxygen carbonyl has 4 to 30 annular atoms；And

R₂Selected from the group being made of the following terms:

In the 5th embodiment in the first aspect, there is provided herein giving for the 4th embodiment of first aspect Body-receptor conjugate polymer, wherein R₁It is H, aryl or heteroaryl.

In the 6th embodiment in the first aspect, there is provided herein giving for the 5th embodiment of first aspect Body-receptor conjugate polymer, wherein the average molecular weight of the conjugation donor-receiver polymer is in about 10,000kDa to about The range of 100,000kDa.

In the 7th embodiment in the first aspect, there is provided herein giving for the 6th embodiment of first aspect Body-receptor conjugate polymer, wherein the solution of the donor-receiver conjugated polymer is absorbed in the peak optical that membrane stage shows Spectrum at least 80nm than solution state red shift.

In the 8th embodiment in the first aspect, there is provided herein giving for the 6th embodiment of first aspect Body-receptor conjugate polymer, it is further characterized in that the donor-receiver conjugated polymer has 2.05eV or lower light Learn band gap.

In the 9th embodiment in the first aspect, there is provided herein giving for the 5th embodiment of first aspect Body-receptor conjugate polymer, wherein the donor-receiver conjugated polymer is selected from the group being made of the following terms:

Wherein m is the integer selected from 5 to 100.

In the second aspect, there is provided herein a kind of compositions, and it includes in fullerene acceptor and non-fullerene acceptor It is at least one；With the donor-receiver conjugated polymer of first aspect.

In first embodiment in the second aspect, there is provided herein the compositions of the second aspect, wherein the richness It strangles alkene receptor and is selected from the group being made of the following terms:

Wherein each n is 1,2,4,5 or 6；

Each Ar is independently selected from by monocyclic aryl, bicyclic aryl, polyaromatic and bicyclic heteroaryl, bicyclic heteroaryl The group of base and polyheteroaromatic composition, wherein each Ar can contain 1 to 5 aryl or heteroaryl, wherein described Each of the aryl or heteroaryl can be condensed or be connected；

Each R^xIndependently selected from by Ar, (C₁-C₄₀) straight chained alkyl, (C₃-C₄₀) branched alkyl and (C₃-C₄₀) naphthenic base The group of composition, wherein one or more non-conterminous C atoms are optionally by-O- ,-S- ,-C (O)-,-C (O-)-O- ,-O-C (O)-、-O-C(O)-O-、-CR⁰=CR⁰⁰Or-C ≡ C- displacement, wherein R⁰And R⁰⁰Be independently straight chained alkyl, branched alkyl or Naphthenic base, and wherein one or more H atoms are optionally replaced by F, Cl, Br, I or CN；Or R^xIt is aryl, heteroaryl, virtue Oxygroup, heteroaryloxy, aryl carbonyl, Heteroarylcarbonyl, aryl-carbonyl oxygen, Heteroarylcarbonyl oxygroup, aryloxycarbonyl or heteroaryl Oxygen carbonyl has 4 to 30 annular atoms；

Each R¹Selected from by (C₁-C₄₀) straight chained alkyl, (C₃-C₄₀) branched alkyl and (C₃-C₄₀) naphthenic base composition group, Wherein one or more non-conterminous C atoms are optionally by-O- ,-S- ,-C (O)-,-C (O)-O- ,-O-C (O)-,-O-C (O)- O-、-CR⁰=CR⁰⁰Or-C ≡ C- displacement, and wherein one or more H atoms are optionally replaced by F, Cl, Br, I or CN；Or R¹It is aryl, heteroaryl, aryloxy group, heteroaryloxy, aryl carbonyl, Heteroarylcarbonyl, aryl-carbonyl oxygen, Heteroarylcarbonyl oxygen Base, aryloxycarbonyl or heteroaryl oxygen carbonyl have 4 to 30 annular atoms, unsubstituted or non-aromatic by one or more Group replaces, wherein R¹The carbon number contained is greater than 1, wherein R⁰And R⁰⁰It is independently straight chained alkyl, branched alkyl or naphthenic base；

Each Ar¹Independently selected from the group being made of bicyclic heteroaryl, bicyclic heteroaryl and polyheteroaromatic, wherein often One Ar¹1 to 5 heteroaryl can be contained, wherein each can condense or connect；

Each Ar²Independently selected from the aryl contained more than 6 atoms in addition to H；And the fullerene ball table Show selected from by C₆₀Fullerene, C₇₀Fullerene and C₈₄The fullerene of the group of fullerene composition.

In the second embodiment in the second aspect, there is provided herein the compositions of the second aspect, wherein described non- Fullerene acceptor is selected from the group being made of the following terms:

Each R₅Independently selected from by Ar, (C₁-C₄₀) straight chained alkyl, (C₃-C₄₀) branched alkyl and (C₃-C₄₀) naphthenic base The group of composition, wherein one or more non-conterminous C atoms are optionally by-O- ,-S- ,-C (O)-,-C (O)-O- ,-O-C (O)-、-O-C(O)-O-、-CR⁰=CR⁰⁰Or-C ≡ C- displacement, wherein one or more H atoms optionally by F, Cl, Br, I or CN displacement, and wherein R⁰And R⁰⁰It is independently straight chained alkyl, branched alkyl or naphthenic base；Or each R₅It is independently virtue Base, heteroaryl, aryloxy group, heteroaryloxy, aryl carbonyl, Heteroarylcarbonyl, aryl-carbonyl oxygen, Heteroarylcarbonyl oxygroup, fragrant oxygen Base carbonyl or heteroaryl oxygen carbonyl have 4 to 30 annular atoms.

In third embodiment in the second aspect, there is provided herein the compositions of the second aspect, wherein described group Close the power conversion efficiency that object has about 5.9% to about 12%.

In the 4th embodiment in the second aspect, there is provided herein the compositions of the second aspect, wherein described non- Fullerene acceptor is selected from the group being made of the following terms:

Wherein each R₆It is (C₁-C₁₄) alkyl；

R₇It is-CH₂CH(R₉)(R₁₀), wherein R₉And R₁₀It is independently (C₁-C₂₀) alkyl；And R₈It is (C₁-C₁₄) alkyl.

In the 5th embodiment in the second aspect, there is provided herein the combinations of the 4th embodiment of the second aspect Object, wherein R₁It is H, F, Cl, Br, I, CN, (C₁-C₄₀) straight chained alkyl, (C₃-C₄₀) branched alkyl, (C₃-C₄₀) naphthenic base, aryl Or heteroaryl.

In the 6th embodiment in the second aspect, there is provided herein the compositions of the second aspect, wherein described give Body-receptor conjugate polymer is selected from the group being made of the following terms:

And

The non-fullerene acceptor is selected from the group being made of the following terms:

Wherein m is the integer selected from 5 to 100.

In the third aspect, there is provided herein a kind of organic electronic (OE) device, it includes the compositions of the second aspect.

In first embodiment in the third aspect, there is provided herein the OE devices in terms of third, it is characterised in that The OE device is organic field effect tube (OFET) device or organic photovoltaic (OPV) device.

In the second embodiment in the third aspect, there is provided herein the OE devices of the first embodiment in terms of third Part, wherein the OPV device has the power conversion efficiency of about 5.9% to about 11.2%.

Subject of the present invention further relates to composition as described herein as coating or printing ink, is especially used to prepare The purposes of OE device and rigidity or flexible organic photovoltaic (OPV) battery and device.

Subject of the present invention further relates to a kind of OE device, is prepared by composition as described herein.Consider in this respect OE device include but is not limited to organic field effect tube (OFET), integrated circuit (IC), thin film transistor (TFT) (TFT), radio frequency Identify (RFID) label, Organic Light Emitting Diode (OLED), organic light-emitting transistor (OLET), electroluminescent display, organic Photovoltaic (OPV) battery, flexibility OPV and O-SC, organic laser diode (O-shaped laser), has organic solar batteries (O-SC) Machine integrated circuit (O-IC), illuminating device, sensor component, electrode material, photoconductor, photoelectric detector, electrofax note Record device, capacitor, electric charge injection layer, Schottky diode, planarization layer, antistatic film, conductive substrates, conductive pattern, light Electric conductor, electrophotographic device, organic memory device, biosensor and biochip.

It was found that disclosed donor-receiver conjugated polymer shows good machinability and Gao Rong in organic solvent Xie Du, and it is therefore particularly suitable for the large-scale production using Solution processing techniques.Meanwhile they show low band gaps, height It is charge carrier mobility, the high external quantum efficiency in BHJ solar battery, good when being combined with more than 12 kinds fullerenes Good form, and be for organic electronic OE device, especially for before the having of the OPV device with high power conversion efficiency The material on way.

Composition, method and the device of the disclosure provide surprising improvement in terms of the efficiency of OE device and its production. It is surprising that performance, service life and the efficiency of the OE device prepared using donor-receiver conjugated polymer as described herein can To be significantly increased.In addition, composition as described herein provides surprising high film forming level.Especially it is possible to improve film Uniformity and quality.In addition to this, subject of the present invention also allows for realizing OE device, and especially OPV device is better Solution printing.

Detailed description of the invention

When being combined with attached drawing, according to following invention description, above and other object and feature of the disclosure It will become obvious, in the drawing:

Fig. 1 depicts PvBDTTAZ film and PvBDTTAZ solution (in chlorobenzene 0.04mg mL^-1) 20 DEG C and 100 DEG C with And the UV-Vis absorption spectrum under form of film.

Fig. 2 depicts the UV-Vis absorption spectrum of PvBDTTAZ-Th film and PvBDTffBT-Th film.

Fig. 3 depicts FeCp₂ ^0/+With the cyclic voltammogram of PvBDTTAZ.

Fig. 4 depicts the current density voltage curve of exemplary PvBDTTAZ:O-IDTBR solar battery.

Fig. 5 depicts external quantum efficiency (EQE) curve of exemplary PvBDTTAZ:O-IDTBR solar battery.

It will be appreciated that attached drawing as described herein is for illustration purposes only.It is described that the drawings are not necessarily drawn to scale, and Emphasis is generally placed upon in the principle for illustrating this introduction.The attached drawing is not intended to limit the range of this introduction in any way.

Specific embodiment

Definition

In entire the application, it is described as having in composition including or in the case where comprising specific components or in side Method be described as having including or comprising specified method steps in the case where, consider that the composition of this introduction can also be substantially It is grouped as by described group or is grouped as by described group, and the method for this introduction can also be substantially made of the method step Or it is made of the method step.

In this application, being referred to as in element or component includes in the inventory of the element or component and/or selected from institute In the case where the inventory for stating element or component, it should be understood that, the element or component can be in the element or component Either one or two of or the element or component can be selected from by two or more groups formed in the element or component.This Outside, it should be understood that, in the case where not departing from the spirit and scope of this introduction, composition, device or side as described herein The element and/or feature of method can combine in many ways, no matter be herein defined as specific or implicit.

Unless specifically stated otherwise, otherwise term " including (include) ", " including (includes) ", " including (including) ", " with (have) ", the use of " with (has) " or " with (having) " generally should be understood as be It is open and unrestricted.

Unless specifically stated otherwise, otherwise the use of odd number includes plural (vice versa) herein.In addition, in term " about " in the case that use is before quantitative values, unless specifically stated otherwise, otherwise this introduction further includes described specific quantitative Value itself.Unless otherwise specified or infer, otherwise term " about " as used herein refer to relative to nominal value change ± 10%.

It will be appreciated that the sequence of step or the sequence for executing certain movements are unessential, as long as this introduction is still It can operate.Furthermore, it is possible to carry out two or more steps or movement simultaneously.

" p-type semiconductor material " or " donor " material is referred to hole as most electric currents or electricity as used herein The semiconductor material of charge carrier, such as organic semiconducting materials.In some embodiments, when p-type semiconductor material deposits When on substrate, it can be provided more than about 10^-5cm²The hole mobility of/Vs.In the case where scene effect device, p-type is partly led Body can also show greater than about 10 electric current on/off ratio.

" n-type semiconductor " or " receptor " material is referred to electronics as most electric currents or electricity as used herein The semiconductor material of charge carrier, such as organic semiconducting materials.In some embodiments, when n-type semiconductor deposits When on substrate, it can be provided more than about 10^-5cm²The electron mobility of/Vs.In the case where scene effect device, N-shaped is partly led Body can also show greater than about 10 electric current on/off ratio.

" mobility " refers to electric charge carrier, such as sky in the case where p-type semiconductor material as used herein Cave (or unit of positive charge) and electronics (or unit of negative electrical charge) in the case where n-type semiconductor are in the influence of electric field Under move through material speed measurement.The parameter depends on device architectures, and fieldtron or space charge can be used Current measurement is limited to measure.

As used herein, when the transistor comprising compound as its semiconductor material is exposed to ring in the compound Border condition, for example, air, environment temperature and humidity for a period of time when show to maintain the current-carrying of about its initial measurement When transport factor, the compound is considered " ambient stable " or " stable at ambient conditions ".For example, If the transistor comprising compound is being exposed to 3 days, the 5 days or 10 day time of environmental condition including air, humidity and temperature Show that the initial value variation relative to it is no more than 20% or the carrier mobility no more than 10% later, then describedization Ambient stable can be described as by closing object.

Fill factor (FF) as used herein is that practical maximum can get power (Pm or Vmp × Jmp) and theory (can not It is practical to obtain) ratio (being given as percentages) of power (Jsc × Voc).Therefore, FF can be used following formula and determine:

FF=(Vmp × Jmp)/(Jsc × Voc)

Wherein Jmp and Vmp is illustrated respectively in current density and voltage at maximum power point (Pm), which is to pass through change What the resistance in circuit obtained until J × V is in its maximum value；And Jsc and Voc respectively indicate short circuit current and Open-circuit voltage.Fill factor is to evaluate the key parameter of the performance of solar battery.Commercially available solar battery usually has about 0.60% or bigger fill factor.

Open-circuit voltage (Voc) as used herein is in no connection external loading between the anode and cathode of device Potential difference.

The power conversion efficiency (PCE) of solar battery as used herein is the power that electric energy is converted into from absorption light Percentage.The PCE of solar battery can by with maximum power point (Pm) divided by the input at standard test condition (STC) Light irradiance (E, with W/m²For unit) and solar battery surface area (Ac, with m²For unit) it calculates.What STC was often referred to It is 25 DEG C of temperature and 1000W/m²Irradiation level, air quality is 1.5 (AM 1.5) spectrum.

As used herein, it can be absorbed photon generates photoelectric current to generate exciton as fruit component (such as film layer) contains One or more compounds, then the component is considered " photosensitive ".

" solution processable " refers to can be used in various solution phase process as used herein compound (such as Polymer), material or composition, the technique include spin coating, printing (such as ink jet printing, intaglio printing, hectographic printing etc.), Spraying, electrospray, drop coating, dip-coating, blade coating etc..

" semi-crystalline polymer " refers to working as warp when cooling or when depositing from solution from molten state as used herein When by the dynamics advantage such as Slow cooling or low evaporation rate of solvent, there is the inherent tendency at least partly crystallized Polymer.Its crystallize or lack can easily by using several analysis methods, such as differential scanning calorimetry (DSC) and/ Or X-ray diffraction (XRD) Lai Jianding.

It " anneals " as used herein and refers to sinking in the environment or under decompression/pressurization to semi-crystalline polymer film Duration of the heat treatment more than 100 seconds after product, and " annealing temperature " refers to that polymer film is sudden and violent during the annealing process At least 60 seconds maximum temperatures of dew.It is not intended to be bound to any particular theory, it is believed that in the conceived case, annealing can draw The increase for playing crystallinity in polymer film, to increase field-effect mobility.The increase of crystallinity can by several method come Monitoring, such as by comparing the measurement of the differential scanning calorimetry (DSC) or X-ray diffraction (XRD) of deposited film and annealed state film Value.

" polymerizable compound " (or " polymer ") refers to including by the more of covalent chemical key connection as used herein The molecule of a one or more repetitive units.Polymerizable compound can be indicated by general formula I:

*-(-(Ma)_x-(Mb)_y-)_z*

General formula I

Wherein each Ma and Mb is repetitive unit or monomer.The polymerizable compound can only have a type of heavy The different repeat units of multiple unit and two or more seed types.When polymerizable compound only has a type of repetitive unit When, it can be referred to as homopolymer.When polymerizable compound has the different repeat units of two or more seed types, can make It is replaced with term " copolymer " or " copolymerization ".For example, copolymerization may include repetitive unit, wherein Ma and Mb indicates two different repetitive units.Unless otherwise stated, the assembling of repeating unit of copolymer can be head to tail, Head to head or tail is to tail.In addition, unless otherwise stated, copolymer can be random copolymer, alternate copolymer or block Copolymer.For example, general formula I can be used to indicate that the Mb's of the Ma and y molar fraction in the copolymer with x molar fraction The copolymer of Ma and Mb, wherein the duplicate mode of comonomer Ma and Mb can be alternate, random, that region is random, area Domain is regular or block, wherein there are most z comonomers.Other than its composition, polymerizable compound can also lead to Cross it the degree of polymerization (n) and molal weight (such as number-average molecular weight (M) and/or weight average molecular weight (Mw), depend on it is a kind of or A variety of measuring techniques) further characterization.

" halogen " or " halogen " refers to fluorine, chlorine, bromine and iodine as used herein.

" alkyl " refers to linear chain or branched chain saturated hydrocarbyl as used herein.The example of alkyl includes methyl (Me), second Base (Et), propyl (such as n-propyl and isopropyl), butyl (such as normal-butyl, isobutyl group, sec-butyl, tert-butyl), amyl (example Such as n-pentyl, isopentyl, neopentyl, tertiary pentyl), hexyl.In various embodiments, alkyl can have 1 to 40 Carbon atom (i.e. C₁-C₄₀Alkyl), such as 1-30 carbon atom (i.e. C₁-C₃₀Alkyl).In some embodiments, alkyl can be with With 1 to 6 carbon atom, and " low alkyl group " can be referred to as.The example of low alkyl group includes methyl, ethyl, propyl (such as n-propyl and isopropyl) and butyl (such as normal-butyl, isobutyl group, sec-butyl, tert-butyl).In some embodiments In, alkyl can be substituted as described herein.Alkyl is not replaced generally by other alkyl, alkenyl or alkynyl.

" alkenyl " refers to the linear or branched alkyl group with one or more carbon-carbon double bonds as used herein.Alkenyl Example includes vinyl, acrylic, cyclobutenyl, pentenyl, hexenyl, butadienyl, pentadienyl, hexadienyl etc..It is described One or more carbon-carbon double bonds can be internal (such as in 2- butylene) or end (such as in 1- butylene).In various embodiment party In case, alkenyl can have 2 to 40 carbon atom (i.e. C₂-C₄₀Alkenyl), such as 2 to 20 carbon atom (i.e. C₂-C₂₀Alkene Base).In some embodiments, alkenyl can be substituted as described herein.Alkenyl is not generally by other alkenyl, alkyl or alkynes Base replaces.

" condensed ring " or " fused moiety " refers to the polycyclic system at least two rings as used herein, wherein the ring At least one of be aromatics and such aromatic ring (carbocyclic ring or heterocycle) at least one can be aromatics or it is non-aromatic and Other rings of carbocyclic ring or heterocycle have common key.These polycyclic systems can be height p- conjugation and as described herein optional It is substituted.

As used herein " hetero atom " refer to any element in addition to carbon or hydrogen atom and including such as nitrogen, Oxygen, silicon, sulphur, phosphorus and selenium.

" aryl " refers to aromatic monocyclic hydrocarbon ring system or polycyclic system as used herein, in polycyclic system two or more Aromatic hydrocarbon ring be fused together (have common key) or at least one aromatic monocyclic hydrocarbon ring and one or more naphthenic base and/or Cycloheteroalkyl ring is condensed.Aryl can have 6 to 24 carbon atoms (such as C in its ring system₆-C₂₄Aryl), it can be with Including multiple condensed ring.In some embodiments, polyaromatic can have 8 to 24 carbon atoms.Aryl it is any suitable Ring position can be covalently attached with the chemical structure of restriction.The example only with the aryl of one or more aromatic carbocyclics includes Phenyl, 1- naphthalene (bicyclic), 2- naphthalene (bicyclic), anthryl (tricyclic), phenanthryl (tricyclic), pentacene (five rings) and similar base Group.The example of the wherein at least one aromatic carbocyclic polycyclic system condensed with one or more naphthenic base and/or cycloheteroalkyl ring is outstanding It includes the benzo derivative of the benzo derivative (i.e. indanyl is 5,6- bicyclic cycloalkyl/aromatic ring system) of pentamethylene, hexamethylene Object (i.e. tetralyl is 6,6- bicyclic cycloalkyl/aromatic ring system), imidazoline benzo derivative (i.e. benzimidazoline base, The bicyclic cycloheteroalkyl of 5,6-/aromatic ring system) and the benzo derivative of pyrans (i.e. benzopyranyl is the miscellaneous alkane of the bicyclic ring of 6,6- Base/aromatic ring system).Other examples of aryl include benzo twoAlkyl, benzodioxole base, chromanyl, Indoline base etc..In some embodiments, aryl can be substituted as described herein.In some embodiments, aryl can To have one or more halogenic substituents, and " halogenated aryl " can be referred to as.Perhaloaryl, i.e., wherein all hydrogen are former Aryl (such as-the C that son is all replaced by halogen atom₆F₅) it include in the definition of " halogenated aryl ".In certain embodiments, Aryl is replaced by other aryl and can be referred to as biaryl.Each of biaryl aryl can be as disclosed herein It is substituted.

As used herein " heteroaryl " refer to containing at least one be selected from oxygen (O), nitrogen (N), sulphur (S), silicon (Si) and At least one of ring present in the aromatic monocyclic system of the ring hetero atom of selenium (Se) or in which ring system is aromatics and contains The polycyclic system of at least one ring hetero atom.Polyheteroaromatic includes two or more heteroaryl rings being fused together and with one The condensed bicyclic heteroaryl ring of a or multiple aromatic carbocyclics, non-aromatic carbocycle and/or non-aromatic cycloheteroalkyl ring.Heteroaryl conduct Entirety can have such as 5 to 22 annular atoms and contain 1-5 ring hetero atom (i.e. 5 yuan of-20 unit's heteroaryl).Heteroaryl Base can connect at any hetero atom or carbon atom with the chemical structure of restriction, to generate stable structure.In general, Heteroaryl ring is free of O -- O bond, S -- S or S-O key.However, the one or more N atoms or S atom in heteroaryl can be by oxygen Change (such as pyridine N-oxides, thiophene S- oxide, thiophene S, S- dioxide).The example of heteroaryl includes such as hereafter institute The 5- or 6-membered monocycle shown and 5 yuan of -6 membered bicyclic system:

Wherein T is O, S, NH, N- alkyl, N- aryl, N- (aryl alkyl) (such as N- benzyl), SiH₂, SiH (alkane Base), Si (alkyl)₂, SiH (aryl alkyl), Si (aryl alkyl)₂Or Si (alkyl) (aryl alkyl).The reality of these heteroaryl rings Example include pyrrole radicals, furyl, thienyl, pyridyl group, pyrimidine radicals, pyridazinyl, pyrazinyl, triazolyl, tetrazole radical, pyrazolyl, It is imidazole radicals, isothiazolyl, thiazolyl, thiadiazolyl group, differentOxazolyl,Oxazolyl,Di azoly, indyl, isoindolyl, benzo Furyl, benzothienyl, quinolyl, 2- methylquinoline base, isoquinolyl, quinoxalinyl, quinazolyl, benzotriazole base, Benzimidazolyl, benzothiazolyl, benzisothia oxazolyl, benzisoxaOxazolyl, benzoDi azoly, benzoOxazolyl, cinnolines Base, 1H- indazolyl, 2H- indazolyl, indolizine base, isobenzofuran-base, naphthyridines base, phthalazinyl, pteridyl, purine radicals,Azoles is simultaneously Pyridyl group, thiazolopyridinyl, imidazopyridyl, furopyridyl, thienopyridine base, Pyridopyrimidine base, pyridine And pyrazinyl, pyrido pyridazinyl, thiophene benzothiazolyl, thienoOxazolyl, Thienoimidazole base etc..Heteroaryl it is other Example includes 4,5,6,7- tetrahydro indole base, tetrahydric quinoline group, benzothiophene and pyridyl group, benzofuran and pyridyl group etc..In In some embodiments, heteroaryl can be substituted as described herein.

In certain embodiments, donor-receiver conjugated polymer as described herein includes the repetitive unit (M1) of formula 1:

Wherein R₁Selected from by H, F, Cl, Br, I or CN and (C₁-C₄₀) straight chained alkyl, (C₃-C₄₀) branched alkyl and (C₃- C₄₀) naphthenic base composition group, wherein one or more non-conterminous C atoms are optionally by-O- ,-S- ,-C (O)-,-C (O)- O-、-O-C(O)-、-O-C(O)-O-、-CR⁰=CR⁰⁰Or-C ≡ C- displacement, wherein R⁰And R⁰⁰It is independently straight chained alkyl, branch Alkyl or cycloalkyl, and wherein one or more H atoms are optionally replaced by F, Cl, Br, I or CN；Or R₁It is aryl, heteroaryl Base, aryloxy group, heteroaryloxy, aryl carbonyl, Heteroarylcarbonyl, aryl carbonyl epoxide, Heteroarylcarbonyl oxygroup, aryloxycarbonyl Or heteroaryl oxygen carbonyl, there are 5 to 30 annular atoms；And

R₂It is-CH₂CH(R₃)(R₄), wherein R₃And R₄It is independently C₁-C₂₀Alkyl.

In certain embodiments, R₁It is H, F, Cl, Br, I, CN, (C₁-C₄₀) straight chained alkyl, (C₃-C₄₀) branched alkyl and (C₃-C₄₀) naphthenic base, Heterocyclylalkyl, aryl, heteroaryl, aryloxy group, heteroaryloxy, aryl carbonyl, Heteroarylcarbonyl, aryl carbonyl Base oxygroup, Heteroarylcarbonyl oxygroup, aryloxycarbonyl, heteroaryl oxygen carbonyl, ester, amide, acyl amino, ether, thioether, amino, ketone, Sulfone, sulfoxide, carbonic ester or urea.

In certain embodiments, R₁It is H, F, Cl, Br, I, CN, (C₁-C₄₀) straight chained alkyl, (C₃-C₄₀) branched alkyl and (C₃-C₄₀) naphthenic base, Heterocyclylalkyl, aryl or heteroaryl, wherein the aryl and heteroaryl optionally by halide, cyano, Nitro, alkyl, naphthenic base, amine, ether, thioether, ester or amide replace.

In certain embodiments, R₃And R₄It is independently (C₂-C₂₀) alkyl, (C₂-C₁₈) alkyl, (C₂-C₁₆) alkyl, (C₂-C₁₄) alkyl, (C₃-C₁₄) alkyl, (C₄-C₁₄) alkyl, (C₅-C₁₄) alkyl, (C₆-C₁₄) alkyl, (C₈-C₁₄) alkyl, (C₈- C₁₂) alkyl, (C₈-C₁₀) alkyl, (C₁₀-C₁₂) alkyl, (C₂-C₄) alkyl, (C₂-C₆) alkyl, (C₄-C₈) alkyl or (C₆-C₈) alkane Base.

In certain embodiments, R₂Selected from the group being made of the following terms:

In certain embodiments, R₁It is H, aryl or heteroaryl, wherein the aryl and heteroaryl are optionally by halogenation Object, cyano, nitro, alkyl, naphthenic base, amine, ether, thioether, ester or amide replace；And R₃And R₄It is independently (C₄-C₁₄) alkane Base.

Donor-receiver conjugated polymer as described herein can also include one or more repetitive units in addition to M1. For example, one or more repetitive units (M2) can be selected from:

π -2 is the fused moiety optionally replaced；

Ar is independently the 5- or 6-membered aryl or heteroaryl optionally replaced at each occurrence；

Z is conjugated linear linking group；And m, m' and m " are independently 0,1,2,3,4,5 or 6.

In some embodiments, π -2 can be the polycyclic (C optionally replaced₈-C₂₂) aryl or 8 yuan of -22 unit's heteroaryl. For example, π -2 can have the ring nucleus that plane and height are conjugated, and can optionally be substituted as disclosed herein.In In various embodiments, π -2 can have (correcting) bigger than about -3.0V reduction potential (relative to SCE electrode and Such as measured in THF solution).In certain embodiments, π -2 can have the reduction potential greater than or equal to about -2.2V.In In specific embodiment, π -2 can have the reduction potential greater than or equal to about -1.2V.The example of suitable ring nucleus includes Naphthalene, anthracene, aphthacene, pentacene, pyrene, cool, fluorenes, indacene, indenofluorene and tetraphenylene and their analog, wherein One or more carbon atoms can be replaced by the hetero atom of such as O, S, Si, Se, N or P.In certain embodiments, π -2 can be with Including at least one electron-withdrawing group.

In certain embodiments, π-2 may include two or more (such as 2-4) condensed ring, wherein each Ring can be 5 member rings, 6 member rings or 7 member rings optionally replaced.In some embodiments, π -2 may include via spiro-atom (such as spiral shell carbon atom) and the second monocycle or polycyclic system covalent bonding monocycle (such as 1,3- dioxolanes group or it include times The substituent group of choosing and/or the derivative of ring hetero atom).

In certain embodiments, π -2 can be selected from:

Wherein p, p', s, s', v and v' are independently selected from C (R₁), N and Si (R₁)；

Q, each of q' and u are independently selected from C (O), C=C (CN)₂、-S-、-S(O)-、-S(O)₂-、-O-、-Si (R₁)(R₂)-、-C(R₁)(R₂)-、-C(R₁)(R₂)-C(R₁)(R₂)-and-CR₁=CR₂-；

R₁And R₂Each of be independently H, halogen, CN, (C at each occurrence₁-C₄₀) alkyl, (C₁-C₄₀) alcoxyl Base, (C₁-C₄₀) alkylthio group, (C₁-C₄₀) halogenated alkyl, (C₆-C₁₄) aryl, 5 yuan of -14 unit's heteroaryl,-(OCH₂CH₂)_tOR^e、- (OCF₂CF₂)_tOR^e、-(OCH₂CF₂)_tOR^e、-(OCF₂CH₂)_tOR^e、-(CH₂CH₂O)_tR^e、-(CF₂CF₂O)_tR^e、-(CH₂CF₂O)_tR^e Or-(CF₂CH₂O)_tR^e；The wherein C_6-14Aryl and 5 yuan of -14 unit's heteroaryl be optionally independently selected from halogen, CN, (C₁-C₄₀) alkyl, (C₁-C₄₀) alkoxy, (C₁-C₄₀) alkylthio group and (C₁-C₄₀) halogenated alkyl 1-4 group replace；T is 1,2,3,4,5,6,7,8,9 or 10；And R^eIt is (C₁-C₂₀) alkyl or (C₁-C₄₀) halogenated alkyl；And b is 1,2,3 or 4.

In various embodiments, linking group Z itself can be conjugated system (for example including two or more double bonds Or three keys) or adjacent component can form conjugated system with it.For example, in the implementation that wherein Z is linearly connected group In scheme, Z can be vinylene (i.e. with a double bond), divalent acetenyl (have three keys) including two Or more conjugated double bond or three keys (C₄-C₄₀) alkenyl or alkynyl or may include Si, N, P etc. it is more heteroatomic its Its acyclic conjugation system.For example, Z can be selected from:

Wherein R₄It can be independently selected from H, halogen, CN, (C₁-C₂₀) alkyl, (C₁-C₂₀) alkoxy and (C₁-C₂₀) halogenated Alkyl.

In certain embodiments, the repetitive unit of formula 1 is indicated by the repetitive unit of formula 2:

Wherein Ar is selected from the group being made of the following terms:

Wherein each R is independently selected from by (C₁-C₄₀) straight chained alkyl, (C₃-C₄₀) branched alkyl and (C₃-C₄₀) naphthenic base The group of composition, wherein one or more non-conterminous C atoms are optionally by-O- ,-S- ,-C (O)-,-C (O)-O- ,-O-C (O)-、-O-C(O)-O-、-CR⁰=CR⁰⁰Or-C ≡ C- displacement, wherein R⁰And R⁰⁰Be independently straight chained alkyl, branched alkyl or Naphthenic base, and wherein one or more H atoms are optionally replaced by F, Cl, Br, I or CN；Or R is aryl, heteroaryl, fragrant oxygen Base, heteroaryloxy, aryl carbonyl, Heteroarylcarbonyl, aryl carbonyl epoxide, Heteroarylcarbonyl oxygroup, aryloxycarbonyl or heteroaryl Oxygen carbonyl has 4 to 30 annular atoms；

R₁It is H, F, Cl, Br, I, CN, (C₁-C₄₀) straight chained alkyl, (C₃-C₄₀) branched alkyl and (C₃-C₄₀) naphthenic base, miscellaneous Naphthenic base, aryl or heteroaryl, wherein the aryl and heteroaryl optionally by halide, cyano, nitro, alkyl, naphthenic base, Amine, ether, thioether, ester or amide replace；

R₂It is-CH₂CH(R₃)(R₄), wherein R₃And R₄It is independently C₁-C₂₀Alkyl.

In certain embodiments, R is (C₁-C₄₀) straight chained alkyl, (C₃-C₄₀) branched alkyl, (C₃-C₄₀) naphthenic base, miscellaneous Naphthenic base, aryl or heteroaryl.In certain embodiments, R is (C₁-C₁₀) straight chained alkyl, (C₃-C₁₀) branched alkyl, (C₃- C₁₀) naphthenic base, Heterocyclylalkyl, aryl or heteroaryl.

In certain embodiments, R₃And R₄It is independently (C₂-C₂₀) alkyl, (C₂-C₁₈) alkyl, (C₂-C₁₆) alkyl, (C₂-C₁₄) alkyl, (C₃-C₁₄) alkyl, (C₄-C₁₄) alkyl, (C₅-C₁₄) alkyl, (C₆-C₁₄) alkyl, (C₈-C₁₄) alkyl, (C₈- C₁₂) alkyl, (C₈-C₁₀) alkyl, (C₁₀-C₁₂) alkyl, (C₂-C₄) alkyl, (C₂-C₆) alkyl, (C₄-C₈) alkyl or (C₆-C₈) alkane Base.

In certain embodiments, R₂Selected from the group being made of the following terms:

In certain embodiments, R is (C₁-C₁₀) alkyl.

In certain embodiments, the donor-receiver conjugated polymer includes the repetitive unit of one or more following formulas:

Wherein n is the integer selected from 5-200；

R is (C₁-C₁₀) alkyl；

R₁It is H, Br, Cl, I, CN, alkyl, naphthenic base, Heterocyclylalkyl, aryl, heteroaryl, ether, amine, thioether, ester, amide Or acyl amino；And

R₂It is-CH₂CH(R₃)(R₄), wherein R₃And R₄It is independently (C₁-C₂₀) alkyl.

In certain embodiments, R₁H, aryl or heteroaryl, wherein the aryl and thiophene optionally by halide, Cyano, nitro, alkyl, naphthenic base, amine, ether, thioether, ester or amide replace；And R₃And R₄It is independently (C₄-C₁₄) alkyl.

In certain embodiments, the donor-receiver conjugated polymer is expressed from the next:

Wherein n is the integer selected from 5-200；

X is S or N (C₁-C₁₀Alkyl)；

R₁It is H, Br, Cl, I, CN, alkyl, naphthenic base, Heterocyclylalkyl, aryl, heteroaryl, ether, amine, thioether, ester, amide Or acyl amino；

R₂It is-CH₂CH(R₃)(R₄), wherein R₃And R₄It is independently (C₁-C₂₀) alkyl.

In certain embodiments, R₁It is H, aryl or thiophene, wherein the aryl and thiophene are optionally by halide, cyanogen Base, nitro, alkyl, naphthenic base, amine, ether, thioether, ester or amide replace.

In certain embodiments, R₃And R₄It is independently (C₂-C₂₀) alkyl, (C₂-C₁₈) alkyl, (C₂-C₁₆) alkyl, (C₂-C₁₄) alkyl, (C₃-C₁₄) alkyl, (C₄-C₁₄) alkyl, (C₅-C₁₄) alkyl, (C₆-C₁₄) alkyl, (C₈-C₁₄) alkyl, (C₈- C₁₂) alkyl, (C₈-C₁₀) alkyl, (C₁₀-C₁₂) alkyl, (C₂-C₄) alkyl, (C₂-C₆) alkyl, (C₄-C₈) alkyl or (C₆-C₈) alkane Base.

In certain embodiments, R₂Selected from the group being made of the following terms:

In certain embodiments, donor-receiver conjugated polymer is with following range of average molecular weight: 10, 000kDa-1,000,000kDa、10,000kDa-9000,000kDa、10,000kDa-800,000kDa、10,000kDa-700, 000kDa、10,000kDa-600,000kDa、10,000kDa-500,000kDa、10,000kDa-400,000kDa、10, 000kDa-300,000kDa、10,000kDa-200,000kDa、10,000kDa-150,000kDa、10,000kDa-130, 000kDa、10,000kDa-120,000kDa、10,000kDa-110,000kDa、20,000kDa-110,000kDa、30, 000kDa-110,000kDa、40,000kDa-110,000kDa、40,000kDa-100,000kDa、40,000kDa-90, 000kDa, 40,000kDa-80,000kDa or 40,000kDa-60,000kDa.In other embodiments, donor-receiver is total Conjugated polymer is with following range of average molecular weight: 20,000kDa-100,000kDa, 10,000kDa-100,000kDa, 30,000kDa-100,000kDa、30,000kDa-90,000kDa、30,000kDa-80,000kDa、30,000kDa-70, 000kDa, 30,000kDa-60,000kDa or 30,000kDa-50,000kDa.In other embodiments, donor-receiver is total Conjugated polymer has the average molecular weight of 40,000kDa to 150,000kDa range.

Donor-receiver conjugated polymer provided herein can show temperature dependency aggregation properties.It is provided herein The temperature dependency aggregation of donor-receiver conjugated polymer can be used many analysis methods well known by persons skilled in the art and comment Valence, including but not limited to measures the light absorption of the sample in test solvent containing donor material at various temperatures and measurement exists The Change of absorption of sample at various temperature in test solvent containing donor material.

It is provided herein to give when changing the temperature of solution and/or compared with membrane stage as demonstrated in following embodiment Body-receptor conjugate polymer solution can show significant red shift in absorption.For example, at 100 DEG C, with weak solution It compares, PvBDTTAZ shows the red shift of about 80nm under membrane stage.

In certain embodiments, it when being measured in the solvent in such as chlorobenzene, 1,2- dichloro-benzenes and a combination thereof, mentions herein The donor-receiver conjugated polymer of confession can be shown in their absorption spectrum more than about 40nm, more than about 50nm, be more than About 60nm, more than about 70nm, more than about 80nm, more than about 90nm, more than about 100nm, more than about 110nm, more than about 120nm, More than about 130nm, more than about 140nm or the red shift more than about 150nm.In other embodiments, when in such as chlorobenzene, 1,2- When measuring in the weak solution in dichloro-benzenes and the solvent of a combination thereof, donor material as described herein can in their absorption spectrum With show about 40nm to about 170nm, about 40nm to about 160nm, about 40nm to about 150nm, about 40nm to about 140nm, about 40nm to about 130nm, about 40nm to about 120nm, about 40nm to about 110nm, about 40nm to about 100nm, about 40nm to about 90nm, The red shift of about 40nm to about 80nm, about 40nm to about 70nm or about 40nm to about 60nm.

In certain embodiments, there is provided herein a kind of compositions, and it includes donor-receiver as described herein conjugation is poly- Close object and solvent (such as 1,2- dichloro-benzenes, 1,3- dichloro-benzenes, 1,4- dichloro-benzenes, 1,2,4- trichloro-benzenes, toluene, ortho-xylene, two Toluene, paraxylene, chlorobenzene, 1,2,4- trimethylbenzene, 1,2,3- trimethylbenzene, 1,3,5- trimethylbenzene, chloroform and its group Close), wherein the donor-receiver conjugated polymer is membranaceous compared with the donor-receiver conjugated polymer under solution state Shown under state red shift about 20nm to about 120nm, about 20nm to about 110nm, about 20nm to about 100nm, about 20nm to about 90nm, The peak optical absorption spectrum of about 20nm to about 80nm, about 30nm to about 80nm or about 30nm to about 60nm.In certain embodiment party In case, relative to the identical donor-receiver conjugated polymer under solution state, the donor-receiver conjugated polymer exists Red shift at least about 20nm, about 30nm, about 40nm, about 50nm, about 60nm, about 70nm, about 70nm, about are shown under membrane stage The peak optical absorption spectrum of 90nm, about 100nm, about 110nm or about 120nm.

A kind of composition is also provided herein, it includes receptor (fullerene derivate or non-fullerene acceptor) and as herein The donor-receiver conjugated polymer.

In certain embodiments, the composition also includes solvent.The selection of solvent can be conjugated based on donor-receiver The characteristic of polymer, receptor and solvent determines, as solubility, stability, donor-receiver conjugated polymer it is desired dense The boiling point of degree, viscosity and solvent.The selection of solvent appropriate is completely within the scope of the technical ability of those skilled in the art.In certain realities It applies in scheme, the solvent is 1,2- dichloro-benzenes, 1,3- dichloro-benzenes, 1,2,4- trichloro-benzenes, chlorobenzene, 1,2,4- trimethylbenzenes and chlorine At least one of imitate.

In certain embodiments, the group being made of the following terms can be selected from fullerene in this article:

Wherein each n is 1,2,4,5 or 6；

Each Ar is independently selected from by monocyclic aryl, bicyclic aryl and polyaromatic and bicyclic heteroaryl, bicyclic miscellaneous The group of aryl and polyheteroaromatic composition, wherein each Ar can contain 1 to 5 aryl or heteroaryl, wherein often One can condense or connect；

Each R^xIndependently selected from by Ar, (C₁-C₄₀) straight chained alkyl, (C₃-C₄₀) branched alkyl and (C₃-C₄₀) naphthenic base The group of composition, wherein one or more non-conterminous C atoms are optionally by-O- ,-S- ,-C (O)-,-C (O-)-O- ,-O-C (O)-、-O-C(O)-O-、-CR⁰=CR⁰⁰Or-C ≡ C- displacement, wherein R⁰And R⁰⁰Be independently straight chained alkyl, branched alkyl or Naphthenic base, and wherein one or more H atoms are optionally replaced by F, Cl, Br, I or CN；Or R^xIt is aryl, heteroaryl, virtue Oxygroup, heteroaryloxy, aryl carbonyl, Heteroarylcarbonyl, aryl-carbonyl oxygen, Heteroarylcarbonyl oxygroup, aryloxycarbonyl or heteroaryl Oxygen carbonyl has 4 to 30 annular atoms, unsubstituted or replaced by one or more nonaromatics；

Each R¹Independently selected from by (C₁-C₄₀) straight chained alkyl, (C₃-C₄₀) branched alkyl and (C₃-C₄₀) naphthenic base group At group, wherein one or more non-conterminous C atoms optionally by-O- ,-S- ,-C (O)-,-C (O-)-O- ,-O-C (O)-,- O-C(O)-O-、-CR⁰=CR⁰⁰Or-C ≡ C- displacement, wherein R⁰And R⁰⁰It is independently straight chained alkyl, branched alkyl or naphthenic base, And wherein one or more H atoms are optionally replaced by F, Cl, Br, I or CN；Or R¹It is aryl, heteroaryl, aryloxy group, miscellaneous Aryloxy group, aryl carbonyl, Heteroarylcarbonyl, aryl-carbonyl oxygen, Heteroarylcarbonyl oxygroup, aryloxycarbonyl or heteroaryl oxygen carbonyl, It has 4 to 30 annular atoms, unsubstituted or replaced by one or more nonaromatics, wherein R¹The carbon number contained is big In 1；

Each Ar¹Independently selected from the group being made of bicyclic heteroaryl, bicyclic heteroaryl and polyheteroaromatic, wherein often One Ar¹1 to 5 heteroaryl can be contained, wherein each can condense or connect；

Each Ar²Independently selected from the aryl contained more than 6 atoms in addition to H；And

Wherein the fullerene ball is indicated selected from by C₆₀Fullerene, C₇₀Fullerene, C₈₄Fullerene and other fullerenes composition Group fullerene.

In one embodiment, fullerene is taken by one or more functional groups selected from the group being made of the following terms Generation:

Wherein n is 1,2,3,4,5 or 6；

Each Ar is independently selected from by monocyclic aryl, bicyclic aryl, polyaromatic and bicyclic heteroaryl, bicyclic heteroaryl The group of base and polyheteroaromatic composition, or 1 to 5 condensed or connection such group can be contained；

Each R^xIndependently selected from by Ar, (C₁-C₄₀) straight chained alkyl, (C₃-C₄₀) branched alkyl and (C₃-C₄₀) naphthenic base The group of composition, wherein one or more non-conterminous C atoms are optionally by-O- ,-S- ,-C (O)-,-C (O)-O- ,-O-C (O)-、-O-C(O)-O-、-CR⁰=CR⁰⁰Or-C ≡ C- displacement, wherein R⁰And R⁰⁰Be independently straight chained alkyl, branched alkyl or Naphthenic base, and wherein one or more H atoms are optionally replaced by F, Cl, Br, I or CN；Or R^xIt is aryl, heteroaryl, virtue Oxygroup, heteroaryloxy, aryl carbonyl, Heteroarylcarbonyl, aryl-carbonyl oxygen, Heteroarylcarbonyl oxygroup, aryloxycarbonyl or heteroaryl Oxygen carbonyl has 4 to 30 annular atoms, unsubstituted or replaced by one or more nonaromatics；

Each R¹Independently selected from by (C₁-C₄₀) straight chained alkyl, (C₃-C₄₀) branched alkyl and (C₃-C₄₀) naphthenic base group At group, wherein one or more non-conterminous C atoms optionally by-O- ,-S- ,-C (O)-,-C (O)-O- ,-O-C (O)-,- O-C(O)-O-、-CR⁰=CR⁰⁰Or-C ≡ C- displacement, wherein R⁰And R⁰⁰It is independently straight chained alkyl, branched alkyl or naphthenic base, And wherein one or more H atoms are optionally replaced by F, Cl, Br, I or CN；Or R¹It is aryl, heteroaryl, aryloxy group, miscellaneous Aryloxy group, aryl carbonyl, Heteroarylcarbonyl, aryl-carbonyl oxygen, Heteroarylcarbonyl oxygroup, aryloxycarbonyl or heteroaryl oxygen carbonyl, It has 4 to 30 annular atoms, unsubstituted or replaced by one or more nonaromatics, wherein R¹The carbon number contained is big In 1；

Each R is independently selected from by (C₁-C₄₀) straight chained alkyl, (C₃-C₄₀) branched alkyl and (C₃-C₄₀) naphthenic base composition Group, wherein one or more non-conterminous C atoms are optionally by-O- ,-S- ,-C (O)-,-C (O-)-O- ,-O-C (O)-,-O- C(O)-O-、-CR⁰=CR⁰⁰Or-C ≡ C- displacement, wherein R⁰And R⁰⁰It is independently straight chained alkyl, branched alkyl or naphthenic base, and And wherein one or more H atoms are optionally replaced by F, Cl, Br, I or CN；Or R is aryl, heteroaryl, aryloxy group, heteroaryl oxygen Base, aryl carbonyl, Heteroarylcarbonyl, aryl-carbonyl oxygen, Heteroarylcarbonyl oxygroup, aryloxycarbonyl or heteroaryl oxygen carbonyl, tool There are 4 to 30 annular atoms, it is unsubstituted or replaced by one or more nonaromatics；

Each Ar¹Independently selected from the group being made of bicyclic heteroaryl, bicyclic heteroaryl and polyheteroaromatic, wherein often One Ar¹1 to 5 heteroaryl can be contained, wherein each can condense or connect；

Each Ar²Independently selected from the aryl contained more than 6 atoms in addition to H；And

Wherein the fullerene ball is indicated selected from by C₆₀Fullerene, C₇₀Fullerene, C₈₄Fullerene and other fullerenes composition Group fullerene.

In some embodiments, the preparation be further characterized by the fullerene be selected from be made of the following terms Group:

Wherein n is 1,2,3,4,5 or 6；

Each R is independently selected from by (C₁-C₄₀) straight chained alkyl, (C₃-C₄₀) branched alkyl and (C₃-C₄₀) naphthenic base composition Group, wherein one or more non-conterminous C atoms are optionally by-O- ,-S- ,-C (O)-,-C (O)-O- ,-O-C (O)-,-O-C (O)-O-、-CR⁰=CR⁰⁰Or-C ≡ C- displacement, wherein R⁰And R⁰⁰It is independently straight chained alkyl, branched alkyl or naphthenic base, and And wherein one or more H atoms are optionally replaced by F, Cl, Br, I or CN；Or R is aryl, heteroaryl, aryloxy group, heteroaryl oxygen Base, aryl carbonyl, Heteroarylcarbonyl, aryl-carbonyl oxygen, Heteroarylcarbonyl oxygroup, aryloxycarbonyl or heteroaryl oxygen carbonyl, tool There are 4 to 30 annular atoms, it is unsubstituted or replaced by one or more nonaromatics.

In some embodiments, the preparation be further characterized by the fullerene be selected from be made of the following terms Group:

In some embodiments, the preparation be further characterized by the fullerene be selected from be made of the following terms Group:

Wherein n is 1,2,3,4,5 or 6；

M is 1,2,4,5 or 6；

Q is 1,2,4,5 or 6；

R¹And R²Independently selected from by (C₁-C₄) straight chain and branched alkyl composition group；And

Wherein the fullerene ball is indicated selected from by C₆₀Fullerene, C₇₀Fullerene, C₈₄Fullerene and other fullerenes composition Group fullerene.

In some embodiments, the preparation be further characterized by the fullerene be selected from be made of the following terms Group:

In certain embodiments, the non-fullerene acceptor is selected from the group being made of the following terms:

Wherein each R₅Independently selected from by Ar, (C₁-C₄₀) straight chained alkyl, (C₃-C₄₀) branched alkyl and (C₃-C₄₀) ring The group of alkyl composition, wherein one or more non-conterminous C atoms are optionally by-O- ,-S- ,-C (O)-,-C (O)-O- ,-O-C (O)-、-O-C(O)-O-、-CR⁰=CR⁰⁰Or-C ≡ C- displacement, wherein R⁰And R⁰⁰Be independently straight chained alkyl, branched alkyl or Naphthenic base, and wherein one or more H atoms are optionally replaced by F, Cl, Br, I or CN；Or R₅It is aryl, heteroaryl, virtue Oxygroup, heteroaryloxy, aryl carbonyl, Heteroarylcarbonyl, aryl-carbonyl oxygen, Heteroarylcarbonyl oxygroup, aryloxycarbonyl or heteroaryl Oxygen carbonyl has 4 to 30 annular atoms, unsubstituted or replaced by one or more nonaromatics.

In certain embodiments, the non-fullerene acceptor is selected from the group being made of the following terms:

Wherein R₆It is (C₁-C₁₄) straight chained alkyl, (C₃-C₁₄) branched alkyl or (C₃-C₁₄) naphthenic base；

R₇It is-CH₂CH(R₉)(R₁₀), wherein R₉And R₁₀It is independently C₁-C₂₀Alkyl；And

R₈It is (C₁-C₁₄) straight chained alkyl, (C₃-C₁₄) branched alkyl or (C₃-C₁₄) naphthenic base.

In certain embodiments, R₆It is (C₄-C₁₀) straight chained alkyl, (C₄-C₁₀) branched alkyl or (C₄-C₁₀) naphthenic base.

In certain embodiments, R₆It is (C₄-C₁₀) straight chained alkyl, (C₄-C₁₀) branched alkyl or (C₄-C₁₀) naphthenic base； And R₈It is (C₁-C₆) straight chained alkyl, (C₁-C₆) branched alkyl or (C₁-C₆) naphthenic base.

In certain embodiments, R₉And R₁₀It is independently (C₁-C₆) alkyl.

In certain embodiments, R₉And R₁₀It is independently (C₁-C₆) alkyl；And R₈It is (C₁-C₆) straight chained alkyl, (C₁- C₆) branched alkyl or (C₁-C₆) naphthenic base.

In an exemplary embodiment, organic electronic (OE) device includes coating or off-set oil containing the preparation Ink.The OE device that is further characterized by of another exemplary implementation scheme is organic field effect tube (OFET) device Part.The OE device that is further characterized by of another exemplary implementation scheme is organic photovoltaic (OPV) device.

The preparation of this introduction can show semiconductor behavior, the light absorption/separation of charge such as optimized in photovoltaic device； Charge transmission in luminescent device is/compound/to shine；And/or high carrier mobility in scene effect device and/or good Current modulation characteristic.In addition, preparation of the invention can have certain processed edges, such as solution processable and/or in ring Good stability (such as air stability) in the condition of border.The preparation of this introduction can be used for preparing p-type, and (donor or hole pass It is defeated), N-shaped (receptor or electron-transport) or bipolar semiconductor material, and then can be used for manufacturing various organic or mixed light Electronic products, structure and device, including organic photovoltaic devices and organic light-emitting transistor.