TW201321427A - New poly(heteroarylene vinylene)s based on diketopyrrolopyrrole - Google Patents

Abstract

The inventions disclosed, described, and/or claimed herein relate to various genera and subgenera of diketopyrrolopyrrole (DPP) polymers, including homopolymers and/or copolymers, comprising a plurality of repeating units, more than 50 mol. % and up to 100 mol. % of the repeating units are repeating units RU of one or more structural formula(e) complying with general structural formula (I) (see application) wherein (a) each R1 and R1' is independently selected from normal, branched, or cyclic organic group, such as for example alkyls or fluorinated derivatives thereof; (b) each hAr1 and hAr1' is independently selected from heteroaryls. The polymers are readily soluble and particularly useful for solution manufacturing organic electronic devices, including transistors and solar cells. Methods for making the polymers and the derivative electronic devices are also described.

Description

Novel poly(heteroarylenevinylene) based on diketopyrrolopyrrole Related application

The present application claims priority to U.S. Provisional Application Serial No. 61/525, the entire disclosure of which is incorporated herein in

Government licensing rights statement

The inventors received partial financial support from the National Science Foundation (DMR-0805259). The federal government reserves certain licenses in the invention.

The different inventions disclosed, illustrated, and/or claimed herein relate to the field of semiconducting organic polymers and their uses, including the fabrication of organic electronic devices such as transistors and solar cells.

Solution processable conjugated polymer and/or copolymer semiconductors have attracted attention in the art due to their ability to fabricate large area, flexible and low cost electronic devices, including organic light emitting diodes (OLEDs), Potential applications in solar cells and/or transistors.

Some of these polymers and/or copolymers known in the prior art have achieved reasonable current carrying capacity in the form of relatively good hole mobility, relatively good electron transport. Rate, or in a few cases, a combination of both hole mobility and high electron mobility (ie " Bipolar "characteristics". Some of the prior art polymers and/or copolymers can be used to produce fairly good properties when used in the manufacture of transistors, or can be used in solar cells to produce solar radiation conversion. The excitation efficiency of electrical energy (3%-5%). The relatively few known bipolar polymers and/or copolymers have not achieved quite good and matched hole mobility and electron mobility levels, namely: This level will allow the fabrication of high efficiency solar cells, or transistors, and derivatization devices comprising a single copolymer, wherein such devices have a sufficiently high switching current ratio for use in practical and competitive end uses.

Conjugated donor-acceptor (DA) polymers and/or copolymers have received attention in the art for the following purposes: custom electronic structures, highest occupied molecular orbital (HOMO), and lowest unoccupied molecular orbital (LUMO) , associated bandgap energy, and strong photon absorption in a wide range of UV, visible, and infrared wavelengths. The choice of electron donor and acceptor subunits in the conjugated polymers and/or copolymers can modulate the HOMO/LUMO energy levels to adjust light absorption and charge transport characteristics.

A class known in the class of polymers includes 1,4-diketo-2,5-dihydropyrrolo[3,4- c ]pyrrole ("DPP") electron accepting subunits having such electron accepting subunits The following structure:

For example, PCT patent application WO 2008/000664 considers a large class of such DPP polymers as organic semiconductors, such organic semiconductors It is potentially suitable for the manufacture of transistors and solar cells (the proposed generic structure is shown below).

'664 PCT has broadly considered the possible uses of a very wide variety of potential combinations of different Ar subunits, including a wide variety of aryl, heteroaryl, fused heteroaryl, ethylene, Acetylene and other potential Ar subunits described herein. More specifically, '664 PCT reported an actual synthesis of a DPP polymer having the following structure:

The thin film, bottom gate field effect transistor fabricated from this DPP polymer (4) is reported to produce "clear p-type transistor behavior" with a field of 0.15 cm ² /Vs Effect mobility, threshold voltage bias of about 0 to 5 V, and switching ratio between 10 ^{4 and} 10 ⁷ , and bipolar mobility of up to 0.1 cm ² /Vs, and the transistors are reported to be It is thermally stable and fairly stable in air for two months. There is no mention of any n-type current carrying capacity. The bulk heterojunction solar cell constructed from the polymer is reported to convert solar energy with an efficiency of up to 3.06%.

Recently, Bijleveld et al. (J. Amer. Chem. Soc. 2009, 131, 16616-16617) have reported a slightly different polymer having the structure shown below:

One kind of M _n = 10,000 g / mol PDPP3T type polymer (where HD = 2- hexyldecyl) to produce a bottom-gate, bottom-contact transistor, the transistor having a bipolar behavior, 0.04 cm ² / Vs in the hole Mobility and electron mobility of 0.01 cm ² /Vs. The polymer was used to fabricate inverters and to fabricate bulk heterojunction solar cells (in combination with PCBM) that produced light conversion with an efficiency of up to 4.7%. Soon after, WO 2010/049321 reported a DPP polymer of the same structural formula but with a molecular weight of 39,500 gr/mole as reported by Bijleveld, which produces a bottom-gate, bottom-contact transistor with balanced double Polar characteristics, hole mobility of 0.43 cm ² /Vs, and electron mobility of 0.35 cm ² /Vs. It is not clear why such a small structural change between the '664 PCT polymer, the Bijleveld polymer and the WO 2010/049321 polymer produces such a large difference in electrical properties.

Recently, Bronstein et al. reported (J.Am.Chem.Soc. 2011, 133, 3272-3275) two related DPP polymers and used them to produce up to 1.95 cm ² / The maximum hole mobility of Vs is in organic field-effect transistors (OFFTs), and in organic photovoltaic devices with 5.4% energy conversion efficiency.

However, also recently, Zhang et al. ( Synthetic Metals , 2010, 160, 1945-1952) reported three other similar DPP polymers containing vinylidene subunits in the polymer chain. And has the following structure:

Solar cells containing these DPP/vinylidene polymers produced OPV efficiencies of only 0.72%, 0.16%, and 0.16%. C6DPPDHPV has the highest reported hole mobility in an OFET, only 5.4 × 10 ^-4 cm ² /Vs, and no conductivity mobility or bipolar behavior is reported. The reason for these considerable differences in characteristics and performance compared to other DPP polymers is not clear, but given the results reported by Zhang et al., one of ordinary skill in the art can be inspired without considering The polymer contains a vinylidene subunit.

However, there remains a need in the art for new and improved polymer and/or copolymer materials and/or compositions derived therefrom that are capable of providing improved processability in combination with improved processability. High and reproducible holes or electron mobility, high solubility, controlled molecular weight and/or film forming ability, low cost, and high thermal and oxidative stability for use in organic electronic devices, especially transistors, Among solar cells or more complex organic electronics and/or circuits. In particular, there remains an unmet need in the art for bipolar organic polymers and/or copolymers having improved cell and electron mobility levels, lower bias voltages, and better on/off current ratios in order to be able to Complementary circuits and electronic devices are fabricated from a single semiconductor polymer. Different embodiments of the different inventions described below are intended to address these problems.

The different inventions disclosed, described and/or claimed herein relate to different genus and subgenus of diketopyrrolopyrrole (DPP) polymers, including homopolymers and/or copolymers, which The polymer comprises a plurality of repeating units, and more than 50 mol% and up to 100 mol% of the repeating units have repeating units RU conforming to one or more structural formulas of the structural formula (I),

Wherein a) each R ¹ and R ^{1 ' is} independently selected from a normal chain, a branched or cyclic organic group, such as an alkyl group or a fluorinated derivative thereof; b) each hAr ¹ and hAr ^{1' is} independently selected from heteroaryl. Examples of such heteroaryl groups include the following structures:

Wherein i) a is an integer equal to 1, 2, 3 or 4; ii) each X, X', X" or X"' is independently selected from the group consisting of O, S, Se, Si(R ³ ) ₂ , and NR ³ wherein R ³ is a normal chain, branched or cyclic organic group such as an alkyl group; iii) each Y, Y', Y" and Y"' are independently selected from N and CR ⁴ , Wherein R ⁴ is hydrogen, halogen, cyano or a normal chain, branched or cyclic organic group such as alkyl, perfluoroalkyl, alkoxy, thioalkyl or thioalkoxy And c) each R ² and R ^{2 ' are} independently selected from hydrogen, cyano or an organic group such as alkyl, fluoroalkyl, alkoxy, aryl, heteroaryl, carboxyalkyl or acetamidine Oxygen.

In some embodiments, the DPP polymers defined above may be homopolymers. In other embodiments, the DPP polymer can be a different type of copolymer comprising repeating units RU having the structural formula (I) shown above and other types of repeating units as further described below.

In some embodiments of the DPP polymer, the polymer-based copolymers, the repeating units RU thereof, are mixed, the blend comprising or consisting of: repeating unit RU1 having the specific structural formula (II)

And a repeating unit RU2 having a specific structural formula (III),

Wherein each of R ¹¹ , R ^{11 '} , R ²¹ and R ^{21 ' is} independently selected from a normal chain, a branched or cyclic alkyl group or a fluorinated derivative thereof; a) each hAr ¹¹ , hAr ^11' , hAr ²¹ and hAr ^{21' are} independently selected from C ₁ -C ₆₀ heteroaryl.

In some embodiments, the DPP copolymer is a block copolymer wherein R ¹² and R ²² are different from each other, and/or R ^{12 '} and R ^{22 '} are different from each other.

Examples of preferred hAr heteroaryl groups for use in combination with such DPP polymers comprising a mixture of repeating units of formula (II) and formula (III) include the following structures:

Wherein i) a is an integer equal to 1, 2, 3 or 4; ii) each X, X', X" or X"' is independently selected from the group consisting of O, S, Se, Si(R ³ ) ₂ , and NR ³ wherein R ³ is a C ₁ -C ₃₀ positive-chain, branched or cyclic alkyl group; iii) each Y, Y', Y" and Y"' are independently selected from N and CR ⁴ , Wherein R ⁴ is hydrogen, halogen, cyano or a C ₁ -C ₃₀ normal chain, branched or cyclic alkyl, perfluoroalkyl, alkoxy, thioalkyl or thioalkoxy group ; b) each R ¹² , R ^{12 '} , R ²² and R ^{22 ' are} independently selected from hydrogen, cyano or C ₁ -C ₃₀ alkyl, fluoroalkyl, alkoxy, aryl, heteroaryl, Carboxyalkyl or ethoxylated, c) the conditions comprising at least one of the groups R ¹¹ , R ^{11 '} , hAr ¹¹ and hAr ^{11 '} in the formula (II) are different from those contained in the formula (III) Its homologues are R ²¹ , R ^{21 '} , hAr ²¹ and hAr ^{21 ', respectively} .

In other embodiments, the DPP copolymers are random copolymers wherein R ¹² and R ²² are identical to each other and R ^{12 '} and R ^{22 '} are identical to each other.

The DPP polymers comprising the repeating units of formula (I), as well as other repeating units of formula (II) and (III), and their different subgenera or subspecies, for the manufacture of electronic devices such as transistors and solar cells And logic circuits such as inverters and reverse (NAND) or inverse (NOR) circuits are useful and can have an unexpectedly superior hole, electron or both (ie "bipolar" characteristics). The ability of the form to conduct current. The specific combinations of hAr and vinylidene polymer subunits of such DPP polymers are associated with such unexpectedly superior properties and utilities.

Further detailed description of the various and/or preferred embodiments of the various inventions, which are broadly described above, are provided below in the Detailed Description section provided below.

Detailed description of the invention

The different inventions disclosed, and/or claimed herein relate to different genus and subgenus of diketopyrrolopyrrole (DPP) polymers for the manufacture of electronic devices such as transistors and solar cells, and Logic circuits, such as inverters and anti- or anti-or circuits, are useful and have an unexpectedly superior ability to use holes or electrons or, in some cases, both holes and electrons (ie, "bipolar" features. The ability to conduct current in the form of . It is believed that the specific combination of DPP, hAr, and vinylidene polymer subunits found in such polymers involves and provides unexpectedly superior properties, processing characteristics, and/or utility.

It is also possible to "tune" the identity of the polymeric subunits and their substituents in order to produce electrical and physical properties in the solid state to promote intermolecular π-π stacking in the solid state and/or Long-range order, which can result in high mobility of current carriers such as holes, electrons or both.

DPP polymer of formula I and its subgenus

The diketopyrrolopyrrole (DPP) polymers of the present invention, and various embodiments and subgenera thereof, include homopolymers and/or copolymers comprising a plurality of repeating units, wherein More than 50% by mole and up to 100% by mole of repeating units having repeating units RU conforming to one or more structural formulas of structural formula (I),

Wherein a) each R ¹ and R ^{1 ' is} independently selected from a C ₁ -C ₃₀ positive-chain, branched or cyclic alkyl group or a fluorinated derivative thereof; b) each hAr ¹ and hAr ^{1' is} independently selected from C ₁ -C ₆₀ heteroaryl groups, which have the following structure:

Wherein i) a is an integer equal to 1, 2, 3 or 4; ii) each X, X', X" or X"' is independently selected from the group consisting of O, S, Se, Si(R ³ ) ₂ , and NR ³ wherein R ³ is a C ₁ -C ₃₀ positive-chain, branched or cyclic alkyl group; iii) each Y, Y', Y" and Y"' are independently selected from N and CR ⁴ , Wherein R ⁴ is hydrogen, halogen, cyano or a C ₁ -C ₃₀ normal chain, branched or cyclic alkyl, perfluoroalkyl, alkoxy, thioalkyl or thioalkoxy group And c) each R ² and R ^{2 ' are} independently selected from hydrogen, cyano or C ₁ -C ₃₀ alkyl, fluoroalkyl, alkoxy, aryl, heteroaryl, carboxyalkyl or acetamidine Oxygen.

The number of repeating units of the DPP polymer can be illustrated by the integer n, which can be any positive integer of 5 or greater, but can also be from 5 to 10,000 or from 10 to 1,000. However, it should be noted that in most embodiments of the DPP polymers described herein, a plurality of repeating units, ie, greater than 50% by mole or greater than 60%, 70%, 80%, 90%, 95%, 98 The repeating unit of % or 99% or up to and/or comprising 100 mol% is a repeating unit RU having one or more structural formulas of the structural formula (I) in accordance with the above description.

In some embodiments of the DPP polymer, greater than 50 mole %, up to 100 mole % (preferably between 90 mole % and 99 mole %) of the repeat unit has a conformational formula One and only one repeating unit RU of a specific structural formula of (I).

In some embodiments of the DPP polymer, greater than 50 mole %, up to less than 100 mole % of the repeat unit has a repeat unit RU conforming to one of the structural formula (I) and unique to a particular structural formula, and A repeating unit between 0 mole % and 50 mole % (preferably between 1 mole % and 10 mole %) has one or more specificities that do not conform to structural formula (I) The structural repeat unit RU*.

In some embodiments the DPP polymers are homopolymers. As used herein, "homopolymer" means all repeating unit repeating units RU of the polymer, and the repeating units RU have one and only one structural formula consistent with structural formula (I).

However, as will be detailed below, it is also possible to prepare copolymers of mixtures having two or more types of "R ¹ " substituents and/or two or more types of "hAr" subunits. Things. Accordingly, in some embodiments, the present invention is directed to a diketopyrrolopyrrole polymer wherein greater than 50 mole percent (preferably greater than 90 mole percent), up to 100 mole percent of repeat units have Repeating units RU of at least two different specific structural formulas of the formula (I).

For example, it is possible to prepare a copolymer comprising more than one type of multi-subunit substructure, such as a diketopyrrolopyrrole copolymer, wherein the repeating unit RU is a mixture consisting of having a specific structural formula ( II) repeat unit RU1

And a repeating unit RU2 having a specific structural formula (III),

Wherein each of R ¹¹ , R ^{11 '} , R ²¹ and R ^{21 ' is} independently selected from a C ₁ - C ₃₀ positive-chain, branched or cyclic alkyl group or a fluorinated derivative thereof; a) Each of hAr ¹¹ , hAr ^{11 '} , hAr ²¹ and hAr ^{21 ' is} independently selected from a C ₁ -C ₆₀ heteroaryl group having the following structure:

Wherein i) a is an integer equal to 1, 2, 3 or 4; ii) each X, X', X" or X"' is independently selected from the group consisting of O, S, Se, Si(R ³ ) ₂ , and NR ³ wherein R ³ is a C ₁ -C ₃₀ positive-chain, branched or cyclic alkyl group; iii) each Y, Y', Y" and Y"' are independently selected from N and CR ⁴ , Wherein R ⁴ is hydrogen, halogen, cyano or a C ₁ -C ₃₀ normal chain, branched or cyclic alkyl, perfluoroalkyl, alkoxy, thioalkyl or thioalkoxy group ; b) each R ¹² , R ^{12 '} , R ²² and R ^{22 ' are} independently selected from hydrogen, cyano or C ₁ -C ₃₀ alkyl, fluoroalkyl, alkoxy, aryl, heteroaryl, a carboxyalkyl group or an ethoxylated group, the conditions of which are at least one of the groups R ¹¹ , R ^{11 '} , hAr ¹¹ and hAr ^{11 '} contained in the formula (II) different from those contained in the formula (III) Homologs are R ²¹ , R ^{21 '} , hAr ²¹ and hAr ^{21 ', respectively} .

Some embodiments of a "mixed" copolymer comprising repeating subunits of formula (II) and formula (III) may be a copolymer in which all of the repeating unit repeats unit RU, the repeating unit RU being a mixture, The mixing consists of a repeating unit RU1 having a specific chemical formula (II) and a repeating unit RU2 having a specific chemical formula (III). In some embodiments of the "mixed" copolymer comprising repeating subunits of Formula II and Formula (III), greater than 50% by mole, up to less than 100% by mole (preferably, between 90% by mole) The repeating unit between 99% by mole and the repeating unit RU1 having the specific chemical formula (II) and the repeating unit RU2 having the specific chemical formula (III), and between 0% and about 50% The repeating unit between the mole % has a repeating unit RU* that does not conform to one or more structural formulas of the structural formula (I). In such embodiments of the "mixed" copolymer comprising repeating subunits of formula (II) and formula (III), the molar ratio (RU1:RU2) of repeating units RU1 to RU2 can range from about 5% to It is in the range of about 95% (preferably, from about 30% to about 70%).

In "mixed" copolymers comprising repeating subunits of formula (II) and formula (III), it is understood that the copolymers may be "block" or random copolymers.

For example, the copolymers of formula (II) are allowed on the DPP subunit. The introduction of more than one "R" substituent on the nitrogen atom can beneficially modify the solubility and/or physical characteristics of the polymers in certain solid or solution states for certain applications. Such "mixed" copolymers may also allow for the presence of multiple types of DPP or hAr groups (which may be beneficial in some applications such as solar cells) where the introduction of different hAr groups can be used to tune and / / Widening the optical absorption band of the copolymers to better absorb the entire solar spectrum and thereby increase the efficiency of collecting solar energy.

The DPP polymers and/or copolymers comprise at least one or more types of 1,4-diketo-2,5-dihydropyrrolo[3,4- c ]pyrrole ("DPP") electron accepting subunits, The electron accepting subunits have the following generic structure:

The DPP subunit provides useful properties because the fused endoamine group is strongly electron withdrawing, planar, and highly conjugated, and can be readily conjugated to the hAr and vinylidene subunits of the polymer. This can result in small band gaps which are highly beneficial for charge transport characteristics applied in transistors and solar cells; and DPP subunits provide broad and strong light absorption in the visible to near infrared wavelengths This is beneficial in solar cell applications. Substituents that change the 2,5-guanamine nitrogen position in the DPP subunit (or in the hAr or vinylidene subunit) can be used to tune the solubility, coplanarity, hydrogen bonding interaction, crystallization of DPP polymers and copolymers. Sex, self-assembly, conjugate length, and electronic structure.

In many embodiments, the terminal "R" group at the 2,5-position of the DPP subunit may be independently selected from the group consisting of R ¹ , R ^{1 '} , R ¹¹ , R ^{11 '} , R ²¹ or R ^{21 '} , such groups may be selected from a wide variety of potentially an organic group, including _{C 1 -C 30, C 1 -C} 20 or C ₁ -C ₁₂ organic group. Preferably, the R ¹ , R ^{1 '} , R ¹¹ , R ^{11 '} , R ²¹ or R ^{21 ' are} selected from the group consisting of: such groups are expected to be up to about 300 ° C or higher. At temperatures that are heat and air stable, and are expected to be stable to oxidation or electron reduction of the hole under the operating conditions of the electronic device from which they are fabricated, such as optionally substituted alkyl, all Fluoroalkyl, alkoxy, perfluoroalkoxy, aryl, heteroaryl, alkaryl, alkaryl and the like. In some embodiments, each R ¹ , R ^{1 '} , R ¹¹ , R ^{11 '} , R ²¹ or R ^{21 ' is} independently selected from a normal chain, a branched or cyclic alkyl group or a fluorinated group thereof Derivatives. In some preferred embodiments, each R ¹ , R ^{1 '} , R ¹¹ , R ^{11 '} , R ²¹ or R ^{21 '} group is a normal or branched alkyl or perfluoroalkyl group. In some embodiments, each R ¹ , R ^{1 '} , R ¹¹ , R ^{11 '} , R ²¹ or R ^{21 '} group is the same group.

The DPP polymers and/or copolymers also comprise independently selected hAr ¹ , hAr ^{1 '} , hAr ¹¹ , hAr ^{11 '} , hAr ²¹ and hAr ^{21 '} "heteroaryl" subunits on the copolymer backbone. The "heteroaryl" subunits each comprise a five membered heteroaryl ring bonded directly to the DPP subunit. Compared to a comparable six-membered aryl or heteroaryl ring, this arrangement is believed to exhibit less undesirable spatial interactions with adjacent DPP subunits (with possible substitutions at adjacent α-positions) Related to). Without wishing to be bound by theory, it is believed that the incorporation of a less space-required five-membered heteroaryl ring to the DPP group adds hAr ¹ , hAr ^{1 '} , hAr ¹¹ , hAr ^{11 '} , hAr ^{21 ,} and hAr ²¹ groups. This higher space requirement can be bonded to by at least the higher space requirements compared to the possibility of coplanar and/or π conjugates of DPP groups bonded thereto. Potentially a six-membered aryl or heteroaryl group of DPP is present. The improved coplanar potential is also believed to increase the potential for improved intermolecular π-π stacking between molecular chains in the solid state.

The hAr heteroaryl subunits and/or rings comprise at least one carbon atom and at least one hetero atom selected from the group consisting of O, N, S, Se, and Si as part of a π-conjugated aromatic ring or ring system . The hAr ¹ , hAr ^{1 '} , hAr ¹¹ , hAr ^{11 '} , hAr ²¹ and hAr ^{21 '} "heteroaryl" subunits may further comprise one or more additional optionally substituted aryl or heteroaryl groups. The optionally substituted aryl or heteroaryl group is bonded or fused to the five-membered heteroaryl ring, which is directly bonded to the diketopyrrole The pyrroleylene group is formed to form a polycyclic or fused ring hAr subunit, as discussed further below. In many embodiments, the hAr ¹ , hAr ^{1 '} , hAr ¹¹ , hAr ^{11 '} , hAr ²¹ and hAr ^{21 '} "heteroaryl" subunits, including any optional substituent, are C ₁ -C ₆₀ , C ₁ -C ₃₀ , C ₁ -C ₂₀ or C ₁ -C ₁₂ subunit.

Nonetheless, the hAr ¹ , hAr ^{1 '} , hAr ¹¹ , hAr ^{11 '} , hAr ²¹ and hAr ^{21 '} "heteroaryl" subunits may optionally comprise one or more peripheral substituents, such as cyano, alkanes. A base, alkoxy, thioalkyl or thioalkoxy substituent to provide the potential to alter the electronic character and/or solubility of the resulting copolymer. Preferably, any such optional substituents for hAr ¹ , hAr ^{1 '} , hAr ¹¹ , hAr ^{11 '} , hAr ²¹ and hAr ^{21 '} "heteroaryl" subunits are not bonded to five The heteroheteroaryl ring (the heteroaryl ring is directly bonded to the DPP group) to minimize possible spatial interaction with the DPP group.

In many embodiments, the hAr ¹ , hAr ^{1 '} , hAr ¹¹ , hAr ^{11 '} , hAr ²¹ and hAr ^{21 '} "heteroaryl" groups may be independently selected from one or all of the heteroaryl groups having the structure Base, ie:

Wherein i) a is an integer equal to 1, 2, 3 or 4, or in some embodiments an integer equal to 1 or 2; ii) each X, X', X" or X"' is independently selected from O, S, Se, Si(R ³ ) ₂ , and NR ³ , wherein R ³ is a C ₁ -C ₃₀ positive-chain, branched or cyclic alkyl group; and iii) each Y, Y' , Y" and Y''' may be independently selected from N and CR ⁴ , wherein R ⁴ is hydrogen, halogen, cyano or a C ₁ -C ₃₀ positive-chain, branched or cyclic alkyl group, Fluoroalkyl, alkoxy, thioalkyl or thioalkoxy.

It should be noted that for hAr ¹ , hAr ^{1 '} , hAr ¹¹ , hAr ^{11 '} , hAr ²¹ and hAr ^{21 '} heteroaryl just shown above, depending on X, X', X" or X"' group The choice of group and Y, Y', Y" and Y"', the resulting heterocyclic ring can have a variety of physical, soluble and electronic characteristics (from electron donation to electron absorption), which can be used for tuning These features, hole or electron transport characteristics and/or optical band gaps of the resulting polymers and copolymers.

In many embodiments, examples of the species of the different hAr ¹ , hAr ^{1 '} , hAr ¹¹ , hAr ^{11 '} , hAr ^{21 ,} and hAr ^{21 '} heteroaryl groups whose structures are shown above may be as follows One of the heterocyclic structures shown is exemplified, namely: Wherein R ³ is a C ₁ -C ₃₀ normal chain, branched or cyclic alkyl group, and R ⁴ is hydrogen, halogen, cyano or a C ₁ -C ₃₀ positive chain, branched or cyclic Alkyl, perfluoroalkyl, alkoxy, thioalkyl or thioalkoxy.

For example, in some embodiments, each hAr ¹ and hAr ^{1 ' is} independently selected from: Wherein R ⁴ and R ^{4 '} are hydrogen, halogen, cyano or a C ₁ -C ₃₀ normal chain, branched or cyclic alkyl, perfluoroalkyl, alkoxy, thioalkyl or Thioalkoxy.

In a further embodiment, each hAr ¹ and hAr ^{1 ' is} independently selected from:

In a further embodiment, each hAr ¹ and hAr ^{1 ' is} independently selected from:

Wherein R ³ and/or R ^{3 '} is a C ₁ -C ₃₀ normal chain, branched or cyclic alkyl group, and R ⁴ and/or R ^{4 '} is hydrogen, halogen, cyano or a C ₁ -C ₃₀ -stranded, branched or cyclic alkyl, perfluoroalkyl, alkoxy, thioalkyl or thioalkoxy.

In a further embodiment, each hAr ¹ and hAr ^{1 ' is} independently selected from: Wherein R ⁴ and R ^{4 '} are hydrogen, halogen, cyano or a C ₁ -C ₃₀ normal chain, branched or cyclic alkyl, perfluoroalkyl, alkoxy, thioalkyl or Thioalkoxy.

In a further embodiment, each hAr ¹ and hAr ^{1 ' is} independently selected from: Wherein R ⁴ is hydrogen, halogen, cyano or a C ₁ -C ₃₀ normal chain, branched or cyclic alkyl, perfluoroalkyl, alkoxy, thioalkyl or thioalkoxy base.

In some embodiments of the copolymer comprising repeating unit RU1 having the specific structural formula (II) and repeating unit RU2 having the specific structural formula (III), each of hAr ¹¹ and hAr ^11' may be independently selected from:

And each of hAr ²¹ and hAr ^21' can be independently selected from: Each of X, X', X" or X"' and each of Y, Y', Y" and Y"' may have any of the meanings already detailed above.

In some preferred embodiments of the copolymer comprising the repeating unit RU1 having the specific structural formula (II) and the repeating unit RU2 having the specific structural formula (III), each of hAr ¹¹ and hAr ^11' may be independently selected from : And each of hAr ²¹ and hAr ^21' can be independently selected from: Wherein R ³ and/or R ^{3 '} is a C ₁ -C ₃₀ normal chain, branched or cyclic alkyl group, and R ⁴ and/or R ^{4 '} is hydrogen, halogen, cyano or a C ₁ -C ₃₀ -stranded, branched or cyclic alkyl, perfluoroalkyl, alkoxy, thioalkyl or thioalkoxy.

The DPP polymer described herein also includes an optionally substituted vinylidene subunit having the following structure: Wherein each of R ² and R ^{2 ' is} independently selected from hydrogen, cyano or C ₁ -C ₃₀ alkyl, perfluoroalkyl, alkoxy, aryl, heteroaryl, carboxyalkyl or ethoxylated. . In many embodiments, each R ² and R ^{2 '} group is hydrogen.

Such an ethylene subunit is considered to play a role in the electronic and physical properties of a polymer which contributes to DPP comprising a repeating unit of the formula (I) and a copolymer comprising repeating units of the formulae (II) and (III). Importantly because they allow for an extended conjugation along the polymer or copolymer backbone in a spatially very undemanded manner, which allows for a high total between the DPP polymer and the subunits of the copolymer. Flatness, this high coplanarity allows for a high degree of intermolecular π-π stacking in the solid state, which can result in a significant increase in hole or electron mobility in the solid state. The functionalities of the ethylene subunits may also increase the solubility of the DPP polymer or copolymer and/or improve their solution processing characteristics.

In addition to the repeating units of structural formula (I), (II) and/or (III), further and additional types of repeating units RU may be present in the DPP polymers or copolymers described herein, in amounts of Less than about 50 (or 40, or 30 or 20 or 10 or 5 or 2 or 1) mole %. Such other repeating units often contain a wide variety of difunctional heteroaryl groups. For example, the DPP polymer and/or copolymer of the present invention may optionally comprise between 0 mole % and 50 mole % of repeat units: the repeat units have the following chemical formula One or more repeating units RU*, ie:

or Where a, and each X or X', and each Y or Y' may have any of the meanings already detailed above. Preferred examples of such repeating units of the formulae (IV) and (V) may include a heteroaryl group having the structure shown below.

Wherein R ⁴ and R ^{4 '} may be independently selected from hydrogen, halogen, cyano or a C ₁ -C ₃₀ normal chain, branched or cyclic alkyl, perfluoroalkyl, alkoxy, thio Alkyl or thioalkoxy.

With respect to the characteristics of the different embodiments of the DPP polymers or copolymers described herein, in some embodiments, those DPP polymers or copolymers may have polystyrene calibration standards by gel permeation chromatography. The number average degree of polymerization determined by the product is at least 10. Similarly, the DPP polymer or copolymer described herein may have, in some embodiments, the number average degree of polymerization determined by gel permeation chromatography using polystyrene calibration standards. More is 100.

In many embodiments, the different DPP polymers and/or copolymers described herein can have unexpectedly high solubility in common organic solvents, which is useful for adjusting ink formulations to accommodate a wide variety of solution printing processes (eg, spraying) Ink printing, etc., is of great benefit for the preparation of desired organic electronic devices, such as photovoltaic cells and/or transistors. Accordingly, in some embodiments, the DPP polymers and/or copolymers have at least 10 mg/ml at one or more temperatures (eg, 35 ° C) selected in the range of 25 ° C to 50 ° C in at least one solvent. Preferably, the solubility is at least 20 mg/ml, and the solvent is selected from the group consisting of toluene, xylene, mesitylene, tetrahydrofuran, chloroform, chlorobenzene, dichlorobenzene, and the like mixture. For example: DPP polymers and/or copolymers may have a solubility in toluene of at least 10 mg/ml at 25 ° C and/or 50 ° C; DPP polymers and / or copolymers in tetrahydrofuran at 25 ° C and / or 50 ° C May have a solubility of at least 10 mg/ml; and/or the DPP polymer and/or copolymer may have at least 10 in a mixture of chloroform and chlorobenzene in a weight ratio of 50:50 at 25 ° C and/or 50 ° C. Solubility in mg/ml.

Synthesis of polymers and / or copolymers

A generic synthesis scheme for the manufacture of polymerizable comonomers required for the synthesis of the polymers and/or copolymers of the present invention is presented below, and Specific examples of such generic synthesis schemes are also provided in the "Examples" section of this disclosure.

The following synthetic schemes illustrate two general methods for making polymerizable bromodiheteroaryl substituted diketopyrrolopyrrole comonomers suitable for use in the manufacture of the polymers of the present invention. The starting heteroaryl nitrile can often be produced by a number of methods known to those skilled in the art, for example from the corresponding heteroaryl aldehyde or bromoheteroaryl aldehyde by condensation with hydroxylamine or by cyanide Manufactured by condensation reaction with a heteroaryl diazonium salt (Mowry, DT Chem. Rev. 1948, 42 , 189-283.; Barclay, RM; Cordes, AW; MacKinnon, CD; Oakley, RT; Reed , RW Materials Chemistry (Chem. Mater.) 1997, 9 , 981-990.).

A polymerizable bromodiheteroaryl-substituted diketopyrrolopyrrole comonomer, such as m1 and m2 in the above figures, each of which can be catalyzed by a well-known palladium-catalyzed Stille condensation reaction with trans-1,2-di (Tributylstannyl)ethylene condensation (optionally in the presence of one or more additional dibromoheteroaryl comonomers) to produce a polymer comprising repeating units of formula (I).

Accordingly, in some embodiments, the invention described herein relates to methods for making the polymers described herein, the methods comprising the steps of: a) obtaining or providing at least one diheteroaryl substituted diketone group A pyrrolopyrrole monomer having the following structure:

Wherein LG ¹ is a leaving group such as a bromine atom, an iodine atom, an organic sulfonic acid group, or the like; b) an ethylene monomer obtained or provided with at least one di- leaving group, the monomer having The following structure:

Wherein LG ² is a leaving group capable of being eliminated by reaction with LG ¹ such as SnR ^2" ₃ (wherein R ^{2 "} alkyl or aryl); c) in a transition metal catalyst In the presence of a complex, a mixture comprising the at least one first diheteroaryl substituted diketopyrrolopyrrole monomer and the at least one dipartition group substituted ethylene monomer is reacted so that A polymer comprising repeating units of formula (I) is produced.

Such transition metal catalyzed coupling/polymerization reactions are well known in the art (particularly in the presence of a nickel or palladium catalyst). For example, suitable palladium catalyzed coupling/polymerization processes include aryl halides or heteroaryl halides (ie, LG ¹ = bromine or iodine) and organotin compounds (LG ¹ based SnR ^2" ₃ , where R ^2" Stille coupling between alkyl or aryl), or aryl halide or heteroaryl halide (ie LG ¹ = bromine or iodine) and organoborate compound (ie LG ² =B(OR) ₂ , Wherein the Suzuki coupling between the R series alkyl groups, or the aryl halide or heteroaryl halide (ie LG ¹ = bromine or iodine) and the organotellurium compound (ie LG ² =SiR ^2" ₃ , wherein R ² Hyama coupling between ^" alkyl or aryl ^" .

Typical soluble palladium catalyst complexes useful in such catalytic coupling/polymerization reactions include palladium acetate, tetrakis(triphenylphosphine)palladium(0), [1,1'-bis(diphenylphosphino). Ferrocene]palladium(II) dichloride or bis(triphenylphosphine)palladium(II) dichloride, and tris(dibenzylideneacetone)dipalladium(0)(iePd ₂ (dba) ₃ ), Typically at a concentration of from about 0.1 wt% to about 20 wt%, and optionally additional and/or excess phosphine ligands (such as triarylphosphine) may be present.

In some embodiments, the reaction mixture is substantially free of any of the diketopyrrolopyrrole monomers substituted with the at least one first diheteroaryl group and the at least one di-group-substituted vinyl monomer. monomer.

In many embodiments of the process for making the polymer of the present invention, the reaction mixture comprises substantially equimolar amounts of at least one diheteroaryl-substituted diketopyrrolopyrrole monomer and at least one di- leaving group. A group of substituted vinyl monomers. However, in other embodiments, other comonomers may be present in the reaction mixture to make the copolymer. For example, in some embodiments, the reaction mixture further includes at least one self-reactive monomer having the structure: LG ¹ -hAr*-LG ² wherein hAr* is a C ₁ -C ₆₀ heteroaryl group, and LG ¹ and LG ² are the leaving groups described above. Examples of suitable C ₁ -C ₆₀ heteroaryl groups include the following structures:

Where a, LG ¹ , LG ² , X, X', X", X"', Y, Y', Y", and Y"' are defined herein elsewhere.

In such embodiments, the self-reactive monomer may self-condense (at least to some extent) in the presence of a transition metal catalyst to form a copolymer block having the following structure (in the DPP copolymer of the present invention) That is: -(hAr*) _x -, wherein x is an integer greater than 1, and is preferably in the range of 2 to 100.

Alternatively, a mixture of DPP/hAr comonomers such as m1 or m2 as shown below may be condensed with bis(tributylstannyl)ethylene to produce random or block copolymers, the copolymers comprising at least some of Repeating units of formula (II) and / or (III). Accordingly, in some embodiments, the invention described herein relates to a process for making a random copolymer, the method comprising the steps of: a) obtaining or providing at least one first diheteroaryl substituted diketone A pyryrrolopyrrole monomer having the following structure:

Wherein LG ¹ is a leaving group; b) obtaining or providing at least one second diheteroaryl substituted diketopyrrolopyrrole monomer having the following structure:

c) obtaining or providing at least one di-group-substituted vinyl monomer having the following structure:

Wherein LG ² is a leaving group capable of being eliminated by reaction with LG ¹ and d) comprising at least a first and a second in the presence of a transition metal catalyst complex A mixture of di-heteroaryl-substituted diketopyrrolopyrrole monomers and at least one di-substituent-substituted ethylene monomer is reacted to produce the copolymers.

In some embodiments, such DPP copolymers are random copolymers wherein R ¹¹ and R ^{11 '} are identical to each other and R ²¹ and R ^{21 '} are identical to each other. In other embodiments, such DPP copolymer is a block copolymer wherein R ¹¹ and R ²¹ are different from each other and/or R ^{11 '} and R ^{21 '} are different from each other.

Although the sequence of the DPP/hAr repeat unit may be random or nearly random, the copolymer prepared by such a method may be random or nearly random, but it is also possible At least one comonomer having the following structure is included in the reaction mixture to disperse additional random hAr* repeating units in such copolymers, ie, the comonomer has the following structure: LG ¹ -hAr*- LG ¹ , wherein the possible structures of hAr* and LG ¹ have been previously described above.

Specific examples of the synthesis of such polymers and their properties are provided below in the Examples section.

Organic electronic device comprising polymer and/or copolymer

Some aspects of the invention relate to novel organic electronic devices comprising a polymer of formula (I) or a copolymer comprising repeating units of formula (II) and (III) as described herein, such devices Including transistors and different logic circuits containing transistors, and too Solar battery. Those applications for end use typically each require the formation of a film of the copolymer of the present invention on a substrate. The organic film of the polymer and the copolymer of the present invention can be produced by a known method such as spin coating, casting, dip coating, ink jet method, knife coating method, screen printing method, And spraying method. By using such a method, it is possible to prepare an organic film having good characteristics such as mechanical strength, toughness, and durability without forming cracks in the films. Therefore, the organic films can be preferably used for organic electronic devices such as photovoltaic cells and OFET elements.

A film comprising a polymer of a repeating unit of formula I or a copolymer comprising repeating units of formula (II), (III), (IV) and (V) is typically prepared by coating a coating liquid on a substrate, The coating liquid is dissolved in a solvent (such as dichloromethane, tetrahydrofuran, chloroform, in the case of a solar cell, and typically an electron accepting material such as a fullerene derivative such as PCBM). Prepared in toluene, chlorobenzene, dichlorobenzene or xylene). Specific examples of such coating methods include spray coating, spin coating, knife coating, dip coating, cast coating, roll coating, bar coating, die coating, ink jet, dispensing, and the like. In this regard, a suitable method and a suitable solvent are selected in consideration of the characteristics of the polymer used. Suitable materials for use as a substrate on which the film of the polymer of the present invention is formed include inorganic substrates such as glass plates, ruthenium plates, ITO plates, and FTO plates; and organic substrates such as plastic plates (for example, PET films, polyimide films). And the polystyrene film), the substrates may optionally be subjected to a surface treatment. Preferably, the substrate has a smooth surface.

Organic film and organic semiconductor layer of organic thin film transistor of the present invention The thickness is not specifically limited. However, the thickness is determined such that the resulting film or layer is a uniform thin layer (i.e., the film or layer does not include gaps or voids that adversely affect its carrier transport properties). The thickness of the organic semiconductor layer is generally not more than 1 μm and preferably from 5 to 200 nm.

Making a transistor comprising the polymer and/or copolymer of the invention

The organic thin film transistor of the present invention typically has a configuration such that it comprises a polymer (containing a repeating unit of formula (I)) or a copolymer (including formula (II), (III), (IV) and/or (V) An organic semiconductor layer of the repeating unit) may be formed on the substrate while also contacting the source electrode, the drain electrode, the gate electrode, and the insulating layer of the transistor.

The organic film prepared above is typically annealed. Annealing occurs when the film is placed on a substrate and is believed to allow for improved ordering of the copolymer molecules in the solid state. The annealing temperature is determined depending on the characteristics of the material constituting the substrate, but is preferably from room temperature to 300 ° C, and more preferably from 50 ° C to 300 ° C. In many embodiments, the transistors and/or circuits comprising the copolymer molecules are thermally annealed at a temperature between about 100 ° C and 250 ° C. When the annealing temperature is too low, the organic solvent remaining in the organic film is not well removed therefrom. In contrast, when the annealing temperature is too high, the organic film tends to be thermally decomposed. Annealing is preferably carried out in a vacuum, nitrogen, argon or air atmosphere. It is also possible to perform annealing in an atmosphere including a gas capable of dissolving an organic solvent of the polymer because the molecular motion of the polymer is accelerated, and thus a good one can be prepared. Organic film. The annealing time is appropriately determined depending on the aggregation speed of the polymer.

An insulating layer is used for the gate of the organic thin film transistor comprising the polymer and/or copolymer of the present invention. Different insulating materials can be used for the insulating layer. Specific examples of such insulating materials include: inorganic insulating materials such as cerium oxide, cerium nitride, aluminum oxide, aluminum nitride, titanium oxide, cerium oxide, tin oxide, vanadium oxide, barium titanate, barium zirconate titanate, zirconium Lead titanate, lead barium titanate, barium titanate, barium titanate, barium magnesium fluoride, barium strontium silicate, barium oxide, and antimony trioxide; organic insulating materials such as polymer materials, such as polyimine, poly Vinyl alcohol, polyvinyl phenol, polystyrene, polyester, polyethylene, polyphenylene sulfide, unsubstituted or halogen-substituted poly-p-xylylene, polyacrylonitrile, and cyanoethyl pullulan, etc. . These materials may be used singly or in combination. Among these materials, it is preferred to use a material having a high dielectric constant and a low electrical conductivity.

Suitable methods for forming such an insulating layer include: dry methods such as CVD, plasma CVD, plasma polymerization, and vapor deposition; wet methods such as spray coating, spin coating, dip coating, spraying Ink coating method, cast coating method, knife coating method, and bar coating method; and the like.

In order to improve adhesion between the insulating layer and the organic semiconductor layer, promote charge transport, and lower gate voltage and leakage current, an organic thin film (intermediate layer) may be formed between the insulating layer and the organic semiconductor layer. The materials used in the intermediate layer are not particularly limited as long as the materials do not chemically affect the characteristics of the organic semiconductor layer, and a molecular film such as an organic material, and a film of a polymer may be used for this purpose. Used to prepare this Specific examples of the material of the isomeric film include a coupling agent such as octadecyltrichloromethane, octyltrichlorodecane, octyltrimethoxydecane, hexamethyldiazepine (HMDS), and octadecyl group. Phosphonic acid. Specific examples of the polymer used to prepare the polymer films include the above-mentioned polymers used in the insulating layer. Such a polymer film can be used as the insulating layer together with the intermediate layer.

The materials of the electrodes (such as the gate electrode, the source electrode, and the drain electrode) of the organic thin film transistor of the present invention are not particularly limited as long as the materials are electrically conductive. Specific examples of such materials include: metals such as platinum, gold, silver, nickel, chromium, chromium, copper, iron, tin, antimony, lead, antimony, indium, aluminum, zinc, tungsten, titanium, calcium, and magnesium; An alloy of a metal; a conductive metal oxide such as indium tin oxide (ITO); an inorganic or organic semiconductor whose conductivity is improved by doping or the like, such as germanium single crystal, polycrystalline germanium, amorphous germanium. , antimony, graphite, carbon nanotubes, polyacetylene, polyparaphenylene, polythiophene, polypyrrole, polyaniline, polythiophene acetylene, polyparaphenylene acetylene, and polyethylene dioxythiophene (PEDOT) and polystyrene sulfonate Acid complex.

The average hole mobility measured from an exemplary transistor including HD-PPTV as explained in Examples 1 and 6 below was in a narrow range of 0.091 to 0.17 cm ² V ^-1 s ^-1 , and the average electron mobility system was 0.012 to 0.019 cm ² V ^-1 s ^-1 , and the current switching ratio is 10 ² to 10 ³ . The values of the hole and electron mobility and the resulting bipolar characteristics in the transistors are surprisingly high compared to the prior art known to the inventors. The threshold voltages for hole and electron transfer are relatively positive, with -9.0 to -1.6 V for p-type channel operation and 22.7 to 32.1 V for n-type channel mode.

The DPP polymers and copolymers described herein can have an unexpectedly superior hole mobility of about 0.1 cm ² V ^-1 s ^-1 or greater, which is measured from a thin film transistor. The thin film transistor has a bottom gate, bottom contact geometry, using doped germanium as the gate material, germanium dioxide as the gate dielectric, gold source and channel widths of 400 to 800 μm and 20 to A 40 μm channel length has a chrome-adhesive drain electrode and these copolymers are used as active semiconductors.

Similarly, the DPP polymers and copolymers described herein can have an unexpectedly superior electron mobility of about 0.01 cm ² /Vsec or greater, as measured from a thin film transistor having a Bottom gate, bottom contact geometry, using doped germanium as gate material, germanium dioxide as gate dielectric, gold source and channel width of 400 to 800 μm and channel length of 20 to 40 μm A ruthenium electrode of a chrome-adhesive layer, and these copolymers are used as active semiconductors.

Some of the DPP polymers and/or copolymers described above exhibit bipolar characteristics and may have a phase equilibrated hole mobility and an electron mobility of about 0.01 cm ² V ^-1 s ^-1 or greater. Mobility and electron mobility are measured from a thin film transistor having a bottom gate, bottom contact geometry, using doped germanium as the gate material, and germanium dioxide as the gate dielectric. A gold source and a gate electrode having a chromium adhesive layer at a channel width of 400 to 800 μm and a channel length of 20 to 40 μm were used, and the copolymers were used as active semiconductors. Although the on/off ratio and threshold voltage observed from a bipolar transistor containing a single active layer of HD-PPTV as illustrated in the examples may not be optimal for some applications, it includes such high holes and electrons. Mobility of mobility bipolar materials may be suitable and unexpectedly economically superior for use in certain low performance and low cost applications, such as RFID tags. We have clearly demonstrated that not only inverters with two bipolar transistors but also more complex electronic logic gates (composed of three or more bipolar transistors and with 2- or more input signals, such as The anti-gate or anti-gate or gate can be constructed by implementing a bipolar polymer semiconductor such as HD-PPTV.

Manufacturing an integrated circuit comprising the polymer and/or copolymer of the present invention

Complementary integrated circuits including the copolymers of the present invention, such as inverters, inverse and logic circuits, inverse or logic circuits, and the like, typically have one or more that can function as n-type or p-channel devices Transistor. The constituent transistors of an integrated circuit are electrically connected to a common substrate or a plurality of separate substrates. The constituent materials of a transistor such as an electrode, an insulator, and the DPP polymer and copolymer described herein are formed by photolithography, soft lithography, spin coating, printing, vapor deposition, and/or self-assembly.

Manufacturing solar cells comprising DPP polymers and/or copolymers

One aspect of the invention described herein is a solar cell comprising the DPP polymer and/or copolymer described above, and also typically comprising an electron accepting material such as fullerene or fullerene derivative. Such as PCBM.

Such a battery can typically be manufactured by first spinning a PEDOT buffer layer over ITO coated glass substrate at 1500 rpm for 60 s and drying at 150 ° C for 10 min under vacuum to form an anode. . The thickness of the PEDOT layer should be about 40 nm.

The solvent used to dissolve the mixture of the polymer and/or copolymer of the present invention and the electron acceptor may be chloroform, chlorobenzene, 1,2-dichlorobenzene or the like. The solvent for the copolymer/fullerene blend may be a single solvent such as chloroform, chlorobenzene, 1,2-dichlorobenzene, or a mixture of two or three different solvents, and a second (third) solvent. It may be 1,8-diiodooctane, 1,8-dibromooctane, 1,8-octanedithiol, and the like. The active blend layer (copolymer and fullerene blend) can be spin coated onto the PEDOT layer from a copolymer/fullerene blend solution at 1000 rpm for 30 s and then in a glove The box was annealed on a hot plate at 150 ° C ± 40 ° C for 10 min. The active layer can also be spin coated in air and dried in a vacuum oven without thermal annealing.

After cooling down, the substrate coated with the copolymer was taken out of the glove box and loaded into a thermal evaporator for deposition of the cathode. A cathode consisting of a 1.0 nm LiF and an 80 nm aluminum layer can be successively deposited onto the copolymer/electron acceptor active layer by a shadow mask in a vacuum of 8 x 10 ^-7 Torr.

Instance

The different inventions described above are further demonstrated by the following specific examples. The examples are not intended to be construed as limiting the scope of the invention, or the scope of the appended claims. Rather, it is to be understood that various other embodiments, modifications, and equivalents may be present, which, after reading the description herein, may be apparent to those of ordinary skill in the art without departing from the spirit of the invention. Or the scope of the appended claims.

Materials trans-1,2-bis (tri-butylstannyl) ethylene was purchased from Alfa Aesar (Alfa Aesar), and the press used as received. Anhydrous chlorobenzene and other chemicals were purchased from Aldrich and used as received.

3,6-bis(5-bromo-thiophen-2-yl)-2,5-di(2-hexylfluorenyl)pyrrolo[3,4-c]pyrrole-1,4-dione (m1) By B ü rgi, L.; Turbiez, M.; Pfeiffer, R.; Bienewald, F.; Kirner, H.-J.; Winnewisser, C. Advanced Materials (Adv. Mater.) 2008, 20 , 2217 and / Or Bijleveld, JC; Zoombelt, AP; Mathijssen, SGJ; Wienk, MM; Turbiez, M.; deLeeuw, DM; Janssen, RAJ , J. Am. Chem. Soc., 2009, 131 , 16616 Method preparation. 3,6-bis(4-bromophenyl)-2,5-di(2-hexyldecyl)-pyrrolo[3,4-c]pyrrole-1,4-dione (m2) by Fukuda, M.; Kodama, K.; Yamamoto, H.; Mito, K. Dyes and Pigments 2004, 63 , 115 reported synthesis.

Characterization of ¹ H NMR spectra was recorded on a 300 MHz Bruker-AF300 spectrometer. UV-visible absorption spectra were recorded on a Perkin-Elmer model Lambda 900 UV/Vis/NIR spectrophotometer. Photoluminescence (PL) emission spectra were obtained using a Model QM-2001-4 spectrofluorometer from Photon Technology International (PTI) Co., Ltd. The molecular weights reported for these polymers were determined on Polymer Lab's Gel Permeation Chromatography (GPC) Model 120 (DRI, PL-BV400 HT Viscometer) relative to polystyrene standards in chlorobenzene at 60 °C. X-ray diffraction (XRD) images were obtained on a Bruker AXS D8 Focus diffractometer using a Cu Kα beam (40 kV, 40 mA; λ = 0.141618 nm). The data obtained from the 2θ angle 2 to 35° at a scan rate of 0.01°/s was calculated from the following equation: d-spacing, ie: nλ=2d sin θ. A differential scanning calorimetry (DSC) scan was obtained on a TA Instrument Q20 at a heating rate of 10 °C/min. Cyclic voltammetry experiments were performed on an EG&G Princeton Applied Research Potentiostat/Galvanostat (Model 273A) using 0.1 M solution of tetrabutylammonium hexafluorophosphate (Bu ₄ NPF ₆ ) in acetonitrile as the electrolyte. A three-electrode cell was used in all experiments. A platinum wire electrode was used as the counter electrode and the working electrode and a silver/silver ion electrode (Ag in a 0.1 M AgNO ₃ solution, Bioanalytical System Co., Ltd.) was used as a reference electrode. The Ag/Ag ⁺ (AgNO ₃ ) reference electrode was calibrated at the beginning of the experiment by running cyclic voltammetry on ferrocene as an internal standard. The potential value obtained with reference to the Ag/Ag ⁺ electrode is then converted to a saturated calomel electrode (SCE) scale. A film of the polymer was coated on the working electrode by dipping the platinum wire into a 10 wt% solution in chloroform/chlorobenzene and drying for 30 min.

Example 1 - Poly[3,6-(2,5-bis(2-hexylfluorenyl)pyrrolo[3,4-c]pyrrole-1,4-dione)- alt -1,2-di-( Synthesis of 2'-thienyl)vinyl-5',5"-diyl], HD-PPTV

Poly[3,6-(2,5-bis(2-hexylfluorenyl)pyrrolo[3,4-c]pyrrole-1,4-dione)- alt -1,2-di-(2'- Thienyl)vinyl-5',5"-diyl], HD-PPTV. 3,6-bis(5-bromo-thiophen-2-yl)-2,5-di(2-hexylfluorenyl) Pyrrolo[3,4-c]pyrrole-1,4-dione (m1) (480 mg, 0.53 mmol) and trans -1,2-bis(tributylstannyl)ethylene (320.8 mg, 0.53 mmol) Dissolved in anhydrous chlorobenzene (18 mL) and purged with argon. Add Pd ₂ (dba) ₃ catalyst (9.7 mg, 0.01 mmol) and P( o -toyl) ₃ ligand (12.9 mg, 0.04 mmol) And degassing. After washing with argon for 5 min, the solution was refluxed for 2 days at 120 ° C. The solution was then quenched and precipitated into methanol. The solid was filtered and subjected to Soxhlet extraction using acetone, and in a vacuum oven Drying to provide a dark green solid (398 mg, yield: 95%). ¹ H NMR (CDCl ₃ ), δ (ppm): 8.93 (br, 2H), 7.01 (br, 4H), 4.09 (br) , 4H), 197 (br, 2H), 1.25 (48H), 0.87 (br, 12H).

Comparative Example 2 - Poly[3,6-(2,5-bis(2-hexylfluorenyl)pyrrolo[3,4-c]pyrrole-1,4-dione)- alt -1,2-diphenyl Synthesis of vinyl-4',4"-diyl], HD-PPTV

Poly[3,6-(2,5-bis(2-hexylfluorenyl)pyrrolo[3,4-c]pyrrole-1,4-dione)- alt -1,2-distyryl-4 ',4"-diyl], HD-PPTV, which contains a six-membered benzene ring at various positions of the "hAr" subunit (prepared by the above reaction in a manner similar to that used in Example 1). The yield of the purple solid was 47%. ¹ H NMR (CDCl ₃ ), δ (ppm): 7.63 (br, 8H), 7.09 (br, 2H), 3.85 (br, 4H), 1.7-1.25 (br, 50H), 0.89 (br, 12H).

Comparative Example 3 - Poly[3,6-(2,5-bis(2-hexylfluorenyl)pyrrolo[3,4-c]pyrrole-1,4-dione)- alt -1,2-diphenyl Synthesis of vinyl-4',4"-diyl], HD-PPTV

Poly{[3,6-(2,5-bis(2-hexylfluorenyl)pyrrolo[3,4-c]pyrrole-1,4-dione)- alt -1,2-distyryl- 4',4"-diyl] -co -3,6-(2,5-bis(2-hexyldecyl)pyrrolo[3,4-c]pyrrole-1,4-dione)- alt - 1,2-di-(2'-thienyl)vinyl-5',5"-diyl]}, PPTV, which contains a six-membered benzene ring at some positions of the "hAr" subunit (as shown above) To synthesize). Black solid, yield: 33%. ¹ H NMR (CDCl ₃ ), δ (ppm): 8.92 (br, 1H), 7.84-6.74 (br, 7H), 4.07 (br, 2H), 3.82 (br, 2H), 1.94-1.25 (br, 49H) ), 0.87 (br, 12H). The actual composition (x) of the random copolymer is 0.5 using the integral of the α-methylene proton resonance as follows: x = δ (4.07) / [δ (4.07) + δ (3.82)] .

Example 4 - Physical Properties of HD-PPTV, HD-PPPV, and PPTPV Copolymers

HD-PPTV and PPTPV have good solubility in high concentrations (10-20 mg/mL) in common organic solvents such as chloroform, chlorobenzene and 1,2-dichlorobenzene, while HD-PPPV only shows poor Solubility (<2 mg/mL). Number average molecular weight of three kinds of copolymer (M _n) in the 21,800 to 88,800 g / mol range, the polydispersity index (PDI) of 2.32 to 3.60, as summarized in Table 1.

The DPP-based copolymers HD-PPTV, HD-PPPV and PPTPV containing indoleamine demonstrate good thermal stability, but for these three poly(arylene vinylene) by differential scanning calorimetry Between No significant thermal transition was observed between 0 °C and 350 °C (see Figure 1).

Photophysical properties. Figures 2a and 2b show the optical absorption spectra of three copolymers of HD-PPTV, HD-PPPV and PPTPV in a dilute solution (1 x 10 ^-6 to 1 x 10 ^-5 M) and as a film. In the toluene solution (Fig. 2a), HD-PPPV and HD-PPTV exhibited maximum absorption (λ _max ) at 538 nm and 887 nm, respectively. In the film (Fig. 2b), HD-PPPV and HD-PPTV exhibited maximum absorption λ _max at 537 nm and 814 nm, respectively. HD-PPPV has an optical band gap of 2.00 eV, which is smaller than for poly(1,4-diketo-2,5-dialkyl-3,6-diphenylpyrrolo[3,4-c]pyrrole) The reported 2.09 to 2.13 eV (see Rabindranath, AR; Zhu, Y.; Heim, I.; Tieke, B. Macromolecules 2006, 39 , 8250). Similarly, HD-PPTV has an optical band gap of 1.22 eV which is slightly smaller than for poly(1,4-diketo-2,5-dioctyl-3,6-di(thiophen-5-yl)pyrrole [3,4-c]pyrrole reported at 1,25 eV (see Bijleveld, JC; Zoombelt, AP; Mathijssen, SGJ; Wienk, MM; Turbiez, M.; de Leeuw, DM; Janssen, RAJ American Chemical Society) (J. Am. Chem. Soc.) 2009, 131 , 16616).

Figures 3a and 3b show the photoluminescence (PL) emission spectra of HD-PPTV and PPTPV. It may be because the weakness exceeds the detection limit and/or quenching in the solid state, and the PL spectrum of the HD-PPTV is not obtained. The HD-PPPV is red-emitting, and the PL maxima in the dilute solution and as the film are at 647 and 653 nm, respectively. This HD-PPPV polymer is similar to other DPP-based polymers and is used in dilute solutions. The film has a large Stokes shift of 109 and 116 nm. Similar to HD-PPPV, the random copolymer PPTPV has a weak PL peak centered at 651 nm in a dilute solution, but the photoluminescence is almost completely quenched in the film.

Electrochemical Characteristics Cyclic voltammetry (CV) was used to initially evaluate the electronic structure and energy levels of HD-PPTV, HD-PPPV, and PPTPV polymers. As shown in Figures 4a, 4b and 4c, the reduction and oxidation scans of the three copolymers all show a quasi-reversible process.

The electronic structures and energy levels extracted from these CV scans are summarized in Table 1 above. Compared to HD-PPTV (-5.14 eV) and PPTPV (-5.21 eV), HD-PPPV has a low HOMO level of -5.48 eV. In addition, HD-PPPV has a high LUMO level of -3.13 eV compared to -3.34 and -3.31 eV in HD-PPTV and PPTPV. Thus, HD-PPPV shows an electrochemical band gap of 2.35 eV greater than 1.80 to 1.90 eV for HD-PPTV and PPTPV. The HOMO/LUMO levels of PPTPV are similar to those of HD-PPTV, probably because they share the same Th-DPP-Th core and the resulting strong intermolecular charge transfer. However, the current intensity of the reduction curve is much lower than the oxidation curve, suggesting that they can have a better ability to transmit holes than electrons.

Crystallinity of poly(arylenevinylene) based on DPP. Each copolymer was dissolved in chloroform/chlorobenzene at 10 to 20 mg/mL, and the solutions were dropped on a glass substrate. The films were then dried in air on a hot plate at 60 °C. The possible crystalline properties of the three poly(arylene vinylene) HD-PPTV, HD-PPPV and PPTPV are examined by X-ray diffraction (XRD) of the drop coatings, as shown in FIG. The HD-PPTV has a (100) reflection peak at 4.78°, corresponding to a d ₁₀₀ pitch of 18.47 Å. Without wishing to be bound by theory, the d ₁₀₀ pitch is considered to correspond to the stacking distance in a layered stack structure, represented by a bulky 2-hexyl fluorenyl chain. HD-PPPV does not have such a peak, and the random copolymer PPTPV shows a weak reflection peak only at 4.89°, corresponding to a d ₁₀₀ spacing of 18.02 Å, indicating that PPTPV may have a layered stack similar to HD-PPTV. . The broad peak at 22.67° for the center of the HD-PPTV is considered to be related to the intermolecular π-π stacking distance between the HD-PPTV polymer chain (3.92 Å) and can indicate the HD-PPTV polymer in the solid state. Relatively high crystalline properties. In contrast, HD-PPPV and HD-PPTV did not show any similar reflection peaks around 22°.

Example 5 - Fabrication and Characterization of Field Effect Transistors

A field effect transistor comprising HD-PPTV, HD-PPPV, and PPTPV polymer as active semiconductor layers was fabricated on a heavily doped germanium substrate having a thermally grown ceria gate insulator (200 nm). A gold electrode (40 nm) with a chrome-adhesive layer (2 nm) acts as a source and drain electrode in the bottom contact/bottom gate transistor, resulting in a channel width (W) of 400 to 800 μm and 20 Channel length (L) up to 40 μm (W/L=20). The substrates were ultrasonically cleaned using acetone and isopropanol and dried by a stream of nitrogen. The surface of the ceria substrate is treated with octyltrichloromethane (OTS-8) to form a hydrophobic self-assembled monolayer . A solution of the polymer 1,2-dichlorobenzene (ODCB) was deposited on the substrate by spin coating. The devices were annealed at different temperatures in a nitrogen-filled dry box. The electrical characteristics of the devices were measured under a nitrogen atmosphere by using a HP4145B semiconductor parameter analyzer.

Figures 6a and 6b show representative current-voltage characteristics of OFETs based on HD-PPTV, HD-PPPV, and PPTPV as polymer semiconductors. Figure 6b shows an overlay of a representative transfer curve ( _Vds = ± 80 V) for a transistor comprising HD-PPTV, HD-PPPV, and PPTPV. A transistor using HD-PPTV (Fig. 6a) shows holes and electronic charge transport with typical bipolar characteristics, such as current modulation and saturation observed on the positive and negative polarities of the applied voltage. The mobility of the charge carriers is calculated from the transfer curve using the standard saturation equation of the metal oxide semiconductor field effect transistor, i.e., I _ds = ( μWC _o /2L ) ( V _g - V _t ) ² . The hole mobility of up to 0.20 cm ² V ^-1 s ^{-1 and} the electron mobility of up to 0.03 cm ² V ^-1 s ^-1 were obtained. The extracted electrical parameters are collected in Table 2.

The average hole mobility measured by an exemplary transistor including HD-PPTV is in a narrow range of 0.091 to 0.17 cm ² V ^-1 s ^-1 , and the average electron mobility is 0.012 to 0.019 cm ² V ^{-1 .} s ^-1 and the current switching ratio is 10 ² to 10 ³ .

The threshold voltage for the hole and electron transfer is -9.0 to -1.6 V for the p-channel operating system and 22.7 to 32.1 V for the n-channel mode.

In the case of HD-PPPV, a low hole mobility of 4.9 × 10 ^-7 cm ² V ^-1 s ^-1 was obtained without electron transport, which is understandable because HD-PPPV has 2.0 eV A large band gap and a high LUMO energy level result in a large injection barrier to electrons from the gold electrode. After annealing at 110 ° C to 200 ° C, PPTPV has a compromise OFET performance with a hole and electron mobility of 3.9 × 10 ^-4 to 2.2 × 10 ^-3 cm ² V ^-1 s ^-1 and 2.9 × 10, respectively. ^-6 to 2.3 × 10 ^-5 cm ² V ^-1 s ^-1 . The highest average mobility in PPTPV organic field effect transistors was observed after annealing at 150 °C (Table 2).

The hole mobility in HD-PPTV transistors is about an order of magnitude higher than the electron mobility, which may result from a larger injection barrier to electrons from the gold electrode. The mobility (0.012 to 0.17 cm ² V ^-1 s ^-1 ) is comparable to that reported for a bipolar transistor based on a single conjugated polymer semiconductor (0.01 to 0.65 cm ² V ^-1 s ^-1 ) And higher than the reported value (0.01-0.05 cm ² V ^-1 s ^-1 ) obtained from a bipolar transistor with a similar bottom contact and bottom gate geometry, see B ü rgi, L.; Turbiez, M Pfeiffer, R.; Bienewald, F.; Kirner, H.-J.; Winnewisser, C. Advanced Materials (Adv. Mater.) 2008, 20 , 2217; Bijleveld, JC; Zoombelt, AP; Mathijssen, SGJ; Wienk, MM; Turbiez, M.; de Leeuw, DM; Janssen, RAJ J. Am. Chem. Soc. 2009, 131 , 16616; Tsai, J.-H.; Lee, W.- Y.; Chen, W.-C.; Yu, C.-Y.; Hwang, G.-H.; Ting, C. Materials Chemistry (Chem. Mater.) 2010, 22 , 3290; Sonar, P.; Singh, SP; Li, Y.; Soh, MS; Dodabalapur, A. Advanced Materials (Adv. Mater.) 2010, 22 , 5409.; and Ashraf, RS; Chen, Z.; Leem, DS; Bronstein, H. ;Zhang,W.;Schroeder,B.;Geerts,Y.;Smith,J.;Watkins,S.;Anthopoulos,TW;Sirringhaus,H.;de Mello,JC;Heeney,M.;McCulloch,I. Chemistry (Chem.Mater.) 2011, 23 , 768.

Example 6 - Fabrication and Characterization of Devices Containing Inverters and Reversing and Reverse Circuits

In view of the bipolar nature of HD-PPTV, a complementary inverter and circuit were successfully fabricated and demonstrated by integrating two or four transistors. 8, 9, and 10 illustrate apparatus including logic circuits including a plurality of transistors including HD-PPTV as active bipolar semiconductors. A complementary inverter having the structure shown in Fig. 7 was fabricated on a substrate having a large channel size (W = 5000 μm and L = 100 μm). The electrical characteristics of the inverter devices are also shown in FIG. The complementary nature of the inverter based on bipolar HD-PPTV transistors results in a sharp switching characteristic of the logic operation with a voltage gain (-dV _out /dV _in ) of 15 to 27.

An apparatus comprising an HD-PPTV for fabricating an inverse logic circuit and the resulting electrical characteristics are shown in FIG. When the input signal is switched between the on state (high voltage) and the off state (low voltage), the output voltage is switched according to the inverse logical operation. If the input signal is in the on state, the output signal of the circuit is disconnected; otherwise, the output is in the on state.

An apparatus comprising an HD-PPTV for fabricating an inverse or logic circuit and the resulting electrical characteristics are shown in FIG. When the input signal is switched between an on state and an off state, the output voltage is switched according to an inverse OR logic operation. If the input signal is in the off state, the output signal of the inverse or circuit is turned on; otherwise, the output is off.

Because the opposite and the reverse circuit constitute the same crystal system, By exchanging the voltage deviation of the power supply and ground, the function of a circuit can be switched from an anti-gate to an anti-gate or from an anti-gate to an anti-gate.

Implementation of the scope of the patent application filed in the priority document

The scope of the 34 patent applications of the priority US Provisional Patent Application No. 61/525,618, filed on Aug. 19, 2011, is hereby incorporated by reference.

The first embodiment (ie, embodiment 1) provides a diketopyrrolopyrrole polymer comprising a plurality of repeating units, wherein greater than 50 mol%, up to 100 mol% of repeating units have conformational formulas (I a repeating unit RU of one or more structural formulas, namely:

Wherein a) each R ¹ and R ^{1 ' is} independently selected from a C ₁ -C ₃₀ positive-chain, branched or cyclic alkyl group or a fluorinated derivative thereof; b) each hAr ¹ and hAr ^{1' is} independently selected from C ₁ -C ₆₀ heteroaryl groups, which have the following structure:

Wherein i) a is an integer equal to 1, 2, 3 or 4; ii) each X, X', X" or X''' is independently selected from the group consisting of O, S, Se, Si(R ³ ) ₂ , and NR ³ , wherein R ³ is a C ₁ -C ₃₀ positive-chain, branched or cyclic alkyl group; iii) each Y, Y', Y" and Y"' are independently selected from N and CR ⁴ Wherein R ⁴ is hydrogen, halogen, cyano or a C ₁ -C ₃₀ normal chain, branched or cyclic alkyl, perfluoroalkyl, alkoxy, thioalkyl or thioalkoxy And c) each R ² and R ^{2 ' are} independently selected from hydrogen, cyano or C ₁ -C ₃₀ alkyl, fluoroalkyl, alkoxy, aryl, heteroaryl, carboxyalkyl or Alkoxy.

A second embodiment is the keto-pyrrolopyrrole polymer according to embodiment 1, wherein more than 50 mol%, up to 100 mol% of repeat units have one and only one specificity in accordance with structural formula (I) Knot The repeating unit RU of the configuration.

A third embodiment is a diketopyrrolopyrrole polymer according to one or more other embodiments, the polymers being homopolymers.

A fourth embodiment is a diketopyrrolopyrrole polymer according to one or more other embodiments, wherein greater than 50 mol%, up to less than 100 mol% of repeat units have conformation to formula (I) One and only one repeating unit RU of a specific structural formula, and the repeating unit between 0% by mole and 50% by mole has repeating units that do not conform to one or more specific structural formulas of the structural formula (I) RU*.

A fifth embodiment is the keto-pyrrolopyrrole polymer according to embodiment 1, wherein more than 50 mol%, up to 100 mol% of the repeat unit has at least two differentities in conformity with the structural formula (I) A repeating unit RU of a specific structural formula.

A sixth embodiment is a diketopyrrolopyrrole polymer according to one or more other embodiments, wherein the repeating unit RU is a mixture consisting of repeating units having the specific structural formula (II) RU1

And a repeating unit RU2 having a specific structural formula (III)

Wherein each of R ¹¹ , R ^{11 '} , R ²¹ and R ^{21 ' is} independently selected from a C ₁ -C ₃₀ positive-chain, branched or cyclic alkyl group or a fluorinated derivative thereof; a) Each of hAr ¹¹ , hAr ^{11 '} , hAr ²¹ and hAr ^{21 ' is} independently selected from a C ₁ -C ₆₀ heteroaryl group having the following structure:

Wherein i) a is an integer equal to 1, 2, 3 or 4; ii) each X, X', X" or X''' is independently selected from the group consisting of O, S, Se, Si(R ³ ) ₂ , and NR ³ , wherein R ³ is a C ₁ -C ₃₀ positive-chain, branched or cyclic alkyl group; iii) each Y, Y', Y" and Y''' are independently selected from N and CR ⁴ wherein R ⁴ is hydrogen, halogen, cyano or a C ₁ -C ₃₀ normal chain, branched or cyclic alkyl, perfluoroalkyl, alkoxy, thioalkyl or thioalkane Alkoxy; b) each R ¹² , R ^{12 '} , R ²² and R ^{22 ' are} independently selected from hydrogen, cyano or C ₁ -C ₃₀ alkyl, fluoroalkyl, alkoxy, aryl, heteroaryl a group, a carboxyalkyl group or an ethoxylated group, the conditions of which are at least one of the groups R ¹¹ , R ^{11 '} , hAr ¹¹ and hAr ^{11 '} contained in the formula (II) are different from those contained in the formula (III) Its homologues are R ²¹ , R ^{21 '} , hAr ²¹ and hAr ^{21 ', respectively} .

A seventh embodiment is a diketopyrrolopyrrole polymer according to one or more other embodiments, wherein the polymer is a block copolymer, wherein R ¹¹ and R ²¹ are different from each other and/or R ^{11 '} And R ^{21 '} are different from each other.

The eighth embodiment is a diketopyrrolopyrrole polymer according to one or more other embodiments, wherein the polymer is a random copolymer in which R ¹¹ and R ^{11 '} are identical to each other and R ²¹ and R ^{21 '} are identical to each other.

A ninth embodiment is a diketopyrrolopyrrole polymer according to one or more other embodiments, wherein the repeating unit is a repeating unit RU, and the repeating unit RU is a mixture The mixture consists of a repeating unit RU1 having a specific chemical formula (II) and a repeating unit RU2 having a specific chemical formula (III).

In a tenth embodiment, there is provided a diketopyrrolopyrrole polymer according to one or more other embodiments, wherein greater than 50% by mole, Up to less than 100% by mole of the repeating unit is a repeating unit RU consisting of a repeating unit RU1 having a specific structural formula (II) and a repeating unit RU2 having a specific structural formula (III), and is between 0% and 50% The repeating unit between the ear % has a repeating unit RU* that does not conform to one or more structural formulas of the structural formula (I).

An eleventh embodiment provides a diketopyrrolopyrrole polymer according to one or more other embodiments, wherein the molar ratios (RU1:RU2) of the repeating units RU1 and RU2 are in the range of 5% to 95% .

A twelfth embodiment provides the diketopyrrolopyrrole polymer according to any one of the above embodiments, wherein each of hAr ¹ and hAr ^{1 ' is} independently selected from: Wherein R ³ is a C ₁ -C ₃₀ normal chain, branched or cyclic alkyl group, and R ⁴ is hydrogen, halogen, cyano or a C ₁ -C ₃₀ positive chain, branched or cyclic Alkyl, perfluoroalkyl, alkoxy, thioalkyl or thioalkoxy.

A thirteenth embodiment provides a diketopyrrolopyrrole polymer according to one or more other embodiments, wherein each hAr ¹ and hAr ^{1 ' is} independently selected from:

In a fourteenth embodiment, there is provided a diketopyrrolopyrrole polymer according to one or more prior embodiments, wherein each hAr ¹ and hAr ^{1 ' is} independently selected from:

In a fifteenth embodiment, there is provided a diketopyrrolopyrrole polymer according to one or more other embodiments, wherein each hAr ¹ and hAr ^{1 ' is} independently selected from:

A sixteenth embodiment is a diketopyrrolopyrrole polymer according to one or more other embodiments, wherein each hAr ¹ and hAr ^{1 ' is} independently selected from:

In a seventeenth embodiment, the ketopyrrolopyrrole polymer of claim 12, wherein each of hAr ¹ and hAr ^{1' is} independently selected from:

The eighteenth embodiment is a diketopyrrolopyrrole polymer according to one or more of the preceding embodiments, wherein each of hAr ¹ and hAr ^{1 ' is} independently selected from:

In a nineteenth embodiment, the diketopyrrolopyrrole polymer according to one or more of the preceding embodiments, wherein each of hAr ¹ and hAr ^{1 ' is} independently selected from:

A twentieth embodiment is a diketopyrrolopyrrole polymer according to one or more prior embodiments, wherein each hAr ¹ and hAr ^{1 ' is} independently selected from:

The twenty-first embodiment is the diketopyrrolopyrrole polymer according to any one of the other embodiments, wherein each of hAr ¹¹ and hAr ^{11' is} independently selected from:

And - each hAr ²¹ and hAr ^{21' are} independently selected from:

A twenty-second embodiment is the diketopyrrolopyrrole polymer according to any one of the other embodiments, wherein the repeat unit between 0 mol% and 50 mol% has one of the following formulas Or multiple repeating units RU*, namely:

A twenty-third embodiment provides the diketopyrrolopyrrole polymer of any of the above embodiments, the polymers having a number determined by gel permeation chromatography using polystyrene calibration standards The degree of homopolymerization is at least 10.

In a twenty-fourth embodiment, there is provided a diketopyrrolopyrrole polymer of any of the above embodiments, wherein the polymer has a polystyrene calibration standard by gel permeation chromatography The determined number average degree of polymerization is at most 100.

In a twenty-fifth embodiment, there is provided a diketopyrrolopyrrole polymer according to any one of the above embodiments, wherein the polymer is selected in the range of 25 ° C to 50 ° C in at least one solvent Or a solubility of at least 10 mg/ml at a plurality of temperatures selected from the group consisting of toluene, xylene, mesitylene, tetrahydrofuran, chloroform, chlorobenzene, dichlorobenzene, and mixture.

In embodiment twenty-six, an electronic device is provided, the electronic device comprising at least one polymer selected from the group consisting of diketopyrrolopyrrole polymers according to any of the above embodiments.

In a twenty-seventh embodiment, the electronic device of any one of the preceding embodiments, the electronic device comprising at least one photovoltaic cell or at least one transistor comprising the at least one polymer.

In a twenty-eighth embodiment, the electronic device includes at least one transistor comprising the at least one polymer.

In a twenty-ninth embodiment, there is provided a method for making a polymer of any one or more of the preceding embodiments, the method comprising the steps of: a) obtaining or providing at least one diheteroaryl group a substituted diketopyrrolopyrrole monomer having the following structure:

Wherein LG ¹ is a leaving group such as a bromine atom;

b) obtaining or providing at least one di-substituent-substituted ethylene monomer having a structure wherein LG ² is a leaving group capable of acting with LG ¹ (for example, SnR ^{2 "} ₃ , wherein R ^2" is alkyl or aryl) is eliminated by reaction; c) in the presence of a transition metal catalyst complex, a diketone group comprising the at least one first diheteroaryl group is substituted A mixture of pyrrolopyrrole monomers and the at least one di-removing group-substituted ethylene monomer is reacted to produce a copolymer of any one or more of the embodiments described herein.

In a thirtieth embodiment, there is provided a method according to one or more other embodiments, wherein the mixture comprises substantially equal molar amount of the at least one first diheteroaryl substituted diketopyrrole A pyrrole monomer and the at least one di-substituent-substituted ethylene monomer.

In a thirtieth embodiment, there is provided a method according to one or more other embodiments, wherein the mixture is substantially free of diketopyrrolopyrrole substituted with the at least one first diheteroaryl group Any monomer other than the vinyl monomer substituted with the at least one di- leaving group.

In a thirty-second embodiment, there is provided a method according to one or more other embodiments, wherein the polymer further comprises at least one self-reactive monomer having the structure: LG ¹ -hAr*- LG ²

Wherein hAr* is selected from C ₁ -C ₆₀ heteroaryl groups, and the heteroaryl groups have the following structure: And a, LG ¹ , LG ² , X, X', X", X"', Y, Y', Y", and Y"' are as defined in the above embodiments.

In a thirtieth embodiment, there is provided a method according to one or more other embodiments, wherein the mixture further comprises at least one self-reactive monomer having the structure: LG ¹ -hAr*-LG ¹

Wherein hAr* is selected from C ₁ -C ₆₀ heteroaryl groups, and the heteroaryl groups have the following structure: And a, LG ¹ , X, X', X", X"', Y, Y', Y", and Y"' are as defined in the related above patent application.

In a thirty-fourth embodiment, there is provided a method for making a random copolymer of one or more of the other embodiments, the method comprising the steps of: a) obtaining or providing at least one first two a heteroaryl-substituted diketopyrrolopyrrole monomer having the following structure:

Wherein LG ¹ is a leaving group such as a bromine atom; b) obtaining or providing at least one second diheteroaryl substituted diketopyrrolopyrrole monomer having the following structure:

c) obtaining or providing at least one di-group-substituted vinyl monomer having the following structure:

Wherein LG ² is a leaving group capable of being eliminated by reaction with LG ¹ (eg, SnR ^2′ ₃ , wherein R ^2′′ is an alkyl or aryl group); d) in a transition metal a mixture comprising the at least first and second diheteroaryl substituted diketopyrrolopyrrole monomers and the at least one dipartition group substituted ethylene monomer in the presence of a catalyst complex The reaction takes place to produce a copolymer of one or more of the other embodiments.

in conclusion

The above description, examples and data provide exemplary illustrations of the different compositions and apparatus of the invention, as well as the manufacture and use of the apparatus, and methods for their manufacture and use. In view of those disclosures, one of ordinary skill in the art will be able to devise the invention as disclosed and claimed herein. Many additional embodiments are apparent, and they can be made without departing from the spirit and scope of the invention. The scope of these patent applications attached below defines some of those embodiments.

1 shows a scanning chart of a differential scanning calorimeter of HD-PPTV, HD-PPV, and PPTPV polymers illustrated in Example 4 at a heating rate of 10 ° C/min under N ₂ .

Figure 2a shows the optical absorption spectra of HD-PPTV, HD-PPPV and PPTPV polymers in dilute toluene solution. Figure 2b shows the optical absorption spectra of HD-PPTV, HD-PPPV and PPTPV as polymer films.

Figure 3a shows the optical absorption spectrum of HD-PPPV in a dilute toluene solution and as a film. Figure 3b shows the optical absorption spectrum of a PPTPV polymer in a dilute toluene solution and as a film.

Figures 4a, 4b and 4c show cyclic voltammograms of HD-PPTV (A), HD-PPPV (B), and PPTPV (C).

Figure 5 shows an X-ray diffraction pattern of drop-cast films of three polymers of HD-PPTV, HD-PPPV, and PPTPV.

Figure 6a shows the output characteristics of an HD-PPTV based field effect transistor after annealing at 150 °C. Figure 6b shows an overlay of a representative transfer curve ( _Vds = ± 80 V) for a transistor comprising HD-PPTV, HD-PPPV, and PPTPV. See example 5.

Figure 7 shows the use of HD-PPTV as an active bipolar semiconductor The structure and results obtained by the manufactured inverter circuit.

Figure 8 shows the structure and results obtained from the reverse circuit fabricated using HD-PPTV as an active bipolar semiconductor.

Figure 9 shows the structure and results obtained from an inverse OR circuit fabricated using HD-PPTV as an active bipolar semiconductor.

Claims (18)

a diketopyrrolopyrrole polymer comprising a plurality of repeating units, wherein more than 50 mol.%, up to 100 mol.% of the repeating unit units have repeating units conforming to one or more structural formulas of the structural formula (I) RU, Wherein a) each R ¹ and R ^{1 ' is} independently selected from a C ₁ -C ₃₀ positive-chain, branched or cyclic alkyl group or a fluorinated derivative thereof; b) each hAr ¹ and hAr ^{1' is} independently selected from C ₁ -C ₆₀ heteroaryl groups, which have the following structure: Wherein i) a is an integer equal to 1, 2, 3 or 4; ii) each X, X', X" or X"' is independently selected from the group consisting of O, S, Se, Si(R ³ ) ₂ , and NR ³ wherein R ³ is a C ₁ -C ₃₀ positive-chain, branched or cyclic alkyl group; iii) each Y, Y', Y" and Y"' are independently selected from N and CR ⁴ , Wherein R ⁴ is hydrogen, halogen, cyano or a C ₁ -C ₃₀ normal chain, branched or cyclic alkyl, perfluoroalkyl, alkoxy, thioalkyl or thioalkoxy group And c) each R ² and R ^{2 ' are} independently selected from hydrogen, cyano or C ₁ -C ₃₀ alkyl, fluoroalkyl, alkoxy, aryl, heteroaryl, carboxyalkyl or acetamidine Oxygen. The ketopyrrolopyrrole polymer of claim 1, wherein more than 50 mol.%, up to 100 mol.% of the repeat units have one and only one specific structural formula conforming to the structural formula (I) Repeat unit RU. Such as the ketopyrrolopyrrole polymers of claims 1 to 2, which are homopolymers. The ketopyrrolopyrrole polymer of claim 2, wherein more than 50 mol.%, up to less than 100 mol.% of the repeat units have one and only one specific structure conforming to the structural formula (I) The repeating unit RU of the formula, and between 0 mol.% and 50 mol.% of the repeating units have repeating units RU* which do not conform to one or more specific structural formulas of the structural formula (I). The ketopyrrolopyrrole polymer of claim 1, wherein the repeating unit RU is a mixture consisting of the repeating unit RU1 having the specific structural formula (II) And a repeating unit RU2 having a specific structural formula (III) Wherein each of R ¹¹ , R ^{11 '} , R ²¹ and R ^{21 ' is} independently selected from a C ₁ -C ₃₀ positive-chain, branched or cyclic alkyl group or a fluorinated derivative thereof; a) Each of hAr ¹¹ , hAr ^{11 '} , hAr ²¹ and hAr ^{21 ' is} independently selected from a C ₁ -C ₆₀ heteroaryl group having the following structure: Wherein i) a is an integer equal to 1, 2, 3 or 4; ii) each X, X', X" or X"' is independently selected from the group consisting of O, S, Se, Si(R ³ ) ₂ and NR ³ Wherein R ³ is a C ₁ -C ₃₀ positive-chain, branched or cyclic alkyl group; iii) each Y, Y', Y" and Y"' are independently selected from N and CR ⁴ , wherein R ⁴ is hydrogen, halogen, cyano or a C ₁ -C ₃₀ normal chain, branched or cyclic alkyl, perfluoroalkyl, alkoxy, thioalkyl or thioalkoxy; b) each R ¹² , R ^{12 '} , R ²² and R ^{22 ' are} independently selected from hydrogen, cyano or C ₁ -C ₃₀ alkyl, fluoroalkyl, alkoxy, aryl, heteroaryl, carboxy An alkyl group or an ethoxylated group, the conditions of which are at least one of the groups R ¹¹ , R ^{11 '} , hAr ¹¹ and hAr ^{11 '} contained in the formula (II) are different from those contained in the formula (III) Homologs are R ²¹ , R ^{21 '} , hAr ²¹ and hAr ^{21 ', respectively} . A diketopyrrolopyrrole polymer according to any one of the preceding claims, wherein each of hAr ¹ and hAr ^{1 ' is} independently selected from: Wherein R ³ is a C ₁ -C ₃₀ normal chain, branched or cyclic alkyl group, and R ⁴ is hydrogen, halogen, cyano or a C ₁ -C ₃₀ positive chain, branched or cyclic Alkyl, perfluoroalkyl, alkoxy, thioalkyl or thioalkoxy. A ketopyrrolopyrrole polymer as claimed in claim 6 wherein each of hAr ¹ and hAr ^{1' is} independently selected from: A ketopyrrolopyrrole polymer as claimed in claim 6 wherein each of hAr ¹ and hAr ^{1' is} independently selected from: A ketopyrrolopyrrole polymer as claimed in claim 6 wherein each of hAr ¹ and hAr ^{1' is} independently selected from: A diketopyrrolopyrrole polymer according to any one of the above claims in the third aspect of the patent application, wherein between 0 mol.% and 50 mol.% of the repeat units have the following formula One or more of the repeating units RU*, a diketopyrrolopyrrole according to any one of the above claims Polymers having a number average degree of polymerization of as little as 10 as determined by gel permeation chromatography using polystyrene calibration standards. A diketopyrrolopyrrole polymer according to any one of the preceding claims, wherein the polymers have at least 10 mg/ml at one or more temperatures selected from the range of 25 ° C to 50 ° C in at least one solvent. Solubility, the solvent is selected from the group consisting of toluene, xylene, mesitylene, tetrahydrofuran, chloroform, chlorobenzene, dichlorobenzene, and mixtures thereof. An electronic device comprising at least one polymer selected from the group consisting of diketopyrrolopyrrole polymers of any of the above claims. An electronic device as claimed in claim 26, comprising at least one photovoltaic cell or at least one transistor comprising the at least one polymer. A process for the manufacture of a polymer or polymers according to the above patent application, the process comprising the steps of: a) obtaining or providing at least one diheteroaryl substituted diketopyrrolopyrrole monomer having the following structure: Wherein LG ¹ is a leaving group such as a bromine atom; b) an ethylene monomer obtained or provided with at least one di-removing group having the following structure: Wherein LG ² is a leaving group capable of being eliminated by reaction with LG ¹ (eg, SnR ^2′ ₃ , wherein R ^2′′ is an alkyl or aryl group); c) in a transition metal Reacting a mixture comprising the at least one first diheteroaryl substituted diketopyrrolopyrrole monomer and the at least one dipartition group substituted ethylene monomer in the presence of a catalyst complex such that A copolymer is produced as one or more of the above patent claims. The method of claim 15, wherein the mixture comprises substantially equal molar amount of the at least one first diheteroaryl-substituted diketopyrrolopyrrole monomer and the at least one di-releasing group. Ethylene monomer. The method of claim 15 or 16, wherein the mixture is substantially free of the diketopyrrolopyrrole monomer substituted with the at least one first diheteroaryl group and the at least one dipartyl group substituted Any monomer other than the ethylene monomer. The method of claim 15 or 16, wherein the mixture further comprises at least one self-reactive monomer having the structure: LG ¹ -hAr*-LG ² wherein hAr* is selected from C ₁ -C ₆₀ Heteroaryl, these heteroaryl groups have the following structure: And a, LG ¹ , LG ² , X, X', X", X"', Y, Y', Y", and Y"' are as defined in the related above patent application.