WO2016003097A1

WO2016003097A1 - Organic semiconductor compound, method for producing same, and organic electronic element and organic solar cell element comprising same

Info

Publication number: WO2016003097A1
Application number: PCT/KR2015/006281
Authority: WO
Inventors: 황도훈; 김지훈; 박종백
Original assignee: 부산대학교 산학협력단
Priority date: 2014-07-03
Filing date: 2015-06-22
Publication date: 2016-01-07

Abstract

The present invention relates to an organic semiconductor compound of a tandem organic solar cell having excellent electrical properties, and a compound exhibiting world-class photoelectric conversion efficiency in a single-layer organic solar cell element, a method for producing same, and an organic electronic element and an organic solar cell element comprising same, the organic semiconductor compound of the present invention having high thermal stability, solubility, and charge mobility, thereby exhibiting excellent performance in the tandem organic solar cell comprising same.

Description

Organic semiconductor compound, preparation method thereof, organic electronic device and organic solar cell device including same

The present invention relates to an organic semiconductor compound, a method for manufacturing the same, and an organic electronic device and an organic solar cell device including the same, and more particularly, thieno [3,2-b] thiophene π-bridges. Intermediate bandgap organic semiconductor compound comprising thieno [3,4-c] pyrrole-4,6 (5H) -dione (TPD), a method for preparing the same, and an organic electronic device and an organic solar cell device including the same It is about.

The organic semiconductor compound of the present invention is a high performance organic semiconductor compound suitable for stacked and single layer organic solar cell devices.

The photovoltaic industry, with more than 6GW installed in 2009, formed an independent industrialized country with a $ 30 billion market, and is expected to continue growing rapidly until the mid-21st century.

Current main products are crystalline silicon solar cells with overwhelming use in the photovoltaic market, but the market share of inorganic thin film solar cells such as a-Si, CdTe and CIGS has been steadily increasing, and in fact, it has reached 20% in 2009. Rose.

In addition, organic solar cells represented by dye-sensitized and organic thin film types are not yet entering the market in earnest, but they can lead the 'ubiquitous solar' era that is expected due to cheap material cost, process cost, and light, flexible and transparent characteristics. Another possibility is presented.

Currently, its performance is somewhat limited due to its low performance, but when high efficiency of 10% or more is secured in the future, it is used in so-called BIPV (building integrated photovoltaic system), which creates a beautiful appearance by generating it in windows or balconies in earnest and produces electricity at the same time. Is expected to be written largely. In the future, it is expected to serve as a variety of energy sources supporting the 21st century solar era, including various flexible displays, military, indoor and disposable solar cells.

However, in the 1970s, when the potential for organic solar cells was first proposed, its efficiency was so low that it was impractical.In 1986, Eastman Kodak's Tang was replaced with copper phthalocyanine (CuPc) and perylene tetracarboxylic acid. As the double layer structure using perylene tetracarboxylic acid derivatives showed the possibility of practical use as various solar cells, interest and research on organic solar cells increased rapidly and brought about a lot of development. Since 1995, the concept of bulk-heterojunction (BHJ) was introduced by Yu et al., And fullerene derivatives with improved solubility, such as PCBM, were developed as n-type semiconductor materials. there was.

In particular, research on organic solar cells has increased rapidly since 2000, and polymer solar cells that can introduce photoactivity as a solution process were introduced at the beginning of 2000 by introducing the concept of bulk-hetero junction with PCBM. By beginning to gain efficiency, the use of P3HT as a photoactive layer generally yielded efficiencies of 4 to 6%. As a result, attempts to develop new materials and device structures have attracted the attention of academia and industry since 2005. It started in earnest.

In the case of the polymer solar cell, the improvement of the efficiency is remarkable due to the new device configuration and the change of the process conditions, so that the donor material having a low bandgap and the charge mobility are still good to replace the existing material. The development of new acceptor materials continues to require research and development.

To date, 8% efficiency has been reported worldwide using single layer organic solar cell devices.

However, a multilayer organic solar cell using an electron donor material that absorbs different light in each monolayer by making such a monolayer into a laminate has been actively studied. This results in the sum of the open voltages, the average short-circuit current, and the FF of two monolayers, and more than twice the performance of single layer organic solar cells has been reported. In general, a stacked organic solar cell is divided into a bottom cell and a top cell. In the lower layer, an electron donor material and an electron acceptor material exhibiting absorption of 300-600 nm are used, and in the upper layer, an electron donor and acceptor material of 600-1000 nm is used. Most of the progress of the research, P3HT: ICBA is used as a lower layer, a stacked organic solar cell using a new material having a low band gap of the upper layer has been reported. Currently, Prof. UCLA of 2012 In the Yang Yang group, 10.6% of the stacked organic solar cell is the best organic solar cell efficiency at present, and has been stagnant since 2012 due to the shortage of materials.

The present invention provides thieno [3,4-c having thieno [3,2-b] thiophene [pi] -bridges suitable for the bottom cell of a high performance stacked organic solar cell to replace P3HT. ] Middle bandgap organic semiconductor compound comprising pyrrole-4,6 (5H) -dione (TPD).

The present invention also provides a method for producing the organic semiconductor compound of the present invention.

The present invention also provides an organic electronic device containing the organic semiconductor compound of the present invention.

The present invention also provides a stacked type and single layer organic solar cell device containing the organic semiconductor compound of the present invention.

The present invention provides an organic semiconductor compound having an intermediate bandgap performance superior to that of P3HT, which is a representative material included in the lower layer of the stacked organic solar cell device, and provides a world-class single layer organic solar cell photoactive organic semiconductor compound. More specifically thieno [3,4-c] pyrrole-4,6 (5H) -dione (TPD) with thieno [3,2-b] thiophene π-bridges An organic semiconductor compound is provided.

The organic semiconductor compound of the present invention is represented by the following Chemical Formula 1:

[Formula 1]

In Chemical Formula 1,

D is C ₆ -C ₃₀ arylene or C ₃ -C ₃₀ heteroarylene;

X is S, Se, O or NR ';

R ₁ and R ₂ independently of one another are hydrogen, C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy, C ₁ -C ₃₀ alkylthio, C ₁ -C ₃₀ alkoxyC ₃ -C ₂₀ heteroaryl or C _6- C ₃₀ arC ₁ -C ₃₀ alkyl;

R 'is hydrogen, C ₁ -C ₃₀ alkyl or C ₆ -C ₃₀ arC ₁ -C ₃₀ alkyl;

The arylene and heteroarylene of D are C ₁ -C ₃₀ alkylthienyl, C ₁ -C ₃₀ alkoxyC ₆ -C ₃₀ aryl, C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy, C ₁ -C ₃₀ alkoxyC ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkylC ₃ -C ₃₀ heteroaryl, C ₁ -C ₃₀ alkylthio, C ₁ -C ₃₀ alkoxyC ₃ -C ₃₀ heteroaryl, C ₆ -C ₃₀ May be further substituted with one or more substituents selected from the group consisting of aryl, C ₃ -C ₃₀ heteroaryl or C ₆ -C ₃₀ arC ₁ -C ₃₀ alkyl;

The alkyl and aralkyl of R ₁ and R ₂ are C ₁ -C ₃₀ alkyl, C ₂ -C ₃₀ alkenyl, C ₂ -C ₃₀ alkynyl, C ₁ -C ₃₀ alkoxy, amino, mono- or di-C ₁ -C ₃₀ alkyl, amino, hydroxy, halogen, cyano, nitro, halo-C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkylsilyl group and C ₆ one or more substituents selected from the group consisting of -C ₃₀ arylsilyl May be further substituted with;

n is an integer from 1 to 2000;

The heteroaryl and heteroarylene include one or more heteroatoms selected from N, O, S, P (= 0), Si and P.

The organic semiconductor compound of the present invention is thieno [3] between an electron acceptor thieno [3,4-c] pyrrole-4,6 (5H) -dione (TPD) and various electron donors (representing D in formula 1). , 2-b] thiophene π-bridges are introduced and copolymerized with various electron donors to form stacked and single layer organic electronic devices, specifically, the lower layer and single layer organic solar cell devices of the stacked organic solar cell devices. It can be used to.

In particular, the organic semiconductor compound of the present invention exhibited an intermediate bandgap similar to P3HT, and exhibits excellent crystallinity due to the introduction of thieno [3,2-b] thiophene π-bridges in the molecule, Improved hole and electron mobility and nano structure can be realized, and the world-class performance in single-layer organic solar cell devices using the same, as well as the world-class performance in stacked organic solar cell devices Was implemented.

Substituents comprising the "alkyl", "alkoxy" and other "alkyl" moieties described herein include both straight and pulverized forms.

“Aryl” described in the present invention is an organic radical derived from an aromatic hydrocarbon by one hydrogen removal, and is a single or fused ring containing 4 to 7, preferably 5 or 6 ring atoms in each ring as appropriate. It includes the system. Specific examples include, but are not limited to, phenyl, naphthyl, biphenyl, anthryl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, peryleneyl, chrysenyl, naphthacenyl, fluoranthenyl, and the like.

The "heteroaryl" described in the present invention includes 1 to 4 heteroatoms selected from B, N, O, S, P (= O), Si and P as aromatic ring skeleton atoms, and the remaining aromatic ring skeleton atoms are carbon. Meaning an aryl group which is 5 to 6 membered monocyclic heteroaryl and polycyclic heteroaryl condensed with one or more benzene rings. In addition, heteroaryl in the present invention also includes a form in which one or more heteroaryl is connected by a single bond. Specific examples include monocyclic heteroaryl such as furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, isoxazolyl, oxazolyl, pyridyl, benzofuranyl, dibenzofuranyl, di Polycyclic heteros such as benzothiofail, benzothiophenyl, isobenzofuranyl, benzoimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzooxazolyl, quinolyl, isoquinolyl, carbazolyl and the like Aryl and the like, but are not limited thereto.

In the organic semiconductor compound of Formula 1 according to an embodiment of the present invention, the D is C ₃ -C ₃₀ heteroarylene, preferably at least one heteroarylene selected from the following structures:

R ₁₁ and R ₁₂ are each independently hydrogen, C ₁ -C ₃₀ alkylthienyl, C ₁ -C ₃₀ alkoxyC ₆ -C ₃₀ aryl, C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy, C ₁ -C ₃₀ alkoxyC ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkylC ₃ -C ₃₀ heteroaryl, C ₁ -C ₃₀ alkylthio, C ₁ -C ₃₀ alkoxyC ₃ -C ₃₀ heteroaryl or C _6- C ₃₀ arC ₁ -C ₃₀ alkyl;

R ₁₃ to R ₂₀ are each independently of the other hydrogen, C ₁ -C ₃₀ alkyl, C ₆ -C ₃₀ aryl, C ₃ -C ₃₀ heteroaryl or C ₆ -C ₃₀ are C ₁ -C ₃₀ alkyl.

In the organic semiconductor compound of Chemical Formula 1 according to an embodiment of the present invention, the organic semiconductor compound may be represented by the following Chemical Formula 2, Chemical Formula 3 or Chemical Formula 4.

[Formula 2]

[Formula 3]

[Formula 4]

In Chemical Formulas 2 to 4,

X is S, Se or O;

R ₁ and R ₂ independently of _one another are C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy, C ₁ -C ₃₀ alkoxyC ₁ -C ₃₀ alkyl or C ₁ -C ₃₀ alkoxyC ₃ -C ₂₀ heteroaryl ;

R ₁₁ and R ₁₂ are each independently hydrogen, C ₁ -C ₃₀ alkylthienyl, C ₁ -C ₃₀ alkoxyC ₆ -C ₃₀ aryl, C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy, C _1- C ₃₀ alkoxyC ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkylC ₃ -C ₃₀ heteroaryl, C ₁ -C ₃₀ alkylthio, C ₁ -C ₃₀ alkoxyC ₃ -C ₃₀ heteroaryl or C ₆ -C ₃₀ arC ₁ -C ₃₀ alkyl;

R ₁₃ to R ₁₆ independently of one another are hydrogen, C ₁ -C ₃₀ alkyl, C ₆ -C ₃₀ aryl, C ₃ -C ₃₀ heteroaryl or C ₆ -C ₃₀ arC ₁ -C ₃₀ alkyl;

n is an integer from 1 to 2000.

In the organic semiconductor compound according to the embodiment of the present invention, R ₁ may be each C ₁ -C ₃₀ alkyl in terms of high charge mobility and high electron density and high solubility in an organic solvent. Preferably C ₆ -C ₃₀ alkyl, more preferably C ₆ -C ₁₈ alkyl; R ₂ may be C ₁ -C ₃₀ alkyl, preferably

Wherein a is an integer from 1 to 5, and R may be branched C ₃ -C ₂₅ alkyl and preferably branched C ₁₁ -C ₂₅ alkyl. As the value of a in R ₂ increases, the characteristics of the organic solar cell device may be further improved due to an increase in crystallinity and an increase in mobility.

In addition, R ₁₁ and R ₁₂ of Chemical Formula 2 are each independently C ₁ -C ₃₀ alkylthienyl, C ₁ -C ₃₀ alkoxyC ₆ to control the electron density in the molecule and to improve the solubility in an organic solvent. -C ₃₀ aryl, C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy, C ₁ -C ₃₀ alkoxyC ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkylC ₃ -C ₃₀ heteroaryl, C ₁ -C ₃₀ alkylthio, C ₁ -C ₃₀ alkoxyC ₃ -C ₃₀ heteroaryl or C ₆ -C ₃₀ arC ₁ -C ₃₀ alkyl, preferably C ₁ -C ₃₀ alkylthienyl, C ₁ -C ₃₀ alkoxyC ₆ -C ₃₀ aryl, C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy, C ₁ -C ₃₀ alkoxyC ₁ -C ₃₀ alkyl or C ₁ -C ₃₀ alkylC ₃ -C ₃₀ heteroarylyl More preferably, C ₁ -C ₃₀ alkylthienyl or C ₁ -C ₃₀ alkoxy.

In one embodiment of the present invention, the organic semiconductor compound of the present invention may be selected from the following structures, but is not limited thereto.

N is an integer of 1 to 2000.

The present invention also provides a method of preparing an organic semiconductor compound represented by Chemical Formula 1 by copolymerizing a tin compound represented by Chemical Formula 5 with a tt-TPD derivative represented by Chemical Formula 6.

[Formula 5]

[Formula 6]

In

Chemical Formulas

5 and 6,

D is C ₆ -C ₃₀ arylene or C ₃ -C ₃₀ heteroarylene;

X is S, Se, O or NR ';

Y is halogen;

The tin compound of Formula 5 and the tt-TPD derivative of Formula 6 may be prepared by a method commonly recognized by those skilled in the art.

The present invention also provides an organic electronic device, in particular an organic thin film transistor or an organic solar cell, comprising the organic semiconductor compound of the present invention. More specifically, an organic electronic device containing the organic semiconductor compound of the present invention in a photoactive layer is provided.

The organic electronic device of the present invention can be any conventional organic electronic device that can be recognized by those skilled in the art, but in general, the organic solar cell is a metal / organic conductor (photoactive layer) / metal (Metal-Semiconductor or Insulator-Metal, MSM, MIM) structure, which has a high work function and uses indium tin oxide (ITO), which is a transparent electrode, as an anode, and Ag, Al, or Ca having a low work function as a cathode.

In particular, the BHJ (Bulk Hetero Junction) structure using an organic semiconductor compound / C60 or an organic semiconductor compound / C70 composite as an electron donor and an electron acceptor as an organic semiconductor will be described as an example.

First, the organic semiconductor compound / C60 composite solution, which is a photoactive layer, is coated on the ITO layer with a thickness of about 100 nm by spin coating or inkjet printing. On top of this, Al or Ca metal is vacuum-deposited and used as a cathode, and an extruder blocking layer (EBL) layer is inserted between the electrode and the photoactive layer to enhance the life of the charge as necessary. As the EBL layer, a mixture of PEDOT (Poly (3,4-Ethylenedioxythiophene)) and PSS (poly (styrenesulfonate)) may be used.

In general, the diffusion distance of excitons in organic electron donor materials is about 10-30 nm, which is much shorter than the proper thickness of electron donor materials for solar absorption (over 100 nm). This is one of the fundamental causes of limiting the efficiency of the organic solar cell, the existing bi-layer (BL) structure is difficult to solve this problem. In addition, since both materials constituting the BL (bi-layer) structure are organic monomolecules, deposition must be performed. In the case of a polymer, it is difficult to manufacture by a simple process such as spin coating. On the other hand, the polymer BHJ structure uses a mixture of electron donor (D) and electron acceptor (A) materials to simplify the manufacturing process and increase the surface area at the D / A (Donor / Acceptor) interface. Not only increases the possibility of, but also increases the charge collection efficiency as an electrode.

In this aspect, the organic solar cell according to the present invention preferably has a BHJ structure, and the organic semiconductor compound according to the present invention is used as an electron donor material and at least one selected from the following electron acceptor materials is mixed to form an active layer. It is preferable.

Among the electron acceptor materials, it is more preferable to use materials such as PCBM and PCBCR, which are designed to be well dissolved in an organic solvent, but are not limited thereto.

In general organic solar cells, electrons are discharged to the cathode and holes are discharged to the anode, whereas inverted organic solar cells are electrons to the anode and holes are discharged to the cathode. . The general organic solar cell uses PEDOT: PSS mainly as a hole transport layer, and thus has a high acidity and an acid layer is formed. Therefore, there is a disadvantage in that the lifetime of the device is short and the device life is short due to the rapid oxidation rate of electrodes such as Al. More preferred is an inverted organic solar cell which is a more stable device.

In addition, the stacked organic solar cell forms two layers of photoactive layers having different absorptions, thereby absorbing the necessary area in each layer, thereby achieving higher efficiency than a single layer organic solar cell. In other words, the inverted stacked organic solar cell flows electrons and holes in opposition to general organic solar cells for stability, and simultaneously forms two photoactive layers to absorb light in a wider area. The stacked organic solar cell device is preferably an inverted stacked organic solar cell device.

In particular, in the stacked organic solar cell device manufactured by the present invention, it is more preferable that the metal-insulator-metal (MIM) structure is repeated once more. That is, the BHJ structure of the electron donor and the electron acceptor is made in the lower layer and the MIM structure is made in the upper layer once again, similar to the MIM structure of the single layer device. Detailed stacked organic solar cell device fabrication is described in the Examples. The stacked organic solar cell device may be an inverted stacked organic solar cell device.

The organic semiconductor compound of the present invention is thieno [3] between the electron acceptor thieno [3,4-c] pyrrole-4,6 (5H) -dione (TPD) and various electron donors (representing D in formula 1). Incorporated, 2-b] thiophene π-bridges copolymerized with various electron donors, exhibiting an intermediate bandgap similar to that of P3HT and containing thieno [3,2-b] teas in the molecule. The introduction of off-pi pi-bridges provides excellent crystallinity, improved hole and electron mobility, and nano structure.

In addition, the organic semiconductor compound of the present invention has higher performance than P3HT which is generally used because it has intermediate bandgap, high open voltage, high FF and thermal stability, which are the conditions of the organic semiconductor that can be used for the lower layer in the stacked organic solar cell. Implement

Furthermore, when the various electron donors included in the organic semiconductor compound of the present invention (representing D in the formula 1) are the same, the alkyl chain length of the thieno [3,2-b] thiophene π-bridges Through regulation, it shows the world's best photoelectric conversion efficiency in single layer organic solar cell.

In addition, the organic semiconductor compound of the present invention exhibits improved performance through combination with various electron donor materials.

In addition, the organic semiconductor compound of the present invention has high thermal stability and high solubility in organic solvents.

Thus, the organic semiconductor compound of the present invention is thieno [3,4-c] pyrrole-4,6 (5H) -dione (TPD) having thieno [3,2-b] thiophene π-bridges. ) Is introduced into the electron acceptor and copolymerized with various electron donors, thereby exhibiting an intermediate bandgap, so that the stacked organic electrons including the same have a high efficiency by combining the organic semiconductor compound of the present invention with a fullerene derivative which is a photoactive layer.

In addition, the organic semiconductor compound of the present invention has high thermal stability and high solubility, so that the organic electronic device including the same has excellent electrical properties, and thus may be very useful in place of P3HT in the lower layer of the organic electronic device, in particular, a stacked organic solar cell. .

In addition, the present invention has been developed as a new electron donor (donor) material and exhibits a very excellent effect as a breakthrough (breakthrough) that can increase the maximum energy conversion efficiency of the existing organic solar cell.

The present invention also provides a method for producing an organic semiconductor compound having high electrical properties.

1 illustrates a bulk heterojunction (BHJ) mode of an organic solar cell.

2 illustrates a structure of an organic solar cell.

3 is a thermal stability (TGA) result of the polymers prepared in Examples 1 to 6.

4 is a UV spectrum of the solution state of the polymers prepared in Examples 1 to 6.

5 is a UV spectrum of the film state of the polymer prepared in Examples 1 to 6.

6 is a UV spectrum of a solution state and a solid film state of the polymer prepared in Example 7.

7 is a UV spectrum of a solution state and a solid film state of the polymer prepared in Example 8.

8 is a HOMO LUMO energy level diagram of the polymers prepared in Examples 1 to 6 measured by Cyclic voltamogram (oxidation).

9 is a HOMO LUMO energy level diagram of the polymers prepared in Examples 7 and 8 measured by Cyclic voltamogram (oxidation).

FIG. 10 is a J-V characteristic curve of single layer organic solar cells manufactured in Examples 9 and 10. FIG.

FIG. 11 is a J-V characteristic curve of a single layer organic solar cell manufactured in Example 11. FIG.

12 is a J-V characteristic curve of a single layer organic solar cell manufactured in Example 12.

FIG. 13 shows the structure of an inverted stacked organic solar cell device of Example 13. FIG.

FIG. 14 shows the structure of materials used in each layer of the inverted stacked organic solar cell device of Example 13. FIG.

FIG. 15 shows the UV-visible absorption spectra of the lower layer and the upper layer photoactive polymer of the inverted stacked organic solar cell device of Example 13. FIG.

Figure 16 shows (a) the current-voltage curve of the upper layer using PTB7: PCBM, (b) the current-voltage curve of the lower layer using P3HT: ICBA generally used as the lower layer photoactive polymer of the stacked organic solar cell, (c) P3HT : Current-voltage curve of an inverted stacked organic solar cell (Comparative Example 1) using ICBA / PTB7: PCBM as the photoactive layer, (d) Polymer 4: Example 4 The single-layer organic layer of Example 10 using the PCB4 as the photoactive layer The current-voltage curve of the solar cell, and (e) the current-voltage curve of the inverted-laminated organic solar cell of Example 13 using the polymer 4: PCBM / PTB7: PCBM of Example 4 as the photoactive layer.

Hereinafter, the present invention will be described in detail by way of examples. However, the following Preparation Examples and Examples are only for illustrating the present invention, and the content of the present invention is not limited by the following Examples.

At this time, if there is no other definition in the technical terms and scientific terms used, it has a meaning commonly understood by those of ordinary skill in the art. In addition, repeated description of the same technical configuration and operation as in the prior art will be omitted.

Example

All reagents required for the synthesis were purchased from Junsei, Aldrich, Alpha and Tsisey. Silicagel was purchased from Merck. Chloroform, Hexane, Methanol and Acetone for HPLC were used by JTBaker. Purchased. Benzo [1,2-b: 4,5-b '] dithiophene (benzo [1,2-b: 4,5-b'] containing an alkoxy or alkylthienyl group which is an electron donor material used in the present invention. dithiophene (BDT) was synthesized by the reported paper (Macromolecules 47 (2014) 1613-1622). UV of the film state was measured by filtration using a 0.45 μm syringe filter and then spin coating. PCB acceptor ([6,6] -phenyl C71-butyric acid methyl ester) was used as an electron acceptor material of the organic solar cell device. ^{The 1} H NMR spectrum was measured using a Varian Mercury Plus 300 MHz spectrometer, and the ultraviolet absorption spectrum was measured by JASCO JP / V-570. Cyclic Voltammetry was measured using CH Instruments Electrochemical Analyzer to determine HOMO Level of materials. JV curve of solar cell was measured using 1Kw Solar simulator (Newport 91192). It was. IPCE characteristics were measured by Solar cell response / Quantum efficiency / IPCE Measurement system (PV Measurements. Inc.).

Preparation Example 1 1,3-bis (5-bromo-6-hexylthieno [3,2-b] thiophen-2-yl) -5- (2-hexyldecyl) -4H-thieno [ 3,4-c] pyrrole-4,6 (5H) -dione (1,3-Bis (5-bromo-6-hexylthieno [3,2-b] thiophen-2-yl) -5- (2-hexyldecyl ) -4H-thieno [3,4-c] pyrrole-4,6 (5H) -dione, Compound 6tt-TPD)

Preparation of 1- (3-bromothienyl) heptanone (Compound 1)

Methylene chloride (100 mL) and 3-bromothiophene (16.3 g, 0.10 mmol) are injected into a 500 mL round flask, followed by slow infusion of AlCl ₃ (26.80 g, 0.20 mmol) at 0 ° C. After 30 minutes, heptanoyl chloride (heptanoyl chloride) (14.90 g, 0.10 mol) is injected and stirred at room temperature for 24 hours. After the reaction was completed, the mixture was quenched with HCl (6M, 200 mL), the organic layer was extracted with chloroform and brine, and the remaining water was removed with anhydrous magnesium sulfate. Pure Compound 1 was obtained by column chromatography (25.10 g, 91%).

¹ H NMR (300 MHz, CD ₂ Cl ₂ , ppm): δ 7.53 (d, 1H), 7.12 (d, 1H), 3.01 (t, 2H), 1.71 (m, 2H), 1.38 (m, 6H), 0.92 (t, 3 H); ¹³ C NMR (75 MHz, CD ₂ Cl ₂ , ppm): δ 193.1, 139.2, 134.2, 132.2, 114.0, 42.2, 32.2, 29.5, 24.7, 23.1, 14.4.

Preparation of ethyl 3-hexylthieno [3,2-b] thiophene-2-carboxylate (Compound 2)

DMF (200 mL) and Compound 1 (35.40 g, 0.13 mol) were injected into a 500 mL round flask, followed by stirring for 1 hour. Then ethyl mercaptoacetate (14.00 mL, 0.13 mol) was slowly added and stirred at 60 ° C. for 12 hours. After completion of the reaction, fractional distillation was carried out through ethyl acetate, the remaining water was removed with anhydrous magnesium sulfate, the solvent was evaporated, and pure compound 2 was obtained by column chromatography (32.10 g, 85%).

¹ H NMR (300 MHz, CD ₂ Cl ₂ , ppm): δ 7.56 (d, 1H), 7.24 (d, 1H), 4.34 (q, 2H), 3.15 (t, 2H), 1.71 (m, 2H), 1.32 (m, 6 H), 0.88 (m, 6 H); ¹³ C NMR (75 MHz, CD ₂ Cl ₂ , ppm): δ 163.2, 143.3, 141.9, 141.1, 131.1, 128.4, 120.4, 61.3, 32.0, 29.7 (overlap), 23.0, 14.5, 14.2.

Preparation of 3-hexylthieno [3,2-b] thiophene-2-carboxylic acid (compound 3)

Add compound 2 (32.10 g, 0.11 mol) to a 250 mL round flask equipped with a condenser, add sodium hydroxide solution (150 mL, 10% solution) and THF (100 mL), and then add tetrabutylammonium iodide. ) Is injected into the catalytic amount. And it stirred at 100 degreeC for 12 hours. After the reaction was completed, the solvent was evaporated, and yellow crystals formed by adding 6M HCl were filtered through a vacuum flask and dried. Compound 3 is obtained as a yellow solid (yield: 97%).

¹ H NMR (300 MHz, CD ₂ Cl ₂ , ppm): δ d 7.66 (d, 1H), 7.31 (d, 1H), 3.20 (t, 2H), 1.79 (m, 2H), 1.33 (m, 6H) , 0.91 (t, 3 H); ¹³ C NMR (75 MHz, CD ₂ Cl ₂ , ppm): δ 145.6, 142.4, 142.1, 132.3, 126.9, 120.5, 32.0, 29.9, 29.7, 23.0, 14.2.

Preparation of 3-hexylthieno [3,2-b] thiophene (Compound 4)

Add compound 3 (14.60 g, 0.05 mol) to a 250 mL round flask equipped with a condenser, add copper powder (2.00 g) and quinoline (80 mL), and stir at 240 ° C for 12 hours. After completion of the reaction, fractional distillation through ethyl acetate and HCl aqueous solution, water remaining with anhydrous magnesium sulfate was removed, the solvent was evaporated, and pure compound 4 was obtained by column chromatography (8.20 g, 67%).

¹ H NMR (300 MHz, CD ₂ Cl ₂ , ppm): δ 7.36 (m, 1H), 7.25 (m, 1H), 7.01 (m, 1H), 2.73 (t, 2H), 1.69 (m, 2H), 1.34 (m, 6 H), 0.89 (t, 3 H); ¹³ C NMR (75 MHz, CD ₂ Cl ₂ , ppm): δ 140.4, 139.1, 135.4, 127.0, 122.2, 120.3, 32.0, 30.3, 29.4, 29.0, 23.0, 14.2.

Preparation of (3-hexylthieno [3,2-b] thiophen-5-yl) trimethylstannan (Compound 5)

Inject a compound 4 (5.0 g, 0.02 mol) into a round 100 mL flask, add tetrahydrofuran (70 mL), and cool to 0 ° C. Thereafter, 2.0 M n -butyllithium (11 mL, 0.02 mol) is slowly injected and stirred at the same temperature for 30 minutes. After 30 minutes, 1M trimethyltin chloride (22.2 mL, 0.05 mol) is slowly injected and stirred at room temperature for 1 hour. When the reaction was completed, fractional distillation through ethyl acetate, the remaining water with anhydrous magnesium sulfate was removed, and the solvent was evaporated to obtain pure Compound 5 (4.90 g, 91%).

¹ H NMR (300MHz, CDCl ₃ , ppm): δ 7.21 (s, 1H), 7.05 (s, 1H), 2.72 (t, 2H), 1.72 (m, 2H), 1.34 (m, 6H), 0.89 ( t, 3H), 0.40 (t, 9H); ¹³ C NMR (75 MHz, CDCl ₃ , ppm): δ 140.1, 128.7, 127.3, 125.9, 124.1, 120.2, 38.7, 37.9, 29.5, 28.1, 25.3, 14.9, 11.1.

5- (2-hexyldecyl) -1,3-bis (6-hexylthieno [3,2-b] thiophen-2-yl) -4H-thieno [3,4- c] pyrrole-4, Preparation of 6 (5H) -dione (Compound 6)

To a round 100 mL flask was placed 1,3-dibromo-5- (2-hexyldecyl) -4H-thieno [3,4-c] pyrrole-4,6 (5H) -dione (2.00 g, 0.37 mmol). Put in and make a vacuum. DMF (50 mL) and bis (triphenylphosphine) palladium (II) dichloride (95 mg, 0.06 mmol) were injected and stirred at 150 ° C. for 30 minutes. Then compound 5 (3.60 g, 0.75 mmol) is injected and stirred at 150 ° C. for 12 h. After completion of the reaction, fractional distillation was performed through ethyl acetate, the remaining water was removed with anhydrous magnesium sulfate, the solvent was evaporated, and pure compound 6 was obtained through column chromatography (2.5 g, 58%).

¹ H NMR (300 MHz, CDCl ₃ , ppm): δ 8.35 (s, 2H), 7.09 (s, 2H), 3.57 (d, 2H), 2.71 (t, 4H), 1.90 (m, 1H), 1.72 (m, 6H), 1.32 (m, 12H), 1.26-1.24 (m, 30H), 0.92-0.84 (m, 12H); ¹³ C NMR (75 MHz, CDCl ₃ , ppm): δ 162.9, 158.3, 140.5, 137.3, 135.4, 127.2, 125.4, 122.8, 120.5, 50.1, 42.4, 41.1, 39.8, 36.3, 36.0, 35.9, 35.5, 35.1, 34.2, 33.3, 32.1, 31.4, 30.5, 29.9, 29.6, 29.3, 28.1, 27.9, 27.5, 22.5, 15.3; Anal. Calcd for C ₄₆ H ₆₃ N: C, 67.19; H, 7.72; N, 1.70. Found: C, 66.87; H, 7.81; N, 1.64.

1,3-bis (5-bromo-6-hexylthieno [3,2-b] thiophen-2-yl) -5- (2-hexyldecyl) -4H-thieno [3,4-c ] Preparation of Pyrrole-4,6 (5H) -dione (Compound 6tt-TPD)

Inject a compound 6 (1.00 g, 0.12 mmol) with DMF (25 mL) into a 250 mL round flask, and slowly inject N-bromosuccinimide (0.53 g, 0.30 mmol) at 0 ° C. After stirring for 3 hours at room temperature, when the reaction is complete, fractional distillation through methylene chloride, the remaining water with anhydrous magnesium sulfate is removed, the solvent is evaporated, recrystallized with MC (methylene chloride) and methanol to give an orange solid Obtain 6tt-TPD (80%).

¹ H NMR (300 MHz, CDCl ₃ , ppm): δ 8.27 (s, 2H), 3.59 (d, 2H), 2.70 (t, 4H), 1.92 (m, 1H), 1.67 (m, 4H), 1.33 -1.25 (m, 36H), 0.89-0.84 (m, 12H); ¹³ C NMR (75 MHz, CDCl ₃ , ppm): δ 165.1, 160.8, 145.3, 136.1, 132.3, 126.1, 125.8, 123.7, 121.4, 51.2, 43.2, 42.1, 37.2, 36.2, 36.0, 35.9, 35.5, 35.1, 34.2, 33.3, 32.1, 31.4, 30.5, 29.9, 29.6, 29.3, 28.1, 27.9, 27.5, 22.5, 15.3; Anal. Calcd for C ₄₆ H ₆₁ N: C, 56.37; H, 6. 27; N, 1.43. Found: C, 55.89; H, 6. 19; N, 1.45.

Preparation Example 2 1,3-bis (5-bromo-6-octylthieno [3,2-b] thiophen-2-yl) -5- (2-hexyldecyl) -4H-thieno [ Preparation of 3,4-c] pyrrole-4,6 (5H) -dione (Compound 8tt-TPD)

8tt-TPD was prepared by the same method as 6tt-TPD of Preparation Example 1.

¹ H NMR (300 MHz, CDCl ₃ , ppm): δ 8.30 (s, 2H), 3.57 (d, 2H), 2.75 (t, 4H), 1.89 (m, 1H), 1.71 (m, 4H), 1.34- 1.26 (m, 46 H), 0.90-0.82 (m, 12 H); ¹³ C NMR (75 MHz, CDCl ₃ , ppm): δ 164.8, 160.2, 144.8, 135.4, 133.3, 128.2, 127.9, 123.5, 120.8, 50.9, 43.3, 42.0, 38.9, 36.1, 35.6, 35.4, 35.0, 34.8, 34.5 , 32.8, 31.9, 30.7, 30.0, 29.1, 28.8, 28.1, 27.6, 27.5, 27.4, 26.1, 23.1, 15.3; Anal. Calcd for C ₅₀ H ₆₉ N: C, 57.95; H, 6.71; N, 1.35. Found: C, 57.70; H, 6.65; N, 1.30.

Preparation Example 3 1,3-bis (5-bromo-6-decylthieno [3,2-b] thiophen-2-yl) -5- (2-hexyldecyl) -4H-thieno [ Preparation of 3,4-c] pyrrole-4,6 (5H) -dione (Compound 10tt-TPD)

10tt-TPD was prepared by the same method as 6tt-TPD of Preparation Example 1.

¹ H NMR (300 MHz, CDCl ₃ , ppm): δ 8.30 (s, 2H), 3.56 (d, 2H), 2.75 (t, 4H), 1.90 (m, 1H), 1.70 (m, 4H), 1.33- 1.25 (m, 54 H), 0.87-0.82 (m, 12 H); ¹³ C NMR (75 MHz, CDCl ₃ , ppm): δ 165.0, 161.1, 145.2, 138.2, 135.9, 130.2, 128.1, 125.3, 121.1, 51.0, 44.4, 43.8, 40.1, 36.8, 36.2, 35.9, 35.6, 35.2, 35.0 , 34.8, 33.5, 32.1, 30.6, 30.1, 29.6, 29.1, 28.7, 28.3, 28.0, 27.3, 27.0, 26.7, 25.9, 25.3, 16.5; Anal. Calcd for C ₅₄ H ₇₇ N: C, 59.38; H, 7. 11; N, 1.28. Found: C, 59.20; H, 6.98; N, 1.30.

Production Example 4 1,3-bis (5-bromo-6-octylthieno [3,2-b] thiophen-2-yl) -5- (5-hexyltridecyl) -4H-thieno Preparation of [3,4-c] pyrrole-4,6 (5H) -dione (Compound 12)

Preparation of 2- (5-hexyltridecyl) isoindolin-1,3-dione (Compound 7)

In a 250 mL round flask, add 7- (4-bromobutyl) pentadecane (15.0 g, 0.043 mol) and phthalimide potassium salt (9.6 g, 0.051 mol), and inject DMF (200 mL). Stir at 16 ° C. for 16 hours. After completion of the reaction, fractional distillation was carried out through hexane, the remaining water was removed with anhydrous magnesium sulfate, the solvent was evaporated, and pure compound 7 was obtained by column chromatography (13.8g, 75%).

¹ H NMR (300 MHz, CDCl ₃ , ppm): δ 7.837.81 (m, 2H), 7.697.67 (d, 2H), 3.65 (t, 2H), 1.671.57 (m, 1H), 1.341.28 (m, 30 H), 0.85 (m, 6 H).

Preparation of 5-hexyltridecane-1-amine (Compound 8)

Inject a compound 7 (10.0 g, 0.024 mol), hydrazine (3.09 g, 0.096 mol) and methanol (100 mL) into a 250 mL round flask and reflux for 12 hours. After completion of the reaction, fractional distillation was carried out through 10% KOH solution (100 mL), the remaining water was removed with anhydrous magnesium sulfate, and the solvent was evaporated to obtain pure compound 8 (6.67g, 82%).

¹ H NMR (300 MHz, CDCl ₃ ): δ 2.68 (t, 2H), 1.52 (m, 1H), 1.301.01 (m, 30H), 0.85 (m, 6H).

Preparation of 5- (5-hexyltridecyl) -4H-thieno [3,4-c] pyrrole-4,6 (5H) -dione (Compound 9)

Thieno [3,4-c] furan-1,3-dione (3.0 g, 0.0194 mol) and compound 8 (6.6 g, 0.0232 mol) were injected with toluene (300 mL) and stirred at 100 ° C for 24 hours. After evaporation of the solvent, the pure compound 9 was obtained by column chromatography (7.5 g, 73%).

¹ H NMR (300 MHz, CDCl ₃ , ppm): δ 7.79 (s, 2H), 3.59 (t, 2H), 1.59 (m, 1H), 1.231.18 (m, 30H), 0.86 (m, 6H). ¹³ C NMR (75 MHz, CDCl ₃ ) δ: 165.1, 145.2, 138.5, 40.2, 39.8, 38.5, 37.1, 36.2, 35.1, 33.3, 32.3, 30.5, 29.8, 29.6, 28.3, 27.0, 26.8, 26.3, 25.9, 25.1. 22.7, 14.1. Anal. Calc. for C ₂₅ H ₄₁ N: C, 71.55; H, 9.85; N, 3.34. Found: C, 71.48; H, 9.92; N, 3.28.

Preparation of 1,3-dibromo-5- (5-hexyltridecyl) -4H-thieno [3,4-c] pyrrole-4,6 (5H) -dione (compound 10)

Compound 9 (5.0 g, 0.012 mol), sulfuric acid (30 mL) and trifluoro acetic acid (100 mL) were added to a 100 mL round flask, followed by N-bromosuccinimide (5.30 g, 0.030 mol). ), And stirred at room temperature for 12 hours. After completion of the reaction, fractional distillation through methylene chloride was followed by removal of the remaining water with anhydrous magnesium sulfate, evaporation of the solvent, and column chromatography to obtain pure Compound 10 (4.9 g, 76%).

¹ H NMR (300 MHz, CDCl ₃ , ppm): δ 3.58 (t, 2H), 1.59 (m, 1H), 1.23-1.19 (m, 30H), 0.87 (m, 6H). ¹³ C NMR (75 MHz, CDCl ₃ ) δ: 170.3, 155.1, 142.5, 41.3, 40.2, 39.3, 38.2, 37.1, 36.4, 34.8, 33.3, 31.7, 30.2, 29.1, 28.6, 27.9, 27.3, 27.0, 26.3, 25.2. 23.1, 16.3. Anal. Calc. for C ₂₅ H ₃₉ N: C, 52.00; H, 6.81; N, 2.43. Found: C, 51.84; H, 6.93; N, 2.54.

5- (5-hexyltridecyl) -1,3-bis (6-octylthieno [3,2-b] thiophen-2-yl) -4H-thieno [ 3,4-c] pyrrole-4 , 6 (5H) -dione (Compound 11)

Compound 10 (3.00 g, 0.005 mol) and catalyst bis (triphenylphosphine) palladium (II) dichloride (95 mg, 0.06 mmol) were added to a 100 mL round flask equipped with a condenser, followed by vacuum. Thereafter, DMF (50 mL) was injected, followed by trimethyl (6-octylthieno [3,2-b] thiophen-2-yl) stannin (5.39 g, 0.012 mol), followed by reflux. . After completion of the reaction, fractional distillation through methylene chloride is followed by removal of the remaining water with anhydrous magnesium sulfate, evaporation of the solvent, and then pure compound 11 (2.5 g, 58%) by column chromatography.

¹ H NMR (300 MHz, CDCl ₃ , ppm): δ 8.30 (s, 2H), 7.08 (s, 2H), 3.66 (t, 2H), 2.69 (t, 4H), 1.73-1.70 (m, 5H), 1.41-1.23 (m, 50 H), 0.97-0.86 (m, 12 H). ¹³ CNMR (75MHz, CDCl ₃ ) δ: 169.1, 160.3, 140.2, 137.5, 127.3, 123.1, 122.8, 122.0, 121.3, 40.2, 39.8, 39.2, 38.9, 38.4, 38.0, 37.8, 37.4, 35.2, 34.7, 34.1, 33.3, 32.9, 31.5, 30.5, 30.1, 29.9, 29.3, 29.2, 28.5, 28.1, 27.4, 25.6, 24.9, 24.5, 22.7, 12.5. Anal. Calc. for C ₅₃ H ₇₇ N: C, 69.15; H, 8.43; N, 1.52. Found: C, 68.98; H, 8.51; N, 1.61.

1,3-bis (5-bromo-6-octylthieno [3,2-b] thiophen-2-yl) -5- (5- hexyltridecyl ) -4H-thieno [3,4- c] Preparation of pyrrole-4,6 (5H) -dione (compound 12)

In a 100 mL round flask, Compound 11 (2.00 g, 0.002 mol) was added, DMF (50 mL) was injected, N-bromosuccinimide (0.97 g, 0.005 mol) was injected, and the light was blocked. Stir for 12 hours in the state. After completion of the reaction, fractional distillation through methylene chloride is followed by removal of the remaining water with anhydrous magnesium sulfate, evaporation of the solvent, and column chromatography to give pure compound 12 (2.3 g, 80%).

¹ H NMR (300 MHz, CDCl ₃ , ppm): δ 8.20 (s, 2H), 3.64 (t, 2H), 2.68 (t, 4H), 1.70-1.65 (m, 5H), 1.32-1.22 (m, 50H ), 0.88-0.83 (m, 12H). ¹³ CNMR (75 MHz, CDCl ₃ ) δ: 170.1, 165.2, 145.1, 140.8, 130.2, 128.2, 125.3, 124.6, 122.2, 41.3, 40.9, 39.9, 39.1, 38.8, 38.0, 37.6, 37.2, 36.3, 35.1, 34.9, 34.2, 33.3, 32.1, 31.6, 30.4, 30.1, 29.3, 29.0, 28.2, 27.9, 27.2, 26.7, 25.3, 24.2, 23.1, 13.1. Anal. Calc. for C ₅₃ H ₇₅ N: C, 59.03; H, 7.01; N, 1.30. Found: C, 58.78; H, 7. 21; N, 1.28.

[실시예 1 내지 3] 유기반도체 화합물(고분자 1, 2 및 3)의 제조Examples 1 to 3 Preparation of Organic Semiconductor Compounds ( Polymers 1, 2 and 3)

After vacuuming in a round flask equipped with a condenser to remove moisture and oxygen, BDT compound (300 mg, 0.03 mmol) and the compound tt-TPD (0.03 mmol) of Preparation Examples 1 to 3 were added thereto, and anhydrous toluene (10 mL) was added thereto. ) Was dissolved. Pd (PPh ₃ ) ₄ catalyst (10 mg, 0.03 eq) was added dissolved in anhydrous DMF (1 mL). After stirring at 120 ° C. for 48 hours, when the reaction was completed, the produced solid was dissolved in chloroform, columned with Florisil to remove the catalyst, recrystallized from methanol to obtain a purple solid, and the obtained solid was converted into methanol and acetone. Purification by using an extractor (Soxhlet) to obtain the polymer compounds 1, 2 and 3, respectively. The weight average molecular weight (Mw), number average molecular weight (Mn), polydispersity index (PDI) and decomposition temperature (T _d ) of the obtained polymer compounds are described in Table 1 below.

[실시예 4 내지 6] 유기반도체 화합물(고분자 4, 5 및 6)의 제조Examples 4 to 6 Preparation of Organic Semiconductor Compounds ( Polymers 4, 5, and 6)

In a round flask equipped with a condenser to remove water and oxygen by vacuuming, BDTT compound (300 mg, 0.03 mmol) and compound tt-TPD (0.03 mmol) of Preparation Examples 1 to 3 were added thereto, and anhydrous toluene (10 mL) was added thereto. ) Was dissolved. Pd (PPh ₃ ) ₄ catalyst (10 mg, 0.03 eq) was added dissolved in anhydrous DMF (1 mL). After 48 hours of stirring at 110 ° C, the reaction product was dissolved in chloroform, columned with Florisil to remove the catalyst, recrystallized from methanol to obtain a purple solid, and the obtained solid was used with methanol and acetone. The product was purified by an extractor (Soxhlet) to obtain

polymer compounds

4, 5, and 6, respectively. The weight average molecular weight (Mw), number average molecular weight (Mn), polydispersity index (PDI) and decomposition temperature (T _d ) of the obtained polymer compounds are described in Table 1 below.

[실시예 7] 유기반도체 화합물(고분자 7)의 제조Example 7 Preparation of Organic Semiconductor Compound (Polymer 7)

After vacuuming in a round flask equipped with a condenser to remove moisture and oxygen, Compound 12 (300 mg, 0.03 mmol) and 2,5-bis (trimethylstannyl) thiophene (0.03 mmol) of Preparation Example 4 were added thereto. Anhydrous toluene (10 mL) was added and dissolved. Pd (PPh ₃ ) ₄ catalyst (10 mg, 0.03 eq) was added dissolved in anhydrous DMF (1 mL). After 48 hours of stirring at 110 ° C, the reaction product was dissolved in chloroform, columned with Florisil to remove the catalyst, recrystallized from methanol to obtain a purple solid, and the obtained solid was used with methanol and acetone. The product was purified by an extractor (Soxhlet) to obtain a polymer compound 7. The weight average molecular weight (Mw), number average molecular weight (Mn), polydispersity index (PDI) and decomposition temperature (T _d ) of the obtained polymer compound are shown in Table 1 below.

[실시예 8] 유기반도체 화합물(고분자 8)의 제조Example 8 Preparation of Organic Semiconductor Compound (Polymer 8)

Polymeric compound in the same manner as in Example 7 except for using 5,5'-bis (trimethylstannyl) -2,2'-bithiophene instead of 2,5-bis (trimethylstannyl) thiophene 8 was prepared, and the weight average molecular weight (Mw), number average molecular weight (Mn), polydispersity index (PDI), and decomposition temperature (T _d ) of the obtained polymer compound are shown in Table 1 below.

Table 1

Polymer		Mw	Mn	PDI	T _d (℃)
Example 1	Polymer 1	90,000	40,000	2.25	434
Example 2	Polymer 2	16,000	70,000	2.28	408
Example 3	Polymer 3	17,000	68,000	2.5	430
Example 4	Polymer 4	190,000	70,000	2.71	431
Example 5	Polymer 5	210,000	80,000	2.62	300
Example 6	Polymer 6	170,000	60,000	2.83	332
Example 7	Polymer 7	204,000	85,000	2.4	323
Example 8	Polymer 8	196,000	70,000	2.8	325

The polymers prepared in Examples 1 to 8 were well dissolved in chloroform, THF, and toluene which are common organic solvents at room temperature. Physical properties and optical properties of the polymers prepared in Examples 1 to 6 of the obtained polymers are shown in FIGS. 3 to 4.

The thermogravimetric analysis (TGA) curves of the polymers prepared in Examples 1 to 6 are shown in FIG. 3, and as shown in FIG. 3, the organic semiconductor compounds of the present invention are thermally very stable.

In addition, UV absorption spectra of the solution state and the solid film state of the polymer prepared in Examples 1 to 6 were measured and shown in FIGS. 4 and 5, respectively.

In addition, UV absorption spectra of the solution state and the solid film state of the polymers prepared in Examples 7 and 8 were measured and shown in FIGS. 6 and 7, respectively.

As shown in FIGS. 4, 6, and 7, the polymers prepared in Examples 1 to 8 commonly exhibit absorptions of 300 to 700 nm in the UV absorption spectrum in the chloroform solution state, and particularly strong vibration peaks are observed. This can be seen as a peak due to strong interactions between molecules.

In addition, in the film UV absorption spectrum of the polymer prepared in Examples 1 to 8, as shown in FIGS. 5, 6, and 7, it is possible to observe the absorption spectrum of a wider region than the absorption spectrum of the solution state. When in the liquid state, the molecules are distributed over a wide range and can move relatively freely, but in the solid film state, it is a result from the tendency of aggregation of individual groups. As a result of calculating the bandgap (bandgap = 1240 / λ _edge ) using the absorption spectrum in the film state, the polymers prepared in Examples 1 to 8 showed a bandgap of 1.72 to 1.90 eV. In particular, the polymers prepared in Examples 7 and 8 exhibited low bandgaps of 1.73 eV and 1.72 eV, respectively.

In addition, the ferrocene / ferrocenium redox system (Ferrocene / Ferrocenium redox system) (-4.8V) based on the reference (Reference) in the solid film state measured by cyclic voltammetry (Cyclic Voltammertry) prepared in Examples 1 to 8 HOMO levels of the polymers were obtained, which are shown in FIGS. 8 and 9. The six polymers prepared in Examples 1 to 6 were calculated to have a HOMO energy level of -5.48 eV, and the two polymers prepared in Examples 7 and 8 were to a HOMO energy level of -5.65 eV and -5.54 eV, respectively. Was calculated. As a result of calculating the LUMO energy level of each polymer by the difference between the calculated HOMO energy level and the band gap calculated in the UV absorption spectrum, it was calculated as -3.65 to -3.90 eV.

[실시예 9 내지 12] 단일층 유기 태양전지 소자의 제작[Examples 9 to 12] Fabrication of Single Layer Organic Solar Cell Device

A single layer organic solar cell device containing an organic semiconductor compound according to the present invention as a photoactive layer was fabricated as follows.

First, UV-O ₃ was treated on clean indium tin oxide (ITO) glass, ZnO NPs (Zinc oxide nanopartile) was spin-coated at 5000 rpm for 1 minute, and then heat-treated at 120 ° C. for 10 minutes to transport 10 nm thick electrons. A layer (Electron transport layer (ETL)) was formed.

After adding the organic semiconductor compound and PCBM (C70) according to the present invention to chlorobenzene, DIO (1,8-diiodooctane) was added to 3 vol% and stirred for 24 hours at 50 ° C. for sufficient mixing of the two organic materials. A semiconductor compound mixture was prepared.

Polymer 1 (Example 1), Polymer 4 (Example 4), Polymer 7 (Example 7) or Polymer 8 (Example 8) were used as the organic semiconductor compound, and Polymer 1 or Polymer 4 was used. 1 or polymer 4: PCBM (C70) is a weight ratio of 1: 1, when using a polymer 7 or polymer 8, polymer 7 or polymer 8: PCBM (C70) is 1: 1.3, 1: 1.5 or 1: 1.7 weight ratio Used as.

Spin coating the organic semiconductor compound mixture on the ETL layer, which is the coating layer, under nitrogen, followed by heat treatment at 120 ° C. for 10 minutes to form a 100 nm photoactive layer, and finally MoO ₃ (10 nm) / Ag (100 nm). The high temperature vapor deposition to produce a single-layer organic solar cell device.

In order to investigate the photovoltaic characteristics of the fabricated single layer organic solar cell device, 100mW solar light under AM 1.5 condition was generated using a solar simulator and a radiant power meter and a 1kW solar simulator (Newport). 91192) was used to measure the current density-voltage (JV) characteristics of the organic solar cell device, and the results are shown in FIGS. 10 to 12. 11 and 12 it was confirmed that the best efficiency when the mixed weight ratio of the polymer 7 or polymer 8: PCBM (C70) is 1: 1.5.

Electrical characteristics of the fabricated single layer organic solar cell device, namely, V _oc (open circuit voltage), J _SC (short-circuit current density), FF (fill factor) and photoelectric conversion efficiency (PCE) Photovoltaic parameters are summarized in Table 2.

TABLE 2

	Photoactive layer	Organic Semiconductor Compound: Weight Ratio of PCBM (C70)	V _oc [V]	J _sc [mA / cm ² ]	FF [%]	PCE [%]
Example 9	Polymer 1	1: 1	0.83	15.8	63	8.23
Example 10	Polymer 4	1: 1	0.81	15.6	66	8.33
Example 11	Polymer 7	1: 1.5	0.86	15.30	70	9.21
Example 12	Polymer 8	1: 1.5	0.78	10.56	62	5.05

The J-V characteristic curves of the single layer organic solar cell devices manufactured in Examples 9 to 12 are illustrated in FIGS. 10 to 12. Each polymer was combined with an additive such as DIO (1,8-diiodooctane) to obtain more improved photoelectric conversion efficiency. As a result, the polymers exhibited high photoelectric conversion efficiency of 8.23, 8.33, 9.21 and 5.05%, respectively. In particular, the organic solar cell device of Example 11 has a photoelectric conversion efficiency of 9% or more, which can be seen as the world's highest photoelectric conversion efficiency.

[실시예 13] 반전 적층형 유기 태양전지 소자의 제작Example 13 Fabrication of Inverted Laminated Organic Solar Cell Device

To investigate the photovoltaic characteristics of an inverted stacked organic solar cell device fabricated using a polymer 4 having an intermediate bandgap (Example 4) as a new electron donor material, as shown in FIG. 13 [ITO / ZnO NPs / organic semiconductor of the present invention] Compound (Polymer 4 of Example 4): PC ₇₁ BM / PEDOT: PSS / ZnO NPs / low band gap organic semiconductor compound: PC ₇₁ BM / MoO ₃ / Ag] An inverted stacked organic solar cell device was fabricated. In the case of the low bandgap organic semiconductor compound introduced in the present invention, PTB7 has a structure as shown in FIG. 14, and this material also used a previously reported material.

First, after UV-O ₃ treatment on clean indium tin oxide (ITO) glass, ZnO NPs were spin-coated at 5000 rpm for 1 minute, and then heat-treated at 120 ° C. for 10 minutes to form a 10 nm-thick electron transport layer (Electron transport). layer: ETL).

Polymer 4 of Example 4 and PC ₇₁ BM were added to chlorobenzene in a weight ratio of 1: 1, and then DIO (1,8-diiodooctane) was added at 3 vol%, followed by 24 hours at 50 ° C for sufficient mixing of the two materials. While stirring, an organic semiconductor compound mixture was prepared. After the organic semiconductor compound mixture was spin-coated on the ETL layer, which is the coating layer, under nitrogen atmosphere, heat-treated at 120 ° C. for 10 minutes to form a 90 nm photoactive layer, followed by PEDOT: PSS (poly (3,4-ethylenedioxythiophene) : poly (styrenesulfonate)) was spin-coated.

After the PEDOT: PSS spin coating is completed, the ZnO NPs is coated once again to form an electron transport layer having a thickness of 10 nm, and PTB7: PC ₇₁ BM, which is a low bandgap organic semiconductor compound, has a weight ratio of 1: 1.5. After adding to chlorobenzene, DIO (1,8-diiodooctane) was added at 3 vol% and stirred for 24 hours at 50 ° C. for sufficient mixing of the two materials to prepare a low bandgap organic semiconductor compound mixture. The low bandgap organic semiconductor compound mixture solution was spin-coated at 2000 rpm on the ETL layer, which was the coating layer, under nitrogen to form an 80 nm photoactive layer. Finally, a high-temperature deposition with MoO ₃ (10 nm) / Ag (100 nm) to fabricate an inverted stacked organic solar cell device.

15 shows the UV-visible absorption spectra of the lower layer and the upper layer photoactive polymer of the inverted stacked organic solar cell device.

In order to investigate the photovoltaic characteristics of the fabricated inverted stacked organic solar cell device, a solar simulator and a radiant power meter were used to generate 100 mW solar light under AM 1.5 conditions, and a 1 kW solar simulator (Newport). 91192) was used to measure the current density-voltage characteristics of the organic solar cell device and the results are shown in FIG. 16.

Electrical characteristics of the inverted stacked organic solar cell device fabricated using the polymer 4, that is, V _oc (open circuit voltage), J _SC (short-circuit current density), FF (fill factor) and PCE (power conversion efficiency) The photovoltaic parameters of are summarized in Table 3.

[비교예 1] 반전 적층형 유기 태양전지 소자의 제작Comparative Example 1 Fabrication of Inverted-Layered Organic Solar Cell Device

An inverted stacked organic solar cell device was manufactured in the same manner as in Example 13 except that P3HT was used instead of Polymer 4 of Example 4 and IC ₆₀ BA was used instead of PC ₇₁ BM. The electrical characteristics of the solar cell device are shown in Table 3 below.

TABLE 3

Cell	Active layer	V _oc [V]	J _sc [mA / cm ² ]	FF [%]	PCE [%]
Upper layer device ^a	PTB7: PC ₇₁ BM (weight ratio of 1: 1.5)	0.74	14.64	73	7.86
Lower layer device ^b	P3HT: IC ₆₀ BA	0.83	8.81	63	4.60
Inverted stacked device ^c of Comparative Example 1	-	1.56	8.12	67	8.47
Lower layer element ^d	Polymer 4: PC ₇₁ BM (weight ratio of 1: 1)	0.84	11.05	73	6.81
Inverted stacked device ^e of Example 13	-	1.58	8.00	74	9.35

a [ITO / ZnO NPs / PTB7: PC ₇₁ BM / MoO ₃ / Ag]

b [ITO / ZnO NPs / P3HT: IC ₆₀ BA / PEDOT: PSS / Ag]

c [ITO / ZnO NPs / P3HT: IC ₆₀ BA / PEDOT: PSS / ZnO NPs / PTB7: PC ₇₁ BM / MoO ₃ / Ag]

d [ITO / ZnO NPs / Polymer 4: PC ₇₁ BM / PEDOT: PSS / Ag]

e [ITO / ZnO NPs / Polymer 4: PC ₇₁ BM / PEDOT: PSS / ZnO NPs / PTB7: PC ₇₁ BM / MoO ₃ / Ag]

As shown in Table 3, the inverted stacked device (Example 13) using the novel organic semiconductor compound according to the present invention, which has not been reported so far, exhibited excellent PCE characteristics of 9.35%.

In general, P3HT used in an inverted stacked organic solar cell was used in combination with a bis-adduct called IC ₆₀ BA (Indene-C60 Bis-Adduct) (Comparative Example 1). In the case of bis-adducts, however, it was difficult to synthesize clean materials and the efficiency change was severe.

However, the inverted stacked organic solar cell of Example 13 including the polymer 4 synthesized in the present invention showed excellent FF of 74% while exhibiting a very high photoelectric conversion efficiency of 9.35%. In inverted stacked organic solar cells, 74% of FF is one of the best device characteristics in the world. This is a much better result than the conventionally used P3HT (Fig. 16). This is due to the excellent crystallinity of the polymer 4 synthesized in the present invention and excellent charge balance between holes and electrons. The properties of these polymers are advantageous for achieving high FF. In particular, as shown in FIG. 16, the present invention has been compared with P3HT: IC ₆₀ BA which is generally used as a lower layer photoactive layer in an inverted stacked organic solar cell. As a result, the photoelectric conversion efficiency of 8.47% was shown for the device of Comparative Example 1 of P3HT: IC ₆₀ BA / PTB7: PC ₇₁ BM (FIG. 16C). That is, it can be seen that the polymer 4, which is a novel organic semiconductor compound of the present invention, serves as a very important material that can exhibit more improved efficiency of the current inverted stacked organic solar cell.

The implementation of a solar cell showing 74% of FF using the organic semiconductor compound of the present invention, Polymer 4, as a photoactive layer is the first report in the world. It is expected to be able.

Claims

An organic semiconductor compound represented by Formula 1 below:

[Formula 1]

In Chemical Formula 1,

D is C 6 -C 30 arylene or C 3 -C 30 heteroarylene;

X is S, Se, O or NR ';

R 1 and R 2 independently of one another are hydrogen, C 1 -C 30 alkyl, C 1 -C 30 alkoxy, C 1 -C 30 alkylthio, C 1 -C 30 alkoxyC 3 -C 20 heteroaryl or C 6- C 30 arC 1 -C 30 alkyl;

R 'is hydrogen, C 1 -C 30 alkyl or C 6 -C 30 arC 1 -C 30 alkyl;

The arylene and heteroarylene of D are C 1 -C 30 alkylthienyl, C 1 -C 30 alkoxyC 6 -C 30 aryl, C 1 -C 30 alkyl, C 1 -C 30 alkoxy, C 1 -C 30 alkoxyC 1 -C 30 alkyl, C 1 -C 30 alkylC 3 -C 30 heteroaryl, C 1 -C 30 alkylthio, C 1 -C 30 alkoxyC 3 -C 30 heteroaryl, C 6 -C 30 May be further substituted with one or more substituents selected from the group consisting of aryl, C 3 -C 30 heteroaryl or C 6 -C 30 arC 1 -C 30 alkyl;

The alkyl and aralkyl of R 1 and R 2 are C 1 -C 30 alkyl, C 2 -C 30 alkenyl, C 2 -C 30 alkynyl, C 1 -C 30 alkoxy, amino, mono- or di-C 1 -C 30 alkyl, amino, hydroxy, halogen, cyano, nitro, halo-C 1 -C 30 alkyl, C 1 -C 30 alkylsilyl group and C 6 one or more substituents selected from the group consisting of -C 30 arylsilyl May be further substituted with;

n is an integer from 1 to 2000;

The heteroaryl and heteroarylene include one or more heteroatoms selected from N, O, S, P (= 0), Si and P.
The method of claim 1,

The D is an organic semiconductor compound, characterized in that C 3 -C 30 heteroarylene.
The method of claim 2,

Wherein D is a heteroarylene selected from the following structures:

R 11 and R 12 are each independently hydrogen, C 1 -C 30 alkylthienyl, C 1 -C 30 alkoxyC 6 -C 30 aryl, C 1 -C 30 alkyl, C 1 -C 30 alkoxy, C 1 -C 30 alkoxyC 1 -C 30 alkyl, C 1 -C 30 alkylC 3 -C 30 heteroaryl, C 1 -C 30 alkylthio, C 1 -C 30 alkoxyC 3 -C 30 heteroaryl or C 6- C 30 arC 1 -C 30 alkyl;

R 13 to R 20 are each independently of the other hydrogen, C 1 -C 30 alkyl, C 6 -C 30 aryl, C 3 -C 30 heteroaryl or C 6 -C 30 are C 1 -C 30 alkyl.
The method of claim 3, wherein

The organic semiconductor compound is an organic semiconductor compound, characterized in that represented by the following formula (2), (3) or (4):

[Formula 2]

[Formula 3]

[Formula 4]

In Chemical Formulas 2 to 4,

X is S, Se or O;

R 1 and R 2 independently of one another are C 1 -C 30 alkyl, C 1 -C 30 alkoxy, C 1 -C 30 alkoxyC 1 -C 30 alkyl or C 1 -C 30 alkoxyC 3 -C 20 heteroaryl ;

R 11 and R 12 are each independently hydrogen, C 1 -C 30 alkylthienyl, C 1 -C 30 alkoxyC 6 -C 30 aryl, C 1 -C 30 alkyl, C 1 -C 30 alkoxy, C 1- C 30 alkoxyC 1 -C 30 alkyl, C 1 -C 30 alkylC 3 -C 30 heteroaryl, C 1 -C 30 alkylthio, C 1 -C 30 alkoxyC 3 -C 30 heteroaryl or C 6 -C 30 arC 1 -C 30 alkyl;

R 13 to R 16 independently of one another are hydrogen, C 1 -C 30 alkyl, C 6 -C 30 aryl, C 3 -C 30 heteroaryl or C 6 -C 30 arC 1 -C 30 alkyl;

n is an integer from 1 to 2000.
The method of claim 4, wherein

The R 1 and R 2 are independently an organic semiconductor compound, characterized in that C 1 -C 30 Alkyl.
The method of claim 5,

The organic semiconductor compound is an organic semiconductor compound, characterized in that selected from the following structure:

N is an integer of 1 to 2000.
A method of preparing an organic semiconductor compound represented by Chemical Formula 1 by copolymerizing a tin compound of Chemical Formula 5 and a tt-TPD derivative of Chemical Formula 6 below:

[Formula 1]

[Formula 5]

[Formula 6]

In Chemical Formulas 1, 5, and 6,

D is C 6 -C 30 arylene or C 3 -C 30 heteroarylene;

X is S, Se, O or NR ';

Y is halogen;

R 1 and R 2 independently of one another are hydrogen, C 1 -C 30 alkyl, C 1 -C 30 alkoxy, C 1 -C 30 alkylthio, C 1 -C 30 alkoxyC 3 -C 20 heteroaryl or C 6- C 30 arC 1 -C 30 alkyl;

R 'is hydrogen, C 1 -C 30 alkyl or C 6 -C 30 arC 1 -C 30 alkyl;

The arylene and heteroarylene of D are C 1 -C 30 alkylthienyl, C 1 -C 30 alkoxyC 6 -C 30 aryl, C 1 -C 30 alkyl, C 1 -C 30 alkoxy, C 1 -C 30 alkoxyC 1 -C 30 alkyl, C 1 -C 30 alkylC 3 -C 30 heteroaryl, C 1 -C 30 alkylthio, C 1 -C 30 alkoxyC 3 -C 30 heteroaryl, C 6 -C 30 May be further substituted with one or more substituents selected from the group consisting of aryl, C 3 -C 30 heteroaryl or C 6 -C 30 arC 1 -C 30 alkyl;

The alkyl and aralkyl of R 1 and R 2 are C 1 -C 30 alkyl, C 2 -C 30 alkenyl, C 2 -C 30 alkynyl, C 1 -C 30 alkoxy, amino, mono- or di-C 1 -C 30 alkyl, amino, hydroxy, halogen, cyano, nitro, halo-C 1 -C 30 alkyl, C 1 -C 30 alkylsilyl group and C 6 one or more substituents selected from the group consisting of -C 30 arylsilyl May be further substituted with;

n is an integer from 1 to 2000;

The heteroaryl and heteroarylene include one or more heteroatoms selected from N, O, S, P (= 0), Si and P.
An organic electronic device comprising the organic semiconductor compound according to any one of claims 1 to 6.
An organic solar cell device comprising the organic semiconductor compound according to any one of claims 1 to 6.
The method of claim 9,

The organic semiconductor compound is an organic solar cell device, characterized in that used as an electron donor material.
A multilayer organic solar cell device using the organic semiconductor compound according to any one of claims 1 to 6 as an electron donor material of a lower layer.
The method of claim 11,

The stacked organic solar cell device is a stacked organic solar cell device, characterized in that the inverted stacked organic solar cell device.