KR101146666B1 - 3-Dimensional Low Molecular Bithiophene Derivatives and Devices using the Same - Google Patents
3-Dimensional Low Molecular Bithiophene Derivatives and Devices using the Same Download PDFInfo
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Abstract
본 발명은 3차원 저분자 비티오펜 유도체(bithiophene derivatives) 및 이를 이용한 소자에 관한 것으로, 보다 상세하게는 선형 공액 사슬(linear conjugated chains)을 갖는 3차원 구조의 저분자 비티오펜 유도체 및 이를 유기 반도체, 정공 수송 물질로 이용한 소자에 관한 것이다. 본 발명에 의하면, 상온 스핀 코팅 공정이 가능하고 안정적일 뿐만 아니라, 전기 전도성이 우수한 비티오펜 유도체를 제공할 수 있다.The present invention relates to a three-dimensional low molecular bithiophene derivatives and a device using the same, and more particularly, to a three-dimensional low molecular bithiophene derivative having linear conjugated chains and organic semiconductors, hole transport It relates to a device used as a material. According to the present invention, it is possible to provide a bithiophene derivative having an excellent electrical conductivity as well as being stable and room temperature spin coating process.
비티오펜 유도체, 3차원, 전기 전도성, 정공 수송 물질, 태양전지, 상온 스핀 코팅 Bithiophene Derivatives, 3D, Electrically Conductive, Hole Transport Materials, Solar Cells, Room Temperature Spin Coating
Description
도 1은 본 발명의 비티오펜 유도체의 중심에 위치한 두 티오펜환의 입체구조를 나타내는 모식도이고,1 is a schematic diagram showing the three-dimensional structure of two thiophene ring located in the center of the bithiophene derivative of the present invention,
도 2는 본 발명의 실시예 1에서 제조한 태양전지 소자의 I-V 그래프이고,2 is an I-V graph of the solar cell device manufactured in Example 1 of the present invention,
도 3은 비교예 1에서 제조한 태양전지 소자의 I-V 그래프이고,3 is an I-V graph of the solar cell device manufactured in Comparative Example 1;
도 4는 비교예 2에서 제조한 태양전지 소자의 I-V 그래프이다.4 is an I-V graph of the solar cell device manufactured in Comparative Example 2. FIG.
본 발명은 비티오펜 유도체 및 이를 이용한 소자에 관한 것으로, 보다 상세하게는 선형 공액 사슬(linear conjugated chains)을 갖는 3차원 구조의 저분자 비티오펜 유도체 및 이를 유기 반도체 또는 정공 수송 물질로 이용한 소자에 관한 것이다.The present invention relates to a bithiophene derivative and a device using the same, and more particularly, to a low molecular bithiophene derivative having a three-dimensional structure having linear conjugated chains and a device using the same as an organic semiconductor or a hole transporting material. .
현재 유기반도체 재료로서 펜타센 등의 저분자 유기재료의 연구가 가속화되 는 한편, 폴리티오펜을 중심으로 한 고분자 유기재료에 대한 연구도 활발하게 진행되고 있다.At present, research on low-molecular organic materials such as pentacene as organic semiconductor materials has been accelerated, and research on high molecular organic materials centered on polythiophene has been actively conducted.
펜타센 등의 저분자 유기재료의 경우 우수한 전하이동도 및 전류점멸비를 갖는 것으로 보고되고 있으나, 박막 형성시 고가의 진공증착 장비를 필요로 하고, 미세패턴 형성에 어려움이 있기 때문에 가격적인 면이나 대면적화에 있어서 적합하지 않은 문제점을 가진다. Low-molecular organic materials such as pentacene have been reported to have excellent charge mobility and current flashing ratio, but they require expensive vacuum deposition equipment when forming thin films, and are difficult to form fine patterns, which makes them inexpensive. There is an unsuitable problem in adaptation.
이에 반하여, 폴리티오펜계 고분자 유기재료의 경우, 저분자 재료와 달리 용액형성이 가능하고, 스크린 인쇄기술이나 잉크분사(Ink-Jet) 기술 및 롤 프린팅 기술 등을 사용하여 박막 형성이 가능하므로 가격적인 면이나 대면적화에 유리한 장점이 있는 것으로 보고되고 있다.On the other hand, polythiophene-based polymer organic materials, unlike low-molecular materials, can be formed in solution, and thin films can be formed using screen printing, ink-jet, roll printing, etc. It is reported that there is an advantage in cotton and large area.
그러나, 상기 고분자 유기재료는 분자량 분포 차이로 인해 서로 다른 산화전위(oxidation potential)를 가지므로, 안정성을 저하시키는 원인이 되어 소자에 적용하는 것이 어려운 반면, 저분자 유기재료는 동일한 산화전위를 갖기 때문에 안정성 면에서 유리한 것으로 밝혀졌다.However, since the polymer organic materials have different oxidation potentials due to the difference in molecular weight distribution, it is difficult to apply them to devices due to deterioration of stability, while the low molecular weight organic materials have the same oxidation potential. It turned out to be advantageous in terms of.
본 발명은 상술한 종래 기술의 문제점을 해결하기 위한 것으로, 본 발명의 목적은 선형 공액 사슬(linear conjugated chains)을 갖는 3차원 구조를 갖는 저분자 비티오펜 유도체를 이용하여, 소자 적용시에 상온 스핀 코팅 공정이 가능하고 안정적일 뿐만 아니라, 전기 전도성이 우수한 저분자 유기재료를 제공하는 것이다. The present invention is to solve the above-mentioned problems of the prior art, an object of the present invention is to use a low-molecular bithiophene derivative having a three-dimensional structure having linear conjugated chains, at room temperature spin coating during application The present invention provides a low molecular weight organic material which is not only processable and stable, but also has excellent electrical conductivity.
본 발명의 다른 목적은 상기 비티오펜 유도체를 유기 반도체(organic semiconductor) 또는 정공 수송 물질(hole conducting material)로 이용한 소자를 제공하는 것이다.Another object of the present invention is to provide a device using the bithiophene derivative as an organic semiconductor or a hole conducting material.
상술한 목적을 달성하기 위한 본 발명의 한 측면은 하기 화학식 1로 표시되는 비티오펜 유도체에 관한 것이다.One aspect of the present invention for achieving the above object relates to a bithiophene derivative represented by the following formula (1).
[화학식 1][Formula 1]
상기 식에서, R1, R2, R3, R4는 각각 독립적으로 하기 화학식 2로 표시된다.In the above formula, R 1 , R 2 , R 3 , R 4 are each independently represented by the following formula (2).
[화학식 2][Formula 2]
Ar은 각각 독립적으로 
R은 수소; 탄소수가 1-10인 선형, 분지형 또는 환형 알킬기; 탄소수가 1-10인 선형, 분지형 또는 환형 알콕시기; 탄소수가 1-10인 선형, 분지형 또는 환형 히 드록시알킬기; 및 탄소수가 1-10인 선형, 분지형 또는 환형 알콕시알킬기로 이루어진 군에서 선택되고, R is hydrogen; Linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms; Linear, branched or cyclic alkoxy groups having 1 to 10 carbon atoms; Linear, branched or cyclic hydroxyalkyl groups having 1-10 carbon atoms; And a linear, branched or cyclic alkoxyalkyl group having 1-10 carbon atoms,
m은 1 내지 4의 정수이며,m is an integer from 1 to 4,
n은 0 또는 1이다. n is 0 or 1;
상기 과제를 해결하기 위한 본 발명의 다른 측면은 상기 비티오펜 유도체를 유기반도체(organic semiconductor) 또는 정공 수송 물질(hole conducting material)로 포함하여 상온 스핀코팅 공정이 가능하고 안정적일 뿐만 아니라, 전기 전도성이 우수한 소자에 관한 것이다.Another aspect of the present invention for solving the above problems is to include a non-thiophene derivative as an organic semiconductor or a hole conducting material to enable room temperature spin coating process and stable, as well as electrical conductivity It relates to an excellent device.
이하에서, 도면을 참조로 하여 본 발명에 관하여 보다 상세하게 설명한다. Hereinafter, the present invention will be described in more detail with reference to the drawings.
본 발명의 비티오펜 유도체는 하기 화학식 1로 표시된다:The bithiophene derivative of the present invention is represented by the following general formula (1):
[화학식 1][Formula 1]
상기 식에서, R1, R2, R3, R4는 각각 독립적으로 하기 화학식 2로 표시된다.In the above formula, R 1 , R 2 , R 3 , R 4 are each independently represented by the following formula (2).
[화학식 2][Formula 2]
Ar은 각각 독립적으로 
R은 수소; 탄소수가 1-10인 선형, 분지형 또는 환형 알킬기; 탄소수가 1-10인 선형, 분지형 또는 환형 알콕시기; 탄소수가 1-10인 선형, 분지형 또는 환형 히드록시알킬기; 및 탄소수가 1-10인 선형, 분지형 또는 환형 알콕시알킬기로 이루어진 군에서 선택되고, R is hydrogen; Linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms; Linear, branched or cyclic alkoxy groups having 1 to 10 carbon atoms; Linear, branched or cyclic hydroxyalkyl groups having 1 to 10 carbon atoms; And a linear, branched or cyclic alkoxyalkyl group having 1-10 carbon atoms,
m은 1 내지 4의 정수이며,m is an integer from 1 to 4,
n은 0 또는 1이다.n is 0 or 1;
본 발명의 비티오펜 유도체는 도 1에서 보는 바와 같이, 분자중심에 위치하는 비티오펜의 3, 3' 위치에 선형 공액 사슬(linear conjugated chain)과 같은 부피가 큰 기(bulky group)를 포함하고 있어, 이들간의 입체장애로 인하여 두 티오펜환은 서로 90걀 가까운 각도를 형성한다. 따라서, 분자중심에 질소 내지 인을 포함하는 저분자 공액 화합물에 비하여 컨쥬게이션을 더욱 용이하게 하는 3차원 공액 구조를 형성한다. 또한, 이러한 3차원 공액 구조는 비티오펜의 3 위치에만 부피가 큰 기를 포함하거나, 3, 3' 위치에 부피가 작은 기를 포함하고 있는 다른 비티오펜 유도체에 비하여 두 티오펜환이 이루는 각도가 훨씬 크기 때문에 유리한 전기전도성을 나타낸다. 한편, 본 발명의 비티오펜 유도체는 분자량이 크지 않아 실제 소자에 적용하였을 때 산화전위가 균일하고 안전적일 뿐만 아니라, 유기용매에 용해성이 우수하여 상온에서 종래에 알려진 코팅방법으로 코팅할 수 있다. 본 발명에서 사용되는 비티오펜 유도체의 분자량은 490 내지 3600의 범위이다.As shown in FIG. 1, the bithiophene derivative of the present invention includes a bulky group such as a linear conjugated chain at 3 and 3 ′ positions of the bithiophene located at the molecular center. However, due to steric hindrance between them, the two thiophene rings form an angle close to 90 eggs. Thus, a three-dimensional conjugated structure is formed that facilitates conjugation more easily than low molecular conjugated compounds containing nitrogen to phosphorus in the molecular center. In addition, the three-dimensional conjugated structure has a much larger angle between the two thiophene rings than other bithiophene derivatives containing bulky groups only at the 3 position of the bithiophene or small groups at the 3, 3 'positions. It exhibits advantageous electrical conductivity. On the other hand, the bithiophene derivative of the present invention does not have a large molecular weight, and when applied to an actual device, the oxidation potential is not only uniform and safe, but also excellent in solubility in an organic solvent, and can be coated by a conventionally known coating method at room temperature. The molecular weight of the bithiophene derivative used in the present invention is in the range of 490 to 3600.
보다 구체적으로, 상기 화학식 1로 표시되는 비티오펜 유도체로서는 하기 화학식 3 또는 4로 표시되는 유도체를 예로 들 수 있다. More specifically, examples of the bithiophene derivative represented by Chemical Formula 1 include derivatives represented by the following Chemical Formula 3 or 4.
[화학식 3](3)
[화학식 4][Formula 4]
한편, 본 발명의 비티오펜 유도체의 합성법으로는 헤테로 방향족 화합물의 대표적인 중합방법인 화학적 또는 전기 화학적 산화 합성법, 니켈이나 팔라듐과 같은 유기 전이금속 화합물을 이용하는 축합중합법이 모두 사용될 수 있으며, 특별히 제한되는 것은 아니다. 보다 구체적으로, 상기 화학식 3으로 표시되는 비티오펜 유도체는 하기 반응식 1로 표시된 반응경로에 따라 합성될 수 있다.On the other hand, as a synthesis method of the bithiophene derivative of the present invention, a chemical or electrochemical oxidative synthesis method, a condensation polymerization method using an organic transition metal compound such as nickel or palladium, which are typical polymerization methods of heteroaromatic compounds, may all be used. It is not. More specifically, the bithiophene derivative represented by Chemical Formula 3 may be synthesized according to the reaction route represented by Scheme 1 below.
[반응식 1]Scheme 1
상기 반응식 1에서 스테닐 유도체와 브로모 화합물의 반응은 용매로서 무수 톨루엔, 디메틸포름알데히드 등을 사용하고, Pd(PPh3)4와 같은 촉매를 부가하여 질소 분위기 하의 환류조건에서 -80 내지 40℃의 온도로 8시간 내지 24시간 이루어지는 것이 바람직하다. The reaction of the stenyl derivative and the bromo compound in Scheme 1 uses anhydrous toluene, dimethylformaldehyde and the like as a solvent, and adds a catalyst such as Pd (PPh 3 ) 4 to -80 to 40 ° C under reflux under a nitrogen atmosphere. It is preferable that the temperature is 8 to 24 hours.
상기와 같은 반응식에 따라 합성되는 본 발명의 비티오펜 유도체는 치환기를 조절함으로써 용액 공정이 보다 용이하게 되도록 할 수 있다. 따라서, 본 발명의 비티오펜 유도체는 종래에 알려진 코팅방법 중 어느 것에 의해서도 상온에서 코팅할 수 있으며, 구체적으로 스크린 인쇄법, 프린팅법, 스핀코팅법, 스핀캐스팅법, 딥핑법(dipping) 또는 잉크분사법을 통해 필요한 두께의 박막으로 형성될 수 있다. The bithiophene derivative of the present invention synthesized according to the reaction scheme as described above may be made to facilitate the solution process by adjusting the substituents. Accordingly, the bithiophene derivative of the present invention can be coated at room temperature by any of the conventionally known coating methods, and specifically, screen printing, printing, spin coating, spin casting, dipping or ink powder. It can be formed into a thin film of the required thickness through the law.
한편, 본 발명의 다른 측면은 상기 비티오펜 유도체를 유기 반도체(organic semiconductor) 또는 정공 수송 물질(hole conducting material)로 이용한 소자에 관한 것이다. Meanwhile, another aspect of the present invention relates to a device using the bithiophene derivative as an organic semiconductor or a hole conducting material.
구체적으로 상기 소자로는 OTFT(Organic Thin Film Transistor), OFET(Organic Field Effect Transistor), 유기 태양 광 전지(Organic Solar Photovoltaic Cell) 또는 유기전계 발광소자(Organic Light Emitting Device)를 예로 들 수 있다. In detail, the device may be an organic thin film transistor (OTFT), an organic field effect transistor (OFET), an organic solar photovoltaic cell, or an organic light emitting device.
또한, 본 발명의 비티오펜 유도체는 당업계에 알려진 통상적인 공정에 의해 OTFT 및 OFET의 유기반도체층, 유기 태양 광 전지의 정공수송층 또는 OLED의 정공수송층에 적용될 수 있다. In addition, the bithiophene derivative of the present invention can be applied to the organic semiconductor layer of OTFT and OFET, the hole transport layer of organic photovoltaic cell or the hole transport layer of OLED by conventional processes known in the art.
이하에서, 실시예를 통하여 본 발명을 보다 상세하게 설명하고자 하나, 하기의 실시예는 설명의 목적을 위한 것으로 본 발명을 제한하고자 하는 것은 아니다. Hereinafter, the present invention will be described in more detail with reference to Examples, but the following Examples are for the purpose of explanation and are not intended to limit the present invention.
제조예Manufacturing example 1: One: 비티오펜Vithiophene 유도체(화학식 3)의 합성 Synthesis of Derivative (Formula 3)
상기 화학식 3으로 표시되는 비티오펜 유도체를 다음과 같은 경로에 의해 합성하였다.A bithiophene derivative represented by Chemical Formula 3 was synthesized by the following route.
(1) 3,3'-디티에닐-2,2'-비티오펜(3,3'-dithienyl-2,2'-bithiophene)의 합성(1) Synthesis of 3,3'-dithienyl-2,2'-bithiophene (3,3'-dithienyl-2,2'-bithiophene)
[반응식 2]
먼저, 2g의 3,3'-디브로모-2,2'-비티오펜과 5.06g(2.2eq)의 2-(트리부틸스테 닐)티오펜(2-(tributylstannyl)thiophene))을 712mg(5%mol)의 Pd(PPh3 )4 를 부가한 40ml의 톨루엔에 용해시켜 커플링 반응을 시켰다. 잔류물을 칼럼 크로마토그래피(실리카겔, 2:1 PE/DCM)로 정제하여 1.65g(81%)의 녹색 고체인 3,3'-디티에닐-2,2'-비티오펜(3,3'-dithienyl-2,2'-bithiophene)(M.p.171℃)을 얻었다.First, 712 mg (2 g of 3,3'-dibromo-2,2'-bithiophene and 5.06 g (2.2 eq) of 2- (tributylstannyl) thiophene) 5% mol) of Pd (PPh 3 ) 4 was dissolved in 40 ml of toluene to which the coupling reaction was carried out. The residue was purified by column chromatography (silica gel, 2: 1 PE / DCM) to give 1.65 g (81%) of 3,3'-dithienyl-2,2'-bithiophene (3,3 ') as a green solid. -dithienyl-2,2'-bithiophene) (Mp171 ° C) was obtained.
1H NMR (CDCl3 ): 6.9 (dd, 1H) 7.0 (dd, 1H) 7.1 (dd, 1H) 7.4 (d, 1H) 7.5(d, 1H) 1 H NMR (CDCl 3 ) : 6.9 (dd, 1H) 7.0 (dd, 1H) 7.1 (dd, 1H) 7.4 (d, 1H) 7.5 (d, 1H)
(2) 테트라브로모-3,3'-디티에닐-2,2'-비티오펜의 합성(2) Synthesis of tetrabromo-3,3'-dithienyl-2,2'-bithiophene
[반응식 3]
이렇게 수득한 3,3'-디티에닐-2,2'-비티오펜(200mg)을 30ml의 클로로포름에 용해시키고, 10ml의 클로로포름에 0.13ml(4.2eq)의 브롬을 용해시킨 용액을 방울방울 부가하였다. 15분간 교반한 뒤 20ml의 NaHSO3 포화용액을 부가하였다. DCM으로 추출한 뒤, 유기상을 NaHCO3 및 NaCl 포화 수용액으로 세척한 후 MgSO4로 건조하였다. 용매를 증발시키고 잔류물을 5ml의 에탄올과 4ml의 클로로포름의 혼합물로 재결정하여 207mg(54%)의 흰색 고체인 테트라브로모-3,3'-디티에닐-2,2'-비티오펜 (M.p.158℃)을 얻었다.The 3,3'-dithienyl-2,2'-bithiophene (200 mg) thus obtained was dissolved in 30 ml of chloroform, and a solution of 0.13 ml (4.2eq) of bromine in 10 ml of chloroform was added dropwise. It was. After stirring for 15 minutes, 20 ml of NaHSO 3 Saturated solution was added. After extraction with DCM, the organic phase is extracted with NaHCO 3 And washed with saturated aqueous NaCl solution and dried over MgSO 4 . The solvent was evaporated and the residue was recrystallized from a mixture of 5 ml of ethanol and 4 ml of chloroform to give 207 mg (54%) of white solid, tetrabromo-3,3'-dithienyl-2,2'-bithiophene (Mp158 C) was obtained.
1H NMR (CDCl3): 6.8 (d, 1H) 6.9 (d, 1H) 7.28 (s, 1H) 1 H NMR (CDCl 3 ): 6.8 (d, 1H) 6.9 (d, 1H) 7.28 (s, 1H)
(3) 화학식 3의 비티오펜 유도체의 합성(3) Synthesis of Bithiophene Derivatives of Formula (3)
[반응식 4]Scheme 4
이렇게 수득한 테트라브로모-3,3'-디티에닐-2,2'-비티오펜(400mg)을 1.68g의 스테닐 유도체 TTSBn(5'-butylsulfanyl-2,2'-bithiophene-5-tributyltin) 및 144mg(5%mol)의 Pd(PPh3)4 와 함께 30ml의 톨루엔에 용해시키고 커플링 반응을 시켰다. 냉각 후 수득한 침전물을 여과시켜 DCM에 녹이고 NH4Cl 및 NaCl의 수용액으로 세척하고 MgSO4로 건조하였다. 용매를 증발시키고 잔류물을 크로마토그래피(실리카겔, 2:1 PE/DCM)로 정제하여 250mg(30%)의 오렌지색 고체인 비티오펜 유도체(M.p.189℃)를 얻었다.Tetrabromo-3,3'-dithienyl-2,2'-bithiophene (400 mg) thus obtained was obtained with 1.68 g of the stenyl derivative TTSBn (5'-butylsulfanyl-2,2'-bithiophene-5-tributyltin). ) And 144 mg (5% mol) of Pd (PPh 3 ) 4 were dissolved in 30 ml of toluene and subjected to a coupling reaction. The precipitate obtained after cooling was filtered, dissolved in DCM, washed with an aqueous solution of NH 4 Cl and NaCl and dried over MgSO 4 . The solvent was evaporated and the residue was purified by chromatography (silica gel, 2: 1 PE / DCM) to give 250 mg (30%) of an orange solid, bithiophene derivative (Mp189 ° C.).
1H NMR (CDCl3): 6.95-6.98 (m, 6H) 7.02 (d, 1H) 7.06 (d, 1H) 7.08 (d, 1H) 7.15 (d, 1H) 7.39 (s, 1H) 1 H NMR (CDCl 3 ): 6.95-6.98 (m, 6H) 7.02 (d, 1H) 7.06 (d, 1H) 7.08 (d, 1H) 7.15 (d, 1H) 7.39 (s, 1H)
제조예Manufacturing example 2: 2: 비티오펜Vithiophene 유도체(화학식 4)의 합성 Synthesis of Derivatives
상기 화학식 4로 표시되는 비티오펜 유도체는 다음과 같이 합성하였다.The bithiophene derivative represented by Chemical Formula 4 was synthesized as follows.
[반응식 5]
상기 제조예 1에서 얻어진 테트라브로모-3,3'-디티에닐-2,2'-비티오펜(100mg)을 0.53g의 스테닐 유도체 TETHex(Thiopheneethylendioxythiophenethiophene) 및 36mg(5%mol)의 Pd(PPh3)4와 함께 10ml의 톨루엔에 용해시키고 커플링 반응을 시킨 것을 제외하고는 제조예 1과 동일하게 실시하여 60mg의 붉은색 고체인 비티오펜 유도체를 얻었다.Tetrabromo-3,3'-dithienyl-2,2'-bithiophene (100 mg) obtained in Preparation Example 1 was 0.53 g of a stenyl derivative TETHex (Thiopheneethylendioxythiophenethiophene) and 36 mg (5% mol) of Pd ( 60 mg of a red solid bithiophene derivative was obtained in the same manner as in Preparation Example 1 except that the mixture was dissolved in 10 ml of toluene together with PPh 3 ) 4 and subjected to a coupling reaction.
1H NMR (CDCl3): 0.88 (t, 6H) 1.28-1.35 (m, 12H) 1.63-1.71 (m, 4H) 2.80 (t, 4H) 4.35-4.43 (m, 8H, EDOT) 6.67 (d, 1H) 6.7 (d, 1H) 6.96-6.97 (m, 3H) 7.0-7.02 (m, 23H) 7.05 (d, 1H) 7.11 (d, 1H) 7.15 (d, 1H) 7.39 (s, 1H) 1 H NMR (CDCl 3 ): 0.88 (t, 6H) 1.28-1.35 (m, 12H) 1.63-1.71 (m, 4H) 2.80 (t, 4H) 4.35-4.43 (m, 8H, EDOT) 6.67 (d, 1H) 6.7 (d, 1H) 6.96-6.97 (m, 3H) 7.0-7.02 (m, 2 3 H) 7.05 (d, 1H) 7.11 (d, 1H) 7.15 (d, 1H) 7.39 (s, 1H)
상기 제조예 1-2에 따라 합성된 비티오펜 유도체의 UV 흡광도를 측정하였고, 그 결과 화학식 3의 비티오펜 유도체의 최대흡수파장은 399nm이고, 화학식 4의 비 티오펜 유도체의 최대흡수파장은 441nm이었으며, 모두 넓은 파장 범위에서 UV를 흡수하는 것을 알 수 있었다.UV absorbance of the bithiophene derivatives synthesized according to Preparation Example 1-2 was measured. As a result, the maximum absorption wavelength of the bithiophene derivative of
실시예Example 1: One: 광전Photoelectric 효율의 측정 Measurement of efficiency
유리 기판 위에 ITO 전극를 형성하고, 그 위에 80nm 두께의 전도성 고분자(Bayer社, Baytron P)층을 형성하였다. 이어서, 제조예 1에서 합성한 비티오펜 유도체와 PCBM([6,6]-phenyl-C61 -butyric acid methylester)을 1:3(w/w)로 혼합하여 스핀캐스팅에 의해 100nm 두께의 유기 반도체층을 형성하였다. 이어서, 상기 유기 반도체층 위에 알루미늄을 사용하여 60nm 두께의 반대전극을 형성함으로써 광전 효율 측정을 위한 태양전지 소자를 제작하였다. An ITO electrode was formed on the glass substrate, and an 80 nm thick conductive polymer (Bayer, Baytron P) layer was formed thereon. Then Production Example 1 A bithiophene derivative PCBM synthesized in-a ([6,6] -phenyl-C 61 butyric acid methylester) 1: 3 (w / w) and mixed with the organic semiconductor in the 100nm thickness by the spin cast to A layer was formed. Subsequently, a solar cell device for measuring photoelectric efficiency was manufactured by forming a counter electrode having a thickness of 60 nm on the organic semiconductor layer by using aluminum.
비교예Comparative example 1-2: 1-2: 광전Photoelectric 효율의 측정 Measurement of efficiency
유기 반도체층 형성시, 비티오펜 유도체로서 3, 3' 위치에 부피가 작은 기를 포함하는 하기 화학식 5의 비티오펜 유도체와 3 위치에만 부피가 큰 기를 포함하는 하기 화학식 6의 비티오펜 유도체를 사용한 것을 제외하고는, 실시예 1과 동일한 방법에 따라 실시하여 광전 효율 측정을 위한 태양전지 소자를 제작하였다.When forming the organic semiconductor layer, except for using a bithiophene derivative of the formula (5) including a small group in the 3, 3 'position and a bithiophene derivative of the formula (6) comprising a bulky group only in the 3 position when forming the organic semiconductor layer Then, according to the same method as in Example 1 to produce a solar cell device for measuring the photoelectric efficiency.
[화학식 5][Chemical Formula 5]
[화학식 6][Formula 6]
ㅍ상기 실시예 1-2 및 비교예 1-2에 따라 제조된 광전소자의 광전 효율을 측정하기 위하여 광전압 및 광전류를 측정하였다.In order to measure the photoelectric efficiency of the photoelectric device manufactured according to Example 1-2 and Comparative Example 1-2, the photovoltage and photocurrent were measured.
광원으로는 제논 램프(Xenon lamp, Oriel, 01193)을 사용하였으며, 상기 제논 램프의 태양 조건(AM 1.5)은 표준 태양전지 (Frunhofer Institute Solar Engeriessysteme, Certificate No. C-ISE369, Type of material: Mono-Si + KG 필터)를 사용하여 보정하였다. 측정된 광전류전압 곡선은 도 2-4에 나타내었다. 상기 광전류전압 곡선으로부터 계산된 전류밀도(Isc), 전압(Voc), 및 충진 계수(fill factor, FF)를 하기 광전효율 계산식을 통해 계산한 광전 효율(ηe)을 하기 표 1에 나타내었다.Xenon lamp (Oriel, 01193) was used as the light source, and the solar condition (AM 1.5) of the xenon lamp was a standard solar cell (Frunhofer Institute Solar Engeriessysteme, Certificate No. C-ISE369, Type of material: Mono-). Si + KG filter). The measured photocurrent voltage curves are shown in FIGS. 2-4. The photoelectric efficiency ηe calculated by the photoelectric efficiency calculation formula for the current density I sc , the voltage V oc , and the fill factor FF calculated from the photocurrent voltage curve are shown in Table 1 below. .
ηe = (Voc Isc FF)/(Pinc)ηe = (V oc I sc FF) / (P inc )
상기 식중, P inc는 100mw/cm2 (1sun)을 나타낸다.In the above formula, P inc is 100mw / cm 2 (1sun).
[표 1][Table 1]
상기 표 1의 결과로부터 알 수 있는 바와 같이, 본 발명에 따른 비티오펜 유도체를 유기 반도체층으로 형성한 광전소자는, 컨쥬게이션을 더욱 용이하게 하는 3차원 공액 구조를 형성함으로써 광전효율이 향상된 것을 알 수 있다.As can be seen from the results of Table 1, the photoelectric device in which the bithiophene derivative according to the present invention is formed of an organic semiconductor layer has been found to have improved photoelectric efficiency by forming a three-dimensional conjugated structure to facilitate conjugation. Can be.
이와 같이 본 발명의 비티오펜 유도체는 새로운 구조의 3차원 저분자 유기 반도체로서 상온 스핀 코팅 공정이 가능하고 안정적일 뿐만 아니라, 전기 전도성이 우수하여 OTFT(Organic Thin Film Transistor), OFET(Organic Field Effect Transistor), 유기 태양 광 전지(Organic Solar Photovoltaic Cell) 및 OLED(Organic Light Emitting Device)에 활용할 수 있다.As described above, the bithiophene derivative of the present invention is a novel three-dimensional low molecular organic semiconductor, which is capable of spin coating at room temperature and is stable, and has excellent electrical conductivity, so that it is organic thin film transistor (OTFT) and organic field effect transistor (OFET). , Organic solar photovoltaic cells and organic light emitting devices (OLEDs).
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