TW201305123A - 可用於有機薄膜太陽能電池之化合物及有機薄膜太陽能電池 - Google Patents
可用於有機薄膜太陽能電池之化合物及有機薄膜太陽能電池 Download PDFInfo
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- TW201305123A TW201305123A TW100126035A TW100126035A TW201305123A TW 201305123 A TW201305123 A TW 201305123A TW 100126035 A TW100126035 A TW 100126035A TW 100126035 A TW100126035 A TW 100126035A TW 201305123 A TW201305123 A TW 201305123A
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- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 9
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- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 8
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- 125000005594 diketone group Chemical group 0.000 description 1
- WINNISSSXBRWMA-UHFFFAOYSA-N dinitromethane Chemical compound [O-][N+](=O)C[N+]([O-])=O WINNISSSXBRWMA-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
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- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
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- YTVNOVQHSGMMOV-UHFFFAOYSA-N naphthalenetetracarboxylic dianhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=C2C(=O)OC(=O)C1=C32 YTVNOVQHSGMMOV-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
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- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/652—Cyanine dyes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
- C07D285/01—Five-membered rings
- C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
- C07D285/14—Thiadiazoles; Hydrogenated thiadiazoles condensed with carbocyclic rings or ring systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
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Abstract
所提供者為一種具有給電子部分、第一電子接受部分及第二電子接受部分之化合物,如式(I)所示:□藉由上述之獨特分子設計,式(I)化合物可提供令人滿意的能量轉換效率。此外,本發明亦提供一種包含上述化合物之有機薄膜太陽能電池。
Description
本發明係關於一種可用於太陽能電池之化合物,特別係關於一種可用於有機薄膜太陽能電池之化合物,其分子中具有給電子部分、第一電子接受部分及第二電子接受部分。
近年來,由於石化資源的過度使用,人類的生存環境開始日益惡化,而為了解決能源問題,有越來越多人相繼投入太陽能發電之研究。
於現有的各種太陽能電池相關技術中,矽晶型及半導體型太陽能電池雖然具有較高的光電轉換效率,但由於其製造成本高,因此在應用上並不易普及於各種領域。
相較之下,由於有機材料製作之太陽能電池具有成本低廉之優點,同時還有製程簡便、易於大面積化以及輕薄可撓曲之特性,故此類產品成為近年來研究人員開發之重點。
目前常見的有機太陽能電池包括染料敏化太陽能電池、高分子有機太陽能電池、小分子有機太陽能電池以及有機/無機複合型有機太陽能電池幾種類型。
針對小分子有機太陽能電池,若將其電子供體材料進行歸納,可發現主要區分為兩大類。第一大類採用的是電子接受部分-給電子部分-電子接受部分之架構(A-D-A),其中常見的給電子部分為例如數量不一的寡聚噻吩,而電子接受部分則為例如二氰伸乙烯基。第二大類採用的則是給電子部分-電子接受部分架構(D-A),其中可使用的給電子部分為例如芳基胺,而電子接受部分則可為例如二氰伸乙烯基。
由於現有的前述兩種架構在實際應用於太陽能電池時,其光電轉換效率仍有很大的改善空間,因此有需要提出一種新穎之分子設計概念,以作為日後發展高效率太陽能電池的基礎。
有感於習知技術之缺憾,發明人遂竭其心智悉心研究,憑其從事該項產業多年所累積之經驗,進而研發出一種可用於小分子有機太陽能電池或固態有機薄膜太陽能電池之新穎化合物,如式(I)所示:
其中:R1至R6係各自獨立選自H、C1-C6之烷基、C1-C6之醚基以及經C1-C6烷基取代之胺基;Ar1係選自、及,其中R9及R10係各自獨立選自H、F、C1-C6之烷基以及C1-C6之醚基;Ar2係選自、及,其中X為O、S或Se,R11及R12係各自獨立選自H、C1-C6之烷基、氰基及苯基;以及R7及R8係各自獨立選自氰基、硝基以及羧酸之C1-C8酯基。
此外,本發明亦揭露一種具有絕佳能量轉換效率的有機薄膜太陽能電池,其包括依序堆疊之第一電極、電洞傳輸層、活性層、電子傳輸層以及第二電極,其中該活性層包括前述式(I)所示之化合物。
為充分說明本發明之目的、特徵及功效,使本發明所屬技術領域中具有通常知識者能瞭解本發明之內容並可據以實施,茲藉由下述具體之實施例,對本發明做一詳細說明如後。
本發明一部分係供一種可用於太陽能電池活性層之化合物,如式(I)所示:
其中R1至R6和R7、R8係各自代表相同或不同之取代基,如文後所述,而Ar1及Ar2則為文後所述之芳香環。藉此,本發明提供一種具有低能隙之有機染料,其可用於小分子有機太陽能電池或固態有機薄膜太陽能電池。
於式(I)所示之化合物中,兩個苯環係可分別由R1至R6在鄰位、間位及/或對位上進行取代或不取代,且其中R1至R6係各自獨立選自H(即不取代)、C1-C6之烷基、C1-C6之醚基以及經C1-C6烷基取代之胺基;於一實施例中,R1至R6係各自獨立選自H、C1-C3之烷基、C1-C3之醚基以及經C1-C3烷基取代之胺基;R1至R6較佳係各自獨立選自H及C1-C6之烷基,例如甲基、乙基、丙基、異丙基、丁基、第三丁基、異丁基、戊基、己基等等。
Ar1可為經取代或未經取代之噻吩、呋喃、苯或噻唑,當其為經取代者時,取代基可為F、C1-C6之烷基或C1-C6之醚基,較佳為F、C1-C3之烷基或C1-C3之醚基。於一實施例中,Ar1為未經取代或經氟取代之噻吩、呋喃、苯或噻唑。
藉此,式(I)所示化合物之結構中的部分結構,即
將可作為強力的給電子部分(electron-donating moiety)。
於式(I)所示之化合物中,Ar2係可選自:
其中X可為O、S或Se,R11及R12係各自獨立選自H、C1-C6之烷基、氰基及苯基。於一實施例中,Ar2係為2,1,3-苯并噻二唑或嘧啶。藉此,Ar2係可作為式(I)所示化合物之結構中的第一電子接受部分(electron-accepting moiety)。
於式(I)所示之化合物中,R7及R8係各自獨立選自氰基、硝基以及羧酸之C1-C8酯基,以於化合物結構中提供例如二氰基伸乙烯、二硝基伸乙烯或二酯基伸乙烯,作為分子之第二電子接受部分。
據此,式(I)所示之化合物之給電子部分、第一電子接受部分及第二電子接受部分即可構成供體-受體-受體(donor-acceptor-acceptor)之架構,而可作為一種新穎之有機光伏材料,其可利用太陽光譜之遠紅光及/或紅外光區域之輻射能量,並提供令人滿意的能量轉換效率。
本發明另一部分係供一種有機薄膜太陽能電池,其包括依序堆疊之第一電極、電洞傳輸層、活性層、電子傳輸層以及第二電極,且其中該活性層包括上述式(I)所示之化合物。
第一電極可為各種透明導電氧化物,例如銦錫氧化物、銦鋅氧化物等,且第一電極係形成於透明基材如玻璃上。此外,銀、鋁、PEDOT:PSS等材料亦可作為第一電極,且並不以此為限。
電洞傳輸層係介於第一電極與活性層之間,且包括電洞傳輸材料,其可為但不限於例如HAT(CN)6、MoO3、PEDOT:PSS、PEDOT:PSS/HAT(CN)6或PEDOT:PSS/MoO3。
活性層係介於電洞傳輸層與電子傳輸層之間,且包括有機光伏材料,例如作為電子供體之前述式(I)化合物與一種電子受體之混合物,而可使用的電子受體可為但不限於例如富勒烯,如C60、C70或C60、C70之衍生物等等,或其他小分子電子受體如PTCBI、PTCDA等等。
本領域具有通常知識者可了解的是,於本文中,「活性層」係可為各種不同形式,且並不限於單層結構。舉例而言,活性層可以是平面混合式異質接面(planar-mixed heterojunction,PMHJ),其包含一電子供體層、一電子受體層以及一介於其間的電子供體及電子受體之混合物層。
電子傳輸層係介於活性層與第二電極之間,且包括電子傳輸材料,其可為但不限於例如2,9-二甲基-4,7-二苯基-1,10-啡啉(2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline,BCP)、Bphen、TPBi、TyPMPB、PTCBI、NTCDA、C60、C70、PTCDA、ZnO、TiO2等等。
第二電極係形成於電子傳輸層上而作為陰極,常見的第二電極可為例如銀,然其他材料諸如Ca、Cs、CsF、Li、LiF、Mg、Al等亦可用於本發明之第二電極。
本發明之有機薄膜太陽能電池除可作為一種獨立的光電轉換裝置外,也可製作成疊層式結構(tandem structure),且結構中不同的次單元可使用相同或不同的活性層材料。
為進一步說明本發明所涉及之化合物及太陽能電池,以使本領域具有通常知識者能製造及使用本發明,以下乃列舉本申請案之發明人已完成的各種實例,並詳細說明化合物之合成方式,其中大部分化學試劑均購自商業來源,且於使用前未進行純化。溶劑於使用前係以蒸餾法進行純化,且所有的化學反應均於氬氣或氮氣環境下進行。
化合物合成流程I
其中各步驟之反應條件為:(i)N-溴代丁二醯亞胺(NBS)、偶氮二異丁腈(AIBN)、氯苯、80℃;(ii)AgNO3、H2O/MeCN、回流;(iii)丙二腈、Al2O3、甲苯、70℃;(iv)[PdCl2(PPh3)2]、甲苯、110℃。
將溶於氯苯(400 mL)之4-溴-7-甲基-2,1,3-苯并噻二唑(45.82 g,200 mmol)、AIBN(6.57 g,40 mmol)及NBS(106.2 g,600 mmol)之混合物於80℃下攪拌加熱4小時。於冷卻至室溫後,過濾反應混合物以移除固態的丁二醯亞胺,並以水和鹽水沖洗濾液,而後以無水MgSO4乾燥濾液,然後再過濾之。以旋轉蒸發法去除濾液中的溶劑,並以矽膠管柱層析法純化粗產物,而以CH2Cl2/己烷(v/v,1:3)進行沖提以獲得白色固體之化合物A(56.1 g,產率83%)。
化合物A之分析數據如下:M.p. 119-120℃;IR(KBr)ν3001,2922,1524,1481,1315,1274,1185,1097,937,880 cm-1;1H NMR(CDCl3,400 MHz)δ7.97-7.90(m,2H),7.40(s,1H);13C NMR(CDCl3,100 MHz)δ152.8,149.6,133.4,131.8,129.4,115.8,33.9;HRMS(m/z,FAB+) Calcd for C7H3 79Br3N2S 383.7567,found 383.7542,Calcd for C7H3 79Br2 81Br1N2S 385.7547,found 385.7553,Calcd for C7H3 79Br1 81Br2N2S 387.7526,found 387.7524,Calcd for C7H3 81Br3N2S 389.7506,found 389.7536。
將硝酸銀水溶液(285 mg,1.68 mmol,水1.7 mL)加入溶於乙腈(8 mL)且持續攪拌之化合物A(260 mg,0.67 mmol)溶液,之後加熱至回流2小時。於冷卻至室溫後,過濾反應混合物以移除AgBr沉澱,並將濾液以CH2Cl2萃取。以鹽水沖洗萃取物,之後以無水MgSO4進行乾燥再進行過濾。以旋轉蒸發法去除萃取物中的溶劑,以獲得白色固體之化合物B(147 mg,產率92%)。
化合物B之分析數據如下:M.p. 185-186℃;IR(KBr)ν3078,3021,2835,2728,1702,1526,1268,1102,937,879 cm-1;1H NMR(CDCl3,400 MHz)δ10.71(s,1H),8.09-8.03(m,2H);13C NMR(CDCl3,100 MHz)δ188.0,153.8,152.1,131.9,131.5,126.7,121.7;HRMS(m/z,FAB+) Calcd for C7H3 79BrN2OS 241.9149,found 241.9149,Calcd for C7H3 81BrN2OS 243.9129,found 243.9137。
將溶於無水甲苯(7 mL)中的化合物B(150 mg,0.62 mmol)、丙二腈(82 mg,1.24 mmol)及鹼式氧化鋁(310 mg)之混合物於70℃下攪拌加熱2小時。於反應混合物冷卻至室溫後,濾除殘餘的鹼式氧化鋁,並以甲苯進行徹底沖洗。以旋轉蒸發法去除濾液中的溶劑,並以矽膠管柱層析法純化粗產物,而以CH2Cl2/己烷(v/v,1:1)沖提以獲得黃色固體之化合物C(120 mg,產率67%)。
化合物C之分析數據如下:M.p. 179-180℃;IR(KBr) ν3097,3032,2229,1573,1517,1380,1126,1044,933,884 cm-1;1H NMR(CDCl3,400 MHz)δ8.73(s,1H),8.53(d,J=7.6 Hz,1H),8.05(d,J=7.6 Hz,1H);13C NMR(CDCl3,100 MHz)δ153.0,152.5,152.2,132.0,130.0,123.0,121.8,113.1,112.3,85.2;HRMS(m/z,FAB+) Calcd for C10H3 79BrN4S 289.9262,found 289.9263,Calcd for C10H3 81BrN4S 291.9241,found 291.9237。
將溶於無水甲苯(25 mL)中的化合物C(1.46 g,5 mmol)、5-(N,N-二甲苯基胺基)-2-(三正丁基錫烷基)噻吩(3.55 g,6.25 mmol)及PdCl2(PPh3)2(175 mg,0.25 mmol)之混合物於氬氣、110℃下攪拌加熱2小時。於反應混合物冷卻至室溫後,以旋轉蒸發法去除溶劑,並以矽膠管柱層析法純化粗產物,而以CH2Cl2/己烷(v/v,1:1)沖提以獲得黑色固體之化合物D(1.34 g,產率55%)。
化合物D之分析數據如下:M.p. 234℃(DSC);IR(KBr)ν 3033,2917,2217,1566,1454,1329,1265,1153,1062,921,827 cm-1;1H NMR(CDCl3,400 MHz)δ8.66(s,1H),8.60(d,J=8.0 Hz,1H),8.22(d,J=4.4 Hz,1H),7.57(d,J=8.0 Hz,1H),7.22-7.17(m,8H),6.50(d,J=4.4 Hz,1H),2.39(s,6H);13C NMR(CDCl3,100 MHz)δ161.0,154.6,151.5,150.6,143.8,135.5,134.0,133.2,130.8,130.2,126.0,124.9,120.9,118.9,114.6,114.3,113.8,78.5,21.1;HRMS(m/z,FAB+) Calcd for C28H19N5S2 489.1082,found 489.1083。
化合物E(2-{[7-(5-
N
,
N
-二甲苯基胺基噻吩-2-基)-2,1,3-苯并噻二唑-4-基]亞甲基}丙二腈)、F(2-{[7-(4-
N
,
N
-二苯基胺基苯基)-2,1,3-苯并噻二唑-4-基]亞甲基}丙二腈)、G(2-{[7-(4-
N
,
N
-
二甲苯基胺基苯基)-2,1,3-苯并噻二唑-4-基]亞甲基}丙二腈)之合成
將溶於無水甲苯(25 mL)中的化合物C(1.46 g,5 mmol)、5-(N,N-二苯基胺基)-2-(三正丁基錫烷基)噻吩(3.38 g,6.25 mmol)及PdCl2(PPh3)2(175 mg,0.25 mmol)之混合物於氬氣、110℃下攪拌加熱2小時。於反應混合物冷卻至室溫後,以旋轉蒸發法去除溶劑,並以矽膠管柱層析法純化粗產物,而以CH2Cl2/己烷(v/v,1:1)沖提以獲得黑色固體之化合物E(1.50 g,產率65%)。
以N,N-二苯基-4-(三正丁基錫烷基)苯胺(3.34 g,6.25 mmol)代替上述的5-(N,N-二苯基胺基)-2-(三正丁基錫烷基)噻吩進行反應,將攪拌加熱時間調整為6小時,即可以類似方式可獲得黑色固體之化合物F(1.12 g,產率49%)。
以N,N-二甲苯基-4-(三正丁基錫烷基)苯胺(3.52 g,6.25 mmol)取代上述的N,N-二苯基-4-(三正丁基錫烷基)苯胺進行反應,將攪拌加熱時間調整為5小時,並將沖提液改為CH2Cl2/己烷(v/v,4:3),即可以類似方式可獲得黑色固體之化合物G(1.64 g,產率68%)。
化合物H(2-{[7-(2-氟-4-
N
,
N
-二甲苯基胺基苯基)-2,1,3-苯并噻二唑-4-基]亞甲基}丙二腈)、I(2-{[7-(3-氟-4-
N
,
N
-二甲苯
基胺基苯基)-2,1,3-苯并噻二唑-4-基]亞甲基}丙二腈)之合成
將溶於無水甲苯(40 mL)中的化合物C(2.43 g,8.33 mmol)、N,N-二甲苯基-4-(三正丁基錫烷基)-3-氟苯胺(5.80 g,10.0 mmol)及PdCl2(PPh3)2(295 mg,0.42 mmol)之混合物於氬氣、110℃下攪拌加熱4小時。於反應混合物冷卻至室溫後,以旋轉蒸發法去除溶劑,並以矽膠管柱層析法純化粗產物,以CH2Cl2/己烷(v/v,1:1)沖提以獲得黑色固體之化合物H(2.59 g,產率62%)。
以N,N-二甲苯基-4-(三正丁基錫烷基)-2-氟苯胺(5.80 g,10.0 mmol)替代上述的N,N-二甲苯基-4-(三正丁基錫烷基)-3-氟苯胺,並將沖提液改為CH2Cl2/己烷(v/v,4:3),即可以類似方式可獲得黑色固體之化合物I(2.58 g,產率62%)。
化合物合成流程II
其中各步驟之反應條件為:(i)正丁基鋰、THF、-78℃,接著為ZnCl2、-35℃,接著為5-溴-2-碘嘧啶、[Pd(PPh3)4]、回流;(ii)正丁基鋰、THF、-100℃,接著為甲酸乙酯、-100℃;(iii)丙二腈、Al2O3、甲苯、70℃。
於-78℃、氬氣環境下,逐滴將正丁基鋰(1.6 M,19.69 mL,31.5 mmol)加入溶於無水THF(90 mL)且持續攪拌之2-[N,N-二(對甲苯基)胺]噻吩(8.31 g,30 mmol)溶液。將反應混合物升溫至-35℃並攪拌15分鐘。將ZnCl2(1 M溶液33 mL溶於無水THF,33 mmol)加入反應混合物中,之後升溫至室溫並攪拌30分鐘,接著將5-溴-2-碘嘧啶(8.55 g,30 mmol)、Pd(PPh3)4(1.73 g,1.5 mmol)及無水THF(120 mL)加入其中。然後將反應混合物於氬氣下加熱至回流2小時。於冷卻至室溫後,將反應混合物倒入水中,並以乙酸乙酯萃取。以鹽水沖洗萃取物,之後以無水MgSO4進行乾燥再進行過濾。以旋轉蒸發法去除溶劑,並以矽膠管柱層析法純化粗產物,而以CH2Cl2/己烷(v/v,1:2)沖提以獲得黃色固體之化合物J(10.84 g,產率83%)。
化合物J之分析數據如下:M.p. 173-174℃;IR(KBr)ν 3028,2916,1605,1551,1374,1119,1056,928 cm-1;1H NMR(CDCl3,400 MHz)δ8.55(s,2H),7.71(d,J=4.4 Hz,1H),7.16-7.10(m,8H),6.43(d,J=4.4 Hz,1H),2,34(s,6H);13C NMR(CDCl3,100 MHz)δ159.5,158.9,157.2,144.4,134.3,130.0,129.8,128.9,124.4,114.7,114.5,21.0;HRMS(m/z,FAB+) Calcd. for C22H18 79BrN3S 435.0405,found 435.0411. Calcd. for C22H18 81BrN3S 437.0384, found 437.0391。
於-100℃、氬氣環境下,逐滴將正丁基鋰(1.6 M,13.13 mL,21 mmol)加入溶於無水THF(350 mL)且持續攪拌之化合物J(8.73 g,20 mmol)溶液中。接著將溶液攪拌30分鐘,然後在5分鐘內逐滴加入無水之甲酸乙酯(16.15 mL,200 mmol)。攪拌30分鐘後,將反應以1.5 M的HCl之THF溶液(15 mL,22.5 mmol)淬火,之後移除冷浴,並將反應混合物攪拌2小時。以旋轉蒸發法去除THF,並以氯仿萃取反應混合物,接著以鹽水沖洗萃取物,以無水MgSO4進行乾燥再進行過濾。以旋轉蒸發法去除溶劑,並以矽膠管柱層析法純化粗產物,而以CH2Cl2沖提以獲得橙色固體之化合物R(3.27 g,產率42%)。
化合物K之分析數據如下:M.p. 176-177℃;IR(KBr)ν3027,2918,2825,2719,1694,1593,1547,1209,1071 cm-1;1H NMR(CDCl3,400 MHz)δ9.92(s,1H),8.88(s,2H),7.88(d,J=4.4 Hz,1H),7.20-7.14(m,8H),6.40(d,J=4.4 Hz,1H),2.36(s,6H);13C NMR(CDCl3,100 MHz)δ187.9,164.1,162.7,158.4,143.7,135.4,133.4,130.2,127.3,125.1,124.1,113.1,21.1;HRMS(m/z,FAB+) Calcd. for C23H19N3OS 385.1249,found 385.1252。
將溶於無水甲苯(60 mL)中的化合物K(1.54 g,4.00 mmol)、丙二腈(528 mg,8.00 mmol)及鹼式氧化鋁(2.00 g)之混合物於70℃下攪拌加熱1小時。於反應混合物冷卻至室溫後,濾除殘餘的鹼式氧化鋁,並以甲苯進行徹底沖洗。以旋轉蒸發法去除濾液中的溶劑,並以矽膠管柱層析法純化粗產物,而以CH2Cl2沖提以獲得黑色固體之化合物L(1.36 g,產率78%)。
化合物L之分析數據如下:M.p. 209℃(DSC);IR(KBr)ν3024,2921,2221,1587,1542,1286,1107,1071,814 cm-1;1H NMR(CDCl3,400 MHz)δ8.93(s,2H),7.91(d,J=4.4 Hz,1H),7.47(s,1H),7.22-7.16(m,8H),6.39(d,J=4.4 Hz,1H),2.37(s,6H);13C NMR(CDCl3,100 MHz)δ164.5,163.0,158.2,152.7,143.3,136.1,135.1,130.3,126.6,125.4,119.8,113.7,112.9,112.8,80.1,21.1;HRMS(m/z,FAB+) Calcd. for C26H19N5S 433.1361,found 433.1358。
除了前述實施例以外,欲合成其他於分子結構中具有給電子部分、第一電子接受部分及第二電子接受部分之化合物,可先將各類經取代或未經取代之二苯基胺與經取代或未經取代之溴化噻吩、呋喃、苯或噻唑進行醋酸鈀(Pd(OAc)2)金屬催化反應,而得到分子結構中具有可作為給電子部分的化合物。之後將所得產物以SnBu3進行取代,再與經溴化且被第二電子接受部分(例如硝基、酯基及/或氰基所取代之伸乙烯)取代之第一電子接受部分(例如苯并噁二唑、苯并硒二唑等)化合物進行Stille偶合反應即可完成。
其中,苯環被不同碳數之醚基取代的二苯基胺可參照PCT專利公開案第2009/141288 A2號中所揭露的方法製備;苯環被不同碳數之胺基取代的二苯基胺可參照文獻J. Am. Chem. Soc. 2002,124,11085-11092中所揭露的方法製備;以各類不同碳數之烷基或醚基取代之溴化噻吩可參照文獻Heterocycles 1997,44,75-80;Macromolecules 2011,47,2006-2015;Macromolecules 2010,43,8709-8710;Tetrahedron Letters 2010,51,4526-4529;及Macromolecules 2009,42,663-670中所揭露的方法製備,而以各類不同碳數之烷基或醚基取代之溴化呋喃亦可參照前述方法由本領域具有通常知識者製備而得;欲製備經溴化且被二氰基伸乙烯取代之2,1,3-苯并噁二唑,可將揭露於中國專利第1847233號之4-甲基苯并噁二唑先進行溴化,再以本文前述化合物合成流程I中的步驟(i)至(iii)進行處理;欲製備經溴化且被二氰基伸乙烯取代之2,1,3-苯并硒二唑,可將揭露於PCT專利公開案第2009/034396 A2號之4-甲基苯并硒二唑先進行溴化,再以本文前述化合物合成流程I中的步驟(i)至(iii)進行處理;此外,可參照Organic Process Research & Development 2003,7,318-323及Tetrahedron Letters 2000,41,10299-10302等文獻,將2,3-二胺基甲苯與經C1-C6之烷基、氰基或苯基取代或未取代之二酮、或反應,接著進行溴化,並以本文前述化合物合成流程I中的步驟(i)至(iii)進行處理,以獲得各種不同的Ar2作為第一電子接受部分;除了二氰基伸乙烯外,第二電子接受部分亦可為獨立由硝基、酯基及/或氰基所取代之伸乙烯,只要將本文前述化合物合成流程I中步驟(iii)的丙二腈用二硝基甲烷、硝基乙腈、氰基取代之酯或其類似物等替換即可。
於使用前,先將化合物D、C60或C70、BCP利用溫度梯度昇華法進行純化,之後於基壓約1×10-6托之高度真空環境下,將化合物與金屬氧化物(如MoO3)之薄膜與金屬電極(如銀)沉積於ITO玻璃基材上,其中ITO之片電阻約為15Ω/sq。前述沉積過程係於室溫下以2-3 之速率進行,且於過程中以晶體振盪器偵測厚度。電池之活性面積平均約為2.5-5 mm2。於各層沉積完畢後,於乾燥氮氣環境下以UV硬化膠(購自Everwide Chemical Co.,Epowide EX)及玻璃進行封裝,並將所得裝置於空氣下進行測試。
藉由控制沉積條件,可將化合物D製成表一所列之各種不同之裝置:
利用SourceMeter Keithley 2636A配合使用氙燈太陽光模擬器(購自Abet Technologies)以量測於AM1.5G之太陽光照射下的電流密度-電壓特性,其中入射光強度係校調至100 mW/cm2,而前述各裝置所量測及計算而得之參數係如表二所示:
依照前述流程將化合物E、F、G製成如表三所示之太陽能電池,並進行測試,其結果如表四所示。
依照前述流程將化合物L製成如表五所示之各種太陽能電池,並進行測試,其結果如表六所示。
據此,本發明在上文中已以較佳實施例揭露,然本領域具有通常知識者應理解的是,該實施例僅用於描述本發明,而不應解讀為限制本發明之範圍。應注意的是,舉凡與該實施例等效之變化與置換,均應視為涵蓋於本發明之範疇內。因此,本發明之保護範圍當以下文之申請專利範圍所界定者為準。
Claims (10)
- 一種式(I)所示之化合物:
- 如申請專利範圍第1項所述之化合物,其中R1至R6係各自獨立選自H及C1-C6之烷基;Ar1係選自 ;Ar2係選自及;R7及R8皆為氰基。
- 如申請專利範圍第2項所述之化合物,其中X為S。
- 如申請專利範圍第2項所述之化合物,其中R9及R10係各自獨立選自H及F。
- 如申請專利範圍第1項所述之化合物,其中R1、R2、R4及R5為H,R3及R6為C1-C6之烷基。
- 如申請專利範圍第5項所述之化合物,其中Ar1係選自
- 如申請專利範圍第6項所述之化合物,其中R9及R10係各自獨立選自H及F。
- 一種有機薄膜太陽能電池,包括依序堆疊之第一電極、電洞傳輸層、活性層、電子傳輸層以及第二電極,其中該活性層包括一式(I)所示之化合物:
- 如申請專利範圍第8項所述之有機薄膜太陽能電池,其中R1、R2、R4及R5為H,R3及R6為C1-C6之烷基,Ar1係選自及,Ar2係選自及,R7及R8皆為氰基。
- 如申請專利範圍第9項所述之有機薄膜太陽能電池,其中X為S,R9及R10係各自獨立選自H及F。
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