TWI382062B - 有機染料及使用此有機染料的染料敏化太陽能電池 - Google Patents
有機染料及使用此有機染料的染料敏化太陽能電池 Download PDFInfo
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- TWI382062B TWI382062B TW098114228A TW98114228A TWI382062B TW I382062 B TWI382062 B TW I382062B TW 098114228 A TW098114228 A TW 098114228A TW 98114228 A TW98114228 A TW 98114228A TW I382062 B TWI382062 B TW I382062B
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 23
- -1 2-mercapto, 1-naphthyl Chemical group 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 125000003545 alkoxy group Chemical group 0.000 claims description 15
- 125000006850 spacer group Chemical group 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 7
- 125000002541 furyl group Chemical group 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000000732 arylene group Chemical group 0.000 claims description 3
- LNDJVIYUJOJFSO-UHFFFAOYSA-N cyanoacetylene Chemical group C#CC#N LNDJVIYUJOJFSO-UHFFFAOYSA-N 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000003107 substituted aryl group Chemical group 0.000 claims description 3
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 239000000975 dye Substances 0.000 description 25
- 150000001875 compounds Chemical class 0.000 description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 229940125904 compound 1 Drugs 0.000 description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 229910010413 TiO 2 Inorganic materials 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- MLIREBYILWEBDM-UHFFFAOYSA-N cyanoacetic acid Chemical compound OC(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 239000002803 fossil fuel Substances 0.000 description 3
- 238000003306 harvesting Methods 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 125000003396 thiol group Chemical class [H]S* 0.000 description 3
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 150000004982 aromatic amines Chemical group 0.000 description 2
- 125000005264 aryl amine group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- ICKPMZSTRBJHKU-UHFFFAOYSA-N 2,3,4-tributylpyridine Chemical compound CCCCC1=CC=NC(CCCC)=C1CCCC ICKPMZSTRBJHKU-UHFFFAOYSA-N 0.000 description 1
- GFEOIXQQLXAANX-UHFFFAOYSA-N 2-cyano-3-[5-[2-[4-(n-phenylanilino)phenyl]ethenyl]thiophen-2-yl]prop-2-enoic acid Chemical compound S1C(C=C(C(=O)O)C#N)=CC=C1C=CC1=CC=C(N(C=2C=CC=CC=2)C=2C=CC=CC=2)C=C1 GFEOIXQQLXAANX-UHFFFAOYSA-N 0.000 description 1
- 238000006000 Knoevenagel condensation reaction Methods 0.000 description 1
- LFZAGIJXANFPFN-UHFFFAOYSA-N N-[3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-thiophen-2-ylpropyl]acetamide Chemical compound C(C)(C)C1=NN=C(N1C1CCN(CC1)CCC(C=1SC=CC=1)NC(C)=O)C LFZAGIJXANFPFN-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000006619 Stille reaction Methods 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XAQHXGSHRMHVMU-UHFFFAOYSA-N [S].[S] Chemical compound [S].[S] XAQHXGSHRMHVMU-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000005595 deprotonation Effects 0.000 description 1
- 238000010537 deprotonation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000004776 molecular orbital Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910000080 stannane Inorganic materials 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- 125000006617 triphenylamine group Chemical group 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/008—Triarylamine dyes containing no other chromophores
-
- 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
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
- H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
-
- 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
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
- H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
-
- 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
- H10K85/653—Aromatic compounds comprising a hetero atom comprising only oxygen as heteroatom
-
- 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
- H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Photovoltaic Devices (AREA)
Description
本發明是有關於一種太陽能電池材料，且特別是有關於一種用於染料敏化太陽能電池(Dye-Sensitized Solar Cell，DSSC)的有機染料，以及使用此有機染料的DSSC。
為因應能源供應與化石燃料消耗所致的環境問題，全球都在研發乾淨、可再生的能源。在多種化石燃料的替代方案中，太陽能顯為較佳者，只要有效率達10%的太陽能轉換系統覆蓋全球陸地的0.16%，即足以提供全世界消耗之化石燃料能量的兩倍。雖然矽或其他半導體基的太陽能電池(光伏打電池)已主導太陽能電池市場數十年，但自從Grtzel等人獲得技術上突破(例如O’Regan,B.;Grtzel,M.Nature
1991,353
,737)以來，染料敏化太陽能電池(DSSC)也已受到相當注意，其中釕基DSSC轉換效率約可達11%。無金屬DSSC的發展雖晚於釕基DSSC，但亦已受到頗多注目，其效率約可達9%。
歷來已有多種無金屬染料用於製作DSSC。發明人之前曾報導過由作為電子供體的芳胺基、作為電子受體的2-氰基丙烯酸基、含噻吩片段之共軛橋接基所構成的無金屬染料(K. R. Justin Thomas,J. T. Lin,Y.-C. Hsu and K.-C. Ho,Chem. Commun.
2005,4098)。與類苯(benzenoid)片段相較下，噻吩片段可提供更有效的共軛，並降低電荷轉移躍遷的能量，因其共振能量較小(29kcal‧mol-1
，苯為36kcal‧mol-1
)。
由此觀之，如使染料分子的橋接基具有共振能量更小(26kcal‧mol-1
)的呋喃片段，其效果十分令人感與趣。
因此，本發明提供一種用於染料敏化太陽能電池的有機染料，其橋接基具有呋喃片段。
本發明並提供一種染料敏化太陽能電池，其是使用本發明之有機染料製作而得者。
本發明之用於DSSC的有機染料由通式(1)所表示：
其中Ar1為經取代或未取代的亞芳基(arylene)，Ar2、Ar3各為經取代或未取代的芳基(aryl)，Sp1為單鍵或可使Ar1與呋喃基共軛的間隔基，Sp2為單鍵或可使呋喃基與Ac共軛的間隔基，Ac是一電子受體基，且Y是一固定基，其中，當Ar2或Ar3為經取代的芳基時，其上取代基是選自由碳數1~5的烷基與碳數1~5的烷氧基所組成的族群。
在一實施例中，上述Ar1為經取代或未取代的1,4-苯基、2,7-芴基(2,7-fluorene)或2,7-咔唑基(2,7-carbazole)。經取代的1,4-苯基、2,7-芴基或2,7-咔唑基上的取代基可選自由碳數1~5的烷基與碳數1~5的烷氧基所組成的族群。其中，1,4-苯基的2-位置與5-位置中可有至少一者被烷基或烷氧基取代，2,7-芴基的9-位置可以被至少一個烷基取代，例如是被兩個乙基取代。
在一實施例中，上述Ar2及Ar3各自獨立為經取代或未取代的苯基、2-芴基(2-fluorenyl)、1-萘基(1-naphthyl)、9-蒽基(9-anthracenyl)、1-芘基(1-pyrenyl)或2-咔示基(2-carbazolyl)。Ar2及Ar3可同時為苯基或2-芴基。
在一實施例中，上述該些間隔基Sp1、Sp2各自為伸乙烯基(vinylene)、氰基伸乙烯基(cyanovinylene)或2,5-噻吩基(2,5-thiophene group)。
在一實施例中，上述電子受體基Ac為2-氰基乙烯基。
在一實施例中，上述固定基Y包括一羧酸基。
在一實施例中，上述電子受體基Ac與固定基Y的組合包括2-氰基丙烯酸基。
在一些實施例中，上述用於染料敏化太陽能電池的有機染料分別具有下式(2)、(3)、(4)、(5)所示的分子結構，其中Ar2與Ar3各自之4-位置可被碳數1~5的烷基與碳數1~5的烷氧基取代。
本發明之染料敏化太陽能電池包括上述本發明之有機染料、電解質，以及光電極。
本發明提出之含呋喃片段的DSSC用有機染料可具有十分接近先前之釕基染料的效能，但因不須使用釕這種貴重金屬，故其成本遠低於後者。
為讓本發明之上述特徵和優點能更明顯易懂，下文特舉實施例，並配合所附圖式作詳細說明如下。
本發明之用於DSSC的有機染料由通式(1)所表示：
其中Ar1為經取代或未取代的亞芳基(arylene)，Ar2、Ar3各為經取代或未取代的芳基，Sp1為單鍵或可使Ar1與呋喃基共軛的間隔基，Sp2為單鍵或可使呋喃基與Ac共軛的間隔基，Ac是一電子受體基，且Y是一固定基，其中，當Ar2或Ar3為經取代的芳基時，其上的取代基是選自由碳數1~5的烷基與碳數1~5的烷氧基所組成的族群。
上述Ar1可為經取代或未取代的1,4-苯基、2,7-芴基或2,7-咔唑基。經取代的1,4-苯基、2,7-芴基或2,7-咔唑基上的取代基可選自由碳數1~5的烷基與碳數1~5的烷氧基所組成的族群。其中，1,4-苯基的2-位置與5-位置中可有至少一者被烷基或烷氧基取代，2,7-芴基的9-位置可被至少一個烷基取代，例如是被兩個乙基取代。上述Ar2及Ar3可各自獨立為經取代或未取代的苯基、2-芴基、1-萘基、9-蒽基、1-芘基或2-咔唑基。Ar2及Ar3可同時為苯基或2-芴基。當Ar2及Ar3同為苯基時，Ar2與Ar3各自之4-位置可被碳數1~5的烷基與碳數1~5的烷氧基取代。上述間隔基Sp1、Sp2各自可為伸乙烯基(vinylene)、氰基伸乙烯基(cyanovinylene)或2,5-噻吩基(2,5-thiophene group)。另外，上述電子受體基Ac與固定基Y的組合可為2-氰基丙烯酸基。
本發明之有機染料的4個實例為以下化合物1
~4
。
化合物1
~4
可以下示合成架構1來合成。
化合物1、3
之合成皆以具有三苯胺片段或二苯胺基-2-芴片段的Wittig試劑開始。Wittig試劑與2-呋喃醛反應形成中間體1b
與3b
，其再進行甲醯化而形成1c
與3c
，接著令1c
(3c
)與氰基乙酸進行Knoevenagel縮合反應，即得所需化合物1
(3
)。至於化合物2
/4
之合成，則是以5-溴-2-呋喃醛與適當的苯硼酸/錫烷化合物進行Suzuki耦合/Stille耦合反應，而形成中間體2b
/4b
，再令中間體2b
/4b
與氰基乙酸反應而形成所需化合物2
/4
。
化合物1
~4
溶於四氫呋喃(THF)時之吸收與發射特性的資料請見表1。
約在400~600nm的主吸收帶可歸因於π-π*軌域與電荷轉移躍遷的重疊。這些化合物的電荷轉移特徵亦可由其吸收帶與發射帶(3225～4895cm-1
)之間的Stokes位移得證。負的溶劑化顯色(solvatochromism)效應，即電荷轉移帶於極性較高溶劑中的藍位移，亦可見於這些化合物。例如，化合物1
在甲苯及乙腈中的最大吸收波長分別為485nm及439nm。此現象可歸因於羧酸的去質子化，其降低了電子受體的強度。
對各化合物而言，在其循環伏安測量時所見的半可逆波形(表1中的E 氧化
)可歸因於芳胺片段的氧化。因為化合物1、2
的分子長度較短，故拉電子的電子受體對芳胺片段的影響較大，而提高了芳胺片段的氧化電位。這些化合物的激發態電位(E 0-0 *
)為-0.74~-0.80V(相對於標準氫電極)，是由E 氧化
及從吸收帶邊緣的0-0能階激發能量(zero-zero excitation energy,E 0-0
)得知，其負值比TiO2
電極的導帶邊緣能量位準(對標準氫電極為-0.5V)更大，而得以確保電子注入過程從能量觀點來看上是容易發生的。
接著，使用作為集光敏化劑的上述染料、銳鈦礦TiO2
奈米晶體顆粒及作為電解質的0.05M I2
/0.5M LiI/0.5M三級丁基吡啶的乙腈溶液，製作有效面積0.25cm2
的DSSC。所得之DSSC在AM 1.5照明下的裝置性能統計資料列於表1，光電流-電壓(J
-V
)曲線顯示於圖1，在不同波長下的光電流轉換效率(IPCE)則顯示於圖2。這些DSSC具有很高的轉換效率(6.12~7.36%)，其最佳者甚至可達到在類似條件下以N719製作之DSSC的轉換效率(7.69%)的96%。
DSSC轉換效率之高低順序為染料化合物1
>2
>3
>4
，是受到幾項因素影響：(a).較低的最高填充分子軌域(HOMO，由循環伏安法[CV]估算而得)有利於被氧化染料之還原，並抑制從TiO2
至染料的反向電子轉移，進而導致較大的V OC
與J SC
(化合物1
、2
)；(b).在較長波長區域有較大吸收的化合物可具有較佳的光能收獲(化合物1
>2
)；(c).較高的TiO2
上染料吸附密度(化合物1
/2
/3
/4
為4.5/4.1/3.8/4.6×10-7
mol‧cm-2
)較有利於光能收獲，故化合物1
>2
>3
。另外，光注入電子與被氧化染料的再結合生命期(τR
)也有以開路下的瞬間光電壓來測量，結果化合物1
、2
、3
、4
及N719的τR
分為4.9ms、5.8ms、4.3ms、3.1ms、10.4ms。此現象與上述電池效率的變化趨勢相符。
以下為上述化合物1
與先前提出之噻吩同類物3-(5-(4-(二苯胺基)苯乙烯基)噻吩-2-基)-2-氰基丙烯酸(D5)之吡較。與乙腈中的化合物1
相較(λ吸收
=439nm(33000M-1
cm-1
)，TiO2
吸附密度=4.5×10-7
mol‧cm-2
)，D5於乙腈中雖有稍佳的光能收獲(λ吸收
=476nm(37600M-1
‧cm-1
))及TiO2
吸附密度(4.8×10-7
mol‧cm-2
)，但以化合物1
製作之DSSC的效能優於在類似條件下以D5製作者(V OC
=0.64V，J SC
=14.61mA‧cm-2
，ff
=0.65，η=6.09%)。此現象的原因可能是：D5的τR
(4.3ms)較短、非鍵結分子間硫-硫交互作用有害於被激發染料對TiO2
的電子注入、噻吩片段稍較容易捕陷電子等。
綜上所述，本發明所提出之含呋喃片段的DSSC用有機染料可具有十分接近先前之釕基染料的效能，但因不須使用釕這種貴重金屬，故其成本遠低於後者。
雖然本發明已以實施例揭露如上，然其並非用以限定本發明，任何所屬技術領域中具有通常知識者，在不脫離本發明之精神和範圍內，當可作些許之更動與潤飾，故本發明之保護範圍當視後附之申請專利範圍所界定者為準。
圖1顯示分別使用染料化合物1
~4
之DSSC的光電流-電壓(J-V
)曲線。
圖2顯示分別使用染料化合物1
~4
之DSSC在不同波長下的光電流轉換效率。
Claims (17)
- 一種用於染料敏化太陽能電池(DSSC)的有機染料，其係由通式(1)所表示：
- 如申請專利範圍第1項所述之用於染料敏化太陽能電池的有機染料，其中Ar1為經取代或未取代的1,4-苯基、2,7-芴基或2,7-咔唑基。
- 如申請專利範圍第2項所述之用於染料敏化太陽能電池的有機染料，其中經取代的1,4-苯基、2,7-芴基或2,7-咔唑基上的取代基是選自由碳數1~5的烷基與碳數1~5的烷氧基所組成的族群。
- 如申請專利範圍第3項所述之用於染料敏化太陽能電池的有機染料，其中該1,4-苯基的2-位置與5-位置中至少有一者被烷基或烷氧基取代。
- 如申請專利範圍第3項所述之用於染料敏化太陽能電池的有機染料，其中該2,7-芴基的9-位置被至少一個烷基取代。
- 如申請專利範圍第5項所述之用於染料敏化太陽能電池的有機染料，其中該2,7-芴基的9-位置被兩個乙基取代。
- 如申請專利範圍第1項所述之用於染料敏化太陽能電池的有機染料，其中Ar2及Ar3各自獨立為經取代或未取代的苯基、2-芴基、1-萘基、9-蒽基、1-芘基或2-咔唑基。
- 如申請專利範圍第7項所述之用於染料敏化太陽能電池的有機染料，其中Ar2及Ar3同時為苯基或2-芴基。
- 如申請專利範圍第1項所述之用於染料敏化太陽能電池的有機染料，其中該些間隔基Sp1、Sp2各自為伸乙烯基(vinylene)、氰基伸乙烯基(cyanovinylene)或2,5-噻吩基(2,5-thiophene group)。
- 如申請專利範圍第1項所述之用於染料敏化太陽能電池的有機染料，其中該電子受體基Ac為2-氰基乙烯基。
- 如申請專利範圍第1項所述之用於染料敏化太陽能電池的有機染料，其中該固定基Y包括一羧酸基。
- 如申請專利範圍第1項所述之用於染料敏化太陽能電池的有機染料，其中該電子受體基Ac與該固定基Y的組合包括2-氰基丙烯酸基。
- 如申請專利範圍第1項所述之用於染料敏化太陽能電池的有機染料，其具有下式(2)所示的分子結構：
- 如申請專利範圍第1項所述之用於染料敏化太陽能電池的有機染料，其具有下式(3)所示的分子結構：
- 如申請專利範圍第1項所述之用於染料敏化太陽能電池的有機染料，其具有下式(4)所示的分子結構：
- 如申請專利範圍第1項所述之用於染料敏化太陽能電池的有機染料，其具有下式(5)所示的分子結構：
- 一種染料敏化太陽能電池，包括如申請專利範圍第1~16項中任一項所述之用於染料敏化太陽能電池的有機染料、電解質，以及光電極。
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| Title |
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| Daniel P. Hagberg, Tomas Edvinsson, Tannia Marinado, Gerrit Boschloo, Anders Hagfeldt, Licheng Sun,"A novel organic chromophore for dye-sensitized nanostructured solar cells", Journal of Chemical Communications, 2006, p2245-2247. Sanghoon Kim * |
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