摘要
本篇論文研究合成有機小分子應用在反式有機太陽能電池中作為
donor，在反式鈣鈦礦太陽能電池中作為電洞傳遞層材料，以及在一般式鈣
鈦礦太陽能電池中作為電子傳遞層材料，並探討這些材料分子的物化性質、
結構與材料性質的關係及材料組裝成元件後的光伏表現。
第一部分研究以diketopyrrolopyrrole (DPP) 作為acceptor ，
ethylenedioxythiophene (EDOT) 、triphenylamine (TPA) 、alkyl thiophene
(AT) 作為donor ， 利用direct alkylation 合成donor–donor–acceptor–donor–
donor (D1–D2–A–D2–D1)類型的四個小分子(SM1, SM2, SM3, SM4)，以及
利用Stille coupling合成acceptor–donor–acceptor (A–D–A)類型的兩個小分子
(SM5, SM6)，作為donor應用在反式有機太陽能電池中(PCBM為acceptor，
ZnO為電子傳遞層，MoO3為電洞傳遞層)，因SM2有最低的HOMO能階，
因此以SM2作為donor所組裝之元件有最高的VOC值，為0.82V。SM5和SM6
為結構異構物，但由於SM6和SM5相比有較好的溶解度和較低的HOMO能
階，因此以SM6所組裝的元件有較好的光電轉換效率。第二部份研究合成雜環 spiro-typed 的分子做為電洞傳遞層材料，分
別以spiro[fluorene-9,9’-xanthene] (SFX) 和spiro[fluorene-9,9’-thioxanthene]
(SFT)為結構核心合成產率高成本低的SFX-TPAM、SFX-TPA、SFT-TPAM、
SFT-TPA等四個化合物。以這四個小分子作為電洞傳遞層(HTL)應用在元
件中，元件架構為glass/ITO/HTL/CH3NH3PbI3/ C60/BCP/Ag。其中以SFXTPAM
作為HTL ， 在不添加dopant 的條件下所組裝的元件和以spiro-
OMeTAD作為電洞傳遞層所組裝的元件相比，有較好的光電轉換效率，為
10.23% 。第三部份的研究則包含三個以fullerene (C60及C70)為結構核心，bis(2-
(2-((tert-butoxycarbonyl)amino)ethoxy)ethyl) malonate (4b)作為取代基，合成
三個電子傳遞層修飾材料(C60-RT2、C60-RT6及C70-RT2)應用在一般式鈣鈦
礦太陽能電池元件中。這三個材料對極性質子溶劑(甲醇、乙醇及水)有很
好的溶解度，在一般式太陽能電池元件的製程中，混在TiO2漿料中使用，
可以製作低溫TiO2。以TiO2+C60-RT2、TiO2+C60-RT6、TiO2+C70-RT6作為
電子傳遞層所組裝之元件光電轉換效率分別為16.37%、18.03%及17.10%，
較以TiO2作為電子傳遞層所組裝之元件效率(14.92%)來得高。

Abstract
This thesis is the work on the organic semiconductors for applications as
electron donor (p-type) materials in organic solar cells (OSCs), hole transporting
materials (HTMs) in inverted perovskite solar cells (p-i-n PSCs) and electron
transporting materials (ETMs) in regular perovskite solar cells (n-i-p PSCs). The
synthesis and physicochemical characterization of new materials (P-type, HTMs
and ETMs) were reported. The structure-property relationship and the
photovoltaic performance of the corresponding cells were investigated.
The first part focuses on synthesis of four donor–donor–acceptor–donor–
donor (D1–D2–A–D2–D1) type small molecules (SM1, SM2, SM3 and SM4),
in which diketopyrrolopyrrole (DPP) was used as an acceptor (DPP) core and
3,4-ethylenedioxythiophene (EDOT), triphenylamine (TPA) or alkyl thiophene
(AT) acted as a donor using direct arylation reaction. The inverted small
molecule solar cell (using PCBM as an acceptor, and ZnO and MoO3 as the
electron and hole transporters, respectively) based on SM2 has the highest value
of Voc (0.82 V) due to SM2 having the lowest HOMO level. Two acceptor–
donor–acceptor type (A–D–A) molecules (SM5 and SM6) were also synthesized
by Stille coupling, in which DPP and EDOT were used as the acceptor and
donor, respectively. SM5 and SM6 are structural isomers, however the inverted
cell based on SM6 has a much higher PCE than that based on SM5, due to SM6
having better solubility and a lower HOMO energy level.
The second part targets on four heterocyclic spiro-typed hole transporting
materials (HTMs) carrying spiro[fluorene-9,9’-xanthene] (SFX) such as SFXTPAM
and SFX-TPA or spiro[fluorene-9,9’-thioxanthene] (SFT) unit such as
SFT-TPAM and SFT-TPA were synthesized through low cost facile route with
high yields. The photovoltaic performance of the inverted PSCs based on these
small molecular hole transporting materials with the device architecture of
glass/ITO/HTM/CH3NH3PbI3/C60/BCP/Ag was studied. Inverted PSC based on
dopant-free SFX-TPAM HTM achieves a power conversion efficiency of10.23% under the illumination of standard one Sun lighting, which is better than
that (8.17%) of the cell based on dopant-free spiro-OMeTAD.
The third part is the preparation and photovoltaic application of three
fullerene based ETMs (C60-RT2, C60-RT6 and C70-RT2), in which fullerene (C60
and C70) as core unit and bis(2-(2-((tert-butoxycarbonyl)amino)ethoxy)ethyl)
malonate (4b) was used as a substituent. All three fullerene exhibit very good
solubility in polar protic solvents (such as methanol, ethanol and water), which
is beneficial for making of low temperature processed ETMs for regular PSCs.
The new fullerene derivatives were mixed with low temperature processed TiO2
to be used as ETMs in regular PSCs (FTO/ETMs/PSK/Spiro-
OMeTAD/MoO3/Ag). Cells based on new ETMs have the PCE of 16.37%
(TiO2+C60-RT2), 18.03% (TiO2+C60-RT6) and 17.10% (TiO2+C60-RT6), which
is higher than that (14.92%) of the cell based on TiO2 ETL. The work of this
thesis provides valuable guideline for designing charge transporting materials
for photovoltaic application.

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