鈣鈦礦太陽能電池(Perovskite Solar Cells， PSCs)中載子傳遞層的功能是將鈣鈦礦層吸收光後激發出的載子萃取並傳遞至外部電路。其中，有機高分子材料因具備好的成膜性、高載子遷移率和可調控能階的性質，在PSCs載子傳輸層的應用上備受關注。先前本實驗室已合成D-A type高分子PIDT-BTCN，其雖具備載子萃取能力，但因結構中的Donor單元IDT具強推電子能力，導致高分子的HOMO能階(-5.44 eV)無法與鈣鈦礦層的價帶(-5.44 eV)形成能障阻擋電洞流向。為了改善高分子與鈣鈦礦層間的能階搭配，本研究透過調整D-A結構中推拉電子的強弱來調整D-A高分子的前置軌域能階，將原先的IDT結構替換成強拉電子能力的benzodifurandione-based oligo(p-phenylene vinylene) (BDOPV)作為Acceptor單元，並分別以含兩個拉電子氰基的benzo[c]thiophene-5，6-dicarbonitrile (BTCN)及3，4-dicyanothiophene (TCN)作為弱Donor單元，合成出高分子PBDOPV-BTCN和PBDOPV-TCN。PBDOPV-BTCN和PBDOPV-TCN的熱裂解溫度分別為245 ℃及256 ℃，高於元件組裝及運作時的溫度(約小於150 ℃)。在鈣鈦礦膜上沉積兩個高分子的水接觸角由原先的45.9度分別提高至80.8度和82.7度。PBDOPV-BTCN、PBDOPV-TCN與鉛鈣鈦礦層間的前置軌域能階顯示，兩個高分子的HOMO能階(-5.06 eV和-5.16 eV)均高於鈣鈦礦層的價帶，而其LUMO能階(-3.46 eV和-3.49 eV)也高於鈣鈦礦層的導帶，此能階排列有助於鈣鈦礦層中的電洞被萃取出並傳遞至電極，同時可對電子形成阻擋效果，因此高分子PBDOPV-BTCN和PBDOPV-TCN較適合作為鈣鈦礦太陽能電池之電洞傳遞層。將兩個高分子作為電洞傳遞層組裝成一般式鉛鈣鈦礦太陽能電池的效率分別為1.36%及1.70%。;In Perovskite Solar Cells (PSCs)， the function of the charge transport layer is to extract the charge carriers generated by the perovskite layer after light absorption and transport them to the external circuit. Among various materials， organic polymers have attracted significant attention for applications in PSC charge transport layers due to their excellent film-forming properties， high carrier mobility， and tunable energy levels. Previously， our laboratory synthesized a D-A type polymer， PIDT-BTCN. Although it possesses charge extraction capabilities， the strong electron-donating ability of the IDT donor unit results in a HOMO energy level (-5.44 eV) that cannot form an energy barrier with the valence band of the perovskite layer (-5.44 eV) to block the flow of holes. To improve the energy level alignment between the polymer and the perovskite layer， this study modulates the frontier orbital energy levels of the D-A polymers by tuning the electron push-pull strength within the D-A structure. The original IDT structure was replaced with benzodifurandione-based oligo(p-phenylene vinylene) (BDOPV)， which exhibits strong electron-withdrawing ability， as the acceptor unit. Additionally， benzo[c]thiophene-5，6-dicarbonitrile (BTCN) and 3，4-dicyanothiophene (TCN)， both containing two electron-withdrawing cyano groups， were used as weak donor units to synthesize the polymers PBDOPV-BTCN and PBDOPV-TCN.The thermal decomposition temperatures of PBDOPV-BTCN and PBDOPV-TCN are 245 °C and 256 °C， respectively， which are higher than the temperatures required for device assembly and operation (approximately below 150 °C). After depositing the two polymers on the perovskite film， the water contact angles increased from the original 45.9° to 80.8° and 82.7°， respectively. The frontier orbital energy level alignments between PBDOPV-BTCN， PBDOPV-TCN， and the lead perovskite layer show that the HOMO energy levels of both polymers (-5.06 eV and -5.16 eV) are higher than the valence band of the perovskite layer， and their LUMO energy levels (-3.46 eV and -3.49 eV) are also higher than the conduction band of the perovskite layer. This energy level arrangement facilitates the extraction and transport of holes from the perovskite layer to the electrode while simultaneously providing an electron-blocking effect. Therefore， the polymers PBDOPV-BTCN and PBDOPV-TCN are more suitable as hole transport layers for perovskite solar cells. When these two polymers were applied as hole transport layers in regular lead perovskite solar cells， the power conversion efficiencies were 1.36% and 1.70%， respectively.
