近(jin)(jin)年來鈣(gai)(gai)鈦(tai)(tai)(tai)(tai)礦(kuang)(kuang)(kuang)材料在光(guang)(guang)(guang)(guang)伏領域的(de)潛力不斷被人們發掘，單(dan)結(jie)鈣(gai)(gai)鈦(tai)(tai)(tai)(tai)礦(kuang)(kuang)(kuang)太(tai)(tai)陽(yang)(yang)能(neng)電(dian)(dian)(dian)(dian)池(chi)(chi)(chi)(chi)(chi)效率屢創新高。為(wei)(wei)進一(yi)步提高光(guang)(guang)(guang)(guang)電(dian)(dian)(dian)(dian)轉(zhuan)化(hua)效率，研究(jiu)者進一(yi)步制備(bei)(bei)了一(yi)系列基于寬(kuan)帶(dai)隙(xi)鈣(gai)(gai)鈦(tai)(tai)(tai)(tai)礦(kuang)(kuang)(kuang)的(de)疊(die)(die)層(ceng)(ceng)太(tai)(tai)陽(yang)(yang)能(neng)電(dian)(dian)(dian)(dian)池(chi)(chi)(chi)(chi)(chi)，比如(ru)鈣(gai)(gai)鈦(tai)(tai)(tai)(tai)礦(kuang)(kuang)(kuang)/硅疊(die)(die)層(ceng)(ceng)太(tai)(tai)陽(yang)(yang)能(neng)電(dian)(dian)(dian)(dian)池(chi)(chi)(chi)(chi)(chi)，鈣(gai)(gai)鈦(tai)(tai)(tai)(tai)礦(kuang)(kuang)(kuang)/鈣(gai)(gai)鈦(tai)(tai)(tai)(tai)礦(kuang)(kuang)(kuang)疊(die)(die)層(ceng)(ceng)太(tai)(tai)陽(yang)(yang)能(neng)電(dian)(dian)(dian)(dian)池(chi)(chi)(chi)(chi)(chi)等。相較于其他種(zhong)類的(de)疊(die)(die)層(ceng)(ceng)太(tai)(tai)陽(yang)(yang)能(neng)電(dian)(dian)(dian)(dian)池(chi)(chi)(chi)(chi)(chi)，鈣(gai)(gai)鈦(tai)(tai)(tai)(tai)礦(kuang)(kuang)(kuang)/有(you)(you)(you)機(ji)(ji)疊(die)(die)層(ceng)(ceng)太(tai)(tai)陽(yang)(yang)能(neng)電(dian)(dian)(dian)(dian)池(chi)(chi)(chi)(chi)(chi)作為(wei)(wei)一(yi)種(zhong)新興技術而備(bei)(bei)受關注。在鈣(gai)(gai)鈦(tai)(tai)(tai)(tai)礦(kuang)(kuang)(kuang)/有(you)(you)(you)機(ji)(ji)疊(die)(die)層(ceng)(ceng)太(tai)(tai)陽(yang)(yang)能(neng)電(dian)(dian)(dian)(dian)池(chi)(chi)(chi)(chi)(chi)中，采(cai)(cai)用(yong)寬(kuan)帶(dai)隙(xi)鈣(gai)(gai)鈦(tai)(tai)(tai)(tai)礦(kuang)(kuang)(kuang)材料作為(wei)(wei)頂(ding)電(dian)(dian)(dian)(dian)池(chi)(chi)(chi)(chi)(chi)吸收短波(bo)長(chang)太(tai)(tai)陽(yang)(yang)光(guang)(guang)(guang)(guang)，采(cai)(cai)用(yong)窄帶(dai)隙(xi)有(you)(you)(you)機(ji)(ji)活(huo)性層(ceng)(ceng)作為(wei)(wei)底電(dian)(dian)(dian)(dian)池(chi)(chi)(chi)(chi)(chi)吸收近(jin)(jin)紅外(wai)長(chang)波(bo)長(chang)太(tai)(tai)陽(yang)(yang)光(guang)(guang)(guang)(guang)，大幅(fu)拓寬(kuan)可(ke)利(li)用(yong)太(tai)(tai)陽(yang)(yang)光(guang)(guang)(guang)(guang)譜范圍并降(jiang)低(di)能(neng)量損失(shi)。同時(shi)，鈣(gai)(gai)鈦(tai)(tai)(tai)(tai)礦(kuang)(kuang)(kuang)子電(dian)(dian)(dian)(dian)池(chi)(chi)(chi)(chi)(chi)可(ke)以(yi)(yi)過濾高能(neng)量光(guang)(guang)(guang)(guang)子以(yi)(yi)保(bao)(bao)護有(you)(you)(you)機(ji)(ji)活(huo)性層(ceng)(ceng)、防止(zhi)其光(guang)(guang)(guang)(guang)降(jiang)解；有(you)(you)(you)機(ji)(ji)子電(dian)(dian)(dian)(dian)池(chi)(chi)(chi)(chi)(chi)可(ke)以(yi)(yi)作為(wei)(wei)封裝層(ceng)(ceng)隔絕水氧，提升(sheng)環(huan)境穩定(ding)性，同時(shi)疊(die)(die)層(ceng)(ceng)太(tai)(tai)陽(yang)(yang)能(neng)電(dian)(dian)(dian)(dian)池(chi)(chi)(chi)(chi)(chi)的(de)中間透明電(dian)(dian)(dian)(dian)極層(ceng)(ceng)還可(ke)以(yi)(yi)緩(huan)解鈣(gai)(gai)鈦(tai)(tai)(tai)(tai)礦(kuang)(kuang)(kuang)頂(ding)電(dian)(dian)(dian)(dian)池(chi)(chi)(chi)(chi)(chi)負(fu)極處(chu)離子擴散等問題，從而使鈣(gai)(gai)鈦(tai)(tai)(tai)(tai)礦(kuang)(kuang)(kuang)-有(you)(you)(you)機(ji)(ji)疊(die)(die)層(ceng)(ceng)太(tai)(tai)陽(yang)(yang)能(neng)電(dian)(dian)(dian)(dian)池(chi)(chi)(chi)(chi)(chi)的(de)穩定(ding)性優(you)于單(dan)結(jie)鈣(gai)(gai)鈦(tai)(tai)(tai)(tai)礦(kuang)(kuang)(kuang)和單(dan)結(jie)有(you)(you)(you)機(ji)(ji)太(tai)(tai)陽(yang)(yang)能(neng)電(dian)(dian)(dian)(dian)池(chi)(chi)(chi)(chi)(chi)。另(ling)外(wai)，鈣(gai)(gai)鈦(tai)(tai)(tai)(tai)礦(kuang)(kuang)(kuang)/有(you)(you)(you)機(ji)(ji)疊(die)(die)層(ceng)(ceng)太(tai)(tai)陽(yang)(yang)能(neng)電(dian)(dian)(dian)(dian)池(chi)(chi)(chi)(chi)(chi)也保(bao)(bao)留(liu)了可(ke)溶液制備(bei)(bei)太(tai)(tai)陽(yang)(yang)能(neng)電(dian)(dian)(dian)(dian)池(chi)(chi)(chi)(chi)(chi)的(de)本征優(you)勢。

開(kai)路(lu)電(dian)(dian)(dian)(dian)壓的(de)提(ti)(ti)(ti)升是提(ti)(ti)(ti)高鈣鈦礦(kuang)/有(you)機疊層太陽(yang)能電(dian)(dian)(dian)(dian)池效(xiao)率的(de)關鍵(jian)因素。在鈣鈦礦(kuang)太陽(yang)能電(dian)(dian)(dian)(dian)池中，寬帶(dai)隙鈣鈦礦(kuang)吸光層與C60電(dian)(dian)(dian)(dian)子傳(chuan)輸(shu)層界面處(chu)經常存在嚴重(zhong)的(de)界面復合，表面態誘導的(de)導帶(dai)費米能級釘扎(zha)效(xiao)應(ying)會造成(cheng)電(dian)(dian)(dian)(dian)壓損失。為降(jiang)低(di)界面處(chu)的(de)電(dian)(dian)(dian)(dian)壓損失從(cong)而提(ti)(ti)(ti)升太陽(yang)能電(dian)(dian)(dian)(dian)池效(xiao)率，鈍化寬帶(dai)隙鈣鈦礦(kuang)吸光層與C60電(dian)(dian)(dian)(dian)子傳(chuan)輸(shu)層的(de)界面是一種有(you)效(xiao)的(de)策略。

在國家自然科學(xue)基金(jin)委、中國科學(xue)院(yuan)先導項(xiang)目和科技部重(zhong)點(dian)研(yan)發(fa)計(ji)劃的(de)(de)(de)支(zhi)持下(xia)，化(hua)(hua)(hua)(hua)學(xue)所(suo)有(you)(you)(you)機(ji)固體院(yuan)重(zhong)點(dian)實驗室(shi)李永舫/孟磊團隊(dui)在前(qian)期研(yan)究(jiu)的(de)(de)(de)基礎(chu)上，對(dui)鈣(gai)鈦(tai)(tai)(tai)礦(kuang)(kuang)/有(you)(you)(you)機(ji)疊層(ceng)太(tai)陽電(dian)(dian)池進行了(le)深入研(yan)究(jiu)。他們研(yan)究(jiu)了(le)具(ju)有(you)(you)(you)順反異構(gou)特性的(de)(de)(de)1,4-環己二胺分(fen)子(zi)(zi)對(dui)于寬(kuan)(kuan)帶(dai)隙(xi)鈣(gai)鈦(tai)(tai)(tai)礦(kuang)(kuang)表(biao)(biao)(biao)面(mian)(mian)(mian)的(de)(de)(de)鈍(dun)(dun)化(hua)(hua)(hua)(hua)機(ji)制（圖(tu)1a），系(xi)統性的(de)(de)(de)揭(jie)示(shi)了(le)兩種順反異構(gou)的(de)(de)(de)鈍(dun)(dun)化(hua)(hua)(hua)(hua)劑分(fen)子(zi)(zi)所(suo)導致的(de)(de)(de)鈣(gai)鈦(tai)(tai)(tai)礦(kuang)(kuang)表(biao)(biao)(biao)面(mian)(mian)(mian)結(jie)(jie)構(gou)差(cha)異，最終(zhong)(zhong)篩選(xuan)出(chu)擁有(you)(you)(you)優勢構(gou)型的(de)(de)(de)順式鈍(dun)(dun)化(hua)(hua)(hua)(hua)分(fen)子(zi)(zi)（cis-CyDAI2）。結(jie)(jie)合理(li)(li)(li)論計(ji)算與(yu)(yu)(yu)X射(she)線研(yan)究(jiu)了(le)順反兩種鈍(dun)(dun)化(hua)(hua)(hua)(hua)劑分(fen)子(zi)(zi)結(jie)(jie)構(gou)導致的(de)(de)(de)鈣(gai)鈦(tai)(tai)(tai)礦(kuang)(kuang)表(biao)(biao)(biao)面(mian)(mian)(mian)結(jie)(jie)構(gou)差(cha)異，通(tong)過研(yan)究(jiu)不同鈍(dun)(dun)化(hua)(hua)(hua)(hua)分(fen)子(zi)(zi)處理(li)(li)(li)的(de)(de)(de)鈣(gai)鈦(tai)(tai)(tai)礦(kuang)(kuang)薄膜(mo)的(de)(de)(de)光(guang)(guang)致發(fa)光(guang)(guang)量子(zi)(zi)產率(lv)(lv)，提(ti)(ti)取(qu)得到了(le)相(xiang)應(ying)的(de)(de)(de)準費米能級(ji)分(fen)裂（圖(tu)1b），發(fa)現(xian)(xian)cis-CyDAI2處理(li)(li)(li)的(de)(de)(de)鈣(gai)鈦(tai)(tai)(tai)礦(kuang)(kuang)薄膜(mo)有(you)(you)(you)更(geng)高的(de)(de)(de)理(li)(li)(li)論開路電(dian)(dian)壓。進一步地，他們通(tong)過紫外光(guang)(guang)電(dian)(dian)子(zi)(zi)能譜與(yu)(yu)(yu)表(biao)(biao)(biao)面(mian)(mian)(mian)開爾文(wen)力顯微鏡等(deng)測(ce)試手段發(fa)現(xian)(xian)，cis-CyDAI2會導致寬(kuan)(kuan)帶(dai)隙(xi)鈣(gai)鈦(tai)(tai)(tai)礦(kuang)(kuang)表(biao)(biao)(biao)面(mian)(mian)(mian)費米能級(ji)上升，削弱表(biao)(biao)(biao)面(mian)(mian)(mian)釘扎效應(ying)，與(yu)(yu)(yu)電(dian)(dian)子(zi)(zi)傳輸層(ceng)有(you)(you)(you)更(geng)好的(de)(de)(de)接觸(chu)。最終(zhong)(zhong)在具(ju)有(you)(you)(you)1.88 eV帶(dai)隙(xi)的(de)(de)(de)寬(kuan)(kuan)帶(dai)隙(xi)鈣(gai)鈦(tai)(tai)(tai)礦(kuang)(kuang)單結(jie)(jie)電(dian)(dian)池中獲得了(le) 1.36 V的(de)(de)(de)開路電(dian)(dian)壓與(yu)(yu)(yu)18.4%的(de)(de)(de)光(guang)(guang)電(dian)(dian)轉換效率(lv)(lv)。該策略(lve)為(wei)寬(kuan)(kuan)帶(dai)隙(xi)鈣(gai)鈦(tai)(tai)(tai)礦(kuang)(kuang)太(tai)陽能電(dian)(dian)池降低電(dian)(dian)壓損失提(ti)(ti)供了(le)全新思(si)路。

最終，他們結合窄帶隙有(you)(you)機材(cai)料底電(dian)池構建了鈣鈦礦/有(you)(you)機疊層(ceng)太陽能電(dian)池（圖1c），獲得了26.4%的光電(dian)轉換效(xiao)率（圖1d）（經第三方認證為(wei)25.7%），為(wei)目前報道的鈣鈦礦/有(you)(you)機疊層(ceng)太陽電(dian)池的最高效(xiao)率。相關(guan)研(yan)究(jiu)成果近期發表在《自然(ran)》上（Nature.2024, DOI:10.1038/s41586-024-08160-y ），文章的共(gong)同(tong)第一作者(zhe)為(wei)博(bo)士生(sheng)蔣鑫(xin)和(he)秦書誠博(bo)士，通訊作者(zhe)為(wei)孟磊研(yan)究(jiu)員、德國(guo)波茨(ci)坦大學Felix Lang教授以(yi)及化學所李永舫研(yan)究(jiu)員。

圖(tu)1. (a) 鈣(gai)(gai)鈦礦鈍化劑(ji)CyDAI2化學(xue)結構 (b) 通過測試(shi)不同條件(jian)(jian)下薄膜(mo)的(de)(de)準費米能(neng)級分裂和器件(jian)(jian)的(de)(de)開路電(dian)壓(ya)總(zong)結的(de)(de)電(dian)壓(ya)損耗示意(yi)圖(tu) (c) 鈣(gai)(gai)鈦礦-有機(ji)疊層太(tai)陽能(neng)電(dian)池結構示意(yi)圖(tu)以(yi)及(ji)掃描(miao)電(dian)鏡(jing)截面圖(tu) (d) 太(tai)陽能(neng)電(dian)池的(de)(de)電(dian)流密(mi)度-電(dian)壓(ya)曲線