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Defect passivation cu lead triiodide perovskite solar cells riantuan ning tthanchoternak caah tampi hman a si cang, asinain α-phase fekmi cung ah defect phunphun nih a chuahpimi thil cu a fiang rih lo; Hika ah, density functional theory hmangin, formamidine lead triiodide perovskite α-phase in δ-phase tiang a rawhnak lam kha a voikhatnak bik kan hmuh i phase thlennak thazaang khamnak cung i tlamtlinlonak phunphun nih a chuahpimi thil kha kan hlathlai. Simulation hmuhmi nih a chimchungmi cu iodine a lawngmi hna nih rawhnak a chuahter deuh lai, zeicahtiah α-δ thlennak caah thazaang khamnak kha a tlawmter ngaingai i perovskite cunglei ah a niam bikmi sernak thazaang an ngei. Ti ah a cawh kho lomi lead oxalate tlawmpal kha perovskite cunglei ah luhternak nih α-phase rawhnak kha a kham ngaingai, iodine a tthialnak le a tthawnnak kha a kham. Cun, hi strategy nih hin interfacial nonradiative recombination kha a zorter ngaingai i solar cell tthatnak kha 25.39% (certified 24.92%) tiang a karhter. A tthen lomi thilri cu 1.5 G thli tlawmternak tangah suimilam 550 chung a tthawng bik in rian a ttuan hnu zongah a hramthawk 92% tthatnak kha a kilven khawh rih.
Perovskite solar cells (PSCs) hna i an thazaang thlennak tthatnak (PCE) cu 26%1 tiang a phan cang. 2015 thawk in, chanthar PSCs nih formamidine triiodide perovskite (FAPbI3) cu ceunak a lakmi tthen ah an duh deuh, zeicahtiah a ttha tukmi lumnak a fekmi le Shockley-Keisser ri 2,3,4 he aa naihmi a duh deuhmi bandgap ruangah a si. Vanchiat ah, FAPbI3 zukcawl pawl cu khaan lumternak ah a senmi α tthennak in a senmi non-perovskite δ tthennak ah thlennak an tuah5,6. Delta phase sernak khamnak caah, a harmi perovskite phunphun an ser. Hi buainak tei khawhnak ding caah a tlangpi in hmanmi strategy cu FAPbI3 cu methyl ammonium (MA+), cesium (Cs+) le bromide (Br-) ions7,8,9 fonhmi he cawh a si. Sihmanhsehlaw, hybrid perovskites cu bandgap kauhnak le photoinduced phase tthennak in an tuar, cu nih cun a chuakmi PSCs10,11,12 hna i riantuan ning le riantuan ning fekmi kha a hrawh.
Nai ah tuahmi hlathlainak nih a langhter ning ahcun, zeihmanh doping um loin a thiangmi single crystal FAPbI3 cu a ttha tukmi crystallinity le a tlawmmi tlamtlinlonak ruangah a ttha tukmi dirhmun a ngei13,14. Cucaah, FAPbI3 tam deuh a tthawnnak karhternak in tlamtlinlonak zorternak cu ttha tein le fek tein a ummi PSCs2,15 hmuh khawhnak ding caah a biapi mi strategy a si. Sihmanhsehlaw, FAPbI3 PSC riantuan lio ah, duhlonak a senmi hexagonal non-perovskite δ phase tiang rawhnak cu a cang kho rih16. Mah thil kalning cu a tlangpi in a rawkmi hmun tampi a um caah ti, lumnak le ceunak nih a tuar khawh deuhmi vawlei cung le rawl kung ramri ah aa thawk tawn17. Cucaah, FAPbI318 i a senmi tthennak kha fek tein chiah khawhnak dingah a cunglei/rawl hnah thlennak a herh. A tlawmmi perovskites, acid-base Lewis molecules, le ammonium halide salts luhternak telh in tlamtlin lonak thlennak strategy tampi nih formamidine PSCs19,20,21,22 ah tthanchonak nganpi an tuah. Nihin tiangah, hlathlainak vialte nih solar cells chung i carrier recombination, diffusion length le band structure tibantuk optoelectronic thilri hna hngalh khawhnak ah tlamtlinlonak phunphun hna an riantuannak kha an zoh dih cang22,23,24. Tahchunhnak ah, density functional theory (DFT) cu tlamtlin lonak phunphun i sernak thazaang le tlaih khawhnak thazaang tlukruannak kha theory lei in chimchungnak caah hman a si, cucu hman khawhmi passivation suaisamnak lamhruainak caah tampi hman a si20,25,26. A tlamtlin lonak a zor tikah, thilri a fekmi a ttha deuh tawn. Sihmanhsehlaw, formamidine PSCs ah, a phunphun in tlamtlin lonak nih a tthawnnak le ceunak thilri hna cungah huham a ngeih ning cu aa dang dih awk a si. Kan theih khawh tawk ahcun, zeitindah tlamtlinlonak nih cubic in hexagonal (α-δ) thlennak a chuahter timi hrampi hngalhthiamnak le α-FAPbI3 perovskite dirhmun fek tein um khawhnak ah a cunglei thlennak nih a ttuanvo a ngeihnak kong cu a ttha tein hngalhthiam a si rih lo.
Hika ah, FAPbI3 perovskite a rawhnak lam kha a senmi α-phase in a senmi δ-phase tiang le DFT hmangin α-in-δ-phase thlennak thazaang khamnak cung i tlamtlinlonak phunphun nih a chuahpimi huham kha kan langhter. I vacancies, cu film sernak le thilri hmannak lio ah fawi tein a chuakmi hna cu α-δ phase thlennak a thawk kho bik lai tiah an chimchung. Cucaah, FAPbI3 cung ah ti ah a cawh kho lomi le chemical in a fekmi a tlawmmi lead oxalate (PbC2O4) kha in situ reaction in kan luhter. Lead oxalate surface (LOS) nih I vacancies sernak kha a kham i lum, ceunak le electric field nih a forh tikah I ions i ṭhialnak kha a kham. A chuakmi LOS nih cun interfacial nonradiative recombination kha a zorter ngaingai i FAPbI3 PSC tthatnak kha 25.39% tiang a tthanchoter (24.92% tiang fehtermi). A tthut lomi LOS thilri nih 1.5 G radiation tlukruannak thli rit (AM) ah suimilam 550 leng a sang bik thazaang hmun (MPP) ah rian a ttuan hnu ah a hramthawk tthatnak 92% a tlaih peng.
FAPbI3 perovskite α phase in δ phase ah thlennak caah a rawkralnak lam hmuh khawhnak ding caah ab initio tuaktannak kan tuah hmasa. A tlingmi tthen thlennak kalning in, FAPbI3 i cubic α-phase chung i a tthen thum a tthenmi [PbI6] octahedron in FAPbI3 i a tthen ruk δ-phase chung i a tthen khat a tthenmi [PbI6] octahedron ah thlennak cu hmuh khawh a si ti kha hmuh a si. tthennak 9. Pb-I nih a hmasa bik kehlan (Int-1) ah pehtlaihnak a ser, cun a thazaang khamnak cu 0.62 eV/cell a phan, hmanthlak 1a ah hmuh khawh a si. Octahedron cu [0\(\bar{1}\)1] lei ah thlen a si tikah, hexagonal short chain cu 1×1 in 1×3, 1×4 tiang a kau i a donghnak ah δ phase ah a lut. Lam dihlak i a sining cu (011)α//(001)δ + [100]α//[100]δ a si. Thazaang phawtzamhnak hmanthlak chungin, a tanglei tthanchonak ah FAPbI3 δ tthennak nucleation hnu ah, thazaang khamnak cu α tthennak thlennak nakin a niam deuh ti kha hmuh khawh a si, cucu tthennak thlennak cu a rang deuh lai tinak a si. Fiang tein, α-phase rawhnak kha kham kan duh ahcun, phase thlennak uknak ah a hmasa bik kehlan cu a biapi tuk.
a kehlei in orhlei ah thlennak kalning – a senmi FAPbI3 tthen (α-phase), a hmasa bik Pb-I pehtlaihnak tthennak (Int-1) le a hnu ah Pb-I pehtlaihnak tthennak (Int-2, Int -3 le Int -4) le a senmi tthen FAPbI3 (delta tthen). b FAPbI3 i α in δ tiang thlennak caah thazaang dawnkhantu hna cu a phunphun intrinsic point tlamtlinlonak cungah hram bunh in an si. Dotted line nih a ttha bikmi crystal (0.62 eV) thazaang khamnak kha a langhter. c Lead perovskite cunglei ah a hrampi hmun tlamtlinlonak sernak thazaang. Abscissa axis cu α-δ thlennak thazaang khamnak a si, cun ordinate axis cu tlamtlin lonak sernak thazaang a si. A sen, a sen le a hring in a ummi hna cu phun I (niam EB-sang FE), phun II (sang FE) le phun III (niam EB-niam FE) an si. d Control ah FAPbI3 i tlamtlinlonak VI le LOS sernak thazaang. e FAPbI3 control le LOS ah ion tthialnak caah dawnkhantu I. f – I ions (orange spheres) le gLOS FAPbI3 (gray, lead; violet (orange), iodine (mobile iodine)) gf control (orhlei: cunglei zohnak; orhlei: cross section, brown) ah an i ṭhialnak hmanthlak langhternak; carbon; a senmi – nitrogen; sen – oxygen; a senmi – hydrogen). Hramthawknak data cu hrampi data file phun in pek a si.
Cu hnu ah a biapi mi thil ah ruahmi a phunphun intrinsic point defects (PbFA, IFA, PbI, le IPb antisite occupancy; Pbi le Ii interstitial atoms; le VI, VFA, le VPb vacancies) hna i an thlennak kha ningcang tein kan hlathlai. atom le thazaang tlukruannak tthencheunak a chuahtertu hna cu hmanthlak 1b le Supplementary Table 1 ah langhter an si. Hngalh a nuammi cu, tlamtlinlonak vialte nih α-δ tthencheunak thlennak thazaang khamnak kha a zorter dih lo (Hmanthlak 1b). A tlawmmi sernak thazaang le a niam deuhmi α-δ phase thlennak thazaang khamnak a ngeimi tlamtlinlonak hna cu phase dirhmun caah a chiatnak lei ah ruah an si tiah kan zumh. A hlan ah report an rak tuah cang bantuk in, lead a tammi cunglei hna cu a tlangpi in formamidine PSC27 caah a ttha tiah ruah an si. Cucaah, lead a tammi dirhmun tangah PbI2-a dongmi (100) cunglei kha kan zoh. Vawlei cung intrinsic point tlamtlin lonak hna i tlamtlin lonak sernak thazaang cu Figure 1c le Supplementary Table 1 ah hmuh khawh a si. Thazaang khamnak (EB) le phase thlennak sernak thazaang (FE) cungah hram bunh in, hi tlamtlin lonak hna hi phun thum ah ṭhen an si. Type I (EB tlawm-FE sang): IPb, VFA le VPb nih phase thlennak caah thazaang khamnak kha tampi in an zorter ko nain, annih cu sernak thazaang sang an ngei. Cucaah, hi bantuk tlamtlinlonak hna nih hin an chuah tlawm tuk caah phase thlennak ah hnahnawhnak tlawmte lawng an ngei tiah kan zumh. Type II (high EB): A tthanchomi α-δ thlennak thazaang khamnak ruangah, anti-site tlamtlinlonak PbI, IFA le PbFA nih α-FAPbI3 perovskite dirhmun fekmi kha a hrawh lo. Type III (niam EB-niam FE): VI, Ii le Pbi tlamtlinlonak hna cu a tlawm deuhmi sernak thazaang nih a senmi rawhnak a chuahter khawh. A hlei in a niam bikmi FE le EB VI zoh tikah, a ttha bikmi strategy cu I rian tlawmter hi a si tiah kan zumh.
VI zorternak caah, FAPbI3 cunglei tthatternak caah PbC2O4 a tlawmmi tthen pakhat kan ser. Phenylethylammonium iodide (PEAI) le n-octylammonium iodide (OAI) tibantuk organic halide chiti passivators he tahchunh ahcun, PbC2O4, a kal khomi halogen ions aa tel lomi cu, chemical lei in a fekmi, ti ah a cawh kho lomi, le thazaang pek tikah fawi tein a rawk. Perovskite i a cunglei ti le electric field ttha tein a dirter. Ti chung i PbC2O4 a cawh khawhnak cu 0.00065 g/L lawng a si, cucu PbSO428 nak hmanh in a niam deuh. A biapi deuhmi cu, LOS a tlawmmi le aa khatmi tthen pawl cu in situ thlennak hmangin perovskite zukcawl cungah nem tein timhtuah khawh a si (a tanglei ah zoh). Supplementary Figure 1 ah langhtermi bantukin FAPbI3 le PbC2O4 karlak i pehtlaihnak DFT zohchunhnak kan tuah. Supplementary Table 2 nih LOS thun hnu ah tlamtlin lonak sernak thazaang kha a langhter. LOS nih VI tlamtlin lonak sernak thazaang kha 0.69-1.53 ​​eV lawng a karhter lo (Figure 1d), cun I a tthawnnak le a chuahnak cunglei ah a karhter (Figure 1e). A hmasa bik ah, I ions cu perovskite cunglei ah an i thial, VI ions cu 0.61 eV thazaang khamnak he lattice dirhmun ah an chiah hna. LOS luhternak hnu ah, steric dawnkhantu nih a chuahpimi thil ruangah, I ions tthialnak caah riantuannak thazaang cu a karh. 1.28 eV. Perovskite cunglei in a chuakmi I ions pawl an i thial lio ah, VOC chung i thazaang khamnak zong cu control sample nakin a sang deuh (Fig. 1e). Control le LOS FAPbI3 ah I ion tthialnak lam hna i hmanthlak suaimi hna cu hmanthlak 1 f le g ah langhter an si. Simulation hmuhmi nih a langhter mi cu LOS nih VI tlamtlin lonak le I a tthawnnak a kham khawh, cucaah α in δ thlennak a kham khawh.
Oxalic acid le FAPbI3 perovskite karlak i pehtlaihnak cu hneksak a si. Oxalic acid le FAPbI3 cawhmi cawhmi hna cawh hnu ah, Supplementary Figure 2 ah hmuh khawhmi bantuk in, a rangmi tlawmpal a chuak. Powder chuahmi cu X-ray diffraction (XRD) (Supplementary Figure 3) le Fourier transform spectroscopy (FT) (Supplementary Figure 4) hmangin PbC2O4 thilri thianghlim a si tiah hngalh khawh a si. Oxalic acid cu isopropyl alcohol (IPA) ah khan chung lumnak ah 18 mg/mL hrawng a thlet khawhnak he a ttha tukmi a si ti kan hmuh, cu cu Supplementary Figure 5 ah hmuh khawh a si. Mah nih hin a hnu riantuannak a fawiter, zeicahtiah IPA cu a tlangpi in passivation solvent a si caah caan tawite hnu ah perovskite layer kha a hrawh lo. Cucaah, perovskite film cu oxalic acid cawhmi ah hnim in asiloah perovskite cungah oxalic acid cawhmi kha spin-coating tuahnak thawngin, a tanglei chemical equation ningin perovskite film cunglei ah a tlawmmi le a ritmi PbC2O4 kha rang tein hmuh khawh a si: H2C2O4 + FAPI3 = PbI3 + FAIO FAI cu IPA ah a cawh khawh i cucaah rawlchuan lio ah a chuak kho. LOS a thuhnak cu lehrulhnak caan le a hramthawknak tlawmtam in uk khawh a si.
Control le LOS perovskite zukcawl hna i scanning electron microscopy (SEM) hmanthlak hna cu hmanthlak 2a,b ah langhter an si. A phichuak nih a langhter mi cu perovskite cunglei sining cu ttha tein a kilven, cun a tlawmmi thil hme tete tampi cu rawl kung cunglei ah an chiah, cu nih cun in-situ reaction in a chuakmi PbC2O4 tthen kha a aiawh awk a si. LOS perovskite film cu a tlawmpal a nem deuhmi a cunglei (Supplementary Figure 6) le control film he tahchunh tikah ti pehtlaihnak angle a ngan deuh (Supplementary Figure 7). Thilri cunglei tthen thleidan khawhnak dingah a ttha ngaimi a tthencheunak electron microscopy (HR-TEM) kha hman a si. Control film (Fig. 2c) he tahchunh ahcun, LOS perovskite (Fig. 2d) cung ah 10 nm hrawng a thuhnak aa khatmi le a tlawmmi a tlawmmi tthen cu fiang tein hmuh khawh a si. PbC2O4 le FAPbI3 karlak i pehtlaihnak zohfelnak caah high-angle annular dark-field scanning electron microscopy (HAADF-STEM) hmangin, FAPbI3 i a ttha lomi hmun le PbC2O4 i a ttha lomi hmun hna an um ti kha fiang tein hmuh khawh a si (Supplementary Figure 8). Oxalic acid thlopnak hnu ah perovskite a cunglei sining cu X-ray photoelectron spectroscopy (XPS) tahnak in langhter a si, hmanthlak 2e-g ah hmuh khawh a si. Figure 2e ah, C 1s 284.8 eV le 288.5 eV hrawng a sangbik hna cu CC le FA signal tthencheunak ah aa telmi an si. Control membrane he tahchunh ahcun, LOS membrane nih 289.2 eV ah a sangbik a langhter, C2O42- ruangah a si. LOS perovskite i O 1s spectrum nih 531.7 eV, 532.5 eV, le 533.4 eV ah chemical in aa dangmi O 1s sangbik pathum a langhter, cucu deprotonated COO, C=O of intact oxalate groups 30 le OH component O atoms he aa tlak (Fig. 2 ). )). Control sample caah, O 1s peak hmete lawng hmuh a si, cucu a cunglei ah oxygen chemisorbed ruangah a si kho. Pb 4f7/2 le Pb 4f5/2 i control membrane sining hna cu 138.4 eV le 143.3 eV ah an um. LOS perovskite nih Pb peak 0.15 eV hrawng a sang deuhmi pehtlaihnak thazaang lei ah aa thlennak a langhter ti kan hmuh, cucu C2O42- le Pb atoms karlak ah a fek deuhmi pehtlaihnak a langhter (Fig. 2g).
a control SEM hmanthlak le b LOS perovskite zukcawl, cunglei zohnak. c Control le d LOS perovskite zukcawl hna i a ttha ngaimi cross-sectional transmission electron microscopy (HR-TEM). e C 1s, f O 1s le g Pb 4f perovskite zukcawl hna i a sangmi XPS. Hramthawknak data cu hrampi data file phun in pek a si.
DFT hmuhmi ning in, VI tlamtlin lonak le I tthialnak nih α in δ ah fawi tein thlennak a chuahter tiah theory in chimchung a si. A hlan thawngpang nih a langhter ning ahcun I2 cu PC-based perovskite zukcawl chungin ceunak le lumnak hnahnawhnak ah chiah hnu ah hmanthlak chung i hnimh lio ah rang tukin a chuak31,32,33. Perovskite α-phase cung i lead oxalate nih a fehter khawhnak fehternak caah, control le LOS perovskite zukcawl pawl kha toluene aa telmi a fiangmi thlalang thawl chungah kan hnim hna i, cu hnuah 24 h chung ni ceunak 1 in kan ceuter hna. Ultraviolet le hmuh khawhmi ceunak (UV-Vis) laknak kha kan tah. ) toluene cawhmi, hmanthlak 3a ah hmuh khawhmi bantuk in. Control sample he tahchunh tikah, LOS-perovskite kongah I2 laknak thazaang a niam deuh ngai ti hmuh a si, cu nih cun compact LOS nih ceunak chung i hnimhnak chungah perovskite film chungin I2 chuahternak kha a kham khawh ti a langhter. A tar cangmi uknak le LOS perovskite zukcawl hmanthlak hna cu hmanthlak 3b le c chung i a ummi ah langhter an si. LOS perovskite cu a sen rih, control film tam deuh cu a sen cang. Ti chung i a ummi film i UV-hmuh khawhmi laknak spectra cu Figs ah hmuh khawh a si. 3b, c. Control film chung i α he aa tlakmi laknak cu fiang tein a zor ti kha kan hmuh. X-ray tahnak cu crystal sining thlennak cazin ttialnak caah tuah a si. Suimilam 24 chung ceunak hnu ah, control perovskite nih a tthawngmi a senmi δ-phase signal (11.8°) a langhter, cu lio ah LOS perovskite nih cun a senmi phase ttha a ngeih peng rih (Figure 3d).
Toluene cawhnuk hna i UV-hmuh khawhmi laknak spectra hna cu control film le LOS film cu ni ceunak 1 tangah suimilam 24 chung an hnim hna. A chunglei nih aa tlukmi toluene ah film pakhat cio an hnim mi thawl pakhat a langhter. b UV-Vis laknak spectra control film le c LOS film 1 ni ceunak tangah 24 h hnim hlan le hnu ah. A chunglei nih hneksaknak zukcawl hmanthlak a langhter. d 24 h hmuh hlan le hnu ah control le LOS zukcawl hna i X-ray thlennak sining hna. Suimilam 24 chung langhter hnu ah control film e le film f LOS SEM hmanthlak hna. Hramthawknak data cu hrampi data file phun in pek a si.
Suimilam 24 chung ceunak hnu ah perovskite film i a hmete thlennak zoh khawhnak ding caah scanning electron microscopy (SEM) tahnak kan tuah, hmanthlak 3e,f ah hmuh khawh a si. Control film ah, rawl kung ngan pipi cu an hrawh hna i hri hmete ah an i cang, cucu δ-phase thilchuak FAPbI3 (Fig. 3e) i a muisam he aa tlak. LOS zukcawl caah, perovskite hnah cu a ttha mi dirhmun ah an um peng (Figure 3f). A phichuak nih a fehtermi cu I tlaunak nih a senmi in a senmi ah thlennak a chuahter, cu lio ah PbC2O4 nih a senmi kha a dirter, I tlaunak kha a kham. A cunglei ah a ummi hmunhma tlawmtam cu rawl kung tam deuh nakin a tam deuh caah,34 hi tthennak hi rawl kung cunglei ah a cang kho deuh. caankhatte ah iodine a chuahter i VI a ser. DFT nih a chimchung bantukin, LOS nih VI tlamtlin lonak sernak kha a kham khawh i perovskite cunglei ah I ions i ṭhialnak kha a kham khawh.
Cun, PbC2O4 tthen nih thli thli chung i perovskite zukcawl hna i ti a doh khawhnak (a tlukmi ti lum 30-60%) cung ah a chuahpimi thil kha hlathlainak tuah a si. Supplementary Figure 9 ah langhter bantuk in, LOS perovskite cu ni 12 hnu zongah a sen rih, control film cu a sen. XRD tahnak ah, control film nih FAPbI3 δ phase he aa tlakmi 11.8° ah a tthawngmi sangbik a langhter, cu lio ah LOS perovskite nih a senmi α phase kha ttha tein a tlaih (Supplementary Figure 10).
Perovskite cunglei ah lead oxalate nih a chuahtermi thil sining hlathlainak caah a fekmi ceunak (PL) le caan thlenmi ceunak (TRPL) kha hman a si. Fig. Figure 4a ah LOS film nih PL thazaang a karhter ti a langhter. PL mapping hmanthlak ah, 10 × 10 μm2 hmun dihlak cung i LOS film a tthawnnak cu control film (Supplementary Figure 11) nakin a sang deuh, cucu PbC2O4 nih perovskite film kha aa khat tein a thlen ti a langhter. Carrier nunchung cu TRPL rawhnak kha exponential function pakhat lawng he naihternak in tuak a si (Fig. 4b). LOS film i a phurtu nunchung cu 5.2 μs a si, cucu 0.9 μs a phurtu nunchung control film nakin a sau deuh, cu nih cun a cunglei nonradiative recombination a zorter ti a langhter.
Glass substrates cung i perovskite zukcawl hna i caan karlak PL i a fekmi PL le b-spectra. c SP curve of the device (FTO/TiO2/SnO2/perovskite/spiro-OMeTAD/Au). d EQE spectrum le Jsc EQE spectrum cu a ttha bikmi thilri in fonhmi an si. d Voc hmanthlak cung i perovskite thilri ceunak thazaang aa hngatchannak. f ITO/PEDOT:PSS/perovskite/PCBM/Au thianhnak khur thilri hmangin a tlangpi in MKRC hlathlainak. VTFL cu a tam bik tlaih khawhnak voltage a si. Hi data chungin tlaihnak tlawmtam (Nt) kha kan tuak. Hramthawknak data cu hrampi data file phun in pek a si.
Thilri riantuan ning cung ah lead oxalate tthen nih a chuahpimi thil sining hlathlainak caah, hlanlio FTO/TiO2/SnO2/perovskite/spiro-OMeTAD/Au pehtlaihnak sining kha hman a si. Formidine chloride (FACl) cu methylamine hydrochloride (MACl) si loin perovskite precursor ah chapmi ah kan hman i thilri riantuan ning ttha deuh hmuh khawhnak ding caah kan hman, zeicahtiah FACl nih crystal tthatnak a pek khawh i FAPbI335 band gap a hrial khawh (a tlingmi tahchunhnak caah Supplementary Figures 1 le 2 zoh). ). 12-14). IPA cu antisolvent ah thim a si, zeicahtiah diethyl ether (DE) asiloah chlorobenzene (CB)36 (Supplementary Figures 15 le 16) he tahchunh tikah perovskite zukcawl ah a ttha deuhmi crystal quality le duh deuhmi dirhmun a pek caah a si. PbC2O4 a thuhnak cu oxalic acid tlawmtam (Supplementary Figure 17) remhnak in tlamtlin lonak thlennak le charge kalnak kha ttha tein aa tluk khawh nakhnga ralring tein remh a si. A ttha bikmi control le LOS thilri hna i a tthencheunak SEM hmanthlak hna cu Supplementary Figure 18 ah langhter an si. Control le LOS thilri hna caah a tlangpi in current density (CD) curves cu Figure 4c ah langhter an si, cun chuahmi parameters hna cu Supplementary Table 3 ah pek an si. A sangbik thazaang thlennak tthatnak (PCE) control cells (234%, 24%, Jc.). 25.75 mA cm-2 (25.74 mA cm-2), Voc 1.16 V (1.16 V) le hnulei (hmailei) zohfelnak. A tlingmi (FF) cu 78.40% (76.69%) a si. A tam bik PCE LOS PSC cu 25.39% (24.79%) a si, Jsc cu 25.77 mA cm-2 a si, Voc cu 1.18 V a si, FF cu hnulei (hmailei Scan to) in 83.50% (81.52%) a si. LOS thilri nih zumhawktlakmi pathumnak-party photovoltaic laboratory ah 24.92% fehtermi photovoltaic riantuan khawhnak a hmuh (Supplementary Figure 19). Lenglei quantum tthatnak (EQE) nih 24.90 mA cm-2 (control) le 25.18 mA cm-2 (LOS PSC) fonhmi Jsc a pek, cucu standard AM 1.5 G spectrum (Fig. .4d) ah tahmi Jsc he aa tlak ngai. ) . Control le LOS PSCs caah tahmi PCEs hna i zatlang tthencheunak cu Supplementary Figure 20 ah hmuh khawh a si.
Figure 4e ah hmuh khawhmi bantuk in, Voc le ceunak thazaang karlak pehtlaihnak cu PbC2O4 nih trap-assisted surface recombination cung ah a chuahpimi thil sining hlathlainak caah tuak a si. LOS thilri caah aa tlakmi hri a tluknak cu 1.16 kBT/sq a si, cucu control thilri caah aa tlakmi hri a tluknak (1.31 kBT/sq) nakin a niam deuh, cu nih cun LOS cu decoys nih a cunglei fonh ṭhannak khamnak caah a ṭha ti kha a fehter. Hmanthlak ah langhtermi bantukin hole thilri (ITO/PEDOT:PSS/perovskite/spiro-OMeTAD/Au) i a muimi IV sining tahnak in perovskite zukcawl i a tlamtlin lonak kha zat in tahnak caah space charge current limiting (SCLC) thiamnak kha kan hman. 4f Langhter. Trap density cu Nt = 2ε0εVTFL/eL2 timi formula in tuak a si, cuka ah ε cu perovskite film i aa pehtlaimi dielectric constant a si, ε0 cu vacuum i dielectric constant a si, VTFL cu trap khah khawhnak ding caah rikhiahnak voltage a si, e cu charge a si, L cu perovskite film a thuhnak a si (6 nom). VOC thilri i a tlamtlin lonak tlawmtam cu 1.450 × 1015 cm–3 ah tuak a si, cucu control thilri i tlamtlinlonak tlawmtam nakin a niam deuh, cucu 1.795 × 1015 cm–3 a si.
A tthen lomi thilri cu nitrogen tangah chun ceunak tangah a sangbik thazaang (MPP) ah caan sau riantuan khawhnak a fekmi zohfel awkah hneksaknak tuah a si (Figure 5a). Suimilam 550 hnu zongah, LOS thilri nih a ttha bik 92% a tlaih peng rih, cu lio ah control thilri riantuan ning cu a hramthawk riantuan ning 60% tiang a tla. Thilri hlun chung i thilri pawl an i phawtzamhnak cu a zuang caan a pahnihnak ion mass spectrometry (ToF-SIMS) (Fig. 5b, c) in tah a si. A cunglei sui uknak hmun ah iodine tampi a khonmi hmuh khawh a si. Inert gas kilvennak dirhmun nih pawngkam rawhralnak a chuahter khomi thil hna cu ti le oxygen tibantuk kha a telh lo, cu nih cun chunglei thilri (cucu, ion tthialnak) nih a chuahpi tiah a langhter. ToF-SIMS hmuhmi ning in, I- le AuI2- ions cu Au electrode ah hmuh an si, perovskite in Au ah I a karhnak a langhter. Control thilri chung i I- le AuI2- ions hna i an signal thazaang cu VOC sample nakin a let 10 hrawng a sang deuh. A hlan report nih a langhter ning ahcun ion luh khawhnak nih spiro-OMeTAD i a khur hruainak ah rang tukin a zorter khawh i a cunglei electrode tthen chemical rawhnak a chuahter khawh, cu nih cun thilri chung i a ummi pehtlaihnak kha a hrawh khawh37,38. Au electrode cu lak a si i spiro-OMeTAD tthen cu chlorobenzene cawhnuk in a tanglei in thianh a si. Cu hnu ah zukcawl cu ramlak thil cangmi X-ray thlennak (GIXRD) (Figure 5d) hmangin kan langhter. A phichuak nih a langhter mi cu control film nih 11.8° ah a fiangmi thlennak sangbik a ngei, cu lio ah LOS sample ah thlennak sangbik thar a lang lo. A phichuak nih a langhter mi cu control film chung i I ions tampi a tlau tikah δ phase chuahter a si, LOS film ahcun hi thil kalning hi fiang tein a kham.
nitrogen thli le UV filter tel loin ni ceunak 1 chung i khar lomi thilri pakhat suimilam 575 chung pehzulh tein MPP zulhnak. LOS MPP uknak thilri le tarnak thilri ah b I- le c AuI2- ions ToF-SIMS phawtzamhnak. A sen, a hring le a senmi hna cu Au, Spiro-OMeTAD le perovskite he aa tlak. d MPP hneksaknak hnu ah perovskite film GIXRD. Hramthawknak data cu hrampi data file phun in pek a si.
PbC2O4 nih ion tthialnak a kham khawh ti fehternak caah lum le kih aa hngatmi hruainak kha tah a si (Supplementary Figure 21). Ion tthialnak thazaang (Ea) cu FAPbI3 film i a thlen khawhnak (σ) kha lumternak (T) aa dangmi tahnak in le Nernst-Einstein pehtlaihnak hmangin hngalh khawh a si: σT = σ0exp(−Ea/kBT), cuka ah σ0 cu aa thleng lomi a si, kB cu Boltnman aa thleng lomi a si. Ea man cu ln(σT) le 1/T tluknak in kan hmuh, cucu control caah 0.283 eV le LOS thilri caah 0.419 eV a si.
A tawinak in, FAPbI3 perovskite rawhnak lam le α-δ thlennak thazaang khamnak cung i tlamtlinlonak phunphun nih a chuahpimi thlennak hngalh khawhnak ding caah ruahnak cheuhnak phunglam kan pek. Hi tlamtlin lonak hna lakah, VI tlamtlin lonak hna cu α in δ ah fawi tein thlennak a chuahter lai tiah theory in an chimchung. Ti ah a cawh kho lomi le chemical in a fekmi a tlawmmi PbC2O4 tthen cu I vacancies sernak le I ions i tthialnak khamnak in FAPbI3 α-phase fekternak caah luhter a si. Hi strategy nih hin interfacial non-radiative recombination kha tampi in a zorter, solar cell tthatnak kha 25.39% tiang a karhter, cun riantuan ning fek tein a tthanchoter. Kan hmuhmi nih a ttha lomi le a fekmi formamidine PSCs hmuh khawhnak ding caah lamhruainak a kan pek i, a tlamtlin lonak nih a chuahtermi α in δ tiang thlennak kha a kham.
Titanium(IV) isopropoxide (TTIP, 99.999%) cu Sigma-Aldrich in cawk a si. Hydrochloric acid (HCl, 35.0–37.0%) le ethanol (anhydrous) cu Guangzhou Chemical Industry in an cawk. SnO2 (15 wt% tin(IV) oxide colloidal dispersion) cu Alfa Aesar in cawk a si. Lead(II) iodide (PbI2, 99.99%) cu TCI Shanghai (China) in cawkmi a si. Formamidine iodide (FAI, ≥99.5%), formamidine chloride (FACl, ≥99.5%), methylamine hydrochloride (MACl, ≥99.5%), 2,2′,7,7′-tetrakis-(N , N-di-p) )-methoxyaniline)-spirofluore99′ (Spiro-OMeTAD, ≥99.5%), lithium bis(trifluoromethane)sulfonylimide (Li-TFSI, 99.95%), 4-tert -butylpyridine (tBP, 96%) cu Xi'an Polymer Light Technology Company (China) in cawk a si. N,N-dimethylformamide (DMF, 99.8%), dimethyl sulfoxide (DMSO, 99.9%), isopropyl alcohol (IPA, 99.8%), chlorobenzene (CB, 99.8%), acetonitrile (ACN). Sigma-Aldrich in cawkmi a si. Oxalic acid (H2C2O4, 99.9%) cu Macklin sin in cawk a si. Chemical vialte cu remhnak dang um loin an hmuhmi ning tein hman an si.
ITO asiloah FTO substrates (1.5 × 1.5 cm2) cu thil sawhnak sii, acetone le ethanol in minutes 10 chung ultrasonically in an thianh hna, cun nitrogen stream tangah an roter hna. TiO2 khamnak tthen cu FTO substrate cung ah titanium diisopropoxybis(acetylacetonate) ethanol (1/25, v/v) ah 500 °C ah 60 min chung chiahmi cawhmi hmangin chiah a si. SnO2 colloidal dispersion cu 1:5 tluk in deionized ti he cawh a si. Minute 20 chung UV ozone in thlopmi a thiangmi vawlei cung ah, SnO2 nanoparticles a tlawmmi cu 4000 rpm ah second 30 chung chiah a si i minutes 30 chung 150 °C ah lumter hmasa a si. Perovskite precursor cawhnuk caah, 275.2 mg FAI, 737.6 mg PbI2 le FACl (20 mol%) cu DMF/DMSO (15/1) cawhmi cawhnuk ah an cawh. Perovskite tthen cu UV-ozone-thlopmi SnO2 tthen cung ah perovskite precursor 40 μL kha 5000 rpm in pawngkam thli ah 25 s chung centrifuge in timhtuahnak a si. A donghnak caan hnu second 5 ah, 50 μL MACl IPA cawhnuk (4 mg/mL) cu cawhnuk dohnak caah a tanglei ah rang tein an thlak. Cun, a thar in timhtuah mi zukcawl pawl cu 150°C ah 20 min chung an hnim hna i cu hnu ah 100°C ah 10 min chung an hnim hna. Perovskite film cu khaan lum tiang a lumter hnu ah, H2C2O4 cawhmi (1, 2, 4 mg 1 mL IPA ah cawhmi) cu 4000 rpm ah 30 s chung perovskite cunglei kha a lumter lo. Spiro-OMeTAD 72.3 mg spiro-OMeTAD, 1 ml CB, 27 μl tBP le 17.5 μl Li-TFSI (1 ml acetonitrile ah 520 mg) cawh in timhtuahnak a ngeimi spiro-OMeTAD cawhmi cu 4000 rpm in 033 s chung ah film cungah spin-coat a si. A donghnak ah, 100 nm a thukmi Au tthen cu 0.05 nm/s (0~1 nm), 0.1 nm/s (2~15 nm) le 0.5 nm/s (16~100 nm) tluk in vacuum ah a thlet. ).
Perovskite solar cells hna i SC riantuan ning cu Keithley 2400 meter tangah solar simulator ceunak (SS-X50) hmangin ceunak thazaang 100 mW/cm2 ah tah a si i calibrated standard silicon solar cells hmangin fehter a si. A dang tein langhter a si lo ahcun, SP curves cu nitrogen in a khatmi kutdonghrolh bawm chungah khaan lum (~25°C) ah hmailei le hnulei zohfelnak (voltage step 20 mV, delay time 10 ms) in tah an si. Tahmi PSC caah 0.067 cm2 a ttha mi hmunhma hngalh khawhnak dingah muisam hmaikhuh hman a si. EQE tahnak cu PVE300-IVT210 system (Industrial Vision Technology(s) Pte Ltd) hmangin pawngkam thli ah tuah a si i thilri cungah rong pakhat lawng a ummi ceunak he tuah a si. Thilri fek tein um khawhnak caah, aa khumh lomi ni ceunak cell pawl hneksaknak cu UV filter tel loin 100 mW/cm2 tthawnnak ah nitrogen kutdonghrolh kuang chungah tuah a si. ToF-SIMS cu PHI nanoTOFII vanlawng caan SIMS hmangin tah a si. A thuknak langhternak cu 400×400 μm a kauhnak 4 kV Ar ion meithal hmangin hmuh a si.
X-ray photoelectron spectroscopy (XPS) tahnak cu Thermo-VG Scientific system (ESCALAB 250) ah monochromatized Al Kα (XPS mode caah) hmangin 5.0 × 10–7 Pa pressure ah tuah a si. Scanning electron microscopy (SEM) cu JESM-JOL-J63030 system ah tuah a si. Perovskite zukcawl hna i an cunglei sining le a rawkralnak cu atomic force microscopy (AFM) (Bruker Dimension FastScan) hmangin tah a si. STEM le HAADF-STEM cu FEI Titan Themis STEM ah tuah a si. UV-Vis laknak spectra cu UV-3600Plus (Shimadzu Corporation) hmangin tah a si. Space charge limiting current (SCLC) cu Keithley 2400 meter ah an khumh. FLS 1000 ceunak spectrometer hmangin carrier nunchung rawhnak i a fekmi ceunak (PL) le caan-thlennak ceunak (TRPL) kha tah a si. PL mapping hmanthlak pawl cu Horiba LabRam Raman system HR Evolution hmangin tah an si. Fourier thlennak infrared spectroscopy (FTIR) cu Thermo-Fisher Nicolet NXR 9650 system hmangin tuah a si.
Hi rian ah, α-phase in δ-phase tiang thlennak lam hlathlainak caah SSW lam laknak phunglam kha kan hman. SSW phunglam ah, a chuak khomi thazaang cunglei cawlcanghnak cu random soft mode (a pahnihnak chuahkehnak) lamhruainak nih a khiah, cu nih cun a chuak khomi thazaang cunglei kha a tlingmi le a dikthliar in hlathlainak a tuah khawh. Hi rian ah, lam zohchunhnak cu 72-atom supercell ah tuah a si, cun DFT level ah a hramthawk/a donghnak dirhmun (IS/FS) pahnih 100 leng an lak. IS/FS pairwise data set cung ah hram bunh in, a hramthawk dirhmun le a donghnak dirhmun aa pehtlaimi lam cu atom karlak i pehtlaihnak in hngalh khawh a si, cun aa thleng khomi unit cunglei ah lam pahnih in kalnak kha thlennak dirhmun lam kha tluang tein hngalh khawhnak caah hman a si. (VK-DESV). Thlennak dirhmun kawl hnu ah, a niam bik khamnak a ngeimi lam cu thazaang khamnak hna kha tthen in hngalh khawh a si.
DFT tuaktannak vialte cu VASP (version 5.3.5) hmangin tuah a si, cuka ahcun C, N, H, Pb, le I atom hna i electron-ion pehtlaihnak cu projected amplified wave (PAW) scheme in a langhter. I thlennak pehtlaihnak riantuannak cu Perdue-Burke-Ernzerhoff parametrization ah a tlangpi in gradient naihternak in a langhter. Vanlawng thlichia caah thazaang ri cu 400 eV ah chiah a si. Monkhorst-Pack k-point grid cu (2 × 2 × 1) a si. Thilri vialte caah, lattice le atomic dirhmun hna cu a sangbik hnahnawhnak tthencheunak cu 0.1 GPa tang le a sangbik thazaang tthencheunak 0.02 eV/Å tang a si hlan tiang tling tein an remh. A cunglei model ah, FAPbI3 cunglei cu tthen 4 a ngei, a tanglei tthen nih FAPbI3 pum a zohchunhmi a fekmi atom a ngei, cun a cunglei tthen pathum cu tthaternak tuah lio ah zalong tein an i chawk kho. PbC2O4 tthen cu 1 ML a thuk i FAPbI3 I-terminal cunglei ah a um, cuka ahcun Pb cu 1 I le 4 O he aa pehtlai.
Hlathlainak suaisamnak kong tam deuh theih na duh ahcun, hi capar he aa pehtlaimi Natural Portfolio Report Abstract kha zoh.
Hi hlathlainak chung ah hmuhmi asiloah hlathlainak tuahmi data vialte cu chuahmi capar ah aa tel, cun a bawmtu thawngpang le raw data file ah aa tel. Hi hlathlainak ah langhtermi raw data cu https://doi.org/10.6084/m9.figshare.2410016440 ah hmuh khawh a si. Hi capar caah hrampi data pek a si.
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