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Wozã defect pasivation geɖe tsɔ na lead triiodide perovskite ɣe ƒe lãmenugbagbeviwo ƒe dɔwɔwɔ nanyo ɖe edzi, gake ŋusẽ si gbɔdzɔgbɔdzɔ vovovowo kpɔna ɖe α-phase ƒe liƒo dzi me mekɔ haɖe o; Le afisia la, míezã density functional theory tsɔ de dzesi formamidine lead triiodide perovskite ƒe gbegblẽmɔ tso α-phase me yi δ-phase me zi gbãtɔ eye míesrɔ̃ nu tso ŋusẽ si gbɔdzɔgbɔdzɔ vovovowo kpɔna ɖe phase ƒe tɔtrɔ ŋusẽ ƒe mɔxenu dzi. Simulasi ƒe emetsonuwo gblɔe ɖi be iodine ƒe teƒe ƒuƒluwo ate ŋu ahe gbegblẽ vɛ wu elabena woɖea ŋusẽ ƒe mɔxenu si le α-δ ƒe akpa ƒe tɔtrɔ dzi kpɔtɔna ŋutɔ eye woƒe wɔwɔme ƒe ŋusẽ le sue wu le perovskite ƒe anyigba dzi. Lead oxalate si me tsi mele o ƒe ƒuƒoƒo gã aɖe si wotsɔ de perovskite ƒe anyigba dzi xea mɔ na α-afã la ƒe gbegblẽ ŋutɔ, si xea mɔ na iodine ƒe ʋuʋu kple eƒe dzodzo. Gakpe ɖe eŋu la, mɔnu sia ɖea interfacial nonradiative recombination dzi kpɔtɔna ŋutɔ eye wòdzia ​​ɣe ƒe lãmenugbagbeviwo ƒe dɔwɔwɔ nyuie ɖe edzi va ɖoa 25.39% (woɖo kpe edzi be 24.92%). Mɔ̃ si womebla ɖe agba me o la ate ŋu alé eƒe dɔwɔwɔ nyuie 92% gbãtɔ me ɖe asi kokoko le dɔwɔwɔ le ŋusẽ si sɔ gbɔ wu me gaƒoƒo 550 le ya ƒe keklẽ si wowɔ abe 1.5 G ene te.
Perovskite ɣe ƒe lãmenugbagbeviwo (PSCs) ƒe ŋusẽ ƒe tɔtrɔ nyuie (PCE) ɖo nuŋlɔɖi kɔkɔtɔ si ŋu woɖo kpee si nye 26%1. Tso ƒe 2015 me la, egbegbe PSCwo lɔ̃a formamidine triiodide perovskite (FAPbI3) abe kekeli-xɔxlɔ̃ ƒe ƒuƒoƒo ene le eƒe dzoxɔxɔ ƒe liƒo nyuie kple bandgap si wodi wu si te ɖe Shockley-Keisser ƒe seɖoƒe si nye 2,3,4 ŋu ta. Nublanuitɔe la, FAPbI3 filmwo toa dzoxɔxɔŋusẽ me toa phase ƒe tɔtrɔ tso α phase yibɔ me yia yellow non-perovskite δ phase me le xɔme ƒe dzoxɔxɔ me5,6. Be woaxe mɔ ɖe delta ƒe akpaa ƒe wɔwɔ nu la, woto perovskite ƒe wɔwɔme vovovo siwo gɔme sese sesẽ vɛ. Mɔnu si bɔ wu be woatsɔ aɖu kuxi sia dzi enye be woatsaka FAPbI3 kple methyl ammonium (MA+), cesium (Cs+) kple bromide (Br-) ions ƒe ƒuƒoƒo7,8,9. Ke hã, hybrid perovskites kpea fu le bandgap kekeɖenu kple photoinduced phase separation, si gblẽa dɔwɔwɔ kple dɔwɔwɔ ƒe liƒo si le PSCs siwo do tso eme la me10,11,12.
Numekuku siwo wowɔ nyitsɔ laa ɖee fia be Crystal ɖeka dzadzɛ FAPbI3 si me doping aɖeke mele o la li ke nyuie ŋutɔ le eƒe kristalo nyuitɔ kple eƒe nɔnɔme madeamedzi suewo ta13,14. Eyata, nusiwo gblẽ dzi ɖeɖe kpɔtɔ to FAPbI3 gbogbotɔ ƒe kristalo dzi ɖeɖe kpɔtɔ me nye mɔnu vevi aɖe si dzi woato akpɔ PSC siwo wɔa dɔ nyuie eye woli ke2,15. Ke hã, le FAPbI3 PSC ƒe dɔwɔwɔ me la, eƒe gbegblẽ va ɖo dzogoe ade ɣi si womelɔ̃ o si menye perovskite δ o ƒe akpa si womelɔ̃ o la ate ŋu adzɔ kokoko16. Zi geɖe la, dɔa dzea egɔme tso anyigba kple nukuwo ƒe liƒo siwo dzi tsi, dzoxɔxɔ kple kekeli te ŋu dzea bɔbɔe wu le teƒe gbogbo aɖewo siwo gblẽ ta17. Eyata, anyigbadzi/nuku ƒe pasivation hiã be woatsɔ ali ke FAPbI318 ƒe akpa yibɔa. Defect pasivation mɔnu geɖewo, siwo dometɔ aɖewoe nye perovskites siwo ƒe lolome le sue, acid-base Lewis molecules, kple ammonium halide salts ƒe dodo ɖe ŋgɔ, wɔ ŋgɔyiyi gã aɖe le formamidine PSCs me19,20,21,22. Vaseɖe fifia la, numekukuwo katã kloe ku ɖe akpa si gbɔdzɔgbɔdzɔ vovovowo wɔna le optoelectronic nɔnɔmewo abe carrier recombination, diffusion length kple band structure le ɣe ƒe lãmenugbagbeviwo me nyanya me22,23,24. Le kpɔɖeŋu me, wozãa density functional theory (DFT) tsɔ gblɔa formation energies kple trapping energy levels of different defects, si wozãna geɖe tsɔ fiaa mɔ practical pasivation design20,25,26. Ne nusiwo gblẽ le eŋu ƒe xexlẽme dzi ɖe kpɔtɔ la, zi geɖe la, mɔ̃a ƒe liƒo nyona ɖe edzi. Gake le formamidine PSCwo me la, ele be mɔnu siwo dzi nɔnɔme madeamedzi vovovowo kpɔna ɖe phase ƒe liƒo kple keklẽŋusẽ ƒe nɔnɔmewo dzi la nato vovo kura. Le míaƒe sidzedze nu la, womese gɔmesese vevi si le alesi gbɔdzɔgbɔdzɔwo nana cubic yi hexagonal (α-δ) phase ƒe tɔtrɔ kple akpa si anyigbadzi passivation wɔna le α-FAPbI3 perovskite ƒe phase ƒe liƒo dzi gɔme nyuie haɖe o.
Le afisia la, míeɖe FAPbI3 perovskite ƒe gbegblẽmɔ tso ameyibɔ α-fase me yi yellow δ-fase me kple ŋusẽ si gbɔdzɔgbɔdzɔ vovovowo kpɔna ɖe ŋusẽ ƒe mɔxenu si nye α-to-δ-phase ƒe tɔtrɔ to DFT dzi la fia. Wogblɔe ɖi be I dɔ ƒuƒluwo, siwo dona bɔbɔe le film wɔwɔ kple mɔ̃a ƒe dɔwɔwɔ me la, anye esiwo adze α-δ ƒe akpa ƒe tɔtrɔ gɔme wu. Eyata míeto lead oxalate (PbC2O4) ƒe ƒuƒoƒo si me tsi mele o eye wòli ke le atikewo me la de FAPbI3 tame to dɔwɔwɔ le teƒea me. Lead oxalate surface (LOS) xea mɔ na I ƒe teƒe ƒuƒluwo ƒe wɔwɔ eye wòxea mɔ na I ions ƒe ʋuʋu ne dzoxɔxɔ, kekeli, kple elektrikŋusẽ do ŋusẽe. LOS si do tso eme ɖea interfacial nonradiative recombination dzi kpɔtɔna ŋutɔ eye wònaa FAPbI3 PSC ƒe dɔwɔwɔ nyona ɖe edzi va ɖoa 25.39% (woɖo kpe edzi be 24.92%). LOS mɔ̃ si womebla ɖe agba me o la lé eƒe dɔwɔwɔ gbãtɔ ƒe 92% me ɖe asi le dɔwɔwɔ le ŋusẽ ƒe teƒe si sɔ gbɔ wu (MPP) gaƒoƒo 550 kple edzivɔ le ya ƒe agbɔsɔsɔme si wowɔ abe ɖe wòle 1.5 G ene me vɔ megbe.
Míewɔ ab initio akɔntabubuwo gbã be míake ɖe FAPbI3 perovskite ƒe gbegblẽmɔ ŋu be wòatrɔ tso α ƒe akpaa ayi δ ƒe akpaa me. To akpa ƒe tɔtrɔ ƒe ɖoɖo si me kɔ nyuie me la, wokpɔe be tɔtrɔ tso dzogoe etɔ̃ ƒe dzogoe-mamã [PbI6] octahedron le cubic α-phase me le FAPbI3 me yi akpa ɖeka ƒe edge-mamã [PbI6] octahedron le hexagonal δ-phase of FAPbI3 me gbɔ. gbagbã 9. Pb-I wɔa kadodo le afɔɖeɖe gbãtɔ me (Int-1), eye eƒe ŋusẽ ƒe mɔxenu ɖoa 0.62 eV/lãmenugbagbevi, abe alesi woɖee fia le Nɔnɔmetata 1a me ene. Ne wotrɔ octahedron la le [0\(\bar{1}\)1] mɔ nu la, kɔsɔkɔsɔ kpui ade si le dzogoe ade me la kekena tso 1×1 va ɖo 1×3, 1×4 eye wògena ɖe δ ƒe akpaa me mlɔeba. Mɔ bliboa ƒe mɔfiame ƒe sɔsɔme nye (011)α//(001)δ + [100]α//[100]δ. Tso ŋusẽ mama ƒe nɔnɔmetata me la, woateŋu akpɔe be le FAPbI3 ƒe δ akpa ƒe nucleation megbe le afɔɖeɖe siwo gbɔna me la, ŋusẽ ƒe mɔxenu la le ʋɛ wu α ƒe akpa ƒe tɔtrɔ tɔ, si fia be akpa ƒe tɔtrɔ awɔ kabakaba. Edze ƒã be afɔɖeɖe gbãtɔ si woawɔ atsɔ akpɔ phase ƒe tɔtrɔ dzi le vevie ŋutɔ ne míedi be míatsi α-phase ƒe gbegblẽ nu.
a Phase ƒe tɔtrɔ ƒe ɖoɖo tso miame yi ɖusime – ameyibɔ FAPbI3 phase (α-phase), gbãtɔ Pb-I kadodo ƒe mama (Int-1) kple Pb-I ƒe kadodo ƒe mama bubu (Int-2, Int -3 kple Int -4) kple yellow phase FAPbI3 (delta phase). b Ŋusẽ ƒe mɔxenuwo na FAPbI3 ƒe α yi δ ƒe akpa ƒe tɔtrɔ si wotu ɖe teƒe ƒe gbɔdzɔgbɔdzɔ vovovo siwo le eme dzi. Fli si dzi woŋlɔ nu ɖo la ɖe ŋusẽ ƒe mɔxenu si le kristalo nyuitɔ (0.62 eV) ŋu fia. c Ŋusẽ si naa teƒe gbãtɔ ƒe gbagbãƒewo wɔwɔ le lead perovskite ƒe anyime. Abscissa axis nye ŋusẽ mɔxenu na α-δ phase ƒe tɔtrɔ, eye ordinate axis nye ŋusẽ si na defect formation. Akpa siwo ƒe vɔvɔli le amadede ɣi, ɣi kple amadede dzẽ me la nye ƒomevi I (EB-fe si lolo le bɔbɔe), ƒomevi II (FE si kɔkɔ) kple ƒomevi III (EB-fe si bɔbɔ ɖe anyi), le wo nɔewo yome. d Ŋusẽ si naa nusiwo gblẽ VI kple LOS ƒe wɔwɔme le FAPbI3 me le dziɖuɖua me. e I mɔxenu na ion ƒe ʋuʋu le FAPbI3 ƒe dziɖuɖu kple LOS me. f – I ions (orange spheres) kple gLOS FAPbI3 (gray, lead; violet (orange), iodine (mobile iodine)) ƒe ʋuʋu ƒe nɔnɔmetata le gf dziɖuɖu me (miame: etame kpɔkpɔ; ɖusime: cross section, brown); carbon; blɔ si me kɔ – nitrogen; dzĩ – ɔksidzin; pink si me kɔ – haidrodzin). Wotsɔa nyatakakatsoƒewo naa le nyatakakatsoƒe ƒe faɛlwo ƒe nɔnɔme me.
Emegbe míesrɔ̃ nu tso teƒe ƒe nɔnɔme madeamedzi vovovowo ƒe ŋusẽkpɔɖeamedzi ŋu ɖe ɖoɖo nu (siwo dometɔ aɖewoe nye PbFA, IFA, PbI, kple IPb antisite ƒe xɔxlɔ̃; Pbi kple Ii domedome atɔmwo; kple VI, VFA, kple VPb ƒe ƒuƒluwo), siwo wobu be wonye nu veviwo. siwo hea atɔm kple ŋusẽ ƒe seƒe ƒe akpa ƒe gbegblẽ vɛ la dze le Nɔnɔmetata 1b kple Kpekpeɖeŋu Tabla 1. Enyo be míade dzesii be menye gbɔdzɔgbɔdzɔwo katãe ɖea ŋusẽ ƒe mɔxenu si le α-δ ƒe akpa ƒe tɔtrɔ dzi kpɔtɔna o (Nɔnɔmetata 1b). Míexɔe se be wobua nɔnɔme madeamedzi siwo ƒe wɔwɔme ƒe ŋusẽ le sue eye α-δ ƒe akpa ƒe tɔtrɔ ƒe ŋusẽ ƒe mɔxenuwo le sue wu siaa be wogblẽa nu le akpa ƒe liƒo ŋu. Abe alesi míegblɔe va yi ene la, zi geɖe la, wobua anyigba siwo dzi lifi sɔ gbɔ ɖo be wowɔa dɔ nyuie na formamidine PSC27. Eyata míetsɔa míaƒe susu ɖoa PbI2-nuwuƒe (100) ƒe anyigba ŋu le nɔnɔme siwo me lifi sɔ gbɔ ɖo me. Woɖe nusiwo gblẽ le anyigba ƒe teƒe ƒe nɔnɔme madeamedziwo ƒe gbegblẽ wɔwɔ ƒe ŋusẽ fia le nɔnɔmetata 1c kple Kpekpeɖeŋu Tabla 1. Wonɔ te ɖe ŋusẽ ƒe mɔxenu (EB) kple phase transition formation energy (FE) dzi, woma nɔnɔme madeamedzi siawo ɖe hatsotso etɔ̃ me. Ƒomevi I (low EB-high FE): Togbɔ be IPb, VFA kple VPb ɖe ŋusẽ ƒe mɔxenu si xea mɔ na phase ƒe tɔtrɔ dzi kpɔtɔna ŋutɔ hã la, woƒe wɔwɔme ƒe ŋusẽ lolo. Eyata míexɔe se be nɔnɔme madeamedzi siawo ƒomevi mekpɔa ŋusẽ boo aɖeke ɖe phase ƒe tɔtrɔwo dzi o elabena ƒã hafi wowɔa wo. Ƒomevi II (EB kɔkɔ): Le α-δ ƒe akpa ƒe tɔtrɔ ƒe ŋusẽ ƒe mɔxenu si nyo wu ta la, anti-site defects PbI, IFA kple PbFA megblẽa nu le α-FAPbI3 perovskite ƒe phase ƒe liƒo ŋu o. Ƒomevi III (EB si bɔbɔ-FE si bɔbɔ): VI, Ii kple Pbi ƒe gbɔdzɔgbɔdzɔ siwo ƒe wɔwɔme ƒe ŋusẽ le sue ŋutɔ ateŋu ahe black phase ƒe gbegblẽ vɛ. Vevietɔ ne míebu FE kple EB VI si bɔbɔ wu ŋu la, míexɔe se be mɔnu si wɔa dɔ wue nye be woaɖe I dɔ ƒuƒluwo dzi akpɔtɔ.
Be míaɖe VI dzi akpɔtɔ la, míewɔ PbC2O4 ƒe ƒuƒoƒo si le ʋeʋẽm be wòana FAPbI3 ƒe anyime nanyo ɖe edzi. Ne wotsɔe sɔ kple organic halide dze pasivators abe phenylethylammonium iodide (PEAI) kple n-octylammonium iodide (OAI) la, PbC2O4, si me halogen ions siwo ʋãna aɖeke mele o la, li ke le atikewo me, melɔ̃na le tsi me o, eye ne wodoe ɖe ŋgɔ la, eƒe dɔwɔwɔ megale dɔ wɔm o bɔbɔe. Nyui li ke le anyigba ƒe tsidzadza kple elektrikŋusẽ ƒe ŋusẽ si le perovskite. PbC2O4 ƒe ʋeʋẽ le tsi me nye 0.00065 g/L ko, si le ʋɛ wu PbSO428 tɔ gɔ̃ hã. Vevietɔ wu la, woate ŋu adzra LOS ƒe ƒuƒoƒo siwo le ʋeʋẽm eye wole ɖeka ɖo blewu le perovskite filmwo dzi to in situ reactions zazã me (kpɔ ete). Míewɔ DFT simulations le interfacial kadodo si le FAPbI3 kple PbC2O4 dome abe alesi woɖee fia le Kpekpeɖeŋu Nɔnɔmetata 1. Kpekpeɖeŋu Tabla 2 ɖe nɔnɔme madeamedzi wɔwɔ ŋusẽ le LOS dodo vɔ megbe fia. Míekpɔe be menye ɖeko LOS dzia VI ƒe nɔnɔme madeamedziwo ƒe wɔwɔme ƒe ŋusẽ ɖe edzi 0.69–1.53 eV (Nɔnɔmetata 1d), ke edzia I ƒe dɔwɔwɔ ƒe ŋusẽ ɖe edzi le ʋuʋu ƒe anyigba kple dodo ƒe anyigba hã dzi (Nɔnɔmetata 1e). Le akpa gbãtɔ me la, I ions ʋuna to perovskite ƒe anyigba dzi, eye wògblẽa VI ions ɖe lattice nɔnɔme me kple ŋusẽ ƒe mɔxenu si nye 0.61 eV. Le LOS ƒe dodo megbe la, le steric mɔxenu ƒe ŋusẽkpɔɖeamedzi ta la, dɔwɔwɔ ƒe ŋusẽ na I ions ƒe ʋuʋu dzina ɖe edzi va ɖoa. 1.28 ƒe eV. Le I ions siwo dzona le perovskite ƒe anyigba dzi ƒe ʋuʋu me la, ŋusẽ ƒe mɔxenu si le VOC me hã lolo wu esi le kpɔɖeŋu si wotsɔ ɖua edzi me (Fig. 1e). Woɖe I ion ƒe ʋuʋu mɔ siwo le dziɖuɖu kple LOS FAPbI3 me ƒe nɔnɔmetatawo fia le nɔnɔmetata 1 f kple g me. Simulasi me tsonuawo ɖee fia be LOS ate ŋu axe mɔ na VI ƒe nɔnɔme madeamedziwo ƒe wɔwɔme kple I ƒe ʋuʋu, si axe mɔ na α yi δ ƒe akpa ƒe tɔtrɔ ƒe nucleation.
Wodo oxalic acid kple FAPbI3 perovskite ƒe nuwɔna kpɔ. Esi wotsaka oxalic acid kple FAPbI3 ƒe tsiwo vɔ la, tsi ɣi gbogbo aɖe va dzɔ, abe alesi woɖee fia le Kpekpeɖeŋu Nɔnɔmetata 2. Wode dzesi atikekui la be enye PbC2O4 nu dzadzɛ to X-ray diffraction (XRD) (Kpekpeɖeŋu Nɔnɔmetata 3) kple Fourier transform infrared spectroscopy (FTIR) (Kpekpeɖeŋu Nɔnɔmetata 4) zazã me. Míekpɔe be oxalic acid lɔ̃na ŋutɔ le isopropyl aha (IPA) me le xɔme ƒe dzoxɔxɔ me eye eƒe ʋeʋẽ anɔ abe 18 mg/mL ene, abe alesi woɖee fia le Kpekpeɖeŋu Nɔnɔmetata 5. Esia na be dɔwɔwɔ emegbe nɔa bɔbɔe elabena IPA, abe pasivation solvent si bɔ ene, megblẽa nu le perovskite ƒe ƒuƒoƒoa ŋu wu ɣeyiɣi kpui aɖe o29. Eyata to perovskite film la nyrɔ ɖe oxalic acid solution me alo spin-coating oxalic acid solution la ɖe perovskite la dzi la, woate ŋu akpɔ PbC2O4 tsɛ kple esi le ʋeʋẽm kabakaba le perovskite film la ƒe anyime le atike ƒe sɔsɔ si gbɔna nu: H2C2O4 + FAPbI3 = PbC2O4 + FAI +HI. Woate ŋu atsɔ FAI alɔ IPA me eye woato esia me aɖee ɖa le nuɖaɣi. Woate ŋu akpɔ LOS ƒe titrime dzi to nuwɔna ƒe ɣeyiɣi kple ŋgɔdonya ƒe agbɔsɔsɔ me.
Scanning electron microscopy (SEM) ƒe nɔnɔmetata siwo nye control kple LOS perovskite filmwo dze le Nɔnɔmetata 2a,b me. Nusiwo do tso eme ɖee fia be wokpɔ perovskite ƒe anyigba ƒe nɔnɔme ta nyuie, eye nu suesuesue gbogbo aɖewo le nukua ƒe anyigba dzi, si wòle be wòatsi tre ɖi na PbC2O4 ƒe ƒuƒoƒo si wowɔ to in-situ reaction me. LOS perovskite film la ƒe anyigba le gbadzaa vie (Kpekpeɖeŋu Nɔnɔmetata 6) eye tsi ƒe kadodo ƒe dzogoe lolo wu ne wotsɔe sɔ kple dziɖuɖu film (Kpekpeɖeŋu Nɔnɔmetata 7). Wozã high-resolution transverse transmission electron microscopy (HR-TEM) tsɔ de vovototo nusi wowɔ la ƒe gota gome. Ne wotsɔe sɔ kple dziɖuɖu film (Fig. 2c) la, ƒuƒoƒo tsɛ si sɔ eye wòle ʋeʋẽm si ƒe titrime anɔ abe 10 nm ene la dzena nyuie le LOS perovskite la tame (Fig. 2d). Ne wozã high-angle annular dark-field scanning electron microscopy (HAADF-STEM) tsɔ lé ŋku ɖe ƒomedodo si le PbC2O4 kple FAPbI3 dome ŋu la, woate ŋu akpɔ FAPbI3 ƒe kristalo nutowo kple PbC2O4 ƒe nuto siwo me nɔnɔme mele o ƒe anyinɔnɔ nyuie (Kpekpeɖeŋu Nɔnɔmetata 8). Wotsɔ X-ray photoelectron spectroscopy (XPS) dzidzedzewo de dzesi perovskite ƒe anyigba ƒe wɔwɔme le oxalic acid ƒe dɔwɔwɔ vɔ megbe, abe alesi woɖee fia le Nɔnɔmetata 2e–g me ene. Le nɔnɔmetata 2e me la, C 1s ƒe taƒoƒo siwo le 284.8 eV kple 288.5 eV nye CC kple FA ƒe dzesi tɔxɛawo tɔ. Ne wotsɔe sɔ kple lãkusi si dzi wokpɔna la, LOS lãkusia ɖe taƒoƒo bubu fia le 289.2 eV, si wogblɔ be C2O42- gbɔe wòtso. LOS perovskite ƒe O 1s spektrum ɖea O 1s ƒe ta etɔ̃ siwo to vovo le atikewɔwɔ me fiana le 531.7 eV, 532.5 eV, kple 533.4 eV, si sɔ kple deprotonated COO, C=O of intact oxalate groups 30 kple O atoms of the OH component (Fig. 2e ). )). Le kpɔɖeŋu si wotsɔ ɖu wo dzi gome la, O 1s ƒe ta sue aɖe koe wokpɔ, si woate ŋu agblɔ be oxygen si wotsɔ chemisorbed le anyigba dzi gbɔ. Pb 4f7/2 kple Pb 4f5/2 ƒe dziɖuɖu ƒe lãkusi ƒe nɔnɔmewo le 138.4 eV kple 143.3 eV, le wo nɔewo yome. Míede dzesii be LOS perovskite ɖea Pb ƒe taƒoƒo ƒe tɔtrɔ si ade 0.15 eV fiana yia kadodoŋusẽ si lolo wu gbɔ, si fia be kadodo sesẽ aɖe le C2O42- kple Pb atɔmwo dome (Fig. 2g).
a SEM nɔnɔmetatawo ƒe dziɖuɖu kple b LOS perovskite filmwo, dziƒokpɔkpɔ. c Elektrɔnik nusuekpɔmɔ̃ (HR-TEM) si wotsɔ kpɔa mɔ̃ dzi kple d LOS perovskite filmwo. XPS si ƒe nɔnɔme deŋgɔ si nye e C 1s, f O 1s kple g Pb 4f perovskite filmwo. Wotsɔa nyatakakatsoƒewo naa le nyatakakatsoƒe ƒe faɛlwo ƒe nɔnɔme me.
Le DFT ƒe emetsonuwo nu la, wogblɔe ɖi le nukpɔsusu nu be VI ƒe gbɔdzɔgbɔdzɔwo kple I ƒe ʋuʋu nana phase ƒe tɔtrɔ tso α yi δ gbɔ bɔbɔe. Nyatakaka siwo woxɔ va yi ɖee fia be I2 dona kabakaba tso perovskite film siwo wotu ɖe PC dzi me le fotoɖeɖe me le filmawo tsɔtsɔ de kekeli kple dzoxɔxɔ ƒe nuteɖeamedzi me vɔ megbe31,32,33. Be míaɖo kpe ŋusẽ si lead oxalate kpɔna ɖe perovskite ƒe α-afã dzi la, míenyrɔ control kple LOS perovskite filmwo ɖe glass-tu siwo me kɔ siwo me toluene le me, eye emegbe míetsɔ ɣe ƒe keklẽ 1 klẽ wo hena gaƒoƒo 24. Míedzidze kekeli si me keklẽŋusẽ le kple esi wokpɔna (UV-Vis) ƒe xɔxlɔ̃. ) toluene solution, abe alesi woɖee fia le Nɔnɔmetata 3a me ene. Ne wotsɔe sɔ kple kpɔɖeŋu si wotsɔ ɖua wo dzi la, wokpɔ I2 ƒe xɔxlɔ̃ ƒe sesẽme si bɔbɔ wu sã le LOS-perovskite gome, si ɖee fia be LOS si le sue ate ŋu axe mɔ na I2 ƒe dodo tso perovskite film la me le kekeli ƒe nyɔnyrɔ̃ me. Woɖe ame tsitsiwo dzi ɖuɖu kple LOS perovskite filmwo ƒe fotowo fia le Nɔnɔmetata 3b kple c ƒe nusiwo wotsɔ de eme me. LOS perovskite la gakpɔtɔ nye yevu, evɔ mɔ̃ si dzi wokpɔna ƒe akpa gãtɔ trɔ zu ɣie. Woɖe UV–visible absorption spectra si le film si wotsɔ nyrɔe me la fia le Figs. 3b, ƒe c. Míede dzesii be edze ƒã be nusiwo woxɔna si sɔ kple α le sinima si dzi wokpɔna me dzi ɖe kpɔtɔ. Wodzidze X-ray tsɔ ŋlɔ alesi kristalo ƒe wɔwɔme trɔe. Le kekeli gaƒoƒo 24 megbe la, perovskite si dzi wokpɔna la ɖe δ-phase dzesi ɣi sesẽ aɖe fia (11.8°), esime LOS perovskite la gakpɔtɔ lé akpa yibɔ nyui aɖe me ɖe asi (Nɔnɔmetata 3d).
UV-visible absorption spectra of toluene solutions si me wotsɔ control film kple LOS film nyrɔ ɖe ɣe ƒe keklẽ 1 te hena gaƒoƒo 24. Nusi wotsɔ de eme la ɖe nugoe aɖe si me wotsɔ film ɖesiaɖe nyrɔ ɖe toluene ƒe agbɔsɔsɔ si sɔ me la fia. b UV-Vis absorption spectra of control film kple c LOS film do ŋgɔ na kple le 24 h ƒe nyɔnyrɔ̃ le ɣe ƒe keklẽ 1 te. Woɖe dodokpɔ film la ƒe foto fia le nusi wotsɔ de eme la me. d X-ray diffraction ƒe nɔnɔmewo le dziɖuɖu kple LOS filmwo me do ŋgɔ na 24 h ƒe ɖeɖefia kple emegbe. SEM nɔnɔmetata siwo nye dziɖuɖu film e kple film f LOS le gaƒoƒo 24 ƒe ɖeɖefia megbe. Wotsɔa nyatakakatsoƒewo naa le nyatakakatsoƒe ƒe faɛlwo ƒe nɔnɔme me.
Míewɔ scanning electron microscopy (SEM) dzidzedzewo be míalé ŋku ɖe perovskite film la ƒe microstructural tɔtrɔwo ŋu le gaƒoƒo 24 ƒe kekeli megbe, abe alesi woɖee fia le Nɔnɔmetata 3e,f me ene. Le dziɖuɖu film me la, wogblẽ nuku gãwo eye wotrɔ wo wozu aŋe suewo, si sɔ kple δ-phase product FAPbI3 ƒe nɔnɔme (Fig. 3e). Le LOS filmwo gome la, perovskite nukuawo gakpɔtɔ le nɔnɔme nyui me (Nɔnɔmetata 3f). Nusiwo do tso eme ɖo kpe edzi be I ƒe bu nana tɔtrɔ tso ameyibɔ ƒe akpa me yia ɣi ƒe akpaa me vevie, gake PbC2O4 ya naa ameyibɔ ƒe akpaa li ke, si xea mɔ na I ƒe bu. iodine si dona le ɣeyiɣi ɖeka me eye wòwɔa VI. Abe alesi DFT gblɔe ɖi ene la, LOS ate ŋu axe mɔ na VI ƒe nɔnɔme madeamedziwo ƒe wɔwɔ eye wòaxe mɔ na I ions ƒe ʋuʋu yi perovskite ƒe anyime.
Gakpe ɖe eŋu la, wosrɔ̃ nu tso ŋusẽ si PbC2O4 ƒe ƒuƒoƒoa kpɔna ɖe perovskite filmwo ƒe tsi ƒe tsitretsitsi dzi le yame ƒe ya me (fafa si sɔ gbɔ 30-60%) ŋu. Abe alesi woɖee fia le Kpekpeɖeŋu Nɔnɔmetata 9 me ene la, LOS perovskite la gakpɔtɔ nye yibɔ le ŋkeke 12 megbe, gake film si dzi wokpɔna la trɔ zu ɣie. Le XRD dzidzedzewo me la, dziɖuɖu film la ɖea ta sesẽ aɖe fiana le 11.8° si sɔ kple FAPbI3 ƒe δ ƒe akpa, esime LOS perovskite léa ameyibɔ α ƒe akpaa me ɖe asi nyuie (Kpekpeɖeŋu Nɔnɔmetata 10).
Wozã kekeli ƒe keklẽ si nɔa anyi kpoo (PL) kple keklẽŋusẽ si wokpɔna le ɣeyiɣi me (TRPL) tsɔ srɔ̃ nu tso lead oxalate ƒe pasivation ŋusẽkpɔɖeamedzi ɖe perovskite ƒe anyigba dzi ŋu. Le Fig. Figure 4a ɖee fia be LOS film la na PL ƒe sesẽme dzi ɖe edzi. Le PL ƒe nɔnɔmetata me la, LOS film ƒe sesẽme le teƒe bliboa si nye 10 × 10 μm2 dzi lolo wu esi le control film la me (Kpekpeɖeŋu Nɔnɔmetata 11), si fia be PbC2O4 wɔa perovskite film la ƒe dɔwɔwɔ ɖekae. Wokpɔa ʋukula ƒe agbenɔƒe to TRPL ƒe gbegblẽ ƒe tsɔtsɔ sɔ kple wo nɔewo kple xexlẽdzesi ƒe dɔwɔwɔ ɖeka (Fig. 4b). LOS film la ƒe agbenɔƒe si tsɔa nu nye 5.2 μs, si didi wu sã wu film si dzi woɖuna si ƒe agbenɔƒe nye 0.9 μs, si fia be anyigbadzi nonradiative recombination dzi ɖe kpɔtɔ.
PL ƒe nɔnɔme si li ke kple b-spektra siwo nye ɣeyiɣi kpui aɖe ƒe PL ƒe perovskite filmwo le glass substrates dzi. c SP ƒe ʋuʋudedi si le mɔ̃a ŋu (FTO/TiO2/SnO2/perovskite/spiro-OMeTAD/Au). d EQE spectrum kple Jsc EQE spectrum ƒo ƒu tso mɔ̃ si wɔa dɔ nyuie wu me. d Kekeli ƒe sesẽme si le perovskite mɔ̃ aɖe ŋu nɔ te ɖe Voc ƒe nɔnɔmetata dzi. f MKRC ƒe numekuku si wozãna ɖaa to ITO/PEDOT:PSS/perovskite/PCBM/Au ƒe do dzadzɛ ƒe mɔ̃ zazã me. VTFL nye mɔ̃memi ƒe ʋuʋudedi si sɔ gbɔ wu. Míebu mɔ̃a ƒe kpekpeme (Nt) tso nyatakaka siawo me. Wotsɔa nyatakakatsoƒewo naa le nyatakakatsoƒe ƒe faɛlwo ƒe nɔnɔme me.
Be woasrɔ̃ nu tso ŋusẽ si lead oxalate layer kpɔna ɖe mɔ̃a ƒe dɔwɔwɔ dzi ŋu la, wozã FTO/TiO2/SnO2/perovskite/spiro-OMeTAD/Au ƒe kadodo ƒe ɖoɖo si wozãna tsã. Míezãa formamidine chloride (FACl) abe kpeɖeŋutɔ na perovskite ŋgɔdola ɖe methylamine hydrochloride (MACl) teƒe be míakpɔ mɔ̃a ƒe dɔwɔwɔ nyuie wu, elabena FACl ate ŋu ana kristalo ƒe nyonyome nyuitɔ eye wòaƒo asa na FAPbI335 ƒe band gap (kpɔ Kpekpeɖeŋu Nɔnɔmetata 1 kple 2 hena tsɔtsɔ sɔ kple wo nɔewo tsitotsito). ). 12-14) me. Wotia IPA be wòanye atike si tsia dzodzodzoetsitsi nu elabena enaa kristalo ƒe nyonyome nyo wu eye wòlɔ̃a mɔfiame le perovskite filmwo me ne wotsɔe sɔ kple diethyl ether (DE) alo chlorrobenzene (CB)36 (Kpekpeɖeŋu Nɔnɔmetata 15 kple 16). Wotrɔ asi le PbC2O4 ƒe titrime ŋu nyuie be wòada asɔ nyuie le defect passivation kple charge transport to asitɔtrɔ le oxalic acid ƒe agbɔsɔsɔ ŋu me (Kpekpeɖeŋu Nɔnɔmetata 17). Woɖe cross-sectional SEM nɔnɔmetata siwo le optimized control kple LOS devices fia le Supplementary Figure 18. Typical current density (CD) curves na control kple LOS devices dze le Figure 4c, eye woɖe parameters siwo woɖe tso eme la le Supplementary Table 3. Maximum power conversion efficiency (PCE) control cells 23.43% (22.94%), Jsc 25.75 mA cm-2 (25.74 mA cm-2), Voc 1.16 V (1.16 V) kple megbe (ŋgɔgbe) ƒe fotoɖeɖe. Nusiwo wotsɔ yɔa nu me (FF) nye 78.40% (76.69%). PCE LOS PSC si sɔ gbɔ wu nye 25.39% (24.79%), Jsc nye 25.77 mA cm-2, Voc nye 1.18 V, FF nye 83.50% (81.52%) tso megbe (yi ŋgɔ Scan yi). LOS mɔ̃a ɖo keklẽŋusẽ ƒe dɔwɔwɔ si ŋu woɖo kpee si nye 24.92% le ame etɔ̃lia ƒe keklẽŋusẽ ƒe nudokpɔƒe si dzi woka ɖo (Kpekpeɖeŋu Nɔnɔmetata 19). External quantum efficiency (EQE) na Jsc si wowɔ ɖekae si nye 24.90 mA cm-2 (dziɖuɖu) kple 25.18 mA cm-2 (LOS PSC), le wo nɔewo yome, si wɔ ɖeka nyuie kple Jsc si wodzidze le standard AM 1.5 G spectrum (Fig. .4d). ) . Woɖe PCE siwo wodzidze ƒe akɔntabubu ƒe mama fia na dziɖuɖu kple LOS PSCwo le Kpekpeɖeŋu Nɔnɔmetata 20 me.
Abe alesi woɖee fia le nɔnɔmetata 4e me ene la, wobu ƒomedodo si le Voc kple kekeli ƒe sesẽ dome be woatsɔ asrɔ̃ nu tso ŋusẽ si PbC2O4 kpɔna ɖe anyigba ƒe gbugbɔgaƒoƒo si mɔ̃ kpena ɖe eŋu dzi. Fli si woɖo na LOS mɔ̃a ƒe dzidzeme nye 1.16 kBT/sq, si bɔbɔ wu fli si woɖo na mɔ̃a ƒe dzidzeme (1.31 kBT/sq), si ɖo kpe edzi be LOS ɖea vi na mɔxexe ɖe anyigba ƒe gbugbɔgaƒoƒo nu to mɔ̃memiwo dzi. Míezãa space charge current limiting (SCLC) mɔ̃ɖaŋununya tsɔ dzidzea perovskite film ƒe nusiwo gblẽ ƒe kpekpeme le agbɔsɔsɔ me to doviviti IV ƒe nɔnɔme si le do me mɔ̃ (ITO/PEDOT:PSS/perovskite/spiro-OMeTAD/Au) dzidzedze me abe alesi woɖee fia le nɔnɔmetata me ene. 4f Fiae. Wobu mɔ̃a ƒe kpekpeme to mɔfiame si nye Nt = 2ε0εVTFL/eL2 me, afisi ε nye perovskite film la ƒe dielectric constant si sɔ, ε0 nye dielectric constant si le vacuum me, VTFL nye seɖoƒe ƒe voltage na mɔ̃a yɔyɔ, e nye charge, L nye perovskite film ƒe titrime (650 nm). Wobu akɔnta be VOC-mɔ̃a ƒe gbagbãƒe ƒe kpekpeme nye 1.450 × 1015 cm–3, si le ʋɛ wu nusi gblẽ le mɔ̃a dzi kpɔkpɔ me, si nye 1.795 × 1015 cm–3.
Wodo mɔ̃ si womebla o la kpɔ le ŋusẽ si sɔ gbɔ wu (MPP) le ŋkeke bliboa ƒe keklẽ te le nitrogen te be woalé ŋku ɖe eƒe dɔwɔwɔ ƒe liƒo ɣeyiɣi didi ŋu (Nɔnɔmetata 5a). Le gaƒoƒo 550 megbe la, LOS mɔ̃a gakpɔtɔ lé eƒe dɔwɔwɔ nyuie wu ƒe 92% me ɖe asi, esime mɔ̃ si dzi wokpɔna ƒe dɔwɔwɔ ɖiɖi va ɖo 60% le eƒe dɔwɔwɔ gbãtɔ me. Wodzidze nusiwo le mɔ̃ xoxoa me ƒe mama to time-of-flight secondary ion mass spectrometry (ToF-SIMS) dzi (Fig. 5b, c). Woate ŋu akpɔ iodine gbogbo aɖe si ƒo ƒu ɖe sika dzikpɔƒe si le etame. Gas si mewɔa dɔ o takpɔkpɔ ƒe nɔnɔmewo ɖe nusiwo gblẽa nu le nutome ŋu abe tsidzadza kple ɔksidzin ene ɖa, si fia be ememe mɔnuwo (si nye ion ƒe ʋuʋu) gbɔe wòtso. Le ToF-SIMS ƒe emetsonuwo nu la, wokpɔ I- kple AuI2- ions le Au electrode me, si fia be I ƒe kaka tso perovskite me yi Au me. Dzesi ƒe sesẽme si le I- kple AuI2- ions me le mɔ̃ si dzi wokpɔna me la lolo wu VOC ƒe kpɔɖeŋua tɔ abe zi gbɔ zi 10 ene. Nyatakaka siwo woxɔ va yi ɖee fia be ion ƒe gege ɖe eme ate ŋu ana spiro-OMeTAD ƒe do ƒe tsɔtsɔme dzi naɖe akpɔtɔ kabakaba eye atikewo naxɔ etame electrode layer, si ana dometsotso si le mɔ̃a me la nagblẽ ɖe edzi37,38. Woɖe Au electrode la ɖa eye wotsɔ chlorbenzene solution kɔ spiro-OMeTAD layer la ŋu tso substrate la me. Emegbe míezã grazing incidence X-ray diffraction (GIXRD) tsɔ de dzesi film la (Nɔnɔmetata 5d). Emetsonuwo ɖee fia be diffraction peak si dze ƒã le control film la ŋu le 11.8°, evɔ diffraction peak yeye aɖeke medze le LOS ƒe kpɔɖeŋua me o. Emetsonuwo ɖee fia be I ions ƒe bu gã le dziɖuɖu film me hea δ ƒe akpaa dzidzi vɛ, evɔ le LOS film me la, woxea mɔ na dɔwɔwɔ sia eme kɔ ƒã.
Gaƒoƒo 575 ƒe MPP kplɔkplɔ atraɖii le mɔ̃ si wometre o ŋu le nitrogen yame kple ɣe ƒe keklẽ 1 UV-filter manɔmee. ToF-SIMS mama b I- kple c AuI2- ions le LOS MPP dziɖuɖu mɔ̃ kple tsitsi dɔwɔnu. Dzĩ, amadede dzẽ kple aŋutiɖiɖi ƒe vɔvɔliwo sɔ kple Au, Spiro-OMeTAD kple perovskite. d GIXRD ƒe perovskite film le MPP dodokpɔ megbe. Wotsɔa nyatakakatsoƒewo naa le nyatakakatsoƒe ƒe faɛlwo ƒe nɔnɔme me.
Wodzidze dzoxɔxɔ si nɔa te ɖe dzoxɔxɔ dzi tsɔ ɖo kpe edzi be PbC2O4 ate ŋu axe mɔ ɖe ion ƒe ʋuʋu nu (Kpekpeɖeŋu Nɔnɔmetata 21). Wokpɔa ion ƒe ʋuʋu ƒe dɔwɔwɔ ƒe ŋusẽ (Ea) to FAPbI3 film ƒe tɔtrɔ le ʋuʋudedi me (σ) dzidzedze le dzoxɔxɔ vovovowo (T) me kple Nernst-Einstein ƒe ƒomedodo zazã me: σT = σ0exp(−Ea/kBT), afisi σ0 nye nusi nɔa anyi ɖaa, kB nye Boltzmann ƒe nɔnɔme madzudzɔmadzudzɔe. Míekpɔa Ea ƒe asixɔxɔ tso ln(σT) ƒe dzidzeme me tsɔ wu 1/T, si nye 0.283 eV na dziɖuɖua kple 0.419 eV na LOS dɔwɔnua.
Kpuie ko la, míena nukpɔsusu ƒe ɖoɖo aɖe si dzi míato ade dzesi FAPbI3 perovskite ƒe gbegblẽmɔ kple ŋusẽ si gbɔdzɔgbɔdzɔ vovovowo kpɔna ɖe ŋusẽ ƒe mɔxenu si le α-δ ƒe akpa ƒe tɔtrɔ dzi. Le nɔnɔme madeamedzi siawo dome la, wogblɔe ɖi le nukpɔsusu nu be VI ƒe nɔnɔme madeamedziwo ana phase ƒe tɔtrɔ tso α yi δ bɔbɔe. Woto PbC2O4 ƒe ƒuƒoƒo si me tsi mele o eye wòli ke le atikewo me vɛ be wòana FAPbI3 ƒe α-afã la nali ke to mɔxexe ɖe I teƒe ƒuƒluwo ƒe wɔwɔme kple I ions ƒe ʋuʋu nu. Aɖaŋu sia ɖea interfacial non-radiative recombination dzi kpɔtɔna ŋutɔ, edzia ɣe ƒe lãmenugbagbeviwo ƒe dɔwɔwɔ ɖe edzi va ɖoa 25.39%, eye wònaa dɔwɔwɔ ƒe liƒo nyona ɖe edzi. Míaƒe emetsonuwo naa mɔfiame hena formamidine PSC siwo wɔa dɔ nyuie eye woli ke gbɔ ɖoɖo to mɔxexe ɖe α yi δ ƒe akpa ƒe tɔtrɔ si gbɔdzɔgbɔdzɔ hena vɛ nu.
Woƒle titanium(IV) isopropoxide (TTIP, 99.999%) tso Sigma-Aldrich gbɔ. Woƒle hydrochloric acid (HCl, 35.0–37.0%) kple ethanol (si me tsi mele o) tso Guangzhou Atikewɔƒe. Woƒle SnO2 (15 wt% tin(IV) oxide colloidal dispersion) tso Alfa Aesar gbɔ. Woƒle lead(II) iodide (PbI2, 99.99%) tso TCI Shanghai (China) gbɔ. Formamidine iodide (FAI, ≥99.5%), formamidine klorid (FACl, ≥99.5%), methylamine haidroklorid (MACl, ≥99.5%), 2,2′,7,7′-tetrakis-(N, N-di-p) )-methoxyaniline)-9,9′-spirobifluorene (Spiro-OMETAD, ≥99.5%), lithium bis (trifluoromethane)sulfonylimide (Li-TFSI, 99.95%), 4-tert -butylpyridine (tBP, 96%) woƒle tso Xi'an Polymer Kekeli Mɔ̃ɖaŋudɔwɔƒe (China). N,N-dimethylformamide (DMF, 99.8%), dimethyl sulfoxide (DMSO, 99.9%), isopropyl aha sesẽ (IPA, 99.8%), klorobenzene (CB, 99.8%), acetonitrile (ACN). Woƒlee tso Sigma-Aldrich gbɔ. Woƒle oxalic acid (H2C2O4, 99.9%) tso Macklin gbɔ. Wozã atikeawo katã abe alesi woxɔe ene tɔtrɔ bubu aɖeke manɔmee.
Wotsɔ atike si wotsɔna klɔa nu, acetone, kple ethanol kɔ ITO alo FTO substrates (1.5 × 1.5 cm2) ŋu ultrasonically hena miniti 10, eye emegbe wotsɔe ƒu gbe le nitrogen ƒe tɔsisi te. Wotsɔ TiO2 mɔxenu ƒe ƒuƒoƒo si le ʋeʋẽm la da ɖe FTO ƒe anyigba dzi to titanium diisopropoxybis(acetylacetonate) ƒe tsi si wotsɔ de ethanol (1/25, v/v) si wotsɔ de 500 °C me hena miniti 60 zazã me. Wotsɔ tsi si me ion mele o ƒo SnO2 ƒe colloidal dispersion la le eƒe lolome ƒe sɔsɔme 1:5 me. Le anyigba dzadzɛ si wotsɔ UV ozone da dɔe hena miniti 20 dzi la, wotsɔ SnO2 nanoparticles ƒe film tsɛ aɖe de 4000 rpm me hena sɛkɛnd 30 eye emegbe wodo dzo nɛ le 150 °C hena miniti 30. Le perovskite precursor solution gome la, wotsɔ 275.2 mg FAI, 737.6 mg PbI2 kple FACl (20 mol%) ƒo ɖe DMF/DMSO (15/1) ƒe ʋeʋẽ si wotsaka me. Wodzra perovskite layer ɖo to centrifuging 40 μL perovskite precursor solution ɖe UV-ozone-treated SnO2 layer tame le 5000 rpm le ya si ƒo xlãe me hena s 25. Le sɛkɛnd 5 le zi mamlɛtɔ megbe la, wotsɔ MACl IPA solution 50 μL (4 mg/mL) ƒu gbe ɖe nusi wotsɔ wɔe dzi kabakaba abe atike si tsia tre ɖe eŋu ene. Emegbe la, wotsɔa dzo ɖe film siwo wodzra yeyee la ŋu le 150°C hena miniti 20 eye emegbe le 100°C hena miniti 10. Esi wofa perovskite film la ɖe xɔme ƒe dzoxɔxɔ nu vɔ la, wotsɔ H2C2O4 solution (1, 2, 4 mg si wotsɔ ƒo ɖe 1 mL IPA me) ƒo ɖe centrifuged me le 4000 rpm hena s 30 be perovskite ƒe anyigba nawɔ dɔ. Wotsɔ spiro-OMeTAD tsi si wodzra ɖo to 72.3 mg spiro-OMeTAD, 1 ml CB, 27 μl tBP kple 17.5 μl Li-TFSI (520 mg le 1 ml acetonitrile me) tsakatsaka ɖe film la dzi le 4000 rpm me le s 30 me. Mlɔeba la, wotsɔ Au ƒe ƒuƒoƒo si ƒe titrime nye 100 nm ƒu gbe le ya si me ya mele o me le 0.05 nm/s (0~1 nm), 0.1 nm/s (2~15 nm) kple 0.5 nm/s (16~100 nm) ƒe duƒuƒu me . ).
Wodzidze perovskite ɣe ƒe lãmenugbagbeviwo ƒe SC dɔwɔwɔ to Keithley 2400 mita le ɣe ƒe nɔnɔmetata ƒe keklẽ (SS-X50) te le kekeli ƒe sesẽme si nye 100 mW/cm2 me eye wotsɔ silicon ɣe ƒe lãmenugbagbeviwo ƒe dzidzenu siwo wodo kpɔ tsɔ ɖo kpe edzi. Negbe ɖe wogblɔe bubui ko la, wodzidze SP ƒe ʋuʋudediwo le asigɛɖaka si me nitrogen yɔ fũu me le xɔme ƒe dzoxɔxɔ (~25°C) me le ŋgɔgbe kple megbe scan ƒe nɔnɔmewo me (voltage step 20 mV, delay time 10 ms). Wozã vɔvɔli ƒe nutsyɔnu tsɔ de dzesi teƒe si wɔa dɔ nyuie si nye 0.067 cm2 na PSC si wodzidze. Wowɔ EQE dzidzedzewo le ya si ƒo xlãe me to PVE300-IVT210 ɖoɖo (Industrial Vision Technology(s) Pte Ltd) zazã me kple kekeli si ƒe amadede nye ɖeka si wotsɔ susu ɖo mɔ̃a ŋu. Be mɔ̃a nali ke la, wowɔ ɣe ƒe keklẽŋusẽ ƒe lãmenugbagbevi siwo womede nu me o ƒe dodokpɔ le nitrogen ƒe asigɛɖaka me le 100 mW/cm2 ƒe nyaƒoɖeamenu me UV-ʋuʋudedi manɔmee. Wodzidzea ToF-SIMS to PHI nanoTOFII ƒe yameʋuɖoɖo ƒe ɣeyiɣi SIMS zazã me. Wozã 4 kV Ar ion tu si ƒe lolome nye 400×400 μm tsɔ wɔ goglome ƒe nɔnɔmetata.
Wowɔ X-ray photoelectron spectroscopy (XPS) dzidzedzewo le Thermo-VG Scientific system (ESCALAB 250) dzi to monochromatized Al Kα (na XPS mode) zazã me le nyaƒoɖeamenu si nye 5.0 × 10–7 Pa. Wowɔ scanning electron microscopy (SEM) le JEOL-JSM-6330F system dzi. Wozã atɔm ŋusẽ ƒe nusuekpɔmɔ̃ (AFM) (Bruker Dimension FastScan) tsɔ dzidze perovskite filmawo ƒe anyigba ƒe nɔnɔme kple woƒe ƒuƒuiƒe. Wowɔa STEM kple HAADF-STEM le FEI Titan Themis STEM. Wozã UV-3600Plus (Shimadzu Corporation) tsɔ dzidze UV–Vis ƒe absorption spectra. Woŋlɔ space charge limiting current (SCLC) ɖe Keithley 2400 mita dzi. Wozã FLS 1000 photoluminescence spectrometer tsɔ dzidze fotoklẽŋusẽ si le nɔnɔme si li ke (PL) kple fotoklẽŋusẽ si wokpɔna le ɣeyiɣi me (TRPL) si me wotsɔa ʋu tsɔna ƒe agbenɔƒe gblẽna. Wozã Horiba LabRam Raman system HR Evolution tsɔ dzidze PL ƒe nɔnɔmetatawo. Wozã Thermo-Fisher Nicolet NXR 9650 ɖoɖo tsɔ wɔ Fourier transform infrared spectroscopy (FTIR).
Le dɔ sia me la, míezãa SSW mɔ ƒe kpɔɖeŋu mɔnu tsɔ srɔ̃a nu tso phase ƒe tɔtrɔ mɔ tso α-phase dzi yi δ-phase dzi. Le SSW mɔnu me la, wokpɔa ŋusẽ si ate ŋu adzɔ ƒe anyigba ƒe ʋuʋu to mɔnu fafɛ si wowɔ le vome (second derivative) ƒe mɔfiame dzi, si na woate ŋu asrɔ̃ nu tso ŋusẽ si ate ŋu adzɔ ƒe anyigba ŋu tsitotsito eye wòanye taɖodzinu. Le dɔ sia me la, wowɔa mɔ ƒe kpɔɖeŋuwo le atɔm 72 ƒe supercell dzi, eye woƒoa gɔmedzedze/mlɔetɔ ƒe nɔnɔme (IS/FS) eve siwo wu 100 nu ƒu le DFT ƒe ɖoɖo nu. Woateŋu anɔ te ɖe IS/FS eveveve ƒe nyatakakawo ƒe ƒuƒoƒo dzi akpɔ mɔ si do ƒome kple xɔtuɖoɖo gbãtɔ kple xɔtuɖoɖo mamlɛtɔ kple atɔmwo ƒe sɔsɔ, eye emegbe wozãa mɔ eve ƒe ʋuʋu le tɔtrɔ ƒe unit ƒe anyigba dzi tsɔ nyaa tɔtrɔ ƒe nɔnɔme ƒe mɔnu nyuie. (VK-DESV) ƒe nyawo. Ne wodi tɔtrɔ ƒe nɔnɔme vɔ la, woate ŋu anya mɔ si dzi mɔxenu le bɔbɔe wu to ŋusẽ ƒe mɔxenuwo ɖoɖo ɖe ɖoɖo nu me.
Wozã VASP (version 5.3.5) tsɔ wɔ DFT ƒe akɔntabubuwo katã, afisi wotsɔ C, N, H, Pb, kple I atɔmwo ƒe elektrɔnik–ion ƒe kadodowo le tsitre ɖi na to projected amplified wave (PAW) scheme me. Woɖea asitɔtrɔ ƒe ƒomedodo ƒe dɔwɔwɔ me to generalized gradient approximation me le Perdue-Burke-Ernzerhoff parametrization me. Woɖo ŋusẽ ƒe seɖoƒe na yameʋu ƒe ƒutsotsoewo be wòanye 400 eV. Monkhorst–Pack k-point grid ƒe lolome nye (2 × 2 × 1). Le xɔtuɖoɖowo katã gome la, wowɔ lattice kple atɔm ƒe nɔƒewo wònyo wu bliboe vaseɖe esime nuteɖeamedzi ƒe akpa si sɔ gbɔ wu la le 0.1 GPa te eye ŋusẽ ƒe akpa si sɔ gbɔ wu la le 0.02 eV/Å te. Le anyigba ƒe nɔnɔmetata me la, FAPbI3 ƒe anyigba ƒe goglome nye ƒuƒoƒo 4, ete ƒuƒoƒoa ƒe atɔm siwo woɖo ɖi siwo srɔ̃a FAPbI3 ƒe ŋutilã, eye ƒuƒoƒo etɔ̃ siwo le etame ate ŋu aʋuʋu faa le optimization ƒe ɖoɖoa me. PbC2O4 ƒe ƒuƒoƒoa ƒe titrime nye 1 ML eye wòle FAPbI3 ƒe I-nuwuƒe ƒe anyigba, afisi Pb bla ɖe 1 I kple 4 O ŋu le.
Ne èdi nyatakaka bubuwo tso numekukua ƒe ɖoɖoa ŋu la, kpɔ Natural Portfolio Report Abstract si do ƒome kple nyati sia.
Nyatakaka siwo katã woxɔ alo wodzro le numekuku sia me la le nyati si wota me, kpakple nyatakaka siwo do alɔe kple nyatakaka xoxowo ƒe faɛlwo me. Nyatakaka xoxo siwo woɖe fia le numekuku sia me la le https://doi.org/10.6084/m9.figshare.2410016440. Wotsɔ nyatakakatsoƒewo na nyati sia.
Green, M. kple ame bubuwo. Ɣe ƒe Lãmenugbagbeviwo ƒe Dɔwɔwɔ Nyuie ƒe Tablawo (57th ed.). ɖoɖowɔɖia. fotoelektrikŋusẽ. dɔwɔnu si woatsɔ awɔ dɔe. mᴐbibia. 29, 3-15 (ƒe 2021) ƒe ɣleti.
Parker J. kple ame bubuwo. Perovskite ƒe ƒuƒoƒo ƒe tsitsi dzi ɖuɖu to alkyl ammonium chloride siwo me dzoxɔxɔ le zazã me. Dzɔdzɔme 616, 724-730 (2023).
Zhao Y. kple ame bubuwo. Inactive (PbI2)2RbCl naa perovskite filmwo li ke na ɣe ƒe keklẽŋusẽ ƒe lãmenugbagbevi siwo wɔa dɔ nyuie ŋutɔ. Dzɔdzɔmeŋutinunya 377, 531-534 (2022).
Tan, K. kple ame bubuwo. Perovskite ɣe ƒe lãmenugbagbevi siwo wogbugbɔ trɔ to dimethylacridinyl dopant zazã me. Dzɔdzɔme, 620, 545-551 (2023).
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