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Ua hoʻohana nui ʻia ka passivation hemahema e hoʻomaikaʻi i ka hana o nā cell solar triiodide perovskite alakaʻi, akā ʻaʻole maopopo ka hopena o nā hemahema like ʻole ma ke kūpaʻa α-phase; Maanei, me ka hoʻohana ʻana i ke kumumanaʻo hana density, ʻike mākou no ka manawa mua i ke ala degradation o ka formamidine lead triiodide perovskite mai α-phase a i δ-phase a aʻo i ka hopena o nā hemahema like ʻole ma ka pale ikehu hoʻololi phase. Ua wānana nā hopena simulation e hiki ke hoʻoulu i ka degradation no ka mea e hoʻohaʻahaʻa nui lākou i ka pale ikehu no ka hoʻololi phase α-δ a loaʻa ka ikehu hoʻokumu haʻahaʻa loa ma ka ʻili perovskite. ʻO ka hoʻokomo ʻana o kahi papa mānoanoa o ka oxalate alakaʻi wai-insoluble ma luna o ka ʻili perovskite e kāohi nui i ka decomposition o ka α-phase, e pale ana i ka neʻe ʻana a me ka volatilization o iodine. Eia kekahi, hoʻemi nui kēia hoʻolālā i ka interfacial nonradiative recombination a hoʻonui i ka pono o nā cell solar i 25.39% (hōʻoia ʻia 24.92%). Hiki i ka hāmeʻa i wehe ʻole ʻia ke mālama i kona pono mua he 92% ma hope o ka hana ʻana ma ka mana kiʻekiʻe loa no 550 mau hola ma lalo o ka hoʻomālamalama ʻana o ka nui o ka ea he 1.5 G.
Ua hōʻea ka pono hoʻololi mana (PCE) o nā cell solar perovskite (PSC) i kahi kiʻekiʻe moʻolelo i hōʻoia ʻia o 26%1. Mai ka makahiki 2015, ua makemake nā PSC hou i ka formamidine triiodide perovskite (FAPbI3) ma ke ʻano he papa omo mālamalama ma muli o kona kūpaʻa thermal maikaʻi loa a me ka bandgap makemake kokoke i ka palena Shockley-Keisser o 2,3,4. ʻO ka mea pōʻino, ke hana nei nā kiʻiʻoniʻoni FAPbI3 i kahi hoʻololi pae mai kahi pae α ʻeleʻele i kahi pae δ non-perovskite melemele ma ka mahana o ka lumi5,6. I mea e pale ai i ka hoʻokumu ʻia ʻana o ka pae delta, ua hoʻomohala ʻia nā ʻano hui perovskite paʻakikī like ʻole. ʻO ke ʻano maʻamau e lanakila ai i kēia pilikia, ʻo ia ka hoʻohui ʻana iā FAPbI3 me ka hui pū ʻana o ka methyl ammonium (MA+), cesium (Cs+) a me nā bromide (Br-) ions7,8,9. Eia nō naʻe, ʻeha nā perovskites hybrid mai ka hoʻonui ʻana o ka bandgap a me ka hoʻokaʻawale ʻana o ka pae photoinduced, kahi e hoʻopilikia ai i ka hana a me ke kūpaʻa hana o nā PSCs hopena10,11,12.
Ua hōʻike ʻia nā haʻawina hou aku nei he kūpaʻa maikaʻi loa ka FAPbI3 kristal hoʻokahi maʻemaʻe me ka ʻole o ka doping ma muli o kona crystallinity maikaʻi loa a me nā hemahema haʻahaʻa13,14. No laila, ʻo ka hōʻemi ʻana i nā hemahema ma ka hoʻonui ʻana i ka crystallinity o ka FAPbI3 nui he hoʻolālā koʻikoʻi ia e hoʻokō ai i nā PSCs maikaʻi a paʻa2,15. Eia nō naʻe, i ka wā o ka hana ʻana o ka FAPbI3 PSC, hiki nō ke hana ʻia ka hōʻino ʻana i ka pae hexagonal non-perovskite δ melemele makemake ʻole ʻia16. Hoʻomaka pinepine ke kaʻina hana ma nā ʻili a me nā palena palaoa i ʻoi aku ka maʻalahi i ka wai, ka wela a me ka mālamalama ma muli o ke alo o nā wahi hemahema he nui17. No laila, pono ka passivation ʻili/palaoa e hoʻopaʻa i ka pae ʻeleʻele o FAPbI318. He nui nā hoʻolālā passivation hemahema, me ka hoʻolauna ʻana o nā perovskites haʻahaʻa, nā molekala Lewis acid-base, a me nā paʻakai ammonium halide, ua holomua nui i ka formamidine PSCs19,20,21,22. A hiki i kēia lā, ua kālele ʻia nā haʻawina āpau i ke kuleana o nā hemahema like ʻole i ka hoʻoholo ʻana i nā waiwai optoelectronic e like me ka recombination o ka mea lawe, ka lōʻihi o ka diffusion a me ke ʻano o ka band i loko o nā cell solar22,23,24. No ka laʻana, hoʻohana ʻia ke kumumanaʻo hana density (DFT) e wānana i nā ikehu hoʻokumu a me nā pae ikehu paʻa o nā hemahema like ʻole, kahi i hoʻohana nui ʻia e alakaʻi i ka hoʻolālā passivation kūpono20,25,26. I ka emi ʻana o ka helu o nā hemahema, hoʻomaikaʻi pinepine ka paʻa o ka hāmeʻa. Eia nō naʻe, i loko o nā formamidine PSC, pono e ʻokoʻa loa nā ʻano hana o ka mana o nā hemahema like ʻole ma ke kūpaʻa pae a me nā waiwai photoelectric. I ko mākou ʻike maikaʻi loa, ʻaʻole maopopo loa ka ʻike kumu o ke ʻano o ka hoʻoulu ʻana o nā hemahema i ka hoʻololi pae cubic i hexagonal (α-δ) a me ke kuleana o ka passivation ʻili ma ke kūpaʻa pae o α-FAPbI3 perovskite.
Maanei, hōʻike mākou i ke ala hoʻohaʻahaʻa o ka FAPbI3 perovskite mai ka ʻeleʻele α-phase a i ka melemele δ-phase a me ka mana o nā kīnā like ʻole ma ka pale ikehu o ka hoʻololi ʻana o ka α-a-δ-phase ma o DFT. ʻO nā hakahaka I, i hana maʻalahi ʻia i ka wā o ka hana ʻana i ke kiʻiʻoniʻoni a me ka hana ʻana o ka hāmeʻa, ua wānana ʻia e hoʻomaka i ka hoʻololi ʻana o ka ʻāpana α-δ. No laila, ua hoʻolauna mākou i kahi papa paʻa o ka lead oxalate (PbC2O4) i hoʻoheheʻe ʻole ʻia i ka wai a paʻa i ka kemika ma luna o FAPbI3 ma o kahi hopena in situ. Hoʻopaʻa ka ʻili oxalate lead (LOS) i ka hoʻokumu ʻana o nā hakahaka I a pale i ka neʻe ʻana o nā ion I i ka wā e hoʻoulu ʻia e ka wela, ka mālamalama, a me nā kahua uila. ʻO ka hopena LOS e hōʻemi nui i ka hui hou ʻana o ka nonradiative interfacial a hoʻomaikaʻi i ka pono o FAPbI3 PSC i 25.39% (hōʻoia ʻia i 24.92%). Ua mālama ka hāmeʻa LOS i wehe ʻole ʻia i ka 92% o kona pono mua ma hope o ka hana ʻana ma ke kiko mana kiʻekiʻe loa (MPP) no nā hola he 550 ma kahi nuipa ea hoʻohālike (AM) o 1.5 G o ka radiation.
Ua hana mua mākou i nā helu ab initio e ʻike i ke ala decomposition o ka FAPbI3 perovskite i ka neʻe ʻana mai ka pae α a i ka pae δ. Ma o kahi kaʻina hana hoʻololi pae kikoʻī, ua ʻike ʻia ua hoʻokō ʻia ka hoʻololi ʻana mai kahi octahedron ʻekolu-dimensional edge-sharing [PbI6] i loko o ka cubic α-phase o FAPbI3 i kahi octahedron ʻelua-dimensional edge-sharing [PbI6] i loko o ka hexagonal δ-phase o FAPbI3. ka haki ʻana 9. Hoʻokumu ʻo Pb-I i kahi pilina ma ka hana mua (Int-1), a hiki i kona pale ikehu i 0.62 eV/cell, e like me ka mea i hōʻike ʻia ma ke Kiʻi 1a. Ke hoʻoneʻe ʻia ka octahedron ma ke kuhikuhi [0\(\bar{1}\)1], hoʻonui ke kaulahao pōkole hexagonal mai 1×1 a i 1×3, 1×4 a komo hope i ka pae δ. ʻO ka lakio kuhikuhi o ke ala holoʻokoʻa he (011)α//(001)δ + [100]α//[100]δ. Mai ke kiʻikuhi hoʻolaha ikehu, hiki ke ʻike ʻia ma hope o ka nucleation o ka pae δ o FAPbI3 i nā pae aʻe, ʻoi aku ka haʻahaʻa o ka pale ikehu ma mua o ka hoʻololi pae α, ʻo ia hoʻi e hoʻolalelale ʻia ka hoʻololi pae. ʻIke loa, ʻo ka hana mua o ka kaohi ʻana i ka hoʻololi pae he mea koʻikoʻi inā makemake mākou e kāohi i ka hoʻohaʻahaʻa ʻana o ka pae α.
ʻO ke kaʻina hana hoʻololi pae mai ka hema a i ka ʻākau - ka pae ʻeleʻele FAPbI3 (α-phase), ka ʻoki mua ʻana o ka pilina Pb-I (Int-1) a me ka ʻoki hou ʻana o ka pilina Pb-I (Int-2, Int -3 a me Int -4) a me ka pae melemele FAPbI3 (delta phase). b Nā pale ikehu i ka hoʻololi pae α a i δ o FAPbI3 ma muli o nā hemahema kiko kūloko like ʻole. Hōʻike ka laina kiko i ka pale ikehu o kahi kristal kūpono (0.62 eV). c Ikehu o ka hoʻokumu ʻana o nā hemahema kiko mua ma ka ʻili o ka perovskite kēpau. ʻO ke axis abscissa ka pale ikehu o ka hoʻololi pae α-δ, a ʻo ke axis ordinate ka ikehu o ka hoʻokumu ʻana o ke kīnā. ʻO nā ʻāpana i hoʻoluʻu ʻia i ka hina, melemele a me ka ʻōmaʻomaʻo he ʻano I (haʻahaʻa EB-kiʻekiʻe FE), ʻano II (kiʻekiʻe FE) a me ke ʻano III (haʻahaʻa EB-haʻahaʻa FE), kēlā me kēia. d Ikehu o ka hoʻokumu ʻana o nā hemahema VI a me LOS o FAPbI3 i ka mana. e I pale i ka neʻe ʻana o ka ion i ka mana a me LOS o FAPbI3. f - hōʻike kiʻi o ka neʻe ʻana o nā ion I (nā poepoe ʻalani) a me gLOS FAPbI3 (hina, kēpau; poni (ʻalani), iodine (iodine lawe lima)) ma ka mana gf (hema: ʻike luna; ʻākau: ʻāpana kea, ʻeleʻele); kalapona; polū māmā - naikokene; ʻulaʻula - oxygen; poni māmā - hydrogen). Hāʻawi ʻia ka ʻikepili kumu ma ke ʻano o nā faila ʻikepili kumu.
A laila ua aʻo pono mākou i ka mana o nā hemahema kiko kūloko like ʻole (me PbFA, IFA, PbI, a me IPb antisite occupancy; Pbi a me Ii interstitial atoms; a me VI, VFA, a me VPb vacancies), i manaʻo ʻia he mau kumu koʻikoʻi. e hōʻike ʻia ana nā mea e hoʻoulu ai i ka hoʻohaʻahaʻa ʻana o ka pae atomika a me ka ikehu ma ke Kiʻi 1b a me ka Papa Hoʻohui 1. ʻO ka mea hoihoi, ʻaʻole nā ​​​​hemahema āpau e hōʻemi i ka pale ikehu o ka hoʻololi ʻana o ka pae α-δ (Kiʻi 1b). Manaʻo mākou he mea hōʻino nā hemahema i loaʻa nā ikehu hoʻokumu haʻahaʻa a me nā pale ikehu hoʻololi pae α-δ haʻahaʻa i ka paʻa o ka pae. E like me ka mea i hōʻike mua ʻia, ua manaʻo ʻia he kūpono nā ʻili waiwai kēpau no ka formamidine PSC27. No laila, ke nānā nei mākou i ka ʻili i hoʻopau ʻia e PbI2 (100) ma lalo o nā kūlana waiwai kēpau. Hōʻike ʻia ka ikehu hoʻokumu kīnā o nā hemahema kiko kūloko o ka ʻili ma ke Kiʻi 1c a me ka Papa Hoʻohui 1. Ma muli o ka pale ikehu (EB) a me ka ikehu hoʻokumu hoʻololi pae (FE), ua hoʻokaʻawale ʻia kēia mau hemahema i ʻekolu ʻano. ʻAno I (EB haʻahaʻa-FE kiʻekiʻe): ʻOiai ʻo IPb, VFA a me VPb e hōʻemi nui i ka pale ikehu i ka hoʻololi pae, he nui ko lākou ikehu hoʻokumu. No laila, ke manaʻoʻiʻo nei mākou he hopena palena ko kēia mau ʻano kīnā i nā hoʻololi pae ʻoiai ʻaʻole lākou i hoʻokumu pinepine ʻia. ʻAno II (EB kiʻekiʻe): Ma muli o ka pale ikehu hoʻololi pae α-δ i hoʻomaikaʻi ʻia, ʻaʻole hōʻino nā kīnā anti-site PbI, IFA a me PbFA i ke kūpaʻa pae o ka α-FAPbI3 perovskite. ʻAno III (EB haʻahaʻa-FE haʻahaʻa): ʻO nā kīnā VI, Ii a me Pbi me nā ikehu hoʻokumu haʻahaʻa hiki ke hoʻoulu i ka hōʻino ʻana o ka pae ʻeleʻele. ʻOi aku ka hāʻawi ʻia ʻana o ka FE haʻahaʻa loa a me EB VI, ke manaʻoʻiʻo nei mākou ʻo ka hoʻolālā kūpono loa ka hōʻemi ʻana i nā hakahaka I.
No ka hōʻemi ʻana i ka VI, ua hoʻomohala mākou i kahi papa mānoanoa o PbC2O4 e hoʻomaikaʻi i ka ʻili o FAPbI3. Ke hoʻohālikelike ʻia me nā mea hoʻololi paʻakai halide organik e like me phenylethylammonium iodide (PEAI) a me n-octylammonium iodide (OAI), ʻo PbC2O4, ʻaʻohe ona ion halogen mobile, he paʻa kemika, ʻaʻole hiki ke hoʻoheheʻe ʻia i ka wai, a maʻalahi hoʻi e hoʻopau ʻia ma hope o ka hoʻoulu ʻana. Hoʻopaʻa maikaʻi ʻia ka makū o ka ʻili a me ke kahua uila o ka perovskite. ʻO ka solubility o PbC2O4 i ka wai he 0.00065 g/L wale nō, ʻoi aku ka haʻahaʻa ma mua o PbSO428. ʻOi aku ka mea nui, hiki ke hoʻomākaukau mālie ʻia nā papa mānoanoa a like o LOS ma nā kiʻiʻoniʻoni perovskite me ka hoʻohana ʻana i nā hopena in situ (e nānā ma lalo). Ua hana mākou i nā simulations DFT o ka pilina interfacial ma waena o FAPbI3 a me PbC2O4 e like me ka mea i hōʻike ʻia ma ke Kiʻi Hoʻohui 1. Hōʻike ka Papa Hoʻohui 2 i ka ikehu hoʻokumu kīnā ma hope o ka hoʻokomo ʻana o LOS. Ua ʻike mākou ʻaʻole wale ka LOS e hoʻonui i ka ikehu hoʻokumu o nā hemahema VI ma 0.69–1.53 eV (Kiʻi 1d), akā hoʻonui pū i ka ikehu hoʻāla o I ma ka ʻili neʻe a me ka ʻili puka (Kiʻi 1e). I ke kahua mua, neʻe nā ion I ma ka ʻili perovskite, e waiho ana i nā ion VI ma kahi kūlana lattice me kahi pale ikehu o 0.61 eV. Ma hope o ka hoʻokomo ʻana o LOS, ma muli o ka hopena o ke keakea steric, piʻi ka ikehu hoʻāla no ka neʻe ʻana o nā ion I i . 1.28 eV. I ka wā o ka neʻe ʻana o nā ion I e haʻalele ana i ka ʻili perovskite, ʻoi aku ke kiʻekiʻe o ka pale ikehu ma ka VOC ma mua o ka laʻana kaohi (Kiʻi 1e). Hōʻike ʻia nā kiʻikuhi schematic o nā ala neʻe ion I ma ka kaohi a me LOS FAPbI3 ma ke Kiʻi 1 f a me g, kēlā me kēia. Hōʻike nā hopena simulation hiki i ka LOS ke kāohi i ka hoʻokumu ʻana o nā hemahema VI a me ka volatilization o I, no laila e pale ana i ka nucleation o ka hoʻololi ʻana o ka pae α a i δ.
Ua hoʻāʻo ʻia ka hopena ma waena o ka waikawa oxalic a me ka FAPbI3 perovskite. Ma hope o ke kāwili ʻana i nā hopena o ka waikawa oxalic a me FAPbI3, ua hoʻokumu ʻia kahi nui o ka precipitate keʻokeʻo, e like me ka mea i hōʻike ʻia ma ke Kiʻi Hoʻohui 2. Ua ʻike ʻia ka huahana pauka he mea PbC2O4 maʻemaʻe me ka hoʻohana ʻana i ka X-ray diffraction (XRD) (Kiʻi Hoʻohui 3) a me ka Fourier transform infrared spectroscopy (FTIR) (Kiʻi Hoʻohui 4). Ua ʻike mākou he mea hoʻoheheʻe loa ka waikawa oxalic i ka isopropyl alcohol (IPA) ma ka mahana o ka lumi me ka solubility ma kahi o 18 mg/mL, e like me ka mea i hōʻike ʻia ma ke Kiʻi Hoʻohui 5. ʻOi aku ka maʻalahi o ka hana ʻana ma hope mai ʻoiai ʻo IPA, ma ke ʻano he mea hoʻoheheʻe passivation maʻamau, ʻaʻole ia e hōʻino i ka papa perovskite ma mua o ka manawa pōkole29. No laila, ma ka hoʻokomo ʻana i ka ʻili perovskite i loko o ka hopena waikawa oxalic a i ʻole ke kau ʻana i ka wili ʻana i ka hopena waikawa oxalic ma luna o ka perovskite, hiki ke loaʻa koke ʻia ka PbC2O4 lahilahi a mānoanoa ma luna o ka ʻili o ka ʻili perovskite e like me ke kaulike kemika ma lalo nei: H2C2O4 + FAPbI3 = PbC2O4 + FAI +HI. Hiki ke hoʻoheheʻe ʻia ka FAI i loko o IPA a pēlā e wehe ʻia ai i ka wā e kuke ai. Hiki ke hoʻomalu ʻia ka mānoanoa o LOS e ka manawa hana a me ka noʻonoʻo mua.
Hōʻike ʻia nā kiʻi microscopy electron scanning (SEM) o nā kiʻiʻoniʻoni kaohi a me nā kiʻiʻoniʻoni LOS perovskite ma nā Kiʻi 2a,b. Hōʻike nā hopena ua mālama maikaʻi ʻia ke ʻano o ka ʻili perovskite, a ua waiho ʻia kahi nui o nā ʻāpana liʻiliʻi ma luna o ka ʻili palaoa, kahi e hōʻike ai i kahi papa PbC2O4 i hoʻokumu ʻia e ka hopena in-situ. Loaʻa i ka kiʻiʻoniʻoni LOS perovskite kahi ʻili palupalu iki (Kiʻi Hoʻohui 6) a me kahi kihi pili wai nui aʻe i hoʻohālikelike ʻia me ka kiʻiʻoniʻoni kaohi (Kiʻi Hoʻohui 7). Ua hoʻohana ʻia ka microscopy electron transverse transmission kiʻekiʻe (HR-TEM) e hoʻokaʻawale i ka papa ʻili o ka huahana. Ke hoʻohālikelike ʻia me ka kiʻiʻoniʻoni kaohi (Kiʻi 2c), ʻike maopopo ʻia kahi papa lahilahi like a mānoanoa me ka mānoanoa o kahi 10 nm ma luna o ka LOS perovskite (Kiʻi 2d). Ma ka hoʻohana ʻana i ka microscopy electron scanning annular dark-field high-angle (HAADF-STEM) e nānā i ka pilina ma waena o PbC2O4 a me FAPbI3, hiki ke ʻike maopopo ʻia ke alo o nā ʻāpana crystalline o FAPbI3 a me nā ʻāpana amorphous o PbC2O4 (Kiʻi Hoʻohui 8). Ua wehewehe ʻia ka ʻano o ka perovskite ma hope o ka mālama ʻana i ka waikawa oxalic e nā ana X-ray photoelectron spectroscopy (XPS), e like me ka mea i hōʻike ʻia ma nā Kiʻi 2e-g. Ma ke Kiʻi 2e, ʻo nā piko C 1s a puni 284.8 eV a me 288.5 eV no nā hōʻailona CC a me FA kikoʻī, kēlā me kēia. Ke hoʻohālikelike ʻia me ka membrane kaohi, ua hōʻike ka membrane LOS i kahi piko hou ma 289.2 eV, i hāʻawi ʻia iā C2O42-. Hōʻike ka spectrum O 1s o LOS perovskite i ʻekolu mau piko O 1s ʻokoʻa kemika ma 531.7 eV, 532.5 eV, a me 533.4 eV, e pili ana i ka COO deprotonated, C=O o nā hui oxalate i hoʻopaʻa ʻia 30 a me nā ʻātoma O o ka ʻāpana OH (Kiʻi 2e). )). No ka hāpana kaohi, ua ʻike ʻia kahi piko O 1s liʻiliʻi wale nō, hiki ke hoʻopili ʻia i ka oxygen chemisorbed ma luna o ka ʻili. Aia nā ʻano membrane kaohi o Pb 4f7/2 a me Pb 4f5/2 ma 138.4 eV a me 143.3 eV, kēlā me kēia. Ua ʻike mākou ua hōʻike ka LOS perovskite i kahi neʻe o ka piko Pb ma kahi o 0.15 eV i ka ikehu hoʻopaʻa kiʻekiʻe, e hōʻike ana i kahi pilina ikaika ma waena o nā ʻātoma C2O42- a me Pb (Kiʻi 2g).
a Nā kiʻi SEM o ka mana a me nā kiʻiʻoniʻoni perovskite LOS b, ka nānā ʻana ma luna. c ʻO ka microscopy electron transmission cross-sectional kiʻekiʻe (HR-TEM) o ka mana a me nā kiʻiʻoniʻoni perovskite LOS d. XPS kiʻekiʻe o e C 1s, f O 1s a me g Pb 4f perovskite. Hāʻawi ʻia ka ʻikepili kumu ma ke ʻano o nā faila ʻikepili kumu.
Wahi a nā hopena DFT, ua wānana ʻia ma ke kumumanaʻo e hiki i nā hemahema VI a me ka neʻe ʻana o I ke kumu maʻalahi o ka hoʻololi ʻana o ka pae mai α a i δ. Ua hōʻike ʻia nā hōʻike mua e hoʻokuʻu koke ʻia ʻo I2 mai nā kiʻiʻoniʻoni perovskite PC i ka wā o ka photoimmersion ma hope o ka hōʻike ʻana i nā kiʻiʻoniʻoni i ka mālamalama a me ke kaumaha wela31,32,33. No ka hōʻoia ʻana i ka hopena paʻa o ka lead oxalate ma ka α-phase o ka perovskite, ua hoʻokomo mākou i nā kiʻiʻoniʻoni kaohi a me nā kiʻiʻoniʻoni LOS perovskite i loko o nā ʻōmole aniani moakaka i loaʻa ka toluene, a laila hoʻomālamalama iā lākou me 1 lā no 24 hola. Ua ana mākou i ka omo ʻana o ka ultraviolet a me ka mālamalama ʻike ʻia (UV-Vis). ) ka hopena toluene, e like me ka mea i hōʻike ʻia ma ke Kiʻi 3a. Ke hoʻohālikelike ʻia me ka laʻana kaohi, ua ʻike ʻia ka ikaika o ka omo ʻana o I2 haʻahaʻa loa i ka hihia o LOS-perovskite, e hōʻike ana hiki i ka LOS compact ke kāohi i ka hoʻokuʻu ʻana o I2 mai ka kiʻiʻoniʻoni perovskite i ka wā o ka hoʻokomo ʻana o ka mālamalama. Hōʻike ʻia nā kiʻi o nā kiʻiʻoniʻoni kaohi kahiko a me nā kiʻiʻoniʻoni LOS perovskite i nā insets o nā Kiʻi 3b a me c. He ʻeleʻele nō ka LOS perovskite, ʻoiai ua melemele ka hapa nui o ke kiʻiʻoniʻoni hoʻomalu. Hōʻike ʻia nā spectra absorption UV-visible o ke kiʻiʻoniʻoni i hoʻokomo ʻia ma nā Kiʻi 3b, c. Ua ʻike mākou ua emi maopopo ka absorption e pili ana iā α i loko o ke kiʻiʻoniʻoni hoʻomalu. Ua hana ʻia nā ana X-ray e palapala i ka ulu ʻana o ke ʻano kristal. Ma hope o 24 mau hola o ka hoʻomālamalama ʻana, ua hōʻike ka perovskite hoʻomalu i kahi hōʻailona δ-phase melemele ikaika (11.8°), ʻoiai ua mālama mau ka LOS perovskite i kahi pae ʻeleʻele maikaʻi (Kiʻi 3d).
ʻO nā spectra absorption UV-ʻike ʻia o nā hopena toluene kahi i hoʻokomo ʻia ai ke kiʻiʻoniʻoni hoʻomalu a me ke kiʻiʻoniʻoni LOS ma lalo o 1 lā no 24 mau hola. Hōʻike ka inset i kahi vial kahi i hoʻokomo ʻia ai kēlā me kēia kiʻiʻoniʻoni i loko o ka nui like o ka toluene. b Nā spectra absorption UV-Vis o ke kiʻiʻoniʻoni hoʻomalu a me c ke kiʻiʻoniʻoni LOS ma mua a ma hope o 24 hola o ka hoʻokomo ʻana ma lalo o 1 lā. Hōʻike ka inset i kahi kiʻi o ke kiʻiʻoniʻoni hoʻāʻo. d Nā ʻano diffraction X-ray o nā kiʻiʻoniʻoni hoʻomalu a me LOS ma mua a ma hope o 24 hola o ka hōʻike ʻana. Nā kiʻi SEM o ke kiʻiʻoniʻoni hoʻomalu e a me ke kiʻiʻoniʻoni f LOS ma hope o 24 mau hola o ka hōʻike ʻana. Hāʻawi ʻia ka ʻikepili kumu ma ke ʻano o nā faila ʻikepili kumu.
Ua hana mākou i nā ana ʻana o ka microscopy electron scanning (SEM) e nānā i nā loli microstructural o ka ʻili perovskite ma hope o 24 mau hola o ka hoʻomālamalama ʻana, e like me ka mea i hōʻike ʻia ma nā Kiʻi 3e,f. I loko o ke kiʻi hoʻomalu, ua luku ʻia nā hua nui a hoʻolilo ʻia i mau nila liʻiliʻi, kahi i kūlike me ke ʻano o ka huahana δ-phase FAPbI3 (Kiʻi 3e). No nā kiʻiʻoniʻoni LOS, noho maikaʻi nā hua perovskite (Kiʻi 3f). Ua hōʻoia nā hopena ʻo ka nalowale o I e hoʻoulu nui i ka hoʻololi ʻana mai ka pae ʻeleʻele i ka pae melemele, ʻoiai ʻo PbC2O4 e hoʻopaʻa i ka pae ʻeleʻele, e pale ana i ka nalowale o I. ʻOiai ʻoi aku ka kiʻekiʻe o ka nui o ka hakahaka ma ka ʻili ma mua o ka nui o ka hua,34 ʻoi aku ka nui o kēia pae e hana ʻia ma ka ʻili o ka hua. e hoʻokuʻu ana i ka iodine a hana i ka VI. E like me ka wānana a DFT, hiki i ka LOS ke kāohi i ka hoʻokumu ʻia ʻana o nā hemahema VI a pale i ka neʻe ʻana o nā ion I i ka ʻili perovskite.
Eia kekahi, ua aʻo ʻia ka hopena o ka papa PbC2O4 ma ke kūpaʻa ʻana o ka makū o nā kiʻiʻoniʻoni perovskite i ka lewa lewa (ka haʻahaʻa pili 30-60%). E like me ka mea i hōʻike ʻia ma ke Kiʻi Hoʻohui 9, ua ʻeleʻele mau ka LOS perovskite ma hope o 12 mau lā, ʻoiai ua melemele ke kiʻiʻoniʻoni hoʻomalu. Ma nā ana XRD, hōʻike ke kiʻiʻoniʻoni hoʻomalu i kahi piko ikaika ma 11.8° e pili ana i ka pae δ o FAPbI3, ʻoiai ua mālama maikaʻi ka LOS perovskite i ka pae α ʻeleʻele (Kiʻi Hoʻohui 10).
Ua hoʻohana ʻia ka photoluminescence kūlana paʻa (PL) a me ka photoluminescence i hoʻonā ʻia i ka manawa (TRPL) e aʻo i ka hopena passivation o ka lead oxalate ma ka ʻili perovskite. Ma ke Kiʻi. Hōʻike ke Kiʻi 4a ua hoʻonui ka ʻili LOS i ka ikaika PL. Ma ke kiʻi palapala ʻāina PL, ʻoi aku ka kiʻekiʻe o ka ikaika o ka ʻili LOS ma luna o ka ʻāpana holoʻokoʻa o 10 × 10 μm2 ma mua o ka ʻili hoʻomalu (Kiʻi Hoʻohui 11), e hōʻike ana ua hoʻopau like ʻo PbC2O4 i ka ʻili perovskite. Hoʻoholo ʻia ke ola o ka mea lawe ma ka hoʻokokoke ʻana i ka palaho TRPL me kahi hana exponential hoʻokahi (Kiʻi 4b). ʻO ke ola o ka mea lawe o ka ʻili LOS he 5.2 μs, ʻoi aku ka lōʻihi ma mua o ka ʻili hoʻomalu me ke ola o ka mea lawe he 0.9 μs, e hōʻike ana i ka hoʻemi ʻia ʻana o ka recombination nonradiative o ka ʻili.
ʻO ka PL kūlana paʻa a me ka b-spectra o ka PL manawa pōkole o nā kiʻiʻoniʻoni perovskite ma nā substrates aniani. c SP curve o ka hāmeʻa (FTO/TiO2/SnO2/perovskite/spiro-OMeTAD/Au). d EQE spectrum a me Jsc EQE spectrum i hoʻohui ʻia mai ka hāmeʻa kūpono loa. d Hilinaʻi o ka ikaika o ka mālamalama o kahi hāmeʻa perovskite ma ka kiʻikuhi Voc. f ʻO ka loiloi MKRC maʻamau e hoʻohana ana i kahi ITO/PEDOT:PSS/perovskite/PCBM/Au mea hana lua maʻemaʻe. ʻO VTFL ka volta hoʻopiha pahele kiʻekiʻe loa. Mai kēia mau ʻikepili ua helu mākou i ka nui o ka pahele (Nt). Hāʻawi ʻia ka ʻikepili kumu ma ke ʻano o nā faila ʻikepili kumu.
No ke aʻo ʻana i ka hopena o ka papa oxalate alakaʻi ma ka hana o ka hāmeʻa, ua hoʻohana ʻia kahi ʻano hoʻopili kuʻuna FTO/TiO2/SnO2/perovskite/spiro-OMeTAD/Au. Hoʻohana mākou i ka formamidine chloride (FACl) ma ke ʻano he mea hoʻohui i ka perovskite precursor ma kahi o ka methylamine hydrochloride (MACl) e hoʻokō i ka hana hāmeʻa maikaʻi aʻe, ʻoiai hiki iā FACl ke hāʻawi i ka maikaʻi o ke kristal a pale i ka band gap o FAPbI335 (e ʻike i nā Kiʻi Hoʻohui 1 a me 2 no ka hoʻohālikelike kikoʻī). ). 12-14). Ua koho ʻia ʻo IPA ma ke ʻano he antisolvent no ka mea hāʻawi ia i ka maikaʻi o ke kristal a me ke kuhikuhi makemake ʻia i nā kiʻiʻoniʻoni perovskite i hoʻohālikelike ʻia me diethyl ether (DE) a i ʻole chlorobenzene (CB) 36 (Nā Kiʻi Hoʻohui 15 a me 16). Ua hoʻomaikaʻi pono ʻia ka mānoanoa o PbC2O4 e kaulike maikaʻi i ka passivation defect a me ka lawe ʻana i ka ukana ma ka hoʻoponopono ʻana i ka nui o ka waikawa oxalic (Kiʻi Hoʻohui 17). Hōʻike ʻia nā kiʻi SEM cross-sectional o nā mea hoʻomalu i hoʻomaikaʻi ʻia a me nā mea LOS ma ke Kiʻi Hoʻohui 18. Hōʻike ʻia nā piʻo density au maʻamau (CD) no nā mea hoʻomalu a me nā mea LOS ma ke Kiʻi 4c, a hāʻawi ʻia nā palena i unuhi ʻia ma ka Papa Hoʻohui 3. ʻO nā cell hoʻomalu hoʻololi mana kiʻekiʻe loa (PCE) 23.43% (22.94%), Jsc 25.75 mA cm-2 (25.74 mA cm-2), Voc 1.16 V (1.16 V) a me ka scan hoʻohuli (mua). ʻO ka mea hoʻopiha (FF) he 78.40% (76.69%). ʻO ka PCE LOS PSC kiʻekiʻe loa he 25.39% (24.79%), ʻo Jsc he 25.77 mA cm-2, ʻo Voc he 1.18 V, ʻo FF he 83.50% (81.52%) mai ka hoʻohuli (Scan mua a i). Ua hoʻokō ka hāmeʻa LOS i kahi hana photovoltaic i hōʻoia ʻia o 24.92% i loko o kahi keʻena hoʻokolohua photovoltaic ʻaoʻao ʻekolu i hilinaʻi ʻia (Kiʻi Hoʻohui 19). Ua hāʻawi ka pono quantum waho (EQE) i kahi Jsc i hoʻohui ʻia o 24.90 mA cm-2 (mana) a me 25.18 mA cm-2 (LOS PSC), kēlā me kēia, kahi i kūlike maikaʻi me ka Jsc i ana ʻia ma ka spectrum AM 1.5 G maʻamau (Kiʻi .4d). . Hōʻike ʻia ka hoʻolaha helu o nā PCE i ana ʻia no ka mana a me nā LOS PSC ma ke Kiʻi Hoʻohui 20.
E like me ka mea i hōʻike ʻia ma ke Kiʻi 4e, ua helu ʻia ka pilina ma waena o Voc a me ka ikaika o ka mālamalama e aʻo i ka hopena o PbC2O4 ma ka hoʻohuihui ʻili i kōkua ʻia e ka pahele. ʻO ka pali o ka laina i hoʻopili ʻia no ka hāmeʻa LOS he 1.16 kBT/sq, ʻoi aku ka haʻahaʻa ma mua o ka pali o ka laina i hoʻopili ʻia no ka hāmeʻa kaohi (1.31 kBT/sq), e hōʻoia ana he pono ka LOS no ka pale ʻana i ka hoʻohuihui ʻili e nā decoys. Hoʻohana mākou i ka ʻenehana hoʻopaʻa palena manawa (SCLC) e ana i ka nui o ka hemahema o kahi kiʻiʻoniʻoni perovskite ma ke ana ʻana i ke ʻano IV pouli o kahi hāmeʻa lua (ITO/PEDOT:PSS/perovskite/spiro-OMeTAD/Au) e like me ka mea i hōʻike ʻia ma ke kiʻi. 4f Hōʻike. Ua helu ʻia ka nui o ka pahele e ke ʻano Nt = 2ε0εVTFL/eL2, kahi ʻo ε ka dielectric constant o ka perovskite film, ʻo ε0 ka dielectric constant o ka vacuum, ʻo VTFL ka voltage palena no ka hoʻopiha ʻana i ka pahele, ʻo e ka uku, ʻo L ka mānoanoa o ka perovskite film (650 nm). Ua helu ʻia ka hemahema o ka mea VOC he 1.450 × 1015 cm–3, ʻoi aku ka haʻahaʻa ma mua o ka hemahema o ka mea hoʻomalu, ʻo ia hoʻi he 1.795 × 1015 cm–3.
Ua hoʻāʻo ʻia ka mea hana i hoʻopaʻa ʻole ʻia ma ke kiko mana kiʻekiʻe loa (MPP) ma lalo o ke ao piha ma lalo o ka naikokene e nānā i kona kūpaʻa hana lōʻihi (Kiʻi 5a). Ma hope o 550 mau hola, ua mālama mau ka mea hana LOS i 92% o kona pono kiʻekiʻe loa, ʻoiai ua hāʻule ka hana o ka mea hoʻomalu i 60% o kāna hana mua. Ua ana ʻia ka hoʻolaha ʻana o nā mea i loko o ka mea hana kahiko e ka spectrometry mass ion lua o ka manawa lele (ToF-SIMS) (Kiʻi 5b, c). Hiki ke ʻike ʻia kahi hōʻiliʻili nui o ka iodine ma ka ʻāpana hoʻomalu gula kiʻekiʻe. ʻAʻole i hoʻokomo ʻia nā kūlana o ka pale kinoea inert i nā mea hoʻohaʻahaʻa i ke kaiapuni e like me ka makū a me ka oxygen, e hōʻike ana he kuleana nā ʻano hana kūloko (ʻo ia hoʻi, ka neʻe ʻana o ka ion). Wahi a nā hopena ToF-SIMS, ua ʻike ʻia nā ion I- a me AuI2- i loko o ka electrode Au, e hōʻike ana i ka hoʻolaha ʻana o I mai ka perovskite i Au. ʻO ka ikaika hōʻailona o nā ion I- a me AuI2- i loko o ka mea hoʻomalu he 10 mau manawa kiʻekiʻe ma mua o ka laʻana VOC. Ua hōʻike ʻia nā hōʻike mua e hiki i ka permeation ion ke alakaʻi i ka emi wikiwiki ʻana o ka conductivity hole o spiro-OMeTAD a me ka corrosion kemika o ka papa electrode luna, no laila e hōʻino ana i ka pilina interfacial i loko o ka hāmeʻa37,38. Ua wehe ʻia ka electrode Au a ua hoʻomaʻemaʻe ʻia ka papa spiro-OMeTAD mai ka substrate me kahi hopena chlorobenzene. A laila ua wehewehe mākou i ke kiʻiʻoniʻoni me ka hoʻohana ʻana i ka grazing incidence X-ray diffraction (GIXRD) (Kiʻi 5d). Hōʻike nā hopena he kiʻiʻoniʻoni diffraction maopopo ka kiʻekiʻe ma 11.8° o ka diffraction film mana, ʻoiai ʻaʻohe piko diffraction hou e ʻike ʻia ma ka LOS sample. Hōʻike nā hopena he nui nā pohō o nā ions I i loko o ke kiʻiʻoniʻoni mana e alakaʻi ai i ka hanauna o ka pae δ, ʻoiai ma ke kiʻiʻoniʻoni LOS ua pale maopopo ʻia kēia kaʻina hana.
575 mau hola o ka hahai mau ʻana o MPP o kahi mea i hoʻopaʻa ʻole ʻia i loko o kahi lewa naikokene a me 1 lā me ka ʻole o kahi kānana UV. Ka hoʻolaha ʻana o ToF-SIMS o nā ion b I- a me c AuI2- i loko o ka mea hoʻomalu LOS MPP a me ka mea hana ʻelemakule. Pili nā aka o ka melemele, ʻōmaʻomaʻo a me ka ʻalani iā ​​Au, Spiro-OMeTAD a me ka perovskite. d GIXRD o ka ʻili perovskite ma hope o ka hoʻāʻo MPP. Hāʻawi ʻia ka ʻikepili kumu ma ke ʻano o nā faila ʻikepili kumu.
Ua ana ʻia ka conductivity e pili ana i ka mahana e hōʻoia i ka hiki iā PbC2O4 ke kāohi i ka neʻe ʻana o ka ion (Kiʻi Hoʻohui 21). Hoʻoholo ʻia ka ikehu hoʻāla (Ea) o ka neʻe ʻana o ka ion ma ke ana ʻana i ka loli o ka conductivity (σ) o ke kiʻiʻoniʻoni FAPbI3 ma nā mahana like ʻole (T) a me ka hoʻohana ʻana i ka pilina Nernst-Einstein: σT = σ0exp(−Ea/kBT), kahi he mau ʻo σ0, ʻo kB ka mau ʻo Boltzmann. Loaʻa iā mākou ka waiwai o Ea mai ka pali o ln(σT) versus 1/T, ʻo ia hoʻi ʻo 0.283 eV no ka mana a me 0.419 eV no ka hāmeʻa LOS.
I ka hōʻuluʻulu manaʻo, hāʻawi mākou i kahi ʻōnaehana kumumanaʻo e ʻike ai i ke ala hōʻino o ka FAPbI3 perovskite a me ka mana o nā kīnā like ʻole ma ka pale ikehu o ka hoʻololi ʻana o ka pae α-δ. Ma waena o kēia mau kīnā, ua wānana ʻia nā hemahema VI e maʻalahi ke kumu o ka hoʻololi ʻana o ka pae mai α a i δ. Hoʻokomo ʻia kahi papa paʻa paʻa o PbC2O4 i hoʻoheheʻe ʻole ʻia i ka wai a paʻa kemika e hoʻopaʻa i ka pae α o FAPbI3 ma ke kāohi ʻana i ka hoʻokumu ʻana o nā hakahaka I a me ka neʻe ʻana o nā ion I. Hoʻemi nui kēia hoʻolālā i ka hui hou ʻole ʻana o ka interfacial, hoʻonui i ka pono o ke kelepona solar i 25.39%, a hoʻomaikaʻi i ke kūpaʻa hana. Hāʻawi kā mākou mau hopena i ke alakaʻi no ka hoʻokō ʻana i nā PSC formamidine kūpono a paʻa hoʻi ma ke kāohi ʻana i ka hoʻololi ʻana o ka pae α a i δ i hoʻokomo ʻia e ka hemahema.
Ua kūʻai ʻia ʻo Titanium(IV) isopropoxide (TTIP, 99.999%) mai Sigma-Aldrich. Ua kūʻai ʻia ka waikawa hydrochloric (HCl, 35.0–37.0%) a me ka ethanol (anhydrous) mai Guangzhou Chemical Industry. Ua kūʻai ʻia ʻo SnO2 (15 wt% tin(IV) oxide colloidal dispersion) mai Alfa Aesar. Ua kūʻai ʻia ʻo Lead(II) iodide (PbI2, 99.99%) mai TCI Shanghai (Kina). ʻO 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)-9,9′-spirobifluorene (Spiro-OMeTAD, ≥99.5%), lithium bis(trifluoromethane)sulfonylimide (Li-TFSI, 99.95%), 4-tert -butylpyridine (tBP, 96%) i kūʻai ʻia mai Xi'an Polymer Light Technology Company (Kina). N,N-dimethylformamide (DMF, 99.8%), dimethyl sulfoxide (DMSO, 99.9%), isopropyl alcohol (IPA, 99.8%), chlorobenzene (CB, 99.8%), acetonitrile (ACN). Kūʻai ʻia mai Sigma-Aldrich. Ua kūʻai ʻia ka waikawa Oxalic (H2C2O4, 99.9%) mai Macklin. Ua hoʻohana ʻia nā kemika āpau e like me ka mea i loaʻa me ka ʻole o nā hoʻololi ʻē aʻe.
Ua hoʻomaʻemaʻe ʻia nā substrates ITO a i ʻole FTO (1.5 × 1.5 cm2) me ka detergent, acetone, a me ka ethanol no 10 min, a laila hoʻomaloʻo ʻia ma lalo o ke kahawai nitrogen. Ua waiho ʻia kahi papa pale TiO2 mānoanoa ma luna o kahi substrate FTO me ka hoʻohana ʻana i kahi hopena o ka titanium diisopropoxybis (acetylacetonate) i loko o ka ethanol (1/25, v/v) i waiho ʻia ma 500 °C no 60 min. Ua hoʻokahe ʻia ka SnO2 colloidal dispersion me ka wai deionized ma ka lakio nui o 1:5. Ma luna o kahi substrate maʻemaʻe i mālama ʻia me ka ozone UV no 20 mau minuke, ua waiho ʻia kahi ʻili lahilahi o nā nanoparticles SnO2 ma 4000 rpm no 30 kekona a laila hoʻomehana mua ʻia ma 150 °C no 30 mau minuke. No ka hopena precursor perovskite, ua hoʻoheheʻe ʻia he 275.2 mg FAI, 737.6 mg PbI2 a me FACl (20 mol%) i loko o ka mea hoʻoheheʻe hui ʻia ʻo DMF/DMSO (15/1). Ua hoʻomākaukau ʻia ka papa perovskite ma ke centrifuging ʻana i 40 μL o ka hopena precursor perovskite ma luna o ka papa SnO2 i mālama ʻia me ka UV-ozone ma 5000 rpm i ka ea ambient no 25 s. 5 kekona ma hope o ka manawa hope loa, ua hoʻokuʻu koke ʻia he 50 μL o ka hopena MACl3 IPA (4 mg/mL) ma luna o ka substrate ma ke ʻano he antisolvent. A laila, ua hoʻomehana ʻia nā kiʻiʻoniʻoni i hoʻomākaukau hou ʻia ma 150°C no 20 min a laila ma 100°C no 10 min. Ma hope o ka hoʻomaʻalili ʻana i ka kiʻiʻoniʻoni perovskite i ka mahana o ka lumi, ua centrifuged ʻia ka hopena H2C2O4 (1, 2, 4 mg i hoʻoheheʻe ʻia i loko o 1 mL IPA) ma 4000 rpm no 30 s e passivate i ka ʻili perovskite. Ua milo ʻia kahi hopena spiro-OMeTAD i hoʻomākaukau ʻia ma ke kāwili ʻana i ka 72.3 mg spiro-OMeTAD, 1 ml CB, 27 µl tBP a me 17.5 µl Li-TFSI (520 mg i loko o 1 ml acetonitrile) ma luna o ke kiʻiʻoniʻoni ma 4000 rpm i loko o 30 s. ʻO ka hope loa, ua hoʻoheheʻe ʻia kahi papa Au 100 nm mānoanoa i loko o ka vacuum ma ka wikiwiki o 0.05 nm/s (0 ~ 1 nm), 0.1 nm/s (2 ~ 15 nm) a me 0.5 nm/s (16 ~ 100 nm).
Ua ana ʻia ka hana SC o nā cell solar perovskite me ka hoʻohana ʻana i kahi mika Keithley 2400 ma lalo o ka hoʻomālamalama ʻana o ka simulator solar (SS-X50) ma ka ikaika o ke kukui o 100 mW/cm2 a ua hōʻoia ʻia me ka hoʻohana ʻana i nā cell solar silicon maʻamau i hoʻoponopono ʻia. Inā ʻaʻole i ʻōlelo ʻia, ua ana ʻia nā pihi SP i loko o kahi pahu mīkina lima i piha i ka nitrogen ma ka mahana o ka lumi (~25°C) ma nā ʻano scan i mua a me hope (kaʻina voltage 20 mV, manawa lohi 10 ms). Ua hoʻohana ʻia kahi pale maka e hoʻoholo i kahi ʻāpana kūpono o 0.067 cm2 no ka PSC i ana ʻia. Ua lawe ʻia nā ana EQE i ka ea ambient me ka hoʻohana ʻana i kahi ʻōnaehana PVE300-IVT210 (Industrial Vision Technology(s) Pte Ltd) me ke kukui monochromatic i kālele ʻia ma ka hāmeʻa. No ke kūpaʻa o ka hāmeʻa, ua lawe ʻia ka hoʻāʻo ʻana o nā cell solar i hoʻopaʻa ʻole ʻia i loko o kahi pahu mīkina lima nitrogen ma ke kaomi 100 mW/cm2 me ka ʻole o kahi kānana UV. Ua ana ʻia ʻo ToF-SIMS me ka hoʻohana ʻana i ka PHI nanoTOFII time-of-flight SIMS. Ua loaʻa ke ana ʻana i ka hohonu me ka hoʻohana ʻana i kahi pū ion Ar 4 kV me kahi ʻāpana o 400 × 400 µm.
Ua hana ʻia nā ana ʻana o ka X-ray photoelectron spectroscopy (XPS) ma kahi ʻōnaehana Thermo-VG Scientific (ESCALAB 250) me ka hoʻohana ʻana i ka monochromatized Al Kα (no ke ʻano XPS) ma ke kaomi o 5.0 × 10–7 Pa. Ua hana ʻia ka scanning electron microscopy (SEM) ma kahi ʻōnaehana JEOL-JSM-6330F. Ua ana ʻia ke ʻano o ka ʻili a me ka ʻoʻoleʻa o nā kiʻiʻoniʻoni perovskite me ka hoʻohana ʻana i ka atomic force microscopy (AFM) (Bruker Dimension FastScan). Mālama ʻia ʻo STEM a me HAADF-STEM ma ka FEI Titan Themis STEM. Ua ana ʻia nā spectra absorption UV–Vis me ka hoʻohana ʻana i ka UV-3600Plus (Shimadzu Corporation). Ua hoʻopaʻa ʻia ke au e kaupalena ana i ka hoʻouka ʻana o ka lewa (SCLC) ma kahi mika Keithley 2400. Ua ana ʻia ka photoluminescence steady-state (PL) a me ka photoluminescence time-resolved (TRPL) o ka palaho o ke ola o ka mea lawe me ka hoʻohana ʻana i ka spectrometer photoluminescence FLS 1000. Ua ana ʻia nā kiʻi palapala ʻāina PL me ka hoʻohana ʻana i kahi ʻōnaehana Horiba LabRam Raman HR Evolution. Ua hana ʻia ka Fourier transform infrared spectroscopy (FTIR) me ka hoʻohana ʻana i kahi ʻōnaehana Thermo-Fisher Nicolet NXR 9650.
Ma kēia hana, hoʻohana mākou i ke ʻano laʻana ala SSW e aʻo ai i ke ala hoʻololi pae mai ka α-phase a i ka δ-phase. Ma ke ʻano SSW, ua hoʻoholo ʻia ka neʻe ʻana o ka ʻili ikehu hiki ke hoʻoholo ʻia e ke kuhikuhi o ke ʻano palupalu random (ʻelua derivative), kahi e ʻae ai i kahi noiʻi kikoʻī a me ka pahuhopu o ka ʻili ikehu hiki. Ma kēia hana, hana ʻia ka laʻana ala ma kahi supercell 72-atom, a ʻoi aku ma mua o 100 mau hui mua/hope (IS/FS) i hōʻiliʻili ʻia ma ka pae DFT. Ma muli o ka hoʻonohonoho ʻikepili pairwise IS/FS, hiki ke hoʻoholo ʻia ke ala e hoʻopili ana i ka ʻano mua a me ka ʻano hope me ka pilina ma waena o nā ʻātoma, a laila hoʻohana ʻia ka neʻe ʻelua ala ma ka ʻili ʻāpana loli e hoʻoholo maʻalahi i ke ʻano o ka mokuʻāina hoʻololi. (VK-DESV). Ma hope o ka ʻimi ʻana i ka mokuʻāina hoʻololi, hiki ke hoʻoholo ʻia ke ala me ka pale haʻahaʻa loa ma ka hoʻonohonoho ʻana i nā pale ikehu.
Ua hana ʻia nā helu DFT āpau me ka hoʻohana ʻana iā VASP (mana 5.3.5), kahi i hōʻike ʻia ai nā pilina electron-ion o nā ʻātoma C, N, H, Pb, a me I e kahi papahana nalu i hoʻonui ʻia (PAW). Ua wehewehe ʻia ka hana pilina hoʻololi e ka hoʻokokoke ʻana o ka gradient maʻamau i ka Perdue-Burke-Ernzerhoff parametrization. Ua hoʻonohonoho ʻia ka palena ikehu no nā nalu mokulele i 400 eV. ʻO ka nui o ka Monkhorst-Pack k-point grid he (2 × 2 × 1). No nā ʻano āpau, ua hoʻomaikaʻi piha ʻia nā kūlana lattice a me atomic a hiki i ka wā i emi ai ka ʻāpana stress kiʻekiʻe loa ma lalo o 0.1 GPa a ʻo ka ʻāpana ikaika kiʻekiʻe loa ma lalo o 0.02 eV/Å. Ma ke kumu hoʻohālike o ka ʻili, he 4 mau papa ka ʻili o FAPbI3, aia nā ʻātoma paʻa i ka papa lalo e hoʻohālike ana i ke kino o FAPbI3, a hiki i nā papa ʻekolu kiʻekiʻe ke neʻe manuahi i ka wā o ke kaʻina hana hoʻomaikaʻi. He 1 ML ka mānoanoa o ka papa PbC2O4 a aia ma ka ʻili I-terminal o FAPbI3, kahi i hoʻopaʻa ʻia ai ʻo Pb i 1 I a me 4 O.
No ka ʻike hou aku e pili ana i ka hoʻolālā haʻawina, e ʻike i ka Natural Portfolio Report Abstract e pili ana me kēia ʻatikala.
Hoʻokomo ʻia nā ʻikepili āpau i loaʻa a i kālailai ʻia paha i loko o kēia haʻawina i loko o ka ʻatikala i paʻi ʻia, a me nā ʻike kākoʻo a me nā faila ʻikepili maka. Loaʻa ka ʻikepili maka i hōʻike ʻia ma kēia haʻawina ma https://doi.org/10.6084/m9.figshare.2410016440. Hāʻawi ʻia ka ʻikepili kumu no kēia ʻatikala.
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