Mwebare kutaayayira omukutu gwa Nature.com. Omuringo gwa browser ogu orikukoresa gwine obushagiki bukye bwa CSS. Kubaasa kutunga ebirungi, nitukushaba kukoresa omuringo musya gwa browser yaawe (nari okuzibira omuringo gw’okukozesa Internet Explorer). Omu bwire obu, kureeba ngu twagumizamu nitushagika, nitworeka omukura tutaine sitayiro nari JavaScript.
Okukyendeeza aha buremeezi kukozesiibwe munonga kutunguura okukora kw’obutafaari bw’eizooba bwa lead triiodide perovskite, kwonka ebirikuruga omu buremeezi obutari bumwe na bumwe aha kuhamira aha α-phase tibikamanyirwe gye; Aha, turikukoresa enteekateeka y‘okukora kw‘oburemeezi, nitumanya omurundi gw‘okubanza omuhanda gw‘okusheenyagurika kwa formamidine lead triiodide perovskite kuruga omu α-phase kuza omu δ-phase kandi twega aha nkora y‘oburemeezi obutari bumwe na bumwe aha nkora y‘okuhindura amaani g‘okuzibira. Ebirugire omu kugyeragyeranisa nibiteekateeka ngu emyanya erimu ayodini neekira kureetera okusheenya ahabw‘okuba neekyendeeza munonga aha nkora y‘okuzibira α-δ phase transition kandi eine amaani g‘okuhanga agarikukirayo obukye aha mutwe gwa perovskite. Okutaho ekicweka ky’omubiri ekirimu ebiriisa bingi ebitarikubaasa kusheesheka omu maizi aha rubaju rwa perovskite nikizibira munonga okuvunda kwa α-phase, ekirikuzibira okufuruka n’okuhinduka kw’ekiriisa kya iodine. Okwongyera ahari ekyo, enkora egi neekyendeeza munonga aha kugaruka omu nkora y‘okuteerana kw‘ebintu ebitari by‘omushana kandi neeyongyera aha busingye bw‘obutafaari bw‘eizooba kuhika ahari 25.39% (ekihamibwe 24.92%). Ekikwato ekitaine nshaho nikibaasa kuguma n’oburungi bwakyo obw’okubanza obw’ebicweka 92 ahari igana bwanyima y’okukora aha maani maingi kumara eshaaha 550 ahansi y’okugyezesa 1.5 G air mass irradiation.
Okuhindura amaani (PCE) g’amashanyarazi g’eizooba ga perovskite (PSCs) kuhikire aha rurengo oruhamibwe oruri ahaiguru rwa 26%1. Kuruga 2015, PSCs z’obunaku obu zikaba nizikunda formamidine triiodide perovskite (FAPbI3) nk’ekicweka ekirikutwara omushana ahabw’okugumaho kwakyo okurungi munonga omu bwire bw’okwotsya n’okukunda bandgap haihi n’ekikomo kya Shockley-Keisser ekya 2,3,4. Ekibi, firimu za FAPbI3 nizihinduka omu muringo gw’okwotsya kuruga omu nkora ya α erikwiragura kuza omu nkora ya kyenju etari ya perovskite δ aha butagasi bw’omu kishengye5,6. Okuzibira okuhangwa kw’omuringo gwa delta, ebicweka bitari bimwe na bimwe ebigumire ebya perovskite bikozirwe. Enkora erikukirayo kumanywa ey‘okusingura ekizibu eki n‘okutabura FAPbI3 n‘omubazi gw‘okuteerana ebiriisa bya methyl ammonium (MA+), cesium (Cs+) na bromide (Br-) ions7,8,9. Kwonka, perovskites z’omutaano nizibonabona ahabw’okugaziha kw’ebicweka by’omubiri n’okutaana kw’ebicweka ebirikureetwa ebishushani, ebirikushiisha okukora n’okuhama kw’emirimo y’ebirikurugamu PSCs10,11,12.
Okucondooza okukozirwe juba kworekire ngu pure single crystal FAPbI3 etaine doping yoona eine obuhame burungi ahabw’okugira ngu neekora gye munonga kandi erimu oburemeezi bukye13,14. Nahabwekyo, okukyendeeza aha buremeezi orikweyongyera aha nkora ya crystallinity ya bulk FAPbI3 n‘enkora nkuru y‘okutunga PSCs2,15 ezirikukora gye kandi ezigumire. Kwonka omu bwire bw‘okukora kwa FAPbI3 PSC, okusheenyagurika kuhika aha nkora ya δ etarikwetengyesa ey‘ekika kya hexagonal eya kyenju etari ya perovskite nikubaasa kubaho16. Enkora neekira kutandika aha itaka n’aha nshonda z’embibo ezirikukirayo kukwatwa amaizi, obutagatsi n’omushana ahabw’okugira ngu hariho emyanya mingi erimu oburemeezi17. Nahabwekyo, okukyendeeza aha itaka/embibo nikyetengyesa kuhamya omurundi gw’ebicupuri ogwa FAPbI318. Enkora nyingi z’okukyendeeza aha buremeezi, otwariiremu n’okutaho ebiriisa by’omubiri ebiine obuhango bukye, ebiriisa bya Lewis ebirimu asidi, n’emwonyo ya ammonium halide, bikozire entunguuka mpango omu formamidine PSCs19,20,21,22. Okuhisya hati, haihi okucondooza kwona kutaire omutima aha murimo gw’oburemeezi obutari bumwe na bumwe omu kumanya emitwarize y’amaisho nk’okugaruka kugaita eby’okutwara, oburaingwa bw’okujanjaara n’omutindo gwa bandi omu butafaari bw’eizooba22,23,24. Nk‘eky‘okureeberaho, enteekateeka y‘okukora kw‘obuhango (DFT) neekoresibwa kuteebereza omu nteekateeka amaani g‘okukora n‘okukwaata amaani g‘oburemeezi obutari bumwe na bumwe, ekirikukoresibwa munonga kwebembera enkora y‘okutambura20,25,26. Omubaro gw’ebizibu ku gurikukyendeera, okuhama kw’ekikwato nikukira kutunguuka. Kwonka omu formamidine PSCs, emiringo y‘okuhindura oburemeezi obutari bumwe na bumwe aha kuhamira aha nkora n‘emitwarize y‘amashanyarazi eshemerire kuba neetaanira kimwe. Okurugiirira aha kumanya kwaitu, okwetegyereza kw‘omutaano oku oburemeezi burikureetaho okuhinduka kw‘omutindo gwa cubic kuza omu hexagonal (α-δ) n‘omurimo gw‘okutambura kw‘ahaiguru aha kuhama kw‘omutindo gwa α-FAPbI3 perovskite n‘okuhitsya hati tikukyetegyereziibwe gye.
Aha, nitushohoza omuhanda gw‘okusheenya FAPbI3 perovskite kuruga omu α-phase erikwiragura kuza omu δ-phase eya kyenju n‘okukwatwaho kw‘oburemeezi obutari bumwe na bumwe aha nkora y‘amaani g‘okuhindura α-to-δ-phase kurabira omu DFT. I emyanya y‘okukoreramu, erikubaho omu bwire bw‘okukora firimu n‘okukora eby‘okukoresa, neeteekateekwaho kuba neekirayo kutandikaho entunguuka y‘omutindo gwa α-δ. Nahabwekyo, tukataho ekicweka ky’omubiri ekitarikubaasa kushohora omu maizi kandi ekigumire omu by’emibazi ekya lead oxalate (PbC2O4) ahaiguru ya FAPbI3 kurabira omu nkora y’omu mwanya. Lead oxalate surface (LOS) neezibira okuhangwa kw‘ebicweka bya I kandi neezibira okufuruka kw‘ebicweka bya I ku birikuhimbisibwa n‘okwotsya, omushana, n‘ebicweka by‘amashanyarazi. LOS erikurugamu neekyendeeza munonga aha kugaruka omu nkora y‘okutambura kw‘omubiri kandi neetunguura oburungi bwa FAPbI3 PSC kuhika ahari 25.39% (ekihamibwe kuhika ahari 24.92%). Ekikwato kya LOS ekitaine bipapura kikaguma kiine 92% y‘oburungi bwakyo obw‘okubanza bwanyima y‘okukora aha nshonga y‘amaani maingi (MPP) kumara eshaaha ezirikurenga 550 aha nkora y‘okugyeragyeranisa (AM) eya 1.5 G y‘okurabira omu mushana.
Twabanza twakora okubara kwa ab initio kutunga omuhanda gw’okuvunda kwa FAPbI3 perovskite kuhika aha kuhinduka kuruga omu α phase kuza omu δ phase. Kurabira omu nkora y‘okuhindura omu nkora y‘okuhindura omu bwijwire, nikishangwa ngu okuhindura kuruga omu nkora y‘okugaaniira aha nshonda [PbI6] ey‘ebicweka bishatu omu nkora ya cubic α-phase ya FAPbI3 kuza aha nkora y‘okugaaniira aha rubaju rumwe [PbI6] omu nkora ya hexagonal δ-phase ya FAPbI3 ni. okuhenda 9. Pb-I neekora omukago omu ntambwe y’okubanza (Int-1), kandi omuzigo gwayo gw’amaani niguhika ahari 0.62 eV/cell, nk’oku kirikworekwa omu kishushani 1a. Oktahedron ku erikuhindurwa omu rubaju rwa [0\(\bar{1}\)1], orujegyere rugufu orw’enkokora mukaaga nirutunguuka kuruga ahari 1×1 kuhika ahari 1×3, 1×4 kandi aha muheru nirutaaha omu nkora ya δ. Omubaro gw‘okuhabura gw‘omuhanda gwona ni (011)α//(001)δ + [100]α//[100]δ. Kuruga omu kishushani ky‘okugabanisa amaani, nikibaasa kushangwa ngu bwanyima y‘okukora nucleation ya δ phase ya FAPbI3 omu mitwarize erikukurataho, omuzigo gw‘amaani guri ahansi y‘ogw‘okuhinduka kw‘omutindo gwa α, ekirikumanyisa ngu okuhinduka kw‘omutindo nikwija kurahuka. Nikireebeka gye ngu eitembezo ry‘okubanza ry‘okutegyeka okuhinduka kw‘omutindo ni rikuru munonga twaba nitwenda kuzibira okusheenyagura kw‘omutindo gwa α.
a Omuringo gw‘okuhindura omu nkora kuruga aha rubaju rwa bumosho kuza aha rwa buryo – omurundi gwa FAPbI3 ogurikwiragura (α-omurundi), okusharaho kw‘okubanza kw‘omukago gwa Pb-I (Int-1) n‘okugaruka kusharaho omukago gwa Pb-I (Int-2, Int -3 na Int -4) n‘omurundi gwa kyenju FAPbI3 (omurundi gwa delta). b Ebizibu by‘amaani aha kuhindura kw‘omutindo gwa α kuza δ ogwa FAPbI3 kurugiirira aha buremeezi bw‘enshonga z‘omunda zitari zimwe na zimwe. Omuringo gw’obutonyezi nigworeka omuzigo gw’amaani gw’ekibiriiti ekihikire (0.62 eV). c Amaani g’okukora oburemeezi bw’enshonga z’okubanza aha mutwe gw’ekyoma kya lead perovskite. Abscissa axis n‘amaani g‘okuzibira α-δ phase transition, kandi ordinate axis n‘amaani g‘okukora oburemeezi. Ebicweka ebiine ekicuucu omu rangi ya enziga, kyenju na kiragara n‘eby‘omuringo I (EB y‘ahansi-FE y‘ahaiguru), eby‘omuringo II (FE y‘ahaiguru) n‘eby‘omuringo III (EB y‘ahansi-FE y‘ahansi), nk‘oku biri. d Amaani g‘okukora oburemeezi VI na LOS ya FAPbI3 omu kuhabura. e I ekirikuzibira okufuruka kwa ion omu kuhabura na LOS ya FAPbI3. f – okujwekyera kw‘enkora y‘okufuruka kw‘ebicweka bya I ions (empimbi z‘omucungwa) na gLOS FAPbI3 (enzirugavu, lead; violet (omucungwa), ayodini (ayodini erikugyendera aha rubaju)) omu kuhabura kwa gf (aha rubaju rwa bumosho: okureeba ahaiguru; aha rubaju rwa buryo: ekicweka ky‘okusharaho, kitaka); kaboni; bururu erikutukura – nitrogen; erangi erikutukura – oxygen; pinka erikutukura – haidrojeni). Enshonga z‘okucondooza niziheebwa omu muringo gwa fairo z‘enshonga z‘okucondooza.
Bwanyima tukacondooza omu nkora aha nkora y‘oburemeezi bw‘enshonga z‘omunda zitari zimwe na zimwe (obariiremu PbFA, IFA, PbI, na IPb antisite occupancy; Pbi na Ii atomu z‘omugati; n‘ebicweka bya VI, VFA, na VPb), ebirikutwarwa nk‘enshonga nkuru. ebirikureetaho okusheenyagurika kw‘omutindo gw‘atomu n‘amaani nibyorekwa omu kishushani 1b n‘ekipande ky‘okwongyeraho 1. Ekirikushemeza, ti buremeezi bwona ngu nibukyendeeza aha nkora y‘okuzibira amaani g‘okuhinduka kw‘omutindo gwa α-δ (ekishushani 1b). Nitwikiriza ngu oburemeezi obuine amaani g‘okukora makye n‘ebizibu by‘amaani g‘okuhindura omu nkora ya α-δ ebiri ahansi nibitwarwa nk‘ebirikushiisha okuhama kw‘omutindo. Nk‘oku kyagambirweho enyima, emyanya erimu ebiriisa by‘ekyoma omu bwijwire neetwarwa nk‘erikukora gye ahari formamidine PSC27. Nahabwekyo, nituta omutima aha rubaju orurimu PbI2-terminated (100) ahansi y‘embeera z‘obugaiga bw‘ekyoma. Amaani g‘okukora oburemeezi bw‘oburemeezi bw‘enshonga z‘omunda z‘ahaiguru nigorekwa omu kishushani 1c n‘ekipande ky‘okwongyeraho 1. Kurugirira aha nkora y‘okuzibira amaani (EB) n‘amaani g‘okukora oburemeezi bw‘okuhindura omu nkora (FE), oburemeezi obu nibubaganisibwamu emiringo eshatu. Ekika I (low EB-high FE): N‘obu IPb, VFA na VPb biraabe nibikyendeeza munonga aha nkora y‘okuzibira amaani g‘okuhindura omu nkora, biine amaani g‘okukora maingi. Nahabwekyo, nitwikiriza ngu emiringo y‘oburemeezi egi eine akakwate kakye n‘okuhindura kw‘emiringo ahabw‘okuba tikurikukira kubaho. Ekika kya II (EB y‘ahaiguru): Ahabw‘okutunguuka kw‘omutindo gw‘amaani g‘okuhindura omu nkora ya α-δ, oburemeezi bw‘okurwanisa omwanya PbI, IFA na PbFA tiburikushiisha okuhama kw‘omutindo gwa α-FAPbI3 perovskite. Ekika kya III (EB-low FE): VI, Ii na Pbi oburemeezi oburimu amaani g‘okukora makye munonga nibubaasa kureetera okusheenyagura kw‘omutindo gw‘ebicupuri. Namunonga kurugiirira aha FE na EB VI eziri ahansi, nitwikiriza ngu enkora erikukirayo kukora gye n‘okukyendeeza aha myanya ya I.
Okukyendeeza VI, tukakora ekicweka ky’omubiri ekirimu PbC2O4 kuboneza aha mutwe gwa FAPbI3. Kugyeragyeranisa n’ebintu ebirikukora nk’ebiriisa by’omunyugunyu nk’eby’okurya ebirimu omunyugunyu (PEAI) na n-octylammonium iodide (OAI), PbC2O4, etarimu ions za halogen ezirikugyendera, neeguma omu by’obuhangwa, terikusheesheka omu maizi, kandi neehwaho juba waaheza kugiteera. Okuhamya kurungi kw’obutagatsi bw’ahaiguru n’omusiri gw’amashanyarazi ogwa perovskite. Okushohozibwa kwa PbC2O4 omu maizi ni 0.00065 g/L yonka, eki n’okukira ahari PbSO428. Ekikuru munonga, emiringo ya LOS erimu obuhango kandi erikushushana neebaasa kutebeekanisibwa omu muringo gworobi aha firimu za perovskite barikukoresa enkora y‘okugarukamu omu mwanya (reeba ahaifo). Twakora okugyeragyeranisa kwa DFT okw‘okuteerana kw‘omubiri ahagati ya FAPbI3 na PbC2O4 nk‘oku kirikworekwa omu kishushani ky‘okwongyeraho 1. Ekishushani ky‘okwongyeraho 2 nikyoreka amaani g‘okukora oburemeezi bwanyima y‘okuteebwamu LOS. Twashanga ngu LOS terikwongyera aha maani g‘okukora oburemeezi bwa VI na 0.69–1.53 eV (ekishushani 1d) kwonka neeyongyera aha maani g‘okukora ga I aha rubaju rw‘okufuruka n‘aha rubaju rw‘okuruga (ekishushani 1e). Omu nkora y’okubanza, I ions nizifuruka aha rubaju rwa perovskite, zisigaho VI ions omu mwanya gw’ekibumbe ky’omubiri (lattice) n’ekizibu ky’amaani kya 0.61 eV. Bwanyima y‘okutaho LOS, ahabw‘ekirikurugamu steric hindrance, amaani g‘okukora ahabw‘okufuruka kwa I ions nigayongyera kuhika. 1.28 eV. Omu bwire bw‘okufuruka kwa I ions kuruga aha mutwe gwa perovskite, omuzigo gw‘amaani omu VOC nagwo niguba guri ahaiguru kukira omu sampo y‘okutegyeka (Fig. 1e). Ebishushani by‘okureeberaho eby‘emihanda y‘okufuruka kwa I ion omu kuhabura na LOS FAPbI3 nibyorekwa omu kishushani 1 f na g, nk‘oku biri. Ebirugire omu kugyeragyeranisa nibyoreka ngu LOS neebaasa kuzibira okuhangwa kw‘oburemeezi bwa VI n‘okuhinduka kwa I, obwo erikuzibira okuhinduka kw‘omutindo gwa α kuza δ.
Enkoragana eri ahagati ya oxalic acid na FAPbI3 perovskite ekakyeberwa. Bwanyima y’okutabura ebirungo bya oxalic acid na FAPbI3, omubaro muhango gw’ebintu ebirikwera gukabaho, nk’oku kirikworekwa omu kishushani ky’okwongyeraho 2. Ekirugire omu nshaho kikamanyirwa aha kintu kya PbC2O4 ekishemeire barikukoresa X-ray diffraction (XRD) (ekishushani ky’okwongyeraho 3) na Fourier ekishushani ky’okwongyeraho spectroS omu4). Twashanga ngu oxalic acid neebaasa kusheesheka munonga omu isopropyl alcohol (IPA) aha bwire bw‘obutagatsi bw‘omu kishengye n‘okusheesheka kwa 18 mg/mL, nk‘oku kirikworekwa omu kishushani ky‘okwongyeraho 5. Eki nikireetera okukora okurikukuratiraho kworoba ahabw‘okuba IPA, nk‘ekirungo ky‘okusheeshasheesha ekya buriijo, tikirikushiisha la peroyonski be9od time ngufu. Nahabwekyo, okuta firimu ya perovskite omu nshaho ya oxalic acid nari okuta omubazi gwa oxalic acid aha perovskite, PbC2O4 egumire kandi erimu obuzibu neebaasa kutunga omu bwangu aha mutwe gwa firimu ya perovskite kurugiirira aha nkora y’eby’obuhangwa egi: H2C2O4 + FAPbI +2O. FAI neebaasa kusheesheka omu IPA reero eihirweho omu bwire bw’okuteeka. Obuhango bwa LOS nibubaasa kukyeberwa obwire bw‘okugarukamu n‘okuta omutima aha birikubanza.
Ebishushani by‘okukyebera eby‘okureeberaho (SEM) eby‘okukyebera n‘ebishushani bya LOS perovskite nibyorekwa omu bishushani 2a,b. Ebirugiremu nibyoreka ngu enkora y’ahaiguru ya perovskite erinzirwe gye, kandi omubaro muhango gw’ebicweka bikye nibiteebwa aha mutwe gw’entangahuuzi, ebiine kujwekyera orubaju rwa PbC2O4 oruhangirwe ahabw’okugarukamu kw’omu mwanya. Firimu ya LOS perovskite eine ekicweka ekirikushemeza kakye (ekishushani ky‘okwongyeraho 6) n‘enkokora mpango y‘okukwatagana n‘amaizi waagyeragyeranisa n‘ekishushani ky‘okutegyeka (ekishushani ky‘okwongyeraho 7). Ekikwato ky’okukyebera ebiri omu nkora (HR-TEM) kikakoresibwa kutaanisa aha rubaju rw’ahaiguru rw’ekintu. Okugyeragyeranisa na firimu y‘okutegyeka (ekishushani 2c), ekicweka ekikye ekirikushushana kandi ekirimu oburaingwa bwa 10 nm nikireebeka gye aha mutwe gwa LOS perovskite (ekishushani 2d). Okukozesa ekikwato ky‘okukyebera ebiri omu mwanya gw‘omwirima (HAADF-STEM) kukyebera enkoragana eri ahagati ya PbC2O4 na FAPbI3, okubaho kw‘ebicweka by‘ekibiriiti bya FAPbI3 n‘ebicweka by‘ekibiriiti bya PbC2O4 nibibaasa kureebwa gye (Ekishushani ky‘okwongyeraho 8). Ekicweka ky’ahaiguru kya perovskite bwanyima y’okukikozesa oxalic acid kikamanyirwa aha bipimo bya X-ray (XPS), nk’oku kirikworekwa omu bishushani 2e–g. Omu kishushani 2e, enshonga za C 1s ezirikwetoroora 284.8 eV na 288.5 eV n‘ez‘obumanyiso bwa CC na FA obw‘omutaano, nk‘oku biri. Okugyeragyeranisa n’ekicweka ky’okutegyeka, ekicweka kya LOS kyorekire enshonga y’okwongeraho ahari 289.2 eV, erikuteekateekwaho C2O42-. O 1s spectrum ya LOS perovskite neeyoreka enshonga ishatu z’eby’obuhangwa ezitarikushushana eza O 1s ahari 531.7 eV, 532.5 eV, na 533.4 eV, ezirikuhikaana na COO etaine purotoni, C=O ey’ebicweka bya oxalate ebitaine kabi koona 30 na atomu za O ez’ekicweka kya OH2e (Fig. ). )). Aha sampo y‘okukyebera, enshonga nkye ya O 1s yonka ekareebeka, erikubaasa kuba neeruga omu oxygen chemisorbed aha mutwe. Emitwarize y‘okutegyeka ebiri omu nkora ya Pb 4f7/2 na Pb 4f5/2 neeshangwa ahari 138.4 eV na 143.3 eV, nk‘oku biri. Twareeba ngu LOS perovskite neeyoreka okuhinduka kw’enshonga ya Pb erikwingana 0.15 eV kuza aha maani g’okukwatira hamwe g’ahaiguru, ekirikworeka okukoragana kw’amaani ahagati ya atomu za C2O42- na Pb (Fig. 2g).
a Ebishushani bya SEM eby‘okutegyeka na b firimu za LOS perovskite, okureeba ahaiguru. c Okukyebera okurikurabira omu bicweka by‘omubiri (HR-TEM) eby‘okutegyeka n‘ebishushani bya LOS perovskite. XPS y’omutindo gw’ahaiguru eya e C 1s, f O 1s na g Pb 4f firimu z’eitaka. Enshonga z‘okucondooza niziheebwa omu muringo gwa fairo z‘enshonga z‘okucondooza.
Okurugirira aha byarugamu bya DFT, nikiteekateekwaho omu nteekateeka ngu oburemeezi bwa VI n‘okufuruka kwa I nibireetaho okuhinduka kw‘omutindo kuruga ahari α kuza ahari δ omu muringo gworobi. Amakuru agahwaire nigoreka ngu I2 neeruga omu firimu za perovskite eziri aha PC omu bwire bw’okuta omu maizi bwanyima y’okuta firimu omu mushana n’omu bwire bw’okwotsya31,32,33. Okuhamya okuhamya oku lead oxalate erikukora aha α-phase ya perovskite, tukata ebishushani bya perovskite eby’okutegyeka n’ebya LOS omu bicupa by’endabirwamu ebirikureebeka gye ebirimu toluene, nk’oku biri, reero twabijwara n’omushana gw’eizooba 1 kumara eshaaha 24 h. Tukapima oku omushana gw’omushana gw’ahaiguru n’ogurikureebeka (UV-Vis) gurikunywa. ) omubazi gwa toluene, nk’oku kirikworekwa omu kishushani 3a. Okugyeragyeranisa n‘eky‘okureeberaho ky‘okukyebera, amaani g‘okunywa I2 gakye munonga gakareebeka omu nshonga ya LOS-perovskite, ekirikworeka ngu LOS egumire neebaasa kuzibira okurekura I2 kuruga omu firimu ya perovskite omu bwire bw‘okuta omu mushana. Ebishushani by‘okutegyeka abakaikuru/abagurusi n‘ebishushani bya LOS perovskite nibyorekwa omu bihandiiko by‘omunda eby‘ebishushani 3b na c. LOS perovskite n’obunaku obu n’erikwiragura, kandi firimu nyingi ezirikutegyeka zihindukire eza kyenju. Ebishushani by‘okunywanisa UV–ebirikureebeka eby‘ekishushani ekirimu amaizi nibyorekwa omu bishushani. 3b, c. Twareeba ngu okunywanisa okurikuhikaana na α omu firimu y‘okutegyeka kukaba nikukyendeera gye. Okupima kwa X-ray kukakorwa kuhandiika okuhinduka kw’omubiri gw’ekibiriiti. Bwanyima y‘eshaaha 24 z‘okumurikira, perovskite y‘okutegyeka ekooreka akamanyiso k‘amaani aka δ-phase aka kyenju (11.8°), obwo perovskite ya LOS ekaba ekiine omutindo murungi gw‘erangi erikutukura (ekishushani 3d).
UV-okureebeka kw‘okunywanisa spectra z‘ebirungo bya toluene omu firimu y‘okutegyeka na firimu ya LOS zaabaire zibiikwa ahansi y‘omushana gw‘eizooba 1 kumara eshaaha 24. Ekishushani ekirimu nikyoreka akacupa aka buri firimu yaabaire erimu omu bwingi bwa toluene oburikwingana. b UV-Vis absorption spectra y‘okutegyeka firimu na c firimu ya LOS etakabaireho n‘enyima y‘eshaaha 24 z‘okubiika ahansi y‘omushana gw‘eizooba 1. Omunda harimu ekishushani ky’ekishushani ky’okugyezesa. d Emitwarize y‘okutambura kwa X-ray ey‘okutegyeka n‘ebishushani bya LOS bitakahikire n‘enyima y‘eshaha 24 z‘okushohoza. Ebishushani bya SEM eby‘okutegyeka firimu e na firimu f LOS bwanyima y‘eshaaha 24 z‘okushohoza. Enshonga z‘okucondooza niziheebwa omu muringo gwa fairo z‘enshonga z‘okucondooza.
Twakora okupima kwa scanning electron microscopy (SEM) kureeba empindahinduka z’omubiri gw’ekishushani kya perovskite bwanyima y’eshaaha 24 z’okumurikira, nk’oku kirikworekwa omu bishushani 3e,f. Omu firimu y‘okutegyeka, embibo empango zikacwekyerezibwa kandi zahinduka obupiira obukye, ebyabaire nibihikaana n‘enkora y‘ekintu kya δ-phase FAPbI3 (Fig. 3e). Aha firimu za LOS, embibo za perovskite niziguma omu mbeera nungi (ekishushani 3f). Ebirugiremu bikahamya ngu okufeerwa I nikureetaho munonga okuhinduka kuruga omu nkora y’erangi erikutukura kuza omu nkora ya kyenju, obwo PbC2O4 erikuhamya enkora y’erangi erikutukura, erikuzibira okufeerwa kwa I. Ahabw’okugira ngu oburemeezi bw’okubura ebintu aha mutwe gw’entangahuuzi nibukira munonga omu nkora y’entangahuuzi nyingi,34 enkora egi neekira kubaho aha nshonda z’entangahuuzi. omu bwire nibwo bumwe kurekura ayodini kandi ekakora VI. Nkoku kyatebereziibwe DFT, LOS neebaasa kuzibira okuhangwa kw’oburemeezi bwa VI n’okuzibira okufuruka kwa I ions kuza aha mutwe gwa perovskite.
Okwongyera ahari ekyo, ebirikuruga omu nkora ya PbC2O4 aha kugumisiriza obutagatsi bwa firimu za perovskite omu mwanya (obutagatsi oburikuhikaana 30-60%) bikakyeberwa. Nkoku kirikworekwa omu kishushani ky‘okwongyeraho 9, perovskite ya LOS ekaba ekiri erikwiragura bwanyima y‘ebiro 12, obwo firimu y‘okutegyeka erikuhinduka eya kyenju. Omu bipimo bya XRD, firimu y‘okutegyeka neeyoreka enshonga y‘amaani ahari 11.8° erikuhikaana n‘omutindo gwa δ ogwa FAPbI3, obwo LOS perovskite erikuguma n‘omutindo gwa α ogurikwiragura gye (Ekishushani ky‘okwongyeraho 10).
Okukyebera oku oxalate y’ekyoma erikwetwa lead oxalate erikukora aha rubaju rwa perovskite. Omu kishushani Ekishushani 4a nikyoreka ngu firimu ya LOS eyongyeire aha amaani ga PL. Omu kishushani kya maapu ya PL, amaani g‘ekishushani kya LOS aha mwanya gwona ogwa 10 × 10 μm2 nigakira ag‘ekishushani ky‘okutegyeka (Ekishushani ky‘okwongyeraho 11), ekirikworeka ngu PbC2O4 neekora gye firimu ya perovskite omu muringo gumwe. Amagara g‘omutwazi nigamanyirwa aha kugyeragyeranisa okuvunda kwa TRPL n‘omurimo gumwe gw‘okureeberaho (Fig. 4b). Amagara g‘okutwara firimu ya LOS ni 5.2 μs, ekirikukira munonga firimu y‘okutegyeka erimu amagara g‘okutwara 0.9 μs, ekirikworeka okugaruka omu nkora okutari kw‘okurabira omu itaka okukye.
PL y‘embeera egumire na b-spectra ya PL y‘akaire kakye ey‘ebishushani bya perovskite aha bishushani by‘endabirwamu. c SP omuhimbo gw‘ekikwato (FTO/TiO2/SnO2/perovskite/spiro-OMeTAD/Au). d EQE spectrum na Jsc EQE spectrum erimu kuruga omu kikwato ekirikukirayo kukora gye. d Okurugiirira aha amaani g‘omushana gw‘ekikwato kya perovskite aha kishushani kya Voc. f Okushwijuma kwa MKRC okwa buriijo orikukoresa ekikwato ky‘okushemeza ekiina kya ITO/PEDOT:PSS/perovskite/PCBM/Au. VTFL niyo nshonga y’okujwisa omutego erikukirayo. Kuruga omu makuru aga tukabara oburemeezi bw’okutega (Nt). Enshonga z‘okucondooza niziheebwa omu muringo gwa fairo z‘enshonga z‘okucondooza.
Okwega aha nkora y‘ekicweka ky‘ekyoma ekirikureeta oxalate aha kukora kw‘ekikwato, omutindo gw‘okukoragana ogw‘obuhangwa ogwa FTO/TiO2/SnO2/perovskite/spiro-OMeTAD/Au gukakoresibwa. Nitukoresa formamidine chloride (FACl) nk‘eky‘okwongyera aha nkora y‘okubanza ya perovskite omu mwanya gw‘okukoresa methylamine hydrochloride (MACl) kubaasa kutunga okukora kurungi kw‘ekikwato, ahabw‘okuba FACl neebaasa kuha omutindo murungi gw‘ekibiriiti n‘okwetantara ekicweka ky‘omubiri ekya FAPbI335 (reeba ebishushani by‘okugyeragyeranisa eby‘okwongyeraho de2). ). 12-14). IPA ekatooranwa nk’omubazi gw’okurwanisa okusheeshasheesha ahabw’okuba neeha omutindo murungi gw’ekibiriiti n’okukunda okuhabura omu firimu za perovskite kugyeragyeranisa na diethyl ether (DE) nari chlorobenzene (CB)36 (Ebishushani by’okwongyeraho 15 na 16). Obuhango bwa PbC2O4 bukabonezibwa n‘obwegyendesereza kubaasa kugyeragyeranisa gye okutambura kw‘oburemeezi n‘okutwara eshagama barikuhindura omu nkora ya oxalic acid (Ekishushani ky‘okwongyeraho 17). Ebishushani bya SEM eby‘okusharaho eby‘okukoresa eby‘okutegyeka ebihikire n‘eby‘okukoresa bya LOS nibyorekwa omu kishushani ky‘okwongyeraho 18. Eby‘okureeberaho by‘okutegyeka n‘eby‘okukoresa bya LOS eby‘omutaano (CD) nibyorekwa omu kishushani 4c, kandi ebipimo ebirugiremu nibiheebwa omu kishushani ky‘okwongyeraho 3. Obushoboorozi bw‘okuhindura amaani maingi (J%2c%)433. 25.75 mA cm-2 (25.74 mA cm-2), Eiraka 1.16 V (1.16 V) n‘okugaruka enyima (omu maisho) okukyebera. Omubaro gw’okujwisa (FF) ni 78.40% (76.69%). PCE LOS erikukirayo PSC ni 25.39% (24.79%), Jsc ni 25.77 mA cm-2, Voc ni 1.18 V, FF ni 83.50% (81.52%) kuruga omu kugaruka enyima (omu maisho Scan kuhika). Ekikwato kya LOS kikatunga okukora kw‘amashanyarazi okuhamibwe okwa 24.92% omu laboratory y‘amashanyarazi ey‘ekicweka kya kashatu eyesigwa (Ekishushani ky‘okwongyeraho 19). Oburungi bw‘aheeru (EQE) bukaha Jsc erimu 24.90 mA cm-2 (okutegyeka) na 25.18 mA cm-2 (LOS PSC), nk‘oku biri, ekyabaire nikihikaana gye na Jsc eyapimirwe omu nkora ya AM 1.5 G (Fig. .4d). ) . Okugabanisa kw‘embariirira kwa PCEs ezipimirwe ahabw‘okutegyeka na LOS PSCs nikworekwa omu kishushani ky‘okwongyeraho 20.
Nkoku kirikworekwa omu kishushani 4e, akakwate akari ahagati ya Voc n‘amaani g‘omushana kakabarwa kwega aha nkora ya PbC2O4 aha kugaruka kw‘eitaka okurikuhwerwa omutego. Okushenda kw‘omurongooti oguteirweho ahabw‘ekikwato kya LOS ni 1.16 kBT/sq, ekiri ahansi y‘okushenda kw‘omurongooti oguteirweho ahabw‘ekikwato ky‘okutegyeka (1.31 kBT/sq), ekirikuhamya ngu LOS n‘ey‘omugasho omu kuzibira okugaruka omu itaka ahabw‘okuteganisa. Nitukoresa tekinologiya y‘okukyendeeza aha nshaho y‘omu mwanya (SCLC) kupima omu bwingi obuhango bw‘oburemeezi bw‘ekishushani kya perovskite turikupima obumanyiso bw‘omwirima IV obw‘ekikwato ky‘ekiina (ITO/PEDOT:PSS/perovskite/spiro-OMeTAD/Au) nk‘oku kirikworekwa omu kishushani. 4f Yoreka. Oburemeezi bw’omutego nibubarwa omu nkora Nt = 2ε0εVTFL/eL2, ahu ε eri omubaro gw’amashanyarazi g’ekicweka kya perovskite, ε0 n’omubaro gw’amashanyarazi g’omuyaga, VTFL n’amaani g’okugarukiraho ag’okwijuza omutego, e n’eshagama, L n’obuhango bw’ekishushani kya perovskite n). Oburemeezi bw‘oburemeezi bw‘ekikwato kya VOC nibubarwa kuba 1.450 × 1015 cm–3, oburi ahansi y‘oburemeezi bw‘ekikwato ky‘okutegyeka, oburi 1.795 × 1015 cm–3.
Ekikwato ekitaine bipapura kikagyezibwa aha mwanya gw‘amaani maingi (MPP) ahansi y‘omushana gw‘omushana gwona ahansi ya nitrogen kukyebera okugumaho kwakyo omu kukora kwakyo okw‘obwire buraingwa (ekishushani 5a). Bwanyima y’eshaaha 550, ekikwato kya LOS kikaba nikiguma kiine 92% y’obushoboorozi bwakyo oburikukirayo, obwo ekikwato ky’okutegyeka kyabaire kikyeire kyahika ahari 60% y’obushoboorozi bwakyo obw’okubanza. Okugabwa kw’ebintu omu kikwato kya ira kukapimwa omu bwire bw’okuguruka (ToF-SIMS) (Fig. 5b, c). Okuteerana kwingi kwa ayodini nikubaasa kureebwa omu mwanya gw’ahaiguru ogurikutegyekwa ezaabu. Embeera z‘okurinda omuyaga ogutarikukora niziihaho ebintu ebirikushiisha eby‘obuhangwa nk‘obutagatsi n‘omwika, ekirikumanyisa ngu enkora z‘omunda (nikwo kugira ngu, okufuruka kw‘ayoni) nizo zirikureetaho. Okurugirira aha byarugamu bya ToF-SIMS, I- na AuI2- ions zikashangwa omu nkora ya Au, ekirikworeka okujanjaara kwa I kuruga omu perovskite kuza omu Au. Obumanyiso bw‘amaani bwa I- na AuI2- ions omu kikwato ky‘okutegyeka nibukira obw‘eky‘okureeberaho kya VOC emirundi nka 10. Amakuru agahwaire nigoreka ngu okutaaha omu ion nikubaasa kureetera okukyendeera kw’ahonaaho omu nkora y’okutwariraho ebiina bya spiro-OMeTAD n’okusheenya kw’eby’obuhangwa eby’omutindo gw’ahaiguru gw’eby’amashanyarazi, obwo nibishiisha okukoragana kw’omu maisho omu kikwato37,38. Ekikwato kya Au kikaihwaho kandi ekicweka kya spiro-OMeTAD kyashemezibwa kuruga omu itaka ry’ahansi n’omubazi gwa chlorobenzene. Bwanyima tukashoboorora firimu turikukoresa okucondooza okurikukwata aha kuriisa (GIXRD) (ekishushani 5d). Ebirugiremu nibyoreka ngu firimu y‘okutegyeka eine enshonga y‘okutambura erikureebwa aha 11.8°, obwo hatariho nshonga nsya y‘okutambura erikureebeka omu sampo ya LOS. Ebirugiremu nibyoreka ngu okufeerwa kwingi kwa I ions omu firimu y‘okutegyeka nikureetaho okuzaarwa kw‘omuringo gwa δ, obwo omu firimu ya LOS enkora egi neezibirwa gye.
Eshaha 575 z‘okukuratira MPP okutarikuhwaho kw‘ekikwato ekitaine kikingire omu mwanya gw‘ekiriisa kya nitrogen n‘omushana gw‘eizooba 1 hatariho ekicweka kya UV. ToF-SIMS okugabwa kwa b I- na c AuI2- ions omu kikwato ky‘okutegyeka LOS MPP n‘ekikwato ky‘okukura. Ebicucu bya kyenju, kiragara n’omucungwa nibihikaana na Au, Spiro-OMeTAD na perovskite. d GIXRD ya firimu ya perovskite bwanyima y‘okukyebera MPP. Enshonga z‘okucondooza niziheebwa omu muringo gwa fairo z‘enshonga z‘okucondooza.
Okutwarira hamwe okurikurugiirira aha bwire bw’obwire kukapimwa kuhamya ngu PbC2O4 neebaasa kuzibira okufuruka kw’ayoni (Ekishushani ky’okwongyeraho 21). Amaani g‘okukora (Ea) g‘okufuruka kw‘ayoni nigamanyirwa aha kupima empindahinduka omu kutwara (σ) kwa firimu ya FAPbI3 aha bwire bw‘obwire obutarikushushana (T) kandi orikukoresa enkoragana ya Nernst-Einstein: σT = σ0exp(−Ea/kBT), ahu σ0 eri ekintu ekitarikuhinduka, kB n‘ekintu ekitarikuhinduka Bol. Nitutunga omuhendo gwa Ea kuruga omu kushenda kwa ln(σT) n‘okugyeragyeranisa na 1/T, okuri 0.283 eV ahabw‘okutegyeka na 0.419 eV ahabw‘ekikwato kya LOS.
Omu bugufu, nituha omutindo gw‘ebiteekateeko gw‘okumanyisa omuhanda gw‘okusheenya FAPbI3 perovskite n‘oku oburemeezi butari bumwe na bumwe burikukwata aha nkora y‘okuzibira amaani g‘okuhinduka kw‘omutindo gwa α-δ. Omuri ebi bizibu, ebizibu bya VI nibiteekateekwaho omu nteekateeka ngu nibibaasa kureetera omu muringo gworobi okuhinduka kw‘omutindo kuruga ahari α kuza ahari δ. Ekicweka kya PbC2O4 ekitarikuhinduka omu maizi kandi ekigumire omu by’emibazi nikiteebwaho kuhamya α-phase ya FAPbI3 orikuzibira okuhangwa kw’ebicweka bya I n’okufuruka kwa I ions. Enkora egi neekyendeeza munonga aha kugaruzaho okutari kw’omushana ahagati y’amaisho, neeyongyera aha busingye bw’obutafaari bw’eizooba kuhika ahari 25.39%, kandi neetunguura okuhama kw’okukora. Ebirugire omu kucondooza kwaitu nibituha obuhabuzi bw‘okuhikiiriza PSCs za formamidine ezihikire kandi ezigumire turikuzibira okuhinduka kw‘omuringo gw‘okureetwaho oburemeezi α kuza δ.
Ekirungo kya Titanium(IV) ekirikwetwa TTIP, 99.999%) kikagurwa kuruga omu kampuni ya Sigma-Aldrich. Asidi y’amaizi (HCl, 35.0–37.0%) hamwe na ethanol (etarimu maizi) bikagurwa kuruga omu kitongore ky’eby’emibazi ekya Guangzhou. SnO2 (15 wt% y’okujanjaara kw’eby’okurya ebirimu ebiriisa) ekagurwa kuruga omu kampuni ya Alfa Aesar. Ekirungo kya Lead(II) (PbI2, 99.99%) kikagurwa kuruga omu kampuni ya TCI Shanghai (China). Omubazi gw’okukyebera (FAI, ≥99.5%), omubazi gw’okukyebera (FACl, ≥99.5%), omubazi gw’okukyebera (MACl, ≥99.5%), 2,2′,7,7′-tetrakis-(N , N-robimei-anilinef)-9)- (Spiro-OMeTAD, ≥99.5%), ebiriisa by’omubiri (Li-TFSI, 99.95%), 4-tert -butylpyridine (tBP, 96%) bikagurwa kuruga omu kampuni ya Xi’an Polymer Light Technology (China). N,N-dimethylformamide (DMF, 99.8%), dimethyl sulfoxide (DMSO, 99.9%), amaarwa g’omubiri (IPA, 99.8%), CB, 99.8%), amaizi g’omubiri (ACN). Ekagurwa omu kampuni ya Sigma-Aldrich. Okisidi asidi (H2C2O4, 99.9%) ekagurwa kuruga omu kampuni ya Macklin. Emibazi yoona ekakoresibwa nk’oku yaatungirwe hatariho kuhindura okundi kwona.
Ebicweka bya ITO nari FTO (1.5 × 1.5 cm2) bikashemezibwa omu muringo gw’okukyebera, asetoni, na ethanol kumara edakiika 10, nk’oku biri, reero byayomezibwa ahansi y’omugyera gwa nitrogen. Omuringo gw’okuzibira TiO2 ogurimu ebiriisa bingi gukateebwa aha itaka rya FTO barikukoresa omubazi gwa titanium diisopropoxybis(acetylacetonate) omu ethanol (1/25, v/v) ogwateirwe aha 500 °C kumara edakiika 60. Okujanjaara kwa SnO2 colloidal kukakyeberwa n’amaizi agarimu deion omu nkora y’obuhango bwa 1:5. Aha itaka erishemeire eririkujanjabwa na UV ozone kumara edakiika 20, ekipande kikye kya SnO2 nanoparticles kikateebwa aha 4000 rpm kumara sekondi 30 reero kyabanza kyayokibwa aha 150 °C kumara edakiika 30. Aha nshonga y’okushohoza ebiriisa by’okubanza, 275.2 mg FAI, 737.6 mg PbI2 na FACl (20 mol%) bikashohozibwa omu DMF/DMSO (15/1) ebirikutabura. Omuringo gwa perovskite gukatebeekanisibwa barikuteera 40 μL y’omubazi gw’okubanza gwa perovskite aha mutwe gw’omuringo gwa SnO2 ogwateirwemu UV-ozone aha 5000 rpm omu mwanya oguri omu mwanya kumara 25 s. Sekondi 5 bwanyima y‘obwire obuhererukire, 50 μL y‘omubazi gwa MACl IPA (4 mg/mL) gukagwa ahonaaho aha itaka nk‘omubazi gw‘okurwanisa okusheeshasheesha. Bwanyima, firimu eziherize kutebeekanisibwa zikateebwa aha 150°C kumara edakiika 20 reero bwanyima aha 100°C kumara edakiika 10. Bwanyima y’okukyendeeza aha firimu ya perovskite kuhika aha butagasi bw’omu kishengye, omubazi gwa H2C2O4 (1, 2, 4 mg ogushazirwe omu 1 mL IPA) gukakyeberwa aha 4000 rpm kumara 30 s kubaasa kukyendeeza aha rubaju rwa perovskite. Omubazi gwa spiro-OMeTAD ogwatebeekanisiibwe okutabura 72.3 mg ya spiro-OMeTAD, miriyoni 1 ya CB, miriyoni 27 ya tBP na miriyoni 17.5 ya Li-TFSI (miriyoni 520 omu miriyoni 1 ya asetonitiri) gukateebwaho omubazi gw‘okuzihindura aha firimu aha 4000 s rpm omunda. Eky’aha muheru, ekicweka kya Au eky’oburaingwa bwa 100 nm kikafuka omu mwanya ogutarimu kintu kyona aha sipiidi ya 0.05 nm/s (0~1 nm), 0.1 nm/s (2~15 nm) na 0.5 nm/s (16~100 nm) . ).
Okukora kwa SC kw’obutafaari bw’eizooba bwa perovskite kukapimwa barikukoresa Keithley mita 2400 ahansi y’omushana gw’eizooba (SS-X50) aha mushana gw’amaani gwa 100 mW/cm2 kandi gwahamibwa barikukoresa obutafaari bw’eizooba bwa silicon obutebeekanisiibwe. Okwihaho kyaba kitagambirwe, SP curves zikapimwa omu glove box eijwiire nitrogen aha bwire bw‘obutagatsi bw‘omu kishengye (~25°C) omu miringo y‘okukyebera ey‘omumaisho n‘enyima (eitembezo ry‘amaani 20 mV, obwire bw‘okukyerererwa 10 ms). Ekicuucu ky‘okukinga amaisho kikakoresibwa kumanyisa omwanya ogurikukora gye ogwa 0.067 cm2 ahabwa PSC eyapimirwe. Okupima kwa EQE kukakorwa omu mwanya oguri omu mwanya barikukoresa enkora ya PVE300-IVT210 (Industrial Vision Technology(s) Pte Ltd) n‘omushana gw‘erangi emwe ogurikuta omutima aha kikwato. Ahabw’okuhamya eby’okukoresa, okukyebera obutafaari bw’eizooba obutaine nshaho kukakorwa omu glovebox ya nitrogen aha 100 mW/cm2 pressure hatariho ekicweka kya UV. ToF-SIMS neepimwa barikukoresa SIMS y‘obwire bw‘okuguruka eya PHI nanoTOFII. Okucondooza aha buhango kukatunga okukozesa embundu ya 4 kV Ar ion erimu omwanya gwa 400×400 μm.
Okupima kwa X-ray okwakozirwe aha nkora ya sayansi eya Thermo-VG (ESCALAB 250) barikukoresa Al Kα (ahabw‘omuringo gwa XPS) aha nkora ya 5.0 × 10–7 Pa. Enkora ya JOLF-SM3 ekakorwa aha nkora ya JOLF-SM3. Enkora y’ahaiguru n’obushaarizi bw’ebishushani bya perovskite bikapimwa barikukoresa eby’okureeberaho by’amaani g’atomu (AFM) (Bruker Dimension FastScan). STEM na HAADF-STEM nizibaho aha FEI Titan Themis STEM. Ebishushani by’okunywanisa UV–Vis bikapimwa barikukoresa UV-3600Plus (ekitongore kya Shimadzu). Omumwanya ogurikukyendeeza aha nkora y’okushohoza (SCLC) gukahandiikwa aha Keithley mita 2400. Okukyebera kw’omushana (PL) n’okukyebera kw’omushana okurikushoboororwa omu bwire (TRPL) kw’okuvunda kw’amagara g’omutwazi kukapimwa barikukoresa ekipimo ky’okujwara kw’omushana ekya FLS 1000. Ebishushani bya maapu ya PL bikapimwa barikukoresa enkora ya Horiba LabRam Raman HR Evolution. Okucondooza okurikuhindura ebiri omu itaka (FTIR) kukakorwa barikukoresa enkora ya Thermo-Fisher Nicolet NXR 9650.
Omu murimo ogu, nitukoresa omuringo gw‘okutooranamu omuhanda gwa SSW kwega omuhanda gw‘okuhindura omu nkora kuruga omu nkora ya α kuza omu nkora ya δ. Omu nkora ya SSW, okutambura kw‘ahaiguru y‘amaani agarikubaasa kubaho nikumanyirwa aha rubaju rw‘omuringo gw‘okutooranamu (second derivative), ekirikubaasisa okwega okuhikire kandi okuhikire aha rubaju rw‘amaani agarikubaasa kubaho. Omu murimo ogu, okutoorana eby‘okureeberaho by‘omuhanda nikukorwa aha supercell y‘atomu 72, kandi ebirikukira ahari 100 eby‘okubanza/eby‘aha muheru (IS/FS) bibiri nibirundaanwa aha rurengo rwa DFT. Okurugirira aha IS/FS pairwise data set, omuhanda ogurikugaita omubumbi w‘okubanza n‘omubumbi gw‘aha muheru nigubaasa kumanyirwa aha kuhikaana ahagati y‘atomu, reero bwanyima okutambura kw‘emiringo ebiri aha rubaju rw‘ekicweka ekirikuhinduka nikukoresibwa kumanyisa gye omuringo gw‘embeera y‘okuhinduka. (VK-EKITEBYO). Bwanyima y‘okusherura embeera y‘okuhindura, omuhanda ogurimu omuzigo oguri ahansi munonga nigubaasa kumanyirwa aha kuha omu nkora emizibu y‘amaani.
Okubara kwa DFT kwona kukakorwa barikukoresa VASP (omuringo 5.3.5), ahu enkoragana ya electron–ion ya atomu za C, N, H, Pb, na I zirikujwekyerwa enteekateeka y‘okuteekateeka kw‘okutunguuka kw‘omuyaga (PAW). Omurimo gw‘okuhindura enkoragana nigushoboororwa omu kugyeragyeranisa kw‘omutaano omu nkora ya Perdue-Burke-Ernzerhoff. Ekipimo ky’amaani g’ebicu by’enyonyi kikateebwaho 400 eV. Ekipande ky‘obubonero k ekya Monkhorst–Pack kiine obuhango bwa (2 × 2 × 1). Aha bihangirwe byona, emyanya ya lattice na atomic ekaba neebonezibwa omu bwijwire kuhitsya obu ekicweka ky’okugyemeserezibwa ekikuru kyabaire kiri ahansi ya 0.1 GPa kandi ekicweka ky’amaani ekikuru kikaba kiri ahansi ya 0.02 eV/Å. Omu muringo gw’ahaiguru, ahaiguru ya FAPbI3 eine emiringo 4, emiringo y’ahansi eine atomu ezitaine mpinduka ezirikugyeragyeranisa omubiri gwa FAPbI3, kandi emiringo eshatu ey’ahaiguru neebaasa kugyendera omu bwengye omu bwire bw’okukora gye. Omuringo gwa PbC2O4 niguhika 1 ML kandi guri aha rubaju rwa I-terminal rwa FAPbI3, ahu Pb erikukwatiraine na 1 I na 4 O.
Okumanya ebindi aha ntebeekanisa y‘okwega, reeba Ripoota y‘okucondooza ey‘obuhangwa Abstract erikukwatagana n‘ekicweka eki.
Ebihandiiko byona ebyatungirwe nari ebyashwijumirwe omu kucondooza oku nibiteebwa omu kihandiiko ekihandiikirwe, hamwe n‘omu makuru agarikuhagira n‘omu fairo z‘ebihandiiko ebitahikire. Ebihandiiko ebitahikire ebyayorekwa omu kucondooza oku nibishangwa aha mukutu gwa intaneeti. Ebihandiiko ebirikuruga omu kihandiiko eki nibiheebwayo.
Ekibira, M. n’abandi. Emeeza z’okukoresa gye obutafaari bw’eizooba (57th ed.). puroguraamu. amashanyarazi g’ebishushani. eby’obugaiga. okushaba. 29, 3-15 (2021).
Parker J. n’abandi. Okutegyeka okukura kw’ebicweka bya perovskite orikukoresa ebiriisa ebirikuhindukahinduka. Obuhangwa 616, 724-730 (2023).
Zhao Y. n’abandi. Ekitarikukora (PbI2)2RbCl nikihamya firimu za perovskite ahabw’obutafaari bw’eizooba oburikukora gye munonga. Sayansi 377, 531-534 (2022).
Tan, K. n’abandi. Obutafaari bw’eizooba obuhindukire bwa perovskite barikukoresa ekirungo kya dimethylacridinyl. Obuhangwa, 620, 545-551 (2023).
Han, K. n’abandi. Formidine lead iodide (FAPbI3): okwetegyereza aha nkora, okureeba n‘amashanyarazi. enshoborora kikorwa. Mat. 28, 2253-2258 (2016).
Massey, S. n’abandi. Okuhamya kw’omuringo gw’erangi erikutukura omu FAPbI3 na CsPbI3. AKS Amashanyarazi g’eby’empurizana. 5, 1974-1985 (2020).
Iwe, JJ, n’abandi. Obutafaari bw’eizooba bwa perovskite oburungi kurabira omu nkora nungi y’okutwara ebintu. Obuhangwa 590, 587-593 (2021).
Saliba M. n’abandi. Okutaho rubidium cations omu butafaari bw’eizooba bwa perovskite nikitunguura okukora kw’amashanyarazi. Sayansi 354, 206-209 (2016).
Saliba M. n’abandi. Obutafaari bw’eizooba oburikwetwa perovskite cesium oburimu ebiriisa bishatu: okutunguuka omu kugumaho, okugaruka kuzaara n’okukora gye munonga. eby’obuhangwa by’amaani. ebya sayansi. 9, 1989-1997 (2016).
Cui X. n’abandi. Entunguuka eyahererukireyo omu kuhamya omurundi gwa FAPbI3 omu butafaari bw’eizooba bwa perovskite oburikukora gye munonga Sol. RRL 6, 2200497 (2022).
Delagetta S. n’abandi. Okutaana kw’ebicweka by’omubiri ebitarikushushana n’eby’obuhangwa n’ebitari by’obuhangwa ebya perovskites. Nat. okugamba. 8, 200 (2017).
Slotkavage, DJ n’abandi. Okwahukana kw’ebicweka ebirikureetwa omushana omu bihingwa bya halide perovskite. AKS Amashanyarazi g’eby’empurizana. 1, 1199-1205 (2016).
Chen, L. n’abandi. Okuhama kw’omutindo gw’omunda n’okutambura kw’omunda kw’ekirungo ky’omubazi gwa formamidine. Anjiva. Emibazi. eby’ensi yoona. Ed. 61. Omu mwaka gwa 2022.
Duinsti, EA etc. Kwetegyereza okuvunda kw‘ekiriisa kya methylenediammonium n‘omurimo gwakyo omu kuhamya omutindo gw‘ekiriisa kya lead triiodide formamidine. J. Emibazi. Omukazi. 18, 10275-10284 (2023).
Lu, HZ n’abandi. Okuteebwaho kw’omuyaga okuhikire kandi okuhamire kw’obutafaari bw’eizooba obw’erangi erikutukura (perovskite) FAPbI3. Sayansi 370, 74 (2020).
Doherty, TAS etc. Ebicweka by‘omubiri ebigumire ebiine ebicweka munaana eby‘omubiri nibizibira okuhangwa kw‘ebicweka by‘omubiri ebiine emitwarize mikye. Sayansi 374, 1598-1605 (2021).
Ho, K. n’abandi. Emiringo y‘okuhindura n‘okusheenya embibo za formamidine na cesium na lead iodide perovskites ahansi y‘okutegyekwa obutagatsi n‘omushana. AKS Amashanyarazi g’eby’empurizana. 6, 934-940 (2021).
Zheng J. n’abandi. Okutunguuka kw’eby’okurya ebitari by’amazima eby’obutafaari bw’eizooba oburikwetwa α-FAPbI3 perovskite. Obuhangwa 592, 381-385 (2021).