.

Дослідження ефектів вібронної взаємодії в кристалах ABX3 i AmBnCpXs різних структур: Автореф. дис… канд. фіз.-мат. наук / М.В. Сторчун, Львів. держ.

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Euea?anueeee aeapaeaaiee oi?aapneoao

?iai? ?aaia Opaiea

NOI?*OH Iepineaaa Aieiaeeiep?aia

OAeE 535.32 + 535.37

Aeine?aeaeaiiy aoaeo?a a?apiiii? aca?iiae?? a

epenoaeao ABX3 ? AmBnCpXs p?cieo nopoeoop

01.04.10 – O?ceea iai?aipia?aeiee?a oa ae?aeaeopee?a

AAOI?AOA?AO

aeenapoaoe?? ia caeiaoooy iaoeiaiai nooiaiy

eaiaeeaeaoa o?ceei-iaoaiaoe/ieo iaoe

Euea?a – 1999

Aeenapoaoe??th ? poeiien

?iaioa aeeiiaia ia eaoaaep? aeniapeiaioaeueii? o?ceee

Euea?anueeiai aeapaeaaiiai oi?aapneoaoo ?iai? ?aaia Opaiea.

Haoeiaee eap?aiee : eaiaeeaeao o?ceei-iaoaiaoe/ieo iaoe,

aeioeaio I?aecepaeei Ieeiea Noaiaiiae/

Euea?anueeee aeapaeaaiee oi?aapneoao ?iai? ?aaia Opaiea

Io?oe?ei? iiiiaioe : aeieoip o?ceei-iaoaiaoe/ieo iaoe,

ipioanip Hinaiei Aiaoie?e ?pio?eiae/

Euea?anueeee aeapaeaaiee oi?aapneoao ?iai? ?aaia Opaiea

eaiaeeaeao o?ceei-iaoaiaoe/ieo iaoe

aeioeaio *ipi?e Caiia?e Iaaeiae/

Oepa?inueeee aeapaeaaiee e?nioaoi?/iee oi?aapneoao

i. Euea?a

Ipia?aeia onoaiiaa : Ee?anueeee iaoe?iiaeueiee oi?aapneoao

?iai? Oapana Oaa/aiea, eaoaaepa iioeee

Caoeno a?aeaoaeaoueny “ 24 ” aa?aciy 1999 ?. i 15 aiae. 30 oa. ia
can?aeaii? niaoe?ae?ciaaii? a/aii? paaee Ae.35.051.09 ipe Euea?anueeiio
aeapaeaaiiio oi?aapneoao? ?iai? ?aaia Opaiea (290005, i.Euea?a,
aoe.Aepaaiiaiiaa, 50).

C aeenapoaoe??th iiaeia iciaeiieoenue a iaoeia?e a?ae?ioaoe?
Euea?anueeiai aeapaeaaiiai oi?aapneoaoo ?i.?aaia Opaiea (290005, i.
Euea?a, aoe. Aepaaiiaiiaa, 5).

Aaoipaoapao pic?neaii 1 ethoiai 1999p.

A/aiee naepaoap

niaoe?ae?ciaaii? paaee

aeieoip o?ceei-iaoaoaiaoe/ieo iaoe,

ipioanip Aeaaee?anueeee E.O.

CAAAEUeHA OA?AEOA?ENOEEA ?IAIOE

Aeooaeuei?noue oaie. Iaoeiai-oaoii/iee i?ia?an aeiaaa? noai?aiiy iiaeo ?
aaeineiiaeaiiy oaoiieiai? aaea inioth/eo ia?aoai?thaa/ia aia?ai?.
Nthaee, a ia?oo /a?ao, iaeaaeaoue ethiiiioi?e ?iciiai i?ecia/aiiy,
noeeioeeyoi?e, aeiceiao?e, aeoeaii aeaiaioe eaca?ia i o. i. Ipiaeaie
paaeiaoeieiiai eiiopieth yaeapieo onoaiiaie, yaeapii? aeaoaeoipii?
aeaeopiiiee, i, iapaoo?, ipiaeaie yaeapii? anopioiceee, einii/ii? oiceee
i oiceee aenieeo aiapaie – ani aiie iia’ycaii c picaeoeii iaoiaeia
aeaoaeooaaiiy iiiicoth/iai aeipiiiithaaiiy. Napaae picieo iaoiaeia
aeaoaeooaaiiy iaeiioepaiioei ? noeeioeeyoeieiee iaoiae pa?nopaoei? i
niaeopiiaopi? iiiicoth/iai aeipiiiithaaiiy. No/anii ia?aoai?thaa/i
aia?ai? ia aiaeiiaiaeathoue onii iio?iaiei aeiiaai : aeniei eaaioiaee i
aia?aaoe/iee aeoiaee oioiethiiianoeaioei?, aonoeia, aoaeoeaiee aoiiiee
iiia? i aia?aaoe/ia ?icaeieaiiy; ei?ioeee aai iaia?aaecaaeaiee /an
iineynai/aiiy, noieeinoue aei aieiae, iaoaii/ieo, oaiia?aoo?ieo i
?aaeiaoeieieo aieeaia. Oiio iiaeaeueoa picoepaiiy iiiaieeaoope iiaeo
iioe/ieo iaoapiaeia caeeoa?oueny aeooaeueiei. Aeey oeueiai iaiaoiaeii
iaea?aeaoe iaeoi/iioo iioipiaoeith ipi ipioeane paeaenaoei? aeaeopiiieo
caoaeaeaiue a oaapaeeo oieao, i, iniaeeai, i?i aoaeoe aiapiiii?
aca?iiaei?. Aaaeeeao pieue o ipioeanao opainoipiaoei? i iiapaoei?
aenieiaiapaaoe/ieo caoaeaeaiue aiaeiapathoue picii eaaci/anoeiee
(aeneoiie, iieypiie, iieypeoiie oa ii.). Aecia/aiiy oiia ?o aeieeiaiiy
oa inioaaiiy i ? iniiaiith caaea/ath ipe noaipaiii iiaeo ethiiiioi?ia,
noeeioeeyoi?ia oa iioeo ia?aoai?thaa/ia aia?ai?.

O ca’yceo ic oeei, iaoith aeenapoaoeieii? piaioe aoei aea/aiiy aoaeoia
aiapiiii? aca?iiaei? a aieueo neeaaeieo epenoaeao, iioaioeieii
ipeaeaoieo aeey noaipaiiy aoaeoeaieo ethiiiioi?ia i noeeioeeyoipia.

Aeey aeinyaiaiiy iinoaaeaii? iaoe iaiao?aeii aoei pica’ycaoe ianooii?
caaea/?:

neioacoaaoe epenoaee ZnI2, ZnI2:Mn, TlCdI3, Tl2ZnI4, Rb2CdI4,
Cs2ZnI4:Tl, Rb2ZnClI4:Tl, Cs2ZnI4:Mn, CsPbCl3(1-x)I3x;

aeine?aeeoe o oepieiio oaiiapaoopiiio ae?aiacii? iioeei – niaeopaeuei?
oapaeoapenoeee aeuacaaaeaieo epenoae?a; niaeope a?aeaeaaiiy ? oioi- oa
paioaaiiethi?ianoeaioe??, caoaeaeaiiy oioiethi?ianoeaioe??, epea?
oapiinoeioeueiaaii? ethi?ianoeaioe??, e?iaoeeo i?neyna?/aiiy;

aeynieoe aoaeoeai?noue iaapiiaaeaeaiiy na?oeinoie a aeine?aeaeoaaieo
epenoaeao;

?aeaioeo?eoaaoe iniiai? nioae iiaeeiaiiy ? ethi?ianoeaioe??
aeine?aeaeoaaieo epenoae?a;

aea/eoe aieea a?apiiii? aca?iiae?? ia ethi?ianoeaioi? oapaeoapenoeee
aeine?aeaeoaaieo epenoae?a ? aecia/eoe aeaye? iapaiaope a?apiiii?
aca?iiae??;

aea/eoe aieea a?apiiieo aca?iiae?e ? iecueeineiaope/iiai epenoae?/iiai
iiey ia aiapaaoe/io nopoeoopo aeii?oeiaeo oeaiop?a Tl+ e Mn2+ a
epenoaeeao A2BX4.

Aea?p ia’?eo?a aeine?aeaeaiue iaoiiaethaaany ianooiieie oaeoaie:

?iaeeaee aaaeeeo iaoae?a ? niieoeaie c aaeeeith ieoiiith aonoeiith ?
aaeeeei aoaeoeaiei aoiiiei iiiapii, ui piaeoue ?o iioaioe?eii
aoaeoeaieie iaoap?aeaie c aenieei eiao?oe??ioii iiaeeiaiiy ?ii?coth/iai
aeipii?ithaaiiy;

oapoaao? epenoaee BX2 ? oeiiaeie iiaeaeueieie ia’?eoaie ipe aea/aii?
aoaeo?a a?apiiii? aca?iiae?? o ipii?aeiiio aeiaaeeo i?ae aeai- ?
opeaei?pieie epenoae?/ieie niieoeaie.

aeoeaiaai? iapianueeeoiiiae?ai? aaeiaai?aee oeio ABX3 ? A2BX4 (aea A ? B
– iaoaee I ? II apoi iap?iaee/ii? nenoaie aeaiaio?a, X – aaeiaai)
iiaeooue aooe aoaeoeaieie iaopeoeyie aeey aeniapeiaioaeueiiai aea/aiiy
aeeiai?/iiai aoaeoo ssia – Oaeeapa.

Haoeiaa iiaecia. Aiapoa aeeiiaii eiiieaenia aeine?aeaeaiiy iioeei –
niaeopaeueieo oapaeoapenoee /enoeo ? aeoeaiaaieo epenoae?a ZnI2,
Tl2ZnI4, TlCdI3, Cs2ZnI4, Rb2ZnCl4, Rb2CdI4. ?acoeueoaoe aeine?aeaeaiue
aeaee iiaeeea?noue aiapoa:

aecia/eoe iapaiaope aeneoii?a o ZnI2, Tl2ZnI4, TlCdI3,; ioe?ieoe
aiapa?th caaipiiaii? ciie ? ae?aeaeope/io iino?eio oeeo epenoae?a;

aecia/eoe aaee/eio aaniethoiiai eaaioiaiai aeoiaeo oioiethi?ianoeaioe??
epenoae?a ZnI2 : Mn, Tl2ZnI4, TlCdI3, Cs2ZnI4 : Mn.

iieacaoe, ui, a epenoaeao Cs2ZnI4 : Tl ? Rb2ZnCl4 : Tl, aoaeoe a?apiiii?
aca?iiae?? ? aecia/aeueieie ipe iiyniaii? nopoeoope ?o niaeop?a
iiaeeiaiiy ? ethi?ianoeaioe??. Aiie iiaeooue neoaeeoe iiaeie
iiaeaeueieie ia’?eoaie aeey aea/aiiy aeeiai?/iiai aoaeoo ssia – Oaeeapa
a iecueeineiaope/ieo epenoae?/ieo nopoeoopao;

aeine?aeeoe iniaeeaino? aeneoii – oiiiiii? aca?iiae?? a epenoaeao ZnI2,
ZnI2 : Mn, Tl2ZnI4, TlCdI3, Cs2ZnI4 : Tl, Cs2ZnI4:Mn, Rb2ZnCl4:Tl,
Rb2CdI4 oa a oaapaeeo pic/eiao CsPbCl3(1-x)I3o (x=0…1);

anoaiiaeoe oaeo ?aeaaeueii? iap?iaee/iino? pici?uaiiy ?ii?a Cl- ? I- a
epenoae?/ieo apaoeao CsPbCl2I ? CsPbClI2 ia a?aei?io a?ae epenoaea
CsPbCl1.5I1.5.

Ipaeoe/ia cia/aiiy iaeapaeaieo pacoeueoao?a. Iopeiai? pacoeueoaoe
aeine?aeaeaiue ethi?ianoeaioieo aeanoeainoae /enoeo ? aeoeaiaaieo
poooaiiae?aieie oeaiopaie epenoae?a BX2, ABX3 ? A2BX4 oa oaapaeeo
pic/ei?a ia ?o iniia? iiaeooue aeeipenoiaoaaoeny ipe oaipaoe/iiio oa
aeniapeiaioaeueiiio aea/aii? ?o aiapaaoe/ii? nopoeoope, iapaiaop?a
a?apiiieo aca?ii\-ae?e ?, oaeei /eiii, nipeythoue picoepaiith iaeano? ?o
ipaeoe/iiai canoinoaaiiy a yeino? ethi?iioip?a, noeeioeeyoip?a ?
eacapieo aeoeaieo aeaiaio?a.

Aaciinapaaeiy ipaeoe/ia oe?ii?noue aeaii? piaioe iieyaa? o :

picpiaoe? eaaipaoipii? oaoiieia?? aepiuoaaiiy epenoae?a ZnI2, ZnI2:Mn,
Tl2ZnI4, Cs2ZnI4:Tl, Cs2ZnI4:Mn ? Rb2ZnCl4:Tl;

paeiiaiaeaoe?? aeeipenoaiiy epenoae?a ZnI2:Mn ? Cs2ZnI4:Mn ye
ethiiiioi??a i?e eiiiaoiie oaiiapaoop?, a epenoae?a Tl2ZnI4 i TlCdI3 –
i?e iecueeeo oaiia?aoo?ao (T(77~K);

ipiiiceoe?? aeeipenoaiiy e?enoae?a Cs2ZnI4:Tl I Rb2ZnCl4:Tl ye iiaeo
iiaeaeueieo ia’?eo?a aeey aeineiaeaeaiiy aeeiaii/iiai aoaeoo ssia –
Oaeea?a o iecueeineiaope/iiio epenoae?/iiio iie?.

Ipiaaaeai? iioeei – niaeopaeuei? aeine?aeaeaiiy ? neeaaeiaith /anoeiith
aeine?aeaeaiue ii oaiao: 1) Oa 055 A “Aeyniaiiy ipioean?a iapaoaipaiiy
aenieiaiapaaoe/ieo aeaeopiiieo caoaeaeaiue o iecueeiaiapaaoe/i? a
epenoaeao AmBnCpXs ” (iiiap aeapaepa?nopaoe?? 0194 V 015649); 2) Oa 279
A “Oaeaee? ipioeane aeipii?ithaaeueiiai piciaaeo aeaeopiiieo caoaeaeaiue
o neeaaeieo aaei?aeieo niieoeao AmBnCpXs ” (iiiap aeapaepa?nopaoe?? 0197
V 013998).

Iniaenoee aianie aeenapoaioa. Aaoip aeenapoaoe?eii? piaioe aeeiiaea
aeniapeiaioaeueio /anoeio piaioe; aecia/eea pyae iioeei-niaeopaeueieo
iapaiaop?a aeine?aeaeoaaieo epenoae?a, ciepaia a pacoeueoao? naiino?eii?
iaoaiaoe/ii? iapiaee aeniapeiaioaeueieo aeaieo ; apaea o/anoue o
iaaiaipaii? oa ?ioapipaoaoe?? aeniapeiaioaeueieo pacoeueoao?a, a oaeiae
o iaienaii? iaoeiaeo noaooae ? aeiiia?aeae.

Aipiaaoe?y pacoeueoao?a aeenapoaoe??. Iniiai? pacoeueoaoe
aeenapoaoe?eii? piaioe aeiiia?aeaeenue ? iaaiaipthaaeenue ia ianooiieo
iaoeiaeo nai?iapao ? eiioapaioe?yo:

EXCON’96. 2nd Int.\,Conf.\,on Excitonic Processes in Condenced Matter.
August 14-17, 1996. Kurort Gohrisch (Bad Shandau), Germany.

ICL’96. Int. Conf. on Luminescence and Optical Spectroscopy of Condenced
Matter. August 18-23, 1996. Prague, Czech Republic.

AOMD’96. The Int. Conf. “Advanced Optical Materials and Devices”. August
26-29, 1996. Riga, Latvia.

XXII Int. School and III Polish – Ukrainian Meeting on Ferroelectrics
Physics. September 16-20, 1996. Kudowa Zdroj, Poland.

ICTMC 11. 11th Int. Conf. on Ternary and Multinary Compounds. September
8-12, 1997. Salford, United Kingdom.

PPMSS’97. 2nd Int. School-Conf. on Physical Problems in Material Science
of Semiconductors. September 8-12, 1997. Chernivtsi, Ukraine.

SCINT 97. Int. Conf. on Inorganic Scintillators and their Application.
September 22-25, 1997. Shanghai, People’s Republic of China.

LUMDETR’97. 3nd Int. Symposium “Luminescence Detectors and Transformers
of Ionizing Radiation”. October 6-10, 1997. Ustron, Poland.

JASZHOWIEC’98. XXVII Int. School on Physics of Semiconducting compounds.
June, 7 – 12th, 1998. Ustron – Jaszhowiec, Poland.

Oepa?inueei – iieuenueeee iaoeiaee nai?iap “O?ceea ? o?i?y iaoap?ae?a
aeaeopiiii? oaoi?ee”. 22-25 /apaiy, 1998. Euea?a, Oepa?ia.

Ca?oia eiioapaioe?y Euea?anueeiai aeapaeoi?aapneoaoo ?i. ?aaia Opaiea.
11-13 ethoiai 1997p.

Ca?oia eiioapaioe?y Euea?anueeiai aeapaeoi?aapneoaoo ?i. ?aaia Opaiea.
9-11 ethoiai 1998p.

Ioae?eaoe??. Ca iaoap?aeaie aeenapoaoe?eii? piaioe iioae?eiaaii 13
ipaoeue, c yeeo 8 iniiaieo iaaaaeaii a e?ioe? aaoipaoapaoo.

Nopoeoopa ? ia’?i aeenapoaoe??. Aeenapoaoe?eia piaioa aeeth/a? anooi, 5
pic\-ae?\-e?a ? aeniiaee, ye? aeeeaaeai? ia 146 noip?ieao iaoeiiieniiai
oaenoo oa aeaio aeiaeaoe?a c 89 penoieaie ? 20 oaaeeoeyie, a oaeiae
nieneo e?oapaoope, yeee aeeth/a? 221 iaeiaioaaiiy.

INHIAHEE CI?NO ?IAIOE

O anooi? iaaiaipth?oueny aeooaeuei?noue oaie, eipioei iienaii ci?no
piaioe, noipioeueiaai? iieiaeaiiy, ui aeiinyoue\-ny ia caoeno, iiaecia,
iaoeiaa ? ipaeoe/ia oe?ii?noue caaea/, ui pica’ycai? ipe aeeiiaii?
aeenapoaoe?eii? piaioe.

O iapoiio picae?e? aeeeaaeaii iniiai? iieiaeaiiy oaip?? a?apiiieo
aca?iiae?e a ?iiieo epenoaeao oa iniaeeaino? a?apiiieo aca?iiae?e o
/enoeo ? aeoeaiaaieo poooaiiae?aieie ?iiaie epenoaeao oeio AX, BX2 ?
ABX3.

Aepoaee picae?e i?enay/aiee iieno epenoae?/ii? aoaeiae aeineiaeaeoaaieo
e?enoaeia ? oaciaeo aeiaa?ai, yei iiaeoaa?aeaeothoue oiiae noaaieueiinoi
inioaaiiy aeineiaeaeoaaieo e?enoaeia; iaoiaee/iei aniaeoai ?iaioe
(iaoiaeeea neioaco i ae?iuoaaiiy /enoeo i aeoeaiaaieo iiiie?enoaeia,
aei?pthaaiiy iioeei – niaeopaeueieo ? niaeopaeueii – e?iaoe/ieo
oapaeoapenoee epenoae?a, iniiae iaoaiaoe/iiai ?iceeaaeo neeaaeieo
niaeo?aeueieo eiioo?ia ia neeaaeiai eiiiiiaioe).

Aeii?thaaiiy cae?enithaaeenue a oe?ieiio niaeo?aeueiiio (1.5-17 aA),
/aniaiio (10-9-10-5 n) oa oaiiapaoopiiio (5-300 K) iioa?aaeao.
Aeaea?aeii caoaeaeaiiy neoaeeei aei?iiiithaaiiy acioiiai eaca?a (EAE-21)
i ?oooiiai ?ic?yaeo (eaiia I?E-375), aeaeoa?i?ai? eaiie EAe(Ae)-400,
enaiiiiai? eaiie AeENO- 120; ?aioaaiianueei? onoaiiaee O?N-55;
neio?io?iiia aei?iiiithaaiiy i?enei?thaa/a DORIS (noaioeiy SUPERLUMI,
HASYLAB, Iiia//eia). Ethiiianoeaioeiy aeineiaeaeoaaeany ia onoaiiaeao,
ciiioiaaieo ia aaaci iiiio?iiaoi?ia IAe?-2, IAe?-12, AeI?-4, AeON-12 i
SPG-2. Eiiaoeea iineynai/aiy oioiethiiianoeaioei? aeineiaeaeoaaeanue ii
iaoiaeo eieo iaeeii/ieo eaaioia.

O o?aoueiio ?icaeiei i?aaenoaaeaii ?acoeueoaoe aeineiaeaeaiue aeneoii –
oiiiiii? aca?iiaei? o e?enoaeao ZnI2, TlCdI3, Tl2ZnI4 ? Rb2CdI4.

Aeey e?enoaea ZnI2 aia?oa anoaiiaeaii iieiaeaiiy aeneoiiieo iieia
aiaeaeaaiiy (4.330 aA aeey n=1 i 4.443 aA aeey n=2), ia iniiai /iai a
?aieao oai?i? aeneoiiia Aaiue? – Iiooa ia/eneaii aia?aith ca’yceo
aeneoiia F=150 iaA i eiai ?aaeion r1=7.2 A, a oaeiae oe?eio caai?iiaii?
ciie Eg=4.48 aA i aeiaeaeo?e/io iinoieio a iaeanoi aeneoiiiiai iieo
iiaeeiaiiy (=6.7. Io?eiaii ?acoeueoaoe aeacothoue, ui aeey e?enoaeia
ZnI2 oa?aeoa?ii aeneoiie i?iiiaeiiai ?aaeona. Niinoa?aaeaia o niaeopao
a?aeaeaaiiy aenieiaia?aaoe/ia eieeaia no?oeoo?a (a iaeanoi 4.46-5.96 aA
c aia?aaoe/iei iioa?aaeii 0.060-0.094 aA), iaeaieueo iiiai?ii, coiiaeaia
O2–oeaio?aie.

Niaeo?e ethiiianoeaioei? e?enoaea ZnI2 i?e caoaeaeaiii eaaioaie ?icieo
aia?aie i?e 77 E oa?aeoa?ecothoueny neeaaeiei eiioo?ii c aaaaoueio (a?ae
7 aei 9) aeecueeeo nioa (Oaae.1). Eeoa aeayei eiiiiiaioe i?e iioe/iiio I
?aioaaiianueeiio caoaeaeaiii niiaiaaeathoue. I?e c?inoaiii oaiia?aoo?e
niinoa?iaa?oueny aioeaaoia ciiuaiiy iieiaeaiiy nioa
oioiethiiianoeaioei?, ia?a?iciiaeie ?o iioaineaiinoae i iiaoe?ei oa
?iciee oiae oaiia?aoo?iiai aaniiiy, ui aeaco? ia iayaiinoue aeaeieueeio
oeaio?ia nai/aiiy. I?e/iio neeaaeiee aeaeyae niaeo?ia ethiiianoeaioei?
aeiaeaoeiai i/euaieo c?aceia a iaeanoi i?ici?inoi e?enoaea oa
i?enooiinoue nioa caoaeaeaiiy ci noi?iie iaioeo aia?aie aiaeiinii
aeneoiiiiai iiea aiaeaeaaiiy naiae/eoue i?i ?o aeiiioeiao i?e?iaeo.
Iaeaioeoieiaaii aeiiiioth/o nioao ?aioaaiiethiiianoeaioei? e?enoaea ZnI2
i?e 2.28 aA ye nai/aiiy aeiiioie Mn2+. E?enoae ZnI2 :Mn aieiaei?
ii?iaiyii aenieei aaniethoiei eaaioiaei aeoiaeii oioiethiiianoeaioei?
((=0.74 i?e 293 E). Iioi?iaoeith i?i aeeaeie caeyaaiiy ?iaiia caoiieaiiy
io?eiaii ic e?eaeo oa?iinoeioeueiaaii? ethiiianoeaioei? (0.15; 0.18;
0.20; 0.23 aA).

Oaae.1: Niaeopaeuei? iapaiaope nioa ethi?ianoeaioe?? epenoaea ZnI2:
iieiaeaiiy iaeneioio E [aA] oa i?aoepeia (H [aA].

Eca, aA X – eaaioe 3.673 3.45 – 4.95

T, K 80 77 77

( nioae E (H E (H E (H

1 3.07 0.08 3.02 0.13 3.08 0.10

2 2.94 0.10 2.87 0.17 2.94 0.16

3 2.85 0.10 2.72 0.14 2.83 0.17

4 2.66 0.20 2.60 0.13 2.66 0.13

5 2.48 0.17 2.47 0.12 2.50 0.12

6 2.28 0.20 2.36 0.12 2.38 0.12

7 2.09 0.19 2.23 0.15 2.27 0.12

8 1.85 0.20

2.16 0.11

9 1.65 0.19

Aeaui i?inoioei i?e 77 E aeaeyaeathoue niaeo?e ethiiianoeaioei? e?enoaea
Tl2ZnI4: oea aea? oepie? nioae, ye? neeueii iapaepeaathoueny (ipe 2.71
aA, (H=0.32 aA oa ipe 2.48 aA, (H=0.22 aA). C iiaeaeuaiiyi oaiia?aoo?e
aei eiiiaioii? ethi?ianoeaioe?y oaeaeei aaneoueny (cie?aia, eaaioiaee
aeoiae oioiethiiianoeaioei? iaaea? aiae 0.7 i?e 77 E iaeaea aei ioey
aaea a aeiaiaciii 160-180 E). No?oeoo?a niaeo?ia caoaeaeaiiy iaeaeaio
eiiiiiaio oioiethiiianoeaioei? ? iaeeiaeiaith. I?iaae a iaeanoi 3.82 aA,
iia’ycaiee c ao?aoaie aia?ai? caoaeaeaiiy o iaeneioii niaeo?o
ooiaeaiaioaeueiiai iiaeeiaiiy, aiaeiiaiaea? iieiaeaiith aeneoiiiiai iiea
iiaeeiaiiy (n=1). Coienianueea ciiuaiiy, iiaoe?eia i oaiia?aoo?ii
iiaaaeiiee iniiaii? nioae oioiethiiianoeaioei? e?enoaea Tl2ZnI4
iaaiaeyoue ia aeoieo, ui oey nioaa (i?e 2.71 aA) aeieea? a pacoeueoao?
aiiaieyoei? aaoieieaeiciaaieo aeneoiiia.

Aeaa /ioei iecueeioaiia?aoo?ii iiee oa?iinoeioeueiaaii? ethiiianoeaioei?
(i?e 103 i 107 E) e?enoaea Tl2ZnI4 aeacothoue ia aoaeoeaia ooai?aiiy i?e
iecueeeo oaiia?aoo?ao Vk-oeaio?ia. Aeaeieaeicaoeiy ae?pie aiaeaoaa?oueny
c iieeeo ?iaiia aeeaeiith 0.10 i 0.12 aA. Caaaeii, e?enoae Tl2ZnI4 i?e
T(77 E i?e caoaeaeaiii a aeneoiiiie nioci iiaeeiaiiy ? aoaeoeaiei
iapaoaipthaa/ai aia?ai? aeaeo?iiiiai caoaeaeaiiy.

Aeey e?enoaea TlCdI3 ii aeneoiiieo iieao aiaeaeaaiiy (i?e 3.158 aA (n=1)
oa 3.283 aA (n=2)) aia?oa aecia/aii, ui aaee/eia Eg=3.326 aA, a F=168
iaA. Aeaeyae niaeo?ia ethiiianoeaioei? e?enoaea TlCdI3, ye aeaeii c Oaa.
2, neeueii caeaaeeoue aiae aia?ai? caoaeaeoth/eo eaaioia. Cie?aia,
iniiaia nioaa ?aioaaiiethiiianoeaioei? (i?e 2.17 aA) ? aeecueeith aei
iieiaeaiiy iaeneioio nioae oioiethiiianoeaioei? Pb2+-oeaio?ia, i ia
niiaiaaea? c aieiaieie nioaaie oioiethiiianoeaioei? e?enoaea TlCdI3 i?e
2.87 aA (aocueea nioaa I) oa 2.37 aA (oe?iea nioaa II). Oiaoi, ipe
paioaai?anueeiio caoaeaeaii? o epenoae? TlCdI3 ipe 77 E a?aeaoaa?oueny
aoaeoeaia iapaaea/a aiapa?? aei aeii?oeiaeo oeaiop?a.

Oaae.2: Iapaiaope niaeop?a ethi?ianoeaioe?? epenoaea TlCdI3: iieiaeaiiy
iaeneioi?a neeaaeiaeo NA Emax, [aA] oa ?o i?aoepeie (H, [aA] ipe p?cieo
aiapa?yo caoaeaeaiiy Eca, [aA].}

Eca 2.846 3.059 3.673 X – eaaioe

T,K 77 77 77 85

( nioae 2 3 4 1 1 3 4 5 2 3

Emax 2.290 2.125 2.524 2.370 2.868 2.131 2.217 2.771 2.167 2.474

(H 0.210 0.122 0.171 0.345 0.037 0.093 0.130 0.307 0.379 0.326

Niaeopaeueii-e?iaoe/i? aeine?aeaeaiiy iaio nioa oioiethi?ianoeaioe?? ipe
77 E aeaee aaee/eie /an?a i?neyna?/aiiy 2.5 in aeey nioae I oa 3.7 in ?
2.20 ien aeey nioae I?. Aipieneiaoe?y oaiiapaoopii? caeaaeiino? aeiaaiai
eiiiiiaioa i?neyna?/aiiy nioae I? aeicaieeea ioe?ieoe aiapa?th
aacaeipii?ithaaeueieo iapaoiae?a (80.6 iaA). C?noaaeaiiy iopeiaieo
pacoeueoao?a c aiaeia?/ieie iapaiaopaie ethi?ianoeaioe??
eoaeiiaaei?aeieo epenoae?a oa aeayeeo iapianueeeo?a, a oaeiae picaeyae
oaipaoe/ieo picpaooie?a ciiii? nopoeoope epenoae?a TlI ? CsPbCl3
aeicaiey? ?aeaioeo?eoaaoe nioao I ye na?/aiiy eao?iiieo eieae?ciaaieo
(ia ?ii? Tl+ iiaeeco aeaoaeoo epenoae?/ii? apaoee) aeneoii?a, a nioao I?
– ye na?/aiiy ai?iiiiai aaoieieae?ciaaiiai aeneoiia. Ni?a?nioaaiiy
aeneoii?a p?cii? ipepiaee iaoiiaeth?oueny, i/aaeaeii, oei oaeoii, ui
aaeaioia ciia epenoaea TlCdI3 oipio?oueny ye 6 s2 – aeaeo?iiieie noaiaie
eaoiiia Tl+, oae i 5 p6- aeaeo?iiieie noaiaie aiiiia I-. Aiae?c
iopeiaieo oaiiapaoopieo caeaaeiinoae ethi?ianoeaioieo iapaiaop?a
na?ae/eoue, ui o epenoae? TlCdI3 iapaaaaea? aeneoiiiee iaoai?ci
iapaaea/? aiapa?? caoaeaeaiiy aei aeii?oeiaeo oeaiop?a.

Aiapoa niinoapaaeai? niaeope aeanii? oioiethi?ianoeaioe?? epenoaea
Rb2CdI4 ipe 77 E oapaeoapecothoueny aeaiia aaon?anueeeie nioaaie ipe
2.94 aA ? ? 2.31 aA I? c i?aoepeiaie 0.084 ? 0.133 aA a?aeiia?aeii. C
pinoii oaiiapaoope aei 120 E I nioaa aaea iiai?noth aaneoueny. Ipe 8 E
I? nioaa aeipii?ithaaiiy ? aeaui ci?uaiith o iecueeiaiapaaoe/io iaeanoue
niaeopa, a ?? e?iaoeea i?neyna?/aiiy oapaeoapeco?oueny eeoa opeaaeei ((
( 2 o 10-5 n) /anii caaanaiiy. Ne?ae a?aei?oeoe, ui aiapaaoe/ia
picae?eaiiy iaio nioa ethi?ianoeaioe?? epenoaea Rb2CdI4 (0.63 aA)
ipaeoe/ii ni?aiaaea? ?c niaeopaeueiei ci?uaiiyi (0.8 aA) neiaeaoiiai
eiiiiiaioa aaoieieae?ciaaiiai aeneoiia a?aeiinii opeieaoiiai a epenoae?
RbI. Iaeiae i?aoepeie iaio nioa aeipii?ithaaiiy aeine?aeaeoaaiiai
epenoaea ? a 3-5 pac iaioeie, ui iiaea coiiaethaaoenue a?eueo neeaaeiith
nopoeoopith epenoaea Rb2CdI4. I/aaeaeii, aeey epenoaea Rb2CdI4 aeanoeaa
neeueia aeneoii-oiiiiia aca?iiae?y. Niaeope caoaeaeaiiy
oioiethi?ianoeaioe?? ipe 8 E aeacothoue, ui oioiiia iiiiiaeaiiy a
epenoae? Rb2CdI4 ianooia? ipe aiapa?yo caoaeaeaiiy aeecueei 17 aA ( 3
Eg.

O /aoaapoiio picae?e? iieno?oueny ipiya aeaeopii – oiiiiieo aca?iiae?e
aeey aeaeopiiieo noai?a a epenoaeao Cs2ZnI4 (Oaae.3) ? Rb2ZnCl4
(Oaae.4), aeoeaiaaieo ?iiaie Tl+. Aaee/eia picuaieaiiy nioa
oioiethi?ianoeaioe?? (0.53 i 0.65 aA a?aeiia?aeii) oa ?o nioa
caoaeaeaiiy (0.14 ? 0.12 aA) aeiapa ocaiaeaeothoueny ?c aeaieie ii
na?/aiith poooaiiae?aieo aeii?oeiaeo ?ii?a a eoa?/ieo eoaeiiaaei?aeieo
epenoaeao. Aeaui a?eueoa aaee/eia picuaieaiiy o aeaiiio aeiaaeeo iiaea
iaoiiaethaaoenue ia eeoa ipiyaii aoaeoo ssia – Oaeeapa, aea ? aieeaii
iecueeineiaope/iiai epenoae?/iiai iiey. Hecueeiaiapaaoe/iee AX-eiiiiiaio
na?/aiiy ipiyaey?oueny eeoa ipe iip?aiyii aenieeo oaiiapaoopao (T(200
E) aeey epenoaea Cs2ZnI4:Tl ? iaa?oue ipe 77 E – aeey ?cinopoeoopiiai
epenoaea Rb2ZnCl4:Tl. Ipioeeaaeiee piciiae?e ?ioaineaiinoae AX – ? AT –
eiiiiiaio na?ae/eoue, ui aeey epenoaea Rb2ZnCl4:Tl aaee/eia
aiapaaoe/iiai aap’?po i?ae oaopaaiiaeueiei T- ? opeaiiaeueiei X-
i?i?ioiaie ? cia/ii iaioa, i?ae o aeiaaeeo ?iaeeaeo Cs2ZnI4:Tl.

Oaae.3: Iapaiaope nioa OE oa nioa caoaeaeaiiy ethi?ianoeaioe?? epenoaea
Cs2ZnI4:Tl – iieiaeaiiy iaeneioio E oa i?aoepeia (H.

T,K 77 210 210 77 77 77 77 77 77

Nioaa AO AO AX A1 A2 1 2 3 4

Emax, aA 2.93 2.93 2.40 4.22 4.36 4.57 4.66 4.73 4.82

(H, aA 0.27 0.41 0.33 0.15 0.16 0.08 0.07 0.06 0.05

Oaae.4: Niaeopaeuei? iapaiaope NE oa nioa caoaeaeaiiy ethi?ianoeaioe??
(aeey AT-nioae) epenoaea Rb2ZnCl4:Tl ipe 77 K: iieiaeaiiy iaeneioio
neeaaeiaeo NA Emax oa ?o i?aoepeie (H.

Nioaa AO A AX A1 A2 1 2 3

Emax, aA 3.074 2.729 2.416 4.680 4.800 5.024 4.491 4.200

(H, aA 0.226 0.276 0.327 0.130 0.140 0.189 0.170 0.241

Aeii?oeiaa ethi?ianoeaioe?y epenoaea Cs2ZnI4:Mn oapaeoapeco?oueny
?aeeiith aaon?anueeith nioaith c iaeneioiii ipe 2.26 aA o pacoeueoao?
iapaoiae?a i?ae 3 d5 p?aiyie ?iia Mn2+ a oaopaaaepe/iiio ioi/aii?, a
naia 4T1g [4G] ( 6A1g [6S]. Ha oaeo ae iaeanoue niaeopa ipeiaaea? ?
iaeanoue na?/aiiy [Mn 2+I4-]2- -oeaiop?a a epenoaeao A2CdI4 iacaeaaeii
a?ae oeio eao?iia A+. Iiaia ni?aiaae?iiy oe??? nioae ethi?ianoeaioe?? ?c
aeii?oeiaei na?/aiiyi epenoaea ZnI2:Mn aeaco? ia oa, ui ?iie Mn2+
iaoiiaeththoue iaeiioeii? oeaiope na?/aiiy a pacoeueoao? cai?uaiiy eeoa
?ii?a Zn2+ o aoceao epenoae?/ii? iaopeoe?. Aeaui ieae/ee aaniethoiee
eaaioiaee aeo?ae oioiethi?ianoeaioe?? epenoaea Cs2ZnI4:Mn ((=0.68) o
iipyaiyii? c (=0.74 epenoaea ZnI2:Mn iiynith?oueny eiioeaiopaoe?eiei
aan?iiyi iaeiiopieueiaaieo aeii?oie (aeeaeie ianoie a?ae 0.09 aei 0.58
aA). *ioepeepaoia iapaepenoae?caoe?y epenoaea aei aaaiieo ci?i ia
ipeaaea.

I’yoee picae?e aena?oeth? aoaeoe aeneoii – oiiiiii? aca?iiae?? o
oaapaeeo pic/eiao CsPbCl3(1-x)I3x (x=0…1). Aeneoiiia na?/aiiy a oeeo
epenoaeao coiiaeaia aioop?eao?iiiei iapaoiaeii 6 s2 ( 6s6p a ?ii? Pb2+.
C pinoii iieypii? eiioeaiopaoe?? ?iaeo a epenoaeao cpinoa? aaee/eia
aeneoii – oiiiiii? aca?iiae??, ciaioo?oueny paae?on iniiaiiai noaio
aeneoiia (a?ae 11.2 aei 7.9 aA, aeea. Oaae.5 ? Oaae.6) oa cpinoa?
?iia?pi?noue ipioean?a aaoieieae?caoe?? aeneoii?a. Aeey x(0.66
ipiyaey?oueny picuaieaiiy (((35 iaA) aeneoiiieo (n=1) nioa a?aeaeaaiiy
aiane?aeie ae?? epenoae?/iiai iiey.

Oaae.5: Niaeopaeueia iieiaeaiiy aeneoiiieo i?e?a o NA e?enoaea CsPbCl3 ?
oaapaeeo pic/ei?a NsPbCl2I ? CsPbCl1.5I1.5 ERn, ?o oepeia caaipiiaii?
ciie Eg, aiapa?y ca’yceo aeneoiia F, ae?aeaeope/ia ipiieeeea?noue a
iaeano? aeneoiiiiai i?eo iiaeeiaiiy ( oa paae?on aeneoiia rn (n=1) ipe
4.2 K.

Epenoae Er1, aA Er2, aA Eg, aA F, iaA ( r1, (

CsPbCl3 2.981 3.030 3.046 65 10.2 10.8

CsPbCl2I 2.987 3.033 3.048 61 10.6 11.2

CsPbCl1.5I1.5 2.989 3.040 3.057 68 10 10.6

Oaae.6: Niaeopaeueia iieiaeaiiy aeneoiiieo i?e?a o NA e?enoaea CsPbI3 ?
oaapaeiai pic/eio CsPbClI2 ERn, ?o oepeia caaipiiaii? ciie Eg, aiapa?y
ca’yceo aeneoiia F, ae?aeaeope/ia ipiieeeea?noue a iaeano? aeneoiiiiai
i?eo iiaeeiaiiy ( oa paae?on aeneoiia rn (n=1) ipe 4.2 K.

Epenoae Er1, aA E’1, aA E’2, aA Eg, aA F, iaA ( r1, (

CsPbClI2 2.990 3.025 3.116 3.146 121 7.5 7.9

CsPbI3 2.996 3.030 3.119 3.149 119 7.6 8.0

Ii niaeopao oioiethi?ianoeaioe?? anoaiiaeaii oaeo iaeaea ?aeaaeueii?
iap?iaee/iino? oiipyaeeoaaiiy ai?ii?a Cl- ? I- a epenoae?/ieo apaoeao
epenoae?a CsPbCl2I ? CsPbClI2. O oie aea /an na?/aiiy eieae?ciaaieo
aeneoii?a o epenoae? CsPbCl1.5I1.5 na?ae/eoue ipi ipenooi?noue aaeeei?
e?eueeino? nopoeoopieo aeaoaeo?a o ca’yceo ?c oeoeooaoe?yie neeaaeo
oaapaeiai pic/eio.

O aeiaeaoeao aei aeenapoaoe?? c?apaii oaaeeoe? ? noaie, ye?
aeiiiiaaathoue epaua cpicoi?oe nooue iienaieo yaeu.

INHIAH? ?ACOEUeOAOE OA AENHIAEE

?icpiaeaii eaaipaoipio oaoiieiaith neioaco c aeo?aeieo eiiiiiaio nie?
ZnI2 ? ?inoo e?enoaeia ZnI2, Tl2ZnI4 ? Cs2ZnI4 c ?iaeeae?a, i/euaieo
iaoiaeii ciiii? ieaaee (CsI, TlI) oa aaaaoiepaoii? noae?iaoe?? (ZnI2).

Aia?oa anoaiiaeaii iieiaeaiiy aeneoiiieo iieia aiaeaeaaiiy (77 E) aeey
e?enoaeia ZnI2 (4.330 (n=1) i 4.443 (n=2) aA) i TlCdI3 (3.158 (n=1) i
3.283 (n=2) aA) oa ia/eneaii aia?aith ca’yceo aeneoiia (150 i 168 iaA
aiaeiiaiaeii) i oe?eio caai?iiaii? ciie (Eg=4.48 aA aeey ZnI2 i Eg=3.33
aA aeey TlCdI3). O epenoae? ZnI2 ooaipththoueny aeneoiie ipii?aeiiai
oeio (r1 ( 7 ( ( a). Iayai?noue neeueii? aeneoii – oiiiiii? aca?iiaei? a
e?enoaei Tl2ZnI4 ipecaiaeeoue aei aeipii?ithaaeueii? ai?a?eyoe?? eeoa
ai?iiieo aaoieieae?ciaaieo aeneoii?a (nioaa 2.71 aA, (H=0.32 aA ipe 77
E).

O epenoae? TlCdI3 (T=77-300 E) paae?co?oueny ipii?aeia aeneoii – oiiiiia
aca?iiaeiy, ia ui aeaco? niiainioaaiiy nai/aiiy eaoiiiieo eieaeiciaaieo
2.868 aA, (H=0.04 aA oa (=2.5 in ipe 77 E) ? aiiiiieo aaoieieae?ciaaieo
aeneoii?a (2.370 aA, (H=0.35 aA ipe 77 E), coiiaeaia aeeaaeii o
oi?ioaaiiy aa?oeie aaeaioii? ciie ye 6 s2 – aeaeo?iiieo noaiia eaoiiia
Tl+, oae i 5 p6- aeaeo?iiieo noaiia aiiiia I-. Aecia/aii aiapa?th
aeoeaaoe?? aacaeipii?ithaaeueii? paeaenaoe?? opeieao – neiaeaoiiai
iapaoiaeo ((e=3.7 in ? (ae=2.20 ien ipe 77 E) aaoieieae?ciaaieo
aeneoii?a Ea(80 iaA. Oeaiopii na?/aiiy o epenoae? TlCdI3 ? iaci?uaiee
aaoieieae?ciaaiee aeneoii I2-+e–oeio c neiaop??th D2h.
Hecueeiaiapaaoe/ia nioaa aeipii?ithaaiiy e?enoaea Rb2CdI4 (ipe 2.31 aA
(H=0.13 A, (( 2 o10-5 n ipe 77 E) coiiaeaia o?eieao – neiaeaoieie
ia?aoiaeaie a pacoeueoao? aeipii?ithaaeueii? aiiaieyoei?
aaoieieae?ciaaieo aeneoii?a. Anoaiiaeaii, ui ipioean oioiiiiai
iiiiiaeaiiy o e?enoaei Rb2CdI4 ii/eia?oueny ipe aia?ai? caoaeaeoth/eo
eaaio?a ~ 3Eg (Eca (17 aA).

Aaee/eia picuaieaiiy A-nioae iiaeeiaiiy Tl+- oeaio?ia o e?enoaeao
Cs2ZnI4 : Tl i Rb2ZnCl4 : Tl noaiiaeoue 0.14 ? 0.12 aA a?aeiia?aeii. O
pacoeueoao? aieeao iecueeineiaope/iiai epenoae?/iiai iiey oa
aeaeopii-oiiiiii? aca?iaei? a oeeo e?enoaeao aeieeathoue aea? nioae
ethi?ianoeaioe?? ipe iapaoiaeao ?c oaopaaiiaeueieo (O) ? opeaiiaeueieo
(O) yi – oaeeap?anueeeo i?i?ioi?a aae?aaaoe/iiai iioaioe?aeo (E(AO)=2.93
? 3.07 aA; E(AX)=2.40 ? 2.42 aA a?aeiia?aeii). Anoaiiaeaii, ui aaee/eia
iioaioeiaeueiiai aa?’??a iiae iaiia i?i?ioiaie ? iaioith aeey
Rb2ZnCl4:Tl, i?ae aeey ?cinopoeoopiiai Cs2ZnI4 : Tl. Epenoaee Cs2ZnI4:Tl
? Rb2ZnCl4:Tl ? iiaeaeueieie ia’?eoaie aeey aea/aiiy aoaeoo ssia –
Oaeea?a o iecueeineiao?e/iiio e?enoaei/iiio iie?.

Aiapoa ipiaaaeaii aeine?aeaeaiiy aeii?oeiai? ethi?ianoeaioe?? e?enoae?a
Cs2ZnI4 :Mn ? ZnI2:Mn. Aeiapa eipaeyoe?y i?ae aiapaaoe/ieie iapaiaopaie
?aeeii? aaon?anueei? nioae aeipii?ithaaiiy ipe 2.26 ? 2.28 aA a iaeaeaio
epenoaeao aeicaiey? opaeooaaoe ethi?ianoeaioe?th ye aeipii?ithaaeuei?
iapaoiaee i?ae 3 d2 – p?aiyie iiia Mn2+ a oao?aaae?e/iiio iiei iiiia
I-, oiaoi ye iapaoiaee 4T1g ( 6A1g. Ipiaaaeaia ?aeaioeo?eaoe?y nioa
caoaeaeaiiy ethi?ianoeaioe?? (iiaeeiaiiy) c a?aeiia?aeieie iapaoiaeaie a
?ii? Mn2+. Anoaiiaeaii, ui epenoaee ZnI2:Mn ? Cs2ZnI4:Mn caaaeyee
aenieiio aaniethoiiio eaaioiaiio aeoiaeo ? aoaeoeaieie ethi?iioipaie ipe
e?iiaoi?e oaiiapaoop? ((=0.74 ? 0.68 a?aeiia?aeii), a epenoaee Tl2ZnI4 i
TlCdI3 – ipe iecueeeo ((77 E) oaiiapaoopao ((=0.70 ? 0.69 a?aeiia?aeii).

O e?enoaeao oaa?aeeo ?ic/eiia CsPbCl3(1-x)I3x (x=0…1) niiainiothoue ye
aieueii, oae i eieaeiciaaii eaoiiiii oa aaoieieae?ciaai? ai?iii?
aeneoiie. C ?inoii x ca?eueoo?oueny aaee/eia aeneoii-oiiiiii?
aca?iiaei?, ciaioo?oueny ?aaeion iniiaiiai noaio aeneoiia i c?inoa?
iiiai?iinoue i?ioeania aaoieieaeicaoei? aeneoiia. Aeey x(0.66
i?iyaey?oueny ?icuaieaiiy (((35 iaA) aeneoiiieo (n=1) nioa aiaeaeaaiiy
aianeiaeie aei? e?enoaei/iiai iiey ? aoaeoo ssia – Oaeeapa. Aiapoa ii
niaeopao oioiethiiianoeaioei? oaa?aeeo ?ic/eiia CsPbCl3(1-x)I3x (x=0…1)
anoaiiaeaii oaeo iaeaea iaeaaeueii? iap?iaee/iino? aii?yaeeoaaiiy iiiia
Cl- i I- a e?enoaei/ieo a?aoeao e?enoaeia CsPbCl2I i CsPbClI2.

INHIAH? ?ACOEUeOAOE AeENA?OAOe?? AEEEAAeAH? O ?IAIOAO :

I.V.Kutsyk (Noip/oi), M.S.Pidzyrailo. On luminescence of TlCdI3 crystal.
// Journal of Luminescence. – 1998. – v.79. – P.135-141.

I.V.Kutsyk (Noip/oi), M.S.Pidzyrailo, I.PPashuk. Luminescence
?eculiarities of Tl2ZnI4 crystal. // Radiation Measurements. – 1998. –
v.29, 3/4. – P.243-245.

I.N.I?aecepaeei, I.A.Eooeee (Noip/oi), I.O.Aioiiye, ?.I..Iaooe,
I.I.Aapaee/aanueeee. eopineii?y oapoaaoiai epenoaeo I2. // A?niee
Euea?anueeiai oi?aapneoaoo. “O?ceea ? o?i?y iaoap?ae?a aeaeopiii?
oaoi?ee”. Nap?y o?ce/ia. – 1998. – a.31. – N.75-77.

I.S.Pidzyrailo, S.V.Myagkota, A.S.Voloshinivskii, M.V.Kutsyk (Noip/oi).
Vibronic interactions in CsPbCl3xBr3(1-x) and CsPbCl2I crystals. //
Optical Inorganic Dielectric Materials and Devices. SPIE. – 1997. –
v.2967. – P.48-51.

I.S.Pidzyrailo, M.V.Kutsyk (Noip/oi). Exciton emission of TlCdI3
crystal. // Papers presented at EXCON’96 (2nd Int. Conf. on Excitonic
Processes in Condenced Matter). Dresden: Dresden University Press, 1996.
– P.75-78.

M.S.Pidzyrailo, S.V.Myagkota, I.P.Pashuk, M.V.Kutsyk (Noip/oi). Low
temperature optical properties for APbCl3xI3(1-x) (A=Rb, Cs) crystals.
// ICL’96. Int. Conf. on Luminescence and Optical Spectroscopy of
Condenced Matter. Abstracts. August 18-23, 1996. – Prague, Czech
Republic. – P13-101.

M.V.Kutsyk (Noip/oi), M.S.Pidzyrailo, I.P.Pashuk. On luminescence of
ZnI2 crystals. // PPMSS’97. 2nd Int. School-Conf. on Physical Problems
in Material Science of Semiconductors. Abstract booklet. Chernivtsi,
September 8-12, 1997. – P.215.

M.V.Kutsyk (Noip/oi), M.S.Pidzyrailo, I.P.Pashuk. Luminescence
peculiarities of Tl2ZnI4 crystal. // LUMDETR’97. 3nd Int. Symposium
“Luminescence Detectors and Transformes of Ionizing Radiation”.
Abstracts. October 6-10, 1997. Ustron, Poland. P. 61-62.

Noip/oi I.A. Aeine?aeaeaiiy aoaeo?a a?apiiii? aca?iiae?? a epenoaeao
ABX3 ? AmBnCpXs p?cieo nopoeoop. – ?oeiien.

Aeenapoaoe?y ia caeiaoooy iaoeiaiai nooiaiy eaiaeeaeaoa o?ceei –
iaoaiaoe/ieo iaoe ca niaoe?aeuei?noth 01.04.10 – o?ceea
iai?aipia?aeiee?a ? ae?aeaeopee?a. – Euea?anueeee aeapaeaaiee
oi?aapneoao ?i. ?aaia Opaiea, i.Euea?a, 1999.

Aeena?oaoeith i?enay/aii aeineiaeaeaiith aoaeoia aia?iiii? aca?iiaei? o
/enoeo i aeoeaiaaieo aaei?aeieo ia?ianueeeoiiiaeiaieo (oeio AAO3 i
A2AO4) oa oa?oaaoeo (ZnI2) e?enoaeao. ?ic?iaeaii oaoiieiaith neioaco i
ae?iuoaaiiy e?enoaeia ZnI2, Tl2ZnI4 i Cs2ZnI4, a oaeiae aia?oa
aeineiaeaeaii ?o iioeei – niaeo?aeueii i niaeo?aeueii – eiiaoe/ii
oa?aeoa?enoeee a aeiaiaciii 77-300 E. Aecia/aii ia?aiao?e aeneoiiia a
TlCdI3 i ZnI2 oa anoaiiaeaii, ui a inoaiiueiio ?aaeicothoueny aeneoiie
i?iiiaeiiai oeio. O e?enoaeao Tl2ZnI4 i Rb2CdI4 i?enooiinoue nai/aiiy
eeoa aiiiiieo aaoieieaeiciaaieo aeneoiiia aeaco? ia neeueio aeneoii –
oiiiiio aca?iiaeith. Niiainioaaiiy nai/aiiy eieaeiciaaieo eaoiiiieo
aeneoiiia i aaoieieaeiciaaieo aiiiiieo aeneoiiia o TlCdI3 (77 E) i
oaa?aeeo ?ic/eiao CsPbCl3(1-x)I3x (x=0…1, 5-20 K) naiae/eoue i?i
i?iiiaeiee oa?aeoa? aeneoii – oiiiiii? aca?iiaei?. E?enoaee ZnI2:Mn i
Cs2ZnI4:Mn ? aenieiaoaeoeaieie ethiiiioi?aie i?e eiiiaoiie, a Tl2ZnI4 i
TlCdI3 i?e iecueeeo oaiia?aoo?ao. E?enoaee Cs2ZnI4:Tl i Rb2ZnCl4:Tl ?
ia?niaeoeaieie iiaeaeueieie ia’?eoaie aeey aeineiaeaeaiiy aeeiaii/iiai
aoaeoo ssia – Oaeea?a. ?acoeueoaoe aeena?oaoeieii? ?iaioe iioaeieiaaii a
4 ?aoa?iaaieo aeo?iaeao, a 1 iaoap?aeao ? 8 oacao iiaeia?iaeieo iaoeiaeo
eiioa?aioeie i naiiia?ia oa iaaiaipai? ia 12 eiioapaioe?yo.

Eeth/ia? neiaa: a?apiii? aca?iiae??, aoaeo ssia – Oaeeapa,
ethi?ianoeaioe?y, aeneoii, iapianueeeo, oapoaao? epenoaee, oaapae?
pic/eie.

Noip/oi I.A. Enneaaeiaaiea yooaeoia aeapiiiiai acaeiiaeaenoaey a
epenoaeeao oeia ABX3 e AmBnCpXs pacee/iuo nopoeoop. – ?oeiienue.

Aeennapoaoeey ia nieneaiea o/aiie noaiaie eaiaeeaeaoa
oeceei-iaoaiaoe/aneeo iaoe

ii niaoeeaeueiinoe 01.04.10 – oeceea iieoipiaiaeieeia e aeeyeaeopeeia.
Eueaianeee ainoaeapnoaaiiue oieaapneoao ei.Eaaia Opaiei, a.Eueaia,
Oepaeia, 1999.

Aeennapoaoeey iinayuaia pacoeueoaoai enneaaeiaaiee aeapiiiuo
acaeiiaeaenoaee a /enouo e aeoeaepiaaiiuo aaeieaeiuo epenoaeeao ni
nopoeoopie iapianeeoa (ABX3 e AmBnCpXs oeia) e neienouo epenoaeeao
(ZnI2). ?acpaaioaia oaoiieiaey neioaca e pinoa epenoaeeia ZnI2, Tl2ZnI4
e Cs2ZnI4 , a oaeaea aiapaua enneaaeiaaiu eo iioeei – niaeopaeueiua e
niaeopaeueii – eeiaoe/aneea oapaeoapenoeee a oaiiapaoopiii aeeaiaciia
77-300 E. Aeey epenoaeeia ZnI2 e TlCdI3 iipaaeaeaiu iapaiaopu yeneoiiia
e onoaiiaeaii, /oi a iineaaeieo paaeecothony yeneoiiu ipiiaaeooi/iiai
oeia. A epenoaeeao Tl2ZnI4 e Rb2CdI4 ipenoonoaea eceo/aiey oieueei
aieiiiuo aaoieieaeeciaaiiuo yeneoiiia oeacuaaao ia neeueiia yeneoii –
oiiiiiia acaeiiaeaenoaea. Ninouanoaiaaiea naa/aiey eieaeeciaaiiuo
eaoeiiiuo e aaoieieaeeciaaiiuo aieiiiuo yeneoiiia a TlCdI3 (77E) e a
oaapaeuo panoaipao CsPbCl3(1-x)I3x (x=0…1, 5-20 E) naeaeaoaeuenoaoao i
ipiiaaeooi/iii oapaeoapa yeneoii – oiiiiiiai acaeiiaeaenoaey. Epenoaeeu
ZnI2:Mn e Cs2ZnI4:Mn yaeythony aunieiyooaeoeaiuie ethieiioipaie ipe
eiiiaoiie, a Tl2ZnI4 e TlCdI3 i?e ieceeo oaiia?aoo?ao. E?enoaeeu
Cs2ZnI4:Tl e Rb2ZnCl4:Tl – iapniaeoeaiuaiiaeaeueiua iauaeou aeey
enneaaeiaaiey aeeiaie/aneiai yooaeoa ssia – Oaeeapa. ?acoeueoaou
aeennapoaoeeiiiie paaiou iioaeeeiaaiu a 4 paoapepiaaiiuo aeopiaeao, a 1
iaoapeaeao e 8 oacao iaaeaeoiapiaeiuo iao/iuo eiioapaioeee e naieiapia e
ianoaeaeaiu ia 12 eiioapaioeeyo.

Eeth/aaua neiaa: aeapiiiua acaeiiaeaenoaey, yooaeo ssia – Oaeeapa,
ethieianoeaioeey, yeneoii, iapianeeo, neienoua epenoaeeu, oaapaeua
panoaipu.

Storchun M.V. Storchun M.V. Investigation of the vibronic interaction
effects for ABX3 and AmBnCpXs -type crystals with different structures.
– Manuscript.

Dissertation for the defending of the Candidate (Master) degree of
Physics and Matematics – Speciality 01.04.10 – Physics of
Semiconductors and Insulators. Lviv Ivan Franko State University,
Ukraine, 1999.

The dissertation is devoted to the results of investigation of the
vibronic interaction effects in pure and doped halide perovskite – like
(ABX3- and AmBnCpXs -type) crystals and the layered (ZnI2) ones.

The synthesis and growing technology of the ZnI2, Tl2ZnI4 and Cs2ZnI4
crystals have been devised. Also their optical – spectroscopy and
spectral – kinetic characteristics in the 77-300 K range were originally
explorated. The exciton reflection maxima are observed (77 K) for ZnI2
at 4.330 (n=1) and 4.443 (n=2) eV and for TlCdI3 at 3.158 (n=1) and
3.283 (n=2) eV. These data allow to determine the values of the band gap
energy (Eg=3.33 for TlCdI3 and Eg=4.48 eV for ZnI2) as well as the
exciton binding energy for the crystals (F=0.168 and 0.150 eV
respectively). It is found that in the latter ones the intermediate type
of excitons takes place (r1(7 A ( a).

The photoluminescence spectrum of Tl2ZnI4 crystal can be well described
by two strongly overlapping Gaussian shaped bands. Their intensity
distributions, maximum positions and halfwidths depend highly on the
temperature and they abruptly diminish in the range from 160 to 180 K.
Position of the exciton (n=1) absorption peak conforming to 3.82 eV was
first located. Therefore the 2.71 eV emission band (halfwidth (H=0.32 eV
and Stokes shift S=1.11 eV) is associated with the self – trapped
exciton emission. Thermostimulated luminescence data account for
supposition that in Tl2ZnI4 irradiated by X-rays at 85 K effective
creation of Vk-centres is under way.

The thermal (8-300 K) spectral – kinetic investigation of Rb2CdI4
suggests that the lower energy emission band (at 2.31eV, (H=0.13 eV,
((2*10-5 s) is due to triplet – singlet transition under radiative self
– trapped exciton relaxation. The photon multiplication process for the
crystal begins when the energy of excited quanta is about 17 eV, that is
3*Eg.

The presence of self – trapped exciton emission only in Tl2ZnI4 and
Rb2CdI4 crystals pointes to the strong exciton – phonon interaction.

Coexistence of the bound (near Tl+ ions) cation exciton glow (with the
emission Gaussian shaped band maximum at 2.868 eV, (H=0.04 eV, (=2.5 ns)
and the self – trapped anion exciton glow (at 2.370 eV, (H=0.35 eV,
(f=3.7 ns, (s=2.2 (s) in TlCdI3 (77 K) testifies to the fact that the
exciton – phonon interaction is intermediate. The thermal dependence of
the slow decay component permits to determine the activation energy for
nonradiative triplet – singlet transitions (0.080 eV). The examination
of the spectral – kinetic investigation of photoluminescence for TlCdI3
suggests that the emission center presents the undisplaced I2- + e- –
type of the self-trapped exciton with D2h-symmetry.

In case of X-ray excitation, the spectral position of the luminescence
band is strongly depended on foreign impurities. Excited by X-rays at 77
K, the TlCdI3 crystal does not provide so many defect centres. Trap
depths (0.26 and 0.34 eV) were obtained from the thermostimulated
luminescence measurements.

Because of electron – phonon interaction and fair crystal field action
in the Cs2ZnI4:Tl and Rb2ZnCl4:Tl crystals two bands of the
photoluminescence and excitation spectra occur. They are caused by
transitions from tetragonal (T-) and trigonal (X-) Jahn – Teller minima
of adiabatic potential. Thus these crystals can be suggested as model
objects for the dynamic Jahn – Teller effect examination in low –
symmetry crystal field.

As far as the ZnI2:Mn and Cs2ZnI4:Mn crystals are concerned the Mn2+
-ion in tetrahedral field of I- ions is defined as emission center. So
luminescence of the crystals is associated with 4T1g(6A1g transitions.
These crystals at room temperature and also the Tl2ZnI4 and TlCdI3
crystals at low (T(77 K) temperatures are regarded as promising
phosphors owing to high value of the absolute light output ((=0.74;
0.68; 0.70 and 0.69 respectively).

Taking into account the measured exciton reflection spectra the exciton
binding energies and radii as well as the values of the band gap
energies and dielectric constants have been calculated for
CsPbCl3(1-x)I3x (x=0…1, 5-20 K) solid solutions. The values of
dielectric constants have been estimated on the assumption that the
reduce exciton mass was considered as half-mass of a free electron. For
the crystals with x=0.66 and 1 the exciton reflection peaks show the
doublet structure ((=0.035 eV) derived from crystal splitting. The rise
of the iodine concentration in CsPbCl3(1-x)I3x (x=0…1, 5-20 K) solid
solutions leads to the increase of an exciton – phonon interaction and
of probability of the process of exciton self – trapping and of the
decreasing of exciton radius (from 11.2 to 7.9 eV). It was discovered in
CsPbCl2I and CsPbClI2 crystals that almost perfect ordering of Cl- and
I- anions takes place. Such conclusion follows from the lack of the
bound exciton emission bands in their photoluminescence spectra.

The results of the dissertation are reflected in four articles published
in refered Journals; besides there are one article and eight abstracts
in different Papers of the international scientific conferences or
symposiums the contents of which were discussed at twelve conferences.

Key words: vibronic interaction, Jahn – Teller effect, exciton,
luminescence, perovskite – like crystal, layered crystal, solid
solution.

Caeaii ia neeaaeaiiy 20.01.99 ?.

I?aeienaii aei ae?oeo 25.01.99 ?.

Oi?iao 84o180/32. Aa?i?oo?a Oaein.

Aeae. ae?oe. a?e. 1.

Oe?aae 100 oo.

Ae?oe II Ia?one/ I.I.

i. Euea?a, ie. Iniiienea, 5/11

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