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Спектроскопія тонких плівок комплексних сполук на основі галогенідів міді та лужних металів: Автореф. дис… канд. фіз.-мат. наук / О.М. Коваленко, Ха

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OA?E?ANUeEEE IAOe?IIAEUeIEE OI?AA?NEOAO ?I.A.I.EA?AC?IA

Ia i?aaao ?oeiieno

Eiaaeaiei Ieaia Ieeiea?aia

OAeE 535.34:548.0

NIAEO?INEII?ss OIIEEO IE?AIE EIIIEAENIEO NIIEOE IA

INIIA? AAEIAAI?Ae?A I?Ae? OA EOAEIEO IAOAE?A

01.04.05.- iioeea, eaca?ia o?ceea

AAOI?AOA?AO

aeena?oaoe?? ia caeiaoooy iaoeiaiai nooiaiy

eaiaeeaeaoa o?ceei-iaoaiaoe/ieo iaoe

Oa?e?a-1999

Aeena?oaoe?y ? ?oeiienii.

?iaioa aeeiiaia a Oa?e?anueeiio iaoe?iiaeueiiio oi?aa?neoao? ?i.
A.I.Ea?ac?ia I?i?noa?noaa ina?oe Oe?a?ie.

Iaoeiaee ea??aiee: aeieoi? o?ceei-iaoaiaoe/ieo iaoe, i?ioani?

Ieeineaanueeee Aieiaeeie?
Einoyioeiiae/, caa?aeoaa/ eaoaae?e

o?ce/ii? iioeee Oa?e?anueeiai
iaoe?iiaeueiiai oi?aa?neoaoo

?i.A.I.Ea?ac?ia

Io?oe?ei? iiiiaioe: aeieoi? o?ceei-iaoaiaoe/ieo iaoe, noa?oee iaoeiaee
ni?a?ia?oiee

Aaeoiia Ieeiea Caoa?iae/, caa?aeoaa/ a?aeae?eo
iieaeoey?ii?

aeaeo?ii?ee i?aai?/ieo e?enoae?a (IOE “?inoeooo
iiiie?enoae?a”

IAI Oe?a?ie)

eaiaeeaeao o?ceei-iaoaiaoe/ieo iaoe
Naa/aiei Ieaia Iaenei?aia ,

aeioeaio eaoaae?e caaaeueii? o?ceee
Oa?e?anueeiai iaoe?iiaeueiiai

oi?aa?neoaoo ?i.A.I.Ea?ac?ia

I?ia?aeia onoaiiaa: O?ceei-oaoi?/iee ?inoeooo iecueeeo oaiia?aoo? ?i.
A.?.A??e?ia

IAI Oe?a?ie; a?aeae?e niaeo?ineii??
eiiaeainiaaieo

iieaeoey?ieo nenoai, i. Oa?e?a.

Caoeno a?aeaoaeaoueny “11” ethoiai 2000 ?. i 14 aiaeei? ia can?aeaii?
niaoe?ae?ciaaii? a/aii? ?aaee Ae 64.051.03 o Oa?e?anueeiio
iaoe?iiaeueiiio oi?aa?neoao? ?i.A.I.Ea?ac?ia (61077, i.Oa?e?a-77, ie.
Naiaiaee,4, aoae. ?i. E.Ae.Neiaeueieeiaa).

C aeena?oaoe??th iiaeia iciaeiieoeny o Oeaio?aeuei?e iaoeia?e
a?ae?ioaoe? Oa?e?anueeiai iaoe?iiaeueiiai oi?aa?neoaoo ?i.A.I.Ea?ac?ia
ca aae?anith: 61077, i.Oa?e?a-77, ie.Naiaiaee, 4.

Aaoi?aoa?ao ?ic?neaiee “5” n?/iy 2000 ?.

A/aiee nae?aoa?

niaoe?ae?ciaaii? a/aii? ?aaee
Iieaea A.I.

CAAAEUeIA OA?AEOA?ENOEEA ?IAIOE

Aeooaeuei?noue oaie. Eiiieaeni? niieoee, ye? i?noyoue ?iie Cu,
i?eoyaothoue oaaao aeine?aeiee?a nai?ie iacae/aeieie aeanoeainoyie.
Aeaye? ?c oeeo niieoe ? noia??iiieie i?ia?aeieeaie, ?io?
aeei?enoiaothoue o oaoi?oe? aacn??aeyii? oioia?ao?? ye oioio?iii?
iaoa??aee. A?eueo?noue ?c oeeo niieoe, iniaeeai o?, ye? aeei?enoiaothoue
ye oaa?ae? aeaeo?ie?oe, aioothoue oeyoii neioaco a?ia?ieo niieoe CuHal c
aaeiaai?aeaie eoaeieo iaoae?a. O ca’yceo c oeei aaaeeeaei ?
aeine?aeaeaiiy aeaeo?iiieo niaeo??a eiiieaenieo niieoe nenoaie
CuHal-MeHal (Me-eoaeiee iaoae), ye? ? iniiaith aeey noai?aiiy
noia??iiieo i?ia?aeiee?a.

A?eueo?noue eiiieaenieo niieoe a nenoai? CuHal-MeHal (ca aeiyoeii
noia??iiieo niieoe oeio RbCu4Cl3I2) e?enoae?cothoueny a i?oi?iia?/io
no?oeoo?o c neeueii a?aei?iieie i?aiao?aie a?aoee. ?iie Cu+
aaoaeiaothoueny a oao?aaae?e ?c ?ii?a Hal- ? oao?aaae?e/i? eiiieaene
CuHal3- noai?ththoue iaeeia?i? aai iiaea?ei? eaioethae, ye? iai?aaeai?
acaeiaae ei?ioei? in? e?enoaeo. A?aenoaiue i?ae aea?aaeaioieie ?iiaie a
eaioethaao iaaaaaoi iaioa i?ae a?aenoaiue i?ae eaioethaaie, ui aeeeeea?
i?eiouaiiy i?i eaac?iaeiii??iee oa?aeoa? aeaeo?iiieo oa aeneoiiieo
caoaeaeaiue a oeeo niieoeao. Aea aeaeo?iii? niaeo?e oa aeneoiie a
eaac?iaeiii??ieo e?enoaeao ia iniia? CuHal aei oeueiai /ano iaeaea ia
aeine?aeaeoaaeenue.

Iniaeeao oe?eaa?noue aeeeeeathoue noia??iii? niieoee, ye?
e?enoae?cothoueny a nenoai? CuHal-MeHal. Noia??iiiee i?ia?aeiee
RbCu4Cl3I2 ia? ?aei?aeii aenieo ?iiio i?ia?aei?noue i?e e?iiaoi?e
oaiia?aoo?? (0,45 Ii-1ni-1). A?aee?eooy oe??? niieoee noeioethaaei
i?iaaaeaiiy aaeeei? e?eueeino? ?ia?o ii aea/aiith aeaeo?ii?ia?aeiino? oa
?ioeo o?ce/ieo aeanoeainoae ?cino?oeoo?ieo noia??iiieo niieoe.
Aeaeo?iii? niaeo?e iiaeeiaiiy noia??iiieo i?ia?aeiee?a ia iniia?
aaeiaai?ae?a i?ae? ?ai?oa ia aeine?aeaeoaaeenue. Aea, ye iieacaee
aeine?aeaeaiiy niaeo??a iiaeeiaiiy eeane/ieo noia??iiieo niieoe AgI,
RbAg4I5, ia?ao?ae a noia??iiiee noai noi?iaiaeaeo?oueny cia/ieie ci?iaie
oa?aeoa?enoee iecueei/anoioieo aeneoiiieo nioa, ye? aeeeeeai? oaciaeie
ia?aoiaeaie oa ?icn?thaaiiyi aeneoii?a ia noai?aieo aeaoaeoaie O?aieaey
oeoeooaoe?yo aioo??oiueiai aeaeo?e/iiai iiey.

Iiaeeea?noue i?aeoe/iiai canoinoaaiiy noia??iiieo i?ia?aeiee?a oa
iaaeinoaoiy aea/ai?noue iioe/ieo niaeo??a niieoe nenoaie CuHal-MeHal
aeacothoue ia aeooaeuei?noue i?iaaaeaiiai a aeena?oaoe?? aeine?aeaeaiiy.

Ca’ycie ?iaioe c iaoeiaeie i?ia?aiaie, ieaiaie, oaiaie.

Aeena?oaoe?y aeeiiaia ia eaoaae?? o?ce/ii? iioeee OAeO a ?aieao IAe?
eaoaae?e “Aeine?aeaeaiiy niaeo??a aeaeo?iiieo oa aeneoiiieo caoaeaeaiue
i?e iecueeeo oaiia?aoo?ao a oiieeo ie?aeao noia??iiieo oa ?ioeo
iio??eieo niieoe a nenoaiao (Ia1Ial)1-o(Me2Hal)o (Me1 =K,Rb,Cs oa ?i.,
Me2 =Ag,Cu, Hal=Cl, Br,I)”, iiia? aea?ae?a?no?aoe?? ?0197U002479,
caoaa?aeaeaii? a?aeiia?aeiith iinoaiiaith I?iina?oe Oe?a?ie.

Iaoa ? caaea/? aeine?aeaeaiiy. Iniiaiith iaoith aeaii? aeena?oaoe?eii?
?iaioe yaey?oueny neioac oiieeo ie?aie eiiieaenieo niieoe nenoaie
CuHal-MeHal oa aea/aiiy ?o niaeo??a iiaeeiaiiy a iaeano?
ooiaeaiaioaeueii? nioae, anoaiiaeaiiy ei?aeyoe?? i?ae aeaeo?iiiei
niaeo?ii iiaeeiaiiy oa aoaeiaith e?enoae?/ii? a?aoee niieoe,
aeine?aeaeaiiy aeneoiiiiai niaeo?o a oe?ieiio ?ioa?aae? oaiia?aoo?, yeee
aeeth/a? oaiia?aoo?e oaciaeo ia?aoiae?a a aeiaaeeo noia??iiieo niieoe.

C oe??th iaoith iaiao?aeii aoei ?ica’ycaoe oae? caaea/?:

– ?ic?iaeoe iaoiaeeee i?eaiooaaiiy oiieeo ie?aie eiiieaenieo niieoe a
nenoai? CuHal-MeHal oa i?ieiio?iethaaoe ?o oaciaee neeaae ca aeiiiiiaith
iioe/ieo oa aeaeo?iiia?ao?/ieo aeine?aeaeaiue;

– aei??yoe niaeo?e iiaeeiaiiy oiieeo ie?aie eiiieaenieo niieoe a
niaeo?aeueiiio ?ioa?aae? 3-6 aA ? ?ioa?aae? oaiia?aoo?, yeee aeeth/a?
oacia? ia?aoiaee;

– ?aeaioeo?eoaaoe iniaeeaino? a niaeo?ao iiaeeiaiiy oa anoaiiaeoe ?o
ca’ycie c e?enoae?/iith no?oeoo?ith aeine?aeaeoaaieo niieoe;

– aecia/eoe ia?aiao?e aeiaaioaeeueiaeo 1s-aeneoiiieo nioa oa aeine?aeeoe
?o oaiia?aoo?i? caeaaeiino?.

Iaoeiaa iiaecia iaea?aeaieo ?acoeueoao?a

– Aia?oa aeine?aeaeai? aeaeo?iii? niaeo?e iiaeeiaiiy oiieeo ie?aie
Cs3Cu2Hal5 i CsCu2Hal3 (Hal=I,Cl) a ?ioa?aae? aia?a?e 3-6 aA ?
oaiia?aoo? 90-290E. Aecia/ai? aia?a?y ca’yceo aeneoii?a ? oe?eia
caai?iiaii? ciie. Anoaiiaeaii ca’ycie i?ae aeaeo?iiiei niaeo?ii ?
e?enoae?/iith no?oeoo?ith niieoe, iieacaii eaac?iaeiii??iee oa?aeoa?
aeaeo?iiieo oa aeneoiiieo caoaeaeaiue a Cs3Cu2Hal5 i CsCu2Hal3.
eieae?ciaaieo a CuHal-eaioethaao neeaaeiiai oeio.

-Aeyaeaiee neaaeee aieea oeoeooaoe?? neeaaeo a oaa?aeiio ?ic/ei?
RbxCs1-xCu2I3 ia ia?aiao?e aeneoiiieo nioa, ui na?ae/eoue i?i
eieae?caoe?th iecueei/anoioieo aeaeo?iiieo caoaeaeaiue a CuI-i?aea?aooe?
niieoe.

– Aia?oa aeine?aeaeai? niaeo?e iiaeeiaiiy oiieeo ie?aie eiiieaenieo
niieoe CsCu2Cl3-xIx (x=0,1,2,3) a ?ioa?aae? aia?a?e 3-6 aA i?e 90 ?
293E. Iieacaii, ui a CsCu2I3 aeneoiie iienothoueny o ?aieao iiaeae?
Aaiue?-Iiooa, a a CsCu2Cl3 i?iyaeythoueny ?ene aeneoii?a O?aieaey.

– Aeine?aeaeaia oaiia?aoo?ia caeaaei?noue ia?aiao??a iecueei/anoioieo
aeneoiiieo nioa Cs3Cu2Hal5 i CsCu2Hal3. Iieacaii, ui cnoa oa ooe?aiiy
aeneoiiieo nioa aecia/a?oueny aeneoii-oiiiiiith aca?iiae??th.

– Aia?oa aeine?aeaeai? niaeo?e iiaeeiaiiy noia??iiieo i?ia?aeiee?a
CsyRb1-yCu4Cl3I2 (y=0;0,5;1). Iieacaii, ui aocuee? nioae, ye?
niinoa??aathoueny a niaeo?? iiaeeiaiiy a ?ioa?aae? 3,5-6 aA, iaeaaeaoue
aeneoiiai, eieae?ciaaiei a Cu(??)Hal ? Cu(???)Hal i?aea?aoeao niieoe ?
aaeeea oe?eia caai?iiaii? ciie ii??aiyiii c Eg a CuI i CuCl
aecia/a?oueny iaioei /eneii ?ii?a Cu a ae?oa?e eii?aeeiaoe?ei?e noa??
e?enoae?/ii? a?aoee niieoe.

– O oaiia?aoo?i?e caeaaeiino? niaeo?aeueiiai iieiaeaiiy oa iai?aoe?eie
iecueei/anoioii? aeneoiiii? nioae niieoe CsyRb1-yCu4Cl3I2 (y=0;0,5;1)
aeyaeai? iniaeeaino?, ye? iia’ycai? c oaciaeie ia?aoiaeaie oa ?
?icoii?yaei/aiiyi eao?iiii? i?aea?aoee niieoee i?e ia?aoiae? a
noia??iiiee noai. Iieacaii, ui aianie a ooe?aiiy nioa ca ?aooiie
aaia?aoe?? aeaoaeo?a O?aieaey a ae?aeaeo?e/i?e oac? i?iyaey?oueny a
niieoeao c aenieith oaiia?aoo?ith ia?aoiaeo a noia??iiiee noai.

Eiie?aoi? iaoeia? ?acoeueoaoe oa iieiaeaiiy, ui aeiinyoueny ia caoeno.

1.?aeaioeo?eaoe?y aeaeo?iiieo oa aeneoiieo nioa a niaeo?ao iiaeeiaiiy
niieoe nenoaie CuHal-MeHal oeyoii ii??aiyiiy ?o c niaeo?aie iiaeeiaiiy
a?ia?ieo niieoe ? aiae?co e?enoae?/ii? no?oeoo?e aeine?aeaeoaaieo
niieoe. Aecia/aiiy aia?a?? ca’yceo aeneoii?a oa oe?eie caai?iiaii? ciie
niieoe.

2.Aenia?eiaioaeueia i?aeoaa?aeaeaiiy eaac?iaeiii??iiai oa?aeoa?o
aeaeo?iiieo oa aeneoiiieo caoaeaeaiue a iio??eieo niieoeao CuHal-MeHal,
eieae?ciaaieo a iiaea?eieo eaioethaao, ye? neeaaeathoueny ?c oao?aaae??a
CuHal4 ? ? no?oeoo?iei aeaiaioii e?enoae?/ii? a?aoee niieoe.

3.Iaa?oiooaaiiy iiaeeeaino? canoinoaaiiy iiaeaeae aeneoii?a O?aieaey ?
Aaiue?-Iiooa aeey iieno aeneoii?a oa aeeoiiieo nioa a ??cieo eiiieaenieo
niieoeao nenoaie CuHal-MeHal.

4. Iniaeeaino? a oaiia?aoo?ieo caeaaeiinoyo iai?aoe?eie oa
niaeo?aeueiiai iieiaeaiiy iecueei/anoioii? aeneoiiii? nioae noia??iiieo
niieoe CsyRb1-yCu4Cl3I2 (y=0;0,5;1) iia’ycai? c oaciaeie ia?aoiaeaie oa
?icoii?yaeeoaaiiyi eao?iiii? i?aea?aoee i?e ia?aoiae? a noia??iiiee
noai.

I?aeoe/ia cia/aiiy iaea?aeaieo ?acoeueoao?a aecia/a?oueny oei, ui
?acoeueoaoe aeine?aeaeaiiy iioe/ieo niaeo??a eiiieaenieo niieoe a
nenoai? CuHal-MeHal aeathoue iia? a?aeiiino? i?i aeaeo?iiiee niaeo?
aeinae?aeaeoaaieo niieoe ? iiaeooue aooe aeei?enoai? aeey iiaeaeueoiai
?icaeoeo oai??? aeaeo?iiiiai niaeo?o aaaaoieiiiiiaioieo niieoe oa oai???
aeneoii?a. Aea/aiiy niaeo??a iiaeeiaiiy noia??iiieo niieoe ia? aaaeeeaa
cia/aiiy aeey aeine?aeaeaiiy i?e?iaee aeniei? ?iiii? i?ia?aeiino?.
Iioe/i? niaeo?e iiaeooue aooe aeei?enoai? aeey aecia/aiiy oaciaiai
neeaaeo niieoe.

Iniaenoee aianie caeiaoaa/a iieyaa? o neioac? oiieeo ie?aie eiiieaenieo
niieoe nenoaie CuHal-MeHal, i?iaaaeaii? aenia?eiaioaeueieo
aeine?aeaeaiue ?o niaeo??a iiaeeiaiiy oa ?o eiii’thoa?i?e ia?iaoe?.
Aaoi? oaeiae i?eeiaea aeoeaio o/anoue a iaaiai?aii? aenia?eiaioaeueieo
aeaieo oa i?aeaioiaoe? ioae?eaoe?e.

Ai?iaaoe?y ?acoeueoao?a aeena?oaoe??. Iniiai? ?acoeueoaoe aeena?oaoe??
aeiiia?aeaeenue ia nai?ia?ao eaoaae?e o?ce/ii? iioeee OAeO oa ia 3-e
I?aeia?iaei?e eiioa?aioe?? “Oece/aneea yaeaiey a oaa?aeuo oaeao” (21-23
n?/iy 1997?., i.Oa?e?a).

Ioae?eaoe??. Ca iaoa??aeai? aeena?oaoe?? iioae?eiaaii 8 i?aoeue, o oiio
/ene? 7 noaoae o iaoeiaeo aeo?iaeao oa 1 oace aeiiia?aeae.

No?oeoo?a oa ianya aeena?oaoe?eii? ?iaioe. Aeena?oaoe?y neeaaea?oueny ?c
ia?aaeiiae, /ioe?ueio ?icae?e?a, aeniiaeo oa nieneo aeei?enoaieo
e?oa?aoo?ieo aeaea?ae ?c 109 iaeiaioaaiue: aiia aeeeaaeaia ia 145
noi??ieao, i?noeoue 65 ?enoie?a oa 13 oaaeeoeue.

INIIAIEE CI?NO ?IAIOE

O ia?aaeiia? iaa?oioiaai? aeooaeuei?noue oaie aeena?oaoe??, iaoa oa
iniiai? caaea/? aeine?aeaeaiiy, iieacai? iaoeiaa iiaecia oa i?aeoe/ia
oe?ii?noue ?acoeueoao?a, iaaaaeai? iniiai? iaoeia? ?acoeueoaoe oa
iieiaeaiiy, ui aeiinyoueny ia caoeno.

O ia?oiio ?icae?e? “O?ce/i? aeanoeaino? eiiieaenieo niieoe ia iniia?
aaeiaai?ae?a n??aea oa i?ae?” iaaaaeaiee e?oa?aoo?iee iaeyae ?ia?o i?i
no?oeoo?o, o?ce/i? aeanoeaino? oa iioe/i? niaeo?e niieoe ia iniia? AgI,
?cino?oeoo?ieo aeine?aeaeoaaiei niieoeai. O iaeyae? iaaiaeyoueny oaeiae
e?oa?aoo?i? aeai? i?i iioe/i? niaeo?e, niaeo?e ethi?ianoeaioe?? oa
o?ce/i? aeanoeaino? noia??iiieo niieoe, ?cino?oeoo?ieo RbCu4Cl3I2. Ia
i?aenoaa? iaeyaeo c?iaeaiee aeniiaie i?i ua iaeo nooi?iue aea/aiiy
iioe/ieo niaeo??a eiiieaenieo niieoe nenoaie CuHal-MeHal.

O ae?oaiio ?icae?e? “Iaoiaee aeine?aeaeaiiy niaeo??a iiaeeiaiiy
eiiieaenieo niieoe ia iniia? aaeiaai?ae?a i?ae?” iienai? iaoiaee
i?eaiooaaiiy oiieeo ie?aie eiiieaenieo niieoe, iaoiaee aei??thaaiiy ?o
niaeo??a iiaeeiaiiy oa aecia/aiiy oiaueie c?ace?a, iaaiaeyoueny aeai?
i?i e?enoae?/io no?oeoo?o aeine?aeaeoaaieo niieoe, iienai? iaoiaee
aecia/aiiy ia?aiao??a aeneoiiieo nioa.

Oiie? ie?aee eiiieaenieo niieoe neioacoaaee oeyoii aeia?iaoaaiiy a
aaeooi? noi?o? aeo?aeieo eiiiiiaio caaeaiiai iiey?iiai neeaaeo ia
i?ae?a??o? aei 100iN i?aeeeaaeee NaCl. Oaciaee neeaae ie?aie
eiio?iethaaany ca niaeo?aie iiaeeiaiiy oa c aeiiiiiaith aeaeo?iiia?ai.
Iioe/iee eiio?ieue aeyaeany iiaeeeaei ?c-ca ??cei? a?aei?ie niaeo??a
iiaeeiaiiy aeine?aeaeoaaieo niieoe.Oiaueia ie?aie aecia/aeanue ca
iaoiaeii Oieainueeiai. Aeey aecia/aiiy ia?aiao??a aeneoiiieo nioa
(niaeo?aeueiiai iieiaeaiiy, iai?aoe?eie, neee inoeeeyoi?a)
aeei?enoiaoaaee eiii’thoa?i? iaoiaee ia?iaee ?acoeueoao?a aei??thaaiiy
niaeo??a iiaeeiaiiy, ye? a?aoiaothoue ao?aoe O?aiaey oa ?ioa?oa?aioe?th
na?oea a oiieeo ie?aeao. I?e aecia/aii? ia?aiao??a aeiaaioaeeueiaeo
1s-aeneoiiieo nioa ca niaeo?ii D(E) i?iaiaeeee ?o ai?ieneiaoe?th
neiao?e/iei eiioo?ii, yeee yaey? niaith e?i?eio eiia?iaoe?th
ei?aioeiaiai oa aaonniaiai eiioo??a . I?e oae?e ai?ieneiaoe?? eiioo?
nioae aeecueeee aei eiioo?o Oiooa.

O?ao?e ?icae?e “Iioe/i? niaeo?e oa aeneoiie a iio??eieo niieoeao nenoaie
MeHal-CuHal (Me=Cs,Rb; Hal=Cl,I)”. O oe?e nenoai? oi?iothoueny niieoee
oeio Ia3Cu2Hal5 i IaCu2Hal3, ye? iathoue i?oi?iia?/io a?aoeo ?c cia/ii
a?aei?iieie ia?aiao?aie aeaiaioa?ii? eii??ee. A niieoeao IaCu2Hal3 ?iie
Cu+ aaoaeiaothoueny a oao?aaae?e/i? ionoioe i?aea?aoee Hal ? eiiieaene
CuHal43- noai?ththoue iiaea?ei? eaioethae , ye? i???ioiaai? acaeiaae
ei?ioei? in? n. Iiaea?ei? eaioethae neeaaeathoueny ?c iaeeia?ieo
eaioetha?a, ye? ca?eaeueii neiao?e/i? a?aeiinii in? a (Mejer G.
Z.anorg.allg.Chem.(1984))

No?oeoo?iei aeaiaioii e?enoae?/ii? a?aoee Cs3Cu2?5 ? iiaea?ei?
eaioethae, ye? i???ioiaai? acaeiaae in? b e?enoaeo. Eaioethae yaeythoue
niaith iine?aeiai?noue o?eaiiaeueieo a?i??ai?ae, ye? neeaaeathoueny ?c
oao?aaae??a ?. Eiaeia a?i??ai?aea ooai?th? eiiieaen Cu2I53- , yeee
i?noeoue aeaa iaaea?aaeaioi? ?iie Cu1+ i Cu2+ (Bigalke K.P., Hans A.,
Hartl H. Z.anorg.allg.Chem.(1988)). Oaea aoaeiaa e?enoae?/ii? a?aoee
iaoiiaeth? neeaaeiee niaeo? iiaeeiaiiy niieoe.

O niaeo?ao niieoe Cs3Cu2?5 ? CsCu2?3 (i.3.1) niinoa??aa?oueny ?yae
aeneoiiieo A- ? A-nioa, iieiaeaiiy yeeo iaaaaeaii a oaae.1, oa oe?ie?
N-nioae. Ia iaeaaei?noue A ? A nioa aeneoiiai aeaco? ?o ii??aiyia
aoce?noue, cia/iee iecueei/anoioiee cnoa oa ooe?aiiy c ?inoii
oaiia?aoo?e ca ?aooiie aeneoii-oiiiiii? aca?iiae?? (?en.1). N nioae ia
caciathoue iii?oiiai cnoao oa ooe?aiiy c ?inoii oaiia?aoo?e, ui
na?ae/eoue i?i ?o ca’ycie c i?aeciiieie ia?aoiaeaie.

A1 ? A1 nioae a?aeiia?aeathoue caoaeaeaiith aeneoii?a o iniiaiee noai
(1s-nioae), ui i?aeoaa?aeaeo?oueny ?o aaeeeith neeith inoeeeyoi?a.
A?eueo neaae? A2 oa A2-nioae ca’ycai? ?c caoaeaeaiiyi aeneoii?a o noai c
aieiaiei eaaioiaei /eneii n=2(2s-nioae). Ca iieiaeaiiyi A1 ? A2-nioa
aoee aecia/ai? aia?a?y ca’ceo aeneoii?a Rex, oe?eia caai?iiaii? ciie Eg
oa ?aae?on aeneoiio aex (oaae.1).

Oaaeeoey 1. Ia?aiao?e aeneoiiieo nioa iio??eieo niieoe.

NiieoeaAA0 aAAA1 aAAA2 aAAA1 aAAA2 aAAN1 aAAN2 aAEg aARex aAaex E
aACs3Cu2?54,454,805,235,825,020,572,8CsCu2?33,894,042,264,525,065,804,18
0,295,41,76

Iiyaa A-nioae a niaeo?? CsCu2?3 iaoiiaeaia Aeaaeae?anueeei ?icuaieaiiyi
aeneoiiieo cii ca ?aooiie aca?iiae?? iaeeia?ieo eaioetha?a o iiaea?eiiio
eaioethao. I?i Aeaaeae?anueea ?icuaieaiiy na?ae/eoue aeecueea cia/aiiy
neee inoeeeyoi?a A-nioae aei noia?ii? neee inoeeeyoi?a A0 oa A1 nioa.
Aca?iiae?y iaeeia?ieo eaioetha?a o iiaea?eiiio eaioethao aeeeeea? oaeiae
?icuaieaiiy aeaeo?iiieo cii, i?i ui na?ae/eoue iiyaa aeaoo nioa (N1 ?
N2) a niaeo?? CsCu2?3.

Aeneoiii? oa aeaeo?iii? caoaeaeaiiy a CsCu2?3 ? Cs3Cu2?5 eieae?ciaai? a
Cu?-i?aea?aooe?, i?i ui na?ae/eoue eiioeaio?aoe?eia caeaaei?noue
niaeo?aeueiiai iieiaeaiiy nioa a iine?aeiaiino? Cu?, CsCu2?3, Cs3Cu2?5
(?en.1), yea i?e o0 noiaeeoueny aei iieiaeaiiy ?ioaineaieo aeii?oeiaeo
nioa Cu+ a CsBr. Ca?aeii eiioeaioe??th ?icaeiooith o noaoo? (Onodera
Y., Toyazawa Y. Excitons in alkali halides //
J.Phys.Soc.Jap.-1967.-v.22,N3.-p.833-844.) i?e oae?e eieae?caoe??
iecueei/anoioi? aeneoiii? nioae a inaaaeia?ia?ieo oaa?aeeo ?ic/eiao oa
eiiieaenieo niieoeao noiaeyoueny c ciaiueoaiiyi eiioeaio?aoe?? iaei???
?c eiiiiiaio (CuI) aei niaeo?aeueiiai iieiaeaiiy aeii?oeiaeo nioa ?ii?a
iaoaeo (Cu) a a?aooe? ae?oai? eiiiiiaioe (CsI), a ia aei iieiaeaiiy
aeneoiiii? nioae a ae?oa?e eiiiiiaio?.?c ciaioaiiyi eiioeaio?aoe?? Cu
aeneoiii? nioae cnoaathoueny a ei?ioeioaeeueiao iaeanoue niaeo?o, ui
na?ae/eoue i?i nei?i/aiiy noia?ii? oe?eie aeicaieaieo cii A, ye?
i?eeyaathoue aei caai?iiaiiai i?ii?aeeo. Niaeo?ineii?/ia ioe?iea A
(oaae.1) i?iaiaeeeanue ca iieiaeaiiyi N-nioa c o?aooaaiiyi aaee/eie Eg:

A =2(AN- Eg).

?ciii?oia aoaeiaa e?enoae?/ieo a?aoie RbCu2I3 ? CsCu2?3 aeicaieeea
neioacoaaoe ie?aee oaa?aeeo ?ic/ei?a RbxCs1-xCu2I3 oa aeine?aeeoe ?o
iioe/i? niaeo?e a onueiio ?ioa?aae? iiey?ieo eiioeaio?aoe?e. Ca
niaeo?aeueiei iieiaeaiiyi aeneoiiieo nioa aoee aecia/ai?
eiioeaio?aoe?ei? caeaaeiino? Eg, Rex oa A. Aeyaeaii, ui c ?inoii
eiioeaio?aoe?? Rb niinoa??aa?oueny nei?i/aiiy ?ioa?aaeo i?ae
iecueei/anoioieie aeneoiiieie nioaaie, ca?eueoaiiy aia?a?? ca’yceo oa
oe?eie caai?iiaii? ciie ca e?i?eiei caeiiii:

Rex(o)=0,1o+0,28 (aA), Eg(o)=0,15o+4,18 (aA)

oa nei?i/aiiy noia?ii? oe?eie aeicaieaieo cii A. E?i?eiee o?ae Eg(o) ?
Rex(o) na?ae/eoue i?i iacia/iee aieea oeoeooaoe?? neeaaeo a
Ia?-i?aea?aooe? oaa?aeeo ?ic/ei?a ia ?o iecueei/anoioiee aeaeo?iiiee
niaeo?, ui ? aeiaeaoeiaei aeieacii eieae?caoe?? aeaeo?iiieo caoaeaeaiue
oa aeneoii?a o iiaea?eieo Cu?-eaioethaao. O oie aea /an, ??no Eg(o) ?
Rex(o) c ?inoii eiioeaio?aoe?? Rb iiynith?oueny a?eueoei aianeii ?iiiiai
ca’yceo Cu-? a niieooe? RbCu2I3 ii??aiyii c CsCu2?3.

O i.3.3 aeena?oaoe?? iaaaaeai? ?acoeueoaoe aeine?aeaeaiiy niaeo??a
iiaeeiaiiy oiieeo ie?aie CsCu2Cl3-xIx. O oe?e nenoai? i?e cai?i?
ai?iiii? i?aea?aoee oaa?ae? ?ic/eie ia ooai?ththoueny, a oi?iothoueny
eiiieaeni? niieoee CsCu2I3(?), CsCu2ClI2 (??), CsCu2Cl2I (???) ?
CsCu2Cl3 (IV). Aeey an?o niieoe i?iaaaeaia ?aeaioeo?eaoe?y aeneoiiieo
nioa a niaeo?ao iiaeeiaiiy. O /ioe?ueioeiiiiiaioieo niieoeao (??) ?
(???) aeyaeai? aeiaeaoeia? ?ioaineai? A1-nioae.

Oi/ niieoee (?) ? (IV) ?cino?oeoo?i?, ?o niaeo?e ia iiae?ai?.
A?aenooi?noue iiae?aiino? aecia/a?oueny, aieiaiei /eiii, iieiaeaiiyi
A-nioae: a niieooe? (?) A-nioaa ?icoaoiaaia ia oii? i?aeciiieo
ia?aoiae?a, oiaoi AA>Eg, a (IV) EB350E ia ae?eyioe? 350-410E
caeaaei?noue Em(O) e?i?eia ? dEm/dT=-1,2 10-3 aA/E. Cia/ii a?eueoee cnoa
caeaaeiino? Em(O) a ?aeii? -oace iiaeeeai iia’ycaiee c ciaiueoaiiyi
ia’?io i?e ia?aoiae?. O niieooe? N(1) iaeanoue ?nioaaiiy -oace iaea
(O=On2-On1=9E), ui i?iyaey?oueny a ??ceiio ceii? Em(O) i?e 450E. I?e
O>410E aaee/eia dEm/dT=-1,5 10-3 aA/E aeecueea aei a?aeiia?aeii?
aaee/eie aeey N(0,5) ? oa?aeoa?ia aeey iaeano? ?nioaaiiy noia??iiii?
-oace.

Oacia? ia?aoiaee aecia/athoue oaeiae neeaaeio caeaaei?noue iai?aoe?eie
A(O) A1-aeneoiiii? nioae. O niieooe? N(0) iai?aoe?eia a oaiia?aoo?iiio
?ioa?aae? 90-170E (-oaca) ?inoa ca eei?eiei caeiiii dA/dT=2,2 10-4 aA/E
(?en.3a). O ?ioa?aae?? oaiia?aoo? 179-200E niinoa??aa?oueny ??cea
c?inoaiiy A a?ae 160 aei 200 iaA (dA/dT=1,33 10-3 aA/E), ui iia’ycaii,
iaaooue, c aaia?aoe??th aaeeei? e?eueeino? aeaoaeo?a O?aieaey, yea
noi?iaiaeaeo?oueny ?icoii?yaeeoaaiiyi eao?iiii? Cu-i?aea?aoe?. O
?ioa?aae? 200-230 E aaee/eia dA/dT ciaiueoo?oueny, ui ei?aeth? c
iecueei/anoioiei cnoaii Em i?e On2 ?, iaaooue, ca’ycaii ?c ciaiueoaiiyi
ia’?io i?e ia?aoiae? ia?oiai ?iaeo. I?e O>Tc2 (-oaca) iai?aoe?eia ?inoa
ii i?eaeecii e?i?eiiio caeiio, aea aaee/eia dA/dT =6,0 10-4 aA/E ?noioii
a?eueoa i?ae o iaeano? -oace. ??no A o iaeano? -oace ie iia’yco?ii c
oaiia?aoo?iith aaia?aoe??th aeaoaeo?a O?aieaey, oiaoi e??i oiiiiii?
neeaaeiai? a caeaaeiino? A(O) aiineoue aianie eiiiiiaioa AF(T), yea
aecia/a?oueny ?icn?thaaiiyi aeneoii?a ia eoeii?anueeeo oeoeooaoe?yo.
Oaeei /eiii iai?aoe?eio aeneoiiii? nioae a noia??iiieo i?ia?aeieeao
iiaeia ae?aceoe ye:

wmetafile8? ??-???????????
???????????yyy????.????1??????????????
???&??yyyy?????Ayyy?yyya ????????&??MathType????
???u?????????”????-?????UeA???Au
???u?????????”????-????Au???°Q???-?????°Q???M??
???M?????M?TH ???u y??????

aea Aph- aianie a iai?aoe?eio ca ?aooiie aeneoii-oiiiiii? aca?iiae??, a

AF- ca ?aooiie ?icn?thaaiiy aeneoii?a ia eoeiiianueeeo oeoeooaoe?yo,
ca’ycaieo c aaia?aoe??th aeaoaeo?a O?aieaey.

O niieoeao N(0,5) ? N(1) a iaeano? ?nioaaiiy ae??eaeo?e/ii? -oace
iai?aoe?eia iae?i?eii c?inoa? c ?inoii oaiia?aoo?e. I?e O>300E a N(0,5)
? O>360E a N(1) ??no A(O) niia?eueith?oueny ? i?e O>400E a niieooe? N(1)
iai?aoe?eia ia?anoa? caeaaeaoe a?ae oaiia?aoo?e. Ia a?aei?io a?ae
RbCu4Cl3I2 a oeeo niieoeao eiiiiiaioa AF(O) aiineoue ?noioiee aeeaae a
ooe?aiiy aeneoiiii? nioae aaea a ae??eaeo?e/i?e -oac?. I?e ca?eueoaii? O
? ia?aoiae? ?c -oace a – ? -oaco eiioeaio?aoe?y aeaoaeo?a O?aieaey
iane/o?oueny ? i?aea?aoea Cu iiai?noth ?icoii?yaeeiao?oueny, ui
iicia/a?oueny ia cieaeaii? caeaaeiino? A(O) a N(0,5) i?e O>320E ?
iiaiiio iane/aii? A a ?aeii? noia??iiii? -oace a N(1). Oaea iane/aiiy
oa?aeoa?ia aeey aeneoiiieo nioa a noia??iiieo i?ia?aeieeao c aenieith
oaiia?aoo?ith oaciaiai ia?aoiaeo (N(0,5) ? N(1)), a a i?ia?aeieeao c
iecueeith oaiia?aoo?ith oaciaiai ia?aoiaeo a -oaco (On

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