.

Спектроскопія радіаційно стійких нелінійно-оптичних кристалів: Автореф. дис… канд. фіз.-мат. наук / О.Б. Біленька, Львів. держ. ун-т ім. І.Франка. —

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Euea?anueeee aea?aeaaiee oi?aa?neoao

?iai? ?aaia O?aiea

A?EAIUeEA Ieueaa Aiaaeai?aia

OAeE 537.311.33+537.226

Niaeo?ineii?y ?aae?aoe?eii no?eeeo

iae?i?eii-iioe/ieo e?enoae?a

01.04.10 – O?ceea iai?ai?ia?aeiee?a ? ae?aeaeo?ee?a

AAOI?AOA?AO

aeena?oaoe?? ia caeiaoooy iaoeiaiai nooiaiy

eaiaeeaeaoa o?ceei-iaoaiaoe/ieo iaoe

Euea?a – 1999

Aeena?oaoe??th ? ?oeiien

?iaioa aeeiiaia ia eaoaae?? aenia?eiaioaeueii? o?ceee Euea?anueeiai
aea?aeaaiiai oi?aa?neoaoo ?iai? ?aaia O?aiea.

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

Aeiaaee ss?ineaa Inoaiiae/

Euea?anueeee aea?aeaaiee oi?aa?neoao ?iai? ?aaia
O?aiea,

i?ioani? eaoaae?e aenia?eiaioaeueii? o?ceee

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

i?ioani? Iaoeianueeee Aiae??e I?anoiae/

caa?aeoaa/ eaoaae?e iai?ai?ia?aeieeiai? aeaeo?ii?ee aea?aeaaiiai
oi?aa?neoaoo “Euea?anueea iie?oaoi?ea”;

aeieoi? o?ceei-iaoaiaoe/ieo iaoe,

i?ioani? Oiiothe Ieaa Eineiiae/

canooiiee aee?aeoi?a c iaoeiai? ?iaioe IAI “Ea?ao” i. Euea?a

I?ia?aeia onoaiiaa: ?inoeooo o?ceee Iaoe?iiaeueii? Aeaaeai?? iaoe
Oe?a?ie, a?aeae?e iae?i?eii? iioeee, i. Ee?a.

Caoeno a?aeaoaeaoueny “17” eenoiiaaea 1999 ?. i 15 aiae. 30 oa. ia
can?aeaii? niaoe?ae?ciaaii? a/aii? ?aaee Ae.35.051.09 i?e Euea?anueeiio
aea?aeaaiiio oi?aa?neoao? ?iai? ?aaia O?aiea (290005, i.Euea?a,
aoe.Ae?aaiiaiiaa, 50).

C aeena?oaoe??th iiaeia iciaeiieoenue a iaoeia?e a?ae?ioaoe?
Euea?anueeiai aea?aeaaiiai oi?aa?neoaoo ?i. ?a.O?aiea (290005, I.Euea?a,
aoe. Ae?aaiiaiiaa, 5).

Aaoi?aoa?ao ?ic?neaiee “ 16 ” aeiaoiy 1999 ?.

A/aiee nae?aoa?

niaoe?ae?ciaaii? ?aaee

aeieoi? o?ceei-iaoaiaoe/ieo iaoe,

i?ioani? _______________ Aeaaee?anueeee E.O.

1

CAAAEUeIA OA?AEOA?ENOEEA ?IAIOE

Aeooaeuei?noue oaie. Iaei??th c aoceiaeo i?iaeai ?icaeoeo eaaioiai?
aeaeo?ii?ee ? eaca?ii? oaoi?ee ? iiooe oa aeine?aeaeaiiy iiaeo
aoaeoeaieo iae?i?eii-iioe/ieo e?enoae?a, i?ici?eo a oe?ie?e iaeano?
niaeo?a oa c aenieith iioe/iith no?ee?noth. ?ica’ycaiiy oe??? i?iaeaie
aeicaiey? aeei?enoiaoaaoe iiooaei? eiaa?aioi? aei?ii?ithaa/? ye i?e
aaia?aoe?? ae?oai? ? aeueo aa?iii?e, oae ? o noaiao ia?aiao?e/ii?
aaia?aoe??. I?e oaoiieia?/i?e ?ic?iaoe? aeacaieo ia?aoai?thaa/?a
eaca?iiai aei?ii?ithaaiiy noaaeyoueny i?aeaeuai? aeiiae uiaei aaee/ei
iae?i?eii-iioe/ieo ni?eeiyoeeainoae, oiia oaciaiai neio?ii?cio oa
ii?ia?a i?iiaiaai? no?eeino? e?enoae?a. Oea noaei ia?aaeoiiaith aeey
noi?ioaaiiy a inoaii? ?iee ie?aiiai iaoeiai-oaoi?/iiai iai?yieo –
iae?i?eii-iioe/iiai iaoa??aeiciaanoaa.

Na?aae iaea?eueo aoaeoeaieo iai?aai?/ieo iae?i?eii-iioe/ieo iaoa??ae?a
inoaii?i /anii aaeaeiny neioacoaaoe ?yae niieoe eeano ieene?a ai?ao?a.
Iai?eeeaae, –BaB2O4 ca aoaeoeai?noth aaia?aoe?? ae?oai? aa?iii?ee cia/ii
ia?aaeuo? oaeee o?aaeeoe?eiee iaoa??ae ye DKDP. Aaea iaeaaiaeaeaii
eiia?oe?eiee aeione eii??ie iae?i?eii-iioe/ieo eaca?ieo ia?aoai?thaa/?a
ia iniia? oaeeo e?enoae?a ? aeineoue aeaoaeueii aea/aii ia?aiao?e
aaia?aoe?? aa?iii?e, oiiae oaciaiai neio?ii?cio, ?o oaiia?aoo?i?
caeaaeiino? aeey ia?aoai?aiiy aei?ii?ithaaiue iaiaeeiiai (=1,06 iei),
?oa?iiaiai (=0,69 iei) oa aeayeeo oei?a aeneia?ieo eaca??a. Iaeiae o
ia?aaaaei?e a?eueoino? i?aoeue, i?enay/aieo o?ceoe? iae?i?eieo e?enoae?a
c? neeaaeiith aoaeiaith aeaiaioa?ii? eii??ee aein? i?aeoe/ii ia
i?eae?eyeiny oaaae aea/aiith iaoai?ci?a eaca?ii-?iaeoeiaaiiiai
aeaoaeoiooai?aiiy oa iaa?oioiaaiiio aecia/aiith ii?ia?a iioe/ii?
no?eeino?.

O ca’yceo c oeei aeooaeueiith ? ?ic?iaea i?aoeec?eieo ae?aaiinoe/ieo
iaoiae?a ioe?iee yeino? iie??iaaieo e?enoae?/ieo iiaa?oiiue, ui caciaee
aieeao iiooaeiiai eaca?iiai ii?ii?iaiiy, oa aea/aiiy iaoai?ci?a
eaca?ii-noeioeueiaaiiai aeaoaeoiooai?aiiy i?ici?eo ae?aeaeo?e/ieo oa
oe?ieiciiieo iai?ai?ia?aeieeiaeo iaoa??ae?a a ?aaeei?
?iioeuenii-ia??iaee/iiai eaca?iiai ii?ii?iaiiy. Ana neacaia aecia/a?
aeooaeuei?noue cae?eniaiiai o oe?e aeena?oaoe?? aeine?aeaeaiiy.

Ca’ycie ?iaioe c iaoeiaeie i?ia?aiaie. Aeena?oaoe?eia ?iaioa aeeiiaia ia
eaoaae?? aenia?eiaioaeueii? o?ceee Euea?anueeiai aea?aeaaiiai
oi?aa?neoaoo ?iai? ?aaia O?aiea o ?aieao aea?aeaaiiai i?iaeoo
07.01.01./009-92 “?ic?iaea oaoiieia??, neioac oa aeine?aeaeaiiy iiaiai
eeano iaoa??ae?a aeey eaca?ieo ia?aoai?thaa/?a”.

Iaoa ? caaea/? aeine?aeaeaiiy. Ia’?eoe aeine?aeaeaiiy. Iaoith
aeena?oaoe?eii? ?iaioe aoei aea/aiiy iiaaae?iee iioe/ieo oa?aeoa?enoee
oa aecia/aiiy ii?iaiaeo cia/aiue iioe/ii? no?eeino? aeayeeo
iae?i?eii-iioe/ieo e?enoae?a a oiiaao iiooaeiiai eaca?iiai ii?ii?iaiiy.
Aeey aeinyaiaiiy iinoaaeaii? iaoe aeiaaaeinue ?ica’ycaoe oae? caaea/?:

aeine?aeeoe iioe/i? oa?aeoa?enoeee e?enoae?a (–BaB2O4, Li2B4O7,
Ca3(VO4)2, GaP) aei eaca?iiai ii?ii?iaiiy;

aea/eoe ci?ie iioe/ieo ia?aiao??a e?enoae?a GaP i?e iiooaeiiio
eaca?iiio ii?ii?iaii?;

?ic?iaeoe ? i?aeoe/ii ?aae?coaaoe iaoiaeeeo ae?iniiao?e/ii?
ae?aaiinoeee yeino? iie??iaaieo iiaa?oiiue aeine?aeaeoaaieo e?enoae?a
aei oa i?ney ae?? iiooaeiiai ?*-eaca?iiai aei?ii?ithaaiiy;

aeine?aeeoe aieea iiooaeiiai ?*-eaca?iiai (?=1,06 i) aei?ii?ithaaiiy
ia niaeo? i?iioneaiiy e?enoae?a ai?ao?a ?–BaB2O4 oa Li2B4O7 ? aecia/eoe
iaae? iioe/ii? no?eeino? ?o iie??iaaieo iiaa?oiiue;

aeine?aeeoe iaoai?ci eaca?ii-?iaeoeiaaiiai ?oeioaaiiy e?enoae?a
ieene?a ai?ao?a i?e ?iioeuenii-ia??iaee/iiio ii?ii?iaii? iaiaeeiiaei
eaca?ii (?=1,06 i);

iiynieoe io?eiai? cia/aiiy ii?iaiaeo no?eeinoae e?enoae?a,
nie?ath/enue ia iiaeaeue aeaooiaiai iaeiie/aiiy aeaoaeo?a a ia’?i?
e?enoae?a.

Aea?? ia’?eo?a aeine?aeaeaiiy coiiaethaaany ianooiieie oaeoaie:

iae?i?eii-iioe/i? e?enoaee ieene?a ai?ao?a a?aecia/athoueny aenieeie
ii?iaaie iioe/ii? no?eeino? ? aaea o?eaaeee /an aeei?enoiaothoueny ye
ooieoe?iiaeuei? aeaiaioe aeey aaia?aoe?? aa?iii?e ? ia?aiao?e/ii?
aaia?aoe?? c aenieeie eiao?oe??ioaie ia?aoai?aiiy;

iae?i?eii-iioe/iee e?enoae i?oiaaiaaeaoa eaeueoe?th aieiae??
i?e?iaeiueith iioe/iith aeoeai?noth ? ? ia?niaeoeaiei oa
iaeiaeine?aeaeaiei iae?i?eiei iaoa??aeii;

iae?i?eiee e?enoae oino?aeo aae?th a?aee?eaa? iiaeeea?noue
aeeiai?/iiai ea?oaaiiy eiai ia?aiao?aie i?e iaeii/ani?e ae??
ciiaeoth/iai io/ea ? iiooaeiiai eaca?iiai ii?ii?iaiiy.

Iaoeiaa iiaecia iaea?aeaieo ?acoeueoao?a:

anoaiiaeaii, ui ci?ie niaeo??a i?iioneaiiy ? iieaciee?a caeiieaiiy
iiiie?enoae?a ?–BaB2O4 ? Li2B4O7 i?e ae?? eaca?iiai (=1,06 iei)
ii?ii?iaiiy iia’ycai? c? ci?iaie a no?oeoo?? i?eiiaa?oiaaiai oa?o;

aia?oa aei??yii niaeo?e iiai?ioii? caeaoiino? ? e?oaiaiai aeeo?i?cio
e?enoaea Ca3(VO4)2 i?e ??cieo oaiia?aoo?ao oa ciaeaeaia ei?aeyoe?y i?ae
ieie;

aia?oa aeyaeaii yaeua aii?o?caoe?? i?eiiaa?oiaaiai oa?o a e?enoae?
?–BaB2O4 i?e iaeiiiooaeiiio eaca?iiio ii?ii?iaii?;

cai?iiiiiaaii iiaeaeue aeaooiaiai iaeiie/aiiy aeaoaeo?a aeey iiyniaiiy
iaoai?cio ?aae?aoe?eieo ci?i a ii?ii?iaieo e?enoaeao ieene?a ai?ao?a;

aia?oa aecia/aii i?i?iaeueio iiooaei?noue iaeeie/iiai eaca?iiai
?iioeuena, yea aecia/a? ii?iaiaa i?iiaiaaa ?oeioaaiiy;

aeyaeaii ci?ie iioe/ieo oa?aeoa?enoee e?enoaea GaP i?e ii?ii?iaii? a
?aaeei? ei?ioeeo eaca?ieo ?iioeuen?a.

I?aeoe/ia cia/aiiy iaea?aeaieo ?acoeueoao?a.

?acoeueoaoe niaeo?ineii?/ieo aeine?aeaeaiue e?enoae?a ieene?a ai?ao?a oa
oino?aeo aae?th i?e aieea? iiooaeiiai eaca?iiai ii?ii?iaiiy iathoue
aaciina?aaeith i?aeoe/io oe?ii?noue:

aecia/aii iaae? iioe/ii? no?eeino? iae?i?eieo e?enoae?a ieene?a
ai?ao?a, ui iaaecae/aeii aaaeeeai aeey i?eeeaaeii? iae?i?eii? iioeee;

?ic?iaeaii iaoiaeeeo ae?iniiao?e/ii? ae?aaiinoeee yeino? iie??iaaieo
iiaa?oiiue, i?eaeaoio aei e?enoae?a ??cieo eean?a neiao???;

aeyaeaii iiaeeeaino? aeeiai?/iiai ea?oaaiiy iioe/ieie ia?aiao?aie
e?enoaea GaP ? ia oe?e iniia? aeei?enoaiiy eiai ye ia?aoai?thaa/a
eaca?iiai aei?ii?iaiiy.

Iniaenoee aianie aeena?oaioa iieyaa? a aaciina?aaeiueiio iaea?aeaii?
an?o aeaieo aenia?eiaioo, ui neeaaeathoue i?aaeiao aeena?oaoe??, o
eiii’thoa?i?e ia?iaoe? oeeo aeaieo. Aeena?oaio i?iyaeea naiino?ei?noue a
aiae?c? aenia?eiaioaeueieo ?acoeueoao?a ia i?aenoaa? ?nioth/eo oai??e, o
?ic?iaoe? ae?iniiao?e/ii? iaoiaeeee aeine?aeaeaiue ci?i ia?aiao??a
iiaa?oiiue iae?i?eieo e?enoae?a i?e ae?? eaca?iiai ii?ii?iaiiy, o
i?aeaioiaoe? e ioi?ieaii? iaoa??ae?a aei ioae?eaoe?e. Iniiai? iieiaeaiiy
oa aeniiaee aeena?oaoe?eii? ?iaioe iaeaaeaoue aaoi?o.

Ai?iaaoe?y ?acoeueoao?a aeena?oaoe??. Iniiai? ?acoeueoaoe
aeena?oaoe?eii? ?iaioe aeiiia?aeaeenue ? iaaiai?thaaeenue ia ianooiieo
iaoeiaeo nai?ia?ao ? eiioa?aioe?yo:

THa?eaei?e iaoeia?e eiioa?aioe??, i?enay/ai?e 40-??//th o?ce/iiai
oaeoeueoaoo (Euea?a, 1993);

XXII International School and III Polish-Ukrainian Meeting of
Ferroelectrics Physics (Wroclaw, Pozna?, Kudowa Zdroj. Poland, 1996);

Ca?oieo iaoeiaeo eiioa?aioe?yo Euea?anueeiai oi?aa?neoaoo (1995 –
1998);

Oe?a?inueei-iieuenueeiio iaoeiaiio nai?ia?? “O?ceea ? o?i?y iaoa??ae?a
aeaeo?iiii? oaoi?ee” (Euea?a, 1998).

Ioae?eaoe??. Ca iaoa??aeaie aeena?oaoe?eii? ?iaioe iioae?eiaaii 8
i?aoeue, a /ene? yeeo 6 noaoae a ?aoa?iaaieo aeo?iaeao ? 2 oace
aeiiia?aeae ia iaoeiaeo eiioa?aioe?yo.

No?oeoo?a ? ia’?i aeena?oaoe??. Aeena?oaoe?eia ?iaioa neeaaea?oueny ?c
anooio, /ioe?ueio ?icae?e?a, aeniiae?a oa nieneo aeei?enoaieo aeaea?ae.
Ianya aeena?oaoe?? 162 noi??iee aeeth/ii c? nieneii e?oa?aoo?e, yeee
i?noeoue 150 iaeiaioaaiue. ?iaioa i?noeoue 42 ?enoiee ? 33 oaaeeoe?.

INIIAIEE CI?NO ?IAIOE.

O anooi? iiaea?oueny iaa?oiooaaiiy aeooaeueiino? ?ic?iaeaii? oaie
aeena?oaoe??, cacia/aii ?? ca’ycie c iaoeiaith i?ia?aiith eaoaae?e,
noi?ioeueiaai? iaoa ? iniiai? caaaeaiiy, iaoeiaa ? i?aeoe/ia oe?ii?noue
io?eiaieo ?acoeueoao?a oa iniiai? iieiaeaiiy, ye? aeiinyoueny ia caoeno.

O ia?oiio ?icae?e? “No?oeoo?a oa iioeei-niaeo?aeuei? ia?aiao?e
aeine?aeaeoaaieo e?enoae?a” iiaeaia ?ioi?iaoe?y i?i iniiai? o?ce/i?
oa?aeoa?enoeee iae?i?eieo e?enoae?a aaoa-ai?aoa aa??th, oao?aai?aoa
e?o?th, i?oiaaiaaeaoa eaeueoe?th oa oino?aeo aae?th. Cie?aia, ?icaeyiooi
no?oeoo?io aoaeiao e?enoae?a, ?o iioe/i? aeanoeaino? oa ciiio no?oeoo?o,
iae?i?eii-iioe/i? oa?aeoa?enoeee aeine?aeaeoaaieo e?enoae?a.

Ae?oaee ?icae?e “Iaoiaeeea aei??thaaiue ? ?ic?aooie?a iioe/ieo ooieoe?e”
i?enay/aiee iaoiaee/iei aniaeoai aeena?oaoe?eii? ?iaioe. Iiaeaia
iaoiaeeea aei??thaaiue ? ?ic?aooie?a iioe/ieo ooieoe?e, iienaia
oaoiieia?/ia oa?aeoa?enoeea aeine?aeaeoaaieo e?enoae?a ? iaoiaeeea
aeaioiaeaiiy e?enoaeia?ao?/ii i???ioiaaieo c?ace?a. Iienaia iaoiaeeea
aei??thaaiiy niaeo??a a?aeaeaaiiy ? i?iioneaiiy, iieaciee?a caeiieaiiy,
ei?ioei aena?oeaii iaoiaeeeo aiae?co E?aia?na-E?ii?aa. A ?icae?e?
iiaeathoueny noaie onoaiiaie ? iaoiaeeea aei??thaaiiy aeenia?n??
iioe/iiai iaa?oaiiy oa ae?iniiao?e/ieo aei??thaaiue. Ie?aia oaaaa
i?eae?eaia iaoiaeeoe? aei??thaaiiy iioe/ieo ia?aiao??a aeine?aeaeoaaieo
c?ace?a a oiiaao eaca?iiai ii?ii?iaiiy.

O o?aoueiio ?icae?e? “Iioe/ia aeoeai?noue ? e?oaiaee aeeo?i?ci
iae?i?eieo e?enoae?a Ca3(VO4)2. Aieea eaca?iiai ii?ii?iaiiy”
i?aaenoaaeaii ?acoeueoaoe aeine?aeaeaiiy e?enoaea i?oiaaiaaeaoa
eaeueoe?th. E?ae iiaeeiaiiy Ca3(VO4)2 eaaeeoue i?e 395 ii (3,14 aA).
Iieaciee caeiieaiiy, aei??yiee ca aeiiiiiaith ae?iniiao?e/iiai iaoiaeo
(i?e =632,8 ii) noaiiaeoue n=1,864, ui aeyaeeiny aeaui iaioei a
ii??aiyii? c e?oa?aoo?ieie aeaieie.

A iiey?eciaaieo niaeo?ao iiaeeiaiiy Ca3(VO4)2 aeyaeaii aea? /?oe? nioae
453 oa 541 ii. Aacoth/enue ia iaaeeaeai?e ciii?e no?oeoo?? e?enoaea
c?iaeaii aeniiaie, ui neeueii ai?cio?iii?e nioc? i?e 453 ii (2,737 aA)
a?aeiia?aea? ia?ao?ae 2?(0)3dx2-y2(V), a nioc? 541 ii (2,292 aA)
a?aeiia?aea? ia?ao?ae 2?(0)3dxz, yz(V). Ia?aoiaee i?ae ?icuaieaieie
i?aeciiaie aaeaioii? ciie, noi?iiaaii? 2p(0) ? 5s(Ca)-noaiaie c
i?aei?ooaaiiyi 3d(V)-noai?a, ? ciie i?ia?aeiino? i?iyaeythoueny i?e 395
ii (3,139 aA) aeey iiey?ecaoe?? A||x ? i?e 420 ii (2,952 aA) aeey A||y.

Aeenia?n?y iiai?ioii? caeaoiino? (AeIC) i?oiaaiaaeaoo eaeueoe?th
oa?aeoa?eco?oueny aiiiaeueiei oiaeii, ui iniaeeai yne?aai aeyaey?oueny
i?e oaiia?aoo?? 77 E. Aeine?aeaeaia oaiia?aoo?ia caeaaei?noue AeIC a
iaeano? 380700 ii i?e 295, 200, 120 ? 77 E (?en. 1). Ca ?ic?aoiaaiei
oaiia?aoo?iei eiao?oe??ioii /O a i?ee?aeia?e iaeano? aecia/aii oe?eio
caai?iiaii? ciie e?enoaea Ca3(VO4)2 aeey aeacaieo oaiia?aoo? (oaae. 1).

Oaae. 1. Oaiia?aoo?iee eiao?oe??io AeIC /O oa oe?eia caai?iiaii? ciie Ag
e?enoaea Ca3(VO4)2.

T, K29520012077/O102, a?aae K1,1091,1581,2741,744Eg,
aA3,1393,1273,1213,115Aaee/eia aia?aaoe/iiai i?ii?aeeo Ca3(VO4)2 i?e
e?iiaoi?e oaiia?aoo?? aeia?a ocaiaeaeo?oueny c? cia/aiiyi Eg, aecia/aiei
ca iieiaeaiiyi aeiaaioaeeueiaiai e?ath nioae aeaniiai iiaeeiaiiy.
Aeine?aeaeoaaiee e?enoae Ca3(VO4)2 iaeaaeeoue aei ieaia?iiai eeano
na?aaeiuei? neiaii?? (C3v), oiaoi i?e iaaieo oiiaao aeiionea? iioe/io
aeoeai?noue. Oaici? a??aoe?? aeey eeano C3v(3m) ia? oo iniaeea?noue, ui
eiai neiao?e/ia /anoeia ??aia ioeth, oiaoi iaa?oaiiy ieiueie
iiey?ecaoe?? acaeiaae aenieineiao?e/ieo iai?yie?a a?aenooi?.
I?eionea?oueny, ui i?e?iaeia a??io?ii?y e?enoaea Ca3(VO4)2
coiiaeth?oueny neaaeith aeeneiao?e/iith aeaoi?iaoe??th eeanoa??a
wmetafile8? ??U????????????
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A`???&??yyyy?????Ayyy¤yyy ??d?????&?
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neaaeee aieea ia aeaeo?iiio no?oeoo?o niieoee, oe?eeii i?aaii??iei ?
i?aeo?ae, i?e yeiio oey no?oeoo?a iiaeaeth?oueny ia i?aenoaa?
?ic?aooie?a aeey eeanoa?a wmetafile8? ??U????????????
???????????yyy????.????1?????????????
A`???&??yyyy?????Ayyy¤yyy ??d?????&?
?MathType??`????uath??????Oaae. 2. Canaeaiino? aoiiieo i?a?oaeae oa
aoaeoeai? ca?yaee (q*) ia aoiiao a eeanoa?ao wmetafile8?
??U???????????? ???????????yyy????.????1??????
???????A`???&??yyyy?????Ayyy¤yyy ??d?????&?
?MathType??`????uath??????Aoiiia
i?a?oaeueTdD3dC13d(V)3,2823,2843,2804s(V)0,1840,1830,1884p(V)0,4720,4710
,4822p(0)4,5044,5024,498Aoaeoeaiee
ca?yaeq*(V)1,0711,0681,061q*(0)-0,428-0,426-0,422I?e aeaoi?iaoe??
aaiaae?e-eeniaaeo oao?aaae??a i?iyaeythoueny iii?oi? ?icuaieaiiy
aia?aaoe/ieo ??ai?a oa ?icoe?aiiy nioa. “?aeaaeueiith” neiao???th
aaiaae?e-eeniaaiai eeanoa?o i?eeiyoi aaaaeaoe neiao??th Td. Iaeieae/?
i?a?oae? 4t2 oa 5a1 ? ia?aaaaeii 2s-noaiaie eenith. A?oia ??ai?a a
aia?aaoe/iiio i?ii?aeeo (-6-4) aA coiiaeaia 2p-aeaeo?iiaie e?aaiae?a,
i?e/iio ooo i?iyaeythoueny eiaaeaioi? aeii?ooaaiiy aoiiieo i?a?oaeae
aaiaae?th. Iacanaeai? i?a?oae? 2e oa aeua ooai?ai? 3d- (2e, 7t2), 4s-
(7a1) oa 4p- (8t2) i?a?oaeyie aaiaae?th, i?noyoue aeii?oee 2p(0)-noai?a.
Aeey i?a?oae? 2e oeae aianie neeaaea? i?eaeecii 40%, aeey 7t2 –
i?eaeecii 35%. Inoaiiy i?noeoue iaeo aeii?oeo 2s-ooieoe?e eenith.

Aeey ioe?iee aieeao no?oeoo?ieo niioai?aiue ia aeaeo?iii? noaie ai?ii?a

wmetafile8? ??U????????????
???????????yyy????.????1?????????????
A`???&??yyyy?????Ayyy¤yyy ??d?????&?
?MathType??`????uath??????

i?iaaaeaii aiaeia?/i? ?ic?aooiee aeey ieae/eo neiao??e (D2d oa C1).
Aia?aaoe/i? noaie a caaaeueieo ?enao ? iiae?ai?, i?e/iio a?a?eaeecaoe?y
2p(0)- oa 3d(V)-i?a?oaeae a eeanoa?ao iiieaeaii? neiao??? D2d ? C1
a?ae??ciy?oueny a?ae “?aeaaeueii?” neiao??? Td anueiai ia 2830%.
Aeecueeeie oaeiae ? aaee/eie aoaeoeaieo ca?yae?a ia aoiiao ? canaeaiino?
aacenieo aoiiieo i?a?oaeae. Iiieaeaiiy neiao??? wmetafile8?
??U???????????? ???????????yyy????.????1??????
???????A`???&??yyyy?????Ayyy¤yyy ??d?????&?
?MathType??`????uath??????E?eaa ?????a iaeano? aiiiaeueiiai oiaeo
aeia?a ai?ieneio?oueny iaeiiinoeeeyoi?iith oi?ioeith:

wmetafile8? ??A???????????
???????????yyy????.????1?????????????`
???&??yyyy?????Ayyy?yyya???????&??MathType??
???u?????????”????-?????°¶???°y???u@th??????aea ciae ()
a?aeiia?aea? R- oa L-aiaioeiii?oiei oi?iai e?enoaea, ???a?aoiao? aianie
o iiai?ioio caeaoi?noue ?ioeo a??iaeoeaieo ia?aoiae?a, , ? E0 –
ia?aiao?e nioae e?oaiaiai aeeo?i?cio, a W(t) –aeia?a i?ioaaoeueiaaia
ooieoe?y:

wmetafile8? ??|???????????
???????????yyy????.????1?????????????
a@???&??yyyy?????Ayyy¶yyy???–?????&?
?MathType??????u?th??????Caeaaeiino? ca’ycai? i?ae niaith
aeenia?n?eiei ni?aa?aeiioaiiyi:

wmetafile8? ??a???????????
???????????yyy????.????1?????????????a
???&??yyyy?????Ayyy¶yyya??–?????&??MathType???
???u?????????”????-?????p???p????p9
???pA???u@th??????Ia iniia? iaea?aeaieo iaie aenia?eiaioaeueieo
aeaieo i?e T=77 K aaeaeiny ia?aa??eoe ni?aa?aeiioaiiy (3).

Aeine?aeaeaiiy aieeao ii?ii?iaiiy ?iioeuenaie Nd-eaca?a (1,06 iei) ia
noai iiaa?oi? Ca3(VO4)2 iaie i?iaiaeeeeny ia c?aceao ?c aeca?eaeueieie
iiaa?oiyie, i???ioiaaieie ii (100)-ieiueiao. Ae?iniiao?e/iei iaoiaeii
aecia/aeeny ci?ie ia?aiao??a ii?ooaiiai oa?o (oiaueia ii?ooaiiai oa?o h,
ia?aiao?e , 2/l ? ). ?acoeueoaoe iiaeai? a oaae. 3. Aaeaeiny aeyaeoe
iaai? ci?ie ia?aiao??a i?e iaaaeeeeo aonoeiao iiooaeiino? 103104 Ao/ni2.
C ae?oaiai aieo, iaoiae ia aeicaieya ia?aaeueoe ??aaiue aonoeie
iiooaeiino? 2,5104 Ao/ni2, ine?eueee ci?ie yeino? iiaa?oi? ciaioothoue
/ooeea?noue naiiai iaoiaeo.

Oaae. 3. Ae?iniiao?e/i? ia?aiao?e iiaa?oi? e?enoaea Ca3(VO4)2 aei oa
i?ney eaca?iiai (=1,06 iei) ii?ii?iaiiy*.

Aeine?aeaeoaai? c?aceeEoo iaae?iiy, a?aae, a?aae, a?aae2/l, iei-1h, iei,
a?aaeCa3(VO4)2

(aei ii?ii?iaiiy)55

604 21

4 06164 10

166 150,07010,260,008216,34Ca3(VO4)2

(i?ney ii?ii?iaiiy)55

604 18

4 05165 04

166 110,08250,310,008713,294* Aonoeia iiooaeiino? eaca?iiai ?iioeuena
neeaaeaea 2,5104 Ao/ni2.

sse iieacaee iao? aeine?aeaeaiiy, e?enoae Ca3(VO4)2 oa?aeoa?eco?oueny
iaaenieeie ii?iaiaeie cia/aiiyie iiaa?oiaai? iioe/ii? no?eeino?.

A /aoaa?oiio ?icae?e? “Aieea eaca?iiai ii?ii?iaiiy ia iioe/i?
oa?aeoa?enoeee e?enoae?a” aea/athoueny noeioeueiaai? aoaeoe, ye?
i?iyaeythoueny i?e eaca?iiio ii?ii?iaii? a iae?i?eieo e?enoaeao ieene?a
ai?ao?a ? oino?aeo aae?th. Niinoa??aaeeny ci?ie niaeo??a i?iioneaiiy
e?enoae?a Li2B4O7 ? –BaB2O4 i?e ii?ii?iaii? iaiaeeiiaei eaca?ii a
?iioeuenii-ia?eiaee/iiio ?aaeei?. A iaeano? 1,52,8 iei i?ici??noue
oao?aai?aoa e?o?th nyaa? iiiaae 0,75 (?en. 2a) ?, ia a?aei?io a?ae
–BaB2O4 o a?ei? i?ici?ino? Li2B4O7 iaia? iniaeeainoae, e??i neaaei?
nioae (~2,7 iei), ui iacia/ii iiieaeo? i?iioneaiiy (ia 3%). Aecia/aii
oe?eio caai?iiaii? ciie Li2B4O7 i?e 290 K (Eg=6,93 aA). Ia iniia?
aiae?co E?aia?na-E?ii?aa i?e aeei?enoaii? aeno?aiieyoe?eiiai iaoiaeo
?annea?a ca iiey?eciaaieie niaeo?aie a?aeaeaaiiy iaea?aeaii ooieoe?? 1()
oa 3() (?en. 2a). Aeey iiey?ecaoe?e E||c ? Ec no?oeoo?a iioe/ieo
ooieoe?e Li2B4O7 a iniiaiiio iiae?aia.

Ca?aeii c eaaioiai-o?i?/iei ?icaeyaeii e?enoaeio?i?/ii? aoaeiae Li2B4O7,
a?oia nioa i?e 6,89,2 aA iia’ycaia c aeaeo?iiieie ia?aoiaeaie i?ae
[BO4]- oa [BO3], ye? oi?iothoue a?aeiia?aei? ciie. Na??y nioa i?e 9,6,
10,7 ? 11,9 aA a?aeiia?aea? caeo/aiith a?eueo iecueeeo aaeaioieo cii, ui
oi?iothoueny noaiaie [BO3]-eeanoa?a, oa cii i?ia?aeiino?, noi?iiaaieo
noaiaie [BO4]- oa [LiO4]- eeanoa??a. Ca o?aoth a?oio nioa
a?aeiia?aeathoue ia?aoiaee ?c eaac?inoiaieo s-noai?a eenith o ciio
i?ia?aeiino?. Iieaciee caeiieaiiy e?enoaea Li2B4O7, (=632,8 ii, T=290 K)
aeyaeany ??aiei 1,5796. Ci?ia oaiia?aoo?e c?acea iaei aieeaa? ia
aaee/eio iieacieea caeiieaiiy, oea iiynith?oueny ia eeoa aeoaea iaeei
oaiia?aoo?iei eiao?oe??ioii iieacieea caeiieaiiy, a e ?iia??iei
ooai?aiiyi ieeniiai oa?o ia iiaa?oi? e?enoaea Li2B4O7 i?e iaa??aaii?
c?acea. Eaca?ii-noeioeueiaaio ci?io iieacieea caeiieaiiy i?eiiaa?oiaaiai
oa?o Li2B4O7 aaeaeiny aeyaeoe iaoiaeii ae?iniiao???. Oey ci?ia
coiiaeth?oueny aeieeiaiiyi ia iiaa?oi? c?acea oiieiai oa?o ieneaeo ai?o.

Aeine?aeaeaii aieea ?iioeueniiai eaca?iiai ii?ii?iaiiy aaeeei?
iiooaeiino? ia iiaaae?ieo aeaeo?iiioe/iiai eiao?oe??ioa r41 XZ-ieanoeiie
(h=135 iei) GaP ia aeiaaeeiao oaeeue caoaeaeaiiy 0,63, 1,15 oa 3,39 iei.
Iaeii/anii aei??thaaeeny caeaaeiino? iieacieea caeiieaiiy a?ae aonoeie
iiooaeiino? caoaeaeoth/iai eaca?iiai ii?ii?iaiiy (=1,06 iei) aeey
aeacaieo aeiaaeei oaeeue. sse aeaeii c ?en. 3a, iaea?eueo iii?oi? ci?ie
iieaciee?a caeiieaiiy ? aeaeo?iiioe/ieo eiao?oe??io?a i?e T=4,2 K
niinoa??aathoueny naia a iaeano? iaeeo aonoei iiooaeiino? caoaeaeoth/iai
eaca?iiai ii?ii?iaiiy (aei 120 Ao/ni2). C ?inoii caoaeaeaiiy c?acee
i?ina?oeththoueny, ui, iiaeeeai, iiynith?oueny ciaioaiiyi eiao?oe??ioo
iiaeeiaiiy a iaeneioi? aeneoiiiiai iiaeeiaiiy. Oaea iiyniaiiy
ciaoiaeeoue aenia?eiaioaeueia i?aeoaa?aeaeaiiy, yea iieyaa? o
ca?eueoaii? aiie?ooaee aei?ii?ithaaiiy, ui i?ieoei /a?ac caoaeaeaiee
ia’?i c?acea. I?e aeaieo i?ioeanao a?ae?a?a? nooo?ao ?ieue niaoeeo?ea
e?enoae?a GaP: i?e aaeeeeo iiooaeiinoyo ii?ii?iaiiy a?aeaoaa?oueny
?oeioaaiiy aeneoii?a oa ?ii?caoe?y oeaio??a c ooai?aiiyi
aeaeo?iiii-ae??eiai? ieacie (AAeI).

Aeey aea/aiiy iioiaeaeaiiy oa nooiino? inoaiiuei? aeine?aeaeoaaeanue
e?iaoeea cacia/aieo i?ioean?a – aei??thaaeanue /aniaa ci?ia
caoaeaeoth/iai oa ciiaeoth/iai eaca?iiai aei?ii?ithaaiiy i?e aae??a?e
oaiia?aoo?? ia cacia/aieo aeiaaeeiao oaeeue. I?e?iiaiaeii??aeiino?, ui
aeieeathoue i?e ii?ii?iaii?, ? ?acoeueoaoii ae?? aeae?eueeio oaeoi??a,
cie?aia, oaeaeeino? oeoeooaoe?? oaiia?aoo?e oa oaeaeeino? anoaiiaeaiiy
??aiii??iiai iaa??ao GaP. sseui eiao?oe??io aeeooc?? iin??a ? niaaeiith
ooieoe??th oaiia?aoo?e, a iiaeeiooa a?aoeith iiooaei?noue – c?inoath/ith
ooieoe??th eiioeaio?aoe?? iin??a, iiaea a?aeaoaaoeny ?icoa?oaaiiy
iaeii??aeiiai noaio aonoeie AAeI. Oe? caeaaeiino? aeoaea /?oei
i?iyaeythoueny aeey e?enoaea GaP, ui iiaea neoaeeoe c?aceii iiyniaiiy
i?e?iaee aeine?aeaeoaaieo yaeu. Nie?ath/enue ia aeai? a?aoiaioe, iiaeia
iiynieoe oaeiae ? iniaeeaino? iiaaae?iee r41 (?en. 3a). Iaea?eueo? eiai
ci?ie (ye ? o aeiaaeeo c iieacieeii caeiieaiiy) c ?inoii iiooaeiino?
ii?ii?iaiiy iathoue i?noea i?e =3,39 iei. O oi?ioaaii? iioe/ieo noaeeo
GaP aeey oe??? aeiaaeeie oaee? nooo?ao ?ieue a?ae?a?athoue aeeaie?
eieae?ciaai? oeaio?e, ui aea?eueiythoueny i?e ae?? ii?ii?iaiiy, yea
iiiaaea? a iaeanoue i?ici?ino?.

I?e aei??thaaii? oaiia?aoo?ieo caeaaeiinoae r41 cao?eniaaii iii?oiee
i?i?ioi (T=205 K), yeee ei?aeth? c ii/aoeii caeo/aiiy a i?ioean
aaaaoioiiiiieo aca?iiae?e. Oe? aca?iiae?? coiiaeththoue oiiiiiee
aiaa?iii?ci, ui nooo?ai aieeaa? ia AIA. Inoaii?e oaeo aeicaiey?
niiae?aaoeny ia iiaeeea?noue aeeiai?/iiai ea?oaaiiy e?i?eieie oa
iae?i?eieie ia?aiao?aie GaP, ui ? aeooaeueiei a no/aniee
iai?ai?ia?aeieeia?e iioiaeaeo?ii?oe?.

Iaea?eueo aaaeeeaeie ia?aiao?aie iioe/ieo iaoa??ae?a, ye?
aeei?enoiaothoueny aeey ?iaioe c eaca?iei aei?ii?ithaaiiyi, ? eiai
iioe/ia i?iiaiaaa no?ee?noue. Iaeiei c iniiaieo oaeoi??a, ui
aecia/athoue i?iiaiaao no?ee?noue ? iayai?noue aeaoaeo?a ?
i?e?ineii?/ieo aeeth/aiue. Aeey i?ioeano oa?i?/iiai eaca?iiai
iioeiaeaeaiiy oa?aeoa?iei ? aoaeo iaeiie/aiiy, yeee iieyaa? a cieaeaii?
ii?iao iioe/iiai i?iaith i?ici?eo ae?aeaeo?ee?a i?e aaaaoie?aoiiio
?iioeueniiio ii?ii?iaii? o ii??aiyii? c ii?iaii i?iaith i?e iaeii?acia?e
ae??. Iinooiiaa iaeiie/aiiy iaeeo no?oeoo?ieo ci?i, ?iaeoeiaaieo
aaaaoi?iioeueniei ii?ii?iaiiyi ei?ioeeie eaca?ieie ?iioeuenaie, ? /e ia
iaeaieiai?oith i?iaeaiith eaca?iiai ?oeioaaiiy iaoa??ae?a. Oeiiaei
?acoeueoaoii iaoeo aenia?eiaio?a i?e aaaaoi?iioeueniiio eaca?iiio
?oeioaaii? (AE?) ? cieaeaiiy /enea eaca?ieo ?iioeuen?a, ye? i?ecaiaeyoue
aei ?oeioaaiiy, i?e ca?eueoaii? ?ioaineaiino? ?iioeuena a na???.

I?e ?icaeyae? aeaii? i?iaeaie ie aeoiaeeee c oaeeo aeaio canaae:

1. Noaoenoe/iiai iaoai?cio, i?e yeiio ?nio? e?ioeaaa ?iia??i?noue
?oeioaaiiy iaeiei ?iioeuenii aoaeue-yei? ?ioaineaiino? ? yeee
canoiniaiee aeey ia?a?nii aeaoaeoieo e?enoae?a.

2. Iaoai?cio iinooiiaeo i?e?ineii?/ieo ci?i, ye? aeieeathoue aiane?aeie
aaia?aoe?? aeaoaeo?a, ui iaeiie/oththoueny a e?enoae? a?ae ?iioeuena aei
?iioeuena. Oaea iaeiie/aiiy i?eaiaeeoue aei ca?eueoaiiy iiaeeiaiiy oa ?
i?e/eiith AE?.

Aaaaeath/e iaoai?ci aaia?aoe?? aeaoaeo?a oa?iioeoeooaoe?eiei ? aeoiaey/e
c oiai, ui aaia?aoe?y aeaoaeo?a a?aeaoaa?oueny i?ae /an ae?? ?iioeuen?a
ii?ii?iaiiy, a o i?ii?aeeo i?ae ?iioeuenaie aecia/aeueieie ? i?ioeane
?aeiia?iaoe?? oa aeeooc?? aeaoaeo?a iaea?aeaii ae?ac aeey ii?iaiai?
aonoeie iiooaeiino? a iiii?iioeueniiio ?aaeei?:

wmetafile8? ??G???????????
???????????yyy????.????1?????????????
a ???&??yyyy?????Ayyy¶yyy`??–?????&??MathType???
???u?????????”????-?????AeO???Ae
???u?????????”????-????p???pE???u@th??????aea cV –
ieoiia oaiei?ii?noue e?enoaea, T0 – ii/aoeiaa oaiia?aoo?a c?acea,
T1=Eg/2kA, T2 – oaiia?aoo?a a oeaio?? oieaeueii? ieyie eaca?iiai io/ea
ia iiaa?oi? e?enoaea, R – eiao?oe??io a?aeaeaaiiy, – eiao?oe??io
iiaeeiaiiy, – o?eaae?noue ?iioeuena. ?ic?aoiaai? ca (4) ii?iaia?
aonoeie iiooaeiino? aeey aeine?aeaeoaaieo e?enoae?a ieene?a ai?ao?a
–BaB2O4 oa Li2B4O7 noaiiaeee a?aeiia?aeii 2,235107 Ao/ni2 oa 2,689107
Ao/ni2.

I?e aoaeue-yeiio ?aaeei? eaca?iiai ii?ii?iaiiy i?iiaiaaa no?ee?noue
caeaaeeoue a?ae aia?a?? ca’yceo (oe?eie caai?iiaii? ciie) e?enoae?a.
Ii??a ?oeioaaiiy e?enoae?/ii? iiaa?oi? nooo?ai caeaaeeoue a?ae ?ici???a
iaiaeii??aeiinoae (oaae. 4).

Oaae. 4. Caeaaei?noue ii?iao eaca?iiai (=1,06 iei) ?oeioaaiiy a?ae
?ici???a iaiaeii??aeiinoae ia iiaa?oi? e?enoae?a –BaB2O4 oa Li2B4O7

l, ieiwmetafile8? ??O????????????
???????????yyy????.????1?????????????
?@???&??yyyy?????Ayyy¤yyy???¤?????&?
?MathType???????uath??????1/4?????Times New
Roman??~???-?????27#???x????uath??????1/4???I?Times New
Roman?I~???-??????? ???2p#???ii?????u@th??????Oaae. 5.
Ae?iniiao?e/i? ia?aiao?e aeine?aeaeoaaieo c?ace?a

? c?aceaIaoa??ae c?aceaEoo iaae.2/l, iei-1h, iei,
a?aae1–BaB2O455345153230,03471,040,004866,95460337173002–BaB2O4*55335153
320,04261,230,006143,18760327169243Li2B4O755443152450,06440,290,0160238,
4160426103074Li2B4O7*55428152320,0730,250,0142224,5160421103285Ca3(VO4)2
55421164100,07010,260,008216,34760409166156GaP553057169220,42481,210,045
338,04460260117001* Ii?ii?iai? c?acee cacia/aieo e?enoae?a aeicith
2,5104 Ao/ni2 (=1,06 iei).

Aaee/eia ia?aiao?a i?iii?oe?eia oiauei? oa?o caa?oaeiaiue ia iiaa?oi?
c?ace?a, ia?aiao? aeaco? aeayeith i??ith ia i?e?iaeo caa?oaeiaiue.
sseui ia?aiao? aeecueeee aei /2, oi iieaciee caeiieaiiy iiaa?oiaaiai
oa?o caa?oaeiaiue ? iaioei ca cia/aiiy iieacieea caeiieaiiy i?aeeeaaeee
(ia’?io e?enoaea); yeui ae ~3/2, oi neooaoe?y ? i?ioeeaaeiith.

A?aeoeeaiiy aaee/eie ia?aiao?a a?ae aeacaieo a?aie/ieo cia/aiue
i?iii?oe?eia eiao?oe??ioo iiaeeiaiiy a oeueiio oa??. Cacia/ai? a oaae. 5
ia?aiao?e aeei?enoiaothoueny eeoa aeey aeoaea oiieeo oa??a c oiaueiaie
~100 A. Ca?eueoaiiy aoaeoeaiiai iieacieea caeiieaiiy aaeni?aiaaiiai oa?o
e?enoaea Li2B4O7 iiyniaii iayai?noth ia eiai iiaa?oi? iaiane/aiiai
ieneaeo ai?o BO (~3/2). Aeey e?enoaeo –BaB2O4, yeee oaae i?noeoue
ai?-eeniaa? a?oie, ui ooai?ththoue e?enoae?/iee ea?ean, oaeiai aoaeoo ia
niinoa??aa?oueny (~/2). C iaaaaeaieo a oaae. 5 aeaieo aeaeii, ui iaa?oue
i?e iaeeo aeicao eaca?iiai ii?ii?iaiiy aaeaeiny cao?enoaaoe iii?oi?
ci?ie ia?aiao??a iioe/ieo iiaa?oiiue, ui aeaco? ia aenieo /ooeea?noue
ae?iniiao?e/iiai iaoiaeo.

A ?acoeueoao? a?eueo iiooaeiiai ii?ii?iaiiy e?enoaea –BaB2O4 ?*-eaca?ii
aeieea? iieaaeaiiy i?eiiaa?oiaaiai oa?o ? cae?eiaoaaiiy i?e?io??uei ia
iiaa?oi? c?acea. Oeae i?ioean iiaea ?icaeyaeaoeny ye ?icoii?yaeeoaaiiy
no?oeoo?e i?eiiaa?oiaaiai oa?o ? ooai?aiiy a aaiiao?e/ieo iaaeao c?acea
neeaaeii? aeaioa?iai? nenoaie “aii?oia ooai?aiiy – e?enoae”. Aeaiee
i?ioean i?aeoaa?aeaeo?oueny aiae?cii iioe/ieo oa?aeoa?enoee, ciyoeo aei
oa i?ney ii?ii?iaiiy (?=1,06 iei, =0,4 in). C?o/iith ? niaeo?aeueia
iaeanoue, yea i?noeoue aeiaaioaeeueiaee e?ae nioae aeaniiai iiaeeiaiiy.
Aeine?aeaeaii niaeo?e iiaeeiaiiy –BaB2O4 aei ? i?ney ii?ii?iaiiy (?en.
4, e?ea? 1,2) ? ioe?iaii aaee/eio caai?iiaii? ciie aeey iaii?ii?iaiiai
c?acea i?e 290 E: Ag=6,43 aA. Nie?ath/enue ia iiaeaeue I’E??? aeey
niaeo?aeueiiai eiao?oe??ioa iiaeeiaiiy ?(h?) ii?ii?iaiiai e?enoaea a
i?ee?aeia?e iaeano? nioae aeaniiai iiaeeiaiiy iiaeia caienaoe:

wmetafile8? ??;???????????
???????????yyy????.????1?????????????
aA???&??yyyy?????Ayyy?yyy???”?????&??MathType??A
???u?????????”????-?????¶????¶
???u@th??????Niaeo?aeueiee o?ae caeaaeiino? e?aeiaiai iiaeeiaiiy,
ioe?iaiee ca oi?ioeith (5), iiaeaiee ia ?en. 4 (e?eaa 4).

I?iiaiaaa i?oei?noue caeiiii??ii iiieaeo?oueny ?c c?inoaiiyi i?ici?ino?
aeine?aeaeoaaieo e?enoae?a a ?*-iaeano? niaeo?a. Aeey oe?ieiciiieo
ae?aeaeo?ee?a aaee/eia e?eoe/iiai iiey i?iaith Ee? i?iii?oe?eia
a?aie/i?e /anoio? ?*-i?iioneaiiy iaoa??aeo. Oea i?aaeei aoei ia?aa??aia
aeey iaoeo ia’?eo?a ? i?aeoaa?aeaeaia eiai i?aaii??i?noue aeey ??ciiai
ae?aiao?o na?oeiai? ieyie Nd-eaca?a ia iiaa?oi? e?enoae?a. Niaoeeo?ea
oa?aeoa?o eaca?ii-?iaeoeiaaieo iioeiaeaeaiue a e?enoae? –BaB2O4 iieyaa?
a iioe?aii? ?oeioaaiiy acaeiaae iai?yi?a aeca?eaeueieo ieiuei 3m
neiao???. Aaiethoe?y eaca?ii-?iaeoeiaaieo aeano?oeoeaieo ci?i o e?enoae?
–BaB2O4 i?i?ethno?iaaia aia?aaoe/iith noaiith; aeicia? ??ai?, ye?
a?aeiia?aeathoue ie?aiei aoaiai iioeiaeaeaiue e?enoaeo Li2B4O7 a neeo
aeaui aeui? i?iiaiaai? no?eeino? ? aeuei ia i?aii?yaeeo.

INIIAI? ?ACOEUeOAOE OA AENIIAEE

1. Aia?oa aei??yi? iiey?eciaai? niaeo?e iiaeeiaiiy e?enoaea
i?oiaaiaaeaoa eaeueoe?y Ca3(VO4)2. Aeyaeai? nioae ?aeaioeo?eiaaii o
a?aeiia?aeiino? ?c ciiiith no?oeoo?ith aeine?aeaeoaaiiai e?enoaeo.

2. Aeine?aeaeaii aeenia?n?th iiai?ioii? caeaoiino? ? eieiaiai aeeo?i?cio
e?enoaea Ca3(VO4)2, aeyaeaii aiiiaeueiee o?ae ia?oi?. Ciaeaeaii
ei?aeyoe?th i?ae io?eiaieie aeaieie ii eieiaiio aeeo?i?cio ? aeenia?n??
iiai?ioii? caeaoiino?. I?e?iaea aeieeiaiiy a??io?ii?? iia’ycaia c?
ci?iith neiao??? eeanoa?a wmetafile8? ??U????????????
???????????yyy????.????1?????????????
A`???&??yyyy?????Ayyy¤yyy ??d?????&?
?MathType??`????uath??????3. A e?enoae? GaP aeine?aeaeaii iiaaae?ieo
aeaeo?iiioe/iiai eiao?oe??ioa r41 i?e aieea? iiooaeiiai ?iioeueniiai
eaca?iiai ii?ii?iaiiy. Aeey ei?aeoiino? aenia?eiaioo oaeiae
aeine?aeaeoaaeenue caeaaeiino? iieacieea caeiieaiiy GaP a?ae aonoeie
iiooaeiino? caoaeaeoth/iai ii?ii?iaiiy. Aeaeo?iiioe/iee eiao?oe??io r41
aeine?aeaeaii ye a oaiia?aoo?iiio ?aaeei?, oae ? a ?aaeei? ci?ie
iiooaeiino? ii?ii?iaiiy. Iieacaii iiaeeea?noue aeei?enoaiiy e?enoaea GaP
a yeino? ia?aoai?thaa/a eaca?iiai aei?ii?ithaaiiy.

4. Aeine?aeaeai? niaeo?e iiaeeiaiiy oa a?aeaeaaiiy e?enoae?a ai?ao?a –
Li2B4O7 ? –BaB2O4. Ia aac? iaoiaeo E?aia?na-E?ii?aa ?ic?aoiaaii
aeenia?n?th iioe/ieo ooieoe?e 1,2() ? aecia/aii oe?eio caai?iiaii? ciie
oa iieaciee caeiieaiiy e?enoaeo Li2B4O7.

5. Ca oai???th aaaaoi?iioeueniiai eaca?iiai ?oeioaaiiy ?ic?aoiaaii
na?aaei? i?ae /an ae?? ?iioeuena ?oei?ai? iiooaeiino? ii?ii?iaiiy aeey
e?enoae?a –BaB2O4 ? Li2B4O7.

6. Iieacaii iiaeeea?noue ca?eueoaiiy ii?iao iiaa?oiaaiai ?oeioaaiiy
e?enoae?/ieo iiaa?oiiue –BaB2O4 oa Li2B4O7 i?e ciaioaii? ?ici???a
iiaa?oiaaeo aeaoaeo?a ca ?aooiie i?aeaeuaiiy yeino? ia?iaee iiaa?oiiue
e?enoae?a.

7. Cai?iiiiiaaiee aa??aio iaoiaeo ae?iniiao?e/ii? ae?aaiinoeee aeicaiey?
iii?oeoe ci?ie iioe/ieo ia?aiao??a iaa?oue i?e iaeeo a ii??aiyii? c
ii?iaiaeie aeicao ii?ii?iaiiy e?enoae?a –BaB2O4, Li2B4O7, Ca3(VO4)2 oa
GaP.

8. ?acoeueoao aieeao eaca?iiai (=1,06 iei, P=40 IAo/ni2) ii?ii?iaiiy ia
niaeo? i?iioneaiiy e?enoaeo –BaB2O4 o?aeoo?oueny ye iiaeeeaa aeieeiaiiy
iieaaeaiiai i?eiiaa?oiaaiai oa?o.

9. Aeyaeaii caeaaei?noue ii?iaiai? iiooaeiino? na?oeiaiai ii?ii?iaiiy
e?enoae?a –BaB2O4, Li2B4O7 oa Ca3(VO4)2 a?ae aeiaaioaeeueiai? a?aieoe?
i?ici?ino?. Iniaeea?noue eaca?ii-?iaeoeiaaieo iioeiaeaeaiue a ia’?i?
e?enoaea –BaB2O4 iieyaa? a ?oeioaaii? c?ace?a acaeiaae aeca?eaeueieo
ieiuei neiao??? 3m.

INIIAI? ?ACOEUeOAOE AeENA?OAOe?? AEEEAAeAI? O ?IAIOAO:

10. A?eaiueea I.A., Iaiueeianueea ?.A., Ii?ic ?.?. Ia?aiao?e o?i?/ieo
ca’yce?a oa iae?i?ei? ni?eeiyoeeaino? aoeaio?e/ieo e?enoae?a. I?aaeei
Aeiaaiai-E?oeea // Oe?a?inueeee o?ce/iee aeo?iae. – 1997. – O.42, ? 5. –
N.557-560.

11. Eeoue E.A., Aeeaiueeay I.A. Eciaiaiea iioe/aneeo iinoiyiiuo
iieoi?iaiaeieeiaiai e?enoaeea GaP a oneiaeyo iiuiiai eaca?iiai
aicaeaenoaey // AE.i?eee.niaeo?ineiiee. – 1993 – O.59, ? 3-4. – N.
364-367.

12. A?eaiueea I.A. I?e?iaeia iioe/ia aeoeai?noue iiiie?enoae?a
i?oiaaiaaeaoa eaeueoe?y Ca3(VO4)2 // A?niee Euea?a.oi-oo. Na?.o?c. –
Euea?a: Na?o. – 1995. – ?27. – N.62-64.

13. A?eaiueea I.A. E?enoae?/ia aoaeiaa oa aeaye? iae?i?eii-iioe/i?
ia?aiao?e iiiie?enoaea Ca3(VO4)2 // A?niee Euea?a. oi-oo. Na?.o?c. –
Euea?a: Na?o. – 1996. – ?28. – N.54-57.

14. Bilen’ka O.B., Dovhyj Ya.O. The girotropy and circular dichroism of
monocrystalline calcium orthovanadate. Abstr. XXII Internat. School and
III Polish – Ukrainian Meeting of Ferroelectrics Physics. Wroclaw,
Poznan, Kudowa Zdroj. Poland, 16 – 20.09.1996. – P. 71.

15. A?eaiueea I.A. Iioe/i? niaeo?e i?oiaaiaaeaoo eaeueoe?th // Oace
aeiiia?aeae THa?eaeii? iaoeiai? eiioa?aioe??, i?enay/aii? 40-??//th
o?ce/iiai oaeoeueoaoo. Euea?a: EAeO. – 1993. – N. 99.

16. A?eaiueea I.A. Oaiia?aoo?ia caeaaei?noue niaeo?a aeeoociiai
a?aeaeaaiiy GaP a iaeano? e?aeiaiai iiaeeiaiiy // A?niee Euea?a. oi-oo.
Na?.o?c., aei. 28 “Oai?aoe/ia oa aenia?eiaioaeueia o?ceea”. – Euea?a:
Na?o. – 1996. – N. 54-57.

17. A?eaiueea I.A. Eaca?ia no?ee?noue e?enoae?a ai?ao?a // A?niee
Euea?a. oi-oo. Na?. o?c., aei. 31 “O?ceea ? o?i?y iaoa??ae?a aeaeo?iiii?
oaoi?ee”. – Euea?a. – 1998. – N. 3-5.

A?eaiueea I.A. Niaeo?ineii?y ?aae?aoe?eii no?eeeo iae?i?eii-iioe/ieo

e?enoae?a. – ?oeiien.

Aeena?oaoe?y ia caeiaoooy iaoeiaiai nooiaiy eaiaeeaeaoa
o?ceei-iaoaiaoe/ieo iaoe ca niaoe?aeuei?noth 01.04.10 – o?ceea
iai?ai?ia?aeiee?a oa ae?aeaeo?ee?a. – Euea?anueeee aea?aeaaiee
oi?aa?neoao ?i. ?aaia O?aiea, Euea?a, 1999.

Aeena?oaoe?y i?enay/aia aeine?aeaeaiith niaeo?aeueieo oa?aeoa?enoee
?aae?aoe?eii-no?eeeo e?enoae?a ieene?a ai?ao?a –BaB2O4 oa Li2B4O7,
iae?i?eii-iioe/ieo oa a??io?iiieo e?enoae?a Ca3(VO4)2 oa iae?i?eieo
e?enoae?a GaP a oiiaao aieeao iiooaeieo iie?a ?iioeueniiai eaca?iiai
aei?ii?ithaaiiy. Aeyaeaii aeenia?n?th iiai?ioii? caeaoiino? ? e?oaiaiai
aeeo?i?cio a Ca3(VO4)2 oa cai?iiiiiaaia ?ioa?i?aoaoe?y i?e?iaee
e?i?eiiai aeeo?i?cio ia iniia? iiaeae? eeanoa??a, iaaiei /eiii
i???ioiaaieo a oao?aaae?e/iiio iie? a?aoee. Iaoai?ci ?iioeueniiai
eaca?ii-?iaeoeiaaiiai iioeiaeaeaiiy e?enoae?a ?icaeyaea?oueny ?c
caeo/aiiyi iiaeae? aeaooiaiai iaeiie/aiiy aeaoaeo?a. Ioe?iaia eaca?ia
no?ee?noue e?enoae?a. Cai?iiiiiaaia ae?iniiao?e/ia ae?aaiinoeea yeino?
iie??iaaieo iiaa?oiiue e?enoae?a aei ? i?ney ae?? iiooaeiiai eaca?iiai
aei?ii?ithaaiiy oa ioe?iaii iiaeeeaino? aeei?enoaiiy e?enoae?a a
eaca?ieo nenoaiao.

Eeth/ia? neiaa: iae?i?eii-iioe/i? e?enoaee, aeaeo?iiioe/iee aoaeo,
i?iiaiaaa no?ee?noue, aaaaoi?iioeuenia eaca?ia ?oeioaaiiy,
ae?iniiao?e/ia ae?aaiinoeea iiaa?oiiue e?enoae?a.

Aeeaiueea I.A. Niaeo?ineiiey ?aaeeaoeeiiii noieeeo iaeeiaeii-
iioe/aneeo e?enoaeeia. – ?oeiienue.

Aeenna?oaoeey ia nieneaiea iao/iie noaiaie eaiaeeaeaoa
oeceei-iaoaiaoe/aneeo iaoe ii niaoeeaeueiinoe 01.04.10 – oeceea
iieoi?iaiaeieeia e aeeyeaeo?eeia. – Eueaianeee ainoaea?noaaiiue
oieaa?neoao ei. Eaaia O?aiei, Eueaia, 1999.

Aeenna?oaoeey iinayuaia enneaaeiaaieth niaeo?aeueiuo oa?aeoa?enoee
?aaeeaoeeiiii noieeeo e?enoaeeia ieenae ai?aoia –BaB2O4 e Li2B4O7,
iaeeiaeii-iioe/aneeo e ae?io?iiiuo e?enoaeeia Ca3(VO4)2 e iaeeiaeiuo
e?enoaeeia GaP a oneiaeyo aeeyiey iiuiuo iieae eiioeueniiai eaca?iiai
iaeo/aiey. Iaia?oaeaia aeenia?ney a?auaoaeueiie niiniaiinoe e e?oaiaiai
aeeo?iecia a Ca3(VO4)2 e i?aaeeiaeaia eioa?i?aoaoeey i?e?iaeu eeiaeiiai
aeeo?iecia ia iniiaa iiaeaee eeanoa?ia, ii?aaeaeaiiui ia?acii
i?eaioe?iaaiiuo a oao?ayae?e/aneii iiea ?aoaoee. Iaoaieci eiioeueniiai
eaca?ii-eiaeooee?iaaiiiai iia?aaeaeaiey e?enoaeeia ?anniao?eaaaony n
i?eaea/aieai iiaeaee ac?uaiiai iaeiieaiey aeaoaeoia. Ioeaiaia eaca?iay
noieeinoue e?enoaeeia. I?aaeeiaeaia yeeeiniiao?e/aneay aeeaaiinoeea
ea/anoaa iiee?iaaiiuo iiaa?oiinoae e?enoaeeia aei e iinea aeaenoaey
iiuiiai eaca?iiai iaeo/aiey e ioeaiaiu aiciiaeiinoe eniieueciaaiey
e?enoaeeia a eaca?iuo nenoaiao.

Eeth/aaua neiaa: iaeeiaeii-iioe/aneea e?enoaeeu, yeaeo?iiioe/aneee
yooaeo, eo/aaay noieeinoue, iiiaieiioeueniia eaca?iia ?ac?ooaiea,
yeeeiniiao?e/aneay aeeaaiinoeea iiaa?oiinoae e?enoaeeia.

Bilen’ka O.B. Spectroscopy of the radiation-resistant nonlinear-optical
crystals. – Manuscript.

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

The dissertation is devoted to the results of the investigation of the
spectral characteristics of the radiation-resistant nonlinear borate
oxides –BaB2O4 and Li2B4O7, nonlinear-optical and girotropic crystals
Ca3(VO4)2 and nonlinear GaP crystals in conditions of the power pulsed
laser irradiation influence.

The shape of the fundamental absorption edge of Ca3(VO4)2 is explorated.
Absorption edge takes place at 395 nm???????eV???refractive coefficient
determined at 632.8 nm is 1.864. In polarized absorption spectra the
band at 453 nm (2.737 eV; 2p(0)3dx2-y2(V)-transition and band at 541 nm
(2.292 eV; 2p(0)3dyz, xz(V)-transition) were observed. The mid-intensity
bands at 3.13 nm?(0.409 eV) and 4.00 ?m (0.310 eV) and group of the
narrow bands at 3.425 ?m (0.362 eV), 3.448 ?m (0.360 eV), 3.509 ?m
(0.353 eV) and 4.525 ?m (0.274 eV) were find.

The temperature dependence of Ca3(VO4)2 opticity dispersion (77295 K) in
the 380700 nm range was investigated. For indicated temperatures the
band gap energy was defined with help of the temperature coefficient .
The girotropy is conditioned by weak distortion of the anionic regular
tetrahedrons wmetafile8? ??U????????????
???????????yyy????.????1?????????????
A`???&??yyyy?????Ayyy¤yyy ??d?????&?
?MathType??`????uath??????The influence of power laser pulse upon
behaviour of linear electrooptical coefficient r41 in GaP for various
exciting wave-lengths is researched. The cause of changes in the crystal
by laser irradiation is an ionization of the centers with origination of
electron-hole plasma. When rising of laser irradiations’ power the most
changes of the r41 coefficient takes place at approximatly 3.39 m. This
fact has been explained by delocalization of deep levels in the crystal.
Temperature dependences of r41 are evidence of the appearance of
many-phonon processes.

Absorption and reflection spectra of Li2B4O7 and –BaB2O4 are
investigated. Lithium tetraborate crystal has an advantage compared with
beta-barium metaborate by transparency parameters in 2.53.5 m region.
Calculation of the spectral absorption coefficient in the
long-wavelength edge of fundamental absorption band allowed to determine
with help of the extrapolation of h to =0 that Eg(Li2B4O7)=6.93 eV at
T=290 K. Owing to polarized reflection data the optical functions’
dispersion (1,2()) were calculated. The band at 6.8-9.2 eV is due to
transitions between [BO4] and [BO3]-states, which formed the top of the
valence zone and bottom of conductive zone respectivly. The bands at
9.6, 10.7 and 11.9 eV are responsible for joining of the lower region of
valence zone originated from [BO3]-states and higher conductive zone
states, formed by [BO4] and [LiO4]-states. Frame oxygen s-states are
responsible for series of bands at 9.8-12.5 eV. Refractive index of
Li2B4O7 (?=632.8 nm, T=290 K) is 1.5796.

The minimum level of the Nd-laser single power pulse intensity for
–BaB2O4 and Li2B4O7, below which a crystal destruction isn’t originated
in spite of enormous number of pulses, was determined. Average within a
pulse temperatures for –BaB2O4 (422.89 K) and Li2B4O7 (462.67 K) are
determined using the many-pulsed laser destruction theory. Dependence of
surface destroy threshold of explored crystals versus surface
unhomogeneities sizes in the presence of power pulsed Nd-laser
irradiation was find. Optical parameters of the purity of crystal
surface has been estimated. They essentially reflectes on the optical
stability. Elaborated ellipsometrical diagnostics allow to define the
changes of optical properties in –BaB2O4, Li2B4O7, Ca3(VO4)2 and GaP
even at irradiation doses smaller than threshold dose. Possibilities of
usage of these crystals in the laser systems are estimated.

Absorption spectrum of –BaB2O4 before and after irradiation by dose of
40 MW/cm2 is investigated. The dependence of light irradiation threshold
of indicated crystals from long-wave boundary of transparency was found.
Peculiarity of the laser-caused injuries in crystal volume (–BaB2O4)
consists in destruction of crystal samples along 3m-planes. The
mechanism of pulsed laser-induced damage in the crystals may be
explained with help of explosive accumulation of defects in crystal
volume.

Key words: non-linear optical crystals, electrooptical effect, radiative
stability, many-pulsed laser destruction, ellipsometrical crystal
surfaces dianostics.

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