Ïîñëå ïåðåêðèñòàëëèçàöèè â ïðîöåññå ãàçîñòàòèðîâàíèÿ (ðèñ. 5.4.7, êðèâàÿ 2) ñåëåêòèâíàÿ ïîëîñà ïîãëîùåíèÿ èñ÷åçàåò.  ðàáîòàõ [103,115,149] ïîêàçàíî, ÷òî ãàçîñòàòèðîâàíèå ïðè âûñîêîé òåìïåðàòóðå >10000Ñ ñîïðîâîæäàåòñÿ ïåðåêðèñòàëëèçàöèåé, êîàëåñöåíöèåé ñ îáðàçîâàíèåì ó÷àñòêîâ êðèñòàëëîâ ñ ðàçëè÷íûìè êîíöåíòðàöèÿìè êèñëîðîäà. Ýòî ïðèâîäèò ê íåîäíîðîäíîìó ðàçìûòèþ ïîëîñû.
Äëÿ êðèñòàëëîâ ZnSe â ðàáîòàõ [103,114] ðàñòâîðåííîìó êèñëîðîäó ñîïîñòàâëåíà ïîëîñà ïîãëîùåíèÿ ~ 10 ìêì. Äëÿ ïåðåõîäîâ Å– ® Å+ â ZnSe ýòî ñîîòâåòñòâóåò ðàñùåïëåíèþ 130 ìýÂ, áîëüøåìó, ÷åì çàçîð (ÅÑ – ÅÎ), ðàâíûé 114 ìýÂ. Ñîãëàñíî ñïåêòðàëüíîìó ñìåùåíèþ ýêñèòîííûõ ïîëîñ (~ 10 ìýÂ) êîíöåíòðàöèÿ ðàñòâîðåííîãî êèñëîðîäà â èññëåäîâàííûõ îáðàçöàõ ~ 0,03 ìîë% (1019cì-3), ÷òî ñîãëàñóåòñÿ ñ âåëè÷èíîé ðàñùåïëåíèÿ è ïîäòâåðæäàåòñÿ ðåçóëüòàòàìè àíàëèçîâ íà êèñëîðîä.
 çàâèñèìîñòè îò êîíöåíòðàöèè ðàñòâîðåííîãî êèñëîðîäà ñïåêòðàëüíîå ïîëîæåíèå ïîëîñ ïîãëîùåíèÿ, ñâÿçàííûõ ñ ïåðåõîäàìè Å– ® Å+, ìîæåò áûòü ðàññ÷èòàíî ïî âåëè÷èíå ðàñùåïëåíèÿ çîíû ïðîâîäèìîñòè èç ñîîòíîøåíèÿ (5.4.3), ïðèâåäåííîãî âûøå èëè èç ðèñ. 5.4.8. Ãðàôèê ðèñ. 5.4.8 ïîçâîëÿåò îïðåäåëèòü äèàïàçîí, â êîòîðîì ìîãóò ïðîÿâèòüñÿ ýòè ïîëîñû êàê â îñíîâíîì îáúåìå êðèñòàëëà, òàê è â âûäåëåíèÿõ.

Ðèñ. 5.4.8. Èçìåíåíèå ñïåêòðàëüíîãî ïîëîæåíèÿ ïîëîñ ïîãëîùåíèÿ ZnSe è ZnS, ñâÿçàííûõ ñ ïåðåõîäàìè Å– ® Å+ â çàâèñèìîñòè îò êîíöåíòðàöèè ðàñòâîðåííîãî êèñëîðîäà è âåëè÷èíû ðàñùåïëåíèÿ çîíû ïðîâîäèìîñòè.
 ñâÿçè ñ ýòèì îòìåòèì, ÷òî ñïåêòðû ÈÊ ïðîïóñêàíèÿ ìîãóò äàâàòü èíôîðìàöèþ î ðàñïðåäåëåíèè è ôîðìàõ ïðèñóòñòâèÿ êèñëîðîäà â êðèñòàëëàõ. Òàê, â îáðàçöàõ CVD ZnS, ðàññìîòðåííûõ âûøå, SÀ ñâå÷åíèå âûÿâëÿåò ñêîïëåíèÿ ñî çíà÷èòåëüíî áîëüøåé [OS], ÷åì â îñíîâíîì îáúåìå (ñì. ðàçä. 4.1).  ïðîïóñêàíèè òàêèõ îáðàçöîâ ïðè áîëüøîì êîëè÷åñòâå ñêîïëåíèé ìîãóò ïîÿâëÿòüñÿ äîïîëíèòåëüíûå ïîëîñû ïîãëîùåíèÿ, îáÿçàííûå ñêîïëåíèÿì.

Ðèñ. 5.4.9. Ñïåêòðû ïðîïóñêàíèÿ ïðè 300Ê CVD ZnSe, ëåãèðîâàííîãî ïðè ðîñòå êèñëîðîäîì, ââåäåííûì â ãàçîâóþ ôàçó â êîëè÷åñòâå 0,9 %. Êðèâàÿ 1 –ýòàëîííûé îáðàçåö, 2 – êîíåö ñì), 3 – ñðåäíÿÿ ÷àñòü êîíäåíñàòà (7 – 9 ñì).
Ñîïîñòàâëåíèå ñïåêòðîâ ñ ñåëåêòèâíûìè ïîëîñàìè (ðèñ. 5.4.9) ïîçâîëÿåò ïî ñìåùåíèþ îäíîòèïíûõ ïîëîñ ïîãëîùåíèÿ ñóäèòü îá èçìåíåíèè â íèõ êîíöåíòðàöèè ðàñòâîðåííîãî êèñëîðîäà. Íàïðèìåð, íà ðèñ. 5.4.9 ïðèâåäåíû òðè ñïåêòðà ïðîïóñêàíèÿ: ýòàëîííîãî îáðàçöà ZnSe (êðèâàÿ 1) è 2-õ ðàçíûõ ó÷àñòêîâ ïðîòÿæåííîãî êîíäåíñàòà (êðèâûå 2 è 3).  öåëîì ñïåêòðû 2-3 ñâèäåòåëüñòâóþò î íåîäíîðîäíîñòè èññëåäóåìîãî êîíäåíñàòà, ïîëó÷åííîãî ïðè ñèëüíîì ëåãèðîâàíèè êèñëîðîäîì ïðè ðîñòå [103]. Äëÿ ZnSe âåñüìà õàðàêòåðíà ïîëîñà ïîãëîùåíèÿ â îáëàñòè ~ 8 ìêì, êîòîðàÿ, ïîâèäèìîìó, ñâÿçàíà ñ ïåðåõîäàìè Å– ® Å+. Îíà íàáëþäàåòñÿ è â ñïåêòðå ýòàëîííîãî îáðàçöà êàê 8,9 ìêì è ñìåùàåòñÿ äëÿ èññëåäóåìûõ îáðàçöîâ äî 8,7 è 8,4 ìêì. Ñìåùåíèå ïîëîñû ñâèäåòåëüñòâóåò îá óâåëè÷åíèè êîíöåíòðàöèè ðàñòâîðåííîãî êèñëîðîäà îò 0,1 ìîë% äî ~ 0,2 ìîë%. Ðàíåå ïðåäïîëàãàëîñü, ÷òî ïîãëîùåíèå, îáÿçàííîå êèñëîðîäó â ÈÊ îáëàñòè, ìîæíî ñîïîñòàâèòü îäíîé, íå ñìåùàþùåéñÿ ñïåêòðàëüíî, ïîëîñå.
Âûâîäû
Ðåçóëüòàòû ðàáîòû ìîãóò áûòü ïðåäñòàâëåíû â âèäå ñëåäóþùèõ îñíîâíûõ âûâîäîâ:
1. Âïåðâûå ïðîâåäåíû èññëåäîâàíèÿ è àíàëèç îñíîâíûõ îïòè÷åñêèõ ñâîéñòâ ñîåäèíåíèé À2Â6 – ZnS è ZnSe – ñ ïðèâëå÷åíèåì òåîðèè àíòèïåðåñåêàþùèõñÿ çîí. Ýòî ïîçâîëèëî ó÷åñòü ïðèñóòñòâèå ôîíîâîé ïðèìåñè êèñëîðîäà, êîòîðàÿ âëèÿåò, äàæå â êîíöåíòðàöèÿõ äî 1 ìîë%, íà çîííóþ ñòðóêòóðó êðèñòàëëà. Ðàññìîòðåíû îñîáåííîñòè ñàìîàêòèâèðîâàííîãî ñâå÷åíèÿ è õàðàêòåðíîå èçìåíåíèå øèðèíû çàïðåùåííîé çîíû â ïðèñóòñòâèè êèñëîðîäà. Àíàëèç ýêñïåðèìåíòàëüíûõ äàííûõ ïîêàçàë, ÷òî ìíîãèå, ðàíåå íå èìåâøèå èíòåðïðåòàöèè îñîáåííîñòè ñïåêòðîâ ëþìèíåñöåíöèè, ïîãëîùåíèÿ, îòðàæåíèÿ è ïðîïóñêàíèÿ, ïîëó÷àþò îáúÿñíåíèå ñ ïîçèöèé òåîðèè àíòèïåðåñåêàþùèõñÿ çîí.
2. Ïðåäëîæåíà çîííàÿ ìîäåëü äëÿ êðèñòàëëîâ ZnS×O, ZnS×Cu(O), ZnSå×O, ZnSå×Cu(O). Ïîäòâåðæäåíî èëè îïðåäåëåíî ïîëîæåíèå óðîâíÿ êèñëîðîäà ÅÎ êàê 0,11 è 0,16 ý ïî îòíîøåíèþ êî äíó çîíû ïðîâîäèìîñòè ÅÑ ÷èñòûõ ñîåäèíåíèé ZnSe è ZnS.  çàâèñèìîñòè îò êîíöåíòðàöèè ðàñòâîðåííîãî êèñëîðîäà ýòà ìîäåëü â ñîãëàñèè ñ ýêñïåðèìåíòàëüíûìè äàííûìè ïîçâîëÿåò îöåíèòü âåëè÷èíû ðàñùåïëåíèÿ çîíû ïðîâîäèìîñòè (D = Å+ – Å–), ñïåêòðàëüíîå ïîëîæåíèå êðàÿ ôóíäàìåíòàëüíîãî ïîãëîùåíèÿ Å–, à òàêæå ïîëîñ SA èëè SAL ñàìîàêòèâèðîâàííîé ëþìèíåñöåíöèè, êàê è ñâÿçàííîãî ýêñèòîíà íà êèñëîðîäíûõ êîìïëåêñàõ.
3. Ïðåäñòàâëåíà íîâàÿ èíòåðïðåòàöèÿ ïîëîñ ëþìèíåñöåíöèè Cu â ñîåäèíåíèÿõ ZnS×O è ZnSe×O, êàê è äóáëåòíîé ñòðóêòóðû ïîëîñ SA è SAL ñàìîàêòèâèðîâàííîãî ñâå÷åíèÿ.
 ÷àñòíîñòè, äâå õîðîøî èçâåñòíûå äëÿ ZnSe ïîëîñû èçëó÷åíèÿ Cu-R è Cu-G îïðåäåëÿþòñÿ îäíèì è òåì æå öåíòðîì, íî îáÿçàíû ïåðåõîäàì èç äâóõ ïîäçîí Å+ è Å– ðàñùåïëåííîé áëàãîäàðÿ ïðèñóòñòâèþ êèñëîðîäà çîíû ïðîâîäèìîñòè.
4. Ïîëó÷åíû ðåçóëüòàòû, õàðàêòåðèçóþùèå ðàñïðåäåëåíèå êèñëîðîäà â êðèñòàëëàõ, êîòîðîå â áîëüøèíñòâå ñëó÷àåâ íåîäíîðîäíîå, ÷òî ñóùåñòâåííî óñëîæíÿåò ñóììàðíûå ñïåêòðû ëþìèíåñöåíöèè è ïîãëîùåíèÿ. Ïðè ýòîì ïîëîñû ñâîáîäíîãî è ñâÿçàííîãî ýêñèòîíà èç ñêîïëåíèé ñ ïîâûøåííûì ñîäåðæàíèåì ðàñòâîðåííîãî êèñëîðîäà îïðåäåëÿþò óçêîëèíåé÷àòûé ñëîæíûé ñïåêòð â êðàåâîé îáëàñòè.
5. Ïîñòðîåíèå ìîäåëè èçëó÷àòåëüíûõ ïåðåõîäîâ, ïîçâîëèëî ïî-íîâîìó ïðåäñòàâèòü ïðèðîäó çåëåíîãî ñâå÷åíèÿ ZnS×Cu. Ïîäòâåðäèëîñü âûñêàçàííîå ðàíåå ïðåäïîëîæåíèå, ÷òî çåëåíîå è ñèíåå ñâå÷åíèå Cu â ZnS îïðåäåëÿþòñÿ ïåðåõîäàìè íà îäèí è òîò æå àêöåïòîðíûé óðîâåíü. Ïðè ýòîì ñïåêòðàëüíîå ïîëîæåíèå çåëåíîé ïîëîñû îïðåäåëÿåòñÿ óìåíüøåíèåì øèðèíû çàïðåùåííîé çîíû Å– â îáëàñòè ñêîïëåíèé êèñëîðîäà. Ýòè âûâîäû ïîäòâåðæäåíû èññëåäîâàíèÿìè ñïåêòðîâ âîçáóæäåíèÿ çåëåíîãî ñâå÷åíèÿ.  ñëó÷àå ZnSå×Cu àíàëîãè÷íûå ïî ïðèðîäå ïîëîñû äîëæíû ñîîòâåòñòâîâàòü ñïåêòðàëüíîìó äèàïàçîíó ~ 700 – 800 íì.
6. Äàíà èäåíòèôèêàöèÿ ïîëîñ ñâÿçàííûõ ýêñèòîíîâ BE íà àêöåïòîðíûõ óðîâíÿõ êèñëîðîäíûõ öåíòðîâ ñàìîàêòèâèðîâàííîãî SA ñâå÷åíèÿ ZnS×O è ZnSe×O. Îáíàðóæåíî, ÷òî ïîëîñû ñâÿçàííûõ íà SA öåíòðàõ ýêñèòîíîâ BESA íàáëþäàþòñÿ â ñïåêòðàõ, ïîëó÷åííûõ èç îáúåìà êðèñòàëëîâ. Ïðè ïîâûøåííîé ïëîòíîñòè âîçáóæäåíèÿ ñîâåðøåííûõ îáðàçöîâ ïîëîñà BESA, ðåçêî óñèëèâàåòñÿ, ñóæàåòñÿ è ïðåâàëèðóåò âî âñåé âèäèìîé îáëàñòè ñïåêòðà. Âûñêàçàíî ïðåäïîëîæåíèå, ÷òî ñâÿçàííûé ýêñèòîí íà êèñëîðîäíûõ öåíòðàõ áóäåò îïðåäåëÿòü ñâå÷åíèå ïðè ëàçåðíîì ýôôåêòå.
7. Èçìåíåíèå çîííîé ñòðóêòóðû, èíèöèèðîâàííîå êèñëîðîäîì, ïðèâîäèò ê óñëîæíåííîé ñèñòåìå óðîâíåé, îïðåäåëÿþùåé ïåðåõîäû ñ ïîãëîùåíèåì. Ïðåäñòàâëåíà ìîäåëü, ñîîòâåòñòâóþùàÿ îñíîâíûì êîìïîíåíòàì ñïåêòðà ïîãëîùåíèÿ (îòðàæåíèÿ, ïðîïóñêàíèÿ), âîçáóæäåíèÿ ëþìèíåñöåíöèè â ñèñòåìå òâåðäûõ ðàñòâîðîâ ZnS×O - ZnSe×O.
Ïîêàçàíî, ÷òî ïðè ââåäåíèè êèñëîðîäà óñèëèâàåòñÿ àáñîðáöèÿ, êîòîðàÿ îáÿçàíà ïåðåõîäàì ÅV ® Å–(+) è õàðàêòåðèçóåòñÿ âåëè÷èíîé êîýôôèöèåíòà ïîãëîùåíèÿ íà óðîâíå ôóíäàìåíòàëüíîãî 5×104-105 ñì-1. Óòî÷íåíû âîçìîæíûå òèïû ïåðåõîäîâ.
Âûäåëåíû ñåëåêòèâíûå ïîëîñû ïîãëîùåíèÿ â áëèæíåì ÈÊ äèàïàçîíå ñïåêòðà, êîòîðûå îïðåäåëÿþòñÿ ïåðåõîäàìè ìåæäó ïîäçîíàìè Å– ® Å+. Ïîêàçàíî, ÷òî ñïåêòðàëüíîå ïîëîæåíèå ýòèõ ïîëîñ çàâèñèò îò êîíöåíòðàöèè êèñëîðîäà. Ïðè íåîäíîðîäíîì ðàñïðåäåëåíèè êèñëîðîäà èìååò ìåñòî èõ ðàçìûòèå.
8. Ïðåäñòàâëåííûå çàâèñèìîñòè ñìåùåíèÿ ýêñèòîííûõ ïîëîñ, êàê è ñàìîàêòèâèðîâàííîé ëþìèíåñöåíöèè, ñ óâåëè÷åíèåì [OS] ìîãóò áûòü èñïîëüçîâàíû äëÿ ïðÿìîãî îïðåäåëåíèÿ êîíöåíòðàöèè ðàñòâîðåííîãî êèñëîðîäà â ZnS èëè â ZnSe â îñíîâíîì îáúåìå êðèñòàëëà (ìàòðèöå) è â ñêîïëåíèÿõ. Ñïåêòðàëüíîå ïîëîæåíèå ýòèõ ïîëîñ ìîæåò áûòü èñïîëüçîâàíî äëÿ êîíòðîëÿ [OS], à òèï ñâå÷åíèÿ – äëÿ îöåíêè îòêëîíåíèÿ ñîñòàâà êðèñòàëëîâ îò ñòåõèîìåòðèè.
Îòìå÷àåòñÿ, ÷òî ïðè áîëüøîì êîýôôèöèåíòå ïîãëîùåíèÿ ñëîæíàÿ ñèñòåìà óðîâíåé ïîâûøàåò ýôôåêòèâíîñòü àáñîðáöèè ñâåòà òâåðäûìè ðàñòâîðàìè ZnS×O è ZnSe×O, ÷òî áëàãîïðèÿòíî äëÿ ñîçäàíèÿ ðÿäà íîâûõ ïðèáîðîâ îïòîýëåêòðîíèêè.
Ïðèíÿòûå îáîçíà÷åíèÿ
(E+ - E–) | Âåëè÷èíà ðàñùåïëåíèÿ çîíû ïðîâîäèìîñòè, èíèöèèðîâàííàÿ èçîýëåêòðîííîé ïðèìåñüþ Δ = (E+ - E-), ìý |
ΔÅ | Ïîëóøèðèíà ïîëîñ ëþìèíåñöåíöèÿ, ìýÂ |
BAC | Àíòèïåðåñåêàþùèåñÿ çîíû (bands anticrossing) |
ÂÅ | Ñâÿçàííûé ýêñèòîí |
BGB | Ðåçêîå íèñïàäàþùåå èçìåíåíèå çàïðåùåííîé çîíû, èíèöèèðîâàííûé èçîýëåêòðîííîé ïðèìåñüþ (band gap bowing) |
SA(I) | Ñàìîàêòèâèðîâàííàÿ ëþìèíåñöåíöèÿ, îáÿçàííàÿ SA êîìïëåêñàì {Zni·×VZn/ /}/× O*S(Se) |
Cu(I) | Ñàìîàêòèâèðîâàííàÿ ëþìèíåñöåíöèÿ, îáÿçàííàÿ Cu(I) êîìïëåêñàì {Ñui·×VZn/ /}/× O*S(Se) |
SAL(II) | Ñàìîàêòèâèðîâàííàÿ ëþìèíåñöåíöèÿ, îáÿçàííàÿ SAL(II) êîìïëåêñàì {Zni··×VZn/ /}´× O*S(Se) |
Cu(II) | Ñàìîàêòèâèðîâàííàÿ ëþìèíåñöåíöèÿ, îáÿçàííàÿ Cu(II) êîìïëåêñàì {Cui··×VZn/ /}´× O*S(Se) |
e | Ýíåðãèÿ ñâÿçè ýêñèòîíà |
EA | Ïîëîæåíèÿ àêöåïòîðíîãî óðîâíÿ |
EO, EN | Óðîâíè èçîýëåêòðîííûõ ïðèìåñåé: êèñëîðîäà, àçîòà â çîííîé ìîäåëè |
EC | Çîíà ïðîâîäèìîñòè |
Å– | Ìèíèìóì íèæíåé ïîäçîíû (ïðîòÿæåííûõ ñîñòîÿíèé) ðàñùåïëåííîé çîíû ïðîâîäèìîñòè |
E+ | Ìèíèìóì âåðõíåé ïîäçîíû (ëîêàëèçîâàííûõ ñîñòîÿíèé) ðàñùåïëåííîé çîíû ïðîâîäèìîñòè |
FE | Ñâîáîäíûé ýêñèòîí |
Í, L | Âûñîêîýíåðãåòè÷åñêàÿ è íèçêîýíåðãåòè÷åñêàÿ ñîñòàâëÿþùèå èçëó÷àòåëüíûõ ïåðåõîäîâ èç ïîäçîí Å+ è Å– ñîîòâåòñòâåííî |
HMAs | òâåðäûå ðàñòâîðû ñ ðåçêèì íåñîîòâåòñòâèåì ñâîéñòâ êîìïîíåíòîâ (highly mismatched alloys – HMAs), êîãäà èìååò ìåñòî èçìåíåíèå çîííîé ñòðóêòóðû |
SO | ñïèí-îðáèòàëüíîå ðàñùåïëåíèå |
Z | Àòîìíûé (ïîðÿäêîâûé) íîìåð ýëåìåíòà |
ÄÂ, ÊÂ | Äëèííîâîëíîâîå, êîðîòêîâîëíîâîå |
ÃÑ | Ãàçîñòàòèðîâàíèå – îáðàáîòêà ïðè âûñîêîì äàâëåíèè ãàçà è âûñîêîé òåìïåðàòóðå |
ÈÊË | Èìïóëüñíàÿ êàòîäîëþìèíåñöåíöèÿ (ñì. ãë. 2) |
ÈÐË | Èìïóëüñíàÿ ðåíòãåíîëþìèíåñöåíöèÿ |
ÈÝÏHMAs | Èçîýëåêòðîííàÿ ïðèìåñü çàìåùåíèÿ ñ ðåçêèì íåñîîòâåòñòâèåì ñâîéñòâ ïî ñðàâíåíèþ ñ àòîìîì ìàòðèöû |
ÈÝÀHMAs | Èçîýëåêòðîííûé àêöåïòîð òèïà HMAs |
ÈÝÄHMAs | Èçîýëåêòðîííûé äîíîð òèïà HMAs |
ÊÄÏ | êðàé “äîïîëíèòåëüíîãî ïîãëîùåíèÿ”, âîçíèêàþùèé íà ñïåêòðîãðàììàõ ZnS×O, ZnSå×O |
ÊË | Êàòîäîëþìèíåñöåíöèÿ |
ÌÊË | Ìèêðîêàòîäîëþìèíåñöåíöèÿ (ñúåìêà â ðàñòðîâîì ýëåêòðîííîì ìèêðîñêîïå) |
ÐÝÌ | Ðàñòðîâûé ýëåêòðîííûé ìèêðîñêîï |
ÑÒÄ | Ñîáñòâåííûå òî÷å÷íûå äåôåêòû |
ÔË | Ôîòîëþìèíåñöåíöèÿ |
ÕÃÕ | Õèìè÷åñêèé ãàçîõðîìàòîãðàôè÷åñêèé àíàëèç (ñì. ãë. 2) |
ÑÏÈÑÎÊ ÈÑÏÎËÜÇÎÂÀÍÍÛÕ ÈÑÒÎ×ÍÈÊÎÂ
7 , / Êîìïëåêñíîå èññëåäîâàíèå â ÐÝÌ îñîáåííîñòåé èîííîé èìïëàíòàöèè ñóëüôèäà öèíêà // Òåçèñû äîêë. III Ðåñïóáë. êîíô. Ýëåêòðîííàÿ ìèêðîñêîïèÿ è âîïðîñû äèàãíîñòèêè. Êèøèíåâ. Ñ. 152-
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