CS249502B2 - Method of compounds' thin layers formation - Google Patents
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Description
Vynález se týká způsobu vytváření tenkých vrstev sloučenin z prvků této sloučeniny, např. ze zinku a síry, z cínu a kyslíku, galia a fosforu, kadmia a selenu, .postupnými reakčními kroky s povrchem substrátu.
Nejdůležitější ze známých způsobů výroby sloučeninových tenkých vrstev z plynné fáze, podle známého stavu techniky, je vakuové naparování, jež je výsledkem buď přímého užití patřičné sloučeniny jako zdroje, nebo současným napařováním rozdílných komponent chemických prvků z různých zdrojů. V prvém případě hlavní nevýhodou je rozklad sloučeniny na její složky, přičemž stechiometrické poměry vrstvy je těžké ovlivňovat a tyto poměry mají obecně tendenci ke změnám během, napařovacího procesu. Když se naparování provádí technikou vytvoření správných stechiometrických poměrů složek předpokládá řízení vypařovacích poměrů složek nebo vhodné ' dodatečné napaření vhodné složky. Stejně jako u naparování ze sloučeniny jsou schopnost tvoření krystalizačních zárodků a krystalická struktura vrstvy nedostatečně řiditelné i při současném naparování rozdílných složek.
jestliže je podložka tvořena monokrystalem, pak při použití známé techniky naparování je možné dosáhnout toho, že vrstva narůstá se stejnou strukturou jako· má podložka.. Výše uvedená, známá problematika epitaxe dopadem molekul je popsána v J. Vac. Sci. Technol., Vol. 10, oN 5, Sept./Oct. 1973. L. L. Chang a kol. „Růst vrstvy epitaxí dopadem paprsků molekul“.
Když je jako zdroj vypařovacího materiálu použita vícesložková sloučenina, její rozklad může být nahrazen, jak známo, použitím techniky rozprašování, přičemž materiál, který má být přenesen ze zdroje na vrstvu, je od zdroje oddělen bombardováním krVv. Nejlepších stechiometrických poměrů se dosáhne obvykle spojením rozprašovací techniky s tak zvaným vysokofrekvenčním rozprašováním, jež je srovnatelné s užitím zpětného odpařování.
Nejdůležitějšími sloučeninami sloučeninových vrstev jsou binární sloučeniny ze skupiny II.....VI a III —V periodické soustavy prvků a jejich kombinace. To je dáno především polovodičovými vlastnostmi těchto sloučenin. Nejidůležitější pro polovodičové aplikace je krystalická struktura vrstvy. Pro řadu aplikací tento· požadavek omezuje použitý materiál na monokrystal, protože jen ten může být vytvořen epitaxně na monokrystalické podložce. Epitaxní nárůst sloučenin je relativně obtížný ve srovnání s epitaxním nárůstem elementárních materiálů jako křemíku a germania. Hlavní příčinou větší komplikovanosti nárůstu ze sloučeniny je, v· případě binárních sloučenin a epitaxe z parní fáze, existence dvou typů parních a pevných fází sloučeniny a dvou komponent elementů. Pro dosažení správných' stechiometrických poměrů musí být prováděno přesné řízení napařovací rychlosti ne bo parciálních tlaků komponent prvků, rovněž jako teploty podložky.
Pro* řadu aplikací je třeba míti polovodičový materiál ve tvaru tenké vrstvy na podložce, jež není monokrystalická, oož je výhodné z hlediska ceny a z hlediska pokrytí velkých ploch tenkou vrstvou. Takové aplikace, kde sloučeniny z prvků II. a VI. skupiny, III. a V. skupiny soustavy prvků, jsou středem zájmu, jsou například sluneční články, některé optoelektronické součástky, zobrazovací prvky, · displaye atd. Rozsáhlé použití takových součástek je však omezeno slabou kvalitou polovodičového materiálu získaného technikou usazování podle stávajícího stavu techniky.
Doprovázející vlastností každé známé metody usazování použité k vytvoření usazeniny na podložce, která není monoflkrysítalrcká, je tvoření krystalizačních zárodků při začátku růstu vrstvy. Vrstva nemá spojitou strukturu, dokud se jednotlivé mikrokrystaly (rostoucí jádra) navzájem nedotknou. Toto obecně nastane při střední tloušťce vrstvy řádově 100 A. Výsledné vrstvy mají amorfní strukturu. Elektrické charakteristiky jsou silně ovlivňovány polykrystalickou strukturou materiálu. Avšak nejen elektrické charakteristiky vrstev jsou ovlivňovány dokonalostí struktury · materiálů, · ale také chemická stabilita, jenž je nutnou podmínkou pro technické použití vrstev. Elektrické a chemické charakteristiky sloučeninových vrstev jsou vedle toho silně závislé na odchylkách stechiometrických poměrů, jež jsou při usazování těžko odstranitelné.
Způsob výroby podle vynálezu se označuje jako epitaxe atomové vrstvy, ve zkratce ALE.
Úkolem vynálezu je odstranění nevýhod dosud známých způsobů vytváření tenkých vrstev, jak byly shora uvedeny.
Podle vynálezu se toho dosahuje tím, že se následně působí na povrch substrátu vždy atomy jediného prvku v parní fázi, přičemž tlak reakční páry a doba působení jsou upraveny tak, aby počet atomů jediného působícího· prvku zasahující povrch byl větší než počet atomů v horní atomové vrstvě povrchu a povrch se · udržuje na teplotě, při níž dochází k povrchové reakci, která současně zabraňuje kondenzaci reakční páry na povrchu.
Reakční pára je přitom tvořena buď sloučeninou působícího prvku nebo působícím prvkem samotným.
Způsob podle vynálezu vede k dosažení důležitých základních vlastností epitaxe i v případě, ždyž se použije substrátu s amorfní strukturou. Dosahuje se totiž sloučeninové vrstvy prosté krystalizačních zárodků a vysoce orientované ve směru růstu vrstvy. Základní rozdíl způsobu podle vynálezu od ostatních způsobů usazování je v tom, že růst vrstvy probíhá postupně po· atomových vrstvách, což je výsledkem povrchové re249502 akce mezi jedním prvkem sloučeniny v plynné fázi a druhým prvkem, který tvoří povrchovou vrstvu atomů v rostoucí sloučeninové vrstvě.
Způsob podle vynalezu lze provádět samočinným řízením, jestliže se teplota rostoucího povrchu udržuje na dostatečné výši, aby se zabránilo kondenzaci prvku při každém jednotlivém reakčním kroku. Pro získání binární vrstvy AB, kde A představuje jeden z prvků skupiny I, II, III а IV, а В prvek ze skupin VII, VI а V, se reakce cyklicky opakuje, tj. plyn A reaguje s povrchem tvořeným prvkem B, čímž se vytváří povrch A se sloučeninovými vazbami A—B, na to se povrch vystaví působení plynu B, čímž se reakcí mezi plynem В a povrchem A opět získávají vazby В —A a povrch B, který se potom opět vystaví působení plynu A atd.
V případě, že se použije skleněný substrát, je podmínkou pro zahájení postupného procesu to, aby jedna ze složek sloučeniny měla dostatečně pevnou vazbu s atomy kyslíku, jez tvoří povrch skla. Tato podmínka je přímo splněna pro většinu sloučenin typu JI—VI а III -V a při použití atomových mezivrstev lze tuto podmínku splnit prakticky pro všechny sloučeniny vhodné pro způsob podle vynálezu.
Jestliže se způsobu podle vynálezu použije pro epitaxi na monokrystalu, pak orientace mřížky substrátu musí splňovat podmínku dílčích atomových rovin v rotaci.
Způsob podle vynálezu lze provádět v zařízení, které obsahuje vakuovou komoru, v níž je umístěn držák substrátu, zdroje par a prostředky, pomocí nichž se substrát vystavuje působení různých vypařovacích zdrojů vždy v patřičném pořadí.
Způsob podle vynálezu a jeho výhody budou dále podrobně popsány v souvislosti s používaným zařízením patrným z přiložených výkresů, kde obr. 1 představuje řez zařízením, obr. 2 je řez podle čáry II—II v obr. 1, obr. 3 ukazuje řez jiným zařízením, obr. 4 je řez podle čáry IV—IV v obr. 3 a obr. 5 ukazuje zařízení, kde reakční vakuotěsná komora ještě dovoluje axiální pohyb nosiče podložky.
Obr. 6 představuje zařízení, kde podložka je uložena nehybně.
Obr. 7 představuje modifikaci řešení uvedeného na obr. 6. U této modifiktace nárůst vrstvy probíhá po dvou stranách podložky, přičemž reakční komora může být prostřednictvím speciálních ventilů evakuována mezi jednotlivými kroky reakce.
V postupu podle vynálezu jsou atomové vrstvy usazovány například z prvku A a prvku B, přičemž A prvek obvykle náleží к jedné ze skupin I, II, III nebo IV periodické soustavy prvků a prvek В náleží к jedné ze skupin VII, VI, resp. V. Nejtypičtější vrstvy vyráběné postupem podle vynálezu jsou ze sloučenin nebo oxidů skupin I—-VII, II až VI nebo II až V. Podle vynálezu prvek A v plynné fázi reaguje s povrchem, ж kterém je prováděn nárůst, povrchové atomy, jež patří do skupiny B, tvoří jednoatomovou vrstvu, následkem čehož je získávána pevná vazba mezi prvky A a B, přičemž všechny nadbytečné atomy prvku A, dopadající na povrch, budou okamžitě vráceny do plynné fáze, pokud A—A vazba není dostatečně silná, к zabránění zpětnému vypařování prvku A. Když při interakci s plynnou fází prvku A má vrstva nárůst pouze o jednu vrstvu atomů, může na povrch vrstvy dopadat počet atomů, nemnoho převyšující počet odpovídajících atomů v monoatomární vrstvě. Po interakci mezi povrchem, na kterém je prováděn nárůst, a plynnou fází prvku A, je povrch vystaven působení plynné fáze prvku B, načež atomy prvku A v povrchové vrstvě tenké vrstvy opět vystupují do silné vazby B—A s atomy В přímo na ně dopadajícími a povrch je tak nyní pokryt jednoatomovou vrstvou prvku B, jestliže vazba В—В je slabá к zabránění vracení prvku В do plynné fáze. Tyto střídající se kroky reakce jsou opakovány, pokud není dosaženo požadované tloušťky usazenin ze sloučeniny AB.
Obrázky 1 a 2 zobrazují vakuové zařízení umístěné v komoře 10, kde podložka 14, na níž je prováděn růst vrstvy, je upevněna na disko 12a otočně uloženém na hřídeli 11. Pod diskem 12 jsou umístěny vypařovací zdroje 13a, 13b, jež jsou vzájemně odděleny a na nichž každý je uspořádán tak, aby měl vhodný tlak par elementárních složek, ze kterých se má vrstva usazovat. Když disk 12a rotuje, podložka 14 je střídavě vystavována působení par prvku A, 13a, a B, 13b, přičemž nárůst vrstvy probíhá podle způsobu popsaným vynálezem.
V příkladu uvedeném na obrázcích 3 a 4 je kotouč z předcházejícího příkladu nahrazen prstencem 12b, upraveném rotačně kolem hřídele 11, a na jehož vnějším obvodě jsou upevněny podložky 14. Vypařovací zdroje 13a, 13b, 13c jsou umístěny radiálně kolem prstence 12b. Rychlost otáčení prstence 12b je nejvýhodnější mezi 1 až 20 otáčkami za vteřinu.
Zařízení podle obr. 1 až 4, kde relativní pohyb je mezi podložkou 14 a parními zdroji 13, může být provedeno také tak, že podložky 14 jsou nepohyblivé a parní zdroje se pohybují. Zařízení může být navrženo také například tak, že podložky 14 jsou uchyceny ke konstrukčnímu prvku podobnému dopravnímu pásu, jenž nese podložky kolem vypařovacích zdrojů. Je samozřejmé, že relativní pohyb podložek a parních zdrojů může být proveden celou řadou způsobů.
Zařízení podle obr. 5 obsahuje vakuovou •komoru 10 a oddělení reakční komory 19a a 19b, kde podložky 14 se mohou při reakci pohybovat, přičemž jsou valkuotěsně s komorami spojeny. Toto uspořádání umožňuje
lepší oddělení jednotlivých kroků reakce a menší ztráty reakčních plynů, ale je po mechanické stránce náročnější. Zlepšeného oddělení jednotlivých reakčních kroků lze dosáhnout užitím mechanických pohyblivých částí podle uspořádání na obr. 6 a 7. Dále podle obr. 5 se hřídel 10a může pohybovat v axiálním směru. Prostředky pro dosažení obou pohybů jsou schematicky znázorněny blokem 24. Blok 23 představuje schematicky řízení pohybu a blok 22 podobně řízení ventilů 15a, 15b. Pozice 21 označuje spojovací prostředky pro spojení s reakčními komorami 19a, 19b.
U zařízení zobrazeném na obr. 6 je podložka nepohyblivě uchycena na základě 12c, která je vyhřívána ma potřebnou teplotu pomocí ohřívací komory 17. Zařízení obsahuje dva parní zdroje 20a, 20b, jež střídavě působí na podložku 14. Toto je umožněno prostřednictvím ventilů 15a, 15b na trubkách 10a, 16b. Tyto ventily se střídavě zavírají a otevírají, takže zatímco jeden z ventilů je otevřen, druhý je zavřen. Prostředky umožňující tento způsob činnosti, jsou schematicky představovány blokem 18 a spínačem K.
Na obr. 7 jsou zvenku reakční komory 10 zdroje různých plynů 20a, 20b. Podložky 14 v komoře 10 jsou drženy v jejich polohách speciálními prostředky 29, 30.
Reakční komora 10 je při rotaci naplněna základními plyny pomocí ventilů 15a, 15b, přičemž plyny jsou během za sebou jdoucích kroků odčerpávány přes ventil 26. Při tomto uspořádání se stěny reakční komory 10 pokrývají sloučeninou současně s probíhajícím nárůstem vrstvy na podložkách 14, jež se pokrývají na obou stranách. Blok 28 představuje prostředky к ovládání ven tilu 26 a blok 25 značí jeho řídicí prostředky.
Teoretický základ předloženého vynálezu je v následujícím popsán podrobněji s odvoláním na různé příklady vynálezu uvedené výše.
Ve zdroji prvku A je rovnováha mezi jeho pevnou fází a tlakem par při teplotě Ta [v případě, že Ta převyšuje teplotu prvku tání A, rozhoduje rovnováha mezi kapalnou a plynnou fází). Odpovídající situace pro prvek В je ve zdroji 13b. V případě samovyrovnávání postupu je teplota To podložky držena výše než teploty zdrojů T a T , to znamená, že páry А а В nekondenzují ,na podložce. V případě, že atomy A tvoří pevnou sloučeninu s kyslíkem s vazební energií dostatečně vysokou к zabránění rozkladu, podložka se pokryje monoatomární vrstvou atomů A s A—O vazbou.
Pokrytí povrchu atomy A může být popsáno rovnicí dPA = - ^An“A°- (1 - Pa) · dt (1 - Pa) dt - -ř-· tA0 (1)
PA = 1 kde
PA = relativní plocha povrchu pokrytí atomy A.
(Ua = hustota srážek atomů A s povrchem jež mají tvořit (v souhlase s kinetickou teorií plynů):
μΑ
-Pa- i | atom 1 | 7,5 x 1017 | 1 |
V2mkŤ 1 | cm2 1 | = [N/m2] | cm2 s |
Ns = hustota povrchových atomů
Ns r 1015 1/cm2 tAO - čas vzájemného působení povrchu s O atomy s reakčním plynem A [s|, íYao = pravděpodobnost povrchové reakce atomu s O atomem povrchu, odpovídající ,,koeficientu zachycení“ v běžných metodách usazování.
Pravděpodobnost povrchové reakce a je komplexní funkcí teploty reakčního povrchu a tlaku reagujícího plynu. Mění se v širokých mezích podle různých prvků a sloučenin. Bylo zjištěno, že pro jednoatomový je vyšší než pro dvouatomový nebo víceatomový.
Z rovnice (1) vyplývá, že relativní pokrytí povrchu A atomy se přibližuje s rostoucím časem jedné.
Významnou výhodou nárůstu podle metody ALE je to, že tlak páry, tvořící sloučeninu, má minimum právě ve směru růstu, čímž nejpevnější možné vazby se vytvářejí ve směru kolmém na povrch.
Jestliže В atomy tvoří sloučeninu v pevné fázi s kyslíkem s vysokou vazebnou energií, podložka při interakci s В zdrojem se bude pokrývat В atomy přesně tak, jak je popsáno pro interakci mezi nimi a A atomy a povrchem skla. Pro prvky typu В to není obecný případ, což znamená, že povrch skleněné podložky bude zůstávat nezměněn během jeho interakce s В párou.
Při dalším kroiku reakce, podložky pokryté monoatomární vrstvou atomů A jsou vystaveny působení zdroje atomů В v plynné fázi. Povrch bude pokryt atomy B, podle rovnice (1), opět tvořících monoatomární vrstvu se sloučeninou A -B vazbou. Podmínky platné pro tlaky páry uvedené monoatomární В vrstvy s vazbami А—В а В atomy v této vrstvě s vazbami В—В se liší, což vy249502 plývá z extrémně selektivního zpětného vypařování B atomů.
Opakováním kroků reakce při rotaci bude povrch podložek pokrýván vrstvou se strukturou
O—A—B-—A—B—A—B—A—B . . ., kde první O vrstvy povrchu podložky a následující A—B vrstvy tvoří vysoce orientovanou vrstvu sloučeniny AB. V případě úplného pokrytí při každém kroku reakce je celková tloušťka vrstvy určena počtem otáček a mřížkovou konstantou sloučeniny.
Při použití několika zdrojů s různými prvky Α! ... An, Bi ... Bm, může narůstat vrstva se strukturou obsahující kombinace sloučenin jako supermřížky, heteroprechody atd.
Podmínky pro nárůst ' podle postupu ALE jak je popsán, mohou být definovány rovnicí (1). Pro úplné pokrytí, jak je popsáno výše, musí být splněny podmínky «ΑΟ · ^A · ÍAO > NS >
«αβ · Má · Íab > Ng , #BA · PU · tbA > Ng .
(2)
V případech, že рд a pb představují tlaky přímo při interakci s reakčním povrchem, jak je znázorněno na obrázcích 1, 2, 3, 4, 5 •a 7, teploty zdrojů Ta a Tb jsou vázány s a μΒ rovnicemi
Aa = f (Pa) = f (Ta) , μα -- f OPb) = f (Tb) .
(3)
K zajištění úplného zpětného vypaření prvků, nemajících sloučeninovou vazbu, která je určujícím faktorem v rovnovážném ALE postupu, musí být teplota T podložky vyšší než teplota Ta a Tb. Horní hranice To je v podstatě určena tlakem par sloučeniny.
Je-li ,k naparování použita skleněná podložka, horní hranice To je však obecně určena bodem měknutí skla, ze kterého je podložka vyrobena. Poznamenejme, že při použití metody ALE má na zmenšení tlaku páry sloučeniny největší vliv orientace mřížky narůstajícího povrchu. Toto bylo· stanoveno například ve spojení s nárůstem CdSe, jenž byl vytvářen při teplotě To s> 500 °C bez znatelného zpětného vypařování sloučeniny.
Je samozřejmé, že k růstu vrstvy metodou· ALE je možné použít několika typů zařízení. Rozhodujícími vlastnostmi jsou teplota povrchu podložky a teplota zdroje a v čase postupná interakce při rotaci mezi podložkou a parami prvku. Zejména použití skupiny sloučeniny typu II—VI otevírá široké možnosti návrhu zařízení v důsledku vysokých tlaků par prvků II. a VI. skupiny periodické soustavy prvků. Dvě základní uspo řádání, rozdílná od znázorněného na obr. 5, jsou uvedena na obrázcích 6 a 7.
Při růstu vrstvy metodou ALE může být interakce s párou složky dosaženo také použitím plynné sloučeniny prvku, přičemž sloučenina se rozkládá na reakčním povrchu, což je .analogické prakticky s chemickou parní depozicí. Tento druh reakce může být ukázán například s HzS místo Sz. Odpovídající povrchové reakce v případě růstu ZnS jsou
HžS (g) + Zn (s) -> Zn (s) + Hz (g) při použití sirovodíku HzS; a jí odpovídající reakce
Sz (g) + 2 Zn (s) —> 2 ZnS (s) při použití čisté síry Sz v· plynném stavu. Podle principu metody ALE reakce probíhají tak dlouho, dokud jsou k dispozici volné atomy Zn (s). Metoda ALE může být prováděna pomocí usazování napařováním jednotlivých prvků. V tomto případě se reakce zúčastňuje inertní plyn nebo plazma.
Při aplikování rovnice (1) na povrch, jenž není úplně pokryt ' atomy, které vstupovaly do povrchové reakce s dotyčnými atomy plynu, je třeba uvažovat pouze aktivní část povrchu. Sloučenina AB v tom případě narůstá a pokrývá pouze část povrchu v každém nebo jednotlivém kroku postupu, přičemž rovnice (1) může být upravena
Pa = Pb* — e — — ·—. Íab (4) pro tu část postupu, kdy reagují A atomy a P — P · e MBA t P - Pa — e — μ . t„ (5) pro reakce, kdy reagují B atomy, přičemž Pb a Pa představují relativní pokrytí povrchu B atomy před krokem reakce, kdy se povrch pokrývá atomy A, respektive představují relativní pokrytí povrchu A atomy před reakčním krokem, kdy se povrch pokrývá atomy B.
Částečné pokrytí jednoho základního prvku je zejména důležité, když rostoucí sloučeninové vrstvy s prvky o nízkém tlaku par nebo· se sloučeninami obsahují rozdílné množství základních prvků.
Důležitý příklad výše uvedeného je růst sloučenin typu III—V na podložce, jež nemusí být předehřátá · na teplotu pro převyšující teplotu To k zajištění úplného zpětného vypařování prvků III. skupiny periodické soustavy prvků. V takovém případě povrchová reakce mezi povrchovými atomy V. skupiny a atomy plynu III. skupiny je omezena k dosažení pouze částečného po249502 krytí atomů III. skupiny, aby na povrchu nebyly přespočetné atomy III. skupiny. Reakce plynu V. skupiny periodické soustavy prvků s povrchem částečně pokrytým atomy III. skupiny soustavy prvků může proběhnout tak, že je zcela zajištěn orientovaný růst metodou ALE bez kyslizačních zárodků.
Další důležitý příklad, ve kterém se užívá reakce s částí povrchu, je růst dioxidu prvků, jež mají také stabilní nebo relativní stabilní monooxidy. Růst dioxidu cínu metodou ALE je názorným příkladem. Za účelem vytvoření SnO2 místo SnO, interakce mezi párou cínu Sn a O povrchem je omezena, aby pokrytí cínem Sn bylo pouze několik procent. Interakce Ož, dosažená pomocí plazmy O? zajišťuje, že maximální počet kyslíkových atomů je vázán s atomy cínu Sn, čímž dochází k nárůstu dioxidu. Silná pobídka pro použití nárůstu metodou ALE v takových příkladech vznikla z pozorování, že vrstva Z SnOz na skleněné desce vykazuje elektrickou vodivost v rovině povrchu při tloušťce 0,001 SnOz. Vodivost nevykazuje tunelový efekt, což je důkaz, že vrstva má souvislou krystalickou strukturu. Takové vrstvy jsou fyzicky velmi pevné a chemicky odolné, což platí pro všechny sloučeninové vrstvy - vyrobené metodou ALE, bez ohledu na to, zda jde o pokrytí reakčního povrchu úplné nebo částečné při jednotlivých krocích reakce.
Příklad 1
Nárůst byl prováděn metodou ALE . pomocí zařízení na obr. 1 a obr. 2 s následujícími hodnotami parametrů: Rychlost rotace: 2 ot/s; materiál podložky: Corning Glass 7 059: teplota podložky 320 °C, bombardování atomů zinku Zn během jedné interakce mezi povrchem a párou Zn okolo 5 . 1015 atomů/cm2, odpovídající efektivnímu tlaku páry zinku asi 10~3 torr a rovnovážné teplotě asi 290 °C pro Zn zdroje, rovnovážná teplota S zdroje 100 °C, odpovídající parnímu tlaku asi 10 ~2 torr a úplného bombardování molekul Sz asi 5. 1016 molekulami, cm2. Za deset minut provádění postupu tloušťka vrstvy byla asi 0,27 pm, za 20 a 30 minut byly tloušťky vrstvy 0,54 prn, resp. 0,80 pm.
Příklad 2
Nárůst metodou SnOz ALE na podložku z Corning Glass 7 059 byl prováděn užitím zařízení podle obr. 1 a 2 následovně:
— teplota podložky 300 °C, — celkové množství atomů Sn během jedné interakce s Sn zdrojem asi 0,,5. 1014 atomů/cm2, — zdroj kyslíku je plazmového typu s 10 až 100 m torr celkového tlaku a 40 m A plazmového proudu. Úplné bombardování O2 iontů — 7.1014 iontů/cm2 během interakce s plazmovým zdrojem, — při rychlosti otáčení 1 ot/s tento postup dává nárůst SnOz vrstvy silné až 0,06 pm ve 25 minutách, přičemž průměrný nárůst během jedné otáčky byl 0,000 04 prn.
Příklad 3
Nárůst- GaP vrstvy metodou ALE na podložkách z Corning Glass 7 069 byl prováděn se zařízením na obr. 1 a 2 následovně:
— teplota podložky 300 °C, — celkové množství Ga atomů během interakce s Ga zdrojem 1015 atomů/cm2, — celkové množství P molekul (nejpravděpodobněji P4) bombardujících povrch během interakce s fosforem je okolo 5.1015 atomů/cm2, — vrstva silná 0,25 um vyrostla při výše uvedených parametrech za 25 -minut při rychlosti otáčení 1 ot/s. Průměrná rychlost nárůstu' byla 0,000 17 pm během každého cyklu.
Příklad 4
Nárůst vrstvy ze ZnS metodou ALE byl prováděn -s použitím zařízení na -obr. 7 s následujícími parametry -systému:
— podložka Corning Glass 7 059, — teplota podložky 470 °C, — teplota zdrojů Zn 390 °C, — teplota zdroje S 120 cc, — čas interakce zdroje Zn — 6 vteřin, — únikový čas páry Zn — 2 vteřiny, — čas interakce zdroje S 2 vteřiny, — únikový čas páry S2 6 vteřin.
Nárůst vytvořený při maximální rychlosti, umožňující ještě -přesné měření tloušťky tak odpovídající plné pokrytí při každém reakčním kroku. Při 140 imin. doby trvání postupu -byla vrstva silná 0,12 pm.
Z pokusů ;se -samořízenou -metodou ALE vyplynula ta -skutečnost, že teoretická rychlost nárůstu nemůže být zvyšována s -rostoucím časem -nebo tlakem interakce při -každém kroku reakce, -asymptoticky přibližována.
Selektivní leptání vrstev ZnS -vytvořených metodami ALE bylo prováděno- leptadlem obsahujícím 60 dílů H3PO1, 5 -dílů HNO3 a jeden díl HF při pokojové teplotě. Rychlost leptání bylo- od 10 pm/s do 150 pm/s ve 'směrní povrchu u vrstev o tloušťkách O,lpim až 0,7 pm, zatímco ve směru kolmém -na povrchovou rovinu nebyl zaznamenán. Leptání vrstev SnCú vytvořených metodou ALE by bylo možné provádět pouze elektronickými metodami.
Claims (3)
1, Zfeob vytváření tenkých vrstev sloučenin z prvků této sloučeniny, jako ze zinku a séry, z cínu( a kyslíku, galia a fosforu, kadmia, a selenu, postupnými ceakčními kroky s povrchem substrátu, vyznačující se tím, že se následně působí na povrch substrátu' vždy atomy jediného prvku v parní fázi, přičemž tlak reakční péry a doba . působení jsou upraveny tak, aby počet atomů jediného působícího prvku zasahující povrch byl větší než počet atomů iv horní ato mové vrstvě povrchu a povrch , se udržuje na teplotě, při níž dochází k povrchové reakci a která současně zabraňuje kondenzaci reakční páry na povrchu.
2. Způsob podle bodu 1, vyznačující se tím, že reakční pára je tvořena sloučeninou působícího prvku.
3. Způsob podle bodu 1, vyznačující se tím, že reakční pára je tvořena působícím prvkem samotným.
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Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CS758087A CS249502B2 (en) | 1974-11-29 | 1975-11-28 | Method of compounds' thin layers formation |
Country Status (26)
Country | Link |
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US (1) | US4058430A (cs) |
JP (1) | JPS5735158B2 (cs) |
AT (2) | AT381122B (cs) |
AU (1) | AU505960B2 (cs) |
BE (1) | BE835906A (cs) |
BR (1) | BR7507724A (cs) |
CA (1) | CA1066174A (cs) |
CH (1) | CH618469A5 (cs) |
CS (1) | CS249502B2 (cs) |
DD (1) | DD122479A5 (cs) |
DE (1) | DE2553048C3 (cs) |
DK (1) | DK152060C (cs) |
FI (1) | FI52359C (cs) |
FR (1) | FR2292517A1 (cs) |
GB (1) | GB1495987A (cs) |
HK (1) | HK64880A (cs) |
HU (1) | HU174175B (cs) |
IL (1) | IL48478A (cs) |
IN (1) | IN143912B (cs) |
IT (1) | IT1049804B (cs) |
NL (1) | NL173824C (cs) |
NO (1) | NO143634C (cs) |
PL (1) | PL118412B1 (cs) |
SE (2) | SE393967B (cs) |
SU (1) | SU810085A3 (cs) |
ZA (1) | ZA757128B (cs) |
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1974
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1975
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- 1975-11-14 AT AT0868675A patent/AT381122B/de not_active IP Right Cessation
- 1975-11-14 IL IL7548478A patent/IL48478A/xx unknown
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- 1975-11-17 GB GB47212/75A patent/GB1495987A/en not_active Expired
- 1975-11-21 BR BR7507724*A patent/BR7507724A/pt unknown
- 1975-11-21 NO NO75753921A patent/NO143634C/no unknown
- 1975-11-24 CH CH1517475A patent/CH618469A5/de not_active IP Right Cessation
- 1975-11-24 IN IN2234/CAL/75A patent/IN143912B/en unknown
- 1975-11-25 US US05/635,233 patent/US4058430A/en not_active Expired - Lifetime
- 1975-11-25 BE BE162146A patent/BE835906A/xx not_active IP Right Cessation
- 1975-11-25 CA CA240,388A patent/CA1066174A/en not_active Expired
- 1975-11-26 IT IT7529660A patent/IT1049804B/it active
- 1975-11-26 DE DE2553048A patent/DE2553048C3/de not_active Expired
- 1975-11-27 SE SE7513336A patent/SE401986B/xx not_active IP Right Cessation
- 1975-11-27 DD DD189734A patent/DD122479A5/xx unknown
- 1975-11-28 FR FR7536480A patent/FR2292517A1/fr active Granted
- 1975-11-28 CS CS758087A patent/CS249502B2/cs unknown
- 1975-11-28 JP JP14168175A patent/JPS5735158B2/ja not_active Expired
- 1975-11-28 DK DK539875A patent/DK152060C/da not_active IP Right Cessation
- 1975-11-28 SU SU752193253A patent/SU810085A3/ru active
- 1975-11-28 HU HU75IU282A patent/HU174175B/hu unknown
- 1975-11-29 PL PL1975185107A patent/PL118412B1/pl unknown
-
1980
- 1980-11-13 HK HK648/80A patent/HK64880A/xx unknown
-
1985
- 1985-11-14 AT AT0868675A patent/ATA868675A/de unknown
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