TW202223121A - 沉積方法 - Google Patents
沉積方法 Download PDFInfo
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- TW202223121A TW202223121A TW110132481A TW110132481A TW202223121A TW 202223121 A TW202223121 A TW 202223121A TW 110132481 A TW110132481 A TW 110132481A TW 110132481 A TW110132481 A TW 110132481A TW 202223121 A TW202223121 A TW 202223121A
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- aluminum nitride
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- 238000000151 deposition Methods 0.000 title claims abstract description 39
- 239000000654 additive Substances 0.000 claims abstract description 92
- 230000000996 additive effect Effects 0.000 claims abstract description 92
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 70
- 238000000034 method Methods 0.000 claims abstract description 44
- 239000000758 substrate Substances 0.000 claims abstract description 27
- 239000011261 inert gas Substances 0.000 claims abstract description 13
- 239000002574 poison Substances 0.000 claims abstract description 13
- 231100000614 poison Toxicity 0.000 claims abstract description 13
- 239000011651 chromium Substances 0.000 claims abstract description 10
- 239000011777 magnesium Substances 0.000 claims abstract description 10
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 10
- 239000010936 titanium Substances 0.000 claims abstract description 10
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000005546 reactive sputtering Methods 0.000 claims abstract description 8
- 239000004065 semiconductor Substances 0.000 claims abstract description 8
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 8
- 229910001873 dinitrogen Inorganic materials 0.000 claims abstract description 7
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 6
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 6
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 5
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 5
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 59
- 239000007789 gas Substances 0.000 claims description 58
- 229910052751 metal Inorganic materials 0.000 claims description 40
- 239000002184 metal Substances 0.000 claims description 40
- 239000000203 mixture Substances 0.000 claims description 37
- 229910052757 nitrogen Inorganic materials 0.000 claims description 32
- 238000004544 sputter deposition Methods 0.000 claims description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 13
- 229910052710 silicon Inorganic materials 0.000 claims description 13
- 239000010703 silicon Substances 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 230000008021 deposition Effects 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052743 krypton Inorganic materials 0.000 claims description 3
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 229910052724 xenon Inorganic materials 0.000 claims description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000005530 etching Methods 0.000 claims description 2
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 abstract description 4
- 229910017083 AlN Inorganic materials 0.000 abstract 3
- 239000008246 gaseous mixture Substances 0.000 abstract 3
- 239000010408 film Substances 0.000 description 72
- 230000007547 defect Effects 0.000 description 29
- 231100000572 poisoning Toxicity 0.000 description 23
- 230000000607 poisoning effect Effects 0.000 description 23
- 238000001878 scanning electron micrograph Methods 0.000 description 10
- 230000007704 transition Effects 0.000 description 7
- 229910052756 noble gas Inorganic materials 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000001808 coupling effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- KFZUDNZQQCWGKF-UHFFFAOYSA-M sodium;4-methylbenzenesulfinate Chemical compound [Na+].CC1=CC=C(S([O-])=O)C=C1 KFZUDNZQQCWGKF-UHFFFAOYSA-M 0.000 description 2
- 241001124569 Lycaenidae Species 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- LUKDNTKUBVKBMZ-UHFFFAOYSA-N aluminum scandium Chemical compound [Al].[Sc] LUKDNTKUBVKBMZ-UHFFFAOYSA-N 0.000 description 1
- RFEISCHXNDRNLV-UHFFFAOYSA-N aluminum yttrium Chemical compound [Al].[Y] RFEISCHXNDRNLV-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010849 ion bombardment Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000006855 networking Effects 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 229910002058 ternary alloy Inorganic materials 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
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Abstract
根據本發明,提供一種自一靶濺射沉積含有一添加劑元素之一含添加劑氮化鋁膜之方法,該添加劑元素選自:鈧(Sc)、釔(Y)、鈦(Ti)、鉻(Cr)、鎂(Mg)及鉿(Hf),該方法包括以下步驟:
在一腔室中提供其上具有一金屬層之一半導體基板;及
藉由該靶之脈衝DC反應性濺射將該含添加劑氮化鋁膜沉積至該金屬層上;
其中沉積該含添加劑氮化鋁膜之該步驟包括依以sccm為單位之一流速將包括氮氣及一惰性氣體之一氣體混合物引入至該腔室中,其中以sccm為單位之該氣體混合物之該流速包括以sccm為單位之一氮氣流速,且其中以sccm為單位之該氮氣流速小於或等於以sccm為單位之該氣體混合物之該流速之約50%,且亦足以使該靶完全中毒。
Description
本發明係關於一種濺射沉積一含添加劑氮化鋁膜之方法。特定言之,本發明係關於自一靶將含有一添加劑元素之一含添加劑氮化鋁膜濺射沉積至一基板之一金屬層上,該添加劑元素選自:鈧、釔、鈦、鉻、鎂及鉿。
體聲波(BAW)裝置用於手機及其他無線應用中,以允許接收及/或發射一特定射頻(RF)。BAW裝置利用壓電效應來自一電輸入產生一機械共振;或自一機械共振產生一電輸出。
已知BAW裝置通常包括在矽(Si)基板上沉積並圖案化之若干層。例如,一BAW裝置可包括兩個金屬電極,其層之間具有一壓電介電層(例如AlN或AlScN)。
隨著無線應用已朝向使用更高頻帶發展,壓電層已變得更薄。期望改良(即,增加)在更高頻帶下使用所需之較薄之膜之壓電耦合性質。含添加劑氮化鋁(例如Al
100‑xSc
xN)薄膜係展現出良好之壓電耦合之有前景的候選者。
為了改良此等材料之耦合性質,期望增加添加劑元素之摻雜度(例如增加Sc含量)。例如,當Al
100‑xSc
xN在4G應用中使用時,Sc含量通常係約6至12 at.%(即,x通常係約6至12)。然而,預期5G及未來幾代網路應用將需要甚至更高濃度之添加劑元素(例如,x=15至20)。因此,期望開發一種用於沉積含添加劑氮化鋁膜(諸如Al
100‑xSc
xN)之一方法,該膜具有一更高含量之添加劑元素(例如>12 at.%,且較佳地≥15 at.%)。
含添加劑氮化鋁亦可應用於壓電微機械系統(壓電MEMS)裝置,諸如麥克風、矽時序裝置、能量採集器及壓電微機械超音換能器(pMUT)。預期此等應用可受益於膜中之一高添加劑元素(例如Sc)含量,以提供改良之性質(諸如一改良之壓電回應)。
物理氣相沉積(PVD)可用於將含添加劑氮化鋁膜濺射沉積至一基板上。然而,此等已知方法通常導致所得膜中之不需要之微晶缺陷之形成。例如,當藉由SEM觀察時,此等微晶缺陷表現為三角形之異常或未對準晶粒。此等缺陷在較高濃度之添加劑元素之情況下變得更普遍。此等微晶缺陷充當具有較差之壓電性質之壓電「死區」,此整體上減小膜之壓電耦合能力。期望開發一種沉積一含添加劑氮化鋁膜之改良方法,其特定言之在該膜包括一高添加劑元素濃度(例如約x >12,且較佳地≥15)之情況下在該膜中具有一降低之缺陷位準。
當在矽基板上沉積含添加劑氮化鋁膜(例如Al
100‑xSc
xN膜)時,預處理矽表面可有助於減小缺陷密度(如使用膜之SEM影像及分析判定)。合適之預處理可包含在本體沉積之前之一預蝕刻、一預清潔或沉積一晶種層。圖1展示使用一已知之方法(a)在無沉積步驟之前之一預蝕刻,及(b)在具有沉積步驟之前之一預蝕刻之情況下在矽基板上沉積之Al
100-xSc
xN膜。圖1中之白色方塊對應於一10 μm×10 μm區域,其可用於判定一100 μm
2區域中之缺陷密度。圖2展示使用一已知之方法:(a)在一無晶種層,(b)在具有一壓縮AlScN晶種層,及(c)在具有一AlN晶種層之情況下在矽基板上沉積之Al
100-xSc
xN膜。圖2(a)至(c)展示當在矽基板上沉積一AlScN膜時,使用一晶種層可如何改良(即,減小)缺陷密度。然而,未知此預處理在減小金屬表面(諸如電極結構)上之缺陷密度方面有效。期望開發一種方法以減小沉積在金屬表面(例如,包括一金屬塗層之矽基板)上之含添加劑氮化鋁膜之缺陷密度。
本發明在其實施例之至少一些中尋求解決上文描述之問題、期望及需求之至少一些。特定言之,在至少一些實施例中,本發明尋求減小含添加劑氮化鋁膜中之缺陷之普遍性(即,減小缺陷密度)。特定言之,為了減小含有一高濃度之添加劑元素(例如約>12%,且較佳地≥15 at.%)之含添加劑氮化鋁膜中之缺陷密度。
根據本發明之一第一態樣,提供一種自一靶濺射沉積含有一添加劑元素之一含添加劑氮化鋁膜之方法,該添加劑元素選自:鈧(Sc)、釔(Y)、鈦(Ti)、鉻(Cr)、鎂(Mg)及鉿(Hf),該方法包括以下步驟:
在一腔室中提供其上具有一金屬層之一半導體基板;及
藉由該靶之脈衝DC反應性濺射將該含添加劑氮化鋁膜沉積至該金屬層上;
其中沉積該含添加劑氮化鋁膜之步驟包括按以sccm為單位之一流速將包括氮氣及一惰性氣體之一氣體混合物引入至該腔室中,其中以sccm為單位之該氣體混合物之該流速包括以sccm為單位之一氮氣流速,且其中以sccm為單位之該氮氣流速小於或等於以sccm為單位之該氣體混合物之該流速之約50%,且亦足以使該靶完全中毒。
使用以sccm為單位之小於或等於以sccm為單位之該氣體混合物之該流速之約50%,且亦足以使該靶完全中毒(即,以一中毒臨限值百分比或高於一中毒臨限值百分比之一比例存在)之一氮氣流速減小沉積在該基板之該金屬層上之含添加劑氮化鋁膜之缺陷密度。此可導致展現改良之壓電性質(諸如改良之壓電耦合)之改良之膜。
該中毒臨限值百分比係依照以sccm為單位之該氣體混合物之該流速之一百分比之以sccm為單位之該氮氣流速足以使該靶完全中毒所依之最小百分比。該中毒臨限值百分比對應於該脈衝DC反應性濺射程序在一「金屬濺射模式」中操作與一「中毒濺射模式」中操作之間之轉變之一轉變點。
使用包括呈足以使該靶完全中毒(即,處於或高於該中毒臨限值百分比)之一比例之一氮氣流量(以sccm為單位)之該氣體混合物之一流速(以sccm為單位)使該脈衝DC反應性濺射步驟在該中毒濺射模式(亦稱為一「化合物模式」或「反應性模式」)中操作。不希望受到任何理論或猜測之約束,據信當氮氣之比例處於或高於該中毒臨限值百分比時,該氮氣流量在該靶之表面上形成氮化物層,以使該靶完全中毒。足以使該靶完全中毒之氮氣之百分比(即,該中毒臨限值百分比)通常取決於程序參數。足以使該靶完全中毒之氮氣之百分比(即,該中毒臨限值百分比)可藉由量測依據該氣體混合物之總流速(以sccm為單位)中之氮氣百分比(以sccm為單位)而變化之靶電壓(在一恆定功率下)來判定,即該靶電壓中之一階躍變化(在恆定功率下)指示該中毒臨限值百分比。例如,當沉積Al
100-xSc
xN(針對一固定功率)時,高於該中毒臨限值百分比之該靶電壓之量值比低於該中毒臨限值百分比之該靶電壓低。在高於該中毒臨限值百分比之情況下,該靶電壓通常保持基本上恆定。有鑑於此,及有鑑於下文提供之進一步解釋,對於熟練之讀者將顯而易見的是,該中毒臨限值百分比,以及因此足以使該靶完全中毒之最小氮氣流速可在沒有過度負擔之情況下容易地判定。
該添加劑元素可係鈧(Sc)或釔(Y)。較佳地,該添加劑元素係鈧(Sc)。該含添加劑氮化鋁膜可係一三元合金。
該含添加劑氮化鋁可對應於Al
100-xX
xN,其中X係添加劑元素。例如,含添加劑氮化鋁可係Al
100-xSc
xN或Al
100-xY
xN。應理解,當組合物以Al
100-xX
xN形式表達時,值「100-x」及「x」被表達為膜之金屬含量之原子百分比,且作為一百分比之「x」在化學計量化學術語中可等同於「0.0x」。該添加劑元素(依照鋁之一原子百分比及該含添加劑氮化鋁膜之添加劑元素含量)可以在0.5 at.%至40 at.%之範圍內,視情況地在8 at.%至40 at.%之範圍內,視情況地在10 at.%至40 at.%之範圍內,視情況地在12 at.%至35 at.%之範圍內,視情況地在15 at.%至30 at.%之範圍內,或視情況地在20 at.%至25 at.%之範圍內之一量存在。亦即,x可在0.5至40之範圍內,視情況地在8至40之範圍內,視情況地在10至40之範圍內,視情況地在12至35之範圍內,視情況地在15至30之範圍內,或視情況地在20至25之範圍內。該添加劑元素可以>8 at.%,>10 at.%,>12 at.%,>15 at.%,>20 at.%,>25 at.%或約30 at.%之一量存在。該添加劑元素可以小於或等於40 at.%之一量存在。該添加劑元素可以上文提供之上限與下限之任何組合存在。本發明之方法可對於沉積具有一高濃度之添加劑元素(例如,高於12 at.%,較佳地≥15 at.%)之含添加劑氮化鋁膜,同時改良或維持缺陷密度、結晶度及紋理之可接受位準特別有效。在此等濃度下,化合物可被視為一合金而非一經摻雜AlN。可使用能量色散X射線(EDAX)分析來判定含添加劑氮化鋁膜之元素組成,包含膜中存在之添加劑元素之量。例如,本發明可用於沉積具有小於約30個缺陷/100 μm
2,較佳地小於約20個缺陷/100 μm
2之一缺陷密度(如使用SEM影像之分析判定)之一含添加劑氮化鋁膜,其中該添加劑元素(依照膜之金屬含量之一百分比)以>12 at.%,視情況地≥15 at.%,視情況地≥20 at.%,視情況地≥25 at.%,或視情況地約30 at.%之一量存在。
以sccm為單位之氮氣流速可小於以sccm為單位之該氣體混合物之流速之約45%,視情況地小於約40%,視情況地小於約35%,且視情況地約30%。
以sccm為單位之該氮氣流速可大於該中毒臨限值百分比,且大於以sccm為單位之該氣體混合物之流速之約15%,視情況地≥20%,視情況地≥25%,或視情況地≥30%。
在沉積該含添加劑氮化鋁膜之步驟期間使用之以sccm為單位之該氮氣流速可在25至250 sccm、視情況地30至200 sccm、視情況地40至150 sccm、視情況地45至100 sccm之範圍內或視情況地係約50 sccm。
以sccm為單位之該氣體混合物之流速進一步包括以sccm為單位之一惰性氣體流速。在沉積該含添加劑氮化鋁膜之步驟期間使用之以sccm為單位之該惰性氣體流速可在25至250 sccm、視情況地30至200 sccm、視情況地40至150 sccm、視情況地45至100 sccm或視情況地50至90 sccm之範圍內。
該氣體混合物可由或基本上由氮氣及惰性氣體組成。流速可由或基本上由氮氣流量及惰性氣體流量組成。
該惰性氣體可係氬氣、氪氣、氙氣或其等之一混合物。較佳地,該惰性氣體由或基本上由氬氣組成。
在沉積該含添加劑氮化鋁膜之步驟期間,腔室可具有在1至10 mTorr,視情況地約2至6 mTorr之範圍內,或視情況地約4 mTorr之一壓力。
該含添加劑氮化鋁膜可具有約2 μm或更小、視情況地約1.5 μm或更小、視情況地約1 μm或更小或視情況地約0.5 μm或更小之一厚度。
該含添加劑氮化鋁膜可具有約0.2 μm或更大、視情況地約0.3 μm或更大或視情況地約0.5 μm或更大之一厚度。
沉積該含添加劑氮化鋁膜之步驟可包括向該基板施加一電偏壓功率。該電偏壓功率可係一RF電偏壓功率。
在沉積該含添加劑氮化鋁膜之步驟期間,該基板可具有約150至300℃,視情況地係約200℃之一溫度。
該半導體基板可係矽晶圓。
該金屬層可選自:鎢(W)、鉬(Mo)、鋁(Al)、鉑(Pt)及釕(Ru)。該金屬層可係一電極結構。該金屬層可係一鎢底層。
該方法可視情況地進一步包括在沉積該含添加劑氮化鋁膜之步驟之前蝕刻該金屬層之一步驟。
該方法可視情況地進一步包括在沉積該含添加劑氮化鋁膜之步驟之前將一晶種層沉積至該金屬層上,使得將該含添加劑氮化鋁膜沉積至該晶種層上之一步驟。僅舉例而言,該晶種層可係氮化鋁(AlN)晶種層或一含添加劑氮化鋁晶種層(諸如AlScN)。
在沉積該含添加劑氮化鋁膜之步驟之前預處理該金屬層可進一步有助於減小缺陷密度,同時有助於保持足夠之膜紋理及結晶度。
根據本發明之一第二態樣,在使用根據第一態樣之方法生產之一半導體基板之一金屬層上存在一含添加劑氮化鋁膜。
雖然本發明已在上文中描述,然其擴展至上文或下文描述、附圖及技術方案中所陳述之特徵之任何組合。例如,關於本發明之一個態樣揭示之任何特徵可與本發明之任何其他態樣之任何特徵相結合。
為避免疑問,當提及諸如「包括(comprsing、comprise及comprises)」之「開放式」術語時,本發明被理解為亦係關於其中開放式術語被諸如「由…組成」及「基本上由…組成」之「封閉式」術語替換之實施例。
發明者已發現一種用於將一含添加劑氮化鋁膜(例如Al
100‑xX
xN)濺射沉積至一基板之一金屬層上之一有利程序。該方法可有助於減小含添加劑氮化鋁膜中之微晶缺陷。當添加劑元素(X)以高濃度(例如,x>12,較佳地x≥15)存在時,本發明之方法具有特定應用。含添加劑氮化鋁膜含有一添加劑元素。添加劑元素可係鈧(Sc)、釔(Y)、鈦(Ti)、鉻(Cr)、鎂(Mg)或鉿(Hf)。下文呈現之結果與氮化鋁鈧(Al
100‑xSc
xN)膜有關。然而,該方法可容易地應用至上文提及之任何添加劑元素,即Sc、Y、Ti、Cr、Mg及Hf。例如,該方法亦適用於沉積氮化鋁釔(Al
100‑xY
xN)膜。
申請人之歐洲專利申請EP2871259、EP3153603中描述關於可在本發明中使用或容易地經調適以在本發明中使用之設備之一般細節,其全部內容以引用之方式併入本文中。
使用一SPTS Sigma
fxP AlN PVD工具(其可購自英國南威爾士紐波特之SPTS技術有限公司)來沉積以下實例之含添加劑氮化鋁膜。該設備包括安置在一腔室中之一基板支撐件。在一沉積程序中,其上具有一金屬層之一半導體基板經定位在基板支撐件上。例如,基板可係其上具有一金屬塗層之矽晶圓。金屬層具有一金屬表面。金屬層可係一電極結構,例如一壓電裝置(諸如一體聲波(BAW)裝置)之一電極。僅舉例而言,金屬層可由鎢(W)、鉬(Mo)、鋁(Al)、鉑(Pt)或釕(Ru)製成。
該設備進一步包括安置在腔室內之一靶。靶係由鋁及添加劑元素形成之一複合靶。多個靶之使用係可能的,然在經濟上可能不太有吸引力。脈衝DC濺射包括在沉積程序期間向靶(陰極)施加DC功率之脈衝。
該方法包含以一流速將一氣體混合物引入至腔室中,且隨後使用脈衝DC反應性濺射來將材料自靶反應性地濺射沉積至金屬層之金屬表面上。
氣體混合物包括氮氣(N
2)及一惰性氣體。惰性氣體可係氬氣、氪氣或氙氣或其等之任何混合物。通常,惰性氣體係氬氣。惰性氣體充當一共濺射非反應性物種,且可改良電漿穩定性。
氣體混合物中N
2氣體之比例可影響沉積程序。不希望受到任何理論或猜測之約束,據信在一非常低之N
2氣體濃度下(或在無N
2氣體之情況下),脈衝DC濺射程序將在一「金屬模式」中運行。在金屬模式中,靶材料將被濺射,與N
2氣體反應很少或沒有反應。隨著N
2氣體之比例增加,一些氮被併入靶之表面,且靶開始中毒。當氣體混合物中之氮之比例足夠高時,氮化物層將形成在靶上,靶將完全中毒,且濺射程序將在一「中毒模式」(亦稱為一「化合物模式」或「反應性模式」)中操作。此在靶之表面完全轉化為氮化物,且靶完全中毒時發生。
「金屬模式」與「中毒模式」之間之轉變在一「轉變點」(或氮氣之「中毒臨限值百分比」)處發生,此對應於氣體混合物中之氮氣比例足夠高以使靶完全中毒(即,導致濺射沉積在「中毒模式」中操作)之點。藉由量測依據氮氣百分比而變化之靶電壓(在恆定靶功率下),可判定特定一組程序條件之中毒臨限值百分比,如圖7中所繪示(如下面更詳細討論)。
所屬領域中普遍接受之看法係在遠離轉變點之一「中毒模式」中操作脈衝DC反應性濺射程序(即,在反應性氣體混合物中使用一非常高百分比之N
2氣體)。例如,在一個已知程序中,N
2氣體對Ar氣體之流速(以sccm為單位)比係50:10 (即,83% N
2氣體)。
然而,與所屬領域中此接受之看法相反,本發明者已意外地發現,使用氣體混合物之總流速之≤50%之一N
2流量(同時仍在「中毒模式」中操作)可減小藉由脈衝DC反應性濺射沉積至一金屬表面上之一含添加劑氮化鋁膜之缺陷密度。此等效應在其中缺陷通常更為普遍之高濃度添加劑元素(例如,>12 at.%,較佳地≥15 at.%)之情況下特別有益。
在一個實例中,藉由脈衝DC反應性濺射將Al
100-xSc
xN膜(x=30)沉積至一紋理化鎢(W)底層上。氣體混合物包括N
2氣體與氬氣。氣體混合物中N
2氣體之比例發生變化,同時所有其他程序參數(諸如腔室壓力及靶功率)保持恆定。本實例中使用之例示性程序參數在表1中展示。
表1
Al 100‑xSc xN | |
脈衝DC功率(kW) | 6 |
脈衝頻率(kHz) | 100 |
脈衝寬度(μs) | 4 |
Ar流速(sccm) | 0至90 |
N 2流速(sccm) | 50 |
壓板RF偏壓功率(W) | 針對所需應力調整 |
壓板溫度(℃) | 200 |
圖3、4、5及6展示在氣體混合物中之N
2氣體之百分比分別為100%、83%、67%及36%之情況下沉積之Al
70Sc
30N膜之SEM影像。結果在下面之表2中總結,且如圖7中圖形展示。
表2
總流量之N 2% | 每100 μm 2之缺陷數目 | 002 FWHM (°) |
100 | >>100 | 1.58 |
83 | >50 | 1.62 |
67 | <30 | 1.57 |
36 | <20 | 1.63 |
圖7包含依據總氣體流量中N
2氣體百分比而變化之靶電壓之一標繪圖。當N
2氣體流量占總氣體流速之約25%時,轉變點(即,中毒臨限值百分比) 72發生。由於靶電壓(在恆定靶功率下)之一陡峭變化,可判定轉變點72。在此實例中,當N
2氣體流量占總氣體流量之比例小於約25%時,設備在一「金屬模式」70中操作。當N
2氣體流量占總氣體流量之比例大於約25%時,靶完全中毒,且設備在一「中毒模式」74中操作。
改變N
2氣體之量(依照總氣體流量之一百分比,以sccm為單位)未顯著影響膜紋理。所有Al
100‑xSc
xN膜均展現良好之晶體定向。然而,出乎意料的是,缺陷密度(即,如藉由分析膜之SEM影像判定之每100 μm
2之缺陷數目)隨著N
2氣體量(依照總氣體流量之一百分比,以sccm為單位)減小而降低。
不希望受到任何理論或猜測之約束,據信在較低N
2氣體比例下,由於惰性氣體(即,此實例中之Ar氣體)之相對較高比例,存在增加之膜轟擊。惰性氣體充當一非反應性共濺射元素,且相對較高比例之惰性氣體具有增加基板表面上之離子轟擊之量之效應。再次,在不受任何理論或猜測約束之情況下,據信增加之膜轟擊對膜成核可能至關重要,且可有助於提供用於具有良好定向之晶體生長之模板。仍在不受任何理論或猜測之約束之情況下,另外據信在膜生長期間,增加之膜轟擊可將足夠之能量轉移至添加劑元素(例如,此實例中相對較重之Sc原子)以克服能障,並將添加劑元素移動至晶體結構內之一更有利位置。因此,作為微晶缺陷被觀察到之未對準晶粒之數目減小。
再次,在不受任何理論或猜測約束之情況下,亦據信一富氮環境促進沉積膜內不同相之形成,此與塊體材料相比具有不同之生長機制。此等不同相表現為未對準之晶粒。然而,減小氣體混合物中氮氣之相對比例使平衡遠離形成此等不同相移動。
因此,本發明之方法可用於沉積具有一高添加劑元素含量之高品質含添加劑氮化鋁膜,同時將缺陷密度減小至可接受位準。由於改良之缺陷密度,改良膜之壓電性質。使用本方法生產之含添加劑氮化鋁膜非常適合於用作壓電裝置中(諸如體聲波(BAW)裝置中)之一壓電層。
70:金屬模式
72:轉變點
74:中毒模式
現在將參考附圖,僅舉例而言描述本發明之實施例,其中:
圖1係(a)在無一預蝕刻;及(b)在具有一預蝕刻之情況下沉積在矽基板上之一Al
100-xSc
xN膜之一SEM影像;
圖2係(a)在無一晶種層;(b)在具有一壓縮AlScN晶種層;及(c)在具有一AlN晶種層之情況下在矽基板上沉積之一Al
100-xSc
xN膜之一SEM影像;
圖3係在氣體混合物中之氮氣之百分比係100%之情況下沉積之一Al
100‑xSc
xN膜之一SEM影像;
圖4係在氣體混合物中之氮氣之百分比係83%之情況下沉積之一Al
100‑xSc
xN膜之一SEM影像;
圖5係在氣體混合物中之氮氣之百分比係67%之情況下沉積之一Al
100‑xSc
xN膜之一SEM影像;
圖6係在氣體混合物中之氮氣之百分比係36%之情況下沉積之一Al
100‑xSc
xN膜之一SEM影像;及
圖7展示依據氣體混合物中之氮氣百分比而變化之靶電壓(在恆定功率下)及缺陷密度(每100 μm
2)之標繪圖。
70:金屬模式
72:轉變點
74:中毒模式
Claims (15)
- 一種自一靶濺射沉積含有一添加劑元素之一含添加劑氮化鋁膜之方法,該添加劑元素選自:鈧(Sc)、釔(Y)、鈦(Ti)、鉻(Cr)、鎂(Mg)及鉿(Hf),該方法包括以下步驟: 在一腔室中提供其上具有一金屬層之一半導體基板;及 藉由該靶之脈衝DC反應性濺射將該含添加劑氮化鋁膜沉積至該金屬層上; 其中沉積該含添加劑氮化鋁膜之該步驟包括依以sccm為單位之一流速將包括氮氣及一惰性氣體之一氣體混合物引入至該腔室中,其中以sccm為單位之該氣體混合物之該流速包括以sccm為單位之一氮氣流速,且其中以sccm為單位之該氮氣流速小於或等於以sccm為單位之該氣體混合物之該流速之約50%,且亦足以使該靶完全中毒。
- 如請求項1之方法,其中該添加劑元素係鈧或釔,較佳地係鈧。
- 如請求項1或2之方法,其中該添加劑元素,依照鋁之一原子百分比及該含添加劑氮化鋁膜之添加劑元素含量,以在0.5 at.%至40 at.%之範圍內,視情況地在8 at.%至40 at.%之範圍內,視情況地在10 at.%至40 at.%之範圍內,視情況地在12 at.%至35 at.%之範圍內,視情況地在15 at.%至30 at.%之範圍內,或視情況地在20 at.%至25 at.%之範圍內之一量存在。
- 如請求項1或2之方法,其中以sccm為單位之該氮氣流速小於以sccm為單位之該氣體混合物之該流速之約45%,視情況地小於約40%,視情況地小於約35%,及視情況地約30%。
- 如請求項1或2之方法,其中以sccm為單位之該氮氣流速大於以sccm為單位之該氣體混合物之該流速之約15%,視情況地≥20%,視情況地≥25%,或視情況地≥30%。
- 如請求項1或2之方法,其中在沉積該含添加劑氮化鋁膜之該步驟期間使用之以sccm為單位之該氮氣流速在25至250 sccm、視情況地30至200 sccm、視情況地40至150 sccm、視情況地45至100 sccm之範圍內或視情況地為約50 sccm。
- 如請求項1或2之方法,其中該惰性氣體係氬氣、氪氣、氙氣或其等之一混合物。
- 如請求項1或2之方法,其中該含添加劑氮化鋁膜具有約2 μm或更小、視情況地約1.5 μm或更小、視情況地約1 μm或更小或視情況地約0.5 μm或更小之一厚度。
- 如請求項1或2之方法,其中該含添加劑氮化鋁膜具有約0.2 μm或更大、視情況地約0.3 μm或更大或視情況地約0.5 μm或更大之一厚度。
- 如請求項1或2之方法,其中沉積該含添加劑氮化鋁膜之該步驟包括向該基板施加一電偏壓功率。
- 如請求項1或2之方法,其中該半導體基板係矽晶圓。
- 如請求項1或2之方法,其中該金屬層選自:鎢(W)、鉬(Mo)、鋁(Al)、鉑(Pt)及釕(Ru)。
- 如請求項1或2之方法,其進一步包括在沉積該含添加劑氮化鋁膜之該步驟之前蝕刻該金屬層之一步驟。
- 如請求項1或2之方法,其進一步包括在沉積該含添加劑氮化鋁膜之該步驟之前將一晶種層沉積至該金屬層上,使得將該含添加劑氮化鋁膜沉積至該晶種層上之步驟。
- 一種使用如請求項1至14中任一項之方法生產之一半導體基板之一金屬層上之含添加劑氮化鋁膜。
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