TW201831699A - 配線構造及其製造方法、濺鍍靶材、與氧化防止方法 - Google Patents
配線構造及其製造方法、濺鍍靶材、與氧化防止方法 Download PDFInfo
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- TW201831699A TW201831699A TW107103938A TW107103938A TW201831699A TW 201831699 A TW201831699 A TW 201831699A TW 107103938 A TW107103938 A TW 107103938A TW 107103938 A TW107103938 A TW 107103938A TW 201831699 A TW201831699 A TW 201831699A
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- Prior art keywords
- copper
- zirconium
- wiring
- silicon
- layer
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- 238000007254 oxidation reaction Methods 0.000 title claims description 36
- 238000005477 sputtering target Methods 0.000 title claims description 34
- 238000000034 method Methods 0.000 title claims description 31
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 230000002265 prevention Effects 0.000 title claims description 7
- 239000013077 target material Substances 0.000 title description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 75
- 239000002184 metal Substances 0.000 claims abstract description 75
- 239000010949 copper Substances 0.000 claims abstract description 67
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229910052802 copper Inorganic materials 0.000 claims abstract description 66
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 45
- 239000010703 silicon Substances 0.000 claims abstract description 44
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 43
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000000758 substrate Substances 0.000 claims abstract description 32
- 239000012535 impurity Substances 0.000 claims abstract description 20
- 230000003647 oxidation Effects 0.000 claims description 35
- 238000010438 heat treatment Methods 0.000 claims description 16
- 230000001590 oxidative effect Effects 0.000 claims description 13
- 239000010410 layer Substances 0.000 description 161
- 229910000676 Si alloy Inorganic materials 0.000 description 31
- DVFDQGVLIIHFAJ-UHFFFAOYSA-N [Si][Zr][Cu] Chemical compound [Si][Zr][Cu] DVFDQGVLIIHFAJ-UHFFFAOYSA-N 0.000 description 30
- 238000000137 annealing Methods 0.000 description 23
- 238000011282 treatment Methods 0.000 description 17
- 238000005259 measurement Methods 0.000 description 14
- 229910045601 alloy Inorganic materials 0.000 description 12
- 239000000956 alloy Substances 0.000 description 12
- 238000004544 sputter deposition Methods 0.000 description 12
- 239000004020 conductor Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 239000010409 thin film Substances 0.000 description 11
- 229910000881 Cu alloy Inorganic materials 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000010408 film Substances 0.000 description 9
- 229910052581 Si3N4 Inorganic materials 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 7
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 7
- 239000011521 glass Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000012811 non-conductive material Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 229910001093 Zr alloy Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- XTYUEDCPRIMJNG-UHFFFAOYSA-N copper zirconium Chemical compound [Cu].[Zr] XTYUEDCPRIMJNG-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005401 electroluminescence Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011573 trace mineral Substances 0.000 description 2
- 235000013619 trace mineral Nutrition 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000010273 cold forging Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- -1 oxygen Chemical compound 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
- H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
- H01L21/28512—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table
- H01L21/2855—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table by physical means, e.g. sputtering, evaporation
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
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- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
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- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
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- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
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- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
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- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
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- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/52—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames
- H01L23/522—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body
- H01L23/532—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body characterised by the materials
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- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/01—Chemical elements
- H01L2924/01014—Silicon [Si]
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- H01L2924/0104—Zirconium [Zr]
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Abstract
本發明之配線構造(10)具備基板(11)、設置於基板(11)上之配線層(12)、及設置於配線層(12)上之金屬層(14)。配線層(12)含有銅。金屬層(14)含有鋯及矽,且其餘部分包含銅及不可避免之雜質。金屬層(14)較佳為,相對於銅、鋯及矽之莫耳數之合計,含有1莫耳%以上且33莫耳%以下之鋯,且含有1莫耳%以上且33莫耳%以下之矽。又,於金屬層(14)中,亦較佳為鋯及矽之莫耳數之合計相對於上述合計為2莫耳%以上且40莫耳%以下。
Description
本發明係關於一種配線構造及其製造方法。又,本發明係關於一種濺鍍靶材。進而,本發明係關於一種氧化防止方法。
作為液晶顯示器、電漿顯示器或有機EL(Electro-Luminescence,電致發光)等顯示裝置之觸控面板等所使用之電路基板之配線膜,大多使用鋁合金。最近,伴隨著裝置之高清化及高速化,謀求配線膜之微細化及薄膜化,而要求電阻率較鋁合金低之配線膜。因此,低電阻且高熔點之銅受到關注。然而,於使用銅之配線膜之情形時,在加熱步驟中會進行氧化而使電阻值增大,因此,需要用以防止氧化之保護層。 於專利文獻1中,作為銅合金濺鍍靶材,提出有如下銅合金濺鍍靶材,其含有合計為0.005~0.5質量%之La、Mg、Li、Si、V、Zr、Hf、Nb中之1種以上,且含有0.1~5 ppm之氧,其餘部分為銅及不可避免之雜質。 又,於專利文獻2中,作為銅配線膜之保護層形成用之靶材,提出有如下靶材,其含有20.0~40.0質量%之Ni,且含有1.0~10.0質量%之Cr、Ti、V、Al、Ta、Co、Zr、Nb、Mo中之任1種或其等之2種以上之元素,其餘部分為銅及不可避免之雜質。 先前技術文獻 專利文獻 專利文獻1:日本專利特開2002-294438號公報 專利文獻2:日本專利特開2013-133489號公報
近年來,要求耐氧化性更優異之銅配線層之保護層。對於由專利文獻1所記載之靶材形成之銅合金薄膜,並未對藉由氧化性氣氛中之熱處理而達成之銅合金薄膜之耐氧化性進行評價。又,由專利文獻2所記載之靶材形成之金屬膜雖然於在大氣環境中以150℃進行熱處理之情形時抑制銅配線之氧化,但於更加嚴酷之高溫條件下、例如300~350℃下進行熱處理之情形時,是否抑制銅配線之氧化尚且不明。 因此,本發明之課題在於,提供一種於具備含有銅之配線層之配線構造中防止該配線層之氧化的技術。 本發明人進行了努力研究,結果認為藉由在含有銅之配線層之上形成包含特定合金之金屬層,可解決上述課題。 本發明係基於上述見解而完成者,藉由提供一種配線構造而解決了上述課題,該配線構造具備基板、設置於該基板上之配線層、及設置於該配線層上之金屬層,且 上述配線層含有銅, 上述金屬層含有鋯及矽,且其餘部分包含銅及不可避免之雜質。 又,本發明提供一種配線構造之製造方法,其包括如下步驟: 於基板上設置含有銅之配線層; 於上述配線層上設置含有鋯及矽且其餘部分包含銅及不可避免之雜質的金屬層;及 對具有該等各層之積層構造進行熱處理。 進而,本發明提供一種氧化防止方法,該氧化防止方法係於具備基板、及設置於該基板上且含有銅之配線層的配線構造之製造過程中之熱處理時防止該配線層之氧化的方法,且 於上述熱處理之前,在上述配線層上形成含有鋯及矽且其餘部分包含銅及不可避免之雜質的金屬層。
以下,針對本發明,基於其較佳之實施形態,一面參照圖式一面進行說明。於圖1中示出本發明之配線構造之一實施形態。該圖所示之配線構造10用作例如電晶體或FET(Field Effect Transistor,場效應電晶體)等各種半導體裝置。配線構造10具備基板11。作為基板11,可使用例如玻璃基板等由非導電性材料所構成之基板。或者可使用在表面形成有ITO(Indium Tin Oxide,氧化銦錫)等透明導電膜之玻璃基板。 於基板11上設置有含有銅之配線層12。所謂含有銅之配線層係含有純銅或銅合金之電路之配線,一般而言,由藉由各種薄膜形成方法而形成於基板11上之薄膜層所構成。配線層12之厚度可根據配線構造10之具體用途而任意地設定,例如可設定為50 nm以上且500 nm以下。 於配線層12包含銅合金之情形時,作為該銅合金,例如可列舉含有選自錳、鎂、鉍及銦等中之1種或2種以上之元素作為合金成分的銅基合金。該等合金成分於銅合金中能夠以0.01莫耳%以上且25莫耳%以下之比率含有。於配線層12包含銅合金之情形時,該銅合金使用與構成下述金屬層14之合金為不同種類者。 亦可在配線層12與基板11之間形成用以提高該等兩者之密接性之密接層13。密接層13之材質係根據基板11之材質而使用適當者。於基板11為例如玻璃之情形時,較佳為使用鈦等作為密接層13,其厚度較佳為10 nm以上且100 nm以下。 配線層12具有作為與基板11對向之面的第1面12a。又,配線層12具有作為位於與第1面12a相反之側之面的第2面12b。第1面12a與上述密接層13相接。於第2面12b上設置有金屬層14。配線層12與金屬層14直接相接,在兩層12、14間未介置其他層。金屬層14以覆蓋配線層12之第2面12b之全域之方式形成。因此,不存在露出至配線層12之第2面12b之區域。關於金屬層14之詳細內容將於下文敍述。 於本實施形態中,配線構造10具有依序具備積層於基板11上之密接層13、配線層12及金屬層14之積層構造15。具有此種構造之配線構造10係藉由如下方法而獲得:例如使用各種薄膜形成方法等成膜密接層13、配線層12及金屬層14,而形成積層構造15。其後,有時進行配線構造10之焙燒或於配線構造10上成膜其他層等高溫下之退火處理(熱處理)。該退火處理例如係出於如下目的而進行:提高配線構造10中之基板11與配線層12之密接性,或者於製造具備配線構造10之電子裝置、具體而言製造具備配線構造10之薄膜電晶體時向配線構造10上成膜SiO2
或SiN等絕緣膜或成膜ITO等配線。該等退火處理一般於氧化性氣氛下進行。所謂氧化性氣氛係指含有O2
、O3
、H2
O、N2
O等氧化性氣體之氣氛,例如可列舉大氣下或含有0.5體積%以上且30體積%以下之上述氧化性氣體之氣氛。退火處理之溫度一般為300℃以上,尤其是350℃以上。退火處理之時間一般為15分鐘以上且120分鐘以下。於不具有金屬層14之先前之配線構造中,若於大氣下等氧化性氣氛下進行上述高溫下之退火處理,則有時構成配線層12之銅會因氧化性氣體之作用而被氧化,導致產生導電性降低等不良情況。配線層12之導電性之降低成為包含配線構造10之電子裝置之性能降低之一個原因。因此,於本發明中,為了防止配線層12之氧化,而以被覆該配線層12中之第2面12b之全域之方式設置有上述金屬層14。具備該金屬層14之本實施形態之配線構造10尤其於高溫之退火條件下效果更加顯著。 於配線構造10中,作為上述金屬層14,使用含有鋯及矽且其餘部分包含銅及不可避免之雜質的合金、即銅-鋯-矽(Cu-Zr-Si)合金(以下,將「含有鋯及矽且其餘部分包含銅及不可避免之雜質的合金」亦稱為「銅-鋯-矽合金」)。藉由將具有該合金組成之金屬層14設置於配線層12之正上方,而配線層12中所含之銅之氧化被有效地抑制,從而判明了本發明人之研究結果。該原因雖然尚不明確,但本發明人推測為如下原因。於將配線構造10如上所述般在氧化性氣氛下進行退火之情形時,於金屬層14中,鋯及矽先於銅被氧化,從而以被覆配線層12之方式形成鋯氧化物與矽氧化物之混合氧化物或鋯與矽之複合氧化物之緻密氧化物層。該緻密氧化物層終止配線層12中所含之銅之氧化之進行。因此,於金屬層14中殘存有非氧化狀態之鋯及矽之期間,非氧化狀態之鋯及矽在配線層12中所含之銅之氧化之前被氧化,因此配線層12中之銅之氧化受到抑制,從而抑制配線層12之電阻之上升。因此,配線構造10即便於在氧化性氣氛下進行退火之後,亦不易受到因退火所引起之氧化之影響。 就使上述氧化抑制之效果更加顯著之觀點而言,構成金屬層14之銅-鋯-矽合金較佳為相對於銅、鋯及矽之莫耳數之合計,含有1莫耳%以上且33莫耳%以下之鋯,進而較佳為含有1莫耳%以上且10莫耳%以下,更佳為含有2莫耳%以上且10莫耳%以下,進而更佳為含有4莫耳%以上且8莫耳%以下。又,就同樣之觀點而言,構成金屬層14之銅-鋯-矽合金較佳為相對於銅、鋯及矽之莫耳數之合計,含有1莫耳%以上且33莫耳%以下之矽,進而較佳為含有1莫耳%以上且10莫耳%以下,更佳為含有2莫耳%以上且10莫耳%以下,進而更佳為含有4莫耳%以上且8莫耳%以下。 進而,就使氧化抑制之效果更加顯著之觀點而言,構成金屬層14之銅-鋯-矽合金較佳為鋯及矽之莫耳數之合計相對於銅、鋯及矽之莫耳數之合計為2莫耳%以上且40莫耳%以下,進而較佳為含有2莫耳%以上且20莫耳%以下者,更佳為含有4莫耳%以上且20莫耳%以下者,進而更佳為含有8莫耳%以上且16莫耳%以下者。 構成金屬層14之銅-鋯-矽合金較佳為如上所述般含有鋯及矽且其餘部分包含銅及不可避免之雜質的合金。然而,於發揮本發明之效果之程度下,容許含有微量之除銅、鋯及矽以外之其他元素。 無論銅-鋯-矽合金是否含有其他元素,不可避免之雜質之比率均較佳為相對於銅、鋯及矽之莫耳數之合計為2莫耳%以下,進而較佳為1莫耳%以下。不可避免之雜質之比率越少越佳。 包含銅-鋯-矽合金之金屬層14例如可藉由各種薄膜形成方法而形成。作為薄膜形成方法,可採用濺鍍或真空蒸鍍等先前公知之方法。於例如進行濺鍍作為薄膜形成方法時,作為銅-鋯-矽合金源,較佳為使用含有鋯及矽且其餘部分包含銅及不可避免之雜質的濺鍍靶材。該靶材中之銅-鋯-矽合金之合金組成與構成金屬層14之銅-鋯-矽合金之合金組成實質上相同。亦即,該濺鍍靶材係包含銅-鋯-矽合金者,於配線構造10中用以形成用以防止該配線層12之氧化之金屬層14。再者,由於與金屬層14同樣之原因,容許該濺鍍靶中含有微量之除銅、鋯及矽以外之其他元素、例如氧,但該元素之含量越少越佳。 再者,上述濺鍍靶材用於濺鍍之情況自不用說,亦能較佳地用作電弧離子鍍覆等真空蒸鍍等各種物理氣相沈積法(PVD,Physical Vapor Deposition)之靶材。又,上述濺鍍靶材除了用以形成圖1所示之構造之配線構造10中之金屬層14以外,亦能夠用以形成如下金屬層,該金屬層係除圖1所示之構造之配線構造10以外,含有鋯及矽且其餘部分包含銅及不可避免之雜質,且為了防止含有銅之配線層之氧化而與該配線層直接相鄰設置。 上述靶材可利用該技術領域中公知之各種方法製造。例如於真空中對熔融後之銅、鋯及矽進行鑄造而使其等合金化。繼而,使用所獲得之鑄塊製造靶材。對靶材進行加工之加工方法並無特別限制,例如可為熱鍛造,亦可為冷鍛造,或者亦可為熱軋。又,亦可利用線切鋸進行切割加工,而形成為板材。作為上述靶材之另一製造方法,例如可列舉使用公知之方法對利用霧化法等製造之銅-鋯-矽合金之粉末進行熱壓(所謂粉末冶金)而製造的方法。於將上述靶材用作濺鍍靶之情形時,只要使用銦等接合材將所獲得之板材貼附於作為濺鍍治具之背襯板即可。再者,於本發明中,所謂靶材,亦包含平面研磨或接合等靶材最後加工步驟前之狀態。於形成銅-鋯-矽合金中之鋯之含有比率較高之金屬層14之情形時,亦能夠採用在進而將鋯或矽之含有比率較高之銅-鋯-矽合金晶片載置於上述靶材上之狀態下進行濺鍍之方法。 利用上述方法形成之金屬層14之厚度可根據配線構造10之具體用途而任意地設定,例如可設定為10 nm以上且100 nm以下,較佳設定為20 nm以上且60 nm以下。藉由將金屬層14之厚度設定為10 nm以上,能夠有效地防止作為保護對象之配線層12中所含之銅之氧化。又,藉由將金屬層14之厚度設定為100 nm以下,能夠不損及金屬層14之生產性。 又,金屬層14只要覆蓋為了實現配線層12之氧化防止之目的所需之部分即可。於本實施形態中,金屬層14僅設置於配線層12之第2面12b之全域,但視需要亦可以被覆配線層12及密接層13整體之方式設置。 如上所述,配線構造10係藉由如下方法而較佳地製造,該方法包括如下步驟:於基板11上設置含有銅之配線層12;於配線層12上設置含有鋯及矽且其餘部分包含銅及不可避免之雜質的金屬層14;及對具有該等兩層12、14之積層構造進行熱處理。並且,根據該製造方法,於配線構造10之製造過程中,即便於在大氣下等氧化性氣氛下進行熱處理之情形時,亦能夠防止配線層12之氧化。換言之,該氧化之防止係藉由在上述熱處理之前於配線層12之上形成含有鋯及矽且其餘部分包含銅及不可避免之雜質的金屬層14而達成。如此,根據本發明,亦提供一種於配線構造10之製造過程中之熱處理時防止配線層12之氧化的氧化防止方法。 利用以上方法製造之配線構造10可直接使用,或者亦可進行後加工而用作各種電子裝置。作為電子裝置,例如可列舉電晶體或FET等各種半導體裝置。只要使用例如玻璃等透明材料作為基板11,則能夠獲得薄膜電晶體(TFT,thin-film transistor)。 作為配線構造10中之後加工,例如能夠為了向配線構造10上成膜氮化矽(SiN)等絕緣層或成膜摻銦氧化錫(ITO)等配線而進而進行以下加工步驟。首先,如圖2(a)所示般,以被覆積層構造15整體之方式形成絕緣層16。亦即,圖2(a)所示之積層構造15成為不存在露出至外表面之區域之狀態。 絕緣層16係由非導電性之材料構成。作為此種材料,例如可列舉各種非氧化物之非導電性材料。尤其是,若使用氮化物非導電性材料作為絕緣層16,則就藉由與具有特定之合金組成之金屬層14之協同效應而抑制配線層12中所含之銅之氧化的方面而言較佳。作為氮化物非導電性材料,例如可列舉氮化矽(SiN)及氮化鋁等含氮陶瓷材料。尤其是於絕緣層16為氮化矽(SiN)之情形時,配線層12中所含之銅之氧化之抑制效果進一步增高。 繼而,如圖2(b)所示般,於絕緣層16形成作為接觸孔之開口部16A,使金屬層14之上表面14a露出至外部。於形成開口部16A時,只要使用例如CF4
/O2
系之蝕刻氣體即可。 繼而,以覆蓋絕緣層16之上表面(外表面)及自開口部16A露出之金屬層14之上表面14a整體之方式,使非晶質(amorphous)之ITO等透明導電體用材料積層,形成積層體。藉由對該積層體實施退火處理(熱處理),而使已結晶化之ITO等透明導電體被覆形成於絕緣層16上及於開口部16A露出之金屬層14上,作為圖2(c)所示之透明導電體層17。 即,藉由進而進行於積層構造15中之金屬層14上設置絕緣層16之步驟、於絕緣層16以露出上述金屬層14之方式設置開口部16A之步驟、以及於上述絕緣層16上及於上述開口部16A中露出之上述金屬層14上之兩者設置透明導電體層17之步驟,亦能夠形成本發明之配線構造。以此方式形成之配線構造10可用作薄膜電晶體等各種半導體裝置。此種配線構造10藉由使用銅-鋯-矽合金作為金屬層14,而成為該金屬層14與透明導電體層17之接觸電阻較低者。再者,於後加工中,絕緣層之形成、接觸孔之形成、透明導電體用材料之積層及退火處理可利用本技術領域中之公知之方法而進行。 實施例 以下,藉由實施例對本發明進一步詳細地進行說明。然而,本發明之範圍並不限制於該實施例。 [實施例1] 以成為以下表1所示之組成之方式,精秤各種起始原料之結晶塊,並將該等結晶塊投入至氧化鎂製之坩堝中。於高頻感應真空熔解爐中對該等結晶塊進行真空加熱而使其等熔融。藉此,將熔液鑄造成碳製之鑄模,獲得鑄塊。使用線切鋸對所獲得之鑄塊進行切割後,藉由車床加工加工成厚度5 mm。將以此方式獲得之靶材之一面焊接於背襯板,製作銅-鋯-矽合金濺鍍靶。 使用鈦之濺鍍靶、純銅之濺鍍靶、及上述中所獲得之銅-鋯-矽合金濺鍍靶製作配線構造。首先,使用鈦之濺鍍靶於下述條件下實施濺鍍,而於玻璃基板上形成厚度25 nm之密接層。其次,使用純銅之濺鍍靶於相同條件下實施濺鍍,而於密接層上形成厚度400 nm之配線層。繼而,使用上述中所獲得之銅-鋯-矽合金濺鍍靶於相同條件下實施濺鍍,而於配線層上形成厚度50 nm之配線層之氧化防止用金屬層。藉此,製作積層構造。 ≪濺鍍條件≫ ・濺鍍方式:DC(Direct-Current,直流)磁控濺鍍 ・排氣裝置:旋轉泵+低溫泵 ・極限真空:1×10-4
Pa以下 ・Ar壓力:0.4 Pa ・基板溫度:室溫・濺鍍功率:1000 W(功率密度3.1 W/cm2
) ・使用基板:EAGLE XG(康寧公司/液晶顯示器用玻璃,註冊商標)、50 mm(縱)×50 mm(橫)×0.7 mm(厚度) 以所獲得之積層構造作為對象,以成為圖3所示之特定形狀之圖案之方式,使用光微影法進行圖案化後,進行退火處理(熱處理),而獲得圖1所示之構造之配線構造。退火處理係於大氣下進行。退火處理之溫度設定為350℃,退火處理時間設為30分鐘。 [實施例2至7] 除了以銅、鋯及矽之比率成為表1所示之值之方式變更添加量以外,以與實施例1同樣之方式製作銅-鋯-矽合金濺鍍靶。使用所獲得之濺鍍靶,以與實施例1同樣之方式,獲得具備圖1所示之構造之配線構造且為圖3所示之特定形狀之圖案者。 [比較例1] 於實施例1中,未形成包含銅-鋯-矽合金之金屬層。除此以外,以與實施例1同樣之方式獲得配線構造。 [比較例2及3] 於形成金屬層時,使用不含矽之銅-鋯合金濺鍍靶,代替使用銅-鋯-矽合金濺鍍靶。除了以銅及鋯之比率成為表1所示之值之方式變更添加量以外,以與實施例1同樣之方式獲得配線構造。 [評價] 對於實施例及比較例中所獲得之配線構造,藉由以下方法對耐氧化性進行評價。又,藉由以下方法測定接觸電阻。進而,測定用以製造實施例及比較例之配線構造之濺鍍靶材中之銅-鋯-矽合金相之比率。將其結果示於表1。再者,實施例4至7以及比較例2及3中之金屬層之銅-鋯-矽合金之組成係以酸溶解濺鍍而成之金屬層從而製成溶液樣品,並利用ICP-ES(Hitachi High-Tech Science股份有限公司製造之PS3500DP)對該溶液樣品進行分析而算出。 [耐氧化性之評價] 在退火處理前與退火處理後分別測定所獲得之配線構造之體積電阻率。測定時使用四端子電阻測定裝置(B-1500A:安捷倫科技公司製造)。將測定順序示於以下。 首先,於製造配線構造時,在退火處理前之積層構造之狀態下,預先測定包含金屬層及配線層之導電部之配線電阻。具體而言,藉由在圖3所示之電流施加墊Pi、Pi間掃描電流值,並測定電壓測定墊Pv、Pv間之電壓值,而獲得配線電阻值。根據所獲得之配線電阻值、上述導電部之線寬、長度、及膜厚,算出導電部之體積電阻率。將該值設為退火處理前之體積電阻率(Ω・cm)。 其次,於退火處理後之配線構造中,利用與退火處理前之體積電阻率之測定同樣之方法,算出體積電阻率。將該值設為退火處理後之體積電阻率(Ω・cm)。 然後,算出退火處理前與退火處理後之體積電阻率之變化率。體積電阻率之變化率(%)係根據{(退火處理後之體積電阻率-退火處理前之體積電阻率)/退火處理前之體積電阻率}×100而算出。 [接觸電阻之測定] 接觸電阻之測定係以如下方式進行。測定係以實施例1至7以及比較例1及3之具有銅鋯合金組成之配線構造作為對象而進行。具體而言,首先,製造具備如圖2(a)所示般包含絕緣層16之剖面構造且具有圖4所示之圖案之配線構造。於CF4
/O2
系之蝕刻氣體下在該配線構造形成圖2(b)所示之開口部16A後,使非晶質之ITO積層,而形成積層體。 繼而,使用光微影法將積層體圖案化後,以250℃進行1小時退火處理,而使ITO結晶化,從而獲得進而形成有包含ITO之透明導電體層的配線構造。形成有透明導電體層之配線構造係具備圖2(c)所示之剖面構造且具有圖4所示之TEG圖案者。 對於形成有透明導電體層之配線構造,於TEG圖案之電流施加墊Pi間掃描電流值,並測定電壓測定墊Pv間之電壓,而求出金屬層與透明導電體層之層間之接觸電阻值Pv/Pi(Ω/10 μm)。測定時使用上述四端子電阻測定裝置。再者,於測定接觸電阻前,流動高於測定電流之電流,確認歐姆電極性。將結果示於表1。再者,該表中,「-」係指未進行測定。 [濺鍍靶中之銅-鋯-矽合金相之比率] 濺鍍靶中之銅-鋯-矽合金相之比率係以用以製造實施例1至7之配線構造之濺鍍靶材之表面作為對象,藉由能量分散型X射線(EDX)分析而算出。詳細而言,使用能量分散型X射線分析裝置(日本電子公司製造之DRY SD100GV)進行元素分析。使用多變量影像解析軟體(Thermo Fisher Scientific公司製造之NSS4)對元素分析之結果進行相分離,算出銅-鋯-矽合金之面積相對於圖像整體之面積的比率(%)。 [X射線繞射測定(XRD)] 以用以製造實施例1至7之配線構造之濺鍍靶材作為對象,實施X射線繞射測定(XRD)。XRD係使用RIGAKU公司製造之RINT-TTR III,並使用Cu Kα(0.15406 nm、50 kV、300 mA)作為X射線源進行測定。將藉由XRD而獲得之繞射圖案示於圖5。 [表1]
根據表1所示之結果可明確,各實施例中之體積電阻率之上升率相較於各比較例變低。由該結果可知,各實施例之配線構造相較於各比較例之配線構造不易被氧化。 又,可知,相較於不具有金屬層之比較例1,各實施例中之接觸電阻值較低。尤其是,相較於具有不含矽之金屬層之比較例3,實施例2至7中之接觸電阻值為同等以下之值。由此可知,藉由將金屬層設為銅-鋯-矽合金,接觸電阻值降低。 進而,亦可知,如表1及圖5所示般,於濺鍍靶中存在銅-鋯-矽合金,又,其存在比率與金屬層中之銅-鋯-矽合金之組成大致一致。即,可知,於實施例6中,濺鍍靶中之銅-鋯-矽合金之存在比率為21 at%,又,金屬層中之銅之組成、鋯之組成、及矽之組成分別為87.8 at%、5.6 at%、6.6 at%,大致一致。 [產業上之可利用性] 根據本發明,於具備含有銅之配線層之配線構造中,即便於高溫且氧化性氣氛下之熱處理後,該配線層之氧化亦得以抑制。
10‧‧‧配線構造
11‧‧‧基板
12‧‧‧配線層
12a‧‧‧第1面
12b‧‧‧第2面
13‧‧‧密接層
14‧‧‧金屬層
14a‧‧‧上表面
15‧‧‧積層構造
16‧‧‧絕緣層
16A‧‧‧開口部
17‧‧‧透明導電體層
Pi‧‧‧電流施加墊
Pv‧‧‧電壓測定墊
圖1係表示本發明之配線構造之一實施形態之沿厚度方向之剖面的模式圖。 圖2(a)係表示本發明之配線構造之另一實施形態之沿厚度方向之剖面的模式圖,圖2(b)係於絕緣層形成有開口部之狀態之配線構造的模式圖(相當於圖2(a)之圖),圖2(c)係於圖2(b)之配線構造進而形成有透明導電體層之狀態的模式圖。 圖3係配線電阻測定用TEG(Test Element Group,測試元件組)形成圖案之上表面的模式圖。 圖4係接觸電阻測定用TEG形成圖案之上表面的模式圖。 圖5係表示在實施例1至7中獲得之濺鍍靶材之X射線繞射之測定結果的圖表。
Claims (11)
- 一種配線構造,其係具備基板、設置於該基板上之配線層、及設置於該配線層上之金屬層者,且 上述配線層含有銅, 上述金屬層含有鋯及矽,且其餘部分包含銅及不可避免之雜質。
- 如請求項1之配線構造,其中上述金屬層中,相對於銅、鋯及矽之莫耳數之合計,含有1莫耳%以上且33莫耳%以下之鋯,且含有1莫耳%以上且33莫耳%以下之矽。
- 如請求項1之配線構造,其中於上述金屬層中,鋯及矽之莫耳數之合計相對於銅、鋯及矽之莫耳數之合計為2莫耳%以上且40莫耳%以下。
- 一種濺鍍靶材,其含有鋯及矽,且其餘部分包含銅及不可避免之雜質;且 上述濺鍍靶材用以形成如請求項1之配線構造中之金屬層。
- 一種配線構造之製造方法,其包括如下步驟: 於基板上設置含有銅之配線層; 於上述配線層上設置含有鋯及矽且其餘部分包含銅及不可避免之雜質的金屬層;及 對具有該等各層之積層構造進行熱處理。
- 如請求項5之配線構造之製造方法,其中於氧化性氣氛下進行上述積層構造之熱處理。
- 一種氧化防止方法,其係於具備基板、及設置於該基板上且含有銅之配線層的配線構造之製造過程中之熱處理時,防止該配線層之氧化之方法;且 於上述熱處理之前,於上述配線層上形成含有鋯及矽且其餘部分包含銅及不可避免之雜質的金屬層。
- 如請求項7之氧化防止方法,其中於氧化性氣氛下進行上述配線構造之製造過程中之熱處理。
- 一種濺鍍靶材,其含有鋯及矽且其餘部分包含銅及不可避免之雜質,且用以形成含有銅之配線層之氧化防止用之金屬層。
- 如請求項9之濺鍍靶材,其中相對於銅、鋯及矽之莫耳數之合計,含有1莫耳%以上且33莫耳%以下之鋯,且含有1莫耳%以上且33莫耳%以下之矽。
- 如請求項9之濺鍍靶材,其中鋯及矽之莫耳數之合計相對於銅、鋯及矽之莫耳數之合計為2莫耳%以上且40莫耳%以下。
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