TWI559402B - 含銅種晶層之原子層沉積技術 - Google Patents
含銅種晶層之原子層沉積技術 Download PDFInfo
- Publication number
- TWI559402B TWI559402B TW100133378A TW100133378A TWI559402B TW I559402 B TWI559402 B TW I559402B TW 100133378 A TW100133378 A TW 100133378A TW 100133378 A TW100133378 A TW 100133378A TW I559402 B TWI559402 B TW I559402B
- Authority
- TW
- Taiwan
- Prior art keywords
- copper
- compound
- precursor
- organometallic
- seed layer
- Prior art date
Links
- 239000010949 copper Substances 0.000 title claims description 73
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 69
- 229910052802 copper Inorganic materials 0.000 title claims description 69
- 238000000231 atomic layer deposition Methods 0.000 title description 15
- 238000000034 method Methods 0.000 claims description 41
- 239000012691 Cu precursor Substances 0.000 claims description 40
- 239000003153 chemical reaction reagent Substances 0.000 claims description 31
- 150000001875 compounds Chemical class 0.000 claims description 25
- 125000002524 organometallic group Chemical group 0.000 claims description 24
- 239000003989 dielectric material Substances 0.000 claims description 19
- 230000004888 barrier function Effects 0.000 claims description 16
- 239000004020 conductor Substances 0.000 claims description 15
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- -1 copper (I) compound Chemical class 0.000 claims description 11
- 239000006227 byproduct Substances 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- 229910002065 alloy metal Inorganic materials 0.000 claims description 7
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 238000000137 annealing Methods 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 150000002901 organomagnesium compounds Chemical class 0.000 claims 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims 1
- HPDFFVBPXCTEDN-UHFFFAOYSA-N copper manganese Chemical compound [Mn].[Cu] HPDFFVBPXCTEDN-UHFFFAOYSA-N 0.000 claims 1
- 229910052707 ruthenium Inorganic materials 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 claims 1
- 230000002269 spontaneous effect Effects 0.000 claims 1
- 239000010410 layer Substances 0.000 description 83
- 239000000543 intermediate Substances 0.000 description 18
- 239000000758 substrate Substances 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000000151 deposition Methods 0.000 description 7
- 230000008021 deposition Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 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 3
- 238000004377 microelectronic Methods 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000006557 surface reaction Methods 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 description 1
- 125000002734 organomagnesium group Chemical group 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910003468 tantalcarbide Inorganic materials 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- 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
- H01L21/28556—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 chemical means, e.g. CVD, LPCVD, PECVD, laser CVD
- H01L21/28562—Selective deposition
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- 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
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76843—Barrier, adhesion or liner layers formed in openings in a dielectric
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- 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
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76853—Barrier, adhesion or liner layers characterized by particular after-treatment steps
- H01L21/76855—After-treatment introducing at least one additional element into the layer
- H01L21/76858—After-treatment introducing at least one additional element into the layer by diffusing alloying elements
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- 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
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76867—Barrier, adhesion or liner layers characterized by methods of formation other than PVD, CVD or deposition from a liquids
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- 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
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76871—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers
- H01L21/76873—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers for electroplating
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- 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
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76871—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers
- H01L21/76874—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers for electroless plating
Landscapes
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
- Chemical Vapour Deposition (AREA)
Description
本說明內容之實施例一般係有關於微電子元件製造領域,且更特別地,係形成用於製造積體電路之互連件之種晶層。
如熟習此項技藝者所知,物理性蒸氣沉積之方向性質造成現今物理性蒸氣沉積銅種晶層形成之方法的限制,此限制會造成難以於具高縱橫比之突顯部之底部及側壁上均一地沉積材料,因此需要一種受控制之薄膜沉積方法來避免此限制發生。
依據本發明之一實施例,係特地提出一種用以製造互連件之方法,包含:將一銅先質化學吸附於形成於一介電材料內之一開口上;將該銅先質曝置於一有機金屬共同試劑而形成一不穩定之銅中間物;以及經由自該不穩定之銅中間物自發性還原除去有機副產物而形成一含銅種晶層。
本揭露內容之標的內容係於此說明書之結束部份明確指出及清楚地請求。本揭露內容之前述及其它特徵由與所附圖式結合之下列說明及所附之申請專利範圍將更完全明白。需瞭解所附之圖式僅描述依據本揭露內容之數個實施例,因此,不被認為係限制其範圍。此揭露內容將經由使用所附圖式以另外之明確性及細節作說明,使得本揭露內容之優點可更輕易地確定,其中:
第1圖例示於一介電材料層形成之一開口之側橫截面圖。
第2圖例示於其內具有一含銅種晶層之第1圖之開口之側橫截面圖。
第3圖係一形成含銅種晶層之方法之一實施例之流程圖。
第4圖係一含銅種晶層之一實施例之簡化的化學反應流程圖。
第5圖例示將一導電材料沉積於第2圖之含銅種晶層上之側橫截面圖。
第6圖例示自第5圖之結構形成一互連件之側橫截面圖。
第7圖例示形成於介電材料層與含銅種晶層間之一障壁層之側橫截面圖。
第8-14圖例示自與含銅種晶層內之銅合金化之金屬形成一障壁層之側橫截面圖。
於下列詳細說明,係參考所附圖式,其藉由例示而顯示所請求之標的可被實施之特別實施例。此等實施例係充份詳細地說明以使熟習此項技藝者能實施此標的內容。需瞭解各種實施例即使不同,亦無需相互排它。例如,有關於一實施例之此處所述之一特別的特徵、結構,或特性可於未偏離請求之標的內容的精神及範圍下於其它實施例中實施。此外,需瞭解每一揭露實施例內之個別元件之位置或配置可於未偏離請求之標的內容的精神及範圍下修改。因此,下列詳細說明非作為限制,且標的內容之範圍與所附申請專利範圍享有權利之完整範圍之等化物一起僅藉由所附之申請專利範圍界定,適當闡釋。於圖式中,相同編號於數個圖之各處係指相同或相似之元件或功能性,且此處所述之元件無需彼此按比例,相反地,個別元件可被放大或縮減以更容易地瞭解本說明內容中之元件。
本說明內容之實施例一般係有關於微電子元件製造之領域,且更特別地係形成用於製造積體電路之互連件之含銅種晶層。含銅種晶層可於原子層沉積方法以銅先質及有機金屬共同試劑形成。
第1-14圖例示用以於互連件之製造中形成種晶層之方法之實施例之橫截面圖及流程圖,該互連件諸如後端製程(BEOL)互連件。如第1圖所示,一開口102可經過一介電材料層104及一第一障壁層106而形成,以露出一基材112之至少一部份108,其中,開口102包括至少一側壁114,藉此,形成一第一中間結構110。需瞭解如熟習此項技藝者所知,開口102可為一穿孔、一凹槽,或其等之組合,諸如,如所示之一雙鑲嵌開口。
基材112可為一含矽材料,其中,露出之基材部份108係相對應於形成於基材112之一電路元件(未示出)或可為一導電軌跡,其可由銅、鋁、銀、金等,與其等之合金所製成。於一實施例,基材112係一銅軌跡。第一障壁層106可為一蝕刻停止層,諸如,碳化矽、氮化矽、氧碳化矽、氧碳氮化矽等。介電材料層104可不受限地包括層間介電質,諸如,二氧化矽、以碳摻雜之二氧化矽、以聚合物為主之材料(例如,氟碳化物、碳氫化物),及低-k之富碳介電質。
如第2圖所示,一含銅種晶層122可沉積於介電材料層104上及於開口102內以接觸基材112,藉此,形成一第二中間結構120。含銅種晶層122可以一原子層沉積(ALD)法形成。ALD法係與化學蒸氣沉積(CVD)法有關,因為金屬源係一揮發性金屬錯合物。但是,沉積不僅係藉由將於一加熱之基材表面上之金屬錯合物熱分解(CVD),而且藉由金屬先質與共同試劑間之重複性交替性表面控制反應而達成,金屬先質及共同試劑之至少一者係於成核方法期間吸附於基材表面上,以起始ALD膜之生長。於一典型之ALD法,金屬先質係以自行限制方式化學吸附於膜表面上(於CVD不會發生之溫度),且任何過量之先質及揮發性副產物係以惰性氣體吹掃而移除。然後,揮發性共同試劑之蒸氣引至表面,且與化學吸附之金屬先質反應而沉積所欲之材料(例如,一金屬膜),影響揮發性副產物之釋放,及產生一適合之表面官能化而提供緊鄰金屬先質蒸氣曝露之反應。與共同試劑之表面反應亦係自行限制,且過量之共同試劑及揮發性副產物係以惰性氣體吹掃移除。由於表面反應之自行限制性質,ALD法之特徵在於高度保形及均一,自行限制之膜生長,此提供高度均一之超薄(例如,少於50 )之膜。
第3及4圖例示本說明內容之ALD法200之一實施例。於步驟210,一銅先質可被引至第1圖之第一中間結構110,而於其上形成一單層(於第4圖以CuL2顯示)。銅先質可為任何適合先質,不受限地包括均配型(即,所有配位基(官能基)係相同)或雜配型之銅(I)及銅(II)化合物。於一實施例,銅先質係銅(II)化合物,其等一般係比銅(I)先質更不具空氣及水份敏感性。銅(II)化合物可不受限地包括第1表中例示之化合物。於第1表,R1、R2、R3,及R4可代表一般之有機取代基或氫。取代模式可自任何組合產生,其中,R1=R2=R3=R4,或R1≠R2≠R3≠R4,或其間之任何允許之組合。
然後,如步驟220所示,過量之銅先質可以吹掃氣體移除。如步驟230所示,單層可曝置於一有機金屬共同試劑(第4圖中以MR2顯示)形成一不穩定之有機銅中間物或一不穩定之有機銅合金中間物(於第4圖個別以CuR2或Cu(M)R2顯示)。如熟習此項技藝者所知,有機銅中間物或有機銅合金中間物被形成會依選擇之銅先質、選擇之有機金屬共同試劑,及/或沉積之操作參數(例如,溫度、壓力等)而定。
如第3圖之步驟240所示,任何過量之有機金屬共同試劑及揮發性反應副產物(於第4圖以ML2顯示)可以惰性氣體吹掃而移除。
有機金屬共同試劑可為任何適合之共同試劑,不受限地包括均配型(即,所有配位基(官能基團)係相同)或雜配型之有機錳、有機鋁、有機鎂、有機鋅,或有機錫化合物。有機金屬化合物可不受限地包括烷基基團、烯基基團、炔基基團等。共同試劑化合物可不受限地包括第2表例示之化合物。於第2表,M可為鋅、鎂,或錳,且R1、R2、R3,及R4可代表一般之取代基或氫。取代模式可自任何組合產生,其中,R1=R2=R3=R4,或其中,R1≠R2≠R3≠R4,或其間之任何允許之組合。
如第3圖之步驟250所示,不穩定之有機銅中間物或不穩定之有機銅合金中間物(於第4圖個別以CuR2或Cu(M)R2顯示)自發地進行還原去除有機副產物,其個別形成銅Cu或銅合金Cu(M)種晶層(見第2圖之含銅種晶層122)。過量之共同試劑及揮發性反應副產物(於第4圖以R-R顯示)可以惰性氣體吹掃移除,如第3圖中之步驟260所示。
於一實施例,其中,含銅種晶層122係自不穩定之有機銅中間物形成,含銅種晶層122可具有少於約1%(原子)之總組合雜質含量。於一實施例,其中,含銅種晶層122係自不穩定有機銅合金中間物形成,合金金屬(例如,錳、鋁、鎂、鋅,或錫)之濃度可於約1原子%與5原子%之間。
需瞭解步驟210至260可以數個週期以相同順序重複,以建立含銅種晶層122(見第2圖)之所欲厚度。需瞭解此數個週期無需具相同之銅先質及/或相同之有機金屬共同試劑。作為一般例子而言,可執行四個週期之銅先質與第一有機金屬共同試劑反應,形成四層實質上純銅之種晶層,其後係一週期之相同銅先質與第二有機金屬共同試劑反應,形成一銅合金種晶層。當然,可使用任何數量及組合之銅先質及有機金屬共同試劑形成呈任何組合之任何數量之銅及銅合金種晶層。
亦需瞭解如熟習此項技藝者所瞭解,第1圖之第一中間基材110可於ALD沉積前藉由曝置於呈溶液或蒸氣相之有機或無機原子層沉積成核促進物質而活化,或可經由曝置於電輻射或電漿而活化。
如第2圖所例示,含銅種晶層之原子層沉積可於經曝置之下層金屬層上直接進行,以使“無底”穿孔減少互連件電阻。
於一實施例,銅先質(第4圖以CuL2顯示)可為雙(二甲基胺基-2-丙氧化物)銅(II),且有機金屬共同試劑(第4圖中以MR2顯示)可為三乙基鋁有機金屬共同試劑。當如上所探討之方法於約100℃實施且於一以銅摻雜之二氧化矽介電質上沉積,可形成具有約2.7 μΩ‧cm之電阻之具有約96%(原子)之銅、約2%(原子)之銅、約2%(原子)之氧之含銅種晶層122。
使用本說明內容之ALD法形成含銅種晶層122提供一受控制之薄膜沉積,且以其性質,於三維結構係高均一性及保形性,因此可避免因物理性蒸氣沉積之方向性質而造成之現今物理性蒸氣沉積銅種晶層形成之方法之限制發生,如熟習此項技藝者所知,此限制會造成難以於具高縱橫比之突顯部之底部及側壁上均一地沉積材料。於一實施例,原子層沉積可於約20℃與150℃間之相對較低之溫度實施。具有低基材溫度及無電將共同試劑(於物理性蒸氣沉積法中必需)能形成更具保形性之種晶層且可除去對介電層,特別是低-k介電質,之電漿損害。
如第5圖所示,開口102可以一導電性材料124填充。導電性材料124可為任何適合之導電性材料,不受限地包括銅、鋁、銀、金、鈷、鎢等,與其等之合金。於一實施例,導電性材料124係銅或其合金。導電性材料124可藉由此項技藝所知之任何技術沉積,其不受限地包括無電式電鍍及電鍍。如第6圖所示,覆蓋介電材料層104之導電性材料124之一部份(非於開口102(見第2圖)內)可被移除,諸如,藉由化學機械拋光,以形成一互連件130。
於本說明內容之一實施例,如第7所示(第2圖之插圖A),一互連障壁層132可於含銅種晶層122與介電材料層104間形成。於一實施例,互連障壁層132可經由含銅種晶層122與介電層104之反應形成,且可能需要或可能不需要用於其形成之熱退火。互連障壁層132可避免銅從互連件130及/或含銅種晶層122擴散至周圍材料內。於另一實施例,含銅種晶層122內之合金金屬(例如,非銅金屬)可用以調整及改良電遷移性能及/或可具有足夠濃度以避免銅擴散。
於本說明內容之一實施例,如第8-13圖所例示,一互連障壁層可自行形成。以第1圖開始,如第8圖所示,一襯裡材料層142,諸如,釕,可被沉積而緊靠介電材料層104及露出之基材部108。如第9圖所示,自如上所述之不穩定有機銅合金中間物形成之含銅種晶層122可沉積於襯裡材料層142上。如第10圖所示,開口102可以諸如銅或其合金之一導電性材料124填充。如第11圖所示,覆蓋介電材料層104之導電性材料124之一部份可被移除形成互連件150。互連件150可經退火(加熱)。如第12圖所示,此退火造成含銅種晶層122內之合金金屬144經襯裡材料層142向介電層104遷移(以箭號152顯示)。如第13及14圖所示,合金金屬144於襯裡材料層142與介電材料層104間形成一互連障壁層146,同時使銅留於襯裡材料層142之相反側上(以包括互連件150之導電性材料顯示)。於一實施例,合金金屬144係錳。需瞭解於開口102以導電性材料124填充形成互連件150前,含銅種晶層122可經退火形成互連障壁層146(見第9圖)。
亦需瞭解本說明內容之標的內容無需限於第1-14圖例示之特別應用。標的內容可應用於其它堆疊之模具應用。再者,標的內容亦可用於微電子元件製造領域範圍外之任何適合應用。
詳細說明內容已經由使用例示、方塊圖、流程圖,及/或範例說明元件及/或方法之各種實施例。於此等例示、方塊圖、流程圖,及/或範例含有一或多個功能及/或操作之範圍內,熟習此項技藝者會瞭解於每一例示、方塊圖、流程圖,及/或範例內之每一功能及/或操作可以廣範圍之硬體、軟體、韌體,或實際上之其等任何組合個別地及/或集合地實施。
所述之標的內容有關係例示不同之其它組件內所含或與其相關連之不同組件。需瞭解此等例示說明僅係例示,且許多另外之結構可被實施以達成相同功能。以概念性意義而言,用以達成相同功能之組件之任何配置係有效地"聯合",使得所欲功能被達成。因此,無論結構或中間組件,此處用以達成特別功能之任何二組件可被視為彼此"聯合",使得所欲功能被達成。同樣地,相聯合之任何二組件可被視為彼此"可操作地連接"或"可操作地耦合",以達成所欲功能,能被如此聯合之任何二組件亦可被視為彼此"可操作地耦合",以達成所欲功能。可操作地耦合之特別例子不受限地包括可物理性相配及/或物理性交互作用之組件,及/或可無線式相互作用及/或無線式交互作用之組件,及/或邏輯式相互作用及/或可邏輯式相互作用之組件。
熟習此項技藝者會瞭解此處使用且特別是於所附申請專利範圍中之用辭一般係意欲作為"開放性"用辭。一般,"包括"或“包含”之用辭需個別被解釋為"不受限地包括"或“不受限地包含”。另外,"具有"一辭需被解釋為"至少具有"。
於詳細說明內容內使用單數及/或複數之用辭於對上下文及/或申請案適合時可自複數轉換成單數及/或自單數轉換成複數。
熟習此項技藝者進一步瞭解若元件數量之指示於申請專利範圍中被使用,此申請專利範圍欲被如此限制之意圖會於此申請專利範圍中明確描述,且於缺乏此描述時,則不存在此意圖。另外,若一特別數量之被引述之請求描述被明確描述,熟習此項技藝者會瞭解此描述典型上需解釋為意指“至少”所述之數量。
於說明書中使用"一實施例"、"一個實施例"、“一些實施例”、“另一實施例”,或"其它實施例"可意指與一或多個實施例有關而描述之一特別之特徵、結構,或特性可被包含於至少一些實施例,但無需於全部之實施例。"一實施例"、"一個實施例"、於詳細說明中之“一些實施例”、“另一實施例”,或"其它實施例"之各種使用無需皆指相同實施例。
雖然某些例示之技術已於此間使用各種方法及系統說明及顯示,但熟習此項技藝者需瞭解無未偏離請求之標的內容或其精神,各種其它之修改可為進行,且等化物可被替代。另外,於未偏離此間所述之中心概念,許多修改可被進行以適於請求標的內容之教示之特別情況。因此,所意欲者係請求之標的內容不限於所揭露之特別範例,而是此請求之標的內容亦可包括落於所附申請專利範圍及其等化物之範圍內之所有實施。
102...開口
104...介電材料層
106...第一障壁層
108...基材之一部份
110...第一中間結構
112...基材
114...側壁
120...第二中間結構
122...含銅種晶層
124...導電性材料
130...互連件
132...互連障壁層
142...襯裡材料層
144...合金金屬
146...互連障壁層
150...互連件
152...箭號
200...ALD法
210,220,230,240,250,260...步驟
第1圖例示於一介電材料層形成之一開口之側橫截面圖。
第2圖例示於其內具有一含銅種晶層之第1圖之開口之側橫截面圖。
第3圖係一形成含銅種晶層之方法之一實施例之流程圖。
第4圖係一含銅種晶層之一實施例之簡化的化學反應流程圖。
第5圖例示將一導電材料沉積於第2圖之含銅種晶層上之側橫截面圖。
第6圖例示自第5圖之結構形成一互連件之側橫截面圖。
第7圖例示形成於介電材料層與含銅種晶層間之一障壁層之側橫截面圖。
第8-14圖例示自與含銅種晶層內之銅合金化之金屬形成一障壁層之側橫截面圖。
200...ALD法
210,220,230,240,250,260...步驟
Claims (20)
- 一種用以製造互連件之方法,包含:將一銅先質化學吸附在形成於一介電材料內之一開口上;將該銅先質曝置於一有機金屬共同試劑而形成一不穩定之銅中間物;以及經由自該不穩定之銅中間物自發性還原除去有機副產物而形成一含銅種晶層。
- 如申請專利範圍第1項之方法,其中,將該銅先質化學吸附包含將選自由一均配型銅(I)化合物、一雜配型銅(I)化合物、一均配型銅(II)化合物,以及一雜配型銅(II)化合物所構成族群之該銅先質化學吸附。
- 如申請專利範圍第2項之方法,其中,將該銅先質化學吸附包含形成一雙(二甲基胺基-2-丙氧化物)銅(II)先質。
- 如申請專利範圍第1項之方法,其中,將該銅先質曝置於該有機金屬共同試劑包含將該銅先質曝置於選自由均配型有機錳化合物、均配型有機鋁化合物、均配型有機鎂化合物、均配型有機鋅化合物、均配型有機錫化合物、雜配型有機錳化合物、雜配型有機鋁化合物、雜配型有機鎂化合物、雜配型有機鋅化合物,及雜配型有機錫化合物所構成族群之該有機金屬共同試劑。
- 如申請專利範圍第4項之方法,其中,將該銅先質曝置於該有機金屬共同試劑包含將該銅先質曝置於三乙基鋁有機金屬共同試劑。
- 如申請專利範圍第1項之方法,其中,形成該含銅種晶層包含形成一銅合金種晶層。
- 如申請專利範圍第1項之方法,其中,化學吸附該銅先質、將該銅先質曝置於該有機金屬共同試劑,及形成該含銅種晶層係以相同順序重複一或多個週期。
- 如申請專利範圍第7項之方法,其中,化學吸附該銅先質、將該銅先質曝置於該有機金屬共同試劑,及形成該含銅種晶層係以一不同之銅先質及/或一不同之有機金屬共同試劑以相同順序重複一或多個週期。
- 如申請專利範圍第1項之方法,其中,化學吸附該銅先質、將該銅先質曝置於該有機金屬共同試劑,及形成該含銅種晶層係於約20℃與150℃間之溫度實施。
- 如申請專利範圍第1項之方法,進一步包含以一導電性材料填充該開口。
- 一種用以製造互連件之方法,包含:在形成於一介電材料內之一開口上形成一襯裡層;將一銅先質化學吸附於該襯裡層上;將該銅先質曝置於一有機金屬共同試劑而形成一不穩定之銅中間物;經由自該不穩定之銅中間物自發性還原除去有機副產物而形成一銅合金種晶層;以及將該銅合金種晶層退火而使該銅合金種晶層內之合金金屬經由該襯裡層遷移而於該介電材料與該襯裡層間形成一障壁。
- 如申請專利範圍第11項之方法,其中,該襯裡層包含釕。
- 如申請專利範圍第11項之方法,其中,形成該銅合金種晶層包含形成一銅錳種晶層。
- 如申請專利範圍第11項之方法,其中,形成該銅先質包含形成選自由一均配型銅(I)化合物、一雜配型銅(I)化合物、一均配型銅(II)化合物,及一雜配型銅(II)化合物所構成族群之該銅先質。
- 如申請專利範圍第14項之方法,其中,形成該銅先質包含形成一雙(二甲基胺基-2-丙氧化物)銅(II)先質。
- 如申請專利範圍第11項之方法,其中,將該銅先質曝置於該有機金屬共同試劑包含將該銅先質曝置於選自由均配型有機錳化合物、均配型有機鋁化合物、均配型有機鎂化合物、均配型有機鋅化合物、均配型有機錫化合物、雜配型有機錳化合物、雜配型有機鋁化合物、雜配型有機鎂化合物、雜配型有機鋅化合物,及雜配型有機錫化合物所構成族群之該有機金屬共同試劑。
- 如申請專利範圍第16項之方法,其中,將該銅先質曝置於該有機金屬共同試劑包含將該銅先質曝置於三乙基鋁有機金屬共同試劑。
- 如申請專利範圍第11項之方法,其中,化學吸附該銅先質、將該銅先質曝置於該有機金屬共同試劑,及形成該含銅種晶層係於約20℃與150℃間之溫度實施。
- 如申請專利範圍第11項之方法,進一步包含以一導電性材料填充該開口。
- 如申請專利範圍第11項之方法,其中,該介電材料係選自由二氧化矽、以碳摻雜之二氧化矽、以聚合物為主之材料,及低-k之介電質所構成之族群。
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/885,097 US20120070981A1 (en) | 2010-09-17 | 2010-09-17 | Atomic layer deposition of a copper-containing seed layer |
Publications (2)
Publication Number | Publication Date |
---|---|
TW201220401A TW201220401A (en) | 2012-05-16 |
TWI559402B true TWI559402B (zh) | 2016-11-21 |
Family
ID=45818127
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW100133378A TWI559402B (zh) | 2010-09-17 | 2011-09-16 | 含銅種晶層之原子層沉積技術 |
Country Status (2)
Country | Link |
---|---|
US (1) | US20120070981A1 (zh) |
TW (1) | TWI559402B (zh) |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8952355B2 (en) | 2011-09-29 | 2015-02-10 | Intel Corporation | Electropositive metal containing layers for semiconductor applications |
US9514983B2 (en) * | 2012-12-28 | 2016-12-06 | Intel Corporation | Cobalt based interconnects and methods of fabrication thereof |
US9966339B2 (en) * | 2014-03-14 | 2018-05-08 | Taiwan Semiconductor Manufacturing Company | Barrier structure for copper interconnect |
US9984975B2 (en) | 2014-03-14 | 2018-05-29 | Taiwan Semiconductor Manufacturing Company | Barrier structure for copper interconnect |
JP6278827B2 (ja) | 2014-05-14 | 2018-02-14 | 株式会社Adeka | 銅化合物、薄膜形成用原料及び薄膜の製造方法 |
US20160032455A1 (en) * | 2014-07-31 | 2016-02-04 | Applied Materials, Inc. | High through-put and low temperature ald copper deposition and integration |
KR102493327B1 (ko) * | 2014-11-21 | 2023-01-27 | 어플라이드 머티어리얼스, 인코포레이티드 | 알코올 보조 ald 막 증착 |
EP3420584B1 (en) * | 2016-02-25 | 2020-12-23 | INTEL Corporation | Methods of fabricating conductive connectors having a ruthenium/aluminum-containing liner |
US10892186B2 (en) | 2017-10-14 | 2021-01-12 | Applied Materials, Inc. | Integration of ALD copper with high temperature PVD copper deposition for BEOL interconnect |
CN111356785A (zh) * | 2017-11-19 | 2020-06-30 | 应用材料公司 | 用于金属氧化物在金属表面上的ald的方法 |
WO2020006532A1 (en) * | 2018-06-30 | 2020-01-02 | Lam Research Corporation | Zincating and doping of metal liner for liner passivation and adhesion improvement |
US20210090991A1 (en) | 2019-09-24 | 2021-03-25 | Intel Corporation | Integrated circuit structures having linerless self-forming barriers |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20020081381A1 (en) * | 2000-10-10 | 2002-06-27 | Rensselaer Polytechnic Institute | Atomic layer deposition of cobalt from cobalt metallorganic compounds |
US20070264816A1 (en) * | 2006-05-12 | 2007-11-15 | Lavoie Adrien R | Copper alloy layer for integrated circuit interconnects |
US20080213994A1 (en) * | 2007-03-01 | 2008-09-04 | Ramanan Chebiam | Treating a liner layer to reduce surface oxides |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6869876B2 (en) * | 2002-11-05 | 2005-03-22 | Air Products And Chemicals, Inc. | Process for atomic layer deposition of metal films |
JP4523535B2 (ja) * | 2005-08-30 | 2010-08-11 | 富士通株式会社 | 半導体装置の製造方法 |
US20100200991A1 (en) * | 2007-03-15 | 2010-08-12 | Rohan Akolkar | Dopant Enhanced Interconnect |
US20090275164A1 (en) * | 2008-05-02 | 2009-11-05 | Advanced Technology Materials, Inc. | Bicyclic guanidinates and bridging diamides as cvd/ald precursors |
US8653663B2 (en) * | 2009-10-29 | 2014-02-18 | Taiwan Semiconductor Manufacturing Company, Ltd. | Barrier layer for copper interconnect |
-
2010
- 2010-09-17 US US12/885,097 patent/US20120070981A1/en not_active Abandoned
-
2011
- 2011-09-16 TW TW100133378A patent/TWI559402B/zh not_active IP Right Cessation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20020081381A1 (en) * | 2000-10-10 | 2002-06-27 | Rensselaer Polytechnic Institute | Atomic layer deposition of cobalt from cobalt metallorganic compounds |
US20070264816A1 (en) * | 2006-05-12 | 2007-11-15 | Lavoie Adrien R | Copper alloy layer for integrated circuit interconnects |
US20080213994A1 (en) * | 2007-03-01 | 2008-09-04 | Ramanan Chebiam | Treating a liner layer to reduce surface oxides |
Non-Patent Citations (2)
Title |
---|
BYOUNG H. LEE, "Low-Temperature Atomic Layer Deposition of Copper Metal Thin Films: Self-Limiting Surface Reaction of Copper Dimenthylamino-2-propoxide with Diethylzinc", Angew. Chem. Int. Ed. May 2009, Vol. 48, pages 4536-4539 * |
Edward J. Hennessy, B.A. Chemistry,"The Development and Application of Metal-Catalyzed Processes for Organic Synthesis", Massachusetts Institute of Technology, June 2005 * |
Also Published As
Publication number | Publication date |
---|---|
TW201220401A (en) | 2012-05-16 |
US20120070981A1 (en) | 2012-03-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TWI559402B (zh) | 含銅種晶層之原子層沉積技術 | |
JP6980020B2 (ja) | ルテニウムドーピングにより強化される耐コバルト凝集性及び間隙充填作用 | |
JP4938962B2 (ja) | ゲッタリング反応物を用いるaldによる金属窒化物堆積 | |
CN106024598B (zh) | 于阻障表面上的钴沉积 | |
KR102189781B1 (ko) | 망간 및 망간 니트라이드들의 증착 방법들 | |
US7144809B2 (en) | Production of elemental films using a boron-containing reducing agent | |
AU2010310750B2 (en) | Self-aligned barrier and capping layers for interconnects | |
US7799674B2 (en) | Ruthenium alloy film for copper interconnects | |
KR102036245B1 (ko) | 구리 배리어 적용들을 위한 도핑된 탄탈룸 질화물 | |
US20060240187A1 (en) | Deposition of an intermediate catalytic layer on a barrier layer for copper metallization | |
US20100151676A1 (en) | Densification process for titanium nitride layer for submicron applications | |
US20080242088A1 (en) | Method of forming low resistivity copper film structures | |
US7858525B2 (en) | Fluorine-free precursors and methods for the deposition of conformal conductive films for nanointerconnect seed and fill | |
JP2005528808A (ja) | 銅膜の堆積 | |
US10847463B2 (en) | Seed layers for copper interconnects | |
KR100622639B1 (ko) | 반도체 소자의 제조 방법 | |
AU2013204566A1 (en) | Self-aligned barrier and capping layers for interconnects |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
MM4A | Annulment or lapse of patent due to non-payment of fees |