IP Library Granted Patent US 12,622,243
Granted Patent B2
US 12,622,243 · App. 18/211,502 · Granted May 5, 2026

Selective liner deposition for via resistance reduction

Inventors: Yang Zhou (Milpitas, CA); Jiajie Cen (San Jose, CA); Zhiyuan Wu (San Jose, CA); Ge Qu (Sunnyvale, CA); Yong Jin Kim (Albany, CA); Zheng Ju (Sunnyvale, CA); Feng Chen (San Jose, CA); Kevin Kashefi (San Ramon, CA)
Assignee: Applied Materials, Inc.
H10W20/035H10W20/056
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Quick Facts
Patent No.
US 12,622,243
App. No.
18/211,502
Granted
May 5, 2026
Kind
B2
Abstract

Methods of forming devices comprise forming a dielectric material on a substrate, the dielectric layer comprising at least one feature defining a gap including sidewalls and a bottom. The methods include passivating a metal material at a bottom of the gap with an alkyl reactant to form a passivation layer on the metal material, the gap defined by the bottom and sidewalls comprising the dielectric material with having a barrier layer thereon. A metal liner is selectively deposited on the barrier layer on the sidewall over the passivation layer on the bottom.

Claims (29)

1 . A method of forming a microelectronic device, the method comprising:

passivating a metal material at a bottom of a gap with an alkyl reactant comprising one or more of an alkyl halide or an alkyl pseudohalide to form a passivation layer on the metal material, the gap defined by the bottom and sidewalls comprising a dielectric material having a barrier layer thereon; and

selectively depositing a metal liner on the barrier layer.

2 . The method of claim 1 , wherein the metal material comprises one or more of ruthenium (Ru), molybdenum (Mo), copper (Cu), cobalt (Co), tantalum (Ta), or tungsten (W).

3 . The method of claim 1 , wherein the barrier layer comprises tantalum nitride (TaN).

4 . The method of claim 1 , further comprising:

selectively depositing the barrier layer on the dielectric material over the metal material.

5 . The method of claim 4 , wherein selectively depositing the barrier layer comprises forming a self-assembled monolayer (SAM) on the metal material, depositing the barrier layer on the sidewalls of the gap, and removing the SAM.

6 . The method of claim 1 , wherein the alkyl reactant is the alkyl halide.

7 . The method of claim 6 , wherein the alkyl halide has a general formula RX, wherein R is an alkyl group having 1 to 20 carbon atoms and X is a halogen comprising one or more of F, CI, Br, I, or CF 3 .

8 . The method of claim 1 , wherein the alkyl reactant is the alkyl pseudohalide.

9 . The method of claim 8 , wherein the alkyl pseudohalide has a general formula of Ps-Ps or Ps-X, where Ps is a pseudohalogen group comprising one or more of cyanide (—CN), cyanate (—OCN), carbonyl (—CO), thiocyanate (—SCN), azide (—Ns), isocyanate (—NCO), isothiocyanate (—NCS), selenocyanate (—SeCN), or isoselenocyanate (—NCSe), and X is a halogen comprising one or more of F, CI, Br, I, or CF 3 .

10 . The method of claim 1 , wherein the metal liner comprises one or more of ruthenium (Ru), cobalt (cobalt), molybdenum (Mo), or tantalum (Ta).

11 . The method of claim 10 , wherein the metal liner consists essentially of ruthenium and a selectivity of the metal liner deposition is greater than or equal to 5.

12 . The method of claim 11 , wherein the metal liner is deposited by chemical vapor deposition.

13 . The method of claim 1 , further comprising removing the passivation layer by exposing the microelectronic device to hydrogen (H 2 ).

14 . The method of claim 13 , wherein exposing the microelectronic device to hydrogen (H 2 ) comprises exposing the microelectronic device to a thermal hydrogen (H 2 ) soak.

15 . The method of claim 13 , wherein exposing the microelectronic device to hydrogen (H 2 ) comprises exposing the microelectronic device to a H 2 plasma treatment.

16 . The method of claim 13 , further comprising a gap fill process to fill the gap with one or more of copper (Cu), cobalt (Co), or tungsten (W).

17 . The method of claim 1 , wherein the method reduces a resistance of a via by at least 20% as compared to a resistance of a via in a microelectronic device where a metal liner is not selectively deposited.

18 . A method of forming a microelectronic device, the method comprising:

forming a dielectric material on a substrate, the dielectric material comprising at least one feature defining a gap including sidewalls and a bottom, the bottom comprising a metal material;

selectively depositing a self-assembled monolayer (SAM) on the metal material;

depositing a barrier layer on the sidewalls of the gap;

removing the self-assembled monolayer (SAM) to expose the metal material;

passivating the metal material with one or more of an alkyl halide or an alkyl pseudohalide to form a passivation layer on the metal material; and

selectively depositing a metal liner on the barrier layer.

19 . The method of claim 18 , wherein the alkyl halide has a general formula RX, wherein R is an alkyl group having 1 to 20 carbon atoms and X is a halogen comprising one or more of F, CI, Br, I, CF 3 , and wherein the alkyl pseudohalide has a general formula of Ps-Ps or Ps-X, where Ps is a pseudohalogen group comprising one or more of cyanide (—CN), cyanate (—OCN), carbonyl (—CO), thiocyanate (—SCN), azide (—N 3 ), isocyanate (—NCO), isothiocyanate (—NCS), selenocyanate (—SeCN), or isoselenocyanate (—NCSe), and X is a halogen comprising one or more of F, CI, Br, I, or CF 3 .

20 . The method of claim 18 , wherein the metal liner is deposited with a selectivity of greater than or equal to 5.

Assignments (2)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Dec 20, 2023
From: CHEN, FENG
To: APPLIED MATERIALS, INC.
Reel/Frame 065921/0359 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Dec 19, 2023
From: ZHOU, YANG; CEN, JIAJIE; WU, ZHIYUAN; QU, GE; KIM, YONG JIN; JU, ZHENG; KASHEFI, KEVIN
To: APPLIED MATERIALS, INC.
Reel/Frame 065910/0408 →
Continuity (1)
Related Publication 20240420997A1 · Dec 19, 2024
References Cited (40)
US 6350687B1 · Avanzino et al. · 2002 [cited by applicant]
US 9677172B2 · Ha et al. · 2017 [cited by applicant]
US 10867905B2 · Wang et al. · 2020 [cited by applicant]
US 20020041028A1 · Choi et al. · 2002 [cited by applicant]
US 20060128142A1 · Whelan et al. · 2006 [cited by applicant]
US 20060128150A1 · Gandikota et al. · 2006 [cited by applicant]
US 20090032766A1 · Rajaratnam et al. · 2009 [cited by applicant]
US 20090104787A1 · Ohmi et al. · 2009 [cited by applicant]
US 20090215269A1 · Boggs et al. · 2009 [cited by applicant]
US 20090218693A1 · Lee · 2009 [cited by applicant]
US 20110244680A1 · Tohnoe et al. · 2011 [cited by applicant]
US 20120052681A1 · Marsh · 2012 [cited by applicant]
US 20120077342A1 · Gao et al. · 2012 [cited by applicant]
US 20160190060A1 · Bristol et al. · 2016 [cited by applicant]
US 20170162511A1 · Ren et al. · 2017 [cited by applicant]
US 20170323781A1 · Kachian et al. · 2017 [cited by applicant]
US 20180061628A1 · Ou · 2018 [cited by applicant]
US 20180233350A1 · Tois et al. · 2018 [cited by applicant]
US 20200321247A1 · Chen et al. · 2020 [cited by applicant]
US 20200350204A1 · Yu et al. · 2020 [cited by applicant]
US 20220028795A1 · Xu et al. · 2022 [cited by applicant]
US 20220122923A1 · Chen et al. · 2022 [cited by applicant]
US 20220275501A1 · Cervantes et al. · 2022 [cited by applicant]
US 20230072614A1 · Qu et al. · 2023 [cited by applicant]
CN 105374689A · 2016 [cited by examiner]
JP 2016086145A · 2016 [cited by applicant]
KR 20120037653A · 2012 [cited by applicant]
KR 20180093823A · 2018 [cited by applicant]
WO 2019018379A1 · 2019 [cited by applicant]
“PCT International Search Report and Written Opinion in PCT/US2024/034429 dated Oct. 8, 2024, 10 pages”. [cited by applicant]
Chen, Xi , et al., “Divide and Protect: Passivating Cu(111) by Cu-(benzotriazole)2”, The Journal of Physical Chemistry 2012, 116, Oct. 5, 2012, 222346-22349. [cited by applicant]
Farm, Elina , et al., “Passivation of copper surfaces for selective-area ALD using a thiol self-assembled monolayer”, Semiconductor Science and Technology 27 (2012) 074004, Jun. 22, 2012, 5 pages. [cited by applicant]
Kokalj, Anton , et al., “Density Functional Theory Study of ATA, BTAH,. and BTAOH as Copper Corrosion Inhibitors: Adsorption onto Cn(III) from Gas Phase”, Langmuir 2010, 26(18), 14582-14593. [cited by applicant]
Kokalj, Anton , et al., “The Effect of Surface Geometry of Copper on Dehydrogenation of Benzotriazole. Part II”, The Journal of Physical Chemistry 2014, 188, Dec. 12, 2013, 944-954. [cited by applicant]
Kokalj, Anton , et al., “What Determines the Inhibition Effectiveness of ATA, BTAH, and BTAOH Corrosion Inhibitors on Copper?”, Journal of the American Chemical Society 2010, 132, Oct. 29, 2010, 16657-16668. [cited by applicant]
Kuznetsov, Yu. I., et al., “Adsorption and passivation of copper by triazoles in neutral aqueous solution”, Int. J. Corros. Scale Inhib., 2014, 3, No. 2,, Mar. 13, 2014, 137-148. [cited by applicant]
Peljhan, Sebastijan , et al., “The Effect of Surface Geometry of Copper on Adsorption of Benzotriazole and CI. Part I”, The Journal of Physical Chemistry 2014, 118, Dec. 12, 2013, 933-943. [cited by applicant]
Pena, Luis Fabian, et al., “Vapor-Phase Cleaning and Corrosion Inhibition of Copper Films by Ethanol and Heterocyclic Amines”, American Chemical Society: Applied Materials & Interfaces 2018, 10, Oct. 18, 2018, 38610-386… [cited by applicant]
Sau, Samaresh Chandra, et al., “An Abnormal N-Heterocyclic Carbene-Copper(I) Complex in Click Chemistry”, Ad. Synth. Catal. 2013, 355, 2982-2991. [cited by applicant]
Wang, Yizhen , et al., “Click-assembling triazole membrane on copper surface via one-step or two-steps and their corrosion inhibition performance”, Applied Surface Science 427 (2018) 1120-1128. [cited by applicant]