US 12,031,209 B2
Reducing agents for atomic layer deposition
Bhaskar Jyoti Bhuyan, San Jose, CA (US); Mark Saly, Santa Clara, CA (US); Lakmal C. Kalutarage, San Jose, CA (US); and Thomas Knisley, Livonia, MI (US)
Assigned to Applied Materials, Inc., Santa Clara, CA (US)
Filed by Applied Materials, Inc., Santa Clara, CA (US)
Filed on Feb. 16, 2021, as Appl. No. 17/176,984.
Prior Publication US 2022/0259734 A1, Aug. 18, 2022
Int. Cl. C23C 16/18 (2006.01); C07F 7/00 (2006.01); C07F 7/02 (2006.01); C07F 7/22 (2006.01); C07F 7/30 (2006.01); C23C 16/455 (2006.01)
CPC C23C 16/45553 (2013.01) [C07F 7/003 (2013.01); C07F 7/025 (2013.01); C07F 7/2224 (2013.01); C07F 7/2284 (2013.01); C07F 7/30 (2013.01); C23C 16/18 (2013.01); C23C 16/45534 (2013.01)] 16 Claims
OG exemplary drawing
 
1. A method of forming a metal film, the method comprising exposing a metal halide film to a reducing agent, the reducing agent comprising one or more of
a. a group IV element containing heterocyclic compound having the formula,

OG Complex Work Unit Chemistry
wherein, each of R1 is independently a C1-C6 alkyl, alkenyl or alkynyl group or C1-C8 cycloalkyl or aryl group, X is a halogen, n is a number in a range of from 1 to 4, M1 is selected from a group consisting of Ge and Sn;
b. a radical initiator having a formula ((R2)3Si)3Si-H, where each R2 is independently H, C1-C6 alkyl, alkenyl or alkynyl group or C1-C8 cycloalkyl or aryl group, a halogen;
c. a diborene species having the formula

OG Complex Work Unit Chemistry
wherein, each of R4a, R4b, R4c and R4d are independently a C1-C6 alkyl group, or a strong electron-donating group, the strong electron-donating group comprises one or more of an N-heterocyclic carbene, an alkyl silane, an alkyl amide or an organic alcohol; or
d. a Sn(II) compound to reduce the metal film and form Sn(IV) compounds, wherein the Sn(II) compounds has a structure according to formula (X), (XI), (XII), (XIII) or (XIV),

OG Complex Work Unit Chemistry
wherein, each of R5 are independently selected from a group consisting of Cp, Cp* and Cp-Rz, where Rz is a C1-C6 alkyl group and z is 1 to 5,
wherein, each of R6 are independently selected from a group consisting of Si(Me)3, Me, Et, iPr and tBu,
wherein, each of R7 are independently selected from a group consisting of Me, CF3 and tBu,
wherein, each of R8 are independently selected from a group consisting of Me, iPr and tBu, and
wherein, each of R9 are independently selected from a group consisting of H, Me, iPr and tBu.