US6368398B2 — Method of depositing films by using carboxylate c…

Claim 1

Independent Claim 180 words

A method of manufacturing a semiconductor structure comprising: providing a semiconductor substrate or substrate assembly; providing a precursor comprising one or more carboxylate complexes of the formula: M n+ (OC(O)R 1 ) u (OR 2 ) v {(R 3 )(R 4 )N[(CH 2 ) w N(R 5 )] x (CH 2 ) y N(R 6 )(R 7 )} z (Formula I) or M n+ (OC(O)R 1 ) u (O) v {(R 3 )(R 4 )N[(CH 2 ) w N(R 5 )] x (CH 2 ) y N(R 6 )(R 7 )} z (Formula II) wherein: M is a metal or metalloid; each R is H or an organic group; n+ is the valence oxidation state of the metal or metalloid; u=1 to n; v=0 to n−1; w=1 to 5; x=0 to 8; y=1 to 5; z>0; and u+v=n for Formula I or u+2v=n for Formula II; and vaporizing the precursor and directing it toward the semiconductor substrate or substrate assembly using a chemical vapor deposition technique to form a film on a surface of the semiconductor substrate or substrate assembly.

Claim 2

Independent Claim 180 words

A method of manufacturing a semiconductor structure comprising: providing a semiconductor substrate or substrate assembly; providing a precursor comprising one or more carboxylate complexes of the formula: M n+ (OC(O)R 1 ) u (OR 2 ) v {(R 3 )(R 4 )N[(CH 2 ) w N(R 5 )] x (CH 2 ) y N(R 6 )(R 7 )} z (Formula I) or M n+ (OC(O)R 1 ) u (O) v {(R 3 )(R 4 )N[(CH 2 ) w N(R 5 )] x (CH 2 ) y N(R 6 )(R 7 )} z (Formula II) wherein: M is a metal or metalloid; each R is H or an organic group; n+ is the valence oxidation state of the metal or metalloid; u=1 to n; v=0 to n−1; w=1 to 5; x=0 to 8; y=1 to 5; z>0; and u+v=n for Formula I or u+2v=n for Formula II; and vaporizing the precursor and directing it toward the semiconductor substrate or substrate assembly using a chemical vapor deposition technique to form a film on a surface of the semiconductor substrate or substrate assembly.

Claim 3

Dependent Claim 17 words

The method of claim 1 wherein the precursor is vaporized in the presence of a carrier gas.

Claim 4

Dependent Claim 17 words

The method of claim 2 wherein the precursor is vaporized in the presence of a reaction gas.

Claim 5

Dependent Claim 48 words

The method of claim 3 wherein: the carrier gas is selected from the group consisting of nitrogen, helium, argon, and mixtures thereof; and the reaction gas is selected from the group consisting of oxygen, nitrous oxide, ammonia, water vapor, hydrogen sulfide, hydrogen selenide, hydrogen telluride, and mixtures thereof.

Claim 6

Dependent Claim 21 words

The method of claim 4 wherein the film is a film of an oxide, sulfide, nitride, selenide, telluride, or mixture thereof.

Claim 7

Dependent Claim 17 words

The method of claim 1 wherein the film is an oxide film and forms a dielectric layer.

Claim 8

Dependent Claim 12 words

The method of claim 1 wherein the precursor is a liquid precursor.

Claim 9

Dependent Claim 20 words

The method of claim 7 wherein the chemical vapor deposition technique comprises flash vaporization, bubbling, microdroplet formation, or combinations thereof.

Claim 10

Dependent Claim 31 words

The method of claim 1 wherein M is selected from the group consisting of Group IA, Group IIA, Group IIIA, Group IIIB, Group IVB, Group VA, Group VB, and the lanthanides.

Claim 11

Dependent Claim 13 words

The method of claim 1 wherein x=0 to 4 and z=0 to 2.

Claim 12

Dependent Claim 9 words

The method of claim 1 wherein n+=1 to 8.

Claim 13

Dependent Claim 24 words

The method of claim 1 wherein each R 1 and R 2 group is independently H or a (C 1 -C 30 )organic group.

Claim 14

Dependent Claim 34 words

The method of claim 1 wherein each R 3 , R 4 , R 5 , R 6 , and R 7 group is independently H or a (C 1 -C 10 )organic group.

Claim 15

Dependent Claim 14 words

The method of claim 13 wherein each organic group is a heteroatom-free organic group.

Claim 16

Dependent Claim 61 words

The method of claim 1 wherein the carboxylate complex is a compound of the formula (Formula III): M n+ (OC(O)R 1 ) u (OR 2 ) v wherein: M is a metal selected from the group consisting of Group IVB and Group VB; each R is H or an organic group; n=1 to 5; u=1 to n; and v=0 to n=1.

Claim 17

Dependent Claim 97 words

The method of claim 1 where in the carboxylate complex is a compound of the formula (Formula IV): M n+ (OC(O)R 1 ) u {(R 3 )(R 4 )N[(CH 2 ) w N(R 5 )] x (CH 2 ) y N(R 6 )(R 7 )} z wherein: M is a metal or metalloid selected from the group consisting of Group IA, Group IIA, Group IIIA, Group IIIB, and the lanthanides; each R is H or an organic group; n=1 to 4; u=1 to n; w=1 to 5; x=0 to 8; y=1 to 5; and z=1 to 5.

Claim 18

Independent Claim 196 words

A method of manufacturing a memory device structure comprising: providing a substrate having a first electrode thereon; providing a precursor comprising one or more carboxylate complexes of the formula: M n+ (OC(O)R 1 ) u (OR 2 ) v {(R 3 )(R 4 )N[(CH 2 ) w N(R 5 )] x (CH 2 ) y N(R 6 )(R 7 )} z (Formula I) or M n+ (OC(O)R 1 ) u (O) v {(R 3 )(R 4 )N[(CH 2 ) w N(R 5 )] x (CH 2 ) y N(R 6 )(R 7 )} z (Formula II) wherein: M is a metal or metalloid; each R is H or an organic group; n+ is the valence oxidation state of the metal or metalloid; u=1 to n; v=0 to n−1; w=1 to 5; x=0 to 8; y=1 to 5; z>0; and u+v=n for Formula I or u+2v=n for Formula II; and forming a first electrode on the substrate; vaporizing the precursor and directing it toward the substrate using a chemical vapor deposition technique to form a dielectric layer comprising an oxide film on the first electrode of the substrate; and forming a second electrode on the dielectric layer.

Claim 19

Independent Claim 196 words

A method of manufacturing a memory device structure comprising: providing a substrate having a first electrode thereon; providing a precursor comprising one or more carboxylate complexes of the formula: M n+ (OC(O)R 1 ) u (OR 2 ) v {(R 3 )(R 4 )N[(CH 2 ) w N(R 5 )] x (CH 2 ) y N(R 6 )(R 7 )} z (Formula I) or M n+ (OC(O)R 1 ) u (O) v {(R 3 )(R 4 )N[(CH 2 ) w N(R 5 )] x (CH 2 ) y N(R 6 )(R 7 )} z (Formula II) wherein: M is a metal or metalloid; each R is H or an organic group; n+ is the valence oxidation state of the metal or metalloid; u=1 to n; v=0 to n−1; w=1 to 5; x=0 to 8; y=1 to 5; z>0; and u+v=n for Formula I or u+2v=n for Formula II; and forming a first electrode on the substrate; vaporizing the precursor and directing it toward the substrate using a chemical vapor deposition technique to form a dielectric layer comprising an oxide film on the first electrode of the substrate; and forming a second electrode on the dielectric layer.

Claim 20

Dependent Claim 12 words

The method of claim 17 wherein the substrate is a silicon wafer.

Claim 21

Dependent Claim 13 words

The method of claim 17 wherein the oxide film forms a ferroelectric layer.

Claim 22

Dependent Claim 31 words

The method of claim 17 wherein M is selected from the group consisting of Group IA, Group IIA, Group IIIA, Group IIIB, Group IVB, Group VA, Group VB, and the lanthanides.

Claim 23

Dependent Claim 21 words

The method of claim 20 wherein M is selected from the group consisting of Ba, Sr, Nb, Ta, Ti, and Bi.

Claim 24

Dependent Claim 13 words

The method of claim 17 wherein x=0 to 4 and z=0 to 2.

Claim 25

Dependent Claim 9 words

The method of claim 17 wherein n+=1 to 8.

Claim 26

Dependent Claim 24 words

The method of claim 17 wherein each R 1 and R 2 group is independently H or a (C 1 -C 30 )organic group.

Claim 27

Dependent Claim 13 words

The method of claim 24 wherein each organic group is a nonaromatic group.

Claim 28

Dependent Claim 34 words

The method of claim 17 wherein each R 3 , R 4 , R 5 , R 6 , and R 7 group is independently H or a (C 1 -C 10 )organic group.

Claim 29

Dependent Claim 15 words

The method of claim 26 wherein each group organic group is a heteroatom-free organic group.

Claim 30

Dependent Claim 61 words

The method of claim 17 wherein the carboxylate complex is a compound of the formula (Formula III): M n+ (OC(O)R 1 ) u (OR 2 ) v wherein: M is a metal selected from the group consisting of Group IVB and Group VB; each R is H or an organic group; n=1 to 5; u=1 to n; and v=0 to n−1.

Claim 31

Dependent Claim 96 words

The method of claim 17 wherein the carboxylate complex is a compound of the formula (Formula IV): M n+ (OC(O)R 1 ) u {(R 3 )(R 4 )N[(CH 2 ) w N(R 5) ] x (CH 2 ) y N(R 6 )(R 7 )} z wherein: M is a metal or metalloid selected from the group consisting of Group IA, Group IIA, Group IIIA, Group IIIB, and the lanthanides; each k is H or an organic group; n=1 to 4; u=1 to n; w=1 to 5; x=0 to 8; y=1 to 5; and z=1 to 5.

Claim 32

Dependent Claim 22 words

The method of claim 17 wherein the precursor is a liquid precursor which is vaporized in the presence of a carrier gas.

Claim 33

Dependent Claim 17 words

The method of claim 30 wherein the precursor is vaporized in the presence of a reaction gas.

Claim 34

Dependent Claim 47 words

The method of claim 31 wherein: the carrier gas is selected from the group consisting of nitrogen, helium, argon, and mixtures thereof; and the reaction gas is,selected from the group consisting of oxygen, nitrous oxide, ammonia, water vapor, hydrogen sulfide, hydrogen selenide, hydrogen telluride, and mixtures thereof.

Claim 35

Independent Claim 167 words

A method of forming a film on a substrate comprising: providing a substrate; providing a precursor comprising one or more carboxylate complexes of the formula: M n+ (OC(O)R 1 ) u (OR 2 ) v {(R 3 )(R 4 )N[(CH 2 ) w N(R 5 )] x (CH 2 ) y N(R 6 )(R 7 )} z (Formula I) or M n+ (OC(O)R 1 ) u (O) v {(R 3 )(R 4 )N[(CH 2 ) w N(R 5 )] x (CH 2 ) y N(R 6 )(R 7 )} z (Formula II) wherein: M is a metal or metalloid; each R is H or an organic group; n+ is the valence oxidation state of the metal or metalloid; u=1 to n; v=0 to n−1; w=1 to 5; x=0 to 8; y=1 to 5; z>0; and u+v=n for Formula I or u+2v=n for Formula lI; and vaporizing the precursor and directing it toward the substrate using a chemical vapor deposition technique to form a film on the substrate.

Claim 36

Independent Claim 167 words

A method of forming a film on a substrate comprising: providing a substrate; providing a precursor comprising one or more carboxylate complexes of the formula: M n+ (OC(O)R 1 ) u (OR 2 ) v {(R 3 )(R 4 )N[(CH 2 ) w N(R 5 )] x (CH 2 ) y N(R 6 )(R 7 )} z (Formula I) or M n+ (OC(O)R 1 ) u (O) v {(R 3 )(R 4 )N[(CH 2 ) w N(R 5 )] x (CH 2 ) y N(R 6 )(R 7 )} z (Formula II) wherein: M is a metal or metalloid; each R is H or an organic group; n+ is the valence oxidation state of the metal or metalloid; u=1 to n; v=0 to n−1; w=1 to 5; x=0 to 8; y=1 to 5; z>0; and u+v=n for Formula I or u+2v=n for Formula lI; and vaporizing the precursor and directing it toward the substrate using a chemical vapor deposition technique to form a film on the substrate.

Claim 37

Dependent Claim 17 words

The method of claim 33 wherein the precursor is vaporized in the presence of a carrier gas.

Claim 38

Dependent Claim 17 words

The method of claim 34 wherein the precursor is vaporized in the presence of a reaction gas.

Claim 39

Dependent Claim 48 words

The method of claim 35 wherein: the carrier gas is selected from the group consisting of nitrogen, helium, argon, and mixtures thereof; and the reaction gas is selected from the group consisting of oxygen, nitrous oxide, ammonia, water vapor, hydrogen sulfide, hydrogen selenide, hydrogen telluride, and mixtures thereof.

Claim 40

Dependent Claim 21 words

The method of claim 36 wherein the film is a film of an oxide, sulfide, nitride, selenide, telluride, or mixture thereof.

Claim 41

Dependent Claim 12 words

The method of claim 37 wherein the film is an oxide film.

Claim 42

Dependent Claim 18 words

The method of claim 38 wherein the oxide film forms a ferroelectric layer in a ferroelectric memory device.

Claim 43

Dependent Claim 12 words

The method of claim 33 wherein the substrate comprises a silicon substrate.

Claim 44

Dependent Claim 26 words

The method of claim 33 wherein the precursor is a liquid precursor and the step of vaporizing comprises flash vaporization, bubbling, microdroplet formation, or combinations thereof.

Claim 45

Dependent Claim 31 words

The method of claim 33 wherein M is selected from the group consisting of Group IA, Group IIA, Group IIIA, Group IIIB, Group IVB, Group VA, Group VB, and the lanthanides.

Claim 46

Dependent Claim 13 words

The method of claim 33 wherein x=0 to 4 and z=0 to 2.

Claim 47

Dependent Claim 9 words

The method of claim 33 wherein n+=1 to 8.

Claim 48

Dependent Claim 24 words

The method of claim 33 wherein each R 1 and R 2 group is independently H or a (C 1 -C 30 )organic group.

Claim 49

Dependent Claim 24 words

The method of claim 45 wherein each R 1 and R 2 group is independently H or a (C 1 -C 30 )aliphatic group.

Claim 50

Dependent Claim 24 words

The method of claim 46 wherein each R 1 and R 2 group is independently H or a (C 1 -C 8 )alkyl moiety.

Claim 51

Dependent Claim 34 words

The method of claim 46 wherein each R 3 , R 4 , R 5 , R 6 , and R 7 group is independently H or a (C 1 -C 5 )alkyl moiety.

Claim 52

Dependent Claim 34 words

The method of claim 33 wherein each R 3 , R 4 , R 5 , R 6 , and R 7 group is independently H or a (C 1 -C 10 )aliphatic group.

Claim 53

Dependent Claim 61 words

The method of claim 33 wherein the carboxylate complex is a compound of the formula (Formula III): M n+ (OC(O)R 1 ) u (OR 2 ) v wherein: M is a metal selected from the group consisting of Group IVB and Group VB; each R is H or an organic group; n=1 to 5; u=1 to n; and v=0 to n−1.

Claim 54

Dependent Claim 96 words

The method of claim 33 wherein the carboxylate complex is a compound of the formula (Formula IV): M n+ (OC(O)R 1 ) u {(R 3 )(R 4 )N[(CH 2 ) w N(R 5 )] x (CH 2 ) y N(R 6 )(R 7 )} z wherein: M is a metal or metalloid selected from the group consisting of Group IA, Group IIA, Group IIIA, Group IIIB, and the lanthanides; each R is H or an organic group; n=1 to 4; u=1 to n; w=1 to 5; x=0 to 8; y=1 to 5; and z=1 to 5.

Claim 55

Independent Claim 174 words

A method of forming a film on a substrate comprising: providing a substrate; providing a liquid precursor comprising one or more carboxylate complexes of the formula: M n+ (OC(O)R 1 ) u (OR 2 ) v {(R 3 )(R 4 )N[(CH 2 ) w N(R 5 )] x (CH 2 ) y N(R 6 )(R 7 )} z (Formula I) or M n+ (OC(O)R 1 ) u (O) v {(R 3 )(R 4 )N[(CH 2 ) w N(R 5 )] x (CH 2 ) y N(R 6 )(R 7 )} z (Formula II) wherein: M is a metal or metalloid; each R is H or an organic group; n+ is the valence oxidation state of the metal or metalloid; u=1 to n; v=0 to n−1; w=1 to 5; x=0 to 8; y=1 to 5; z>0; and u+v=n for Formula I or u+2v=n for Formula II; generating microdroplets of the liquid precursor; vaporizing the microdroplets using a heated carrier gas; and directing the vaporized microdroplets toward the substrate to form a film on the substrate.

Claim 56

Independent Claim 174 words

A method of forming a film on a substrate comprising: providing a substrate; providing a liquid precursor comprising one or more carboxylate complexes of the formula: M n+ (OC(O)R 1 ) u (OR 2 ) v {(R 3 )(R 4 )N[(CH 2 ) w N(R 5 )] x (CH 2 ) y N(R 6 )(R 7 )} z (Formula I) or M n+ (OC(O)R 1 ) u (O) v {(R 3 )(R 4 )N[(CH 2 ) w N(R 5 )] x (CH 2 ) y N(R 6 )(R 7 )} z (Formula II) wherein: M is a metal or metalloid; each R is H or an organic group; n+ is the valence oxidation state of the metal or metalloid; u=1 to n; v=0 to n−1; w=1 to 5; x=0 to 8; y=1 to 5; z>0; and u+v=n for Formula I or u+2v=n for Formula II; generating microdroplets of the liquid precursor; vaporizing the microdroplets using a heated carrier gas; and directing the vaporized microdroplets toward the substrate to form a film on the substrate.

Claim 57

Dependent Claim 133 words

A chemical vapor deposition precursor comprising two or more carboxylate complexes of the formula: M n+ (OC(O)R 1 ) u (OR 2 ) v {(R 3 )(R 4 )N[(CH 2 ) w N(R 5 )] x (CH 2 ) y N(R 6 )(R 7 )} z (Formula I) or M n+ (OC(O)R 1 ) u (O) v {(R 3 )(R 4 )N[(CH 2 ) w N(R 5 )] x (CH 2 ) y N(R 6 )(R 7 )} z (Formula II) wherein: M is a metal or metalloid; each R is H or an organic group; n+ is the valence oxidation state of the metal or metalloid; u=1 to n; v=0 to n−1; w=1 to 5; x=0 to 8; y=1 to 5; z>0; and u+v=n for Formula I or u+2v for Formula II.

Claim 58

Dependent Claim 133 words

A chemical vapor deposition precursor comprising two or more carboxylate complexes of the formula: M n+ (OC(O)R 1 ) u (OR 2 ) v {(R 3 )(R 4 )N[(CH 2 ) w N(R 5 )] x (CH 2 ) y N(R 6 )(R 7 )} z (Formula I) or M n+ (OC(O)R 1 ) u (O) v {(R 3 )(R 4 )N[(CH 2 ) w N(R 5 )] x (CH 2 ) y N(R 6 )(R 7 )} z (Formula II) wherein: M is a metal or metalloid; each R is H or an organic group; n+ is the valence oxidation state of the metal or metalloid; u=1 to n; v=0 to n−1; w=1 to 5; x=0 to 8; y=1 to 5; z>0; and u+v=n for Formula I or u+2v for Formula II.

Claim 59

Dependent Claim 145 words

A chemical vapor deposition precursor comprising: at least one compound of the formula (Formula III): M n+ (OC(O)R 1 ) u (OR 2 ) v wherein: M is a metal selected from the group consisting of Group IVB and Group VB; each R is H or an organic group; n=1 to 5; u=1 to n; and v=0 to n−1;and at least one compound of the formula (Formula IV): M n+ (OC(O)R 1 ) u {(R 3 )(R 4 )N[(CH 2 ) w N(R 5 )] x (CH 2 ) y N(R 6 )(R 7 )} z wherein: M is a metal or metalloid selected from the group consisting of Group IA, Group IIA, Group IRA, Group MB, and the lanthanides; each R is H or an organic group; n=1 to 4; u=1 to n; w=1 to 5; x=0 to 8; y=1 to 5; and z>0.

Claim 60

Dependent Claim 145 words

A chemical vapor deposition precursor comprising: at least one compound of the formula (Formula III): M n+ (OC(O)R 1 ) u (OR 2 ) v wherein: M is a metal selected from the group consisting of Group IVB and Group VB; each R is H or an organic group; n=1 to 5; u=1 to n; and v=0 to n−1;and at least one compound of the formula (Formula IV): M n+ (OC(O)R 1 ) u {(R 3 )(R 4 )N[(CH 2 ) w N(R 5 )] x (CH 2 ) y N(R 6 )(R 7 )} z wherein: M is a metal or metalloid selected from the group consisting of Group IA, Group IIA, Group IRA, Group MB, and the lanthanides; each R is H or an organic group; n=1 to 4; u=1 to n; w=1 to 5; x=0 to 8; y=1 to 5; and z>0.

Annuity Stage	Window Opens	Payment Deadline	Surcharge Period Until	Estimated Fee	Status
3.5 Years (Year 4)	2005-04-08	2005-10-08	2006-04-09	$2000.00	Window Closed / Lapsed
7.5 Years (Year 8)	2009-04-08	2009-10-08	2010-04-09	$3760.00	Window Closed / Lapsed
11.5 Years (Year 12)	2013-04-08	2013-10-08	2014-04-09	$7700.00	Window Closed / Lapsed

Method of depositing films by using carboxylate complexes

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