Codeposition of hafnium-germanium oxides on substrates used in or for semiconductor devices

1. A method of depositing a thin film of germanium oxide and an oxide of a non-germanium metal by atomic layer deposition (ALD) onto a substrate in an ALD chamber, comprising the steps of:

a) chemisorbing a first precursor compound onto the substrate, the first precursor compound including the non-germanium metal;

b) allowing a first co-reactant compound to react with the first precursor compound chemisorbed onto the substrate thereby forming a thin film of an oxide of the non-germanium metal, the first co-reactant compound including oxygen;

c) chemisorbing a second precursor compound onto the thin film of the oxide of the non-germanium metal, wherein the second precursor compound comprises at least one member selected from the group consisting of:

1) a germanium tetraalkoxide of the formula Ge(OR1)(OR2)(OR3)(OR4), wherein each of the groups R1, R2, R3, and R4 is selected from:

i) the formula (CH2)nCH3, wherein n ranges from 0 to 3;

ii) the formula C(CH3)3; or

iii) the formula CH(CH3)2;

and wherein each of the R1, R2, R3, and R4 groups may be the same or different, and

2) a germanium alkylamine of the formula Ge(NR1R2)(NR3R4)(NR5R6), wherein each of the groups R1, R2, R3, R4, R5 and R6 is selected from:

i) the formula (CH2)nCH3, wherein n ranges from 0 to 3;

ii) the formula C(CH3)3; or

iii) the formula CH(CH3)2;

and wherein each of the R1, R2, R3, R4, R5 and R6 groups may be the same or different, and

d) allowing a second co-reactant compound to react with the second precursor compound chemisorbed onto the thin film of an oxide of the non-germanium metal thereby forming a thin film of germanium oxide on the thin film of the oxide of the non-germanium metal.

2. The method of claim 1 , wherein the non-germanium metal is selected from the group consisting of:

a) zirconium;

b) niobium;

c) molybdenum;

d) ruthenium

e) iridium;

f) hafnium;

g) lead;

h) tin;

i) tantalum;

j) titanium;

k) tungsten;

l) osmium;

m) vanadium;

n) chromium;

o) rhenium;

p) rhodium; and

q) columbium.

3. The method of claim 1 , wherein the non-germanium metal is selected from the group consisting of:

a) titanium;

b) hafnium;

c) lead;

d) tin; or

e) zirconium.

4. The method of claim 1 , wherein the non-germanium metal is hafnium.

5. The method of claim 1 wherein the second precursor is tetrakis methoxide germanium, tetrakis ethoxide germanium, or tetrakis isopropoxide germanium.

6. The method of claim 1 , wherein the second precursor is tetrakis ethylmethylamino germanium, tetrakis dimethylamino germanium, or tetrakis diethylamino germanium.

7. The method of claim 1 , wherein the first precursor is an alkylamine of the formula M(NR)m, wherein:

M is one of zirconium, niobium, molybdenum, ruthenium, iridium, hafnium, lead, tin, tantalum, titanium, tungsten, osmium, vanadium, chromium, rhenium, and rhodium and niobium;

each R is selected from:

a) the formula (CH2)nCH3, wherein n ranges from 0 to 3;

b) the formula C(CH3)3; or

c) the formula CH(CH3)2;

each R may be the same or different; and

m is the valence number of the metal M.

8. The method of claim 7 , wherein the metal M is selected from the group consisting of:

a) titanium;

b) hafnium; and

c) zirconium.

9. The method of claim 7 , wherein m is 4 and each R is CH3.

10. The method of claim 7 , wherein m is 4 and each R is CH2CH3.

11. The method of claim 9 , wherein the metal M is selected from the group consisting of:

a) titanium;

b) hafnium; and

c) zirconium.

12. The method of claim 11 , wherein the metal M is selected from the group consisting of:

a) titanium;

b) hafnium; and

c) zirconium.

13. The method of claim 1 , wherein first precursor is an alkoxide of the formula MRm, wherein:

M is one of zirconium, niobium, molybdenum, ruthenium, iridium, hafnium, lead, tin, tantalum, titanium, tungsten, osmium, vanadium, chromium, rhenium, and rhodium and niobium;

each R is selected from:

a) the formula O(CH2)nCH3, wherein n ranges from 0 to 3, and m is the valence number of the metal M;

b) the formula OC(CH3)3; or

c) the formula OCH(CH3)2; and

each R is the same or different.

14. The method of claim 13 , wherein the metal M is selected from the group consisting of:

a) titanium;

b) hafnium;

c) lead;

d) tin; and

e) zirconium.

15. The method of claim 14 , wherein each R is OC(CH3)3.

16. The method of claim 1 , wherein the first precursor is a diketonate of the formula MR″m, wherein:

M is a metal and is one of zirconium, niobium, molybdenum, ruthenium, iridium, hafnium, lead, tin, tantalum, titanium, tungsten, osmium, vanadium, chromium, rhenium, and rhodium, and niobium, m is the valence number of the metal M;

R″ is of the formula

either R is the same or different alkyl or alkoxide;

each R″ is the same or different; and

m is the valence number of the metal M.

17. The method of claim 16 , wherein the alkyls are those of the formula:

a) (CH2)nCH3, wherein n ranges from 0 to 3;

b) C(CH3)3; or

c) CH(CH3)2.

18. The method of claim 16 , wherein the alkoxides are those of the formula:

a) O(CH2)nCH3, wherein n ranges from 0 to 3;

b) OC(CH3)3; or

c) OCH(CH3)2.

19. The method of claim 16 , wherein the metal M is selected from the group consisting of:

a) titanium;

b) hafnium;

c) lead;

d) tin; and

e) zirconium.

20. The method of claim 16 , wherein the first precursor is lead bis(2,2,6,6-tetramethyl-3,5-heptanedionate), zirconium tetrakis(2,2,6,6-tetramethyl-3,5-heptanedionate), tin tetrakis(2,2,6,6-tetramethyl-3,5-heptanedionate), zirconium tetrakis(2,4-pentanedionate), and titanium tetrakis(2,4-pentanedionate).

21. The method of claim 1 , wherein the first and second coreactant compounds are H2O.

22. The method of claim 1 , wherein the first and second coreactant compounds are O2, O3, or a nitrogen oxide.

23. The method of claim 1 , wherein a combination of the thin film of germanium oxide on the thin film of the oxide of the non-germanium metal consists essentially of germanium, the non-germanium metal, and oxygen.