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

• US 20050266700A1
• Filed: 05/05/2005
• Published: 12/01/2005
• Est. Priority Date: 05/05/2004
• Status: Active Grant

• Current Assignee: Gregory M. Jursich, Ronald S. Inman
• Original Assignee: Gregory M. Jursich, Ronald S. Inman
• Inventors: Jursich, Gregory M., Inman, Ronald S.
• Granted Patent: US 7,312,165 B2
• Time in Patent Office: Days
• US Class Current: 438/785
• CPC Class Codes: C23C 16/40 Oxides
• CPC Class Codes: C23C 16/45531 specially adapted for making ternary or higher compositions
• CPC Class Codes: H01L 21/02181 the material containing hafnium, e.g. HfO2
• CPC Class Codes: H01L 21/02205 the layer being characterised by the precursor material for deposition
• CPC Class Codes: H01L 21/0228 deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
• CPC Class Codes: H01L 21/3141 Deposition using atomic layer deposition techniques [ALD]
• CPC Class Codes: H01L 21/31604 Deposition from a gas or vapour H01L21/31691, H01L21/31695 take precedence
• CPC Class Codes: H01L 21/31645 Deposition of Hafnium oxides, e.g. HfO2

Abstract

Methods of film deposition using metals and metal oxides. A thin film of germanium oxide and an oxide of a non-germanium metal is deposited by ALD by alternating deposition of first and second precursor compounds, wherein the first precursor compound includes a metal other than germanium, and the second precursor compound includes germanium.

Claims

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, the second precursor compound including germanium; 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 a germanium tetraalkoxide of the formula Ge(OR¹)(OR²)(OR³)(OR⁴), wherein each of the groups R¹, R², R³, and R⁴ 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;

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

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

7. The method of claim 1, wherein the second precursor is 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:

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;

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

8. The method of claim 7, wherein the second precursor is tetrakis ethylmethylamino germanium, tetrakis dimethylamino germanium, or tetrakis diethylamino germanium.

9. 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)_rCH₃, 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.

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

a) titanium;

b) hafnium; and

c) zirconium.

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

12. The method of claim 9, wherein m is 4 and each R is CH₂CH₃.

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

a) titanium;

b) hafnium; and

c) zirconium.

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

a) titanium;

b) hafnium; and

c) zirconium.

15. The method of claim 1, wherein first precursor is an alkoxide of the formula MR_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 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.

16. The method of claim 15, wherein the metal M is selected from the group consisting of:

a) titanium;

b) hafnium;

c) lead;

d) tin; and

e) zirconium.

17. The method of claim 16, wherein each R is OC(CH₃)₃.

18. 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.

19. The method of claim 18, 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.

20. The method of claim 18, 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.

21. The method of claim 18, wherein the metal M is selected from the group consisting of:

a) titanium;

b) hafnium;

c) lead;

d) tin; and

e) zirconium.

22. The method of claim 18, 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)

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

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

25. 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.