Method of depositing germanium-containing films

• US 7,141,488 B2
• Filed: 04/02/2004
• Issued: 11/28/2006
• Est. Priority Date: 04/05/2003
• Status: Expired due to Fees

• Current Assignee: Rohm and Haas Electronic Materials LLC (DuPont de Nemours, Inc.)
• Original Assignee: Rohm and Haas Electronic Materials LLC (DuPont de Nemours, Inc.)
• Inventors: Shenai-Khatkhate, Deodatta Vinayak, Woelk, Egbert
• Primary Examiner(s): Smoot, Stephen W.
• Application Number:
  US10/816,356
• Publication Number:
  US 20040197945A1
• Time in Patent Office: 970 Days
• Field of Search: 438/478
• US Class Current: 438/478
• CPC Class Codes: C07F 7/0807 comprising Si as a ring atom
• CPC Class Codes: C07F 7/30 Germanium compounds
• CPC Class Codes: C23C 16/18 from metallo-organic compounds
• CPC Class Codes: C23C 16/22 characterised by the deposition of inorganic material, other than metallic material
• CPC Class Codes: C23C 16/28 Deposition of only one other non-metal element

Abstract

Germanium compounds suitable for use as vapor phase deposition precursors for germanium films are provided. Methods of depositing films containing germanium using such compounds are also provided. Such germanium films are particularly useful in the manufacture of electronic devices.

Claims

1. A method of depositing a film containing germanium on a substrate comprising the steps of:

a) conveying two or more germanium compounds in a gaseous phase to a deposition chamber containing the substrate, wherein a first germanium compound is a halogermanium compound of the formula X¹<sub>4−

a</sub>GeR_a, wherein a=0–

3, each X¹ is independently a halogen, and each R is independently chosen from H, alkyl, alkenyl, alkynyl, aryl, and NR⁴R⁶, wherein each R⁴ and R⁶ are independently chosen from H, alkyl, alkenyl, alkynyl and aryl, and wherein a second germanium compound has the formula

2. The method of claim 1 wherein the two or more germanium compounds are provided from a single vapor delivery device.

3. The method of claim 1 wherein the first germanium compound is provided from a first vapor delivery device and the second germanium compound is provided from a second vapor delivery device.

4. The method of claim 3 wherein the first germanium compound is chosen from germanium tetrachloride and germanium tetrabromide.

5. The method of claim 1 wherein c′

=1–

3.

6. The method of claim 1 wherein a′

=c′

=0, b′

=1–

2 and d′

=2–

3.

7. A method of depositing a film containing germanium on a substrate comprising the steps of:

a) conveying two or more germanium compounds in a gaseous phase to a deposition chamber containing the substrate, wherein a first germanium compound is a halogermanium compound of the formula X¹<sub>4−

a</sub>GeR_a, wherein a=0–

3, each X¹ is independently a halogen, and each R is independently chosen from H, alkyl, alkenyl, alkynyl, aryl, and NR⁴R⁶, wherein each R⁴ and R⁶ are independently chosen from H, alkyl, alkenyl, alkynyl and aryl, provided that the first germanium compound is chosen from GeCl₄, GeBr₄ and GeI₄ when a =0 and each X¹ is the same; and

wherein a second germanium compound has the formula

8. The method of claim 7 wherein d′

=1–

4.

9. The method of claim 7 wherein a=1–

3.

10. The method of claim 7 wherein the first germanium compound is chosen from tetrachloro germane, tetrabromo germane, tetraiodo germane, chloro tribromo germane, dichloro dibromo germane, trichloro bromo germane, trichloro iodo germane, dichloro diiodo germane, trichloro iodo germane, tribromo iodo germane, dibromo diiodo germane, bromo triiodo germane, dichloro bromo iodo germane, chloro dibromo iodo germane, chloro bromo diiodo germane, trichloro fluoro germane, dichloro difluoro germane, chloro trifluoro germane, tribromo fluoro germane, dibromo difluoro germane, bromo trifluoro germane, iodo trifluoro germane, diiodo difluoro germane, triiodo fluoro germane, chloro bromo iodo fluoro germane, dichloro bromo fluoro germane, chloro dibromo fluoro germane, dibromo iodo fluoro germane, bromo diiodo fluoro germane, dichloro iodo fluoro germane and chloro diiodo fluoro germane;

and iso-propyl (dimethylamino) germanium dichloride;

methyl (dimethylamino) germanium dichloride;

methyl (dimethylamino) germanium dibromide;

dichloro (diethylamino) germane;

dichloro ethyl (diethylamino) germane;

dichloro tert-butyl (diethylamino) germane;

dichloro bis(dimethylamino) germane; and

chloro ethyl (dimethylaminopropyl) (dimethylamino) germane;

dichloro tert-butyl (dimethylamino) germane;

chloro di-iso-propyl (dimethylamino) germane;

trimethyl germanium chloride;

methyl germanium trichloride;

trimethyl germanium fluoride;

trimethyl germanium bromide;

tris(trifluoromethyl) germanium iodide;

methyl germanium trifluoride;

dimethyl germanium difluoride;

dichloro methyl germane;

dimethyl germanium dichloride;

trimethyl germanium iodide;

vinyl germanium trichloride;

ethyl germanium trichloride;

chloro tert-butyl dimethyl germane;

allyl germanium trichloride;

tert-butyl germanium trichloride;

diethyl germanium dichloride;

trimethyl germanium chloride;

n-butyl germanium trichloride;

trimethyl germanium bromide;

di-n-butyl germanium dichloride;

phenyl germanium dichloride;

tri-n-butyl germanium bromide;

tri-n-butyl germanium chloride; and

benzyl germanium trichloride.

11. A method of depositing a film containing germanium on a substrate comprising the steps of:

a) conveying two or more germanium compounds in a gaseous phase to a deposition chamber containing the substrate, wherein a first germanium compound is a halogermanium compound of the formula X¹<sub>4−

a</sub>GeR_a, wherein a=0–

3, each X¹ is independently a halogen, and each R is independently chosen from H, alkyl, alkenyl, alkynyl, aryl, and NR⁴R⁶, wherein each R⁴ and R⁶ are independently chosen from H, alkyl, alkenyl, alkynyl and aryl, and wherein a second germanium compound has the formula

12. The method of claim 11 wherein the second germanium compound is chosen from alkyl germanes, amino germanes and halogermanium compounds.

13. The method of claim 12 wherein the second germanium compound is chosen from tetramethyl germane, tetraethyl germane, tetra-n-propyl germane, methyl germane, dimethyl germane, trimethyl germane, ethyl germane, diethyl germane, trimethyl germane, dimethyl diethyl germane, tert-butyl methyl germane, tert-butyl dimethyl germane, tert-butyl trimethyl germane, tert-butyl ethyl germane, tert-butyl diethyl germane, tert-butyl trimethyl germane, tert-butyl iso-propyl germane, methyl tert-butyl iso-propyl germane, iso-propyl germane, di-iso-propyl germane, di-iso-propyl dimethyl germane, tri-iso-propyl germane, tri-iso-propyl methyl germane, di-iso-propyl diethyl germane, (dimethylamino) germane, bis-(dimethylamino) germane, methyl (dimethylamino) germane, ethyl (dimethylamino) germane, diethyl (diethylamino) germane, tert-butyl (dimethylamino)germane, tert-butyl bis(dimethylamino) germane, ethyl tert-butyl bis(dimethylamino) germane, iso-propyl (dimethylamino)germane, iso-propyl (diethylamino) germane, di-iso-propyl bis(dimethylamino) germane, n-propyl (dimethylamino) germane, n-propyl (diethylamino) germane;

tert-butyl dimethyl germanium chloride, tert-butyl dimethyl germanium bromide, tert-butyl diethyl germanium chloride, tert-butyl diethyl germanium iodide, dimethyl germanium dichloride, trimethyl germanium chloride, trimethyl germanium bromide, tert-butyl germanium trichloride, iso-propyl germanium chloride, iso-propyl germanium trichloride, di-iso-propyl germanium dibromide, iso-propyl dimethyl germanium chloride, iso-propyl methyl germanium dichloride, and iso-propyl dimethyl germanium bromide.

14. The method of claim 11 wherein the two or more germanium compounds are present in a mole ratio of 5:

95 to 95;

5.

15. The method of claim 14 wherein the two or more germanium compounds are present in a mole ratio of 25:

75 to 75;

25.