Method and apparatus for production of metal film or the like

• US 7,208,421 B2
• Filed: 03/07/2003
• Issued: 04/24/2007
• Est. Priority Date: 03/08/2002
• Status: Expired due to Fees

• Current Assignee: Canon Anelva Corporation (Canon Inc.)
• Original Assignee: Mitsubishi Heavy Industries, Ltd.
• Inventors: Yahata, Naoki, Tonegawa, Hiroshi, Ooba, Yoshiyuki, Koshiro, Ikumasa, Nishimori, Toshihiko, Ogura, Yuzuru, Sakamoto, Hitoshi
• Primary Examiner(s): Vinh; Lan
• Application Number:
  US10/384,932
• Publication Number:
  US 20040029384A1
• Time in Patent Office: 1,509 Days
• Field of Search: 438/641, 438/642, 438/674, 438/675, 438/706, 438/710, 216/58, 216/67, 216/69, 156/345.3, 156/345, 156/52
• US Class Current: 438/715
• CPC Class Codes: C23C 16/08 from metal halides
• CPC Class Codes: C23C 16/14 Deposition of only one other metal element
• CPC Class Codes: C23C 16/4488 by in situ generation of reactive gas by chemical or electrochemical reaction
• CPC Class Codes: H01J 2237/3326 high speed
• CPC Class Codes: H01J 37/321 the radio frequency energy being inductively coupled to the plasma
• CPC Class Codes: H01J 37/32357 Generation remote from the workpiece, e.g. down-stream
• CPC Class Codes: H01L 21/28556 by chemical means, e.g. CVD, LPCVD, PECVD, laser CVD H01L21/28518 - H01L21/28537 and H01L21/28568 take precedence
• CPC Class Codes: H01L 21/76879 by selective deposition of conductive material in the vias, e.g. selective C.V.D. on semiconductor material, plating plating on semiconductors in general H01L21/288

Abstract

In a metal film production apparatus, a copper plate member is etched with a Cl₂ gas plasma within a chamber to form a precursor comprising a Cu component and a Cl₂ gas; and the temperatures of the copper plate member and a substrate and a difference between their temperatures are controlled as predetermined, to deposit the Cu component of the precursor on the substrate, thereby forming a film of Cu. In this apparatus, Cl* is formed in an excitation chamber of a passage communicating with the interior of the chamber to flow a Cl₂ gas, and the Cl* is supplied into the chamber to withdraw a Cl₂ gas from the precursor adsorbed onto the substrate, thereby promoting a Cu film formation reaction. The apparatus has a high film formation speed, can use an inexpensive starting material, and can minimize impurities remaining in the film.

Claims

1. A metal film production method which comprises:

independently disposing an etched member, formed from a metal forming a high vapor pressure halide, at a position opposed to a substrate in a chamber accommodating the substrate in an interior thereof;

etching the etched member with a source gas plasma containing a halogen within the chamber to form a precursor comprising a metallic component and the halogen; and

controlling temperatures of the etched member and the substrate so as to effect a temperature of the substrate lower than a temperature of the etched member and so as to provide a temperature difference at least equal to or more than 100 degrees C. between the temperature of the substrate and the temperature of the etched member, thereby adsorbing the precursor onto the substrate,

said metal film production method further comprising;

separately generating radicals of another halogen; and

replenishing the generated radicals of the other halogen around a vicinity of the substrate to extract a halogen from the precursor adsorbed onto the substrate, thereby depositing the metallic component on the substrate for performing the predetermined film formation.

2. The metal film production method according to claim 1, wherein the radicals of the other halogen are obtained by applying a high frequency electric field to the other halogen flowing through a tubular passage communicating with the interior of the chamber to convert the source gas into a plasma.

3. The metal film production method according to claim 1, wherein the radicals of the other halogen are obtained by supplying microwaves to the other halogen flowing through a tubular passage communicating with the interior of the chamber to convert the other halogen into a plasma.

4. The metal film production method according to claim 1, wherein the radicals of the other halogen are obtained by heating the other halogen flowing through a tubular passage communicating with the interior of the chamber to dissociate the source gas thermally.

5. The metal film production method according to claim 1, wherein the radicals of the other halogen are obtained by supplying electromagnetic waves, such as laser light or electron beams, to the other halogen flowing through a tubular passage communicating with the interior of the chamber to dissociate the other halogen.

11. The metal film production method according to any one of claims 1 to 10, wherein

the etched member formed from the metal is formed from a composite metal comprising a plurality of metallic components, and

the predetermined film formation is performed by depositing the plurality of metallic components on the substrate from a plurality of the precursors comprising the metallic components and the halogen source gas which have been obtained as a result of etching of the etched member by the halogen plasma.

12. The metal film production method according to any one of claims 1 to 10, wherein

the etched member formed from the metal is formed from a composite metal comprising one or more metallic components and one or more nonmetallic components, and

the predetermined film formation is performed by depositing the metallic components and the nonmetallic components simultaneously on the substrate from one or more of the precursors comprising the metallic components and the source gas and one or more of the precursors comprising the nonmetallic components and the source gas which have been obtained as a result of etching of the etched member by the source gas plasma.

6. A metal film production method which comprises:

independently disposing an etched member, formed from a metal forming a high vapor pressure halide, at a position opposed to a substrate in a chamber accommodating the substrate in an interior thereof;

etching the etched member with a source gas plasma containing a halogen within the chamber to form a precursor comprising a metallic component and the halogen; and

controlling temperatures of the etched member and the substrate so as to effect a temperature of the substrate lower than a temperature of the etched member and so as to provide a temperature difference at least equal to or more than 100 degrees C. between the temperature of the substrate and the temperature of the etched member, thereby adsorbing the precursor onto the substrate,

said metal film production method further comprising;

controlling plasma conditions of another halogen generated by a reaction between the each precursor adsorbed onto the substrate in order to dissociate the other halogen so as to increase a dissociation rate of the other halogen, and

replenishing the dissociated other halogen around a vicinity of the substrate to extract a halogen from the precursor, thereby depositing the metallic component on the substrate for performing the predetermined film formation.

7. The metal film production method according to claim 6, wherein control of the plasma conditions is realized by decreasing an amount of the source gas supplied.

8. The metal film production method according to claim 6, wherein control of the plasma conditions is realized by increasing an amount of a high frequency electric power for forming the other halogen plasma.

9. The metal film production method according to claim 6, wherein control of the plasma conditions is realized by supplying a rare gas, having a mass equal to or larger than a mass of Ne, into the chamber in addition to the source gas.

10. The metal film production method according to claim 6, wherein control of the plasma conditions is realized by supplying electromagnetic waves into the chamber to dissociate the other halogen.

13. A metal film production method comprising:

independently disposing an etched member, formed from a composite metal comprising a plurality of metallic components forming high vapor pressure halides, at a position opposed to a substrate in a chamber accommodating the substrate in an interior thereof;

etching the etched member with a source gas plasma containing a halogen within the chamber to form a plurality of precursors comprising the metallic components and the halogen; and

controlling temperatures of the etched member and the substrate so as to effect a temperature of the substrate lower than a temperature of the etched member and so as to provide a temperature difference between the temperature of the substrate and the temperature of the etched member at least equal to or more than 100 degrees C., thereby depositing the metallic components of the plurality of precursors on the substrate to perform predetermined film formation.

14. A metal film production method comprising:

independently disposing an etched member, formed from a composite metal comprising one or more metallic components and one or more nonmetallic components forming high vapor pressure halides, at a position opposed to a substrate in a chamber accommodating the substrate in an interior thereof;

etching the etched member with a source gas plasma containing a halogen within the chamber to form one or more precursors comprising the metallic components and the halogen and one or more precursors comprising the nonmetallic components and the halogen; and

controlling temperatures of the etched member and the substrate so as to effect a temperature of the substrate lower than a temperature of the etched member and so as to provide a temperature difference between the temperature of the substrate and the temperature of the etched member at least equal to or more than 100 degrees C., thereby depositing the metallic components and the nonmetallic components simultaneously on the substrate to perform predetermined film formation.

15. An interconnection structure forming method for forming an interconnection by burying a metal film in a depression, such as a trench or a hole, formed in a substrate, comprising:

making a film formation reaction and an etching reaction coexistent, said film formation reaction being a reaction in which a precursor comprising a metallic component and a source gas by applying the source gas plasma to the metallic component is adsorbed onto the substrate, and then the metallic component is deposited to form a metal film of a metal of the metallic component, and said etching reaction being a reaction in which the metal film formed by said film formation reaction is etched with a plasma of the source gas; and

exercising control such that a speed of said film formation reaction is higher than a speed of said etching reaction, thereby stacking the metal film in the depression sequentially, starting at a bottom of the depression, to form a predetermined interconnection.

18. The interconnection structure forming method according to any one of claims 15 to 17, wherein the metal film is formed by a metal film production apparatus, which

disposes an etched member, formed from a metal forming a high vapor pressure halide, in a chamber accommodating the substrate in an interior thereof;

etches the etched member with a source gas plasma containing a halogen within the chamber to form the precursor comprising the metallic component and the source gas; and

controls temperatures of the etched member and the substrate so as to effect a temperature of the substrate lower than a temperature of the etched member and so as to provide a predetermined temperature difference between the temperature of the substrate and the temperature of the etched member, thereby depositing the metallic of the precursor on the substrate to perform predetermined film formation.

16. A multilayer interconnection structure forming method for forming an interconnection by burying a metal film in a depression, such as a trench or a hole, in multiple layers formed in a substrate for formation of the multilayer interconnection structure, comprising:

making a film formation reaction and an etching reaction coexistent, said film formation reaction being a reaction in which a precursor comprising a metallic component and a source gas by applying the source gas plasma to the metallic component is adsorbed onto the substrate, and then the metallic component is deposited to form a metal film of a metal of the metallic component, and said etching reaction being a reaction in which the metal film formed by said film formation reaction is etched with a plasma of the source gas; and

exercising control such that a speed of said film formation reaction is higher than a speed of said etching reaction, thereby stacking the metal film in the depression sequentially, starting at a bottom of the depression, to form the multilayer interconnection structure integrally.

17. The multilayer interconnection structure forming method according to claim 16, further comprising forming a barrier metal layer on a surface of the depression of the substrate prior to formation of the metal film with electrical conductivity.