CHALCOGENIDE-CONTAINING PRECURSORS, METHODS OF MAKING, AND METHODS OF USING THE SAME FOR THIN FILM DEPOSITION

• US 20130267082A1
• Filed: 12/29/2010
• Published: 10/10/2013
• Est. Priority Date: 02/03/2010
• Status: Active Grant

• Current Assignee: L'Air Liquide Societe Anonyme Pour L'Etude et L'Exploitation Des Procedes Georges Claude (L'Air Liquide SA)
• Original Assignee: L'Air Liquide Societe Anonyme Pour L'Etude et L'Exploitation Des Procedes Georges Claude (L'Air Liquide SA)
• Inventors: Gatineau, Julien, Ishii, Hana, Minoura, Mao
• Granted Patent: US 9,240,319 B2
• Time in Patent Office: Days
• US Class Current: 438/508
• CPC Class Codes: C23C 16/18 from metallo-organic compounds
• CPC Class Codes: C23C 16/30 Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
• CPC Class Codes: C23C 16/305 Sulfides, selenides, or tellurides
• CPC Class Codes: C23C 16/45553 characterized by the use of precursors specially adapted for ALD
• CPC Class Codes: H01L 21/02568 Chalcogenide semiconducting materials not being oxides, e.g. ternary compounds

Abstract

Disclosed are chalcogenide-containing precursors for use in the manufacture of semiconductor, photovoltaic, LCD-TFT1 or fiat panel type devices. Also disclosed a methods of synthesizing the chalcogenide-containing precursors and vapor deposition methods, preferably thermal ALD, using the chaicogenide-containing precursors to form chaicogenide-containing films.

Claims

1. A method for the deposition of a chalcogenide-containing film, comprising the steps of:

a) introducing into a reactor containing at least one substrate a vapor of at least one chalcogenide-containing precursor selected from the group consisting of Me₂Ge(TeMe)₂, Me₂Ge(TetBu)₂, tBu₂Ge(TetBu)₂, Me₂Ge(TeSiMe₃)₂, (Me₃Si)₂Ge(TeSiMe₃)₂, Me₂Si(TeMe)₂, Me₂Si(TetBu)₂, tBu₂Si(TetBu)₂, Me₂Si(TeSiMe₃)₂, (Me₃Si)₂Si(TeSiMe₃)₂, MeGe(TeMe)₃, MeGe(TetBu)₃, (SiMe₃)Ge(TeSiMe₃)₃, MeSi(TeMe)₃, MeSi(TetBu)₃ and (SiMe₃)Si(TeSiMe₃); and

b) depositing at least part of the at least one chalcogenide-containing precursor onto the at least one substrate to form a chalcogenide-containing film on at least one surface of the at least one substrate using a vapor deposition process.

2. The method of claim 1, wherein the at least one chalcogenide-containing precursor is (MeTe)₂GeMe₂.

3. The method of claim 1, further comprising introducing one or more doping elements to the chalcogenide-containing film, wherein the one or more doping elements are selected from the group consisting of silicon, nitrogen, and oxygen.

4. The method of claim 1, further comprising introducing a reactant into the reactor, wherein the reactant is selected from the group consisting of H₂, NH₃, amines, imines, hydrazines, SiH₄, Si₂H₆, Si₃H₈, B₂H₆, hydrogen-containing fluids, oxygen, ozone, moisture, alcohol (ROH, wherein R is a C1-C6 alkyl), and mixtures thereof.

5. The method of claim 1, wherein the vapor deposition process is chemical vapor deposition (CVD), atomic layer deposition (ALD), plasma enhanced chemical vapor deposition (PECVD), or plasma enhanced atomic layer deposition (PEALD).

6. The method of claim 1, wherein the reactor has a pressure ranging from about 1.33 Pa to about 133.3 kPa.

7. The method of claim 1, wherein the reactor has a temperature ranging from about 10°

C. to about 500°

C.

8. The method of claim 1, wherein the at least one substrate comprises a metal film or a metal nitride film.

9. The method of claim 1, further comprising introducing into the reactor a second precursor comprising an element selected from the group consisting of germanium (Ge), antimony (Sb), bismuth (Bi), indium (In), and zinc (Zn).

10. The method according to claim 9, wherein the element of the second precursor reacts with M of at least part of the at least one chalcogenide-containing precursor to form the chalcogenide-containing film.

11. The method of claim 10, wherein the second precursor is a germanium (Ge)-containing precursor and the chalcogenide-containing film is a GeM material.

12. The method of claim 10, wherein the second precursor is an antimony (Sb)-containing precursor and the chalcogenide-containing film is a SbM material.

13. The method of claim 11, further comprising introducing into the reactor a third precursor, the third precursor being an antimony (Sb)-containing precursor, wherein the chalcogenide-containing film deposited is a GeSbM material.