Methods of forming a thin film structure, and a gate structure and a capacitor including the thin film structure

• US 20060013946A1
• Filed: 07/15/2005
• Published: 01/19/2006
• Est. Priority Date: 07/15/2004
• Status: Abandoned Application

• Current Assignee: Samsung Electronics Co. Ltd.
• Original Assignee: Samsung Electronics Co. Ltd.
• Inventors: Kang, Sang-Bom, Shin, Yu-Gyun, Park, Hong-Bae, Jin, Beom-Jun
• Application Number:
  US11/182,893
• Publication Number:
  US 20060013946A1
• Time in Patent Office: Days
• US Class Current: 427/79
• CPC Class Codes: C23C 16/401 containing silicon
• CPC Class Codes: C23C 16/45531 specially adapted for making ternary or higher compositions
• CPC Class Codes: C23C 16/45553 characterized by the use of precursors specially adapted for ALD
• CPC Class Codes: H01L 21/02148 the material containing hafnium, e.g. HfSiOx or HfSiON
• CPC Class Codes: H01L 21/02181 the material containing hafnium, e.g. HfO2
• CPC Class Codes: H01L 21/0228 deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
• CPC Class Codes: H01L 21/28194 by deposition, e.g. evaporation, ALD, CVD, sputtering, laser deposition H01L21/28202 takes precedence
• CPC Class Codes: H01L 21/3141 Deposition using atomic layer deposition techniques [ALD]
• CPC Class Codes: H01L 21/31616 Deposition of Al2O3
• CPC Class Codes: H01L 21/31645 Deposition of Hafnium oxides, e.g. HfO2
• CPC Class Codes: H01L 29/517 the insulating material comprising a metallic compound, e.g. metal oxide, metal silicate H01L29/518 takes precedence

Abstract

A thin film structure is formed that includes hafnium silicon oxide using an atomic layer deposition process. A first reactant including tetrakis ethyl methyl amino hafnium (TEMAH) is introduced onto a substrate. A first portion of the first reactant is chemisorbed to the substrate, whereas a second portion of the first reactant is physorbed to the first portion of the first reactant. A first oxidant is provided onto the substrate. A first thin film including hafnium oxide is formed on the substrate by chemically reacting the first oxidant with the first portion of the first reactant. A second reactant including amino propyl tri ethoxy silane (APTES) is introduced onto the first thin film. A first portion of the second reactant is chemisorbed to the first thin film, whereas a second portion of the second reactant is physorbed to the first portion of the second reactant. A second oxidant is provided onto the first thin film. A second thin film including silicon oxide is formed on the first thin film by chemically reacting the second oxidant with the first portion of the second reactant.

Claims

1. A method of forming a thin film structure, comprising:

introducing a first reactant comprising tetrakis ethyl methyl amino hafnium (TEMAH) onto a substrate;

chemisorbing a first portion of the first reactant to the substrate, and physorbing a second portion of the first reactant to the first portion of the first reactant;

providing a first oxidant onto the substrate;

forming a first thin film comprising hafnium oxide on the substrate by chemically reacting the first oxidant with the first portion of the first reactant;

introducing a second reactant comprising amino propyl tri ethoxy silane (APTES) onto the first thin film;

chemisorbing a first portion of the second reactant to the first thin film, and physorbing a second portion of the second reactant to the first portion of the second reactant;

providing a second oxidant onto the first thin film; and

forming a second thin film comprising silicon oxide on the first thin film by chemically reacting the second oxidant with the first portion of the second reactant.

2. The method of claim 1, wherein the first oxidant comprises at least one selected from the group consisting of ozone (O₃), water (H₂O) vapor, hydrogen peroxide (H₂O₂), methanol (CH₃OH), and ethanol (C₂H₅OH).

3. The method of claim 1, wherein the second oxidant comprises at least one selected from the group consisting of ozone, water vapor, hydrogen peroxide, methanol, and ethanol.

4. The method of claim 1, wherein the thin film structure substantially comprises a gate insulation layer of a transistor.

5. The method of claim 1, wherein the thin film structure comprises a dielectric layer of a capacitor.

6. The method of claim 1, wherein introducing the first reactant, chemisorbing the first portion of the first reactant, physorbing the second portion of the first reactant, providing the first oxidant, forming the first thin film, introducing the second reactant, chemisorbing the first portion of the second reactant, physorbing the second portion of the second reactant, providing the second oxidant, and forming the second thin film are performed at temperature of about 150 to about 400°

C.

7. The method of claim 1, wherein introducing the first reactant, chemisorbing the first portion of the first reactant, physorbing the second portion of the first reactant, providing the first oxidant and forming the first thin film are performed at least once.

8. The method of claim 1, wherein introducing the second reactant, chemisorbing the first portion of the second reactant, physorbing the second portion of the second reactant, providing the second oxidant, and forming the second thin film are performed at least once.

9. The method of claim 1, wherein introducing the first reactant, chemisorbing the first portion of the first reactant, physorbing the second portion of the first reactant, providing the first oxidant, forming the first thin film, introducing the second reactant, chemisorbing the first portion of the second reactant, physorbing the second portion of the second reactant, providing the second oxidant, and forming the second thin film are performed at least once.

10. The method of claim 1, further comprising:

removing the second portion of the first reactant;

removing an unreacted portion of the first oxidant;

removing the second portion of the second reactant; and

removing an unreacted portion of the second oxidant.

11. A method of forming a gate structure, comprising:

forming a gate insulation layer comprising hafnium silicon oxide on a substrate by an atomic layer deposition process using tetrakis ethyl methyl amino hafnium (TEMAH), amino propyl tri ethoxy silane (APTES), and oxidants;

forming a gate conductive layer on the gate insulation layer; and

forming a gate pattern comprising a gate insulation layer pattern and a gate conductive layer pattern by partially etching the gate conductive layer and the gate insulation layer.

12. The method of claim 11, wherein forming the gate insulation layer comprises:

introducing a first reactant comprising the TEMAH onto the substrate;

chemisorbing a first portion of the first reactant to the substrate, and physorbing a second portion of the first reactant to the first portion of the first reactant;

removing the second portion of the first reactant;

providing a first oxidant onto the substrate;

forming a first thin film comprising hafnium oxide on the substrate by chemically reacting the first oxidant with the first portion of the first reactant;

removing an unreacted portion of the first oxidant;

introducing a second reactant comprising the APTES onto the first thin film;

chemisorbing a first portion of the second reactant to the first thin film, and physorbing a second portion of the second reactant to the first portion of the second reactant;

removing the second portion of the second reactant;

providing a second oxidant onto the first thin film;

forming a second thin film comprising silicon oxide on the first thin film by chemically reacting the second oxidant with the first portion of the second reactant; and

removing an unreacted portion of the second oxidant.

13. The method of claim 12, wherein the first oxidant comprises at least one selected from the group consisting of ozone, water vapor, hydrogen peroxide, methanol, and ethanol.

14. The method of claim 12, wherein the second oxidant comprises at least one selected from the group consisting of ozone, water vapor, hydrogen peroxide, methanol, and ethanol.

15. The method of claim 12, wherein introducing the first reactant, chemisorbing the first portion of the first reactant, physorbing the second portion of the first reactant, removing the second portion of the first reactant, providing the first oxidant, forming the first thin film, removing the unreacted portion of the first oxidant, introducing the second reactant, chemisorbing the first portion of the second reactant, physorbing the second portion of the second reactant, removing the second portion of the second reactant, providing the second oxidant, forming the second thin film, and removing the unreacted portion of the second oxidant are performed at temperature of about 150 to about 400°

C.

16. The method of claim 12, wherein introducing the first reactant, chemisorbing the first portion of the first reactant, physorbing the second portion of the first reactant, removing the second portion of the first reactant, providing the first oxidant, forming the first thin film, and removing the unreacted portion of the first oxidant are performed at least once.

17. The method of claim 12, wherein introducing the second reactant, chemisorbing the first portion of the second reactant, physorbing the second portion of the second reactant, removing the second portion of the second reactant, providing the second oxidant, forming the second thin film, and removing the unreacted portion of the second oxidant are performed at least once.

18. A method of forming a capacitor comprising:

forming a lower electrode on a substrate;

forming a dielectric structure comprising hafnium silicon oxide on the lower electrode by an atomic layer deposition process using tetrakis ethyl methyl amino hafnium (TEMAH), amino propyl tri ethoxy silane (APTES), and oxidants; and

forming an upper electrode on the dielectric structure.

19. The method of claim 18, wherein forming the dielectric structure comprises:

introducing a first reactant comprising the TEMAH onto the substrate;

chemisorbing a first portion of the first reactant to the substrate, and physorbing a second portion of the first reactant to the first portion of the first reactant;

removing the second portion of the first reactant;

providing a first oxidant onto the substrate;

forming a first thin film comprising hafnium oxide on the substrate by chemically reacting the first oxidant with the first portion of the first reactant;

removing an unreacted portion of the first oxidant;

introducing a second reactant comprising the APTES onto the first thin film;

chemisorbing a first portion of the second reactant to the first thin film, and physorbing a second portion of the second reactant to the first portion of the second reactant;

removing the second portion of the second reactant;

providing a second oxidant onto the first thin film;

forming a second thin film comprising silicon oxide on the first thin film by chemically reacting the second oxidant with the first portion of the second reactant; and

removing an unreacted portion of the second oxidant.

20. The method of claim 19, wherein the first oxidant comprises at least one selected from the group consisting of ozone, water vapor, hydrogen peroxide, methanol, and ethanol.

21. The method of claim 19, wherein the second oxidant comprises at least one selected from the group consisting of ozone, water vapor, hydrogen peroxide, methanol, and ethanol.

22. The method of claim 19, wherein introducing the first reactant, chemisorbing the first portion of the first reactant, physorbing the second portion of the first reactant, removing the second portion of the first reactant, providing the first oxidant, forming the first thin film, removing the unreacted portion of the first oxidant, introducing the second reactant, chemisorbing the first portion of the second reactant, physorbing the second portion of the second reactant, removing the second portion of the second reactant, providing the second oxidant, forming the second thin film, and removing the unreacted portion of the second oxidant are performed at temperature of about 150 to about 400°

C.

23. The method of claim 19, wherein introducing the first reactant, chemisorbing the first portion of the first reactant, physorbing the second portion of the first reactant, removing the second portion of the first reactant, providing the first oxidant, forming the first thin film, and removing the unreacted portion of the first oxidant are performed at least once.

24. The method of claim 19, wherein introducing the second reactant, chemisorbing the first portion of the second reactant, physorbing the second portion of the second reactant, removing the second portion of the second reactant, providing the second oxidant, forming the second thin film, and removing the unreacted portion of the second oxidant are performed at least once.