Method of forming a layer and method of forming a capacitor of a semiconductor device having the same

• US 20060063346A1
• Filed: 06/10/2005
• Published: 03/23/2006
• Est. Priority Date: 06/10/2004
• Status: Abandoned Application

• Current Assignee: Samsung Electronics Co. Ltd.
• Original Assignee: Samsung Electronics Co. Ltd.
• Inventors: Lee, Jong-Cheol, Choi, Han-Mei, Kim, Young-Sun, Nam, Gab-Jin, Kim, Sung-Tae, Im, Ki-Vin, Yoo, Cha-Young
• Application Number:
  US11/149,708
• Publication Number:
  US 20060063346A1
• Time in Patent Office: Days
• US Class Current: 438/393
• CPC Class Codes: C23C 16/45531 specially adapted for making ternary or higher compositions
• CPC Class Codes: C23C 16/4554 Plasma being used non-continuously in between ALD reactions C23C16/56 takes precedence
• CPC Class Codes: C23C 16/45553 characterized by the use of precursors specially adapted for ALD
• CPC Class Codes: C23C 16/515 using pulsed discharges
• CPC Class Codes: H01L 21/02178 the material containing aluminium, e.g. Al2O3
• CPC Class Codes: H01L 21/02181 the material containing hafnium, e.g. HfO2
• CPC Class Codes: H01L 21/02189 the material containing zirconium, e.g. ZrO2
• CPC Class Codes: H01L 21/02274 in the presence of a plasma [PECVD]
• 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 21/31616 Deposition of Al2O3
• CPC Class Codes: H01L 21/31691 with perovskite structure
• CPC Class Codes: H01L 28/40 Capacitors
• CPC Class Codes: H01L 28/65 comprising a noble metal or a noble metal oxide, e.g. platinum (Pt), ruthenium (Ru), ruthenium dioxide (RuO2), iridium (Ir), iridium dioxide (IrO2)

Abstract

In a method of forming a layer using an atomic layer deposition process, after a substrate is loaded into a chamber, a reactant is provided onto the substrate to form a preliminary layer. Atoms in the preliminary layer are partially removed from the preliminary layer using plasma formed from an inert gas such as an argon gas, a xenon gas or a krypton gas, or an inactive gas such as an oxygen gas, a nitrogen gas or a nitrous oxide gas to form a desired layer. Processes for forming the desired layer may be simplified. A highly integrated semiconductor device having improved reliability may be economically manufactured so that time and costs required for the manufacturing of the semiconductor device may be reduced.

Claims

1. A method of forming a layer comprising:

forming a preliminary layer comprising atoms on a substrate by an atomic layer deposition (ALD) process; and

partially removing the atoms from the preliminary layer using a plasma, the plasma being formed from a gas.

2. The method of claim 1, wherein the plasma is generated adjacent to the substrate.

3. The method of claim 1, wherein the plasma is generated separate from the substrate.

4. The method of claim 1, wherein the gas includes an inert gas, an inactive gas or a mixture thereof.

5. The method of claim 4, wherein the inert gas includes at least one gas selected from the group consisting of a helium (He) gas, a xenon (Xe) gas, a krypton gas (Kr), and an argon (Ar) gas.

6. The method of claim 4, wherein the inactive gas includes at least one gas selected from the group consisting of an oxygen gas (O₂), a hydrogen (H₂) gas, an ammonia (NH₃) gas, a nitrous oxide gas (N₂O), and a nitrogen dioxide (NO₂) gas.

7. The method of claim 1, wherein the layer includes metal, metal oxide, or metal nitride.

8. A method of forming a layer comprising:

chemisorbing a reactant to a substrate; and

partially removing atoms from a chemisorbed reactant using a plasma.

9. The method of claim 8, wherein the reactant includes an organic metal compound.

10. The method of claim 9, wherein the organic metal compound includes at least one compound selected from the group consisting of an alkoxide compound, an amino compound, a cyclopentadienyl compound, a diketonate compound and an alkyl compound.

11. The method of claim 10, wherein the alkoxide compound includes at least one compound selected from the group consisting of B[OCH₃]₃, B[OC₂H₅]₃, Al[OCH₃]₃, Al[OC₂H₅]₃, Al[OC₃H₇]₃, Ti[OCH₃]₄, Ti[OC₂H₅]₄, Ti[OC₃H₇]₄, Zr[OC₃H₇]₄, Zr[OC₄H₉]₄, Zr[OC₄H₈OCH₃]₄, Hf[OC₄H₉]₄, Hf[OC₄H₈OCH₃]₄, Hf[OSi(C₂H₅)₃]₄, Hf[OC₂H₅]₄, Hf[OC₃H₇]₄, Hf[OC₄H₉]₄, Hf[OC₅H₁₁]₄, Si[OCH₃]₄, Si[OC₂H₅]₄, Si[OC₃H₇]₄, Si[OC₄H₉]₄, HSi[OCH₃]₃, HSi[OC₂H₅]₃, Si[OCH₃]₃F, Si[OC₂H₅]₃F, Si[OC₃H₇]₃F, Si[OC₄H₉]₃F, Sn[OC₄H₉]₄, Sn[OC₃H₇]₃[C₄H₉], Pb[OC₄H₉]₄, Pb₄O[OC₄H₉]₆, Nb[OCH₃]₅, Nb[OC₂H₅]₅, Nb[OC₃H₇]₅, Nb[OC₄H₉]₅, Ta[OCH₃]₅, Ta[OC₂H₅]₅, Ta[OC₄H₉]₅, Ta[OC₂H₅]₅, Ta[OC₂H₅]₅[OC₂H₄N(CH₃)₂], P[OCH₃]₃, P[OC₂H₅]₃, P[OC₃H₇]₃, P[OC₄H₉]₃ and PO[OCH₃]₃.

12. The method of claim 10, wherein the amino compound includes at least one compound selected from the group consisting of Hf(NCH₃CH₃)₄, Hf(NCH₃C₂H₅)₄, Hf(NC₂H₅C₂H₅)₄, Hf(NCH₃C₃H₇)₄, Hf(NC₂H₅C₃H₇)₄ and Hf(NC₃H₇C₃H₇)₄.

13. The method of claim 10, wherein the cyclopentadienyl compound includes at least one compound selected from the group consisting of Ru(Cp)₂ (wherein, “

Cp”

represents a cyclopentadienyl group), Ru(CpC₂H₅)₂, Ru(CpC₃H₇)₂, La(CpC₃H₇)₃, Ru(CpC₄H₉)₂, Y(CpC₄H₉)₃ and La(CpC₄H₉)₃.

14. The method of claim 10, wherein the diketonate compound includes at least one compound selected from the group consisting of Ba(THD)₂ (wherein, “

THD”

represents tetramethyl heptanedionate), Sr(THD)₂, La(THD)₃, Pb(THD)₂, Zr(THD)₂, Ba(METHD)₂ (wherein, “

METHD”

represents methoxyethoxy tetramethyl heptanedionate), Ru(METHD)₃ and Zr(METHD)₄.

15. The method of claim 10, wherein the alkyl compound includes at least one compound selected from the group consisting of Al(CH₃)₃, Al(CH₃)₂Cl, Al(CH₃)₂H, Al(C₂H₅)₃, Al(CH₂CH₂(CH₃)₂)₃, Ga(CH₃)₃, Ga(CH₃)₂(C₂H₅), Ga(C₂H₅)₃, Ga(C₂H₅)₂Cl, Ga(CH₂CH₂(CH₃)₂)₃, Ga(CH₂C(CH₃)₃)₃, In(CH₃)₃, ((CH₃)₂(C₂H₅)N)In(CH₃)₃, In(CH₃)₂Cl, In(CH₃)₂(C₂H₅), In(C₂H₅)₃, Sn(CH₃)₄, Sn(C₂H₅)₄, Zn(CH₃)₂, Zn(C₂H₅)₂, Cd(CH₃)₂ and Hg(CH₃)₂.

16. A method of forming a layer comprising:

loading a substrate into a chamber;

introducing a reactant into the chamber;

chemisorbing the reactant to the substrate to form a preliminary layer on the substrate; and

partially removing atoms from the preliminary layer using a plasma.

17. The method of claim 16, further comprising removing a non-chemisorbed reactant from the chamber using the plasma while removing the atoms from the preliminary layer.

18. The method of claim 16, wherein introducing the reactant, chemisorbing the reactant and removing the atoms are repeatedly performed at least once.

19. A method of forming a layer comprising:

loading a substrate into a chamber;

introducing a first reactant into the chamber;

chemisorbing the first reactant to the substrate to form an absorption layer on the substrate;

partially removing atoms from the absorption layer using a plasma to form a preliminary layer on the substrate; and

introducing a second reactant into the chamber to form a layer on the substrate.

20. The method of claim 19, wherein the layer includes metal oxynitride.

21. The method of claim 19, wherein the second reactant includes an oxygen (O)-containing compound or a nitrogen (N)-containing compound.

22. The method of claim 19, wherein the second reactant has a plasma phase.

23. The method of claim 19, further comprising introducing a purge gas into the chamber to remove a non-chemisorbed first reactant from the chamber before removing the atoms from the absorption layer.

24. The method of claim 19, further comprising introducing a purge gas into the chamber to remove a non-chemisorbed first reactant and impurities generated by the plasma from the chamber before introducing the second reactant.

25. The method of claim 19, wherein introducing the first reactant, chemisorbing the first reactant and removing the atoms are repeatedly performed at least once before introducing the second reactant.

26. The method of claim 19, wherein introducing the first reactant, chemisorbing the first reactant, removing the atoms and introducing the second reactant are repeatedly performed at least once.

27. The method of claim 19, further comprising introducing a purge gas into the chamber to remove an unreacted second reactant from the chamber after introducing the second reactant.

28. The method of claim 27, wherein the purge gas has a plasma phase.

29. A method of forming a capacitor of a semiconductor device comprising:

loading a substrate including a lower electrode into a chamber;

providing a reactant onto the substrate to form a preliminary layer on the lower electrode;

partially removing atoms from the preliminary layer to form a dielectric layer on the lower electrode; and

forming an upper electrode on the dielectric layer.

30. The method of claim 29, wherein each of the lower and the upper electrodes includes a silicon compound, metal, metal oxide, metal nitride or metal oxynitride.

31. A method of forming a capacitor of a semiconductor device comprising:

loading a substrate including a lower electrode into a chamber;

providing a first reactant onto the substrate to form an absorption layer on the lower electrode;

partially removing atoms from the absorption layer to form a preliminary layer on the lower electrode;

providing a second reactant onto the preliminary layer to form a dielectric layer on the lower electrode; and

forming an upper electrode on the dielectric layer.