Production Method for Semiconductor Device and Substrate Processing Apparatus

• US 20080124945A1
• Filed: 02/15/2006
• Published: 05/29/2008
• Est. Priority Date: 02/17/2005
• Status: Active Grant

• Current Assignee: Kokusai Electric Corp.
• Original Assignee: Hitachi Kokusai Electric Incorporated (Hitachi, Ltd.)
• Inventors: Sato, Taketoshi, Mizuno, Norikazu, Miya, Hironobu, Okuda, Kazuyuki, Toyoda, Kazuyuki, Sakai, Masanori, Asai, Masayuki, Horita, Hideki
• Granted Patent: US 7,779,785 B2
• Time in Patent Office: Days
• US Class Current: 438/778
• CPC Class Codes: C23C 16/345 Silicon nitride
• CPC Class Codes: C23C 16/403 of aluminium, magnesium or beryllium
• CPC Class Codes: C23C 16/45536 Use of plasma, radiation or electromagnetic fields
• CPC Class Codes: C23C 16/45546 specially adapted for a substrate stack in the ALD reactor
• CPC Class Codes: C23C 16/509 using internal electrodes
• CPC Class Codes: H01L 21/0214 the material being a silicon oxynitride, e.g. SiON or SiON:H
• CPC Class Codes: H01L 21/0217 the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz H01L21/02126 and H01L21/0214 take precedence
• CPC Class Codes: H01L 21/02178 the material containing aluminium, e.g. Al2O3
• CPC Class Codes: H01L 21/02211 the compound being a silane, e.g. disilane, methylsilane or chlorosilane
• 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 21/02332 into an oxide layer, e.g. changing SiO to SiON
• CPC Class Codes: H01L 21/0234 treatment by exposure to a plasma
• CPC Class Codes: H01L 21/3141 Deposition using atomic layer deposition techniques [ALD]
• CPC Class Codes: H01L 21/3162 on a silicon body
• CPC Class Codes: H01L 21/3185 of siliconnitrides

Abstract

Disclosed is a producing method of a semiconductor device comprising a first step of supplying a first reactant to a substrate to cause a ligand-exchange reaction between a ligand of the first reactant and a ligand as a reactive site existing on a surface of the substrate, a second step of removing a surplus of the first reactant, a third step of supplying a second reactant to the substrate to cause a ligand-exchange reaction to change the ligand after the exchange in the first step into a reactive site, a fourth step of removing a surplus of the second reactant, and a fifth step of supplying a plasma-excited third reactant to the substrate to cause a ligand-exchange reaction to exchange a ligand which has not been exchange-reacted into the reactive site in the third step into the reactive site, wherein the first to fifth steps are repeated predetermined times.

Claims

1. A producing method of a semiconductor device comprising:

a first step of supplying a first reactant to a substrate accommodated in a processing chamber to cause a ligand-exchange reaction between a ligand of the first reactant and a ligand as a reactive site existing on a surface of the substrate;

a second step of removing a surplus of the first reactant from the processing chamber,

a third step of supplying a second reactant to the substrate to cause a ligand-exchange reaction to change the ligand after the exchange in the first step into a reactive site,

a fourth step of removing a surplus of the second reactant from the processing chamber, and

a fifth step of supplying a plasma-excited third reactant to the substrate to cause a ligand-exchange reaction to exchange a ligand which has not been exchange-reacted into the reactive site in the third step into the reactive site, wherein

the first to fifth steps are repeated predetermined times until a film having a predetermined thickness is formed on the surface of the substrate.

2. The producing method of the semiconductor device as claimed in claim 1, wherein the ligand-exchange reaction in each of the third and fifth steps is a step of carrying out a ligand removing reaction in which the ligand existing at the surface of the substrate is removed to form the reactive site.

3. The producing method of the semiconductor device as claimed in claim 1, wherein a ligand-exchange reaction is carried out between the reactive site generated as a result of the exchange reaction in the fifth step and the ligand of the first reactant supplied in a subsequent first step.

4. A producing method of a semiconductor device comprising:

a thin film forming to comprising;

supplying a first reactant into a processing chamber in which a substrate is accommodated to cause the first reactant to be adsorbed on a surface of the substrate;

removing a surplus of the first reactant from the processing chamber;

supplying a second reactant into the processing chamber to cause the second reactant to react with the first reactant adsorbed on the surface of the substrate to form a thin film of at least one atomic layer; and

removing a surplus of the second reactant from the processing chamber; and

a plasma processing step of supplying a plasma-excited gas into the processing chamber to improve a film quality of the thin film after the thin film forming;

wherein

the thin film forming and the plasma processing are repeated predetermined times until a thin film having a predetermined thickness is formed.

5. The producing method of the semiconductor device as claimed in claim 4, wherein the plasma-excited gas is an oxygen atom-containing gas.

6. The producing method of the semiconductor device as claimed in claim 5, wherein the first reactant is a gas including aluminum, the second reactant is ozone gas, the plasma-excited gas is an oxygen plasma gas, and the thin film to be formed is an aluminum oxide thin film.

7. The producing method of the semiconductor device as claimed in claim 4, wherein the plasma-excited gas is a gas including nitrogen atom.

8. The producing method of the semiconductor device as claimed in claim 7, wherein the first reactant is a gas including silicon, the second reactant is a gas including nitrogen, the thin film to be formed is a silicon nitride thin film, and the plasma processing is carried out between the supplying of the first reactant and the supplying of the second reactant.

9. The producing method of the semiconductor device as claimed in claim 4, wherein the first reactant is a gas including silicon, the second reactant is a gas including nitrogen, the plasma-excited gas is a gas including plasma-excited nitrogen, and the thin film to be formed is a silicon nitride thin film.

10. The producing method of the semiconductor device as claimed in claim 9, wherein the plasma-excited gas includes plasma-excited nitrogen gas and plasma-excited ammonia gas.

11. The producing method of the semiconductor device as claimed in claim 10, wherein the plasma-excited gas includes a gas obtained by plasma-exciting a gas mixture in which nitrogen gas and ammonia gas are mixed at a ratio of 1:

1 to 6;

1.

12. The producing method of the semiconductor device as claimed in claim 10, wherein the plasma processing is carried out under a pressure of 0.5 Torr or lower.

14. The producing method of the semiconductor device as claimed in claim 12, wherein in the thin film forming, a thin film of two to five atomic layers is formed.

13. A producing method of a semiconductor device comprising:

a thin film forming of repeating the followings to form a thin film of several atomic layers on a substrate,

supplying a first reactant into a processing chamber in which a substrate is accommodated to cause the first reactant to be adsorbed on a surface of the substrate;

removing a surplus of the first reactant from the processing chamber,

supplying a second reactant into the processing chamber to cause the second reactant to react with the first reactant adsorbed on the surface of the substrate to form a thin film of at least one atomic layer, and

removing a surplus of the second reactant from the processing chamber; and

a plasma processing of supplying an oxygen atom-containing gas into the processing chamber to improve a film quality of the thin film after the thin film forming, wherein

the thin film forming and the plasma processing are repeated predetermined times until a thin film having a predetermined thickness is formed.

15. A producing method of a semiconductor device comprising:

a oxide film forming of repeating the followings to form an oxide film having a desired thickness on a silicon film,

supplying a first reactant into a processing chamber in which a substrate, the silicon film is exposed from a surface of which, is accommodated to cause the first reactant to be adsorbed onto a surface of the silicon film,

removing a surplus of the first reactant from the processing chamber,

supplying a second reactant into the processing chamber to cause the second reactant to react with the first reactant adsorbed on the surface of the silicon film to form a thin film of at least one atomic layer, and

removing a surplus the second reactant from the processing chamber; and

a plasma nitriding processing of nitriding a surface of the oxide film using a gas including a nitrogen atom after the oxide film forming.

16. A substrate processing apparatus, comprising:

a processing chamber in which a substrate is to be accommodated;

a first supply section to supply a first reactant into the processing chamber;

a second supply section to supply a second reactant into the processing chamber;

a third supply section to supply a third reactant into the processing chamber;

a exhausting section to evacuate the processing chamber;

an exciting section to plasma-excite the third reactant; and

a control section to control the first to third supply section, the exhaust section and the exciting section, wherein

the control section controls the first to third supply section, the exhausting section and the exciting section, to repeat the following first to fifth steps predetermined times until a thin film having a desired thickness is formed;

the first step of supplying the first reactant to the substrate accommodated in the processing chamber to cause a ligand-exchange reaction between a ligand as a reactive site existing on a surface of the substrate and a ligand of the first reactant;

the second step of removing a surplus of the first reactant from the processing chamber;

the third step of supplying a second reactant to the substrate to cause a ligand-exchange reaction to change the ligand after the exchange in the first step into a reactive site;

the fourth step of removing a surplus of the second reactant from the processing chamber; and

the fifth step of supplying a plasma-excited third reactant to the substrate to cause a ligand exchange reaction to exchange a ligand which has not been exchange-reacted into the reactive site in the third step into the reactive site.

17. A substrate processing apparatus, comprising:

a processing chamber in which a substrate is to be accommodated;

a first supply section to supply a first reactant into the processing chamber;

a second supply section to supply a second reactant into the processing chamber;

a third supply section to supple a third reactant into the processing chamber;

an exhausting section to evacuate the processing chamber;

an exciting section to plasma-excite the third reactant; and

a control section to control the first to third supply section, the exhaust section and the exciting section, wherein

the control section controls the first to third supply section, the exhausting section and the exciting section, to repeat a thin film forming and a plasma processing predetermined times until a thin film having a desired thickness is formed,

the thin film forming comprising;

supplying the first reactant into the processing chamber in which the substrate is accommodated to cause the first reactant to be adsorbed on a surface of the substrate;

removing a surplus of the first reactant from the processing chamber;

supplying the second reactant into the processing chamber to cause the second reactant to react with the first reactant adsorbed on the surface of the substrate to form a thin film of at least one atomic layer; and

moving a surplus of the second reactant from the processing chamber, and

the plasma processing of supplying the plasma-excited third reactant into the processing chamber to improve a film quality of the thin film after the thin film forming.

18. A substrate processing apparatus, comprising:

a processing chamber in which a substrate is to be accommodated,

a first supply section to supply a first reactant into the processing chamber;

a second supply section to supply the first reactant into the processing chamber;

an exhausting section to exhaust an atmosphere in the processing chamber;

a third supply section to supply an oxygen atom-containing gas into the processing chamber;

a plasma section to bring the oxygen atom-containing gas into a plasma state; and

a control section to control the first to third supply section, the exhausting section and the plasma section, wherein

the control section controls the first to third supply section, the exhausting section and the plasma section, to repeat a thin film forming and a plasma processing predetermined times until a thin film having a desired thickness is formed,

the thin film forming comprising;

supplying the first reactant into the processing chamber to cause the first reactant to be adsorbed on a surface of the substrate;

removing a surplus of the first reactant from the processing chamber;

supplying the second reactant into the processing chamber to cause the second reactant to react with the first reactant adsorbed on the surface of the substrate to form a thin film of one atomic layer; and

moving a surplus of the second reactant from the processing chamber, and

the plasma processing step of supplying an oxygen atom containing gas into the processing chamber to improve a film quality of the thin film after the thin film forming.