Method of manufacturing semiconductor device including forming a film containing a first element, a second element and carbon, substrate processing apparatus, and recording medium

• US 9,978,587 B2
• Filed: 07/21/2015
• Issued: 05/22/2018
• Est. Priority Date: 07/23/2014
• Status: Active Grant

• Current Assignee: Kokusai Electric Corp.
• Original Assignee: Hitachi Kokusai Electric Incorporated (Hitachi, Ltd.)
• Inventors: Shimamoto, Satoshi, Hirose, Yoshiro, Yamamoto, Ryuji
• Primary Examiner(s): Garber, Charles
• Assistant Examiner(s): PATERSON, BRIGITTE A
• Application Number:
  US14/804,604
• Publication Number:
  US 20160024659A1
• Time in Patent Office: 1,036 Days
• CPC Class Codes: C23C 16/0272 Deposition of sub-layers, e.g. to promote the adhesion of the main coating
• CPC Class Codes: C23C 16/30 Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
• CPC Class Codes: C23C 16/45531 specially adapted for making ternary or higher compositions
• CPC Class Codes: H01L 21/02129 the material being boron or phosphorus doped silicon oxides, e.g. BPSG, BSG or PSG
• CPC Class Codes: H01L 21/0214 the material being a silicon oxynitride, e.g. SiON or SiON:H
• CPC Class Codes: H01L 21/02167 the material being a silicon carbide not containing oxygen, e.g. SiC, SiC:H or silicon carbonitrides H01L21/02126 and H01L21/0214 take precedence
• CPC Class Codes: H01L 21/022 the layer being a laminate, i.e. composed of sublayers, e.g. stacks of alternating high-k metal oxides adhesion layers or buffer layers H01L21/02304, H01L21/02362
• 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 21/02304 formation of intermediate layers, e.g. buffer layers, layers to improve adhesion, lattice match or diffusion barriers
• CPC Class Codes: H01L 21/02321 introduction of substances into an already existing insulating layer H01L21/02227 and subgroups take precedence
• CPC Class Codes: H01L 21/0234 treatment by exposure to a plasma
• CPC Class Codes: H01L 21/67017 Apparatus for fluid treatment H01L21/67126, H01L21/6715 take precedence

Abstract

A technique includes forming a film containing a first element, a second element and carbon on a substrate by performing a cycle a predetermined number of times. The cycle includes non-simultaneously performing supplying a first precursor having chemical bonds between the first elements to a substrate, supplying a second precursor having chemical bonds between the first element and carbon without having the chemical bonds between the first elements to the substrate, and supplying a first reactant containing the second element to the substrate.

Claims

1. A method of manufacturing a semiconductor device, comprising forming a film containing a first element, a second element and carbon on a substrate by performing a cycle a predetermined number of times, the cycle including non-simultaneously performing:

supplying a carbon-free first precursor to the substrate to form a seed layer that has a thickness of one atomic layer or more and contains the first element, wherein the first precursor includes chemical bonds between atoms of the first element;

supplying a second precursor to the substrate to form a first layer containing the first element and carbon on the seed layer, wherein the second precursor includes chemical bonds between the first element and carbon without having the chemical bonds between atoms of the first element, wherein the second precursor contains the first element, carbon and a halogen element; and

supplying a first reactant containing the second element to the substrate to modify the seed layer and the first layer into a second layer, wherein the second layer contains the first element, the second element and carbon,

wherein a carbon concentration in the second layer is controlled by;

increasing a ratio of the thickness of the seed layer to a thickness of a laminated layer of the seed layer and the first layer so as to decrease the carbon concentration in the second layer; and

increasing a ratio of the thickness of the laminated layer of the seed layer and the first layer to the thickness of the seed layer so as to increase the carbon concentration in the second layer.

2. The method of claim 1, wherein the cycle is performed the predetermined number of times under a condition in which at least some of the chemical bonds between the first element and carbon contained in the second precursor are maintained.

3. The method of claim 1, wherein the supplying the second precursor is performed under a condition in which at least some of the chemical bonds between the first element and carbon contained in the second precursor are maintained without being broken.

4. The method of claim 1, wherein the supplying the first reactant is performed under a condition in which at least some of the chemical bonds between the first element and carbon contained in the first layer are maintained without being broken.

5. The method of claim 1, wherein the cycle is performed the predetermined number of times under a condition in which the second precursor is pyrolyzed and at least some of the chemical bonds between the first element and carbon contained in the second precursor are maintained.

6. The method of claim 1, wherein a space in which the substrate exists is purged between the supplying the first precursor and the supplying the second precursor.

7. The method of claim 1, wherein a supply amount of the first precursor is set greater than a supply amount of the second precursor.

8. The method of claim 1, wherein a supply flow rate of the first precursor is set greater than a supply flow rate of the second precursor.

9. The method of claim 1, wherein a supply time of the first precursor is set longer than a supply time of the second precursor.

10. The method of claim 1, wherein the cycle further includes performing supplying a second reactant containing a third element to the substrate, and

the film further containing the third element is formed on the substrate by performing the cycle the predetermined number of times.

11. The method of claim 1, wherein the first precursor contains the first element and a halogen element.

12. The method of claim 1, wherein the second precursor has at least two chemical bonds between the first element and carbon in one molecule.

13. The method of claim 1, wherein the first reactant includes at least one selected from a group consisting of a nitrogen-containing gas, a carbon-containing gas, a nitrogen- and carbon-containing gas, an oxygen-containing gas, a boron-containing gas and a boron-, nitrogen- and carbon-containing gas.

14. A non-transitory computer-readable recording medium storing a program that causes a computer to perform a process of forming a film containing a first element, a second element and carbon on a substrate by performing a cycle a predetermined number of times, the cycle including non-simultaneously performing:

supplying a carbon-free first precursor to the substrate to form a seed layer that has a thickness of one atomic layer or more and contains the first element, wherein the first precursor includes chemical bonds between atoms of the first element;

supplying a second precursor to the substrate to form a first layer containing the first element and carbon on the seed layer, wherein the second precursor includes chemical bonds between the first element and carbon without having the chemical bonds between atoms of the first element; and

supplying a reactant containing the second element to the substrate to modify the seed layer and the first layer into a second layer, wherein the second layer contains the first element, the second element and carbon,

wherein a carbon concentration in the second layer is controlled by;

increasing a ratio of the thickness of the seed layer to a thickness of a laminated layer of the seed layer and the first layer so as to decrease the carbon concentration in the second layer; and

increasing a ratio of the thickness of the laminated layer of the seed layer and the first layer to the thickness of the seed layer so as to increase the carbon concentration in the second layer.