Method of manufacturing semiconductor device, method of processing substrate, substrate processing apparatus and computer-readable recording medium
A method of manufacturing a semiconductor device, includes: alternately performing (i) a first step of alternately supplying a first raw material containing a first metal element and a halogen element and a second raw material containing a second metal element and carbon to a substrate by a first predetermined number of times, and (ii) a second step of supplying a nitridation raw material to the substrate, by a second predetermined number of times, wherein alternating the first and second steps forms a metal carbonitride film containing the first metal element having a predetermined thickness on the substrate.
1. A method of manufacturing a semiconductor device, comprising forming a film containing a first metal element and carbon on a substrate by alternately performing one or more times:
(a) supplying a first raw material containing the first metal element and a halogen element, to the substrate to form a first layer containing the first metal element and the halogen element with a thickness of less than one atomic layer, the first raw material being supplied to the substrate under a condition where a pyrolytic reaction of the first raw material does not occur; and
(b) supplying a second raw material, containing a second metal element and the carbon, to the substrate causing the halogen element contained in the first layer to react with the second metal element contained in the second raw material to be transformed into a gaseous material and discharged, and to make the carbon contained in the second raw material remain on a surface of the first layer to thereby form a second layer containing the first metal element and the carbon,
wherein at least one of the first metal element and the second metal element is a transition metal element.
2. The method of claim 1 , wherein the first layer includes a discontinuous layer.
3. The method of claim 1 , wherein the first layer includes a discontinuous chemical adsorption layer of molecules of the first raw material.
4. The method of claim 1 , wherein the first layer includes a chemical adsorption layer having a thickness of less than one molecular layer constituted by molecules of the first raw material.
5. The method of claim 1 , wherein the first metal element includes at least one metal element selected from a group of metal elements consisting of titanium, tantalum, hafnium, zirconium, molybdenum and tungsten.
6. The method of claim 1 , wherein the second metal element includes at least one metal element selected from a group of metal elements consisting of titanium, tantalum, hafnium, zirconium, molybdenum, tungsten and aluminum.
7. The method of claim 1 , wherein the first raw material includes at least one raw material selected from a group of raw materials consisting of TiCl 4 , TiF 4 , TaCl 5 , TaF 5 , HfCl 4 , HfF 4 , ZrCl 4 , ZrF 4 , MoCl 5 , MoF 5 , WCl 6 and WF 6 , and
wherein the second raw material includes at least one raw material selected from a group of raw materials consisting of Hf[C 5 H 4 (CH 3 )] 2 (CH 3 ) 2 , Zr[C 5 H 4 (CH 3 )] 2 (CH 3 ) 2 , Hf[N(C 2 H 5 )(CH 3 )] 4 , Zr[N(C 2 H 5 )( C H 3 )] 4 , Hf[N(CH 3 ) 2 ] 4 , Ti[N(CH 3 ) 2 ] 4 and Al(CH 3 ) 3 .
8. The method of claim 1 , wherein (b) further comprises bonding the first metal element contained in the first layer and the carbon contained in the second raw material.
9. The method of claim 1 , wherein (b) further comprises transforming the halogen element contained in the first layer and the second metal element contained in the second raw material into at least one gaseous material selected from a group of gaseous materials consisting of a gaseous material containing the halogen element, a gaseous material containing the second metal element, and a gaseous material containing the halogen element and the second metal element, and discharging the at least one gaseous material.
10. A substrate processing apparatus comprising:
a process chamber configured to accommodate a substrate;
a first raw material supply system configured to supply a first raw material containing a first metal element and a halogen element to the substrate in the process chamber;
a second raw material supply system configured to supply a second raw material containing a second metal element and carbon to the substrate in the process chamber;
a heater configured to heat the substrate in the process chamber;
a pressure regulating part configured to adjust an internal pressure of the process chamber; and
a control unit configured to control the first raw material supply system, the second raw material supply system, the heater and the pressure regulating part so as to form a film containing the first metal element and the carbon on the substrate by alternately performing one or more times:
(a) supplying the first raw material containing the first metal element and the halogen element to the substrate to form a first layer containing the first metal element and the halogen element with a thickness of less than one atomic layer the first raw material being supplied to the substrate under a condition where a pyrolytic reaction of the first raw material does not occur; and
(b) supplying a second raw material, containing a second metal element and the carbon, to the substrate causing the halogen element contained in the first layer to react with the second metal element contained in the second raw material to be transformed into a gaseous material and discharged, and to make the carbon contained in the second raw material remain on a surface of the first layer to thereby form a second layer containing the first metal element and the carbon,
wherein at least one of the first metal element and the second metal element is a transition metal element.
11. A non-transitory computer-readable recording medium storing a program that causes a computer to perform a process comprising forming a film containing a first metal element and carbon on a substrate by alternately performing one or more times:
(a) supplying a first raw material containing the first metal element and a halogen element to the substrate to form a first layer containing the first metal element and the halogen element with a thickness of less than one atomic layer the first raw material being supplied to the substrate under a condition where a pyrolytic reaction of the first raw material does not occur; and
(b) supplying a second raw material, containing a second metal element and the carbon, to the substrate causing the halogen element contained in the first layer to react with the second metal element contained in the second raw material to be transformed into a gaseous material and discharged, and to make the carbon contained in the second raw material remain on a surface of the first layer to thereby form a second layer containing the first metal element and the carbon,
wherein at least one of the first metal element and the second metal element is a transition metal element.