MANUFACTURING METHOD OF SEMICONDUCTOR DEVICE, INSULATING FILM FOR SEMICONDUCTOR DEVICE, AND MANUFACTURING APPARATUS OF THE SAME
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Abstract
An object to provide an insulating film for a semiconductor device, which has characteristics of low permittivity, a low leak current, and high mechanical strength, undergoes small time-dependent change of these characteristics, and has excellent water resistance, and to provide a manufacturing apparatus of the same, and a manufacturing method of the semiconductor device using the insulating film. The production process comprises a film forming step of supplying a mixed gas containing a carrier gas and a raw material gas, which is a gasified material having borazine skeletal molecules, into a chamber, causing the mixed gas to be in a plasma state, applying a bias to the substrate placed in the chamber, and carrying out gas-phase polymerization by using the borazine skeletal molecule as a fundamental unit so as to form the insulating film on the substrate; and a reaction promoting step of, after the film forming step, bringing the bias applied to the substrate to a different magnitude from the bias in the film forming step, supplying the mixed gas while gradually reducing only the raw material gas, which is the gasified material having the borazine skeletal molecules, treating the insulating film with a plasma mainly comprising the carrier gas.
34 Citations
56 Claims
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1-30. -30. (canceled)
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31. A manufacturing method of a semiconductor device, comprising:
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a film forming step of supplying a mixed gas containing a carrier gas and a raw material gas, which is a gasified material having borazine skeletal molecules shown in a chemical formula described below, into a chamber, causing electromagnetic waves to enter the chamber so as to cause the mixed gas to be in a plasma state, and carrying out gas-phase polymerization by using the borazine skeletal molecule as a fundamental unit so as to form an insulating film for the semiconductor device on a substrate placed in the chamber; and a reaction promoting step of promoting cross-linking reaction of the borazine skeletal molecules in the formed insulating film for the semiconductor device after the film forming step, wherein in the reaction promoting step, a bias is applied to the substrate, and the cross-linking reaction of the borazine skeletal molecules in the formed insulating film for the semiconductor device is promoted by plasma mainly comprising a gas not containing the raw material gas; wherein, each of R1 and R2 in the above described chemical formula is a hydrogen atom or an alkyl group, an alkenyl group, a monoalkylamino group, or a dialkylamino group, which are having a carbon number of 5 or less, and R1 and R2 may be the same or different from each other, with the proviso that cases in which all of R1 and R2 are hydrogen atoms are excluded. - View Dependent Claims (33, 34, 35, 36, 37, 38, 53, 54, 55, 56)
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37. The manufacturing method of the semiconductor device according to claim 31 or claim 32, wherein
power of the electromagnetic waves in the film forming step and the reaction promoting step is equal to or more than 1590 W/m2 and equal to or less than 127400 W/m2. -
38. The manufacturing method of the semiconductor device according to claim 31 or claim 32, wherein
the substrate is disposed at a height position where an electron density in the vicinity of the substrate is equal to or less than one twentieth of a highest electron density in the plasma. -
53. An insulating film for a semiconductor device formed by the manufacturing method of the semiconductor device according to claim 31 or claim 32, comprising:
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a borazine skeletal structure, wherein in infrared absorption measurement of the borazine skeletal structure, a ratio [B/A] of an absorption peak intensity A at wave numbers of 1200 to 1600 cm−
1 and an absorption peak intensity B at wave numbers of 3000 to 3600 cm−
1 in the measurement is equal to or less than 0.5.
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54. An insulating film for a semiconductor device formed by the manufacturing method of the semiconductor device according to claim 31 or claim 32, comprising:
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a borazine skeletal structure, wherein in laser Raman spectroscopy measurement of the borazine skeletal structure at an excitation wavelength of 413 nm using Kr laser as a light source, a ratio [D/(D+G)] is equal to or more than 0.4 and equal to or less than 0.6, wherein, in the measurement, an intensity of a spectrum peak of wave numbers of 1100 to 1400 cm−
1 is D, and an intensity of a spectrum peak of wave numbers of 1400 to 1700 cm−
1 is G.
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55. An insulating film for a semiconductor device formed by the manufacturing method of the semiconductor device according to claim 31 or claim 32, comprising:
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a borazine skeletal structure, wherein in X-ray photoelectron spectroscopy measurement of the borazine skeletal structure, the positions of spectrum peaks of boron atoms, nitrogen atoms, and carbon atoms in the film are 189.0 eV to 191.0 eV, 397.0 eV to 399.0 eV, and 283.0 eV to 285.5 eV, respectively; and
the rate of oxygen atoms among constituent elements of the interior of the film is equal to or less than 10%.
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56. The insulating film for the semiconductor device according to claim 53, wherein change of permittivity of the insulating film for the semiconductor device is equal to or less than 0.1 under an environment having a temperature of 25°
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32. A manufacturing method of a semiconductor device, comprising:
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a film forming step of supplying a mixed gas containing a carrier gas and a raw material gas, which is a gasified material having borazine skeletal molecules shown in a chemical formula described below, into a chamber, causing electromagnetic waves to enter the chamber so as to cause the mixed gas to be in a plasma state, and carrying out gas-phase polymerization by using the borazine skeletal molecule as a fundamental unit so as to form an insulating film for the semiconductor device on a substrate placed in the chamber; and a reaction promoting step of promoting cross-linking reaction of the borazine skeletal molecules in the formed insulating film for the semiconductor device after the film forming step, wherein in the reaction promoting step, a bias is applied to the substrate, only the raw material gas, which is the gasified material having the borazine skeletal molecules, is gradually reduced while supplying the mixed gas, and the cross-linking reaction of the borazine skeletal molecules in the formed insulating film for the semiconductor device is promoted by plasma mainly comprising the carrier gas; wherein, each of R1 and R2 in the above described chemical formula is a hydrogen atom or an alkyl group, an alkenyl group, a monoalkylamino group, or a dialkylamino group, which are having a carbon number of 5 or less, and R1 and R2 may be the same or different from each other, with the proviso that cases in which all of R1 and R2 are hydrogen atoms are excluded.
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39. A manufacturing method of a semiconductor device, comprising:
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a film forming step of supplying a mixed gas containing a carrier gas and a raw material gas, which is a gasified material having borazine skeletal molecules shown in a chemical formula described below, into a chamber, causing electromagnetic waves to enter the chamber so as to cause the mixed gas to be in a plasma state, and carrying out gas-phase polymerization by using the borazine skeletal molecule as a fundamental unit so as to form an insulating film for the semiconductor device on a substrate placed in the chamber; and a reaction promoting step of promoting cross-linking reaction of the borazine skeletal molecules in the formed insulating film for the semiconductor device after the film forming step, wherein in the reaction promoting step, the cross-linking reaction of the borazine skeletal molecules in the formed insulating film for the semiconductor device is promoted by ultraviolet ray radiation treatment; wherein, each of R1 and R2 in the above described chemical formula is a hydrogen atom or an alkyl group, an alkenyl group, a monoalkylamino group, or a dialkylamino group, which are having a carbon number of 5 or less, and R1 and R2 may be the same or different from each other, with the proviso that cases in which all of R1 and R2 are hydrogen atoms are excluded.
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40. A manufacturing method of a semiconductor device, comprising:
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a film forming step of supplying a mixed gas containing a carrier gas and a raw material gas, which is a gasified material having borazine skeletal molecules shown in a chemical formula described below, into a chamber, causing electromagnetic waves to enter the chamber so as to cause the mixed gas to be in a plasma state, and carrying out gas-phase polymerization by using the borazine skeletal molecule as a fundamental unit so as to form an insulating film for the semiconductor device on a substrate placed in the chamber; and a reaction promoting step of promoting cross-linking reaction of the borazine skeletal molecules in the formed insulating film for the semiconductor device after the film forming step, wherein in the reaction promoting step, the cross-linking reaction of the borazine skeletal molecules in the formed insulating film for the semiconductor device is promoted by electron beam radiation treatment; wherein, each of R1 and R2 in the above described chemical formula is a hydrogen atom or an alkyl group, an alkenyl group, a monoalkylamino group, or a dialkylamino group, which are having a carbon number of 5 or less, and R1 and R2 may be the same or different from each other, with the proviso that cases in which all of R1 and R2 are hydrogen atoms are excluded.
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41. A manufacturing method of a semiconductor device, comprising:
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a film forming step of supplying a mixed gas containing a carrier gas and a raw material gas, which is a gasified material having borazine skeletal molecules shown in a chemical formula described below, into a chamber, causing electromagnetic waves to enter the chamber so as to cause the mixed gas to be in a plasma state, and carrying out gas-phase polymerization by using the borazine skeletal molecule as a fundamental unit so as to form an insulating film for the semiconductor device on a substrate placed in the chamber; and a reaction promoting step of promoting cross-linking reaction of the borazine skeletal molecules in the formed insulating film for the semiconductor device after the film forming step, wherein in the reaction promoting step, the cross-linking reaction of the borazine skeletal molecules in the formed insulating film for the semiconductor device is promoted by ion radiation treatment; wherein, each of R1 and R2 in the above described chemical formula is a hydrogen atom or an alkyl group, an alkenyl group, a monoalkylamino group, or a dialkylamino group, which are having a carbon number of 5 or less, and R1 and R2 may be the same or different from each other, with the proviso that cases in which all of R1 and R2 are hydrogen atoms are excluded.
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42. A semiconductor device manufacturing apparatus, comprising:
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gas supplying means for supplying a mixed gas containing a carrier gas and a raw material gas, which is a gasified material having borazine skeletal molecules shown in a chemical formula described below, into a chamber; plasma generating means for causing electromagnetic waves to enter the chamber so as to cause the mixed gas to be in a plasma state; promoting means for promoting cross-linking reaction of the borazine skeletal molecules; and bias applying means for applying bias to the substrate, controlling means for controlling the gas supplying means, the plasma generating means, the promoting means, and the bias applying means;
whereinthe controlling means carries out a film forming step of supplying the mixed gas into the chamber by the gas supplying means, causing the mixed gas to be in the plasma state by the plasma generating means, and forming a film on a substrate placed in the chamber as an insulating film for the semiconductor device by carrying out gas-phase polymerization by using the borazine skeletal molecule as a fundamental unit; and after the film forming step, as the promoting means, the controlling means carries out a reaction promoting step of applying a bias to the substrate by the bias supplying means, generating plasma mainly comprising a gas not containing the raw material gas by the gas supplying means and the plasma generating means, and promoting the cross-linking reaction of the borazine skeletal molecules in the formed insulating film for the semiconductor device by the plasma; wherein, each of R1 and R2 in the above described chemical formula is a hydrogen atom or an alkyl group, an alkenyl group, a monoalkylamino group, or a dialkylamino group, which are having a carbon number of 5 or less, and R1 and R2 may be the same or different from each other, with the proviso that cases in which all of R1 and R2 are hydrogen atoms are excluded. - View Dependent Claims (44, 45, 46, 47, 48, 49)
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48. The semiconductor device manufacturing apparatus according to claim 42 or claim 43, wherein
the plasma generating means causes power of the electromagnetic waves in the film forming step and the reaction promoting step to be equal to or more than 1590 W/m2 and equal to or less than 127400 W/m2. -
49. The semiconductor device manufacturing apparatus according to claim 42 or claim 43, further comprising:
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lifting/lowering means for changing a height position of the substrate, wherein the lifting/lowering means disposes the substrate at a height position where an electron density in the vicinity of the substrate is equal to or less than one twentieth of a highest electron density in the plasma.
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43. A semiconductor device manufacturing apparatus, comprising:
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gas supplying means for supplying a mixed gas containing a carrier gas and a raw material gas, which is a gasified material having borazine skeletal molecules shown in a chemical formula described below, into a chamber; plasma generating means for causing electromagnetic waves to enter the chamber so as to cause the mixed gas to be in a plasma state; promoting means for promoting cross-linking reaction of the borazine skeletal molecules; and bias applying means for applying bias to the substrate, controlling means for controlling the gas supplying means, the plasma generating means, the promoting means, and the bias applying means;
whereinthe controlling means carries out a film forming step of supplying the mixed gas into the chamber by the gas supplying means, causing the mixed gas to be in the plasma state by the plasma generating means, and forming a film on a substrate placed in the chamber as an insulating film for the semiconductor device by carrying out gas-phase polymerization by using the borazine skeletal molecule as a fundamental unit; and after the film forming step, as the promoting means, the controlling means carries out a reaction promoting step of applying a bias to the substrate by the bias supplying means, gradually reducing only supply of the raw material gas, which is the gasified borazine skeletal molecules, by the gas supplying means, generates plasma mainly comprising the carrier gas by the plasma generating means, and promoting the cross-linking reaction of the borazine skeletal molecules in the formed insulating film for the semiconductor device by the plasma; wherein, each of R1 and R2 in the above described chemical formula is a hydrogen atom or an alkyl group, an alkenyl group, a monoalkylamino group, or a dialkylamino group, which are having a carbon number of 5 or less, and R1 and R2 may be the same or different from each other, with the proviso that cases in which all of R1 and R2 are hydrogen atoms are excluded.
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50. A semiconductor device manufacturing apparatus, comprising:
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gas supplying means for supplying a mixed gas containing a carrier gas and a raw material gas, which is a gasified material having borazine skeletal molecules shown in a chemical formula described below, into a chamber; plasma generating means for causing electromagnetic waves to enter the chamber so as to cause the mixed gas to be in a plasma state; promoting means for promoting cross-linking reaction of the borazine skeletal molecules, wherein the promoting means is ultraviolet ray radiation means for irradiating the substrate with ultraviolet rays; and controlling means for controlling the gas supplying means, the plasma generating means, and the promoting means;
whereinthe controlling means carries out a film forming step of supplying the mixed gas into the chamber by the gas supplying means, causing the mixed gas to be in the plasma state by the plasma generating means, and forming a film on a substrate placed in the chamber as an insulating film for the semiconductor device by carrying out gas-phase polymerization by using the borazine skeletal molecule as a fundamental unit; and after the film forming step, the controlling means carries out a reaction promoting step of promoting the cross-linking reaction of the borazine skeletal molecules in the formed insulating film for the semiconductor device by ultraviolet ray radiation by the ultraviolet ray radiation means; wherein, each of R1 and R2 in the above described chemical formula is a hydrogen atom or an alkyl group, an alkenyl group, a monoalkylamino group, or a dialkylamino group, which are having a carbon number of 5 or less, and R1 and R2 may be the same or different from each other, with the proviso that cases in which all of R1 and R2 are hydrogen atoms are excluded.
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51. A semiconductor device manufacturing apparatus, comprising:
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gas supplying means for supplying a mixed gas containing a carrier gas and a raw material gas, which is a gasified material having borazine skeletal molecules shown in a chemical formula described below, into a chamber; plasma generating means for causing electromagnetic waves to enter the chamber so as to cause the mixed gas to be in a plasma state; promoting means for promoting cross-linking reaction of the borazine skeletal molecules, wherein the promoting means is electron beam radiation means for irradiating the substrate with an electron beam; and controlling means for controlling the gas supplying means, the plasma generating means, and the promoting means;
whereinthe controlling means carries out a film forming step of supplying the mixed gas into the chamber by the gas supplying means, causing the mixed gas to be in the plasma state by the plasma generating means, and forming a film on a substrate placed in the chamber as an insulating film for the semiconductor device by carrying out gas-phase polymerization by using the borazine skeletal molecule as a fundamental unit; and after the film forming step, the controlling means carries out a reaction promoting step of promoting the cross-linking reaction of the borazine skeletal molecules in the formed insulating film for the semiconductor device by electron beam radiation by the electron beam radiation means; wherein, each of R1 and R2 in the above described chemical formula is a hydrogen atom or an alkyl group, an alkenyl group, a monoalkylamino group, or a dialkylamino group, which are having a carbon number of 5 or less, and R1 and R2 may be the same or different from each other, with the proviso that cases in which all of R1 and R2 are hydrogen atoms are excluded.
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52. A semiconductor device manufacturing apparatus, comprising:
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gas supplying means for supplying a mixed gas containing a carrier gas and a raw material gas, which is a gasified material having borazine skeletal molecules shown in a chemical formula described below, into a chamber; plasma generating means for causing electromagnetic waves to enter the chamber so as to cause the mixed gas to be in a plasma state; promoting means for promoting cross-linking reaction of the borazine skeletal molecules, wherein the promoting means is ion radiation means for irradiating the substrate with ions; and controlling means for controlling the gas supplying means, the plasma generating means, and the promoting means;
whereinthe controlling means carries out a film forming step of supplying the mixed gas into the chamber by the gas supplying means, causing the mixed gas to be in the plasma state by the plasma generating means, and forming a film on a substrate placed in the chamber as an insulating film for the semiconductor device by carrying out gas-phase polymerization by using the borazine skeletal molecule as a fundamental unit; and after the film forming step, the controlling means carries out a reaction promoting step of promoting the cross-linking reaction of the borazine skeletal molecules in the formed insulating film for the semiconductor device by ion radiation by the ion radiation means; wherein, each of R1 and R2 in the above described chemical formula is a hydrogen atom or an alkyl group, an alkenyl group, a monoalkylamino group, or a dialkylamino group, which are having a carbon number of 5 or less, and R1 and R2 may be the same or different from each other, with the proviso that cases in which all of R1 and R2 are hydrogen atoms are excluded.
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Specification