JP2006228923A - Method for manufacturing thin film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a thin film by which embedding characteristic to super-microfabricated hole required for high integration of LIS or precise step coverage can be realized. <P>SOLUTION: The method is used to manufacture a thin film containing metal atoms on a substrate through Plasma CVD method. In concrete, the thin film containing metal atoms is formed, while pulse vias voltage is being applied onto the substrate. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing a metal atom-containing thin film on a substrate by plasma CVD, and more particularly, to produce a thin film for controlling the shape of a metal atom-containing thin film by applying a pulse bias voltage to the substrate. Regarding the method. The method for producing a thin film of the present invention is particularly useful when producing a copper thin film.

  In LSI wiring, copper is used as a wiring material to avoid wiring delay and electromigration problems. For the production of wiring using copper, the plasma CVD method is used, and a method for controlling the film formation shape to cope with the miniaturization has been reported. For example, Patent Document 1 reports a method of improving the embedding characteristics by applying a bias to a substrate.

Japanese Patent Laid-Open No. 11-87267

Along with further higher integration of LIS, realization of embedding characteristics in ultrafine holes and precise step coverage is required.
Accordingly, an object of the present invention is to provide a method for producing a thin film that can satisfy these requirements.

  As a result of repeated studies, the present inventors have found that the shape of the thin film to be manufactured can be controlled by applying a pulse voltage to the substrate.

  The present invention has been made on the basis of the above knowledge, and is a method for producing a metal atom-containing thin film on a substrate by a plasma CVD method. A thin film for forming a metal atom-containing thin film while applying a pulse bias voltage to the substrate. A manufacturing method is provided.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the thin film which can implement | achieve the embedding characteristic to an ultrafine hole and a precise | minute level | step difference coverage can be provided.

  The metal atom-containing thin film produced by the method for producing a thin film of the present invention contains a metal element as a component constituting the film. Examples of the metal atom-containing thin film include a metal thin film, a metal nitride thin film, a metal carbide thin film, and a metal oxide thin film, and one kind of metal atom may be included in the composition of these metal atom-containing thin films. It may be more than types.

The composition of the metal thin film includes titanium, zirconium, hafnium, vanadium, niobium, tantalum, molybdenum, tungsten, iron, ruthenium, cobalt, rhodium, iridium, platinum, copper, silver, gold, gallium, indium, tin, and the like. Examples thereof include alloys. Examples of the composition of the metal nitride thin film include titanium nitride, zirconium nitride, hafnium nitride, vanadium nitride, niobium nitride, tantalum nitride, and aluminum nitride. Examples of the composition of the metal carbide thin film include titanium carbide, zirconium carbide, niobium carbide, and tantalum carbide. The composition of the metal oxide thin film includes titanium oxide, zirconium oxide, hafnium oxide, vanadium oxide, niobium oxide, tantalum oxide, iron oxide, ruthenium oxide, aluminum oxide, germanium oxide, tin oxide, lanthanum oxide, praseodymium oxide, and oxidation. Neodymium, erbium oxide, lead titanate (PT), lead zirconate titanate (PZT), lanthanum-doped lead zirconate titanate (PLZT), bismuth titanate (BT), silicon-BT composite oxide (BTS), lanthanum Addition bismuth titanate (BLT), silicon-BLT composite oxide, bismuth strontium tantalate (SBT), tantalum-niobium composite oxide, titanium-tantalum composite oxide, barium titanate, strontium titanate, lithium niobate, YBa ₂ Cu ₃ O _{7- δ-type} oxide (YB ), REBC type oxide of Y site YBC was replaced by lanthanide _{elements, Bi 2 Sr 2 Ca 2 Cu} 2 O 8, Bi 2 Sr 2 Ca 2 Cu 3 O 10, hafnium - aluminum complex oxide, silicon - titanium composite Oxide, silicon-zirconium composite oxide, silicon-hafnium composite oxide, silicon-tantalum composite oxide, rare earth-silicon composite oxide, rare earth-aluminum composite oxide, rare earth-silicon-aluminum composite oxide, rare earth element added Type optical glass.

  The method for producing a thin film of the present invention has a particularly excellent pattern when a metal thin film such as copper, ruthenium or platinum, a conductive metal nitride thin film such as tantalum nitride, or a conductive metal oxide thin film such as ruthenium oxide is formed. For example, it is useful as a method for manufacturing a copper thin film wiring for LIS having a trench structure with a high aspect ratio.

  In the method for producing a thin film of the present invention, a metal atom-containing thin film can be produced according to the conventional plasma CVD method except that a pulse bias voltage is applied to the substrate. The thickness of the thin film produced by the thin film production method of the present invention is appropriately selected depending on the application.

  In the present invention, if the pulse frequency of the pulse bias voltage applied to the substrate is lower than 1 Hz, the film thickness at the bottom of the trench may be non-uniform, and if it is higher than 1 MHz, the bias voltage may not be applied. 1 Hz to 1 MHz is preferable, and 10 Hz to 0.4 MHz is a more preferable range.

  Further, if the pulse bias voltage (potential difference with respect to the ground potential) applied to the substrate is higher than −0.1 V in the DC voltage component of the substrate potential with respect to the ground potential, the bias voltage may not be effective. If it is lower than −1000 V, sputtering may be large, so a range of −0.1 to −1000 V is preferable, and a range of −0.1 to −500 V is more preferable.

  In addition, the duty ratio of the pulse bias voltage applied to the substrate (on-off ratio of the bias voltage during one pulse period) is in the range of 0 to 99%, together with the above-described parameters of the pulse bias voltage, depending on the shape of the thin film. Can be adjusted.

  For example, when a copper thin film is manufactured to form a copper wiring on a substrate having a fine trench pattern, when a copper seed layer is formed for a plating process, a pulse bias voltage such that the substrate potential is higher than −10V is set. Alternatively, the duty ratio may be reduced to 1% or less, and when a fine trench pattern is directly buried by CVD, a pulse bias voltage is set so that the substrate potential is lower than −20 V, or the duty ratio is 5%. What is necessary is just to make it large with the following.

  In the thin film manufacturing method of the present invention, it is preferable to pulse the plasma main discharge because the amount of charge accumulated in the substrate can be suppressed to a small value, so that damage to devices in the substrate can be prevented. The frequency of 1 Hz to 1 MHz is preferable, and 10 Hz to 0.4 MHz is more preferable.

  Further, by synchronizing the pulse frequency of the plasma main discharge and the frequency of the pulse bias voltage applied to the substrate, the directivity of ions flowing into the substrate surface toward the substrate can be improved, and as a result, a trench is provided. The film formation shape on the substrate can be controlled more favorably.

  In the thin film manufacturing method of the present invention, in order to selectively increase the thin film deposition rate in the vertical direction, the thin film may be formed while performing ion irradiation with an ion energy of 5 to 500 eV. If the ion energy is less than 20 eV, the irradiation effect may not appear. If the ion energy exceeds 200 eV, sputtering may increase or the amount of impurities and defect density in the resulting thin film may increase. 200 eV is preferred.

  In the method for producing a thin film of the present invention, an assist plasma is used to increase the amount of hydrogen atoms irradiated on the surface of the thin film to reduce the amount of impurities in the thin film, increase the crystal size, and improve the surface smoothness. You may apply.

  The CVD raw material used in the method for producing a thin film of the present invention contains one or more precursors for supplying metal elements to the thin film, and may contain an organic solvent and a stabilizer as necessary. The form is selected according to the method of transporting the CVD raw material described later.

  As said precursor, one or two or more types selected from the group consisting of compounds used as organic ligands such as alcohol compounds, glycol compounds, β-diketone compounds, cyclopentadiene compounds and organic amine compounds, and metals These compounds, metal halides, alkyl metals and the like. The precursor metal species include group 1 elements such as lithium, sodium, potassium, rubidium and cesium, group 2 elements such as beryllium, magnesium, calcium, strontium and barium, scandium, yttrium and lanthanoid elements (lanthanum, cerium). , Praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium), group 3 elements such as actinoid elements, group 4 elements of titanium, zirconium, hafnium, vanadium, niobium, Group 5 element of tantalum, Group 6 element of chromium, molybdenum, tungsten, Group 7 element of manganese, technetium, rhenium, Group 8 element of iron, ruthenium, osmium, Koval , Rhodium, iridium group 9 elements, nickel, palladium, platinum group 10 elements, copper, silver, gold group 11 elements, zinc, cadmium, mercury group 12 elements, aluminum, gallium, indium, thallium group 13 elements Germanium, tin, lead group 14 elements, arsenic, antimony, bismuth group 15 elements, and polonium group 16 elements.

  Examples of the alcohol compound used as the organic ligand include alkyls such as methanol, ethanol, propanol, isopropanol, butanol, 2-butanol, isobutanol, tertiary butanol, amyl alcohol, isoamyl alcohol, and tertiary amyl alcohol. Alcohols: 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2- (2-methoxyethoxy) ethanol, 2-methoxy-1-methylethanol, 2-methoxy-1,1-dimethylethanol, 2- Ethoxy-1,1-dimethylethanol, 2-isopropoxy-1,1-dimethylethanol, 2-butoxy-1,1-dimethylethanol, 2- (2-methoxyethoxy) -1,1-dimethylethanol, 2- Propoxy-1 1-diethylethanolamine, 2-second-butoxy-1,1-diethyl ethanol, ether alcohols such as 3-methoxy-1,1-dimethyl propanol.

  Examples of the glycol compound used as the organic ligand include 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 2,4-hexanediol, 2,2-dimethyl-1, 3-propanediol, 2,2-diethyl-1,3-propanediol, 1,3-butanediol, 2,4-butanediol, 2,2-diethyl-1,3-butanediol, 2-ethyl-2 -Butyl-1,3-propanediol, 2,4-pentanediol, 2-methyl-1,3-propanediol, 2-methyl-2,4-pentanediol, 2,4-hexanediol, 2,4- Examples thereof include dimethyl-2,4-pentanediol.

  Examples of the β-diketone compound used as the organic ligand include acetylacetone, hexane-2,4-dione, 5-methylhexane-2,4-dione, heptane-2,4-dione, and 2-methyl. Heptane-3,5-dione, 5-methylheptane-2,4-dione, 6-methylheptane-2,4-dione, 2,2-dimethylheptane-3,5-dione, 2,6-dimethylheptane- 3,5-dione, 2,2,6-trimethylheptane-3,5-dione, 2,2,6,6-tetramethylheptane-3,5-dione, octane-2,4-dione, 2,2 , 6-trimethyloctane-3,5-dione, 2,6-dimethyloctane-3,5-dione, 2,2-dimethyl-6-ethyloctane-3,5-dione, 2,2,6,6- Tetramethyl Kutan-3,5-dione, 2,9-dimethylnonane-4,6-dione, 2,2,6,6-tetramethyl-3,5-nonanedione, 2-methyl-6-ethyldecane-3,5- Alkyl-substituted β-diketones such as dione and 2,2-dimethyl-6-ethyldecane-3,5-dione; 1,1,1-trifluoropentane-2,4-dione, 1,1,1-trifluoro -5,5-dimethylhexane-2,4-dione, 1,1,1,5,5,5-hexafluoropentane-2,4-dione, 1,3-diperfluorohexylpropane-1,3- Fluorine-substituted alkyl β-diketones such as dione; 1,1,5,5-tetramethyl-1-methoxyhexane-2,4-dione, 2,2,6,6-tetramethyl-1-methoxyheptane-3 , 5-dione, 2,2,6 - ether substituted β- diketones such as tetramethyl-1- (2-methoxyethoxy) heptane-3,5-dione can be cited.

  Examples of the cyclopentadiene compound used as the organic ligand include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, propylcyclopentadiene, isopropylcyclopentadiene, butylcyclopentadiene, second butylcyclopentadiene, isobutylcyclopentadiene, third Examples include butylcyclopentadiene, dimethylcyclopentadiene, and tetramethylcyclopentadiene.

  Examples of the organic amine compound used as the organic ligand include methylamine, ethylamine, propylamine, isopropylamine, butylamine, secondary butylamine, tertiary butylamine, isobutylamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine. , Ethylmethylamine, propylmethylamine, isopropylmethylamine, bis (trimethylsilyl) amine, and the like.

  The organic solvent used for the above CVD raw material is not particularly limited, and a known general organic solvent can be used. Examples of the organic solvent include alcohols such as methanol, ethanol, 2-propanol and n-butanol; acetates such as ethyl acetate, butyl acetate and methoxyethyl acetate; tetrahydrofuran, tetrahydropyran, morpholine, ethylene glycol dimethyl ether, Ethers such as diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, dibutyl ether and dioxane; ketones such as methyl butyl ketone, methyl isobutyl ketone, ethyl butyl ketone, dipropyl ketone, diisobutyl ketone, methyl amyl ketone, cyclohexanone and methylcyclohexanone; hexane , Cyclohexane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, heptane, octane, Hydrocarbons such as ene and xylene; 1-cyanopropane, 1-cyanobutane, 1-cyanohexane, cyanocyclohexane, cyanobenzene, 1,3-dicyanopropane, 1,4-dicyanobutane, 1,6-dicyanohexane, Hydrocarbons having a cyano group such as 1,4-dicyanocyclohexane, 1,4-dicyanobenzene; pyridine, lutidine, and the like, depending on the solubility of the solute, the relationship between the use temperature and boiling point, the flash point, etc. , Used alone or as a mixed solvent of two or more. When these organic solvents are used, the total amount of the precursor components in the organic solvent is preferably 0.01 to 2.0 mol / liter, particularly 0.05 to 1.0 mol / liter. .

  Examples of the stabilizer include ethylene glycol ethers such as glyme, diglyme, triglyme and tetraglyme, 18-crown-6, dicyclohexyl-18-crown-6, 24-crown-8, dicyclohexyl-24-crown- 8, crown ethers such as dibenzo-24-crown-8, ethylenediamine, N, N′-tetramethylethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, 1,1,4,7,7 -Polyamines such as pentamethyldiethylenetriamine, 1,1,4,7,10,10-hexamethyltriethylenetetramine, triethoxytriethyleneamine, cyclic polyamines such as cyclam, cyclen, pyridine, pyrrolidine, Heterocyclic compounds such as piperidine, morpholine, N-methylpyrrolidine, N-methylpiperidine, N-methylmorpholine, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, oxazole, thiazole, oxathiolane, methyl acetoacetate, ethyl acetoacetate, Β-ketoesters such as 2-methoxyethyl acetoacetate or β-diketones such as acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, dipivaloylmethane, etc. A nucleophilic reagent is mentioned, and when these stabilizers are used, the amount used is preferably 0.1 mol to 10 mol, more preferably 1 to 4 mol, relative to 1 mol of the precursor.

Below, the copper CVD raw material used when manufacturing a copper thin film using the manufacturing method of the thin film of this invention is explained in full detail.
As a CVD material for copper, a material using a known copper compound for a precursor can be used without any particular limitation. Examples of the copper compound include copper halides such as copper chloride, copper bromide, and copper iodide, cyclopentadienyl copper complex formed using the cyclopentadiene compound as a ligand, and the alcohol compound used as a ligand. Copper alkoxide compounds, and copper β-diketone complex compounds formed using the β-diketone compound as a ligand.

  Examples of the copper β-diketone complex compound include a copper (II) complex represented by the following general formula (1) and a copper (II) complex represented by the following general formula (2).

In the above general formula (1) and general formula (2), the groups represented by R ^{1 to} R ⁶ are methyl, ethyl, propyl, isopropyl, butyl, secondary butyl, tertiary butyl, isobutyl, pentyl, isopentyl. , Tertiary pentyl, secondary isopentyl, 3-pentyl, hexyl, cyclohexyl, 1-methylcyclohexyl, 1,1-dimethylbutyl, heptyl, 2-heptyl, isoheptyl, tertiary heptyl, n-octyl, isooctyl, tertiary octyl 2-ethylhexyl, trifluoromethyl, perfluoropropyl, perfluorohexyl, 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, 2- (2-methoxyethoxy) ethyl, 1-methoxy-1,1- Dimethylmethyl, 2-methoxy-1,1-dimethylethyl, 2-ethoxy 1,1-dimethylethyl, 2-propoxy-1,1-dimethylethyl, 2-isopropoxy-1,1-dimethylethyl, 2-butoxy-1,1-dimethylethyl, 2-secondbutoxy-1,1 -Dimethylethyl, 2-methoxy-1,1-diethylethyl, 2-ethoxy-1,1-diethylethyl, 2-propoxy-1,1-diethylethyl, 2-isopropoxy-1,1-diethylethyl, -Butoxy-1,1-diethylethyl, 2-methoxy-1-ethyl-1-methylethyl, 2-propoxy-1-ethyl-1-methylethyl, 2- (2-methoxyethoxy) -1,1-dimethyl Examples include ethyl, 2-propoxy-1,1-diethylethyl, 3-methoxy-1,1-dimethylpropyl, and the like.

  In the general formula (2), examples of the organic compound having nucleophilicity represented by L include ethylene, propylene, butene, pentene, hexene, 2-methylhexene-3-yne, and 1,2-diphenylethylene. Alkene compounds such as Tolane, Alkyne compounds such as Tolan, 1,3-butadiene, 2-methyl-1,3-butadiene, cyclooctane-1,5-diene, 1,5-dimethylcyclooctane-1,5-diene, etc. A hydrocarbon compound having an unsaturated bond typified by a diene compound, a nitrogen-containing hydrocarbon compound having an unsaturated bond such as isonitrile, and a silane compound represented by the following general formula (3) or (4).

In the general formulas (3) and (4), examples of the alkyl group having 1 to 4 carbon atoms represented by R ^{7 to} R ¹⁰ and R ^{a to} R ^c include methyl, ethyl, propyl, isopropyl, butyl, second Examples of the aryl group having 6 to 12 carbon atoms represented by R ^{7 to} R ¹⁰ include phenyl, naphthyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, and the like. 4-vinylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 4-butylphenyl, 4-isobutylphenyl, 4-tert-butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 2,3-dimethylphenyl, 2 , 4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethyl Phenyl, and examples of the alkoxy group having 1 to 4 carbon atoms represented by R ^a to R ^c, methyloxy, ethyloxy, propyloxy, isopropyloxy, butyloxy, second butyloxy, 3-butyloxy, iso-butyloxy Examples of the alkylene group having 1 to 4 carbon atoms represented by X include methylene, ethylene, propylene, methylethylene, dimethylmethylene, butylene, 1-methylpropylene, 2-methylpropylene and the like.

Below, the transport method of said CVD raw material in the manufacturing method of the thin film of this invention is demonstrated.
In the method for producing a thin film of the present invention, as a method for transporting the above-mentioned CVD raw material to the substrate on which the thin film is deposited, the CVD raw material is vaporized by heating and / or decompressing in the raw material container and used as necessary. Gas transport method that introduces into the deposition reaction part with carrier gas such as argon, nitrogen, helium, etc., transports the CVD raw material to the vaporization chamber in a liquid or solution state, and vaporizes by heating and / or decompressing in the vaporization chamber Thus, there is a liquid transport method introduced into the deposition reaction section. In the case of the gas transport method, the precursor itself is a raw material for CVD. In the case of the liquid transport method, a solution obtained by dissolving the precursor in an organic solvent or the liquid precursor itself is the CVD raw material.

  In addition, in the multi-component CVD method for producing a multi-component thin film, the CVD raw material is vaporized and supplied independently for each component (single source method), and the multi-component raw material is mixed in advance with a desired composition. There is a method of vaporizing and supplying raw materials (cocktail sauce method). In the case of the cocktail source method, a mixture of only two or more precursors or a mixed solution obtained by adding an organic solvent to the mixture is a CVD raw material.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited by the following examples.

[Example 1]
A copper thin film was produced on the pattern formation substrate by applying a pulse bias voltage to the pattern formation substrate and performing ion irradiation under the following conditions by the CVD apparatus shown in FIG. The obtained thin film was observed by cross-sectional SEM. The observation results are shown in FIG. 2 (photograph) and FIG. 3 (schematic diagram).
(conditions)
CVD raw material; bis (1,1,1,5,5,5-hexafluoropentane-2,4-dionato) copper ethanol solution (0.146 mol / liter), liquid supply amount: 4.5 sccm, vaporization chamber temperature 195 ° C., carrier gas; hydrogen 10 sccm + Ar 80 sccm, substrate temperature: 150 ° C., reaction section pressure 0.1 torr, plasma main discharge power: 5 W, plasma main discharge is continuous discharge, assist plasma discharge power; 150 W, substrate pulse bias voltage; 10 V (DC), pulse bias voltage application pulse frequency: 1 kHz, pulse bias voltage duty ratio: 5%, substrate pulse bias power: 0.5 W, ion energy: 30 eV, film formation time: 80 minutes

[Example 2]
A copper thin film was produced on the pattern formation substrate by applying a pulse bias voltage to the pattern formation substrate and performing ion irradiation under the following conditions by the CVD apparatus shown in FIG. The obtained thin film was observed by cross-sectional SEM. The observation results are shown in FIG. 4 (photograph) and FIG. 5 (schematic diagram).
(conditions)
CVD raw material; bis (1,1,1,5,5,5-hexafluoropentane-2,4-dionato) copper ethanol solution (0.146 mol / liter), liquid supply amount: 4.5 sccm, vaporization chamber temperature 195 ° C., carrier gas; hydrogen 60 sccm + Ar 30 sccm, substrate temperature; 150 ° C., reaction part pressure 0.1 torr, plasma main discharge power; 45 W, plasma main discharge pulse frequency; 1 kHz, assist plasma discharge power: 150 W, substrate pulse bias voltage; -150 V (DC), pulse bias voltage application pulse frequency: 1 kHz, pulse bias voltage duty ratio: 50%, substrate pulse bias power: 5 W, ion energy: 170 eV, film formation time: 480 minutes

[Example 3]
A copper thin film was produced on the pattern formation substrate by applying a pulse bias voltage to the pattern formation substrate and performing ion irradiation under the following conditions by the CVD apparatus shown in FIG. The obtained thin film was observed by cross-sectional SEM. The observation results are shown in FIG. 6 (photograph) and FIG. 7 (schematic diagram).
(conditions)
CVD raw material; bis (2,2-dimethyl-6-ethyldecane-3,5-dionato) copper in ethylcyclohexane solution (0.1 mol / liter), liquid supply amount: 9 sccm, vaporization chamber temperature; 240 ° C., carrier gas; Hydrogen 60 sccm + Ar 30 sccm, substrate temperature: 150 ° C., reaction section pressure 0.1 torr, plasma main discharge power: 45 W, plasma main discharge pulse frequency: 1 kHz, assist plasma discharge power: 150 W, substrate pulse bias voltage: −150 V (DC), pulse Bias voltage application pulse frequency: 1 kHz, pulse bias voltage duty ratio: 50%, substrate pulse bias power: 5 W, ion energy: 170 eV, film formation time: 480 minutes

  As is clear from the observation results (FIGS. 2 to 7) of the copper thin films produced in Examples 1 to 3, according to the thin film production method of the present invention, excellent embedding characteristics in ultrafine holes and precise It is possible to realize step coverage.

FIG. 1 is a schematic diagram showing an example of a CVD apparatus used in the thin film manufacturing method of the present invention used in Examples 1 to 3. FIG. 2 is a cross-sectional SEM photograph of the copper thin film produced by the thin film production method of the present invention in Example 1. FIG. 3 is a schematic diagram of the copper thin film and the pattern forming substrate shown in the cross-sectional SEM photograph of FIG. FIG. 4 is a cross-sectional SEM photograph of the copper thin film produced by the thin film production method of the present invention in Example 2. FIG. 5 is a schematic diagram of the copper thin film and the pattern forming substrate shown in the cross-sectional SEM photograph of FIG. FIG. 6 is a cross-sectional SEM photograph of the copper thin film produced by the thin film production method of the present invention in Example 3. FIG. 7 is a schematic diagram of the copper thin film and the pattern forming substrate shown in the cross-sectional SEM photograph of FIG.

Claims (10)

  A method for producing a thin film containing metal atoms on a substrate by plasma CVD, wherein the thin film containing metal atoms is formed while applying a pulse bias voltage to the substrate.   The method for producing a thin film according to claim 1, wherein the metal atom-containing thin film is a copper thin film.   The method for producing a thin film according to claim 1 or 2, wherein a pulse frequency of the pulse bias voltage applied to the substrate is 1 Hz to 1 MHz.   The method for producing a thin film according to any one of claims 1 to 3, wherein a DC voltage component of the pulse bias voltage applied to the substrate is -0.1 to -1000V.   The method for producing a thin film according to any one of claims 1 to 4, wherein a duty ratio of the pulse bias voltage applied to the substrate is 0 to 99%.   The method for producing a thin film according to claim 1, wherein the plasma main discharge is pulsed.   The method for producing a thin film according to claim 6, wherein a pulse frequency of the plasma main discharge is 1 Hz to 1 MHz.   The method for producing a thin film according to claim 6 or 7, wherein a pulse frequency of the plasma main discharge and a frequency of the pulse bias voltage applied to the substrate are synchronized.   The method for producing a thin film according to any one of claims 1 to 8, wherein the metal atom-containing thin film is formed while performing ion irradiation with an ion energy of 5 to 500 eV. The manufacturing method of the thin film in any one of Claims 1-9 which uses the beta-diketone complex compound of copper as a CVD raw material.