WO2005112082A1 - Cyclic pulsed two-level plasma atomic layer deposition apparatus and method - Google Patents

Cyclic pulsed two-level plasma atomic layer deposition apparatus and method Download PDF

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Publication number
WO2005112082A1
WO2005112082A1 PCT/KR2005/001382 KR2005001382W WO2005112082A1 WO 2005112082 A1 WO2005112082 A1 WO 2005112082A1 KR 2005001382 W KR2005001382 W KR 2005001382W WO 2005112082 A1 WO2005112082 A1 WO 2005112082A1
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gas
reaction chamber
reaction
plasma
purge
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PCT/KR2005/001382
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English (en)
French (fr)
Inventor
Young Hoon Park
Hong Joo Lim
Sahng Kyoo Lee
Tae Wook Seo
Ho Seung Chang
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Ips Ltd.
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Publication of WO2005112082A1 publication Critical patent/WO2005112082A1/en

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
    • C23C16/45536—Use of plasma, radiation or electromagnetic fields
    • C23C16/45538—Plasma being used continuously during the ALD cycle
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
    • C23C16/45536—Use of plasma, radiation or electromagnetic fields
    • C23C16/4554—Plasma being used non-continuously in between ALD reactions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/34—Nitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/448—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
    • C23C16/452—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials by activating reactive gas streams before their introduction into the reaction chamber, e.g. by ionisation or addition of reactive species
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45544—Atomic layer deposition [ALD] characterized by the apparatus
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges

Definitions

  • the present invention relates to a plasma atomic layer deposition method, and more particularly, to cyclic pulsed two-level plasma atomic layer deposition apparatus and method which can reduce a damage generating in a silicon substrate by minimizing plasma energy applied to a reaction chamber in forming a semiconductor device on the silicon substrate.
  • U.S. Patent No. 5,916,365 filed by Arthur Sherman and entitled 'Sequential Chemical Vapor Deposition' discloses a pulsed two-level plasma atomic layer deposition method in which plasma is applied at reaction gas supply cycle of an atomic layer deposition method to form a high quality thin film at low temperature.
  • the patent does not suggest a method to solve a damage generated in a semiconductor substrate by plasma and problems in reliability of plasma ignition and repeatability of plasma generation.
  • the present invention provides cyclic pulsed two-level plasma atomic layer deposition apparatus and method by which a high quality thin film is formed at low temperature by applying a low plasma energy to prevent a damage to a semiconductor substrate.
  • the present invention provides cyclic pulsed two-level plasma atomic layer deposition apparatus and method which solve problems that the characteristics of a semiconductor device are deteriorated due to a damage to the semiconductor device or circuit on a substrate or that yield directly related to the manufacturing costs of semiconductors is deteriorated.
  • the present invention provides cyclic pulsed two-level plasma atomic layer deposition apparatus and method which minimize the intensity of plasma energy applied to a reaction chamber and adjust the time and cycle of application of plasma until the pressure and temperature in the reaction chamber become stable so that reliability of plasma ignition and the repeatability of generation of plasma are highly maintained and a high quality thin film can be formed at low process temperature, compared to the conventional methods such as a plasma enhanced chemical vapor deposition (PECVD), a cyclically pulsed plasma atomic layer deposition method, or plasma enhanced atomic layer deposition (PEALD).
  • PECVD plasma enhanced chemical vapor deposition
  • PEALD plasma enhanced atomic layer deposition
  • the present invention provides cyclic
  • a high quality thin film can be deposited at low temperature without damaging a silicon substrate in the reaction chamber by applying a possibly lowest plasma energy by previously activating the reaction gas supplied to the reaction chamber.
  • plasma energy having low intensity is applied to the reaction gas supplied to the reaction chamber after neutral radicals exhibiting a great chemical reactivity are generated through the reaction gas activation unit, at least the reaction gas is thermally activated, or both functions are applied. Then, a thin film having a desired thickness can be deposited at low temperature even when plasma energy having lower energy than the plasma energy in the conventional technology is applied to the reaction chamber during an atomic layer deposition process. Thus, damages generated in a semiconductor device or a circuit board can be remarkably reduced. Also, This method prevents deterioration of the characteristics of a semiconductor device having an ultra-narrow line width and improves yield very effectively.
  • the source gas is supplied to the reaction chamber and absorbed on the substrate loaded in the reaction chamber. Then, the supply of the source gas is stopped and the source gas remaining in the reaction chamber is purged with the purge gas.
  • the activated reaction gas is supplied to the reaction chamber and plasma is applied to the reaction chamber to make the source gas absorbed on the substrate and the reaction gas react with each other.
  • the activated reaction gas is directly supplied to the reaction chamber to purge the source gas.
  • the source gas remaining in the reaction chamber is purged by supplying the purge gas or directly purged by the reaction gas supplied to the reaction chamber through the reaction gas activation unit.
  • FIG. 1 is a flow chart for explaining a cyclic pulsed two-level plasma atomic layer deposition method according to an embodiment of the present invention
  • FIG. 2 is a view schematically illustrating an apparatus for implementing the cyclic pulsed two-level plasma atomic layer deposition method according to the present invention ;
  • FIG. 3 is a graph showing a process order of a reaction gas supply cycle by time to implement the cyclic pulsed two-level plasma atomic layer deposition method according to the present invention ;
  • FIG. 4 is a graph showing an example of an unstable state of pressure in a reaction chamber in the process of FIG. 3;
  • FIG. 5 is a graph showing an example of indicating the intensity of a two-level RF power to apply two-level plasma to the reaction chamber in the process of FIG. 3.
  • a silicon substrate 218 is loaded on a substrate support plate 212 in a reaction chamber 200.
  • source gas including an element 'a' is supplied to the reaction chamber 200 through a source gas supply pipe 220 to be absorbed on the silicon substrate 218.
  • first plasma G (30001C, 3002C, and 3003C) is applied to the reaction chamber 200.
  • Step 1 a first application cycle 3001C of the first plasma G can be skipped, that is, the application of plasma can be made from the next step, that is, Step 2 (102 and 302A) by skipping the plasma application cycle 3001C of the first plasma G.
  • the first plasma G changes to a first plasma G ⁇ (3002C and 3003C).
  • Step 2 the source gas remaining in the reaction chamber 200 without being absorbed on the silicon substrate 218 is purged through an exhaust unit 208 using the purge gas. Simultaneously, the first plasma G or the first plasma G ⁇ is continuously applied to the reaction chamber 200.
  • the purge gas is supplied using the source gas supply pipe 220, reaction gas supply pipes 222A and 222B, or a separate supply pipe (not shown).
  • Step 2 the first application cycle 3001C and the second application cycle 3002C of the first plasma G can be skipped, that is, the application of plasma can be made from the next step, that is, Step 3 (103 and 303 A) by skipping the plasma application cycles 3001C and 3002C of the first plasma G.
  • the first plasma G is changed to the first plasma G " .
  • Step 3 (103 and 303 A)
  • reaction gas including an element 'b' is passed through the reaction gas supply pipes 222A and 222B and a reaction gas activation unit 206 and then is supplied to the reaction chamber 200 so that the first part of the deposition process in which an 'a' or 'ab' thin film is formed is performed.
  • the reaction gas activated by the reaction gas activation unit 206 and the source gas absorbed on the silicon substrate 218 perform a deposition reaction with the assistance of the first plasma G.
  • the first plasma G (the first plasma G ⁇ or the first plasma G " ) is continuously applied to the reaction chamber 200.
  • Step 3 is a cycle in which the pressure state of the reaction gas supplied to the reaction chamber 200 is mainly settled.
  • Step 4 while the reaction gas including the element 'b' passed through the reaction gas activation unit 206 is continuously supplied to the reaction chamber 200, the second plasma 3004C is applied in the reaction chamber 200 so that plasma ions and radicals are generated. Accordingly, the second part of the deposition process in which the 'a' or 'ab' thin film is deposed is performed.
  • Step 2 (102 and 302A) is skipped so that the remaining source gas in the reaction chamber 200 can be purged with the purge gas.
  • Step 5 (105 and 305 A)
  • the supply of the reaction gas and the application of the second plasma are stopped at a process time point t5 and the reaction gas remaining in the reaction chamber 200 is purged with the purge gas through the exhaust unit 208.
  • the first plasma H (3005C) is applied to the reaction chamber 200.
  • Step 1 though Step 5 are repeated by a desired number of N times.
  • the source gas, the reaction gas, and the purge gas are referred to as process gas.
  • FIG. 2 shows the configuration of a thin film deposition apparatus for implementing the present invention.
  • the thin film deposition apparatus includes the reaction chamber 200 providing space where the thin film deposition process is directly performed, a process gas supply and control unit 210 supplying the process gas such as the source gas, the reaction gas, and the purge gas, the reaction gas activation unit 206 for activating the reaction gas in advance, the exhaust unit 208, an RF power generation unit 204 and a matcher 202 for applying plasma to the reaction chamber 200, the source gas supply pipe 220 connecting the process gas supply and control unit 210 and the reaction chamber 200 to supply the source gas to the reaction chamber 200, the reaction gas supply pipes 222A and 222B connecting the process gas supply and control unit 210 and the reaction gas activation unit 206 to the reaction chamber 200 to supply the reaction gas, and an exhaust pipe 226 connecting the reaction chamber 200 and the exhaust unit 208 to purge the process gas in the reaction chamber 200.
  • a process gas supply and control unit 210 supplying the process gas such as the source gas, the reaction
  • the substrate supporting platform 212 on which the silicon substrate or wafer 218 can be loaded is installed in the reaction chamber 200.
  • the RF power generation unit 204 and the matcher 202 for applying RF power to apply plasma to the reaction chamber 200 are connected to the reaction chamber 200.
  • the RF power generation unit 204 and the matcher 202 together are referred to as an RF power supply unit and can control the intensity of plasma energy.
  • a ground 214 that is one of electrodes can be connected to the substrate supporting platform 212 installed in the reaction chamber 200 or separately installed in the reaction chamber 200 which is not shown herein.
  • the plasma applied to the reaction chamber 200 is divided into two groups of the first plasma G (3001C, 3002C, and 3003C) and the first plasma H (3005C), and the second plasma (3004C).
  • the first plasma G (3001C, 3002C, and 3003C) and the first plasma H (3005C) are plasma having a relatively lower energy intensity and continuously applied to the reaction chamber 200 during the cycles of Step 1 (101 and 301A), Step 2 (102 and 302A), Step 3 (103 and 303A), and Step 5 (105 and 305A).
  • the second plasma (3004C) is plasma having a relatively higher energy intensity than those of the first plasma G (3001C, 3002C, and 3003C) and the first plasma H (3005C) and continuously applied to the reaction chamber 200 during the cycle of only Step 4 (104 and 304A) to make the source gas and the reaction gas react with each other.
  • two independent RF power supply units may be used or a single RF power supply unit may be used and controlled to variably apply plasmas having two different energy intensities according to the process cycles.
  • the two-level plasma and the reaction gas activation unit By using the two-level plasma and the reaction gas activation unit, while the thin film deposition reaction temperature is lowered and a damage to the substrate due to the plasma is reduced, a high quality thin film can be formed and the reliability of plasma ignition and the repeatability of the plasma generation can be improved.
  • the process gas supply and control unit 210 for controlling the supply of the process gas is connected to the reaction chamber 200 through the source gas supply pipe 220.
  • the process gas supply and control unit 210 and the reaction chamber 200 are connected via the reaction gas activation unit 206 and the reaction gas supply pipe 222A and 222B so that the reaction gas is supplied to the reaction chamber 200 after being activated.
  • the process gas supply and control unit 210 can be configured to be able to supply and control of the purge gas.
  • the purge gas is supplied to the reaction chamber 200 using an additional supply pipe (not shown).
  • the reaction gas activation unit 206 for activating the reaction gas is connected between the reaction gas supply pipes 222A and 222B.
  • the reaction gas activation unit 206 may be configured to have a reaction gas activation function simply by heat or a reaction gas activation function by plasma, or both functions.
  • the heat or plasma energy sources needed for activation can be configured to be a variable type.
  • the exhaust unit 208 for exhausting the process gas is connected to the reaction chamber 200 through the exhaust pipe 226.
  • the process temperature can be lowered and a damage generated in the substrate can be remarkably reduced by lowering the intensity of plasma energy applied to the substrate in the reaction chamber.
  • the second plasma (3004C) is supplied by lowering the energy intensity thereof by 1/3 through 1/2 compared to the conventional technology, the damage to the substrate by the plasma can be remarkably reduced.
  • the energy intensities of the first plasma G (3001A, 3002C, and 3003C) and the first plasma H (3005C) are made to be not more than 1/2 of the energy intensity of the second plasma (3004C).
  • the source gas typically includes a metal element.
  • the reaction gas in order to implement the thin film deposition process, for example, to form a nitride thin film, the reaction gas must includes nitrogen. That is, when the source gas is formed to include one of compounds of titanium (Ti), tantalum (Ta), or tungsten (W) metals and the reaction gas is formed by one of nitrogen (N ), ammonia (NH ), or hydrazine (N H ) gases, nitride thin films such as titanium nitride (TiN), tantalum nitride (TaN), or tungsten nitride (WN) are formed.
  • the reaction gas is formed of a mixture of a gas including the element 'b' and hydrogen (H ) gas. That is, the reaction gas may be formed of a mixture of nitrogen (N ) gas and hydrogen (H ) gas, a mixture of ammonia (NH ) and hydrogen (H ) gas, or a mixture of hydrazine (N H ) gas and hydrogen (H ) gas.
  • N ) gas and hydrogen (H ) gas a mixture of nitrogen (N ) gas and hydrogen (H ) gas
  • NH NH , or H radicals are supplied onto the silicon substrate 218 so that a metal nitride thin film is formed.
  • reaction gas when the reaction gas is formed of a gas including oxygen (O ) or a mixture of the gas including oxygen (O ) gas and hydrogen (H ) gas, an oxide thin film is formed.
  • reaction gas is formed to include hydrogen (H ) gas, since the metal compound of the source gas is deoxidized in Steps 3 and 4, a metal thin film is formed.
  • FIG. 2 shows the concept of a cyclic pulsed two-level plasma atomic layer deposition apparatus to implement the present invention.
  • Step 1 the source gas including the element 'a' is supplied to the reaction chamber 200 through the source gas supply pipe 220 to be absorbed on the surface of the silicon substrate 218.
  • the application of the first plasma G (3001A, 3002C, and 3003C) to the reaction chamber 200 is initiated.
  • Step 2 the supply of the source gas is stopped and the purge gas is supplied to the reaction chamber 200 so that the source gas remaining in the reaction chamber 200 without being absorbed on the silicon substrate 218 is purged.
  • Argon (Ar), helium (He), nitrogen (N ), or hydrogen (H ) gas is used as the purge gas.
  • the first plasma G (3001C, 3002C, and 3003C) are continuously applied.
  • Step 3 (103 and 303 A)
  • the supply of the purge gas is discontinued and the reaction gas including the element 'b' is supplied to the reaction chamber 200 through the reaction gas supply pipes 222A and 222B.
  • the reaction gas supplied to the reaction chamber 200 passes through the reaction gas activation unit 206.
  • radicals are picked up by means of a plasma generation function in the reaction gas activation unit 206.
  • the reaction gas may be thermally activated in the reaction gas activation unit 206 or by the above-mentioned two functions.
  • the first plasma G (3001C, 3002C, and 3003C) is continuously applied during the process cycle of Step 3.
  • the first part of the deposition process takes place, that is, a deposition reaction occurs on the substrate as the source gas absorbed on the substrate in the reaction chamber 200 reacts with the reaction gas supplied to the reaction chamber 200 with the assistance of the first plasma G applied to the reaction chamber 200. Simultaneously, during this process cycle, the turbulence state of pressure generated when the reaction gas is supplied to the reaction chamber 200 is stabilized.
  • Step 4 the reaction gas including the element 'b' is continuously supplied to the reaction chamber 200.
  • the second plasma (3004C) having energy intensity greater than that of the first plasma G is applied to the reaction chamber 200. Since the pressure of the reaction gas in the reaction chamber at this time is already stable, the thin film deposition process is actively performed with the assistance of the second plasma applied to the reaction chamber 200 so that an 'a' or 'ab' thin film is formed on the silicon substrate 218.
  • the second part of the deposition process is performed which is a thin film deposition phenomenon actively occurring as not only the ions and radicals gained when the reaction gas supplied onto the substrate passes through the reaction gas activation unit 206 but also the ions and radicals generated by the second plasma having high energy intensity applied to the reaction chamber 200 are mixed.
  • Step 5 (105 and 305 A) that is a final process cycle, the supply of the reaction gas and the application of the second plasma are discontinued.
  • the reaction gas remaining in the reaction chamber 200 is purged by the purge gas.
  • Step 1 through Step 5 are repeated by a desired number of N times.
  • Step 1 the source gas including the element 'a' is supplied to the reaction chamber 200 via the source gas supply pipe 220 to be absorbed on the surface of the silicon substrate 218.
  • Step 2 the supply of the source gas is stopped and the purge gas is supplied to the reaction chamber 200 so that the source gas remaining in the reaction chamber 200 without being absorbed on the substrate is purged.
  • Step 3 (103 and 303 A), the supply of the purge gas is stopped and the reaction gas including the element 'b' is supplied to the reaction chamber 200 through the reaction gas supply pipes 222A and 222B.
  • the reaction gas supplied to the reaction chamber 200 passes through the reaction gas activation unit 206. In doing so, radicals are picked up by the plasma in the reaction gas activation unit 206, the reaction gas is thermally activated in the reaction gas activation unit 206, or the reaction gas is activated by these two processes.
  • the first plasma G (3001C, 3002C, and 3003C) is continuously applied to the reaction chamber 200 during the process cycles of Step 1 through Step 3.
  • the first part of the deposition process is performed by the first plasma G in Step 3 and simultaneously the turbulence state in the pressure of the reaction gas in the reaction chamber 200 is stabilized.
  • Step 4 (104 and 304A)
  • the reaction gas including the element 'b' is continuously supplied to the reaction chamber 200 through the reaction gas supply pipes 222A and 222B.
  • the second plasma (3004C) is applied to the reaction chamber 200.
  • the thin film deposition phenomenon is actively performed on the substrate between the source gas absorbed on the substrate and the reaction gas so that the 'a' or 'ab' thin film is formed on the silicon substrate 218.
  • the deposition reaction is actively performed not only by the mixture of the ions and the radicals gained while the reaction gas in the reaction chamber 200 passes through the reaction gas activation unit 206, but also by the ions and the radicals generated by the second plasma (3004C) applied to the reaction chamber 200, so that the second part of the deposition process is performed.
  • the first plasma G (3001A, 3003B, and 3003C) and the first plasma H (3005C) directly or indirectly contribute to the deposition reaction between the source gas and the reaction gas.
  • the plasma applied to the reaction chamber 200 is plasma (3001C, 3002C, 3003C, 3004C, and 3005C) having two-step energy intensity.
  • the first plasma G (3001C, 3002C, and 3003C) and the first plasma H (3005C) have the same energy intensity which is about 1/2 of that of the second plasma (3004C).
  • the energy intensity of the second plasma (3004C) is 1/3 through 1/2 of the conventional technology.
  • Step 5 105 and 305 A
  • the supply of the reaction gas is stopped at the initial stage of the process cycle t5 and the application of the second plasma is turned off. Also, by supplying the purge gas, the reaction gas remaining in the reaction chamber 200 is purged. Simultaneously, the first plasma H (3005C) is continuously applied to the reaction chamber 200.
  • Step 1 through Step 5 are repeated by a desired number of N times.
  • the plasma energy applied to the reaction chamber 200 is applied in two steps of the first plasma G (3001C, 3002C, and 3003C) and the first plasma H (3005C), and the second plasma (3004C).
  • the energy intensity of the first plasma G (3001C, 3002C, and 3003C) and the first plasma H (3005C) are the same and applied to the reaction chamber 200 throughout Step 1 (101 and 301A), Step 2 (102 and 302A), Step 3 (103 and 303A), and Step 5 (105 and 305A).
  • the application of the first plasma G (3001C, 3002C, and 3003C) may start from the point tl of Step 1 (101 and 301 A) or the point t2 of Step 2 (102 and 302A), in which the first plasma G (3001C, 3002C, and 3003C) changes to the first plasma G ⁇ (3002C and 3003C) (not shown). Also, the application of the first plasma G (3001C, 3002C, and 3003C) may start from the point t3 of Step 3 (103 and 303 A), in which the first plasma G (3001C, 3002C, and 3003C) changes to the first plasma G 2 (3003C) (not shown).
  • the energy intensity of the second plasma (3004C) is about 1/3 through 1/2 of the conventional technology and applied only in Step 4 (104 and 304A) in which the reaction gas is supplied and stabilized.
  • the first plasma G (3001C, 3002C, and 3003C) and the first plasma H (3005C) are continuously applied except for Step 4 (104 and 304A).
  • the non-corresponding plasma application cycle is omitted.
  • the plasma energy application unit in the reaction chamber 200 may include two pairs of independent electrodes, or it may be possible to include a single pair of electrodes and control the plasma energy intensity and the application timing.
  • the reliability of ignition of the second plasma 3004C and the repeatability of the generation of the second plasma 3004C are improved.
  • the first plasma G' (3002C and 3003C) and the first plasma G" (3003C) may be applied.
  • the second plasma (3004C) is applied to the reaction chamber while the reaction gas is continuously supplied in Step 4 (104 and 304A).
  • the deposition reaction is performed by the second plasma (3004C) that is a main plasma so that the reliability of ignition of the second plasma (3004C) and the repeatability of the generation of the second plasma (3004C) are further improved.
  • the process gas including nitrogen is formed as the reaction gas. That is, when the source gas is formed to include one of compounds of titanium (Ti), tantalum (Ta), or tungsten (W) metals and the reaction gas is formed by one of nitrogen (N ), ammonia (NH ), or hydrazine (N H ) gases, nitride thin films such as titanium nitride (TiN), tantalum nitride (TaN), or tungsten nitride (WN) are formed.
  • the source gas is formed to include one of compounds of titanium (Ti), tantalum (Ta), or tungsten (W) metals and the reaction gas is formed by one of nitrogen (N ), ammonia (NH ), or hydrazine (N H ) gases
  • nitride thin films such as titanium nitride (TiN), tantalum nitride (TaN), or tungsten nitride (WN) are formed.
  • the reaction gas may be formed of a mixture of nitrogen (N ) gas and hydrogen (H ) gas, a mixture of ammonia (NH ) and hydrogen (H ) gas, or a mixture of hydrazine (N H ) gas and hydrogen (H ) gas.
  • N nitrogen
  • H hydrogen
  • NH, NH , or H radicals are supplied onto the silicon substrate 218 so that a metal nitride thin film is formed.
  • the reaction gas is formed of a gas including oxygen (O ) or a mixture of the gas including oxygen (O ) gas and hydrogen (H ) gas, an oxide thin film is formed.
  • the reaction gas is formed to include hydrogen (H ) gas, since the metal compound of the source gas is deoxidized in Steps 3 and 4, a metal thin film is formed.
  • FIG. 3 is a graph showing the process steps of Step 1 through Step 5 of the flow chart of FIG. 1 by the order of the process time.
  • the source gas is supplied to the reaction chamber 200 to be absorbed on the silicon substrate 218 loaded on the substrate support plate 212 in the reaction chamber 200.
  • the first plasma G (3001C, 3002C, and 3003C) are applied to the reaction chamber 200.
  • the purge gas is supplied to the reaction chamber 200 to purge the source gas remaining in the reaction chamber 200 without being absorbed on the silicon substrate 218 through the exhaust unit 208.
  • the first plasma G (3001C, 3002C, and 3003C) for which application is started from Step 1 (101 and 301 A) may not be applied in Step 1 (101 and 301 A) and may be applied in Step 2 (102 and 302A) or Step 3 (103 and 303 A).
  • the degree of the turbulence state is lower than a case in which the supply of the purge gas is stopped.
  • the supply of the purge gas can be stopped when Step 3 (103 and 303 A) begins, as in the conventional technology.
  • the intensity of the second plasma (3004C) applied to Step 4 (104 and 304A) may be instable with the change in the pressure or ignition of the second plasma may fail.
  • the reaction gas is continuously supplied to the reaction chamber 200 in Step 4 (104, 304A, 314B, and 3004C) after the reaction gas is supplied to the reaction chamber 200 in Step 3 (103, 303A, and 313B) and thus the pressure in the reaction chamber 200 is stabilized
  • the ignition conduction of the second plasma (3004C) is stabilized when the second plasma (3004C) is applied without changing the flow rate of the reaction gas.
  • the failure of the ignition is prevented so that reliability is improved.
  • this step is repeated at every process cycle, the repeatability of the generation of the second plasma (3004C) repeated at every supply cycle of the reaction gas can be highly maintained.
  • the intensity of the RF power to apply plasma to the reaction chamber 200 is 300 through 1200 watts for the second plasma (3004C). This value varies according to the source gas, the reaction gas, and the process conditions and is about 1/3 through 1/2 of the conventional technology.
  • the energy intensity of each of the first plasma G (3001C, 3002C, and 3003C) and the first plasma H (3005C), which is the same as that of each of the first plasma G ⁇ and the first plasma G 2 is about 1/2 of the energy intensity of the second plasma (3004C).
  • the damage to the substrate can be remarkably reduced by the second plasma (3004C).
  • the purge gas may be continuously supplied to the reaction chamber while the second plasma (3004C) is applied to the reaction chamber 200 in this process step.
  • Step 5 the supply of the reaction gas is stopped and the purge gas continuously supplied purges the reaction gas remaining in the reaction chamber.
  • the supply of the purge gas is stopped in Step 2 (102 and 302A)
  • the supply of the reaction gas is stopped in Step 5 (105 and 305 A) and the purge gas is supplied again to purge the reaction gas remaining in the reaction chamber 200.
  • the supply of the purge gas starts in Step 2 (102 and 302A)
  • the supply of the purge gas is stopped at the point t6 of Step 5 (105 and 305 A). Otherwise, the supply of the purge gas continues.
  • RF power which is remarkably lower than the conventional technology is applied so that a thin film is deposited.
  • plasma having two different energy intensities to reduce the energy intensity of the plasma a high quality thin film is formed at low temperature and the damage to the substrate by the plasma is remarkably reduced. That is, the reaction gas in an already activated state is supplied to the substrate and plasma having low energy intensity is continuously applied to the reaction chamber so that and a high quality thin film is formed even when the energy intensity of the plasma applied to the reaction chamber to make the reaction gas react is quite lowered.
  • the present invention can prevent deterioration of the characteristics of a semiconductor device with an ultra- narrow line width and improve yield.

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PCT/KR2005/001382 2004-05-18 2005-05-12 Cyclic pulsed two-level plasma atomic layer deposition apparatus and method WO2005112082A1 (en)

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