WO2021054227A1 - Procédé de formation de film d'oxyde métallique et dispositif de formation de film - Google Patents

Procédé de formation de film d'oxyde métallique et dispositif de formation de film Download PDF

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WO2021054227A1
WO2021054227A1 PCT/JP2020/034165 JP2020034165W WO2021054227A1 WO 2021054227 A1 WO2021054227 A1 WO 2021054227A1 JP 2020034165 W JP2020034165 W JP 2020034165W WO 2021054227 A1 WO2021054227 A1 WO 2021054227A1
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metal oxide
forming
oxide film
inhibitor
gas
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PCT/JP2020/034165
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English (en)
Japanese (ja)
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澤遠 倪
加藤　大輝
原田　豪繁
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東京エレクトロン株式会社
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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
    • C23C16/06—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 metallic material
    • C23C16/18—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 metallic material from metallo-organic compounds

Definitions

  • the present disclosure relates to a method for forming a metal oxide film and a film forming apparatus.
  • Patent Documents 1 and 2 A technique for forming a conformal film using an inhibitor when forming a film in a trench is known (see, for example, Patent Documents 1 and 2).
  • the inhibitor include methanol, ethanol and the like in Patent Document 1, and HCl, CO 2 , CO, HCN, XeF 6 , HBr, HI and the like in Patent Document 2.
  • the present disclosure provides a technique capable of forming a conformal metal oxide film in a recess.
  • the method for forming the metal oxide film according to one aspect of the present disclosure includes a step of adsorbing an inhibitor containing a heterocyclic compound excluding alcohols and amines in a recess formed in the substrate, and the above-mentioned inhibitor adsorbing.
  • the step of forming a precursor layer on the substrate by supplying a precursor gas containing a metal complex to the recess, and the precursor by supplying an oxide gas to the recess in which the precursor layer is formed. It has a step of oxidizing the layer to form a metal oxide layer.
  • a conformal metal oxide film can be formed in the recess.
  • a flowchart showing a method for forming a metal oxide film of one embodiment A process sectional view showing a method for forming a metal oxide film of one embodiment. A process sectional view showing a method for forming a metal oxide film of one embodiment. A process sectional view showing a method for forming a metal oxide film of one embodiment. A process sectional view showing a method for forming a metal oxide film of one embodiment. A process sectional view showing a method for forming a metal oxide film of one embodiment. A process sectional view showing a method for forming a metal oxide film of one embodiment. A process sectional view showing a method for forming a metal oxide film of one embodiment. The figure which shows an example of the film forming apparatus used in the method of forming the metal oxide film of one Embodiment. The figure which shows the calculation result of the adsorption energy by the simulation
  • a metal oxide film for example, a zirconium oxide (ZrO 2 ) film, is widely used as a high-k film contained in logic ICs such as MPU and ASIC, and memory ICs such as DRAM and NAND.
  • the metal oxide film is, for example, an atomic layer deposition (ALD) in which a precursor gas containing a metal complex and an oxidation gas are alternately supplied in a processing container with a purge in between, and the metal oxide film is deposited on a substrate in the processing container. : Atomic Layer Deposition) Formed by the process.
  • ALD atomic layer deposition
  • the film thickness at the upper part of the trench becomes thicker than the film thickness at the lower part, and a conformal metal oxide film can be obtained. Have difficulty.
  • the present inventors before supplying the precursor gas, the present inventors supply an inhibitor containing alcohols, amines or a heterocyclic compound into the processing vessel to apply more inhibitors to the upper part of the trench than to the lower part. It was found that the deposition of the precursor on the upper part of the recess was suppressed by adsorbing.
  • an inhibitor containing alcohols, amines or a heterocyclic compound into the processing vessel to apply more inhibitors to the upper part of the trench than to the lower part. It was found that the deposition of the precursor on the upper part of the recess was suppressed by adsorbing.
  • the method for forming the metal oxide film of one embodiment is a method of forming a metal oxide film on a substrate in which recesses such as trenches and holes are formed on the surface by an ALD process, and the substrate in which the recesses are formed is treated. It is executed while being contained in a container.
  • a substrate to which the ALD process can be applied can be widely used.
  • the substrate to which the ALD process can be applied is, for example, a semiconductor substrate made of silicon or the like. Examples of the substrate include semiconductor substrates used in the manufacture of semiconductor devices having a capacitor insulating film and a gate insulating film.
  • FIG. 1 is a flowchart showing a method for forming a metal oxide film of one embodiment.
  • a step S1 for supplying an inhibitor a step S2 for supplying a precursor gas, a step S3 for purging, a step S4 for supplying an oxidizing gas, and a step of purging
  • a plurality of cycles including S5 and the like are executed.
  • FIG. 2A to 2F are process cross-sectional views showing a method of forming a metal oxide film of one embodiment.
  • the target substrate 200 on which the metal oxide film is formed has an insulating film 201 in which the recess 202 is formed.
  • the insulating film 201 may be, for example, a SiO 2 film or an Al 2 O 3 film.
  • step S1 as shown in FIG. 2A, the recess 202 is supplied with an inhibitor 203 containing at least one of alcohols, amines and a heterocyclic compound.
  • Alcohols are alcohol compounds represented by the formula R 1 OH (in the formula, R 1 represents a monovalent hydrocarbon group), and amines are the formula R 2 R 3 R 4- N (formula R 2 R 3 R 4-N). among, R 2, R 3 and R 4 represents a hydrogen atom or a monovalent hydrocarbon group, at least one of R 2, R 3 and R 4 is a monovalent hydrocarbon group .R 2, R 3 and R 4 may be the same as or different from each other).
  • the carbon number of R 1 , R 2 , R 3 and R 4 may be, for example, 1 to 8.
  • the hydrocarbon groups of R 1 , R 2 , R 3 and R 4 may be linear, branched or cyclic and may be saturated or unsaturated.
  • R 1 , R 2 , R 3 and R 4 may have substituents as long as they do not interfere with the effects of the present disclosure.
  • Specific examples of R 1 , R 2 , R 3 and R 4 include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, t-butyl group and isobutyl group, allyl group, phenyl group and the like. ..
  • alcohols include methyl alcohol (methanol), ethyl alcohol (ethanol), n-propyl alcohol (1-propanol), isopropyl alcohol (2-propanol), and t-butyl alcohol (2-methyl-2-propanol).
  • Alcohols such as isobutyl alcohol (2-methyl-1-propanol), allyl alcohols, phenols and the like.
  • amines include diethylamine, methylamine, ethylamine, isopropylamine, aniline and the like.
  • a heterocyclic compound is a cyclic compound containing at least two different elements in the ring.
  • Specific examples of the heterocyclic compound include pyridine, oxazole, tetrahydrofuran, quinuclidine and the like.
  • the supply of inhibitor 203 may be carried out in a diluted gas environment.
  • the inhibitor 203 may be supplied after replacing the inside of the processing container with a diluting gas.
  • the diluent gas may be supplied to the processing container together with the inhibitor 203.
  • the inhibitor 203 may be supplied while supplying the dilution gas to the treatment container, or the inhibitor 203 and the dilution gas are mixed and the inhibitor 203 (mixed gas) diluted with the dilution gas is supplied to the treatment container. May be supplied.
  • the diluting gas include an inert gas such as nitrogen (N 2 ) gas and a rare gas, carbon dioxide (CO 2 ) gas and carbon monoxide (CO) gas.
  • the diluting gas is selected from the group consisting of helium (He) gas, neon (Ne) gas, argon (Ar) gas, krypton (Kr) gas, xenone (Xe) gas, N 2 gas, CO 2 gas and CO gas. It is preferable to contain at least one kind of gas.
  • step S1 the inhibitor 203 is adsorbed on the exposed surface of the insulating film 201 of the recess 202 in the first cycle, but in the second and subsequent cycles, the metal oxide formed in steps S2 to S5.
  • the inhibitor 203 will be adsorbed on the surface of the layer 206. Therefore, it is preferable that the inhibitor 203 is easily adsorbed on the metal oxide layer 206.
  • the likelihood of adsorption of the inhibitor 203 to the metal oxide layer 206 is determined by, for example, the adsorption energy of the inhibitor 203 (for example, alcohols, amines and heterocyclic compounds) on the surface (surface site) of the metal oxide layer 206.
  • the "adsorption energy” is given as a value obtained by subtracting the energy before adsorption from the energy when the inhibitor 203 is adsorbed on the surface site, and a negative value means that the adsorption state is stable. Further, the larger the adsorption energy (negative value), the easier it is for the inhibitor 203 to be adsorbed on the surface site, and the stronger the adsorption force is.
  • the adsorption energy is obtained by, for example, the density functional theory (PBE / DNP) using the DMol3 module of the software Materials Studio.
  • FIG. 2B shows the step S1 of supplying the inhibitor in the first cycle, so that the insulating film 201 of the recess 202 is exposed, but in the step S1 of supplying the inhibitor in the second and subsequent cycles.
  • the surface of the recess 202 is covered with the metal oxide layer 206. That is, in the first cycle, the inhibitor 203 is adsorbed on the exposed surface of the insulating film 201 of the recess 202, but in the second and subsequent cycles, the inhibitor 203 is adsorbed on the surface of the metal oxide layer 206.
  • step S1 it is preferable to supply the inhibitor 203 containing the heterocyclic compound.
  • the inhibitor 203 can be easily removed in the purging step S3 or the purging step S5 performed after the step S2 for supplying the precursor gas.
  • Alcohols and amines have protic properties and donate protons (H +) to the metal oxide when adsorbed on the surface of the metal oxide, so that they have a strong ability to bind to the surface of the metal oxide.
  • heterocyclic compounds have aprotic properties and do not donate protons (H +) to metal oxides when adsorbed on the surface of metal oxides, so metal oxides are compared to alcohols and amines. The force to bond to the surface of is weak.
  • the inhibitor 203 containing the heterocyclic compound when used in step S1, the inhibitor 203 can be easily removed in the purging step S3 or the purging step S5 performed after the precursor gas supply step S2. As a result, it is possible to prevent the inhibitor 203 from being mixed into the target metal oxide film.
  • the substrate 200 is subjected to O 2 atmosphere, O 3 atmosphere, O 2 plasma, and O after at least one of steps S2 to S5. 3
  • the step of exposing to plasma or a combination thereof may be performed.
  • the substrate 200 has an O 2 atmosphere and an O 3 atmosphere from the viewpoint that the inhibitor 203 adsorbed on the surface of the metal oxide can be removed in a short time. , O 2 plasma, O 3 plasma, or a combination thereof.
  • step S2 as shown in FIG. 2C, the precursor gas containing the metal complex 204 is supplied to the recess 202.
  • the metal complex 204 contained in the precursor gas is chemically adsorbed in the recess 202, so that the precursor layer is formed from the precursor gas.
  • the precursor gas comes into contact with the surface (treated surface) of the recess 202, and the metal complex 204 is chemically adsorbed on the surface of the recess 202.
  • the metal atom in the metal complex 204 reacts with a functional group such as a hydroxyl group formed on the surface of the recess 202, so that the metal complex 204 (precursor) is chemically bonded to the surface of the recess 202.
  • a precursor layer composed of a plurality of precursors bonded to the surface of the recess 202 is formed.
  • the inhibitor 203 is adsorbed on the upper surface 202c of the recess 202 more than the bottom surface 202a and the inner wall 202b in step S1, it is adsorbed on the upper surface 202c of the recess 202.
  • the amount of metal complex 204 to be produced is reduced. Therefore, in step S2, the metal complex 204 is easily adsorbed on the bottom surface 202a and the inner wall 202b of the recess 202, and a precursor layer having a uniform thickness can be obtained.
  • a "precursor gas” means a gas composed of a precursor (precursor) containing a metal complex 204.
  • the structure of the precursor differs before and after chemisorption on the substrate, but in the present specification, these are collectively referred to as a precursor for convenience.
  • step S2 various metal complexes 204 can be used depending on the type of metal constituting the target metal oxide film.
  • the metal complex 204 may be any as long as it can be chemically adsorbed on the surface of the recess 202.
  • the metal complex 204 is represented by, for example, the following formula (1).
  • M indicates a metal center, shows the ligand (ligand) L 1 ⁇ L 4 are each independently. L 1 ⁇ L 4 may be the being the same or different. ]
  • the central metal may be hafnium, zirconium, aluminum, tantalum, tungsten, titanium, niobium, molybdenum, cobalt, nickel and the like. That is, the metal complex may be a hafnium complex, a zirconium complex, an aluminum complex, a tantalum complex, a tungsten complex, a titanium complex, a niobium complex, a molybdenum complex, a cobalt complex, a nickel complex or the like.
  • the metal complex is preferably a hafnium complex, a zirconium complex, an aluminum complex, a tantalum complex, or a tungsten complex from the viewpoint of obtaining a metal oxide film having a high dielectric constant. Specific examples of the metal complex include tris (dimethylamino) cyclopentadienyl zirconium (Zr [N (CH 3 ) 2 ] 3 [C 5 H 5 ]).
  • the ligand examples include alcohols such as t-butyl alcohol, isopropyl alcohol and isobutyl alcohol, amines such as dimethylamine, ethylmethylamine, diethylamine and t-butylamine, cyclopentadiene, butadiene and benzene.
  • alcohols such as t-butyl alcohol, isopropyl alcohol and isobutyl alcohol
  • amines such as dimethylamine, ethylmethylamine, diethylamine and t-butylamine, cyclopentadiene, butadiene and benzene.
  • the ligand may have a functional group containing a hydrogen atom.
  • the oxidant 205 contained in the oxidizing gas supplied in step S4 described later may react with the functional group to generate H 2 O. Therefore, when the ligand has a functional group containing a hydrogen atom and the oxidizing gas is a gas containing an oxidizing agent 205 that reacts with the functional group to generate H 2 O, the effect of the present disclosure is remarkably exhibited. Will be done.
  • the functional group containing a hydrogen atom include a hydrocarbon group.
  • the conditions for supplying the precursor gas in step S2 are not particularly limited, and conventionally known conditions can be applied as conditions for forming the precursor layer by the ALD process.
  • the supply of precursor gas may be carried out in a diluted gas environment.
  • the precursor gas may be supplied after replacing the inside of the processing container with a diluting gas.
  • the diluted gas may be supplied into the processing container together with the precursor gas.
  • the precursor gas may be supplied while supplying the dilution gas into the processing container, the precursor gas and the dilution gas are mixed, and the precursor gas (mixed gas) diluted by the dilution gas is supplied into the processing container. May be supplied to.
  • the details of the diluting gas are the same as the details of the diluting gas described in step S1.
  • step S3 purge gas is supplied into the processing container.
  • the precursor gas and the inhibitor 203 remaining in the processing container are removed from the processing container.
  • the purge gas is supplied into the processing container, the precursor gas and the inhibitor 203 in the processing container are exhausted together with the purge gas and removed from the processing container.
  • the purge gas examples include an inert gas such as N 2 gas and a rare gas, CO 2 gas and CO gas. Gas corresponding to the precursor gas, oxidizing gas and H 2 O removal gas is not included in the purge gas.
  • the conditions for supplying the purge gas in step S3 are not particularly limited.
  • the step S3 may be performed, for example, by evacuating the inside of the processing container without supplying the purge gas into the processing container. Further, the step S3 may be performed by supplying the purge gas into the processing container and then evacuating the inside of the processing container without supplying the purge gas into the processing container. Further, the step S3 may be performed by a cycle purge in which the supply of the purge gas and the evacuation are repeated.
  • step S4 as shown in FIG. 2E, an oxidizing gas containing an oxidizing agent 205 is supplied to the recess 202.
  • the precursor layer is oxidized by the oxidizing gas to form the metal oxide layer 206.
  • the oxidizing gas is supplied into the processing container, the oxidizing agent 205 contained in the oxidizing gas comes into contact with the precursor layer, and the metal complex 204 (precursor) constituting the precursor layer and the oxidizing agent 205 Reacts with.
  • the precursor is oxidized to form a metal oxide layer 206 made of a metal oxide.
  • the ligand 207 is eliminated from the precursor.
  • the oxidation gas is a gas containing H 2 O (for example, a gas containing H 2 O) or a gas containing an oxidizing agent that reacts with a functional group containing a hydrogen atom of the metal complex 204 to produce H 2 O (for example, a metal).
  • complex 204 is reacted with a functional group gas oxidizer that generates H 2 O) containing a hydrogen atom of the.
  • the gas corresponding to the inhibitor 203 is not included in the oxidizing gas.
  • the oxidizing agent that reacts with the functional group containing a hydrogen atom of the metal complex 204 to generate H 2 O include O 3 , H 2 / O 2 mixture, O 2 plasma, O 2 , and H 2 O 2. And so on.
  • H 2 O derived from the oxidation gas is adsorbed on the metal oxide film by hydrogen bonds.
  • a gas containing an oxidizing agent such as O 3 , H 2 / O 2 mixture, O 2 plasma, O 2 , H 2 O 2 or the like is used as the oxidizing gas, the function containing the hydrogen atom contained in the oxidizing agent and the metal complex 204 H 2 O derived from the reaction with the group is adsorbed on the metal oxide film by hydrogen peroxide.
  • the oxidation gas is at least selected from the group consisting of O 3 , H 2 / O 2 mixture, O 2 plasma, O 2 and H 2 O 2 from the viewpoint that the metal oxide layer 206 can be formed under low temperature conditions. It is preferably a gas containing one kind, and more preferably a gas containing at least one selected from the group consisting of O 3 , H 2 / O 2 mixture, and O 2 plasma.
  • the conditions for supplying the oxidizing gas in step S4 are not particularly limited.
  • Oxidation gas supply may be performed in a diluted gas environment.
  • the inside of the processing container may be replaced with a diluting gas, and then the oxidation gas may be supplied.
  • the diluted gas may be supplied into the processing container together with the oxidizing gas.
  • the oxidation gas may be supplied while supplying the dilution gas into the processing container, or the oxidation gas and the dilution gas are mixed and the oxidation gas (mixed gas) diluted by the dilution gas is supplied into the processing container. You may.
  • the details of the diluting gas are the same as the details of the diluting gas described in step S1.
  • step S5 purge gas is supplied into the processing container.
  • the oxidizing gas remaining in the processing container, the ligand 207 derived from the precursor, and the inhibitor 203 are exhausted and removed from the processing container.
  • the details of the purge gas in step S5 and the conditions for supplying the purge gas may be the same as those in step S3 described above.
  • step S6 it is determined whether or not the number of repetitions of the cycles of steps S1 to S5 has reached a predetermined number of times. In step S6, when it is determined that the number of repetitions of the cycles of steps S1 to S5 has reached a predetermined number of times, the process ends. On the other hand, in step S6, when it is determined that the cycle of steps S1 to S5 has not reached a predetermined number of times, the process returns to step S1.
  • the predetermined number of times is determined according to the film thickness of the target metal oxide film.
  • the method for forming the metal oxide film of one embodiment before supplying the precursor gas to the recess 202, more alcohols, amines or heterocycles are formed in the upper portion of the recess 202 than in the lower portion. Inhibitor 203 containing the formula compound is adsorbed. Since alcohols, amines or heterocyclic compounds have a large adsorption energy for the metal oxide layer 206, they are easily adsorbed on the surface of the metal oxide layer 206.
  • the inhibitor 203 containing more alcohols, amines or heterocyclic compounds is adsorbed on the upper part of the recess 202 than on the lower part
  • the precursor gas containing the metal complex 204 is supplied to the recess 202
  • the recess 202 is adsorbed. Adsorption of the metal complex 204 on the upper surface 202c of 202 is inhibited. Therefore, a precursor layer having a uniform thickness can be obtained.
  • the thickness of the metal oxide layer 206 formed by oxidizing the precursor layer with the oxidizing gas becomes uniform. That is, a conformal metal oxide film can be formed in the recess 202.
  • the method for forming a metal oxide film of one embodiment can be suitably used in, for example, an application for forming a gate insulating film and a capacitor insulating film.
  • the step covering property of the insulating film has become an important issue due to the complicated trench structure and the increase in the aspect ratio of the trench. Therefore, according to the method for forming a metal oxide film of one embodiment, ideal conformal film formation with high step coverage and low loading effect is possible.
  • the method for forming the metal oxide film of one embodiment can be carried out under low temperature conditions, a conformal metal oxide film can be formed even under low temperature conditions. Further, by applying the above-mentioned metal oxide film forming method to the semiconductor device manufacturing method, damage due to heat to the semiconductor substrate in the metal oxide film forming process such as a capacitor insulating film and a gate insulating film can be reduced. , A conformal insulating film can be formed. That is, according to the method for forming a metal oxide film of one embodiment, a semiconductor device having a conformal insulating film (capacitor insulating film, gate insulating film, etc.) can be obtained.
  • a conformal insulating film capacitor insulating film, gate insulating film, etc.
  • all of the plurality of cycles include the step S1 of supplying the inhibitor 203, but the present disclosure is not limited to this.
  • at least a portion of the plurality of cycles may include step S1 of supplying the inhibitor 203.
  • the step S1 of supplying the inhibitor 203 may be omitted in at least a part of the plurality of cycles.
  • a purge step of supplying purge gas into the processing container may be performed between the steps S1 and S2 in at least a part of the plurality of cycles.
  • the inhibition performance can be reduced and the productivity (film formation rate) is improved.
  • the balance between productivity and uniformity can be adjusted by changing the number of cycles in which the purging step is performed between the step S1 and the step S2 among the plurality of cycles.
  • the number of cycles in which the purging step is performed between the step S1 and the step S2 out of a plurality of cycles is set so as not to completely remove the inhibitor 203.
  • FIG. 3 is a diagram showing an example of a film forming apparatus used in the method for forming a metal oxide film of one embodiment.
  • the vertical heat treatment apparatus 1 has a vertically long shape extending in the vertical direction as a whole.
  • the vertical heat treatment apparatus 1 has a vertically long processing container 10 extending in the vertical direction.
  • the processing container 10 is formed of, for example, quartz.
  • the processing container 10 has, for example, a double pipe structure of a cylindrical inner pipe 11 and a ceilinged outer pipe 12 placed concentrically on the outside of the inner pipe 11.
  • the lower end of the processing container 10 is hermetically held by, for example, a stainless steel manifold 20.
  • the manifold 20 is fixed to, for example, a base plate (not shown).
  • the manifold 20 has an injector 30 and a gas exhaust unit 40.
  • the injector 30 is a gas supply unit that introduces various gases into the processing container 10.
  • the various gases include the gases used in the method of forming a metal oxide film of one embodiment. That is, the various gases include a precursor gas, an oxidizing gas, an inhibitor, and a purge gas.
  • a pipe 31 for introducing various gases is connected to the injector 30.
  • the pipe 31 is provided with a flow rate adjusting unit (not shown), a valve (not shown), or the like such as a mass flow controller for adjusting the gas flow rate.
  • the number of injectors 30 may be, for example, one (see FIG. 1) or a plurality (not shown).
  • the gas exhaust unit 40 exhausts the inside of the processing container 10.
  • a pipe 41 is connected to the gas exhaust unit 40.
  • the pipe 41 is provided with a variable opening valve 42, a vacuum pump 43, and the like that can control the pressure inside the processing container 10.
  • a furnace port 21 is formed at the lower end of the manifold 20.
  • the hearth 21 is provided with, for example, a stainless steel disk-shaped lid 50.
  • the lid 50 is provided so as to be able to move up and down by an elevating mechanism 51, and is configured so that the furnace port 21 can be hermetically sealed.
  • a quartz heat insulating cylinder 60 is installed on the lid 50.
  • the wafer boat 70 is carried into the processing container 10 by raising the lid 50 using the elevating mechanism 51, and is housed in the processing container 10. Further, the wafer boat 70 is carried out from the processing container 10 by lowering the lid 50.
  • the wafer boat 70 has a groove structure having a plurality of slots (support grooves) in the longitudinal direction, and the wafers W are loaded in the slots at vertical intervals in a horizontal state. A plurality of wafers placed on the wafer boat 70 form one batch, and various heat treatments are applied in batch units.
  • a heater 80 is provided on the outside of the processing container 10.
  • the heater 80 has, for example, a cylindrical shape, and heats the processing container 10 to a predetermined temperature.
  • the vertical heat treatment apparatus 1 is provided with a control unit 100 including, for example, a computer.
  • the control unit 100 includes a data processing unit including a program, a memory, and a CPU.
  • the program incorporates instructions (each step) to send a control signal from the control unit 100 to each unit of the vertical heat treatment apparatus 1 to execute the method for forming the metal oxide film of one embodiment.
  • the program is stored in a storage medium such as a computer storage medium such as a flexible disk, a compact disk, a hard disk, an MO (magneto-optical disk), and a memory card, and is installed in the control unit 100.
  • control unit 100 controls the elevating mechanism 51 to carry the wafer boat 70 holding the plurality of wafers W into the processing container 10, and airtightly closes the opening at the lower end of the processing container 10 with the lid 50 to seal the wafer. To do.
  • control unit 100 controls the opening degree variable valve 42 to adjust the inside of the processing container 10 to the set pressure, and controls the heater 80 to adjust the wafer W to the set temperature. Further, the control unit 100 rotates the wafer boat 70.
  • control unit 100 supplies the precursor gas, the oxidizing gas, the inhibitor, and the purge gas from the injector 30 into the processing container 10 at a predetermined timing so as to execute the method for forming the metal oxide film of one embodiment. To do. As a result, a metal oxide film is formed on the surface of each of the plurality of wafers W.
  • control unit 100 controls the elevating mechanism 51 after boosting the inside of the processing container 10 to the atmospheric pressure, and transfers the wafer boat 70 holding the processed wafer W together with the lid 50 from the inside of the processing container 10. Carry out.
  • the metal oxide film can be formed on a plurality of wafers W at once by using the vertical heat treatment apparatus 1.
  • FIG. 4 is a diagram showing the calculation result of the adsorption energy by the simulation.
  • trimethylamine [NMe 3 (upside down)] trimethylamine [NMe 3 (TMA)]
  • NMe 3 (TMA)] trimethylamine [NMe 3 (TMA)]
  • ethane [C 2 H 6] diethyl ether [DEE]
  • dimethyl ether [DME] tetrahydrofuran [THF]
  • Water [H 2 O] Oxazole [oxazole]
  • Dimethylamine [DMA] Methanol [Methanol]
  • Ethanol [EtOH] Quinclideine, 1-propanol [1-PrOH] and t-
  • the calculation result of the adsorption energy of butanol [t-BuOH] with respect to the (111) plane of t-ZrO 2 is shown.
  • trimethylamine [NMe 3 (upside down)] and trimethylamine [NMe 3 (TMA)] show a case where the mode of adsorption of t—ZrO 2 on the (111) plane is different.
  • trimethylamine [NMe 3 (TMA)] shows a case where nitrogen (N) is adsorbed toward the (111) plane side of t-ZrO 2
  • trimethylamine [NMe 3 (upside down)] is nitrogen ( The case where N) is adsorbed toward the side opposite to the (111) plane of t-ZrO 2 is shown.
  • trimethylamine [NMe 3 (upside down)] adsorption energy of trimethylamine [NMe 3 (TMA)] and ethane [C 2 H 6] can be -1.00eV ⁇ -0.50eV
  • T-ZrO 2 is weakly adsorbed on the (111) plane.
  • the adsorption energy of diethyl ether [DEE], dimethyl ether [DME], tetrahydrofuran [THF], water [H 2 O] and oxazole [oxazole] was -1.50eV ⁇ -1.00eV.
  • adsorption energies of pyridine [Py], dimethylamine [DMA], methanol [MeOH], ethanol [EtOH], quinuclidine [Quinuclidine], 1-propanol [1-PrOH] and t-butanol [t-BuOH] are It was higher than -1.50 eV.
  • organic compounds such as diethyl ether [DEE], dimethyl ether [DME], methanol [THF], and oxazole [oxazole], which have the same adsorption energy as H 2 O, and adsorption.
  • high energy pyridin than H 2 O [Py] dimethylamine [DMA], methanol [MeOH], ethanol [EtOH], quinuclidine [quinuclidine], 1-propanol [1-PrOH] and t- butanol [t-BuOH ]
  • an inhibitor containing an organic compound it is preferable to use an inhibitor containing an organic compound.
  • the inhibitor can be easily adsorbed on the surface of the ZrO 2 layer.
  • the oxidizing gas is a gas containing H 2 O or a gas containing an oxidizing agent that reacts with a functional group containing a hydrogen atom of the metal complex to generate H 2 O
  • the surface of the ZrO 2 layer is subjected to in step S4. At least a part of the physically adsorbed H 2 O is removed by the inhibitory gas. This can suppress the lowering of self-controllability in ALD processes due to the H 2 O. As a result, it is possible to suppress the formation of multiple layers of ZrO 2 layers in one cycle, and to form a conformal ZrO 2 film.
  • pyridine [Py] dimethylamine [DMA]
  • methanol [MeOH] methanol having particularly higher adsorption energies than H 2 O
  • an inhibitor containing an organic compound such as [EtOH], quinuclidein, 1-propanol [1-PrOH], and t-butanol [t-BuOH].
  • an inhibitor containing a heterocyclic compound having an aprotic property it is preferable to use an inhibitor containing a heterocyclic compound having an aprotic property.
  • the film forming apparatus is a batch type apparatus for processing a plurality of wafers at once
  • the film forming apparatus may be a single-wafer type apparatus that processes wafers one by one.
  • the volume of the processing container for accommodating the wafer is larger in the batch type device than in the single-wafer type device, when the film formation process is performed using the batch type device, the film formation is performed using the single-wafer type device. the amount of H 2 O generated in the processing vessel than perform processing increases. Therefore, the technique of the present disclosure is particularly effective in the case of a batch type apparatus.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Vapour Deposition (AREA)
  • Formation Of Insulating Films (AREA)

Abstract

Selon un mode de réalisation, la présente invention concerne un procédé de formation d'un film d'oxyde métallique qui comporte : une étape consistant à amener une partie évidée formée dans un substrat à adsorber un inhibiteur comprenant un composé hétérocyclique à l'exclusion d'alcools et d'amines ; une étape consistant à former une couche de précurseur sur le substrat par introduction d'un gaz précurseur contenant un complexe métallique dans la partie évidée dans laquelle l'inhibiteur a été adsorbé ; et une étape d'oxydation de la couche de précurseur par introduction d'un gaz d'oxydation dans la partie évidée dans laquelle la couche de précurseur a été formée, pour former une couche d'oxyde métallique..
PCT/JP2020/034165 2019-09-20 2020-09-09 Procédé de formation de film d'oxyde métallique et dispositif de formation de film WO2021054227A1 (fr)

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WO2024006092A1 (fr) * 2022-06-27 2024-01-04 Applied Materials, Inc. Procédé de formation de films d'alp sio2 conformes

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WO2023181289A1 (fr) * 2022-03-24 2023-09-28 株式会社Kokusai Electric Appareil de traitement de substrat, procédé de traitement de substrat, procédé de fabrication d'appareil à semi-conducteur et programme
WO2024107567A1 (fr) * 2022-11-17 2024-05-23 Lam Research Corporation Films non conformes déposés à l'intérieur d'un évidement à l'aide d'un dépôt de couche atomique

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JP2014510733A (ja) * 2011-03-15 2014-05-01 メカロニックス シーオー． エルティディ． 新規な４ｂ族有機金属化合物及びその製造方法
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WO2024006092A1 (fr) * 2022-06-27 2024-01-04 Applied Materials, Inc. Procédé de formation de films d'alp sio2 conformes

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