WO2018016871A1 - Procédé de fabrication de film mince de nitrure de silicium au moyen d'un dépôt de couche atomique de plasma - Google Patents

Procédé de fabrication de film mince de nitrure de silicium au moyen d'un dépôt de couche atomique de plasma Download PDF

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WO2018016871A1
WO2018016871A1 PCT/KR2017/007764 KR2017007764W WO2018016871A1 WO 2018016871 A1 WO2018016871 A1 WO 2018016871A1 KR 2017007764 W KR2017007764 W KR 2017007764W WO 2018016871 A1 WO2018016871 A1 WO 2018016871A1
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thin film
silicon nitride
nitride thin
plasma
silicon
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PCT/KR2017/007764
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English (en)
Korean (ko)
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장세진
이상도
박중진
김성기
양병일
박건주
박정주
석장현
이상익
김명운
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(주)디엔에프
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Priority claimed from KR1020170090707A external-priority patent/KR102014175B1/ko
Application filed by (주)디엔에프 filed Critical (주)디엔에프
Priority to US16/319,452 priority Critical patent/US20190249296A1/en
Priority to CN201780044836.3A priority patent/CN109478497A/zh
Priority to JP2019503328A priority patent/JP7045360B2/ja
Publication of WO2018016871A1 publication Critical patent/WO2018016871A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/02—Well-drilling compositions
    • C09K8/04—Aqueous well-drilling compositions
    • C09K8/06—Clay-free compositions
    • C09K8/12—Clay-free compositions containing synthetic organic macromolecular compounds or their precursors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment

Definitions

  • the present invention relates to a method of manufacturing a silicon nitride thin film using a plasma atomic layer deposition method, and more particularly to a method of manufacturing a high purity silicon nitride thin film using a plasma atomic layer deposition method comprising a plasma excitation step of two steps.
  • Silicon nitride thin films have a high resistance to hydrogen fluoride (HF). Therefore, the memory and the high-density integrated circuit: increasing (large scale integrated circuit LSI) in the manufacturing process of a semiconductor device, such as a silicon oxide film (SiO 2) etching stopper layer and the deviation of the resistance value of the gate electrode at the time of etching or the like Or as a diffusion barrier for dopants.
  • a semiconductor device such as a silicon oxide film (SiO 2) etching stopper layer and the deviation of the resistance value of the gate electrode at the time of etching or the like Or as a diffusion barrier for dopants.
  • the lowering of the film forming temperature is required.
  • LPCVD low pressure chemical vapor deposition
  • a deposition temperature of up to 760 ° C is required.
  • the silicon nitride thin film is formed using the ALD (Atomic Layer Deposition) method, the lower deposition temperature can be satisfied.
  • the ALD method two kinds of (or more) raw materials used for film formation under arbitrary film forming conditions (temperature, time, etc.) are alternately supplied on a substrate, adsorbed in units of atomic layers, and subjected to surface reaction.
  • This is a technique for forming a film by using a film.
  • the first source gas and the second source gas flow alternately along the surface of the object to be adsorbed, thereby adsorbing the source gas molecules in the first source gas to the surface of the processing body, and the source gas molecules of the adsorbed first source gas.
  • a film having a thickness of one molecular layer is formed.
  • a high quality thin film can be formed on the surface of a workpiece.
  • Japanese Patent Laid-Open No. 2004-281853 discloses a method of forming a silicon nitride film by alternately supplying dichlorosilane (DCS: SiH 2 Cl 2 ) and ammonia (NH 3 ) by the ALD method.
  • DCS dichlorosilane
  • NH 3 ammonia
  • the above method is a method of forming a silicon nitride thin film at a low temperature of 300 ° C to 600 ° C by supplying ammonia radicals (NH 3 * ) in which ammonia is activated by plasma.
  • the silicon nitride thin film formed by the above method has a high wet etching rate due to an increase in the concentration of chlorine (Cl), which causes a decrease in the resistance to hydrogen fluoride, and thus has a low etching selectivity (selectivity) for the oxide film.
  • a method of introducing carbon atoms (C) into the silicon nitride thin film may be considered, but the introduction of carbon atoms into the silicon nitride thin film in the low temperature region below 400 ° C It may be a cause of structural defects and cause deterioration of insulation resistance.
  • Korean Patent Registration No. 0444842 discloses a technique for forming a high-stress silicon nitride thin film at low temperature (390 ° C. to 410 ° C.) by the ALD method, but it is an chlorine which is an unnecessary atom contained in a chemical ligand. Atom (Cl) remains in the thin film to cause particles on the surface of the substrate has a disadvantage in that the formation of excellent film quality is difficult.
  • US 2013-183835 describes a method and apparatus for forming a high stress silicon nitride thin film at low temperatures.
  • a high power plasma is used, it is difficult to induce decomposition of a precursor including silicon and to form an excellent film quality by including impurities caused by it.
  • the Applicant performs a two-step plasma excitation step using an organic silicon precursor containing a silicon-nitrogen bond (Si-N bond), so that the low stress strength, high wet etching of the thin film, which is a problem of the conventional low deposition temperature ALD method, is applied.
  • the present invention was completed by confirming that the silicon nitride thin film of high purity can be provided with improved productivity while solving the rate and the low step coverage.
  • the present invention provides a method for producing a silicon nitride thin film comprising a two-step plasma excitation step for the above-mentioned object.
  • the method of manufacturing a silicon nitride thin film comprises the steps of adsorbing an organic silicon precursor containing a silicon-nitrogen bond (Si-N) on a substrate; And exciting the first plasma while injecting the first reaction gas and then exciting the second plasma while injecting the second reaction gas to provide one or more reactive sites.
  • Si-N silicon-nitrogen bond
  • the first reaction gas may be a mixture of nitrogen gas and hydrogenation gas.
  • the hydrogenation gas is not limited as long as it is a hydrogen gas (H 2 ) or a reaction gas containing a nitrogen atom (N) and a hydrogen atom (H) at the same time. May be one or two selected from hydrogen (H 2 ), ammonia (NH 3 ), hydrazine (N 2 H 4 ), and the like.
  • the first reaction gas may be a mixture of nitrogen gas and hydrogenation gas at a flow rate of 300: 1 to 1: 1.
  • it is preferable to inject the reaction gas mixed in the above-described flow rate ratio into the apparatus, but simultaneously injecting each of nitrogen gas and hydrogenated gas into the apparatus at a flow rate that satisfies the above-described flow rate ratio may also be an aspect of the present invention.
  • the second reaction gas may be a reaction gas including a nitrogen atom (N) but not a hydrogen atom (H), preferably nitrogen gas Can be.
  • the first plasma and the second plasma may be each excited by a power of 500 W or less.
  • the temperature of the substrate may be in the range of 50 to 400 °C.
  • the organic silicon precursor including the silicon-nitrogen bond may be one or two or more selected from those represented by the following Chemical Formulas 1, 2 and 3.
  • R 1 to R 3 , R 11 to R 17 , and R 21 to R 24 are each independently hydrogen, (C 1 -C 5) alkyl or (C 2 -C 5) alkenyl;
  • n and m are each independently an integer of 0 to 3
  • p is an integer of 1 to 3.
  • the present invention provides a silicon nitride thin film having an oxygen atom content of 10 atomic% or less and a silicon-nitrogen / silicon-hydrogen area ratio (Si-N / Si-H) of 90 or more based on all atoms present in the silicon nitride thin film. do.
  • the silicon nitride thin film according to the exemplary embodiment of the present invention may have a step coverage of 80% or more.
  • an organic silicon precursor having a predetermined Si—N bond may be introduced to provide a silicon nitride thin film including a high quality Si—N bond at lower film forming temperature conditions.
  • the present invention by adjusting the plasma excitation conditions despite the lower film forming temperature conditions, it is possible to minimize the impurities in the silicon nitride thin film as well as the realization of excellent thin film efficiency. In particular, it is possible to significantly reduce the content of oxygen atoms in the silicon nitride thin film by inhibiting oxidation due to atmospheric exposure after the process.
  • the area ratio of absorption of the desired silicon-nitrogen bond is repeated (based on the silicon-hydrogen bond) by repeating the unit cycle by appropriately adjusting each reaction gas type and the flow rate thereof in the plasma excitation step. It is possible to provide a silicon nitride thin film satisfying the high productivity. In addition, since the silicon nitride thin film according to the present invention has excellent step coverage, a fine pattern having an atomic layer thickness can be formed very uniformly, and an improved wet etching rate (etch resistance) can be realized.
  • FIG. 1 is a diagram illustrating a deposition method of a silicon nitride thin film according to the present invention
  • Example 3 is a result of analyzing by using infrared spectroscopy of the silicon nitride thin film prepared in Example 9 and Comparative Examples 1 to 6,
  • Example 4 is a transmission electron microscope analysis result of the silicon nitride thin film prepared in Example 1, Example 3, Example 7 and Comparative Example 1, Comparative Example 2, Comparative Example 6,
  • Example 5 is an evaluation of the etching characteristics of the hydrogen fluoride of the silicon nitride thin films prepared in Example 3 and Comparative Example 2, the results of the thickness change analysis before and after etching using a transmission electron microscope,
  • Example 6 is a component analysis result of the silicon nitride thin film prepared in Example 3, Example 5, Comparative Example 2, Comparative Example 4.
  • silicon nitride thin film in the present invention means to be produced by repeatedly performing the unit cycle described below according to the present invention, the physical properties of the desired silicon nitride thin film by the process conditions and the number of repetitions of each unit cycle (for example, , Stress intensity, wet etch rate and step coverage).
  • atomic layer in the present invention means a unit layer constituting the silicon nitride thin film.
  • the present invention provides a silicon nitride thin film containing a high level of silicon-nitrogen bonds by performing a two-step plasma excitation step using an organic silicon precursor having a predetermined silicon-nitrogen bond (Si-N bond) containing no halogen. Can be provided.
  • Si-N bond silicon-nitrogen bond
  • the impurity content in the silicon nitride thin film can be minimized as well as the atomic layer formed by the unit cycle can effectively adsorb the organic silicon precursor including the subsequent silicon-nitrogen bond.
  • the atomic layer formed by the unit cycle provides one or more reactive sites capable of strongly bonding with the organosilicon precursor including a subsequent silicon-nitrogen bond, thereby enabling the implementation of an improved deposition rate. And excellent properties of silicon nitride thin film.
  • the present invention is remarkable compared to the plasma enhanced atomic layer deposition method including a plasma excitation step of one step.
  • the unit cycle of the method of manufacturing a silicon nitride thin film by plasma enhanced atomic layer deposition according to an embodiment of the present invention is characterized in that it comprises a plasma excitation step of two steps.
  • the method for manufacturing a silicon nitride thin film by plasma enhanced atomic layer deposition comprises the steps of adsorbing an organic silicon precursor containing a silicon-nitrogen bond on the substrate; And exciting the first plasma while injecting the first reaction gas and then exciting the second plasma while injecting the second reaction gas to provide one or more reactive sites.
  • the step of adsorbing the organic silicon precursor may be carried out at a film forming temperature of 50 to 400 °C range.
  • the step of adsorbing the organic silicon precursor may be carried out at a deposition temperature of 50 to 350 °C range.
  • the step of adsorbing the organic silicon precursor is a deposition temperature of less than 350 °C to implement the improved stress strength of the thin film In the subsequent two stages of plasma power can be adjusted appropriately.
  • the step of adsorbing the organic silicon precursor may be performed under a vapor pressure of 0.1 to 100 torr, preferably 0.1 to 80 torr, more preferably 1 to 50 torr under a vapor pressure.
  • the substrate according to an embodiment of the present invention is not limited as long as it is a substrate used in a conventional plasma enhanced atomic layer deposition, and a non-limiting example thereof may include a semiconductor substrate, a conductor substrate or an insulator substrate. In addition, the substrate may be any pattern or layer formed.
  • the organic silicon precursor including the silicon-nitrogen bond according to an embodiment of the present invention is not limited as long as it includes a silicon-nitrogen bond, but may be selected from those represented by the following Chemical Formulas 1, 2, and 3.
  • R 1 to R 3 , R 11 to R 17 , and R 21 to R 24 are each independently hydrogen, (C 1 -C 5) alkyl or (C 2 -C 5) alkenyl;
  • n and m are each independently an integer of 0 to 3
  • p is an integer of 1 to 3.
  • the organosilicon precursor including the silicon-nitrogen bond has high volatility and reactivity even at room temperature (23 ° C.) to 40 ° C. and under atmospheric pressure, and thus high deposition rate is achieved by plasma-enhanced atomic layer deposition in spite of the deposition temperature below 400 ° C. Not only can it be implemented, but also high thermal stability and stress strength of the thin film can be realized.
  • the organic silicon precursor according to the present invention exhibits strong bonding force with the atomic layer formed by the unit cycle including the two steps of plasma excitation step, thereby implementing a significantly improved step coverage. This effect is expected to be induced by performing the sequential plasma generation step according to the invention described above.
  • the organic silicon precursor including the silicon-nitrogen bond may be selected from the following structures, but is not limited thereto.
  • Adsorption of the organic silicon precursor may be injected for 1 to 90 seconds, preferably from 1 to 60 seconds, more preferably from 3 to 30 seconds in terms of forming a stable atomic layer. have.
  • the organic silicon precursor may further include a purge step.
  • the purge step may use at least one purge gas selected from nitrogen gas, argon gas, helium gas, neon gas, and the like.
  • the purge step is an unadsorbed organosilicon precursor and any non-adsorbed organic silicon precursor which may be injected at a flow rate in the range of 1 to 10,000 sccm (square cubic centimeters) for 1 to 1,000 seconds using the purge gas. Remove impurities.
  • the step of exciting the first plasma by exciting the plasma under the first reaction gas, the silicon-nitrogen bond
  • the containing organic silicon precursor reacts with some or all of the chemisorbed layer to form and fix an atomic layer comprising silicon-nitrogen bonds.
  • Exciting the first plasma according to an embodiment of the present invention is performed under a first reaction gas in which nitrogen gas (N 2 ) and hydrogenation gas are mixed. Its steps impart properties that are easy to combine with subsequent organic silicon precursors.
  • the first reaction gas may be injected at a flow rate in the range of 1,000 to 100,000 sccm (square cubic centimeters), preferably at a flow rate in the range of 3,000 to 50,000 sccm, more preferably 5,000 to 10,000 sccm. have.
  • Exciting the first plasma according to an embodiment of the present invention may improve the area ratio of the silicon-nitrogen bond in the finally formed silicon nitride thin film by exciting the first plasma under the first reaction gas mixed with the above-described composition.
  • it shows remarkable compared to the example using a single reaction gas.
  • the organic silicon precursor reacts with the chemisorbed layer to form an atomic layer, and at the same time, impurities generated after the reaction may be removed by hydrogenation.
  • the hydrogenated gas is not limited as long as it is a reaction gas containing hydrogen gas or nitrogen atom (N) and hydrogen atom (H) at the same time, non-limiting examples thereof include hydrogen (H 2 ), ammonia (NH 3 ) and and the like can be mentioned hydrazine (N 2 H 4).
  • Exciting the first plasma according to the present invention may be performed under a first reaction gas in which the nitrogen gas and the hydrogenation gas are mixed at a flow ratio of 300: 1 to 1: 1.
  • the flow rate ratio is preferably 250: 1 to 20: 1, more preferably 200: 1 to 50: 1. It may be to satisfy the flow rate ratio of.
  • the reaction gas mixed in the above-described flow rate ratio into the apparatus, but simultaneously injecting each of nitrogen gas and hydrogenated gas into the apparatus at a flow rate that satisfies the above-described flow rate ratio may also be an aspect of the present invention.
  • the effect induced in the step of exciting the first plasma according to the present invention described above shows a synergy compared to the effect under a single reaction gas when performed under a first reaction gas mixed with nitrogen gas and hydrogenation gas.
  • the reaction gas it is not preferable because impurities formed by the excess hydrogen atoms caused by plasma are formed.
  • Exciting the first plasma according to an embodiment of the present invention may be performed at a deposition temperature of 50 to 400 °C range.
  • the film forming temperature may be interpreted as the same meaning as the substrate temperature of the present invention, and the film temperature, pressure and power of the power applied to generate the plasma may be appropriately adjusted to control the properties of the silicon nitride thin film. to be.
  • the step may be a step of exciting the first plasma at a power of 500 W or less at the deposition temperature in the above-described range.
  • the step may be the step of exciting the first plasma at a power in the range of 150 W to 500 W at a deposition temperature of 50 to 200 °C range.
  • the step may be the step of exciting the first plasma at a power of less than 50 W to 150 W at the deposition temperature of more than 200 °C.
  • the first plasma may be irradiated for 1 to 120 seconds, preferably 1 to 90 seconds, more preferably 3 to minimize impurities For 60 seconds.
  • the step of exciting the first plasma according to an embodiment of the present invention may further include a purge step.
  • the purge step may use the first reaction gas or one or more purge gases selected from nitrogen gas, argon gas, helium gas, neon gas, and the like.
  • the purge step uses any of the unreacted organic silicon precursor and any unreacted organic silicon precursor which may be injected at a flow rate in the range of 1 to 10,000 sccm (square cubic centimeters) for 1 to 1,000 seconds using the purge gas. Remove impurities.
  • the step of exciting the second plasma is to generate a plasma under the second reaction gas to excite the first plasma Removing impurities in the atomic layer of the silicon-nitrogen bond formed in the step of forming and subsequent organic silicon precursors serve to form one or more reactive sites for implementing enhanced adsorption with the chemisorbed layer.
  • the second reaction gas may be a reaction gas including a nitrogen atom (N) but not a hydrogen atom (H), preferably may be a nitrogen gas.
  • the impurity bond remaining in the atomic layer is replaced with nitrogen, thereby satisfying the absorption area ratio (based on the silicon-hydrogen bond) of the higher silicon-nitrogen bond.
  • the adsorption force with the subsequent organic silicon precursor can be significantly improved.
  • the second reaction gas may be injected at a flow rate in the range of 1,000 to 100,000 sccm (square cubic centimeters), preferably at a flow rate in the range of 3,000 to 50,000 sccm, more preferably 5,000 to 10,000 sccm. have.
  • the step may be to excite the second plasma at a power of 500W or less, and may be to excite the second plasma to a power in the range of 50 to 400W, more preferably 50 to 200W. .
  • the second plasma may be irradiated for 1 to 200 seconds, preferably 10 to 120 seconds, more preferably 30 in terms of minimizing impurities. To 90 seconds.
  • the method may further include a purge step after exciting the second plasma according to an embodiment of the present invention.
  • the purge step may use the second reaction gas or one or more purge gases selected from argon gas, helium gas, neon gas, and the like.
  • the purge step is injected at a flow rate in the range of 1 to 10,000 sccm (square cubic centimeters) for 1 to 1,000 seconds using the second reaction gas or the purge gas to effectively remove any impurities, particularly hydrogen atoms. Remove
  • the unit cycle of the method of manufacturing a silicon nitride thin film by plasma enhanced atomic layer deposition according to an embodiment of the present invention is excited by a two-step plasma using a reaction gas satisfying a predetermined composition as described above, Nevertheless, a high purity silicon nitride thin film can be provided.
  • the silicon nitride thin film according to the present invention may include strongly bonded silicon-nitrogen bonds, which may significantly improve not only high stress strength but also physical characteristics, such as etching characteristics (eg, wet etching rate) and step coverage.
  • the etching characteristics may be resistance to conventional cleaning solutions or oxidized etching solutions.
  • the cleaning solution or oxidized etchant include hydrogen peroxide (H 2 O 2 ), ammonium hydroxide (NH 4 OH), aqueous phosphate (aqueous H 3 PO 4 solution), aqueous hydrogen fluoride (aqueous HF solution) and buffer oxidation Etched solution (buffered oxide etch (BOE) solution) and the like, but is not limited thereto.
  • the silicon nitride thin film according to the present invention is particularly excellent in resistance to aqueous hydrogen fluoride solution
  • the etching resistance in the present invention is a resistance to hydrogen fluoride aqueous solution or buffered oxide etch (BOE) solution (BOE) solution It may mean, but is not limited to.
  • the method of manufacturing a silicon nitride thin film by plasma-enhanced atomic layer deposition according to an embodiment of the present invention, by changing the composition of the organic silicon precursor, the reaction gas, etc. and changing their supply time within the above-described range, etc.
  • the manufacturing method according to the invention can be changed.
  • the silicon nitride thin film according to the embodiment of the present invention is an atomic layer including silicon-nitrogen bonds deposited with excellent bonding force, and is a silicon nitride thin film of high purity in which impurities such as oxygen atoms, hydrogen atoms, and carbon atoms are minimized.
  • the silicon nitride thin film has an oxygen atom content of 10 atomic% or less based on the total atoms present in the silicon nitride thin film, and a silicon-nitrogen / silicon-hydrogen area ratio (Si-N / Si-H) of 90 or more. Can be.
  • the silicon nitride thin film has a good oxygen atom content in the range of 0.1 to 10 atomic%, and a silicon-nitrogen / silicon-hydrogen area ratio (Si-N / Si-H) in the range of 100 to 400. It may be.
  • the silicon nitride thin film may be a high purity silicon nitride thin film having a silicon / nitrogen atomic composition ratio (Si / N) in the range of 0.70 to 0.89.
  • the silicon nitride thin film may have a content of hydrogen atoms in the range of 0.1 to 30 atomic%, and a content of carbon atoms in the range of 0 to 0.5 atomic%.
  • the silicon nitride thin film having a step coverage of 80% or more can be provided. That is, it can be seen that the silicon nitride thin film according to the present invention does not cause adsorption disturbance or adsorption interference of the organic silicon precursor during the process.
  • the step coverage of the silicon nitride thin film according to an embodiment of the present invention may be preferably 80 to 120%, more preferably 90 to 100%, but is not limited thereto.
  • the silicon nitride thin film according to an embodiment of the present invention has improved etching characteristics.
  • PEALD plasma enhanced atomic layer deposition
  • Methylaminomethylsilyl) trimethylsilyl amine was injected for 15 seconds to adsorb onto the substrate to form a chemisorbed layer, followed by purge by injection of nitrogen (N 2 ) for 32 seconds at a flow rate of 6000 sccm.
  • Nitrogen (N 2 ) was purged by injection at 6000 sccm flow rate for 10 seconds. Nitrogen (N 2 ) is injected into the substrate for 60 seconds at a flow rate of 6000 sccm, plasma is generated at 75W power to form one or more reaction sites, and nitrogen (N 2 ) is injected at a flow rate of 6000 sccm for 20 seconds to purge. It was.
  • the silicon nitride thin film was manufactured by repeating 240 times using the above method as a unit cycle (1 cycle). 1 and Table 1 show specific deposition conditions.
  • the silicon nitride thin film was manufactured by performing the same method as in Example 1, but repeating the unit cycle 240 times according to the specific deposition conditions in Table 1 below.
  • the thickness was measured through an ellipsometer and transmission electron microscope, and the molecular vibration of the Si-N bond and the Si-H bond was observed using an infrared spectrometer, Its area ratio was compared.
  • the ratio of silicon atoms and nitrogen atoms and the elemental composition of the silicon nitride thin film were confirmed using an Auger electron spectrometer, and the content of impurities (oxygen, carbon, hydrogen, etc.) in the silicon nitride thin film was determined using secondary ion mass spectrometry. It is expressed in%.
  • the etching resistance to hydrogen fluoride was etch resistance (0.009 ⁇ / sec) of silicon nitride thin film formed using bis (dimethylaminomethylsilyl) trimethylsilyl amine and ammonia at 770 ° C using low pressure chemical vapor deposition (LPCVD). ).
  • PEALD plasma enhanced atomic layer deposition
  • Si wafer silicon wafer substrate
  • the thin film efficiency is excellent due to the excellent deposition resistance as well as the excellent deposition rate. It was also confirmed that the thin film prepared therefrom contained a high level of silicon-nitrogen bonds.
  • the silicon nitride thin film having improved film quality characteristics can be provided with more favorable productivity by performing two steps of plasma excitation.
  • the present invention it is possible to form a silicon nitride thin film of excellent quality despite the low temperature process conditions.

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Abstract

La présente invention concerne un procédé de fabrication d'un film mince de nitrure de silicium de haute pureté au moyen d'un dépôt de couche atomique de plasma. Plus précisément, la présente invention permet d'obtenir une efficacité de film mince améliorée et un couverture graduelle par exécution d'une étape d'excitation de plasma à deux étages et permet de fournir un film mince de nitrure de silicium de haute pureté ayant une vitesse de dépôt améliorée malgré une faible température de formation de film.
PCT/KR2017/007764 2016-07-22 2017-07-19 Procédé de fabrication de film mince de nitrure de silicium au moyen d'un dépôt de couche atomique de plasma WO2018016871A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US16/319,452 US20190249296A1 (en) 2016-07-22 2017-07-19 Method for manufacturing silicon nitride thin film using plasma atomic layer deposition
CN201780044836.3A CN109478497A (zh) 2016-07-22 2017-07-19 利用等离子体原子层沉积法的氮化硅薄膜的制备方法
JP2019503328A JP7045360B2 (ja) 2016-07-22 2017-07-19 プラズマ原子層蒸着法を用いたシリコン窒化薄膜の製造方法

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KR20160093165 2016-07-22
KR10-2016-0093165 2016-07-22
KR10-2017-0090707 2017-07-18
KR1020170090707A KR102014175B1 (ko) 2016-07-22 2017-07-18 플라즈마 원자층 증착법을 이용한 실리콘 질화 박막의 제조방법

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Citations (5)

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KR20130016171A (ko) * 2008-11-12 2013-02-14 에어 프로덕츠 앤드 케미칼스, 인코오포레이티드 응력받은 ＳｉＮ 막에 대한 아미노 비닐실란 전구체
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