CN109487233A - A kind of low temperature preparation method of silicon oxide film - Google Patents

A kind of low temperature preparation method of silicon oxide film Download PDF

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Publication number
CN109487233A
CN109487233A CN201811420829.1A CN201811420829A CN109487233A CN 109487233 A CN109487233 A CN 109487233A CN 201811420829 A CN201811420829 A CN 201811420829A CN 109487233 A CN109487233 A CN 109487233A
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silicon oxide
oxide film
low temperature
film
microwave
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不公告发明人
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Hefei Anderkeming Semiconductor Technology Co Ltd
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Hefei Anderkeming Semiconductor Technology Co Ltd
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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
    • C23C16/22—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
    • C23C16/40—Oxides
    • C23C16/401—Oxides containing silicon
    • 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

Abstract

The present invention provides a kind of low temperature preparation method of silicon oxide film, and in 0~300 DEG C of temperature range, using microwave plasma as energy source, the oxygen free radical reaction that the first reactant comprising silicon source and oxidative reaction gas generate forms silicon oxide film.Under microwave condition, oxidative reaction gas can produce a large amount of oxygen radicals, facilitate the film for growing high quality；Simultaneously as without deflecting electric field, therefore greatly reduce the destruction to device surface or photoresist.At 100 DEG C, by the SiO film for the plasma P EALD preparation that microwave generates, in the HF solution of 100:1, etch-rate is 3~4A/sec, suitable at 350 DEG C, the wet etching speed of SiO film of radio frequency PEALD deposition.

Description

A kind of low temperature preparation method of silicon oxide film
[technical field]
The present invention relates to silicon oxide film technical fields, are especially a kind of low temperature preparation method of silicon oxide film.
[background technique]
Semiconductor device and Organic Light Emitting Diode (OLED) display technology more and more require low temperature, high quality Silicon oxide film.In current preparation method, plasma enhanced atomic layer deposition (PEALD) be it is unique it is a kind of can compared with Silicon oxide film under low temperature；In the method, people often use amino silane as presoma, are provided by plasma Energy, therefore reduce the demand to heat, can the higher silicon oxide film of deposition quality at a lower temperature.
But generally speaking, the silicon oxide film quality deposited under low temperature is still more of poor quality than high temperature deposition, concentrates It is presented as that the rate of wet etching is higher, such as silica (SiO) film deposited at 350 DEG C, in the HF solution of 100:1, erosion Etching speed is about 3.5A/sec；And silica (SiO) film deposited at 100 DEG C, its etch-rate reaches under equal conditions 10A/sec or more.In order to improve the quality of cryogenic oxidation silicon (SiO) film, the power of radio frequency plasma need to be increased, however, Increasing its power will lead to device surface or photoresist because ion bombardment is destroyed.Therefore, how to prepare at low temperature high-quality The technical issues of silicon oxide film of amount is current urgent need to resolve.
[summary of the invention]
The present invention provides a kind of low temperature preparation method of silicon oxide film, can obtain in 0~300 DEG C of temperature range wet The rate of method etching is lower than the silicon oxide film of traditional in-situ plasma enhancing atomic layer deposition.
Technical solution of the invention is as follows:
A kind of low temperature preparation method of silicon oxide film, which is characterized in that in 0~300 DEG C of temperature range, with microwave etc. As energy source, the oxygen free radical reaction that the first reactant comprising silicon source and oxidative reaction gas generate is formed gas ions Silicon oxide film.Under microwave condition, oxidative reaction gas can produce a large amount of oxygen radicals, help to grow high quality Film；Simultaneously as without deflecting electric field, therefore greatly reduce the destruction to device surface or photoresist.At 100 DEG C, lead to The SiO film for crossing the plasma P EALD preparation of microwave generation, in the HF solution of 100:1, etch-rate is 3~4A/ Sec is suitable at 350 DEG C, the wet etching speed of SiO film of radio frequency PEALD deposition.
Further, above-mentioned silicon oxide film low temperature preparation method the following steps are included:
1) in PEALD reaction chamber, by silicon to set temperature；
2) using inert gas as delivery gas, the first reactant comprising silicon source is imported in reaction chamber；
3) excessive first reactant is pumped out, uses inert gas purge；
4) a large amount of oxygen radicals are generated by microwave generator using oxidative reaction gas as the second reactant；
5) oxidative reaction gas and other gaseous by-products are pumped out, with inert gas purge, and it is heavy with this to complete PEALD Long-pending a cycle；
6) step 1) -5 is repeated) until reaching required film thickness.
Preferably, first reactant is one of amino silane, alkoxy silane, aminoalkoxysilane or more Kind.
It is further preferred that the amino silane is R0 1R0 2R0 3Si(NR0 4R0 5)、R0 1R0 2Si(NR0 3R0 4)(NR0 5R0 6)、 R0 1Si(NR0 2R0 3)(NR0 4R0 5)(NR0 6R0 7) or Si (NR0 1R0 2)(NR0 3R0 4)(NR0 5R0 6)(NR0 7R0 8), wherein R0Including hydrogen original One of son, straight chained alkyl, branched alkyl, alkenyl, alkynyl, naphthenic base, aromatic hydrocarbyl are a variety of, such as diisopropylamine silicon Alkane, bis- (tert-butylamino) silane, bis- (diethylamino) silane etc..
Equally it is further preferred that the alkoxy silane is R1 1R1 2R1 3Si(OR1 4)、R1 1R1 2Si(OR1 3)(OR1 4)、 R1 1Si(OR1 2)(OR1 3)(OR1 4) or Si (OR1 1-4), wherein R1Including hydrogen atom, straight chained alkyl, branched alkyl, alkenyl, alkynyl, One of naphthenic base, aromatic hydrocarbyl are a variety of, such as trimethoxymethylsila,e, diethoxymethylsilane.
Equally it is further preferred that the aminoalkoxysilane is R2 1R2 2Si(NR2 3R2 4)(OR2 5)、R2 1Si (NR2 2R2 3)(OR2 4)(OR2 5)、R2 1Si(NR2 2R2 3)(NR2 4R2 5)(OR2 6)、Si(NR2 1R2 2)(NR2 3R2 4)(NR2 5R2 6)(OR2 7)、 Si(NR2 1R2 2)(NR2 3R2 4)(OR2 5)(OR2 6) or Si (NR2 1R2 2)(OR2 3)(OR2 4)(OR2 5), wherein R2Including hydrogen atom, straight chain One of alkyl, branched alkyl, alkenyl, alkynyl, naphthenic base, aromatic hydrocarbyl are a variety of, such as bis- (tert-butylamino) methoxies Butyldimethylsilyl, tert-butylamino ethyoxyl dimethylsilane.
Further, above-mentioned oxidative reaction gas is oxygen (O2), nitrous oxide (N2O), carbon dioxide (CO2) It is one or more of.
Further, above-mentioned inert gas is helium (He), argon gas (Ar), neon (Ne), xenon (Xe), nitrogen (N2) in One or more.
Further, above-mentioned temperature range is preferably less than 200 DEG C；It is highly preferred that depositing temperature is lower than 100 DEG C.
Further, pressure of the above-mentioned reaction chamber in deposition reaction is 0.5~10Torr；Preferably, the pressure of reaction chamber It is by force 1~5Torr；It is further preferred that the pressure of reaction chamber is 3~5Torr, it is higher to obtain more high deposition rate, quality Film.
Further, the power of microwave used is 0.5kW~6kW；Preferably, the power of microwave used is 1kW~3kW.
Further, the microwave plasma is generated by the microwave generator of ten thousand machine instruments (MKS), and frequency is 2.455GHz, the operation pressure for generating microwave is 2~8Torr.
Beneficial effects of the present invention are as follows:
Under microwave condition, oxidative reaction gas can produce a large amount of oxygen radicals, help to grow the thin of high quality Film；Meanwhile the present invention uses microwave plasma for energy source, due to not having deflecting electric field and ion bombardment, subtracts significantly The destruction to substrate surface or photoresist is lacked；By-product is gas, is easily removed, and film purity is higher；Through the invention The SiO film for the plasma P EALD preparation that microwave generates, in the HF solution of 100:1, etch rate is 3~4A/sec, It is suitable at 350 DEG C, the wet etching rate of SiO film of radio frequency PEALD deposition；Since microwave generates a large amount of oxygen radicals, because This can significantly improve film deposition rate, and deposition rate can reach 1.5A/cycle, be significantly higher than traditional in-situ plasma The deposition rate (about 1A/cycle) of PEALD silicon oxide film.
[Detailed description of the invention]
Fig. 1 shows the FT-IR map of the silicon oxide film in embodiment 1,2.
[specific embodiment]
The present invention is described in further details with specific embodiment below, but the present invention is not only limited in detail below in fact Apply example.In the present invention, silica, Si oxide, SiO, SiOxMeaning it is identical.
Embodiment provided below is not intended to limit the invention covered range, and described step is also not use Sequence is executed to limit its.Those skilled in the art combine existing common knowledge to do conspicuous improvement to the present invention, also fall Enter the present invention claims protection scope within.
A kind of low temperature preparation method of silicon oxide film, comprising the following steps:
1) in PEALD reaction chamber, by silicon, preferably shorter than 300 DEG C, or it is lower than 200 DEG C, or be lower than 100 DEG C. Substrate can be silicon single crystal wafer, silicon carbide wafer, aluminium oxide (sapphire) chip, sheet glass, metal foil, organic polymer Film, polymer, glass, silicon or metal three-dimensional article.Substrate can be coated with multiple material well known in the art, including oxidation The film of silicon, amorphous carbon, silicon oxide carbide, silicon oxynitride, silicon carbide, GaAs, gallium nitride etc..Substrate can also pass through a series of Pretreatment can be corona treatment, heat treatment, chemical treatment, ultraviolet light exposure, beam bombardment and combinations thereof.These Deposition pre-treatment can be carried out under inertia, oxidation and/or the atmosphere of reduction.
2) using inert gas as delivery gas, the first reactant comprising silicon source is imported in reaction chamber.Indifferent gas Body can be helium (He), argon gas (Ar), neon (Ne), xenon (Xe), nitrogen (N2One or more of).
Preferably, first reactant is one of amino silane, alkoxy silane, aminoalkoxysilane or more Kind.Mode of movement can be bubbling, direct liquid injection conveying, steam suction etc..
It is further preferred that the amino silane is R0 1R0 2R0 3Si(NR0 4R0 5)、R0 1R0 2Si(NR0 3R0 4)(NR0 5R0 6)、 R0 1Si(NR0 2R0 3)(NR0 4R0 5)(NR0 6R0 7) or Si (NR0 1R0 2)(NR0 3R0 4)(NR0 5R0 6)(NR0 7R0 8), wherein R0Including hydrogen original One of son, straight chained alkyl, branched alkyl, alkenyl, alkynyl, naphthenic base, aromatic hydrocarbyl are a variety of, such as diisopropylamine silicon Alkane, bis- (tert-butylamino) silane, bis- (diethylamino) silane etc..
Equally it is further preferred that the alkoxy silane is R1 1R1 2R1 3Si(OR1 4)、R1 1R1 2Si(OR1 3)(OR1 4)、 R1 1Si(OR1 2)(OR1 3)(OR1 4) or Si (OR1 1-4), wherein R1Including hydrogen atom, straight chained alkyl, branched alkyl, alkenyl, alkynyl, One of naphthenic base, aromatic hydrocarbyl are a variety of, such as trimethoxymethylsila,e, diethoxymethylsilane.
Equally it is further preferred that the aminoalkoxysilane is R2 1R2 2Si(NR2 3R2 4)(OR2 5)、R2 1Si (NR2 2R2 3)(OR2 4)(OR2 5)、R2 1Si(NR2 2R2 3)(NR2 4R2 5)(OR2 6)、Si(NR2 1R2 2)(NR2 3R2 4)(NR2 5R2 6)(OR2 7)、 Si(NR2 1R2 2)(NR2 3R2 4)(OR2 5)(OR2 6) or Si (NR2 1R2 2)(OR2 3)(OR2 4)(OR2 5), wherein R2Including hydrogen atom, straight chain One of alkyl, branched alkyl, alkenyl, alkynyl, naphthenic base, aromatic hydrocarbyl are a variety of, such as bis- (tert-butylamino) methoxies Butyldimethylsilyl, tert-butylamino ethyoxyl dimethylsilane.
3) excessive first reactant is pumped out, uses inert gas purge；
4) it is imported oxidative reaction gas as the second reactant in reaction chamber and at microwave remote plasma Reason.Oxidizing gas includes but is not limited to oxygen (O2), nitrous oxide (N2O), carbon dioxide (CO2) one or more.Far Journey plasma is generated by the microwave generator of MKS, frequency 2.455GHz, generate the operation pressure of microwave for 2~ 8Torr。
5) oxidative reaction gas and byproduct of reaction (CO are pumped outx、NOxDeng being gas, facilitate removal, improve film Quality), with inert gas purge, and complete with this cycle of PEALD deposition.
6) step 1) -5 is repeated) until reaching required film thickness.
Performance test
1. the measurement of wet etching speed completes etching by using 100: 1 dilution HF solution, and makes with convention heat sink product Standby silicon oxide film compares.
2. using the thickness and the refractive index at 632nm of reflectometer or polarised light ellipsometer measurement film (Refractiveindex, RI).
3. carrying out density measure using X ray reflection method (XRR).
4. being formed using the element of x-ray photoelectron spectroscopy (XPS) and secondary ion mass spectrometry (SIMS) (SIMS) analysis measurement film.
Embodiment 1
A kind of low temperature preparation method of silicon oxide film, comprising the following steps:
1) in PEALD reaction chamber, the silicon wafer of 775 μm of thickness, diameter 300mm are heated to 200 DEG C；
2) with helium (He, boot speed 300sccm) as delivery gas, by diisopropylamine silane (DIPAS) as the One reactant is imported in reaction chamber with the boot speed of 0.2mg/min, and importing the time is 0.5 second, and the air pressure of reaction chamber is tieed up It holds in 3.5Torr；
3) excessive DIPAS is pumped out, purges 10sec with He gas, purging speed is 500sccm；
4) by O2It is imported in reaction chamber as the second reactant through microwave generator, boot speed 500sccm, microwave The time that generator opens generation microwave is 0.5 second, output power 3000W；Maintain the pressure of reaction chamber in 3.5Torr；
5) excessive O is pumped out2With byproduct of reaction, 10sec is purged with He, purging speed is 500sccm, and is completed with this The a cycle of PEALD deposition, such step 1) -5) it is repeated up to and reaches required film thickness.
After 200 deposition cycles, film with a thickness of 285A, show that deposition rate is the 1.43A/ period；Film exists Refractive index at 632nm is 1.458, and the infrared spectroscopy of film is as shown in Figure 1；In the HF solution of 100:1, etch rate is 3.3A/sec；It is tested through XPS, SiO2In film silicone content be 33.5%, oxygen content 66.5%, carbon content detection limit with Under；XRR density measure shows that the density of film is 2.28g/cm3。
Embodiment 2
A kind of low temperature preparation method of silicon oxide film, comprising the following steps:
1) in PEALD reaction chamber, the silicon wafer of 775 μm of thickness, diameter 300mm are heated to 100 DEG C；
2) with argon gas (Ar, boot speed 300sccm) as delivery gas, will be bis- (tert-butylamino) silane (BTBAS) It is imported in reaction chamber in a manner of steam suction as the first reactant, importing the time is 0.6 second, and the air pressure of reaction chamber is tieed up It holds in 4.5Torr；
3) excessive BTBAS is pumped out, purges 10sec with Ar gas, purging speed is 500sccm；
4) by O2It is imported in reaction chamber as the second reactant through microwave generator, boot speed 350sccm, microwave The time that generator opens generation microwave is 0.5 second, output power 2000W；Maintain the pressure of reaction chamber in 4.5Torr；
5) excessive O is pumped out2With byproduct of reaction, 10sec is purged with argon gas, purging speed is 500sccm, and is completed with this The a cycle of PEALD deposition, such step 1) -5) it is repeated up to and reaches required film thickness.
After 200 deposition cycles, film with a thickness of 316A, show that deposition rate is the 1.58A/ period.Film exists Refractive index at 632nm is 1.460.The infrared spectroscopy of film is as shown in Figure 1.In the HF solution of 100:1, etch rate is 3.9A/sec；It is tested through XPS, SiO2Silicone content is 32.8% in film, and oxygen content 66.7%, carbon content is below 0.5%； XRR density measure shows that the density of film is 2.25g/cm3。
Embodiment 3
A kind of low temperature preparation method of silicon oxide film, comprising the following steps:
1) in PEALD reaction chamber, the silicon wafer of 775 μm of thickness, diameter 300mm are heated to 300 DEG C；
2) anti-using trimethoxymethylsila,e as first with neon (Ne, boot speed 300sccm) as delivery gas Object is answered to import in reaction chamber with the boot speed of 0.5mg/min, importing the time is 0.5 second, and the air pressure of reaction chamber maintains 3Torr；
3) excessive trimethoxymethylsila,e is pumped out, purges 10sec with Ne gas, purging speed is 500sccm；
4) by N2O is imported in reaction chamber as the second reactant through microwave generator, and boot speed 500sccm is micro- The time that wave producer opens generation microwave is 0.5 second, output power 1000W；Maintain the pressure of reaction chamber in 3Torr；
5) excessive N is pumped out2O and byproduct of reaction purge 10sec with Ne, and purging speed is 500sccm, and is completed with this The a cycle of PEALD deposition, such step 1) -5) it is repeated up to and reaches required film thickness.
After 200 deposition cycles, film with a thickness of 290A, show that deposition rate is the 1.45A/ period；Film exists Refractive index at 632nm is 1.459；In the HF solution of 100:1, etch rate 3.1A/sec；It is tested through XPS, SiO2 Silicone content is 33.5% in film, and oxygen content 66.1%, nitrogen content 0.4%, carbon content is below detection limit；XRR is close The density of degree measurement display film is 2.29g/cm3。
Embodiment 4
A kind of low temperature preparation method of silicon oxide film, comprising the following steps:
1) in PEALD reaction chamber, the silicon wafer of 775 μm of thickness, diameter 300mm are heated to 150 DEG C；
2) with argon gas (Ar, boot speed 300sccm) as delivery gas, will be bis- (tert-butylamino) methoxy silicon Alkane is imported in reaction chamber as the first reactant with the boot speed of 0.45mg/min, and importing the time is 0.5 second, reaction chamber Air pressure maintain 2.5Torr；
3) excessive bis- (tert-butylamino) methoxy methyl base silanes are pumped out, uses N2Gas purges 10sec, purges speed For 500sccm；
4) by oxygen (O2) imported in reaction chamber as the second reactant through microwave generator, boot speed is 500sccm, the time that microwave generator opens generation microwave is 0.5 second, output power 6000W；Maintain the pressure of reaction chamber By force in 2.5Torr；
5) excessive O is pumped out2With byproduct of reaction, 10sec is purged with Ar, purging speed is 500sccm, and is completed with this The a cycle of PEALD deposition, such step 1) -5) it is repeated up to and reaches required film thickness.
After 200 deposition cycles, film with a thickness of 296A, show that deposition rate is the 1.48A/ period；Film exists Refractive index at 632nm is 1.460；In the HF solution of 100:1, etch rate 3.8A/sec；It is tested through XPS, SiO2 Silicone content is 33.3% in film, oxygen content 66.4%, carbon content 0.3%；XRR density measure shows that the density of film is 2.25g/cm3。
Embodiment 5
A kind of low temperature preparation method of silicon oxide film, comprising the following steps:
1) in PEALD reaction chamber, the silicon wafer of 775 μm of thickness, diameter 300mm are heated to 80 DEG C；
2) with xenon (Xe, boot speed 300sccm) as delivery gas, will be bis- (diethylamino) silane as first Reactant is imported in reaction chamber with the boot speed of 0.4mg/min, and importing the time is 0.5 second, and the air pressure of reaction chamber maintains In 3.5Torr；
3) excessive bis- (diethylamino) silane are pumped out, purges 10sec with Xe gas, purging speed is 500sccm；
4) by oxygen (O2) imported in reaction chamber as the second reactant through microwave generator, boot speed is 500sccm, the time that microwave generator opens generation microwave is 0.5 second, output power 3500W；Maintain the pressure of reaction chamber By force in 3.5Torr；
5) excessive O is pumped out2With byproduct of reaction, 10sec is purged with Xe, purging speed is 500sccm, and is completed with this The a cycle of PEALD deposition, such step 1) -5) it is repeated up to and reaches required film thickness.
After 200 deposition cycles, film with a thickness of 316A, show that deposition rate is the 1.58A/ period；Film exists Refractive index at 632nm is 1.461；In the HF solution of 100:1, etch rate 4.1A/sec；It is tested through XPS, SiO2 Silicone content is 33.1% in film, oxygen content 66.2%, carbon content 0.7%；XRR density measure shows that the density of film is 2.24g/cm3。
Embodiment 6
A kind of low temperature preparation method of silicon oxide film, comprising the following steps:
1) in PEALD reaction chamber, the silicon wafer of 775 μm of thickness, diameter 300mm are heated to 180 DEG C；
2) anti-using diethoxymethylsilane as first with neon (Ne, boot speed 300sccm) as delivery gas Object is answered to import in reaction chamber with the boot speed of 0.35mg/min, importing the time is 0.5 second, and the air pressure of reaction chamber maintains 5Torr；
3) excessive diethoxymethylsilane is pumped out, purges 10sec with Ne gas, purging speed is 500sccm；
4) by N2O is imported in reaction chamber as the second reactant through microwave generator, and boot speed 500sccm is micro- The time that wave producer opens generation microwave is 0.5 second, output power 2500W；Maintain the pressure of reaction chamber in 5Torr；
5) excessive N is pumped out2O and byproduct of reaction purge 10sec with Ne, and purging speed is 500sccm, and is completed with this The a cycle of PEALD deposition, such step 1) -5) it is repeated up to and reaches required film thickness.
After 200 deposition cycles, film with a thickness of 300A, show that deposition rate is the 1.50A/ period；Film exists Refractive index at 632nm is 1.459；In the HF solution of 100:1, etch rate 3.7A/sec；It is tested through XPS, SiO2 Silicone content is 33.3% in film, oxygen content 66.3%, nitrogen content 0.4%；XRR density measure shows that the density of film is 2.27g/cm3。
Comparative example 1 (at 350 DEG C, radio frequency PEALD deposition)
A kind of low temperature preparation method of silicon oxide film, comprising the following steps:
1) in PEALD reaction chamber, the silicon wafer of 775 μm of thickness, diameter 300mm are heated to 350 DEG C；
2) with helium (He, boot speed 300sccm) as delivery gas, by diisopropylamine silane (DIPAS) as the One reactant is imported in reaction chamber with the boot speed of 0.25mg/min, and importing the time is 0.5 second, and the air pressure of reaction chamber is tieed up It holds in 1.0Torr；
3) excessive DIPAS is pumped out, purges 10sec with He gas, purging speed is 500sccm；
4) by O2It is imported in reaction chamber as the second reactant, boot speed 500sccm, in-situ plasma is opened Opening the time is 0.5 second, output power 300W；Maintain the pressure of reaction chamber in 1.0Torr；
5) excessive O is pumped out2With byproduct of reaction, 10sec is purged with He, purging speed is 500sccm, and is completed with this The a cycle of PEALD deposition, such step 1) -5) it is repeated up to and reaches required film thickness.
After 300 deposition cycles, film with a thickness of 351A, show that deposition rate is the 1.17A/ period；Film exists Refractive index at 632nm is 1.457；In the HF solution of 100:1, etch rate 3.5A/sec.It is tested through XPS, SiO2 Silicone content is 33.4% in film, and oxygen content 66.6%, carbon content is below detection limit；XRR density measure shows film Density be 2.27g/cm3.
The detection of 1 product film performance of table

Claims (10)

1. a kind of low temperature preparation method of silicon oxide film, which is characterized in that in 0~300 DEG C of temperature range, with microwave etc. from As energy source, the oxygen free radical reaction that the first reactant comprising silicon source and oxidative reaction gas generate forms oxygen for daughter SiClx film.
2. the low temperature preparation method of silicon oxide film according to claim 1, which comprises the following steps:
1) in PEALD reaction chamber, by silicon to set temperature；
2) using inert gas as delivery gas, the first reactant comprising silicon source is imported in reaction chamber；
3) excessive first reactant is pumped out, uses inert gas purge；
4) using oxidative reaction gas as the second reactant by microwave generator import reaction chamber in, and with microwave etc. from Daughter processing；
5) oxidative reaction gas and gaseous by-product are pumped out, completes one of PEALD deposition with inert gas purge, and with this Period；
6) step 1) -5 is repeated) until reaching required film thickness.
3. the low temperature preparation method of silicon oxide film according to claim 2, which is characterized in that first reactant is One or more of isopropyl amine silane, bis- (diethylamino) silane, bis- (tert-butylamino) silane.
4. the low temperature preparation method of silicon oxide film according to claim 3, which is characterized in that the amino silane is R0 1R0 2R0 3Si(NR0 4R0 5)、R0 1R0 2Si(NR0 3R0 4)(NR0 5R0 6)、R0 1Si(NR0 2R0 3)(NR0 4R0 5)(NR0 6R0 7) or Si (NR0 1R0 2)(NR0 3R0 4)(NR0 5R0 6)(NR0 7R0 8), wherein R0Including hydrogen atom, straight chained alkyl, branched alkyl, alkenyl, alkynyl, One of naphthenic base, aromatic hydrocarbyl are a variety of；The alkoxy silane is R1 1R1 2R1 3Si(OR1 4)、R1 1R1 2Si(OR1 3) (OR1 4)、R1 1Si(OR1 2)(OR1 3)(OR1 4) or Si (OR1 1-4), wherein R1Including hydrogen atom, straight chained alkyl, branched alkyl, alkene One of base, alkynyl, naphthenic base, aromatic hydrocarbyl are a variety of；The aminoalkoxysilane is R2 1R2 2Si(NR2 3R2 4) (OR2 5)、R2 1Si(NR2 2R2 3)(OR2 4)(OR2 5)、R2 1Si(NR2 2R2 3)(NR2 4R2 5)(OR2 6)、Si(NR2 1R2 2)(NR2 3R2 4) (NR2 5R2 6)(OR2 7)、Si(NR2 1R2 2)(NR2 3R2 4)(OR2 5)(OR2 6) or Si (NR2 1R2 2)(OR2 3)(OR2 4)(OR2 5), wherein R2 Including one of hydrogen atom, straight chained alkyl, branched alkyl, alkenyl, alkynyl, naphthenic base, aromatic hydrocarbyl or a variety of.
5. the low temperature preparation method of silicon oxide film according to claim 2, which is characterized in that the oxidative reaction gas Body is the one or more of oxygen, nitrous oxide, carbon dioxide.
6. the low temperature preparation method of silicon oxide film according to claim 2, which is characterized in that the inert gas is helium One or more of gas, argon gas, neon, xenon.
7. the low temperature preparation method of silicon oxide film according to claim 1 or 2, which is characterized in that the temperature range It is 0~200 DEG C.
8. the low temperature preparation method of silicon oxide film according to claim 2, which is characterized in that the reaction chamber is depositing Pressure when reaction is 0.5~10Torr.
9. the low temperature preparation method of silicon oxide film according to claim 2, which is characterized in that the power of microwave used is 0.5kW~6kW.
10. the low temperature preparation method of silicon oxide film according to claim 2, which is characterized in that the microwave plasma Body is generated by microwave generator, frequency 2.455GHz, and the operation pressure for generating microwave is 2~8Torr.
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