CN104561928A - Method for depositing silicon dioxide film on glass substrate - Google Patents

Method for depositing silicon dioxide film on glass substrate Download PDF

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Publication number
CN104561928A
CN104561928A CN201410811446.2A CN201410811446A CN104561928A CN 104561928 A CN104561928 A CN 104561928A CN 201410811446 A CN201410811446 A CN 201410811446A CN 104561928 A CN104561928 A CN 104561928A
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China
Prior art keywords
silicon
glass substrate
film
cvd
silicon dioxide
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CN201410811446.2A
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吕斌
李文杰
朱恒伟
吕建国
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Zhejiang University ZJU
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Zhejiang University ZJU
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Priority to CN201410811446.2A priority Critical patent/CN104561928A/en
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—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
    • C23C16/402—Silicon dioxide
    • 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

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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)
  • Inorganic Chemistry (AREA)
  • Chemical Vapour Deposition (AREA)

Abstract

The invention relates to the field of a chemical vapor deposition (CVD) process, particularly a low pressure chemical vapor deposition (LPCVD) method for depositing a silicon dioxide film on a glass substrate. In the CVD deposition process, a silicon source and oxygen are separately introduced into the reaction chamber, the silicon source is firstly utilized to deposit a silicon film on the glass substrate, and the oxygen is utilized to oxidize the silicon film, thereby obtaining the silicon dioxide film. The method specifically comprises the following steps: 1) chemically cleaning the glass substrate; 2) vacuumizing CVD equipment; 3) depositing the silicon film; 4) oxidizing the silicon film; and 5) cooling at room temperature, and finally obtaining the silicon dioxide film on the glass substrate, wherein in the deposition process of the steps 3) and 4), the pressure in the quartz tube is kept in a low-pressure environment of 150-250Pa all the time. The method can be used for preparing the compact, stable and uniform pure SiO2 film on the glass substrate. The SiO2 film is compact, uniform and firm, and has the advantages of abrasion resistance, high erosion resistance, high acid/alkali resistance, high light transmission rate and the like, and is colorless and transparent.

Description

A kind of method of cvd silicon dioxide film on the glass substrate
Technical field
The present invention relates to chemical Vapor deposition process field, particularly relate to a kind of preparation method of low-pressure chemical vapor deposition of silica membrane.
Background technology
Silicon-dioxide (SiO 2) film obtains a wide range of applications in fields such as semi-conductor, microelectronics, optics and thin film sensors with the performance of its excellence.SiO in microelectronics 2film is used as the passivation protection layer etc. of diffusion mask layer, the insulated gate of MOS device, the dielectric isolation layer of multilayer wiring and device surface.SiO 2film also, that light transmission good characteristic low with its specific refractory power is used for surfacecti proteon and the antireflection coatings of optical element.In addition, SiO 2film has good insulativity, stability and mechanical characteristics, hardness is high, fine structure, rete are firm, wear-resistant corrosion-resistant, fusing point is high and for the insulation layer of multilayer film sensor.For this reason, for many years people to SiO 2film manufacturing method and performance etc. conduct extensive research.
SiO 2the preparation method of film has a lot, as chemical vapor deposition (CVD), thermal evaporation, sputtering, Sol-Gel etc.Wherein maximum with plasma enhanced chemical vapor deposition (PECVD) application in chemical Vapor deposition process.PECVD utilizes glow discharge that rarefied gas is ionized, under high-frequency electric field, produce non-equilibrium plasma, and plasma body is at deposited on substrates film former.PECVD can realize SiO at a lower temperature 2the deposition of film, but to deposit the film hardness obtained low, and the too fast meeting of sedimentation rate causes film cylindrical brilliant serious, and homogeneity and repeatability are easily affected, and easily occur fringing effect.
And be that deposition obtains pure SiO 2film, uses silane (SiH usually 4) and oxygen (O 2) as pioneer's reactant, under the effect of PECVD, form ion and reactive deposition obtains SiO 2film.But the film large-area uniformity that this method prepares is poor, and structure is more loose, greatly reduces SiO 2barrier property.Therefore, be necessary that working out one can prepare the pure SiO of Large-Area-Uniform 2the CVD method of film.
Summary of the invention
The object of the invention is at solution CVD deposition SiO 2in thin-film process, utilize silane (SiH 4) and oxygen (0 2) the film large-area uniformity for preparing as pioneer's reactant is poor, the problem that structure is comparatively loosened, provides one to use low-pressure chemical vapor deposition (LPCVD) deposition techniques to prepare the pure SiO of Large-Area-Uniform on the glass substrate 2the method of film.
The invention provides a kind of method of cvd silicon dioxide film on the glass substrate, it is characterized in that: in CVD deposition process, silicon source and oxygen are separately passed into reaction chamber, first utilize silicon source to deposit one deck silicon fiml on the glass substrate, and then utilize oxygen by silicon fiml oxidation thus obtain silica membrane; Concrete steps comprise:
1) substrate of glass dry is placed in the silica tube of CVD device through matting;
2) vacuumize;
3) pass into shielding gas and reducing gas in silica tube, heated up by tube furnace, pass into silicon source after rising to design temperature, silicon source and reducing gas react deposited silicon film on the glass substrate simultaneously; Close silicon source and reducing gas flow valve;
4) oxygen is passed into, at a set temperature oxidation silicon fiml;
5) in oxygen and shielding gas atmosphere, tube furnace is cooled with room temperature, take out sample;
Wherein, in step 3), 4) in deposition process, quartzy intraductal pressure is in the low pressure environment of 150Pa-200Pa always.
Further, matting described in step 1) is priority acetone, deionized water, dehydrated alcohol carry out ultrasonic cleaning to substrate of glass, and is dried up by the substrate of glass nitrogen cleaned; The ultrasonic cleaning time is each 5-15min.
Further, step 2) described in vacuumize as priority mechanical pump and molecular pump vacuumize tube furnace, be evacuated to silica tube internal gas pressure and reach 1 × 10 -3pa.
Further, described shielding gas is argon gas, and described reducing gas is hydrogen; Described silicon source is silane.
Further, during step 3) deposited silicon film, silane flow rate is 5-20sccm, and hydrogen flowing quantity is 2-10sccm, and argon flow amount is 100-200sccm, and the depositing temperature of silicon fiml is 500-700 DEG C, and depositing time is 5-20min.
Further, during step 4) silicon oxide film, oxygen flow is 10-30sccm, and argon flow amount is 100-200sccm, and silicon fiml oxidizing temperature is 500-700 DEG C, and oxidization time is 10-20min.
Further, keep hydrogen and argon atmosphere in silica tube in temperature-rise period in step 3), temperature rise rate is 5-15 DEG C/min.
Beneficial effect of the present invention is under low pressure, in CVD deposition process, silicon source and oxygen is separately passed into reaction chamber, first utilizes silicon source to deposit one deck silicon fiml on the glass substrate, and then utilizes oxygen that silicon fiml oxidation is obtained silica membrane; Silane (SiH is utilized under so effective solution CVD 4) and oxygen (0 2) the film large-area uniformity for preparing as pioneer's reactant is poor, the problem that structure is comparatively loosened, finally deposited one deck densification, stable, uniform SiO on the glass substrate 2film; Whole preparation process is controlled, easy and simple to handle, safety non-pollution; And the SiO prepared 2pellicle film is by pure SiO 2composition, inclusion-free, dense uniform, firmly wear-resistant, erosion-resisting characteristics is high, acid-proof alkaline is strong, water white transparency, light transmission rate are high.
Accompanying drawing explanation
Fig. 1 is chemical vapor deposition (CVD) structure drawing of device, 1 tube furnace; 2 silica tubes; 3 substrate of glass; 4 valves.
Fig. 2 is the surface Scanning Electron microscope figure of the sample prepared in embodiment.
Embodiment
The present invention is further illustrated below in conjunction with embodiment.
(1) matting, drying: get substrate of glass in specimen holder, specimen holder is placed in beaker.Adding acetone to flooding glass, beaker being placed in ultrasonic cleaning machine and cleaning 5-15min.Specimen holder is taken out and puts into another beaker, adding deionized water to flooding glass, beaker being placed in ultrasonic cleaning machine and cleaning 5-15min.Specimen holder is taken out and puts into another beaker, adding dehydrated alcohol to flooding glass, beaker being placed in ultrasonic cleaning machine and cleaning 5-15min.Take out substrate of glass, dry up under a nitrogen.
(2) deposited silicon film: if Fig. 1 is the chemical vapor deposition unit structure iron that the present embodiment uses, wherein 1 is tube furnace; 2 is silica tube, places sample substrate to be grown in silica tube, and silica tube forms the electroless plating reaction chamber of a sealing; 3 is substrate of glass, sample substrate namely to be grown; 4 is valve, and valve is the passage that each gas enters silica tube.Be placed in the silica tube of CVD equipment by dry for step (1) complete substrate of glass, open mechanical pump, gas pressure in vacuum is extracted into 10 below Pa, opens molecular pump, reaction chamber internal gas pressure reaches 1 × 10 by the time -3closure molecule pump during Pa.3sccm hydrogen and 150sccm argon gas are passed in silica tube simultaneously.Set temperature is 550 DEG C, and the heating-up time is 50min, and when temperature rises to 550 DEG C, open silane gas flow valve, arranging silane flow rate is 10sccm.Hydrogen and silane flow rate valve is closed after deposition 10min.Air pressure in this deposited silicon film process in silica tube remains on always and is no more than 200Pa.
During above-mentioned deposited silicon film, each gas flow can control to pass into following flow range: silane flow rate 5-20sccm, and hydrogen flowing quantity is 2-10sccm, and argon flow amount is 100-200sccm; The depositing temperature of silicon fiml can carry out at 500-700 DEG C, and temperature rise rate can be controlled in 5-15 DEG C/min, and depositing time controls in 5-20min.
(3) silicon fiml oxidation: open oxygen gas flow valve, arranging oxygen flow is 20sccm, keeps the argon gas of 150sccm, at 550 DEG C, is oxidized 15min.In silicon fiml oxidising process, the air pressure in silica tube remains on 150-180Pa always.During silicon oxide film, each processing parameter can at following scope control: oxygen flow is 10-30sccm, and argon flow amount is 100-200sccm, and silicon fiml oxidizing temperature is 500-700 DEG C, and oxidization time is 10-20min.
(4) cooling sampling: after end to be oxidized, under oxygen and argon atmosphere, raise tube furnace lid, make silica tube be exposed to air and cool with room temperature.To be cooled to room temperature time, close all gas, take out after quartzy intraductal pressure reaches normal pressure sample go forward side by side line correlation test.As the surface Scanning Electron microscope figure that Fig. 2 is the sample prepared in the present embodiment, by seeing obtained SiO2 thin film deposition layer compact structure, evenly in figure.
Finally, it is also to be noted that what enumerate above is only a specific embodiment of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be had.All distortion that those of ordinary skill in the art can derive from content disclosed by the invention and byte or associate, all should think protection scope of the present invention.

Claims (7)

1. the method for a cvd silicon dioxide film on the glass substrate, it is characterized in that: in CVD deposition process, silicon source and oxygen are separately passed into reaction chamber, first utilizes silicon source to deposit one deck silicon fiml on the glass substrate, and then utilize oxygen by silicon fiml oxidation thus obtain silica membrane; Concrete steps comprise:
1) substrate of glass dry is placed in the silica tube of CVD device through matting;
2) vacuumize;
3) pass into shielding gas and reducing gas in silica tube, heated up by tube furnace, pass into silicon source after rising to design temperature, silicon source and reducing gas react deposited silicon film on the glass substrate simultaneously; Close silicon source and reducing gas flow valve;
4) oxygen is passed into, at a set temperature oxidation silicon fiml;
5) in oxygen and shielding gas atmosphere, tube furnace is cooled with room temperature, take out sample;
Wherein, in step 3), 4) in deposition process, quartzy intraductal pressure is in the low pressure environment of 150Pa-200Pa always.
2. the method for a kind of cvd silicon dioxide film on the glass substrate according to claim 1, it is characterized in that matting described in step 1) is priority acetone, deionized water, dehydrated alcohol carry out ultrasonic cleaning to substrate of glass, and dried up by the substrate of glass nitrogen cleaned; The ultrasonic cleaning time is each 5-15min.
3. the method for a kind of cvd silicon dioxide film on the glass substrate according to claim 1, is characterized in that: step 2) described in vacuumize as priority mechanical pump and molecular pump vacuumize tube furnace, be evacuated to silica tube internal gas pressure and reach 1 × 10 -3pa.
4. the method for a kind of cvd silicon dioxide film on the glass substrate according to claim 1, it is characterized in that: described shielding gas is argon gas, described reducing gas is hydrogen; Described silicon source is silane.
5. the method for a kind of cvd silicon dioxide film on the glass substrate according to claim 4, it is characterized in that: during deposited silicon film, silane flow rate is 5-20sccm, hydrogen flowing quantity is 2-10sccm, argon flow amount is 100-200sccm, the depositing temperature of silicon fiml is 500-700 DEG C, and depositing time is 5-20min.
6. the method for a kind of cvd silicon dioxide film on the glass substrate according to claim 4, it is characterized in that: during silicon oxide film, oxygen flow is 10-30sccm, argon flow amount is 100-200sccm, and silicon fiml oxidizing temperature is 500-700 DEG C, and oxidization time is 10-20min.
7. the method for a kind of cvd silicon dioxide film on the glass substrate according to claim 4, is characterized in that: keep hydrogen and argon atmosphere in silica tube in temperature-rise period in step 3), temperature rise rate is 5-15 DEG C/min.
CN201410811446.2A 2014-12-24 2014-12-24 Method for depositing silicon dioxide film on glass substrate Pending CN104561928A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106835065A (en) * 2016-10-17 2017-06-13 中国矿业大学(北京) A kind of Nano diamond silane surface vacuum pyrolysis depositing device
CN108447770A (en) * 2018-03-08 2018-08-24 清华大学 The preparation method of silica membrane
CN108603288A (en) * 2015-11-16 2018-09-28 库伯斯股份有限公司 The method for producing aluminium oxide and/or aluminium nitride
CN109136882A (en) * 2018-09-07 2019-01-04 上海申和热磁电子有限公司 A kind of improvement SiO2The chemical vapor deposition method of film compactness
CN112992672A (en) * 2019-12-16 2021-06-18 山东有研半导体材料有限公司 Preparation method of silica-based back-sealing film
CN113363134A (en) * 2020-03-05 2021-09-07 上海新微技术研发中心有限公司 Method for depositing silicon oxide film
CN116103619A (en) * 2022-10-27 2023-05-12 重庆文理学院 Preparation method of silicon oxide film

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CN101023517A (en) * 2004-09-16 2007-08-22 S.O.I.泰克绝缘体硅技术公司 Method of manufacturing a silicon dioxide layer
CN102011105A (en) * 2010-10-12 2011-04-13 上海宏力半导体制造有限公司 Process for depositing silica at low pressure

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CN101023517A (en) * 2004-09-16 2007-08-22 S.O.I.泰克绝缘体硅技术公司 Method of manufacturing a silicon dioxide layer
CN102011105A (en) * 2010-10-12 2011-04-13 上海宏力半导体制造有限公司 Process for depositing silica at low pressure

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108603288A (en) * 2015-11-16 2018-09-28 库伯斯股份有限公司 The method for producing aluminium oxide and/or aluminium nitride
CN108603288B (en) * 2015-11-16 2020-01-14 库伯斯股份有限公司 Method for producing aluminum oxide and/or aluminum nitride
CN106835065A (en) * 2016-10-17 2017-06-13 中国矿业大学(北京) A kind of Nano diamond silane surface vacuum pyrolysis depositing device
CN106835065B (en) * 2016-10-17 2019-03-29 中国矿业大学(北京) A kind of Nano diamond silane surface vacuum pyrolysis depositing device
CN108447770A (en) * 2018-03-08 2018-08-24 清华大学 The preparation method of silica membrane
CN108447770B (en) * 2018-03-08 2020-07-28 清华大学 Preparation method of silicon dioxide film
CN109136882A (en) * 2018-09-07 2019-01-04 上海申和热磁电子有限公司 A kind of improvement SiO2The chemical vapor deposition method of film compactness
CN109136882B (en) * 2018-09-07 2020-09-18 上海新欣晶圆半导体科技有限公司 SiO improvement2Chemical vapor deposition method for film compactness
CN112992672A (en) * 2019-12-16 2021-06-18 山东有研半导体材料有限公司 Preparation method of silica-based back-sealing film
CN112992672B (en) * 2019-12-16 2022-10-14 山东有研半导体材料有限公司 Preparation method of silicon-based silicon dioxide back sealing film
CN113363134A (en) * 2020-03-05 2021-09-07 上海新微技术研发中心有限公司 Method for depositing silicon oxide film
CN116103619A (en) * 2022-10-27 2023-05-12 重庆文理学院 Preparation method of silicon oxide film

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Application publication date: 20150429