KR20130022438A - The method of forming silicon carbide film comprising silicon nano-crystals - Google Patents

The method of forming silicon carbide film comprising silicon nano-crystals Download PDF

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KR20130022438A
KR20130022438A KR1020110083618A KR20110083618A KR20130022438A KR 20130022438 A KR20130022438 A KR 20130022438A KR 1020110083618 A KR1020110083618 A KR 1020110083618A KR 20110083618 A KR20110083618 A KR 20110083618A KR 20130022438 A KR20130022438 A KR 20130022438A
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South Korea
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silicon
silicon carbide
carbide film
film
gas
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KR1020110083618A
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Korean (ko)
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김태엽
구재본
양용석
이수재
정순원
백강준
유인규
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한국전자통신연구원
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Publication of KR20130022438A publication Critical patent/KR20130022438A/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
    • C23C16/24—Deposition of silicon only
    • 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
    • C23C16/32—Carbides
    • C23C16/325—Silicon carbide
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

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  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Chemical Vapour Deposition (AREA)

Abstract

A method of forming a silicon carbide film containing nanocrystalline silicon is provided. The forming method includes injecting plasma gas onto a substrate to form a silicon carbide film including nanocrystalline silicon. The plasma gas includes a methane (CH4) gas and a silane (SiH4) gas, and the silicon carbide film includes silicon carbide (SiC) or silicon oxycarbide (SiOC). The silicon carbide film and the nanocrystalline silicon are formed at the same time.

Description

Method of Forming Silicon Carbide Film Comprising Silicon Nano-Crystals

The present invention relates to a method of forming a silicon carbide film containing nanocrystalline silicon, and more particularly, to a method of forming a silicon carbide film containing nanocrystalline silicon using a plasma deposition method.

Nano-crystal silicon (Si-NCs) has been recognized as a key element in the development of next-generation silicon-based optoelectronic devices and nano devices have attracted a lot of attention recently.

Processes for forming nanocrystalline structures based on silicon materials include a variety of process methods such as chemical vapor deposition (CVD), magnetron sputtering, and ion implantation. In order to form a nanocrystalline structure of a silicon material, in general, nanocrystal silicon is spontaneously formed by performing a heat treatment process after depositing silicon oxide or silicon nitride on a silicon substrate by a chemical vapor deposition method.

However, in such a process method, since the nanocrystalline silicon can be formed only by performing a heat treatment process at a high temperature (for example, 1000 ° C. or more), there is a problem in that the application range as a silicon-based optoelectronic device cannot be expanded. In particular, the temperature of the manufacturing process of an electronic display device such as a liquid crystal display (LCD), an organic electroluminescent display (OELD), and the like is a very important process condition. It is an obstacle to application in electronic display devices such as EL display devices.

In addition, since the method of forming nanocrystalline silicon on silicon carbide is not disclosed, it is difficult to develop a technology of a silicon carbide thin film mainly used in the next generation solar cell field.

One technical problem to be achieved by the present invention is to provide a method of forming a silicon carbide film containing nanocrystalline silicon.

A plasma gas is injected onto a substrate to provide a method of forming a silicon carbide film including nanocrystalline silicon.

The plasma gas may include a methane (CH 4) gas and a silane (SiH 4) gas, and the silicon carbide layer may include silicon carbide (SiC) or silicon oxycarbide (SiOC). The silicon carbide film and the nanocrystalline silicon are characterized in that formed at the same time.

The present invention provides a method of forming a silicon carbide film containing nanocrystalline silicon using a plasma deposition method.

Silicon carbide containing silicon carbide or silicon oxycarbide has high transmittance and luminous efficiency characteristics, and the nanocrystalline silicon (Si-NCs) has high luminous efficiency by acting as quantum dots having various energy levels. . Therefore, by forming a silicon carbide film containing nanocrystalline silicon according to the present invention, it is possible to increase the luminous efficiency of the silicon carbide film applied to the field of the next-generation solar cell.

In the method of forming a silicon carbide film including nanocrystalline silicon according to the present invention, a silane (SiH4) gas and a methane (CH4) gas are injected into a plasma gas to simultaneously form the nanocrystalline silicon and the silicon carbide film. This allows for a simple process and can be formed at low temperatures, thus reducing manufacturing costs.

In addition, the silicon carbide film including nanocrystalline silicon according to the present invention may be applied to various fields such as transistors, switching devices, memory devices, and solar cells.

1 is a cross-sectional view showing the structure of a silicon carbide film containing nanocrystalline silicon according to the present invention.
2 is a process flowchart showing a method of forming a silicon carbide film including nanocrystalline silicon according to the present invention.
3A to 3D are cross-sectional views illustrating a method of forming a nonvolatile memory device including a silicon carbide film according to an embodiment of the present invention.
4 is a cross-sectional view showing a structure and a manufacturing method of a solar cell including a silicon carbide film according to another embodiment of the present invention.
5 is a high-resolution transmission electron microscopy (HRTEM) photograph of a silicon carbide film including nanocrystalline silicon formed according to an embodiment of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS The above and other objects, features, and advantages of the present invention will become more readily apparent from the following description of preferred embodiments with reference to the accompanying drawings. However, the present invention is not limited to the embodiments described herein but may be embodied in other forms. Rather, the embodiments disclosed herein are provided so that the disclosure can be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.

In this specification, when it is mentioned that a film is on another film or substrate, it means that it may be formed directly on another film or substrate, or a third film may be interposed therebetween. Further, in the drawings, the thicknesses of the films and regions are exaggerated for an effective explanation of the technical content. Also, while the terms first, second, third, etc. in various embodiments of the present disclosure are used to describe various regions, films, etc., these regions and films should not be limited by these terms . These terms are only used to distinguish any given region or film from another region or film. Thus, the membrane referred to as the first membrane in one embodiment may be referred to as the second membrane in another embodiment. Each embodiment described and exemplified herein also includes its complementary embodiment.

1 is a cross-sectional view showing a silicon carbide film according to the present invention, Figure 2 is a process flowchart showing a method of forming a silicon carbide film according to the present invention.

1 and 2, the silicon carbide film 110 is formed on the substrate 100. The silicon carbide film 110 may include silicon carbide (SiC) or silicon oxycarbide (SiOC). The silicon carbide film 110 may include silicon nanocrytals (Si-NCs) 120.

The silicon carbide film 110 may be formed by a plasma deposition method, for example, plasma enhanced chemical vapor deposition (PECVD) or inductively coupled plasma CVD (ICP-CVD).

In order to form the silicon carbide layer 110, the substrate 100 is loaded into a plasma deposition chamber. (S11 of FIG. 2) After loading the substrate 100, plasma gas is injected into the plasma deposition chamber. (S12 of FIG. 2) The plasma gas may include a silane (SiH4) gas and a methane (CH4) gas. For example, the silicon carbide film 110 may be formed with a process pressure of about 0.5 Torr and a power of about 5W. The flow rate of the silane (SiH 4) gas may be fixed at 10 sccm, and the flow rate of the methane (CH 4) gas may be between 10 sccm and 60 sccm. The silicon carbide film 110 may be formed at approximately 250 ° C.

The silicon carbide layer 110 may be formed by injecting the plasma gas (S13 of FIG. 2). The nanocrystalline silicon (Si-NCs) 120 may simultaneously form the silicon carbide layer 110. Can be formed.

3A to 3D are cross-sectional views illustrating a method of forming a nonvolatile memory device including a silicon carbide film according to an embodiment of the present invention.

Referring to FIG. 3A, a method of forming a nonvolatile memory device according to an exemplary embodiment of the present invention includes forming a buffer film 210 and a silicon carbide film 220 on a substrate 200 in sequence. The substrate 200 may be a glass substrate. The buffer film 210 may be a silicon nitride film, a silicon oxide film, or a silicon carbide film. The buffer film 210 may be selected in consideration of thermal expansion or an interface state with another thin film. For example, the silicon nitride film may be formed to be 170nm to 230nm, the silicon oxide film may be formed to 70nm to 130nm.

The silicon carbide film 220 may be silicon carbide (SiC) or silicon oxycarbide (SiOC). The silicon carbide film 220 may include nanocrystalline silicon (Si-NCs) 225. The silicon carbide film 220 may be formed by a plasma deposition method, for example, plasma enhanced chemical vapor deposition (PECVD) or inductively coupled plasma CVD (ICP-CVD). The silicon carbide film 220 may be formed by injecting a silane (SiH 4) gas and a methane (CH 4) gas.

For example, the silicon carbide film 220 may be formed with a process pressure of about 0.5 Torr and a power of about 5W. The flow rate of the silane (SiH 4) gas may be fixed at 10 sccm, and the flow rate of the methane (CH 4) gas may be between about 10 sccm and 60 sccm. The silicon carbide film 220 may be formed at approximately 250 ° C.

When the nonvolatile memory device is used as a driving device of a flat panel display, as the thickness of the silicon carbide film 220 increases, the density of the driving current and the leakage current may increase. The silicon carbide film 220 may be formed to a thickness of approximately 40 nm to 60 nm in consideration of driving current and leakage current characteristics.

Referring to FIG. 3B, a tunneling insulating film 230 is formed on the silicon carbide film 220. The tunneling insulating film 230 may be a silicon oxide film, a silicon nitride film, or a silicon carbide film. The tunneling insulating film 230 may modify the surface of the silicon carbide film 220 by injecting nitrous oxide (N 2 O) gas onto the substrate 200 having the silicon carbide film 220.

The tunneling insulating layer 230 may be formed by a plasma deposition method, for example, plasma enhanced chemical vapor deposition (PECVD) or inductively coupled plasma CVD (ICP-CVD). For example, the tunneling insulating film 230 may be formed by inputting nitrous oxide gas at a flow rate of approximately 1.5 sccm to 5 sccm, and may be formed at a power of approximately 50 W to 550 W and a temperature of approximately 250 ° C. to 350 ° C.

For example, the tunneling insulating layer 230 may be formed at the same temperature as the temperature at which the silicon carbide film 220 is formed. The tunneling insulating layer 230 may be formed to have a thickness of approximately 2.0 nm to 3.0 nm to improve low operating voltage and memory retention characteristics.

Referring to FIG. 3C, the charge storage layer 240 and the blocking insulating layer 250 may be sequentially formed on the tunneling insulating layer 230. Each of the charge storage layer 240 and the blocking insulating layer 250 may be formed of a silicon nitride layer or a silicon oxide layer.

For example, when the charge storage layer 240 is formed of a silicon nitride layer, the blocking insulating layer 250 may be formed of a silicon oxide layer, and the charge storage layer 240 may be formed of a silicon oxide layer. The blocking insulating film 250 may be formed of a silicon nitride film. In this case, the silicon nitride film may be introduced at a flow rate of approximately 6: 4 silane gas (SiH 4) and ammonia gas (NH 3), and may be formed at a temperature of 300 ° C. and a power of 200 W. The silicon oxide film may introduce silane gas (SiH 4) and nitrous oxide gas (N 2 O) at a flow rate of approximately 6: 4, and may be formed at a temperature of 300 ° C. and a power of 250 W. The silicon nitride film may be formed to a thickness of about 15nm to 25nm, the silicon oxide film may be formed to a thickness of about 5nm to 15nm.

The charge storage layer 240 may include a material different from that of the blocking insulating layer 250. The gate electrode layer 260 may be formed on the blocking insulating layer 250. The gate electrode layer 260 may include at least one of aluminum (Al), chromium (Cr), silver (Ag), and gold (Au). The gate electrode layer 260 may be formed by crystallizing a laser on amorphous silicon.

Referring to FIG. 3D, the gate electrode layer 260, the blocking insulating layer 250, the charge storage layer 240, and the tunneling insulating layer 230 are sequentially patterned to partially expose the upper surface of the silicon carbide layer 220. Can be. A gate pattern 270 including the gate electrode layer 260, the blocking insulating layer 250, the charge storage layer 240, and the tunneling insulating layer 230 may be formed.

The silicon carbide layer 220 under the gate pattern 270 is defined as a channel region, and an ion implantation process is performed on the exposed silicon carbide layer 220 using the gate pattern 270 as a mask. The region 226 and the drain region 227 may be formed. As a result, a nonvolatile memory device according to an embodiment of the present invention can be formed.

4 is a cross-sectional view showing a structure and a manufacturing method of a solar cell including a silicon carbide film according to another embodiment of the present invention.

Referring to FIG. 4, a transparent conductive oxide layer 301 is stacked on a substrate 300, and p-type, i-type, and n-type semiconductor layers 302, 303, and 304 are sequentially formed, and a metal electrode thereon. 305 may be formed.

The substrate 300 may be glass, metal, plastic, or ceramics. The glass may include quartz glass, borosilicate glass, soda glass, lead glass, or lanthanum glass. The metal may comprise silver, copper, nickel, silicon, aluminum, iron, or stainless steel. The plastic may include polyimide, polyethersulfone, norbornene-based ring-opening polymer, or hydrogenated additives. The substrate 300 may have a shape of a lump, a plate, or a film.

The p-type, i-type, and n-type semiconductor layers 302, 303, and 304 may include silicon carbide. The silicon carbide film may be silicon carbide (SiC) or silicon oxycarbide (SiOC). The silicon carbide film may include nanocrystalline silicon. The silicon carbide film may be formed by a plasma deposition method, for example, plasma enhanced chemical vapor deposition (PECVD) or inductively coupled plasma CVD (ICP-CVD). The silicon carbide film may be formed using a silane (SiH 4) gas and a methane (CH 4) gas.

For example, the silicon carbide film may be formed with a process pressure of about 0.5 Torr and a power of about 5W. The flow rate of the silane (SiH 4) gas may be fixed at 10 sccm, and the flow rate of the methane (CH 4) gas may be between about 10 sccm and 60 sccm. The silicon carbide film may be formed at approximately 250 ° C. The silicon carbide film may have a thickness of about 0.005 μm to 20 μm.

The p-type, i-type, and n-type semiconductor layers 302, 303, and 304 may be a composite thin film including the silicon carbide film. The composite thin film may control conversion efficiency of each of the p-type, i-type, and n-type semiconductor layers 302, 303, and 304 by adjusting the content composition of amorphous silicon and crystalline silicon.

The i-type semiconductor layer 303 may form a p-type semiconductor layer by doping boron atoms, and may form an n-type semiconductor layer by doping arsenic, phosphorous, or antimony atoms. When the p-type, i-type, and n-type semiconductor layers 302, 303, and 304 are amorphous, a polycrystalline semiconductor thin film may be formed through high energy light treatment such as an excimer laser. Thereby, the solar cell containing the silicon carbide film containing nanocrystalline silicon can be manufactured.

5 is a high-resolution transmission electron microscopy (HRTEM) photograph of a silicon carbide film including nanocrystalline silicon formed according to an embodiment of the present invention.

Referring to FIG. 5, in order to form a silicon carbide film including nanocrystalline silicon according to the present invention, the flow rates of the silane (SiH 4) gas and the methane (CH 4) gas are injected at 20 sccm and 10 sccm, respectively, and the process pressure of the plasma is increased. The silicon carbide film is formed at 0.5 Torr, 5 W of power, and 250 ° C. of process temperature. The average diameter of the nanocrystalline silicon is 7nm, the nanocrystalline silicon may be crystallized with a hexagonal structure having a (0001) direction.

Claims (1)

In the method of forming a silicon carbide film containing nanocrystalline silicon by injecting a plasma gas on the substrate,
The plasma gas includes a methane (CH4) gas and a silane (SiH4) gas,
The silicon carbide film includes silicon carbide (SiC) or silicon oxycarbide (SiOC),
And the silicon carbide film and the nanocrystalline silicon are formed at the same time.
KR1020110083618A 2011-08-22 2011-08-22 The method of forming silicon carbide film comprising silicon nano-crystals KR20130022438A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101439422B1 (en) * 2014-04-15 2014-09-12 문갑영 Using a plasma method for producing a silicon-nano-particles colloid and cathode active material, lithium secondary cell using thereof
CN106044774A (en) * 2016-05-31 2016-10-26 上海纳晶科技有限公司 Preparation method of low-temperature, low-cost and high-purity ultra-fine silicon carbide particles
CN113488555A (en) * 2021-07-06 2021-10-08 安徽华晟新能源科技有限公司 Heterojunction cell, preparation method and solar cell module

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101439422B1 (en) * 2014-04-15 2014-09-12 문갑영 Using a plasma method for producing a silicon-nano-particles colloid and cathode active material, lithium secondary cell using thereof
WO2015160127A1 (en) * 2014-04-15 2015-10-22 문갑영 Method for preparing silicon nanocomposite dispersion using plasma, and anode active material and lithium secondary battery using same
CN106255662A (en) * 2014-04-15 2016-12-21 文甲永 Utilize the manufacture method of isoionic silicon nano composite material dispersion liquid and cathode active material and lithium secondary battery
CN106255662B (en) * 2014-04-15 2018-03-20 文甲永 Utilize the manufacture method and cathode active material and lithium secondary battery of the silicon nano composite material dispersion liquid of plasma
US10770722B2 (en) 2014-04-15 2020-09-08 Kab Young MOON Method for preparing silicon nanocomposite dispersion using plasma, and anode active material and lithium secondary battery using same
US10811679B2 (en) 2014-04-15 2020-10-20 Sino Applied Technology Co., Ltd. Method for preparing silicon nanocomposite dispersion using plasma, and anode active material and lithium secondary battery using same
CN106044774A (en) * 2016-05-31 2016-10-26 上海纳晶科技有限公司 Preparation method of low-temperature, low-cost and high-purity ultra-fine silicon carbide particles
CN106044774B (en) * 2016-05-31 2018-02-27 上海纳晶科技有限公司 A kind of preparation method of low temperature low cost high-purity silicon carbide ultrafine dust
CN113488555A (en) * 2021-07-06 2021-10-08 安徽华晟新能源科技有限公司 Heterojunction cell, preparation method and solar cell module

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