KR101788927B1 - Method for manufacturing a porous thin film - Google Patents

Method for manufacturing a porous thin film Download PDF

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KR101788927B1
KR101788927B1 KR1020150131424A KR20150131424A KR101788927B1 KR 101788927 B1 KR101788927 B1 KR 101788927B1 KR 1020150131424 A KR1020150131424 A KR 1020150131424A KR 20150131424 A KR20150131424 A KR 20150131424A KR 101788927 B1 KR101788927 B1 KR 101788927B1
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South Korea
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thin film
substrate
source powder
nanoparticles
chamber
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KR1020150131424A
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Korean (ko)
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KR20170033931A (en
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이선영
김형섭
박윤찬
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한양대학교 에리카산학협력단
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    • 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
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02203—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being porous
    • 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
    • H01L21/02002—Preparing wafers
    • H01L21/02005—Preparing bulk and homogeneous wafers
    • H01L21/0203—Making porous regions on the surface
    • 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
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • 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
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02587—Structure
    • H01L21/0259—Microstructure
    • H01L21/02601—Nanoparticles

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  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Nanotechnology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

Preparing a source powder comprising agglomerated agglomerates of nanoparticles comprising a metal oxide, preparing the source powder in a powder storage tank, contacting the powder storage tank Using the pressure difference of the chamber, accelerating the source powder, and providing the accelerated source powder onto the substrate in the chamber, thereby producing a thin film comprising the metal oxide on the substrate A method of manufacturing a porous thin film can be provided.

Description

TECHNICAL FIELD The present invention relates to a method for manufacturing a porous thin film,

The present invention relates to a method for producing a porous thin film, and more particularly, to a method for manufacturing a porous thin film produced by using agglomerates of agglomerated nanoparticles containing metal oxides.

BACKGROUND ART [0002] As semiconductor device technologies such as semiconductor memory devices, light emitting diodes, system semiconductor devices, power semiconductor devices, and super capacitors have been developed, thin film production methods having excellent characteristics have been researched to improve device reliability and lifetime.

Particularly, a method of manufacturing a thin film which can uniformly deposit on a complex substrate, select a desired region on a substrate of a specific type, enable localized deposition, and reduce a process time and a process cost by a simplified process Researches are being actively conducted.

For example, Korean Patent Publication No. KR20130013876A (Applicant: GS Caltex Co., Ltd., Application No. KR20110075780A) discloses a method of heating a substrate in a reaction space and then injecting a lithium precursor gas, phosphorus or boron precursor gas, The precursor gases react with each other to form a solid electrolyte thin film on the substrate by metal organic chemical vapor deposition (MOCVD), thereby uniformly depositing a thin film on the substrate, Discloses a technique for manufacturing a thin film and a manufacturing apparatus for minimizing damage of the thin film.

It is necessary to study a manufacturing method and a manufacturing apparatus of a thin film which can broaden the selection of a substrate on which a thin film is deposited and simplify a thin film manufacturing process and thereby reduce a process time and a process cost.

Korean Patent Publication No. KR20130013876A

SUMMARY OF THE INVENTION The present invention provides a method of manufacturing a porous thin film having a reduced process cost and process time.

It is another object of the present invention to provide a method for manufacturing a porous thin film whose porosity is controlled according to the roughness of a substrate.

 Another aspect of the present invention is to provide a method of manufacturing a porous thin film having controlled porosity according to the size of nanoparticles provided on a substrate.

It is another object of the present invention to provide a method of manufacturing a porous thin film in which porosity is controlled according to the diameter of agglomerated nanoparticles aggregated on a substrate.

The technical problem to be solved by the present invention is not limited to the above.

In order to solve the above-mentioned technical problems, the present invention provides a method for producing a porous thin film.

According to one embodiment, the method for preparing a porous thin film includes: preparing a source powder including agglomerated nano particles containing a metal oxide; The method comprising the steps of: preparing the metal powder in a powder storage tank; accelerating the source powder using a pressure difference between the powder storage tank and the chamber; and providing the accelerated source powder onto the substrate in the chamber, And then depositing a thin film on the substrate.

According to one embodiment, the method of manufacturing the porous thin film may include decreasing the porosity of the thin film as the diameter of the nanoparticles decreases.

According to one embodiment, the method of manufacturing the porous thin film may include controlling the porosity of the thin film according to the thickness of the thin film.

According to one embodiment, when the thickness of the thin film is equal to or greater than the reference thickness, voids may be formed in the thin film.

According to one embodiment, the step of creating a void in the thin film may include the step of deforming the thin film as the accelerated source powder collides with the thin film above the reference thickness.

According to one embodiment, the step of deforming the thin film comprising the metal oxide may include breaking down the aggregate colliding with the thin film to be separated into the nanoparticles.

According to one embodiment, the manufacturing method of the porous thin film may include that the reference thickness is the diameter of the aggregate.

According to one embodiment, the method of manufacturing the porous thin film may further comprise adjusting the roughness of the substrate before providing the accelerated source powder onto the substrate in the chamber.

According to one embodiment, adjusting the roughness of the substrate may comprise polishing, etching, and coating the surface of the substrate.

According to one embodiment, the method of manufacturing the porous thin film may include increasing the porosity of the porous film as the roughness of the substrate increases.

According to one embodiment, the interior of the chamber may include an atmospheric atmosphere.

According to one embodiment, the source powder may include an organic binder coating layer covering the aggregate surface.

According to an embodiment of the present invention, a source powder, which is an agglomerate of nanoparticles containing a metal oxide, is supersonically accelerated by a pressure difference between a powder storage tank and a chamber, , ≪ / RTI > Accordingly, the process is performed in a low vacuum and atmospheric atmosphere, so that the process time and process cost are reduced, the use of the coating material and the substrate is free, the use of the chemical is not required, and the process stability is high.

In addition, when the thickness of the thin film formed by depositing the source powder on the substrate is larger than the diameter of the aggregated body, that is, the reference thickness, the aggregated body colliding with the thin film is broken and separated into the nanoparticles, Due to the breakdown of the agglomerates constituting the thin film due to the impact energy of the agglomerates and the structural movement of the agglomerates, a porous thin film in which voids are generated inside the thin film and / or on the surface thereof can be produced. As described above, the formation of the thin film is caused by a simple physical or structural deformation such as destruction and migration of the aggregate, and it controls the diameter of the nanoparticles constituting the aggregate, the roughness of the substrate, and the thickness of the thin film A method of manufacturing a porous film having controlled porosity can be provided.

1 is a flowchart illustrating a method of manufacturing a porous thin film according to an embodiment of the present invention.
2 is a view for explaining a manufacturing apparatus for manufacturing a porous thin film according to a method of manufacturing a porous thin film according to an embodiment of the present invention.
3 is a view for explaining that a source powder is provided on a substrate according to an embodiment of the present invention.
4 is a view for explaining that a source powder is provided on a substrate to a reference thickness or less according to an embodiment of the present invention.
5 is a view for explaining that a source powder is provided on a substrate at a reference thickness or more to form a porous thin film according to an embodiment of the present invention.
FIG. 6 is SEM images of a thin film containing the metal oxide when nanoparticles containing a metal oxide according to a comparative example are provided on a substrate.
FIG. 7 is a graph showing the roughness of Si wafer, FTO glass, and Al 2 O 3 substrate applicable as a substrate in the manufacture of a thin film including a metal oxide according to an embodiment of the present invention.
FIG. 8 is SEM images of the thin film formed on a Si wafer, an FTO glass, and an Al 2 O 3 substrate according to an embodiment of the present invention.
9 is a graph showing the surface roughness of the Al 2 O 3 substrate when the polishing conditions of the Al 2 O 3 substrate are changed.
10 is SEM images of the thin film produced when a thin film is prepared on an Al 2 O 3 substrate having a different surface roughness.
11 is SEM images of a thin film including a metal oxide formed when the thickness of a thin film formed on a substrate is less than or equal to a reference thickness and according to an embodiment of the present invention.
Figure 12 is SEM images of the surface of a prepared thin film when the sizes of aggregates provided on the substrate are different according to an embodiment of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the technical spirit of 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 an element is referred to as being on another element, it may be directly formed on another element, or a third element 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 the various embodiments of the present disclosure are used to describe various components, these components should not be limited by these terms. These terms have only been used to distinguish one component from another. Thus, what is referred to as a first component in any one embodiment may be referred to as a second component in another embodiment. Each embodiment described and exemplified herein also includes its complementary embodiment. Also, in this specification, 'and / or' are used to include at least one of the front and rear components.

The singular forms "a", "an", and "the" include plural referents unless the context clearly dictates otherwise. It is also to be understood that the terms such as " comprises "or" having "are intended to specify the presence of stated features, integers, Should not be understood to exclude the presence or addition of one or more other elements, elements, or combinations thereof.

In addition, " porosity " described herein is used in the sense of " volume of void included in same volume ".

In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear. The scope of the present invention is not limited to the specific embodiments but should be construed according to the appended claims. It will also be appreciated that many modifications and variations will be apparent to those skilled in the art without departing from the scope of the invention.

FIG. 1 is a flow chart for explaining a method of manufacturing a porous thin film according to an embodiment of the present invention, and FIGS. 2 to 4 are views for explaining a method of manufacturing a porous thin film according to an embodiment of the present invention.

Referring to FIG. 1, a source powder is prepared (S100). The source powder may be an aggregate 230 of nano particles 200 containing a metal oxide. The metal oxide may include at least one of Fe, W, Cu, Mo, and Ni. For example, the diameters of the nanoparticles 200 may be 500 nm or less, and the diameters D of aggregates of the nanoparticles 200 may be 30 μm or less. The step of preparing the source powder may include a pulverization step, an aggregation step, a reduction heat treatment step, and a coating step.

In the pulverizing step, the metal oxide may be mechanically grinded to produce the nanoparticles 200 containing the metal oxide. For example, the mechanical milling may be a ball milling process. For example, the size of the nanoparticles may be 500 nm or less.

In the coagulation step, the nanoparticles 200 produced may be prepared as aggregates 230 by a spray dryer. The nanoparticles 200 may be mixed with an admixture and then injected into the spray dryer. Depending on the operating conditions and collection position of the spray dryer, the aggregates 230 of varying sizes may be obtained. For example, the aggregate (10 to 30 占 퐉) at the lower end of the drying tank of the dry sprayer and 1 to 5 占 퐉 at the middle of the exhaust pipe at the injection speed of 2500 cc / h, the injection pressure of 80 kPa, 230 may be manufactured. For example, the admixture may be PCA (Polycarboxylic Acid).

In the reduction heat treatment step, the produced aggregate 230 may be thermally treated under a hydrogen atmosphere to be plastically deformed into the aggregate 230 in the form of a network. For example, the heat treatment temperature may be 550 to 700 ° C.

In the coating step, an organic binder coating layer may be formed on the surface of the agglomerate 230 in the form of a network. For example, the method of coating the organic binder on the surface of the aggregate 230 may be a sol-gel method. The kind of the organic binder is not particularly limited. For example, it may be any one of low density binders such as stearic acid or wax series.

The source powder comprising the aggregate 230 may be prepared in a powder storage tank 640 (S200). The powder storage tank 640 may be connected to the chamber 500 in which the source powder is provided. The source powder may be accelerated using the pressure difference between the powder storage tank 640 and the chamber 500 connected to the powder storage tank 640 (S300). According to one embodiment, the source powder in the powder storage tank 640 may be injected into the chamber 500 and the injected source powder may be injected into the powder storage tank 640 and the chamber 500, By supersonic acceleration, and can be injected into the chamber 500 due to the pressure difference between them. The type of equipment in which the source powder is injected into the chamber 500 is not particularly limited. For example, it may be a nozzle or a needle. In addition, the inside of the chamber 500 may be an atmospheric atmosphere.

Referring to FIGS. 1 and 2, the accelerated source powder may be provided on the substrate 100 in a dry manner (S400). The substrate 100 may be any one of an Si wafer, an FTO glass, and an Al 2 O 3 substrate.

2 and 3, the accelerated source powder is provided on the substrate 100 in the chamber 500, and is formed on the substrate 100, A thin film 250 containing a metal oxide can be produced. The thin film 250 may be formed by adsorbing the accelerated source powder on the substrate 100. When the thickness T1 of the thin film 250 is thinner than the standard thickness of the aggregate 230 provided on the substrate 100, a substantially void is formed in the thin film 250 It may not exist. In other words, when the thickness of the thin film 250 is thinner than the reference thickness, the thin film 250 may have low porosity. The reference thickness may be substantially the same as the diameter D of the aggregate 230.

1 and 4, the accelerated source powder is continuously provided on a substrate 100 in the chamber such that the thickness T2 of the thin film 250 is greater than the thickness T2 of the substrate 100 provided on the substrate 100. [ When the thickness T2 of the thin film 250 is thicker than the reference thickness, the aggregate 230 colliding with the thin film 250 is broken , And nanoparticles (200). The impact of the agglomerate 230 on the thin film 250 may cause structural deformation of the inside and / or the surface of the thin film 250 to cause the inside of the thin film 250 and / (void) can be generated. Accordingly, the thin film 250 having the porous property of controlling the porosity of the thin film 250 may be formed according to the thickness of the thin film 250 formed on the substrate 100. Structural deformation of the interior and / or surface of the membrane 250 caused by collision of the agglomerate 230 may cause destruction of the agglomerate 230 constituting the membrane 250 and / ). ≪ / RTI >

The size and / or distribution of the voids of the porous membrane 250 may be adjusted such that the aggregate 230 and / or the aggregate 230 colliding with the membrane 230 constituting the membrane 250 Or may be determined by the size and / or distribution of the nanoparticles 200 that are broken and separated. Accordingly, as the size of the nanoparticles 200 constituting the aggregate 230 is smaller, the thin film 250 having a dense and tight structure can be formed. In other words, as the diameter of the nanoparticles 200 decreases, the porosity of the porous film 250 can be reduced.

The degree of porosity of the thin film 250 may be adjusted by adjusting the roughness of the substrate 100 before the accelerated source powder is provided on the substrate 100, Lt; / RTI > The larger the roughness of the substrate 100 is, the easier the nanoparticles 200 separated from the aggregates 230 and / or the aggregates 230 form a thin film of a dense tight structure on the substrate 100 I can not. Accordingly, as the roughness of the substrate 100 increases, the porosity of the thin film 250 can be increased.

Unlike the above-described embodiments of the present invention, when the thin film containing a metal oxide is formed by a dip coating, a spray coating, or a sol-gel method, The chemical is used in the process of producing the solution containing it, the process safety is low, and the loss of the raw material is high. Also, as the drying process is added, process time and process cost can be increased. In addition, when a thin film containing the metal oxide is produced by using the solution containing the metal oxide, cracks are generated in the thin film containing the metal oxide due to the volume expansion of the thin film have.

Further, when a thin film containing the metal oxide is produced by a physical vapor deposition process (PVD) process, the manufacturing cost may increase due to high vacuum conditions, and the target material may be thermally or electrically deformed. In addition, when a thin film containing the metal oxide is produced by a CVD (chemical vapor deposition) process, there is a problem that materials capable of being coated at a high reaction temperature are limited.

However, as described above, according to the embodiment of the present invention, the source powder, which is the aggregate 230 of the nanoparticles 200 including the metal oxide, is supersonic, due to the pressure difference between the powder storage tank and the chamber. ), And can be deposited dry on the substrate 100 in the chamber. Accordingly, the process is performed in a low vacuum and atmospheric atmosphere, so that the process time and process cost are reduced, the use of the coating material and the substrate is free, the use of the chemical is not required, and the process stability is high.

When the thickness of the thin film formed by depositing the source powder on the substrate 100 is larger than the diameter of the aggregate, that is, the reference thickness, the aggregate 230 colliding with the thin film 250 is broken, The nanoparticles 200 are separated into a plurality of nanoparticles 200 and the nanoparticles 200 are separated from the nanoparticles 200 by the breakage of the aggregates 230 constituting the thin film 250 due to the collision energy of the aggregates 230 with respect to the thin film 250, A porous thin film 250 in which voids are formed inside and / or on the thin film 250 can be manufactured. As described above, the formation of the thin film 250 is caused by a simple physical or structural deformation such as destruction and migration of the aggregate 230. The diameter of the nanoparticles 200 constituting the aggregate 230, A method of manufacturing a porous thin film having a controlled porosity can be provided through a simple method of controlling the roughness of the substrate 100 and the thickness of the thin film 250.

Hereinafter, an apparatus for manufacturing a thin film including a metal oxide according to one embodiment of the present invention described above will be described with reference to FIG.

5 is a view for explaining a manufacturing apparatus for manufacturing a thin film including a metal oxide according to a method of manufacturing a thin film including a metal oxide according to an embodiment of the present invention.

5, a thin film manufacturing apparatus includes a chamber 500, a stage 510, a nozzle 520, a camera 530, a control unit 532, a chamber pressure regulating unit 540, a pump 542 An air compressor 610, a filter 620, a regulator 630, a powder storage tank 640, and a spray generator 642.

The stage 510 may be disposed in the chamber 500. The substrate 100 may be seated on the stage 510. The stage 110 may be configured to move in first and second directions parallel to the paper surface and in a third direction perpendicular to the paper surface.

The air compression unit 510 may compress air to provide compressed air. Dust, oil, and the like can be removed while the compressed air passes through the filter 520. The compressed air may be supplied to the powder storage tank 540 through the regulator 530.

A source powder containing a metal oxide may be stored in the powder storage tank 540. The metal oxide may include at least one of Fe, W, Cu, Mo, and Ni, as described with reference to FIG. The source powder may comprise the aggregate 230, wherein the nanoparticles 200 comprising the metal oxide are aggregated, as described with reference to FIG.

The spray generator 542 may be disposed within the powder storage tank 540. By the spray generator 542, the source powder stored in the powder storage tank 540 can be sprayed. The powdered source powder is sprayed onto the substrate 100 in the chamber 500 by the compressed air provided from the air compression unit 510 so that the powder stored in the powder storage tank 540 and the chamber 500, As shown in Fig.

The chamber pressure regulator 540 and the pump 542 can maintain the inside of the chamber 500 in a low vacuum state. Accordingly, the pressure difference between the powder storage tank 540 and the chamber 500 is kept substantially constant, and the sprayed source powder is accelerated by the pressure difference, (Not shown). According to one embodiment, the inside of the chamber 500 may be an atmospheric atmosphere. The chamber pressure regulator 540 may be controlled by the controller 532.

With the source powder injected onto the substrate 100, a thin film containing the metal oxide can be produced on the substrate 100, as described with reference to Fig.

The camera 530 may photograph the thin film formed on the substrate 100 and transmit the thin film to the controller 532. The user can observe the formation process of the thin film through the control unit 532.

Hereinafter, characteristics evaluation results of the porous thin film produced according to the above-described embodiment of the present invention will be described.

6 is a SEM micrograph of a thin film containing the metal oxide (Fe 2 O 3) in the case of providing a nanoparticle comprising a metal oxide (Fe 2 O 3) according to a comparative example of an embodiment of the present invention on a substrate Images. 6 (a), 6 (b) and 6 (c) are SEM images of the surface of the thin film containing the metal oxide (Fe 2 O 3 ). 6 (b) is an enlarged view of FIG. 6 (a), and FIG. 6 (c) is an enlarged view of FIG. 6 (b). 6 (d) is an FIB-SEM image of the side surface of the thin film containing the metal oxide (Fe 2 O 3 ).

6, the metal oxide is iron oxide (Fe 2 O 3) a ball-milling (ball milling) to, iron oxides of 500nm or less (Fe 2 O 3) was prepared in nanoparticles. The iron oxide (Fe 2 O 3) nanoparticles were stored in a powder storage tank of a thin film production apparatus and dry-deposited on a substrate in a chamber in an atmospheric environment through a supersonic nozzle to obtain iron oxide (Fe 2 O 3 ) was prepared.

Using an FIB-SEM (Focused Ion Beam Scanning Electron Microscope) unit, and the iron oxide (Fe 2 O 3) instead of aggregates of nanoparticles, wherein the iron oxide (Fe 2 O 3) according to comparative example for the above-described embodiment The surface and side images of the thin film containing the metal oxide (Fe 2 O 3 ) prepared by spraying nanoparticles on the substrate were measured.

6 (a), 6 (b) and 6 (c), the metal oxide (Fe 2 O 3 ) prepared by spraying the iron oxide (Fe 2 O 3 ) nanoparticles onto the substrate It was confirmed that the porous structure was not formed well on the surface of the thin film. It was also confirmed that a mill scale, which is a by-product of iron oxide (Fe 2 O 3 ) nanoparticles, was laminated on the surface of the thin film.

As shown in FIG. 6 (d), it was confirmed that the porous structure was not formed well in the inside of the thin film, like the surface of the thin film. Accordingly, it was found that when the thin film was prepared by spraying the iron oxide (Fe 2 O 3 ) nanoparticles, which were not agglomerated agglomerated nanoparticles, on the substrate in a dry state, the porous thin film was not formed.

FIG. 7 is a graph showing the roughness of Si wafer, FTO glass, and Al 2 O 3 substrate applicable as a substrate in the manufacture of a thin film including a metal oxide according to an embodiment of the present invention.

Referring to FIG. 7, the surface roughness of the Si wafer, the FTO glass, and the Al 2 O 3 substrate was measured using a surface shape measuring instrument.

As can be seen from FIG. 7, the surface roughness of the Si wafer and the FTO glass was 0.01 μm, and the surface roughness of the Al 2 O 3 substrate was 0.37 μm. Thus, it was found that the surface roughness of the Al 2 O 3 substrate was significantly larger than the surface roughness of the FTO glass.

FIG. 8 is SEM images of the thin film formed on a Si wafer, an FTO glass, and an Al 2 O 3 substrate according to an embodiment of the present invention. Specifically, (a) of FIG. 8 (b) of an SEM image of a thin film formed on the Si wafer, Figure 8 is a SEM image of a thin film formed on the FTO glass, (c) of Fig. 8 Al 2 O 3 SEM image of the thin film formed on the substrate.

8, the metal oxide is iron oxide (Fe 2 O 3) a ball-milling (ball milling) to, iron oxides of 500nm or less (Fe 2 O 3) was prepared in nanoparticles. The iron oxide (Fe 2 O 3 ) nanoparticles were mixed with PCA (Polycarboxylic Acid) as an admixture, and then injected and sprayed into a spray dryer. Aggregates of the iron oxide (Fe 2 O 3 ) nanoparticles of 10 to 30 μm at the lower end of the drying tank of the dry atomizer and 1 to 5 μm at the middle of the exhaust pipe were obtained according to the collecting position of the dry atomizer. The aggregates were subjected to heat treatment at a temperature of 550 to 700 ° C under a hydrogen atmosphere to be subjected to plastic deformation, and an organic binder coating layer was formed on the surface of the aggregates to prepare a source powder. The source powder was stored in a powder storage tank of a thin film production apparatus and was then dry-deposited on a substrate (Si wafer, FTO glass, Al 2 O 3 substrate) in a chamber in an atmospheric environment through a supersonic nozzle To prepare a thin film containing the iron oxide (Fe 2 O 3 ).

(Fe 2 O 3 ) formed on the substrate (Si wafer, FTO glass, Al 2 O 3 substrate) according to the above-described embodiment using a scanning electron microscope (SEM) Images were measured.

8 (a) and 8 (b), when the thin film containing the metal oxide (Fe 2 O 3 ) is produced by spraying the aggregate on the Si wafer and the FTO glass , A porous structure was formed on the thin film, but it was confirmed that the porous structure was uneven.

8 (c), when the thin film containing the metal oxide (Fe 2 O 3 ) is produced by spraying the aggregate on the Al 2 O 3 substrate, It was confirmed that a porous structure was formed on the thin film formed on the Al 2 O 3 substrate in the same manner as the thin film formed on the FTO glass. However, it was confirmed that the porous structure of the thin film was more uniformly formed than the porous structure of the thin film formed on the Al 2 O 3 substrate.

7, and from the result of the results of Figure 8, the roughness having a value of 0.01㎛ Si wafer and the FTO glass phase on the Al 2 O 3 substrate having a relatively large roughness value 0.37㎛ than the case of manufacturing the thin film , It was confirmed that the porous structure of the thin film produced according to the embodiment of the present invention was more uniformly formed. Accordingly, it can be seen that as the roughness of the substrate used increases, the porosity of the thin film produced increases in manufacturing the thin film according to the embodiment of the present invention.

9 is a graph showing the surface roughness of the Al 2 O 3 substrate when the polishing conditions of the Al 2 O 3 substrate are changed.

The surface of the Al 2 O 3 substrate was polished by changing the polishing rate to 150 rpm and the polishing time to 2 min and changing the sand paper numbers to 100, 400 and 1000, and then the surface roughness value was measured using a shape measuring machine.

As can be seen from FIG. 9, when the sand paper number is 100, the surface roughness of the Al 2 O 3 substrate is 0.13 μm and the sand paper number is 400, the surface roughness of the Al 2 O 3 substrate is 0.16 μm, When the sand paper number was 1000, it was confirmed that the surface roughness of the Al 2 O 3 substrate was 0.17 μm.

10 are SEM images of Al 2 O 3 substrates having different surface roughnesses.

Surface images of Al 2 O 3 substrates with different surface roughness were measured using SEM (Scanning Electron Microscope) equipment.

Referring to FIG. 10, it can be seen that the surface structure of the Al 2 O 3 substrate is easily controlled according to the sand paper number, that is, the type of the sand paper. In other words, when the porous thin film according to the embodiment of the present invention is manufactured on a substrate having a surface roughness value controlled by using a sand paper, the porosity of the porous thin film can be easily controlled .

11 is SEM images of a thin film including a formed metal oxide when the thickness of the thin film formed on the substrate is less than or equal to a reference thickness according to an embodiment of the present invention. 11 (a) and 11 (b) show the case where the thickness of the thin film formed on the substrate is smaller than the diameter (5 탆) of the aggregate (thin film thickness: (a) (b) 2 to 3 탆), and Fig. 11 (c) shows an SEM image of the thin film formed on the substrate when the thickness of the thin film formed on the substrate is larger than the diameter (5 탆) ). ≪ / RTI >

11, an agglomerate of the iron oxide (Fe 2 O 3 ) nanoparticles having a diameter of 5 μm produced in the same manner as described with reference to FIG. 8 was sprayed onto the Al 2 O 3 substrate, Fe 2 O 3 ) was prepared.

The thickness of the thin film containing iron oxide (Fe 2 O 3 ) formed on the Al 2 O 3 substrate was measured using a Scanning Electron Microscope (SEM) apparatus to measure the diameter of the agglomerate of the iron oxide (Fe 2 O 3 ) The thickness of the thin film containing the iron oxide (Fe 2 O 3 ) formed on the Al 2 O 3 substrate is preferably not more than 5 μm (thin film thickness: (a) less than 2 μm, (b) a surface image of the thin film formed was measured on: (5.19㎛ film thickness) wherein the iron oxide (Fe 2 O 3) in the case of aggregates of the nanoparticles is greater than the diameter (5㎛).

11 (a) and 11 (b), when the thickness of the thin film containing iron oxide (Fe 2 O 3 ) formed on the Al 2 O 3 substrate is less than the thickness of the iron oxide (Fe 2 O 3 ) is smaller than the diameter (5㎛) of aggregates of nanoparticles (film thickness: (a) 2㎛ less, (b) 2 ~ 3㎛) , the Al 2 O 3 deposition of the aggregate on the substrate is not easily done or , It was confirmed that non-uniform lamination occurred and that the porous network was not formed in the thin film.

On the other hand, as shown in FIG. 11 (c), when the thickness of the thin film containing iron oxide (Fe 2 O 3 ) formed on the Al 2 O 3 substrate is smaller than the thickness of the aggregate of iron oxide (Fe 2 O 3 ) When the diameter was larger than 5 mu m (thin film thickness: 5.19 mu m), it was confirmed that a porous network was formed in the thin film. It is considered that the porous thin film produced voids inside and / or on the surface of the thin film due to the destruction of the aggregate and the structural movement of the aggregate as the stacking of the aggregate proceeds on the substrate . Therefore, when the thickness of the thin film containing iron oxide (Fe 2 O 3 ) formed on the Al 2 O 3 substrate is larger than the diameter of the aggregate of the iron oxide (Fe 2 O 3 ) nanoparticles, that is, the reference thickness, It was found that the porous network structure was well formed in the thin film.

FIG. 12 is SEM images of the surface of a prepared thin film when aggregate sizes provided on a substrate are different according to an embodiment of the present invention. 12 (a) is a SEM image of a surface of the prepared thin film when the diameter of the aggregate is 1 to 5 m, and Fig. 12 (b) is a SEM image of the thin film when the diameter of the aggregate is 10 to 30 m, SEM image of the surface of the prepared thin film.

12, FIG prepared in the same manner as described with reference to 81 to 5㎛ the iron oxide having a diameter of (Fe 2 O 3) aggregates of the nanoparticles and from 10 to 30㎛ the iron oxide having a diameter of (Fe 2 O 3 ) Agglomerates of nanoparticles were sprayed on the Al 2 O 3 substrate to prepare a thin film containing the iron oxide (Fe 2 O 3 ).

(Fe 2 O 3 ) nanoparticles having a diameter of 1 to 5 μm on the Al 2 O 3 substrate using an SEM (Scanning Electron Microscope) apparatus, and a thin film having a diameter of 10 to 30 μm The surface image of the thin film formed by spraying agglomerates of iron oxide (Fe 2 O 3 ) nanoparticles was measured.

12 (a) and 12 (b), the porous structure of the thin film formed by spraying aggregates of iron oxide (Fe 2 O 3 ) nanoparticles having a diameter of 1 to 5 μm on the Al 2 O 3 substrate (Fe 2 O 3 ) nanoparticles having a diameter of 10 to 30 μm were sprayed onto the Al 2 O 3 substrate to form uniformly more uniformly than the porous structure of the thin film formed by spraying agglomerates of the iron oxide (Fe 2 O 3 ) nanoparticles having a diameter of 10 to 30 μm. As a result, the smaller the size of the agglomerate of the iron oxide (Fe 2 O 3 ) nanoparticles provided on the Al 2 O 3 substrate, the better the network structure was formed in the thin film.

When the thickness of the thin film formed by depositing the source powder on the substrate is larger than the diameter of the aggregated body, that is, the reference thickness, the aggregated body colliding with the thin film is broken and separated into the source particles, Due to the collision energy of the agglomerate on the agglomerates, the aggregation of the agglomerates and the structural movement of the agglomerates, a porous thin film having voids formed therein and / or on the surface can be produced. Accordingly, a method of fabricating a porous thin film having controlled porosity can be provided through a very simple method of controlling the nanoparticles forming the aggregate, the roughness of the substrate, and the thickness of the thin film.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the scope of the present invention is not limited to the disclosed exemplary embodiments. It will also be appreciated that many modifications and variations will be apparent to those skilled in the art without departing from the scope of the invention.

100: substrate
200: nanoparticles
230: Aggregate
250: Thin film
500: chamber
510: stage
520: Nozzle
530: Camera
532:
540: chamber pressure regulator
542: Pump
610: air compression unit
620: filter
630: Regulator
640: Powder storage tank
642: Spray generator

Claims (12)

Preparing a source powder comprising agglomerates of agglomerated nanoparticles comprising a metal oxide;
Preparing the source powder in a powder storage tank;
Accelerating the source powder using a pressure difference between the powder storage tank and the chamber; And
Providing the accelerated source powder on a substrate in the chamber to produce a thin film comprising the metal oxide on the substrate,
Wherein the source powder is accelerated at a supersonic speed so that in the course of providing the source powder onto the substrate, the aggregate is separated into nanoparticles,
The thin film is produced by a dry process,
Wherein the porosity of the thin film is controlled according to the thickness of the thin film.
The method according to claim 1,
Wherein the porosity of the thin film decreases as the diameter of the nanoparticles decreases.
delete The method according to claim 1,
Wherein voids are generated in the thin film when the thickness of the thin film is equal to or greater than a reference thickness.
5. The method of claim 4,
The step of generating a void in the thin film may include:
Wherein the accelerated source powder collides with the thin film over the reference thickness to deform the thin film.
delete 5. The method of claim 4,
Wherein the reference thickness is a diameter of the agglomerate.
The method according to claim 1,
Before providing the accelerated source powder onto the substrate in the chamber,
And adjusting the roughness of the substrate.
9. The method of claim 8,
Wherein adjusting the roughness of the substrate comprises:
And polishing, etching, and coating the surface of the substrate.
9. The method of claim 8,
Wherein porosity of the porous film is increased as the roughness of the substrate is increased.
The method according to claim 1,
Wherein the inside of the chamber is in an air atmosphere.
The method according to claim 1,
Wherein the source powder comprises an organic binder coating layer covering the surface of the agglomerate.
KR1020150131424A 2015-09-17 2015-09-17 Method for manufacturing a porous thin film KR101788927B1 (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101194375B1 (en) * 2011-04-25 2012-10-25 한국과학기술원 Photo absorbing layer including spherical cu2ingase2 agglomolates, and solar cells using the same, and the fabrication method thereof

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KR20130013876A (en) 2011-07-29 2013-02-06 지에스칼텍스 주식회사 Method of deposition solid electrolyte film and apparatus for the same

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101194375B1 (en) * 2011-04-25 2012-10-25 한국과학기술원 Photo absorbing layer including spherical cu2ingase2 agglomolates, and solar cells using the same, and the fabrication method thereof

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