KR101940138B1 - Preparation method of sintered structures of nano-sized particles - Google Patents
Preparation method of sintered structures of nano-sized particles Download PDFInfo
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- KR101940138B1 KR101940138B1 KR1020150114933A KR20150114933A KR101940138B1 KR 101940138 B1 KR101940138 B1 KR 101940138B1 KR 1020150114933 A KR1020150114933 A KR 1020150114933A KR 20150114933 A KR20150114933 A KR 20150114933A KR 101940138 B1 KR101940138 B1 KR 101940138B1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
- B82B3/0009—Forming specific nanostructures
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
- B82B3/0009—Forming specific nanostructures
- B82B3/0019—Forming specific nanostructures without movable or flexible elements
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The present invention relates to a method of making a sintered nanoparticle structure, comprising: forming a nanoparticle structure on a substrate; And irradiating and sintering the nanoparticle structure with an electron beam. The method according to the present invention enables selective sintering of the nanoparticle structures on the substrate by controlling the electron beam irradiated region, can sinter the nanoparticle structure in a desired pattern, and is superior to the conventional sintering process using high temperature heat It is easy to sinter in a quick manner. In addition, the nanoparticle structure sintered by the above-described method can exhibit effects such as improvement in mechanical stiffness and electrical characteristics.
Description
The present invention relates to a method of making a sintered nanoparticle structure.
Nanotechnology is a technology that utilizes and studies nanostructures with zero-dimensional and one-dimensional structures below 100 nm. Since nanostructures exhibit characteristics such as quantum confinement effect, Hall-petch effect, lowering of melting point, resonance phenomenon, and excellent carrier mobility compared with conventional bulk and thin film type structures, And devices requiring high efficiency (for example, chemical batteries, solar cells, semiconductor devices, chemical sensors, photoelectric devices, etc.).
These nanostructures are manufactured in a "top-down" fashion and are now being manufactured in a "bottom-up" fashion to grow nanostructures from nanometer-scale building blocks. As the "bottom-up" method, thermal chemical vapor deposition (CVD), metal-organic chemical vapor deposition (MOCVD), pulsed laser deposition (PLD) Liquid phase growth methods such as vapor-liquid-solid method using a catalytic reaction such as atomic layer deposition (ALD), self-assembly and hydrothermal method, have. For example, Korean Patent Laid-Open Nos. 10-2010-0097549, 2006-224296, and 2006-306688 can be referred to.
In particular, ion assisted aerosol lithography (IAAL) can pattern high-purity nanoparticles generated in the gaseous state and can form nanoparticles without the limitation of the materials of the substrate and the particles, It can be applied to the field.
However, the 3-dimensional nanostructure manufactured using the IAAL technique has a problem that it is easily damaged by external force, which may hinder its application to various application fields.
A problem to be solved by the present invention is to provide a method for producing a sintered nanoparticle structure using an electron beam.
Another object of the present invention is to provide a sintered nanoparticle structure with improved electrical and mechanical properties.
Another object of the present invention is to provide an electronic device including the sintered nanoparticle structure.
In order to solve the problems according to the present invention,
Forming a nanoparticle structure on the substrate; And
And irradiating the nanoparticle structure with an electron beam to sinter the nanoparticle structure.
In the present invention, the nanoparticle structure may be a three-dimensional structure made of nanoparticles or a layered structure.
According to one embodiment, the nanoparticle structure formed on the substrate may be partially selected and sintered.
According to one embodiment, the size of the three-dimensional structure after the electron beam irradiation can be contracted symmetrically or asymmetrically.
According to one embodiment, the nanoparticle structure formed on the substrate can be partially selected and sintered.
According to one embodiment, the sintering method comprises:
Placing a mask in which fine patterns are perforated on a substrate on which the nanoparticle structure is formed and irradiating the mask with an electron beam to selectively sinter the nanoparticle structure located in the perforated portion,
Or by selectively sintering by adjusting the electron beam irradiation magnification.
According to one embodiment, the irradiation time of the electron beam for sintering the nanoparticle structure may be 0.01 second to 1 hour.
According to one embodiment, the electron beam may be irradiated with an energy density of 1 x 10 -7 to 1 x 10 8 W / cm 2 .
According to one embodiment, the nanoparticles may be formed using a combination of spark discharge, corona discharge, or both.
According to one embodiment, the size of the nanoparticles constituting the nanoparticle structure may be 1 nm to 300 nm.
According to one embodiment, the apparatus for generating an electron beam
An electron gun that generates electrons;
A condenser lens for collecting the electron beam generated from the electron gun at one point;
A deflection coil for adjusting the direction of the electron beam;
A diaphragm for adjusting an irradiation amount of the electron beam to be irradiated; And
And an objective lens for adjusting the focus of the electron beam to be irradiated.
According to one embodiment, the nanoparticle structure may be composed of at least one selected from a single metal, two or more complex metals, or oxides thereof.
According to one embodiment, the metal may be at least one of copper, tin, silver, zinc, platinum, palladium, gold, indium, cadmium, titanium and aluminum or oxides thereof.
According to one embodiment, the nanoparticle structure may be formed by an ion assisted aerosol lithography (IAAL) method.
According to one embodiment, the nanoparticle structure may be in the form of a flower having three or more petals.
The nanoparticle layer structure
Generating metal nanoparticles through a spark discharge in a spark discharge tube equipped with a conductive substrate; And
And the metal nanoparticles are deposited on the conductive substrate.
According to one embodiment, the metal nanoparticles may be an oxide of titanium.
According to one embodiment, the layer structure of the metal nanoparticles may be a porous layer of metal nanoparticles.
According to one embodiment, the conductive substrate may be an FTO or ITO substrate, or a transparent substrate coated with at least one of FTO and ITO.
The present invention provides an electronic device manufactured by the above manufacturing method.
The present invention provides a solar cell including the electronic device.
In order to solve the other problems of the present invention, there is provided a sintered nanoparticle structure produced by the above method.
In order to solve still another problem of the present invention, there is provided an electronic device or a solar cell device including the sintered nanoparticle structure.
The sintering method of the nanoparticle structure using the electron beam according to the present invention is advantageous in that the selective sintering can be performed and a method capable of manufacturing a sintered nanoparticle structure faster and easier than the conventional sintering process using high temperature heat to be.
In addition, the nanoparticle structure sintered in the above-described manner can exhibit such effects as improving stability against external force due to an increase in mechanical rigidity and improving electrical characteristics due to reduction in electrical resistance by increasing the structural density.
FIG. 1 is a conceptual diagram for explaining the principle of transferring energy from a nanoparticle image by an electron beam when an electron beam is irradiated.
2 is a conceptual diagram illustrating the concept of Joule's heating.
3 is a schematic diagram showing the general structure of a SEM column that can be used in the present invention.
4 is a flow chart showing a selective sintering process of a substrate on which a nanoparticle structure is formed.
5 shows an SEM image of a nanoparticle structure according to electron beam irradiation time.
FIG. 6 is a SEM image of a nanoparticle structure according to an electron beam irradiation time of a nanoparticle structure made of nanoparticles smaller than the nanoparticle of FIG. 5.
7 shows a cross-sectional SEM image of a nanoparticle structure before and after electron beam irradiation.
8A shows an SEM image of a portion irradiated with an electron beam after the selective sintering process.
FIG. 8B shows an SEM image of a portion where the electron beam is not irradiated after the selective sintering process.
9A shows a measurement method of conductive AFM (Atomic Force Microscopy).
FIG. 9B is a voltage-current curve showing the results of the conductive AFM measurement according to the electron beam intensity.
10 is an SEM image showing shrinking phenomenon of the nanoparticle structure before and after electron beam irradiation.
11 is an SEM image of a selectively sintered nanoparticle structure substrate.
12 is a graph showing changes in scattering intensity and wavelength of a nanoparticle structure according to electron beam sintering intensity.
13 shows a manufacturing process of a TiO 2 porous layer using electron beam sintering.
14 is a cross-sectional SEM image of a solar cell including a TiO 2 porous layer after sintering.
15 is a graph of a short-circuit current (J sc ) -external voltage (V oc ) curve of an electronic device according to Example 13 and Comparative Example 3.
Hereinafter, the present invention will be described in more detail.
As used herein, the term " nanoparticle structure " is meant to encompass not only three-dimensional structures made of nanoparticles but also planar structures (layers, films, or film shapes).
A three-dimensional structure refers to a three-dimensional three-dimensional structure having a wide size ranging from several nm to several 탆 in size. Such a nanoparticle structure may be formed by accumulation of nanoparticles having a size of several nanometers to several micrometers, or may be formed into a bulk (chunk) shape.
The " fine pattern " may have various shapes in a pattern having a line width of several nanometers to several tens of micrometers.
The nanoparticles are materials that can be sintered by an electron beam, for example, metal nanoparticles or metal oxide nanoparticles, and the kind of metal may be a single component or a composite component. Here, the term 'metal nanoparticle' can be used to cover both metal oxide nanoparticles and composite metal nanoparticles.
According to the present invention,
Forming a nanoparticle structure on the substrate; And
Irradiating the nanoparticle structure with an electron beam and sintering the nanoparticle structure;
To a sintered nanoparticle structure according to an electron beam sintering method.
The present invention also provides a sintered nanoparticle structure in the manner described above.
The present invention relates to a method for sintering a nanoparticle structure using an electron beam, which can replace a conventional sintering process which has been carried out at a high temperature, can more easily and quickly sinter the nanoparticle structure, And the degree of sintering can be controlled easily.
According to one embodiment, the nanoparticle structure may be a three-dimensional structure composed of nanoparticles, and the size of the nanoparticles may be 1 to 300 nm.
The nano-structure sintered with the electron beam can be made more dense, the density and stiffness can be controlled from the morphology, and according to one embodiment, the density and rigidity are strengthened, .
The intensity of the electron beam irradiated can be controlled by the current, the acceleration voltage, the irradiation time of the electron beam, and the area of the irradiation region. By controlling the elements, the degree of sintering of the nanoparticle structure can be controlled, The physical and electrical properties such as morphology, density and size can be controlled.
Sintering by electron beam irradiation can be sintered by the principle that the metal particles are heated by heat energy derived from the kinetic energy of the accelerated electron beam.
Further, as the intensity of the accelerating voltage is increased, sintering on the nanoparticle structure can occur over a deeper and wider region. Further, as the element number of the metal particles forming the nanoparticle structure becomes smaller, electron transfer occurs more rapidly , The sintering speed may be faster. The principle described above is shown in Fig.
Further, the size of the nanoparticle structure may be contracted after the electron beam irradiation, and the degree of shrinkage may be increased in proportion to the intensity of the irradiated electron beam. It is also possible to produce a structure having an asymmetric structure by varying the degree of shrinkage and sintering by selective irradiation of electron beams.
According to one embodiment, the sintering process by electron beam irradiation may be conducted for several seconds to several hours, for example, 0.01 seconds to 1 hour or 0.1 seconds to 30 minutes, preferably 30 seconds to 20 minutes But the present invention is not limited thereto and the irradiation time can be adjusted according to the energy intensity of the electron beam and the area of the irradiation area.
Also, the irradiation energy density of the electron beam used to produce the sintered nanoparticle structure according to the present invention may be 1.0 x 10 -7 to 1.0 x 10 8 W / cm 2 .
The electron beam sintering method according to the present invention can also be described as being sintered in the conductive particles by joule heating from the electric current flowing through the conductive particles.
Therefore, the principle of the sintering process according to the present invention can be explained in two ways. First, sintering reaction by heat energy derived from the kinetic energy of the accelerated electron beam. Second, sintering reaction by Joule heating. FIG. 2 illustrates the reaction principle of Joule's heating.
The following formula 1 shows the temperature variation of the nanoparticles upon Joule heating on a nanoparticle structure made of nanoparticles.
[Formula 1]
In the above formula (1)
v is the volume of the nanoparticles,
c v , p is the specific heat capacity of the nanoparticles,
Q is Joule's Heating as expressed by
[Formula 2]
In
I p is the intensity of the current passing through the nanoparticles,
R c is the contact resistance due to the interface between the particle and the particle and the surface of the particle,
t is elapsed time.
In the above formula, R c is a value determined from the following
[Formula 3]
In Equation (3)
ρ c is the resistivity value of the nanoparticle material at the contact,
z o is the distance between the nanoparticles,
A c is a value indicating a contact area between nanoparticles as a 2 / r,
a is the contact radius between the nanoparticles,
r is the radius of the particle.
The contact radius and the contact resistance of the nanoparticles can be determined from the equations (1) to (3), and the equation (1) can be expressed by the following equation (4).
[Formula 4]
Therefore, from the above equation, the temperature change caused by the electron beam irradiation is proportional to the intensity of the current, which can be related to the intensity of the electron beam, and is inversely proportional to the distance between the nanoparticles constituting the nanostructure and the radius of the atom .
Further, in the sintering method according to the present invention, since the sintering reaction occurs only at the portion irradiated with the electron beam, the sintering region, shape and area on the substrate can be selected and sintered as desired.
The apparatus for generating an electron beam for sintering can be used without limitation as long as it generates an electron beam, and may preferably be a device having a columnar structure of a scanning electron microscope as shown in Fig.
The electron beam generating apparatus includes:
An electron gun that generates electrons;
A condenser lens for collecting the electron beam generated from the electron gun at one point;
A deflection coil for adjusting the direction of the electron beam;
A diaphragm for adjusting an amount of the irradiated electron beam; And
And an objective lens positioned at an upper end of the irradiation area and controlling the focus of the electron beam to be irradiated.
According to one embodiment, the irradiation area of the electron beam can be adjusted using the magnification of the objective lens.
According to the present invention, sintering in a selective region is possible by utilizing the fact that sintering is not performed in an area not irradiated with an electron beam. That is, it is necessary to heat the entire region by sintering the partial region by applying heat as a whole. However, by using the electron beam, it is possible to adjust the irradiation magnification or irradiate the electron beam with a desired portion and pattern using a mask pattern, Lt; RTI ID = 0.0 > sintering < / RTI > For example, a nanoparticle structure can be selectively sintered in the fine pattern shape using a mask having a fine pattern shape. A method of fabricating a sintered nanoparticle structure using a mask drilled with the fine pattern is schematically shown in FIG. 4. Referring to FIG. 4, the method may include the following steps.
Positioning a mask having a fine pattern perforated on the substrate on which the nanoparticle structure is formed; And
And selectively sintering the nanoparticle structure located in the perforated portion by irradiating the mask with an electron beam. The nanoparticle structure can be selectively sintered according to a fine pattern.
According to the present invention, the metal nanoparticles may be at least one of copper, tin, silver, zinc, platinum, palladium, gold, indium, cadmium, titanium and aluminum or oxides thereof, Or a combination of two or more metals.
The size of the nanoparticles constituting the nanoparticle structure may be 1 to 300 nm, preferably 5 to 200 nm, and more preferably 5 to 100 nm. As the size of the nanoparticles becomes smaller, the sintering can be performed in a shorter time, the porosity decreases, and a nanoparticle structure having a higher density can be formed. In the case of particles larger than the above range, the energy required for sintering is increased The sintering efficiency may be lowered. It is also possible to use various sizes of particles together to increase the sintering efficiency.
The sintered nanoparticle structure according to the present invention can be manufactured by a conventional method of forming nano / microstructures and nanoparticles such as photolithography or chemical methods, thermal deposition methods, and ion assisted aerosol lithography (IAAL) But may be formed by a patterning technique to fabricate a micro or nano-sized three-dimensional structure at a desired position using ion assisted aerosol lithography (IAAL), according to one embodiment. .
In addition, the nanoparticle structure may have a flower-like structure having three or more petals. Such a structure has an effect of locally increasing the electric field intensity at the portion between the leaf and the leaf and the sharp shape of the structure. , And a place where the electric field is large in size is called a hot spot. A surface plasmon phenomenon may actively occur at the position of the hot spot.
In addition, the nanoparticle structure formed by the above-described method can be sintered with an electron beam to control the optical characteristics by electrical and mechanical characteristics and shrinkage phenomenon.
The sintered nanoparticle structure may be applied to various electronic devices, for example, an electronic device using an organic or inorganic semiconductor device. Examples of the electronic device usable in the embodiment of the present invention include a compound semiconductor light emitting diode (LED), an inorganic solar cell made of silicon or a compound semiconductor, an organic light emitting diode (OLED), an organic photovoltaic, a nonvolatile memory cell, a tandem solar cell, , But the present invention is not limited thereto.
For example, the nanoparticle structure may include at least one functional layer selected from an upper electrode layer, a lower electrode layer, and other organic and inorganic layers to which a nanoparticle structure is applied,
Introducing a nanoparticle structure layer before, during, or after forming the functional layer; And
And irradiating the nanoparticle structure layer with an electron beam to sinter the nanoparticle structure.
More specifically,
Placing a conductive substrate on an electrode of a reactor equipped with an electrode in a body and applying a voltage using a voltage supply means;
Simultaneously or individually generating ions or nanoparticles by spark discharge;
Inducing and depositing nanoparticles or ion particles generated by spark discharge on the conductive substrate to form a nanoparticle structure and a nanoparticle layer; And
And irradiating and sintering the nanoparticle structure and nanoparticle layer formed on the substrate with an electron beam.
The conductive substrate may be one commonly used for electronic devices, and the surface of the substrate may be a conductor, a semiconductor or a nonconductor. For example, a transparent substrate coated with indium tin oxide (ITO) or fluorine-containing tin oxide Substrate.
The method of manufacturing a nanoparticle structure using the spark discharge is a method of generating bipolar charged nanoparticles and ions simultaneously by spark discharge, injecting the charged nanoparticles into a reactor where electrodes exist, It can be deposited on a substrate located on the electrode or electrode regardless of the polarity. The spark discharge chamber is useful for manufacturing nanoparticles of various materials as disclosed in Korean Patent Application Publication No. 10-2009-0089787 (published on Aug. 24, 2009). Such a spark discharge may be performed, for example, by applying a voltage of about 1 to about 10 kV, preferably about 4 to about 10 kV, and when applying corona discharge together, a voltage of about 1 to about 10 kV Can be applied. Also, the polarity of the polarity opposite to the polarity of the charged particles can be applied to the electrode at an intensity of 0.1 to 8 kV.
The electric device including the nanoparticle structure sintered by the electron beam can improve the characteristics of the device such as the output efficiency. Such an effect is due to the increase in conductivity due to the improvement of the electron transfer ability between the particles by electron beam sintering .
Hereinafter, examples and experimental examples of a method for producing a nano three-dimensional structure sintered with an electron beam will be described. However, the following examples are only illustrative of the present invention and should not be construed as limiting the scope of protection of the present invention.
Production Example 1
Using a method for forming a three-dimensional nanoparticle structure using the IAAL technique described in Korean Patent Registration No. 1349976, four petals (Ag) nanoparticles each having a diameter ranging from 1 to 50 nm in diameter Was formed on the substrate.
Production Example 2
A flower-shaped nanoparticle structure having four petals, made of silver (Ag) nanoparticles, produced in the same manner as in Production Example 1 and having a diameter ranging from 1 to 30 nm in diameter, was formed on the substrate.
Production Example 3
A flower-shaped nanoparticle structure having four petals, made of silver (Ag) nanoparticles, prepared in the same manner as in Preparation Example 1 and having a diameter corresponding to a range of 1 to 300 nm, was formed on a substrate.
Of nano three-dimensional structures Morphology Change measurement
Example 1
The nanoparticle structures of Preparation Example 1 were sintered under the electron beam irradiation conditions shown in Table 1 below, and morphology changes of the nanoparticle structures were observed according to irradiation time. The SEM image according to the measurement result is shown in FIG.
Example 2
The nanoparticle structures of Preparation Example 2 were sintered under the electron beam irradiation conditions shown in Table 1 below to observe morphology changes of the nanoparticle structures according to the irradiation time. An SEM image according to the measurement result is shown in FIG.
Example 3
The nanoparticle structures of Preparation Example 3 were observed for morphology changes of the nanoparticle structures sintered under the electron beam irradiation conditions shown in Table 1 below. An SEM image showing the above results is shown in Fig.
(A)
(μm 2 )
(minute)
Figures 5 and 6 show the porosity change of the nanoparticle structure with electron beam irradiation time. From FIGS. 5 and 6, it can be seen that the longer the irradiation time of the electron beam is, the more dense the morphology is formed.
5 and 6 show that Example 2 having smaller metal nanoparticles sintered at a shorter irradiation time than Example 1 under the same accelerating voltage and current conditions, It is possible to form a more dense morphology than the nanoparticle structure of Example 1.
From the results of FIG. 7, the difference in the density of the nanoparticle structure before and after the electron beam irradiation is remarkably shown, and this effect can improve the mechanical properties and electrical characteristics of the sintered nanoparticle structure.
Stiffness evaluation of nanoparticle structures
Example 4
An electroconductive mask punched in the form of " SNU " was placed on the substrate on which the nanoparticle structure produced in Production Example 3 was formed, and an electron beam was irradiated under the conditions shown in Table 2 below to form a substrate, And sintered. After completion of the sintering, the mask was removed, and the substrate irradiated with the electron beam was subjected to an ultrasonic wave decomposition step under the conditions of a power of 200 W and a frequency of 40 kHz.
(kV)
The results of the sintering process using the mask and the ultrasonic degradation are shown in Fig.
Figures 8a and 8b show SEM images of nanoparticle structures located on a substrate after the sonication process, Figure 8a shows the nanoparticle structures located in the perforations of the mask, Figure 8b shows the nanoparticle structures And the nanoparticle structure located at the non-existent portion. 8A and 8B, the nanoparticle structure of the portion irradiated with the electron beam stably maintains its shape on the substrate even after the ultrasonic wave decomposition process, whereas a portion of the nanoparticle structure covered with the mask is not irradiated with the electron beam, It can be seen that This indicates that the stiffness of the nanoparticle structure is significantly increased due to electron beam sintering.
Evaluation of electrical resistance of nanoparticle structures
Comparative Example 1
The nanoparticle structure prepared in Preparation Example 3 was measured by the conductive AFM measurement method of FIG. 9A to obtain a current-voltage curve of FIG. 9B.
Example 5
The nano-particle structure was irradiated with electron beams under the conditions shown in Table 3 on the nanoparticle structure prepared in Production Example 3, and the nanoparticle structure was sintered. The nanoparticle structure was measured by the AFM measurement method of FIG. 9A to obtain the current-voltage curve of FIG. 9B.
Example 6
The nano-particle structure was irradiated with electron beams under the conditions shown in Table 3 on the nanoparticle structure prepared in Production Example 3, and the nanoparticle structure was sintered. The nanoparticle structure was measured by the conductive AFM measurement method of FIG. 9A to obtain the current-voltage curve of FIG. 9B.
From the current-voltage curve in Fig. 7B, it can be seen that the curvature slopes of Examples 1 and 2, which are nanoparticle structures sintered by electron beams, are significantly larger than the slopes of the voltage-current curves of Comparative Example 1, Indicating that the electrical resistance of the later nanoparticle structures has decreased. In addition, the slope of Example 6 appears more sharply than the slope of Example 5, indicating that the more the irradiation intensity of the electron beam is, the more the electric resistance can be reduced. Further, such characteristics may be derived from the effect that the morphology of the nanoparticle structure becomes dense as the electron beam irradiation intensity becomes stronger.
Shrinkage evaluation
Example 7
The nanoparticle structure was sintered by irradiating electron beams under the conditions shown in Table 4 on the substrate on which the nanoparticle structure manufactured in Production Example 3 was formed. FIG. 10 shows an SEM image of the nanoparticle structure on the substrate before and after the electron beam irradiation, and FIG. 11 is an SEM image showing the difference between the electron beam irradiated region and the unexposed region on the same substrate.
It can be seen from FIGS. 10A, 10B and 11 that the size of the nanoparticle structure is contracted after the electron beam irradiation. From FIG. 11, it can be seen that shrinkage occurs only in the region irradiated with the electron beam on the same substrate. It can be seen that selective sintering occurred only in the irradiated region.
Optical property evaluation
Comparative Example 2
FIG. 12 shows the results of measurement of the scattering intensity using a dark-field microscope on the substrate on which the nanoparticle structure manufactured in Production Example 3 was formed (No exposure).
Examples 8 to 12
The nanoparticle structures produced in Production Example 3 were irradiated with electron beams under the irradiation conditions shown in Table 2 below, and the sintered nanoparticle structures were measured for dark-field microscopy to measure the scattering intensity The results are shown in Fig.
(minute)
(kV)
(A)
(W)
(W / mm 2 )
FIG. 12 shows that as the intensity of the irradiated electron beam increases, the scattering intensity decreases and a blue shift of the wavelength occurs. This characteristic shows that the nanoparticle structure shrinks more depending on the sintering degree depending on the electron beam intensity , And the size of the nanoparticle structure may be reduced. Therefore, it is possible to control the size of the nanoparticle structure by controlling the intensity of the electron beam, and it is possible to control the optical characteristics using the nanoparticle structure.
Through E-beam TiO 2 Porous layer production
Production Example 4
TiO 2 particles were generated in a spark discharge tube equipped with an FTO-coated glass substrate and the generated TiO 2 was deposited on the glass substrate for 2 hours to form a TiO 2 porous layer. The above manufacturing process is shown in Fig.
14 is a cross-sectional SEM image of a solar cell including a TiO 2 porous layer produced before and after sintering.
The thickness of the TiO 2 porous layer formed on the glass substrate was 100 nm to 300 nm.
Example 13
The TiO 2 porous layer prepared in Preparation Example 4 was irradiated with an electron beam in an area of 10 x 20 mm 2 for 10 minutes at 30 μA.
A solar cell was prepared using the prepared porous layer. The results of measuring the efficiency and characteristics of the manufactured solar cell are shown in Table 6 and FIG.
Comparative Example 3
A solar cell was fabricated using the TiO 2 porous layer prepared in Preparation Example 4. The Jsc, Voc, FF (Fill Factor) and efficiency of the manufactured solar cell were measured and the results are shown in Table 6 and FIG.
It can be seen from Table 3 and FIG. 15 that the Jsc of the TiO 2 layer of Example 13 subjected to the electron beam sintering has a larger value, which means that electron-transporting ability in the TiO 2 layer is remarkably improved by electron beam sintering . In addition, it can be seen from the cross-sectional view of the solar cell including the porous layer of FIG. 14 that the porosity hardly changes after sintering. From this, it is possible to improve the electron transferring ability while maintaining the effect of the porosity of the TiO 2 layer . Further, Table 3 shows that the efficiency of the solar cell can be improved from the effect of increasing the conductivity by the improvement of the electron transfer.
Claims (21)
Irradiating the nanoparticle structure with an electron beam at an energy density of 1 x 10 -7 to 1 x 10 8 W / cm 2 and sintering the nanoparticle structure,
The electron beam
An electron gun that generates electrons;
A condenser lens for collecting the electron beam generated from the electron gun at one point;
A deflection coil for adjusting the direction of the electron beam;
A diaphragm for adjusting an irradiation amount of the electron beam to be irradiated; And
And an objective lens for adjusting the focus of the electron beam to be irradiated.
Wherein the nanoparticle structure is a three-dimensional structure or a layered structure of nanoparticles.
Wherein the size of the three-dimensional structure is shrunk symmetrically or asymmetrically after the electron beam is irradiated.
Wherein the nanoparticle structure formed on the substrate is partially selected and sintered.
As a method of partially selecting and sintering,
A nanoparticle structure is formed on a substrate, a mask having fine patterns perforated therein is placed, an electron beam is irradiated to the mask to selectively sinter the nanoparticle structure located in the perforated portion,
Wherein the electron beam irradiation magnification is controlled to selectively sinter the nanoparticle structure.
Wherein the irradiation time of the electron beam for sintering the nanoparticle structure is 0.01 seconds to 1 hour.
Wherein the nanoparticles are formed using a combination of spark discharge, corona discharge, or both.
Wherein the nanoparticles have a size of 1 to 300 nm.
Wherein the nanoparticle structure comprises at least one selected from a single metal or two or more composite metals or oxides thereof.
Wherein the metal comprises at least one of copper, tin, silver, zinc, platinum, palladium, gold, indium, cadmium, titanium and aluminum or oxides thereof.
Wherein the nanoparticle structure is formed by ion assisted aerosol lithography (IAAL).
Wherein the nanoparticle structure is a flower-shaped structure having three or more petals.
The nanoparticle layer structure
Generating metal nanoparticles through a spark discharge in a spark discharge tube equipped with a conductive substrate; And
Wherein the metal nanoparticles are formed by depositing the metal nanoparticles on the conductive substrate.
Wherein the metal nanoparticle is an oxide of titanium.
Wherein the nanoparticle layer structure is a porous layer structure of metal nanoparticles.
Wherein the conductive substrate is a FTO (fluorine-containing tin oxide) or ITO (indium tin oxide) substrate, or a transparent substrate coated with at least one of FTO and ITO.
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