KR20200028859A - Light sintering apparatus - Google Patents

Abstract

The present invention discloses a photo-sintering device. Light sintering apparatus according to an embodiment of the present invention includes a white light irradiation unit for irradiating white light on the ceramic precursor layer formed on the substrate; A reflector reflecting white light emitted from the white light irradiation unit; A support portion disposed under the substrate and including a heat source for applying heat to the ceramic precursor layer; A power supply supplying power to the white light irradiation unit; A capacitor connected to the power supply to supply high power to the white light irradiation unit; And a controller that controls at least two or more pulse cycles of the white light emitted from the white light irradiator.

Description

Light sintering device {LIGHT SINTERING APPARATUS}

The present invention relates to a photo-sintering apparatus, and more particularly, to a photo-sintering apparatus capable of sintering a ceramic precursor layer in a low temperature process for a short time.

2. Description of the Related Art Recently, a print-based printed electronic technology has been attracting attention in the manufacture of electronic devices or devices. Printed electronic technology has the advantages of low facility investment cost, eco-friendliness, and large-scale mass production due to the small process because electrodes can be formed by simple processes such as printing, sintering, and inspection.

Among the elements of printed electronic technology, sintering technology is an important part because it directly determines the quality of electrodes. Thermal sintering, laser sintering, plasma sintering, and microwave sintering have been developed as existing sintering methods, but they are difficult to commercialize due to their limitations. Therefore, a white light extreme wave light sintering method has been developed to overcome the problems.

In particular, in the case of white light extreme wave technology, when performing the sintering process of the ceramic precursor layer, there is little damage to the substrate on which the pattern is formed and it has an advantage of shortening the time of the sintering process.

However, the sintering method using the white light extreme wave causes the substrate to be distorted due to the high temperature and the substrate is distorted due to the uneven irradiation of light due to the high temperature during the continuous light sintering process using the existing light irradiation equipment and conveyor belt. As a result, non-uniformity problems of sintering are occurring.

However, for practical application in industrial sites, it is necessary to have high electrical conductivity after sintering as well as uniformity of sintering and no damage to the substrate. Therefore, in order to solve the problems, a solution from an equipment point of view is required.

Republic of Korea Registered Patent No. 10-1637122, "High temperature planar heating element manufacturing method" Korean Patent Publication No. 10-2005-0101328, "Method and system for uniformly heat-treating materials"

The purpose of the embodiments of the present invention is to sinter the ceramic precursor layer by performing heat sintering using a heat source and photo sintering using a super cycle, thereby reducing a rapid temperature difference between the ceramic precursor layer and the substrate to minimize thermal shock. And to expand the application range of the substrate.

The purpose of the embodiments of the present invention is to sinter the ceramic precursor layer in a single process without restricting the material of the ceramic precursor layer by performing a photo sintering process using a super cycle.

The purpose of the embodiments of the present invention is to sinter the ceramic precursor layer through a heat sintering and light sintering process, thereby producing a ceramic precursor layer through a heat sintering process in a very short time, and sintering the ceramic precursor layer at a low temperature to obtain a ceramic precursor. This is to improve a problem that may occur when the layer is exposed to a high temperature environment for a long time (eg, substrate destruction, durability reduction due to residual thermal stress, etc.).

Light sintering apparatus according to embodiments of the present invention includes a white light irradiation unit for irradiating white light on the ceramic precursor layer formed on the substrate; A reflector reflecting white light emitted from the white light irradiation unit; A support portion disposed under the substrate and including a heat source for applying heat to the ceramic precursor layer; A power supply supplying power to the white light irradiation unit; A capacitor connected to the power supply to supply high power to the white light irradiation unit; And a controller that controls white light emitted from the white light irradiation unit to be irradiated with at least two or more pulse cycles.

The pulse parameters of the at least two or more pulse cycles are different, and the pulse parameters may be at least one of pulse intensity, pulse gap, pulse width, and number of pulses.

The at least two or more pulse cycles include a first pulse cycle and a second pulse cycle, the first pulse cycle being performed through a first power supply and a first capacitor, and the second pulse cycle is a second power supply and It can be performed through the second capacitor.

The controller may change the pulse parameter of the pulse cycle according to the material of the ceramic precursor layer.

The ceramic precursor layer includes a ceramic precursor, and the controller can change the pulse parameter of the pulse cycle according to the constituent components of the ceramic precursor.

The pulse gap between the two or more pulse cycles may be 10 ms to 1 min.

The heat source may be a heating plate, a heater or an oven.

The target temperature of the substrate may be 100 ℃ to 700 ℃.

The support part may further include a slider that moves the substrate in a horizontal direction.

The slider may move the substrate below the white light irradiation unit when the substrate reaches a target temperature.

The support part may be a conveyor belt that moves the substrate in a horizontal direction.

According to embodiments of the present invention, by performing a heat sintering using a heat source and a photo sintering using a super cycle to sinter the ceramic precursor layer, the temperature difference between the ceramic precursor layer and the substrate is reduced, thereby minimizing thermal shock. And the application range of the substrate can be expanded.

According to embodiments of the present invention, by performing a photo sintering process using a super cycle, the ceramic precursor layer can be sintered in a single process without limitation on the material of the ceramic precursor layer.

More specifically, according to embodiments of the present invention, by sintering the ceramic precursor layer through a heat sintering and light sintering process, the ceramic precursor layer is manufactured in a very short time compared to the ceramic precursor layer produced through the heat sintering process, and the ceramic precursor layer is at a low temperature. Sintering may improve problems that may occur when the ceramic precursor layer is exposed to a high-temperature environment for a long time (eg, substrate destruction, durability reduction due to residual thermal stress, etc.).

1A and 1B are schematic diagrams showing a light sintering apparatus according to an embodiment of the present invention.
1C is a device connection diagram of an optical sintering apparatus according to an embodiment of the present invention.
1D is a schematic diagram showing a pulse intensity pattern of a super cycle using a light sintering apparatus according to an embodiment of the present invention.
2A and 2B are schematic views showing a light sintering apparatus according to an embodiment of the present invention including a plurality of white light irradiation units.
Figure 2b is a device connection diagram of a light sintering apparatus according to an embodiment of the present invention comprising a plurality of white light irradiation unit.
3A and 3B are schematic views showing a light sintering apparatus according to another embodiment of the present invention including a plurality of white light irradiation units.
Figure 4 is a flow chart showing a light sintering method using a light sintering apparatus according to an embodiment of the present invention.
5A and 5B show a scanning electron microscope (SEM) measurement image of a ceramic thin film sintered using a single heat sintering.
6A and 6B show a scanning electron microscope (SEM) measurement image of a ceramic thin film sintered using a single light sintering.
7A and 7B show a scanning electron microscope (SEM) measurement image of a sintered ceramic thin film using an optical sintering apparatus according to an embodiment of the present invention that simultaneously performs thermal sintering and light sintering.
8 is a graph showing sheet resistance of a ceramic precursor layer depending on the presence or absence of a heater.
9A to 9E are SEM images showing the surface of the ceramic precursor layer according to the intensity of the irradiated extreme white light.
10 is an XRD graph of the surface of the ceramic precursor layer subjected to photo-sintering and the ceramic precursor layer subjected to heat sintering.
11 is a graph showing the electrical conductivity of the ceramic precursor layer before and after sintering.
12 is a graph showing the resistivity according to the thickness of the ceramic precursor layer when performing light sintering at the same light intensity.
13 is a graph showing ATR FT-IR (attenuated total reflectance Fourier transformed infra-red) of the ceramic precursor layer, each of which was subjected to heat sintering and light sintering.
14A to 14C are SEM images showing a surface according to the intensity of light irradiated to the ceramic precursor layer including LSM.
15 is a graph of XRD analysis of the surface of the ceramic precursor layer after thermal sintering or photo sintering the ceramic precursor layer including LSM.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings and the contents described in the accompanying drawings, but the present invention is not limited or limited by the embodiments.

The terminology used herein is for describing the embodiments and is not intended to limit the present invention. In the present specification, the singular form also includes the plural form unless otherwise specified in the phrase. As used herein, "comprises" and / or "comprising" refers to the components, steps, operations and / or elements mentioned above, the presence of one or more other components, steps, operations and / or elements. Or do not exclude additions.

As used herein, "example", "example", "side", "example", etc. should be construed as any aspect or design described being better or more advantageous than another aspect or designs. It is not done.

Also, the term 'or' refers to the inclusive 'inclusive or' rather than the exclusive 'exclusive or'. That is, unless stated otherwise or unclear from the context, the expression 'x uses a or b' means any of the natural inclusive permutations.

Also, the singular expression (“a” or “an”) used in the specification and claims generally means “one or more” unless the context clearly indicates otherwise that it is related to the singular form. It should be interpreted as.

The terminology used in the description below has been selected to be general and universal in the related technical field, but may have other terms depending on the development and / or change of technology, conventions, and preferences of technicians. Therefore, the terms used in the following description should not be understood as limiting the technical idea, but should be understood as exemplary terms for describing the embodiments.

Also, in certain cases, some terms are arbitrarily selected by the applicant, and in this case, detailed meanings will be described in the corresponding description. Therefore, the terms used in the description below should be understood based on the meaning of the term and the entire contents of the specification, not just the name of the term.

Meanwhile, terms such as first and second may be used to describe various components, but components are not limited by the terms. The terms are used only to distinguish one component from another component.

Also, when a part such as a film, layer, area, configuration request, etc. is said to be "above" or "on" another part, not only when it is directly above another part, but also another film, layer, area, component in the middle Also includes the case where a back is interposed.

Unless otherwise defined, all terms (including technical and scientific terms) used in the present specification may be used as meanings commonly understood by those skilled in the art to which the present invention pertains. In addition, terms defined in the commonly used dictionary are not ideally or excessively interpreted unless specifically defined.

On the other hand, in the description of the present invention, when it is determined that a detailed description of related known functions or configurations may unnecessarily obscure the subject matter of the present invention, the detailed description will be omitted. In addition, terms used in the present specification (terminology) are terms used to properly represent an embodiment of the present invention, which may vary according to a user, an operator's intention, or a custom in a field to which the present invention pertains. Therefore, definitions of these terms should be made based on the contents throughout the present specification.

1A and 1B are schematic diagrams showing a light sintering apparatus according to an embodiment of the present invention.

More specifically, FIG. 1A is a schematic diagram showing a light sintering apparatus according to an embodiment of the present invention during light sintering, and FIG. 1B is light according to an embodiment of the present invention before / after light sintering is performed. It is a schematic diagram showing a sintering apparatus.

Therefore, since FIGS. 1A and 1B include the same components, the same components will be omitted.

Light sintering apparatus according to an embodiment of the present invention is a white light irradiation unit 110 for irradiating white light on the ceramic precursor layer formed on the substrate (S), the reflector 120 for reflecting the white light emitted from the white light irradiation unit 110, It is disposed on the lower portion of the substrate (S), a support 130 including a heat source (heat source) for applying heat to the ceramic precursor layer, the power supply 150 for supplying power to the white light irradiator 110, power supply 150 ) Is connected to the white light irradiation unit 110, the capacitor 161, 162 for supplying a high power instantaneously and the white light emitted from the white light irradiation unit 110 includes a controller 170 for controlling to be irradiated with at least two or more pulse cycles.

In general, a single heat sintering process or a single photo sintering process was performed as a sintering process for sintering the ceramic precursor layer.

However, in a single heat sintering process, when sintering a metal material, sintering is possible at a low temperature of 200 ° C to 300 ° C, but when sintering a ceramic precursor layer containing a ceramic material, sintering proceeds at a high temperature of 700 ° C or higher. There is a problem that a phase change occurs at the interface between the substrate S and the ceramic precursor layer.

In addition, since the heat sintering process does not locally occur over a long period of time, the time required is large, and the wasted energy is also considerable.

However, the light sintering apparatus according to an embodiment of the present invention simultaneously performs heat sintering using a heat source and a light sintering process using ultra-short white light that can concentrate energy locally in a very short time in milliseconds (ms). By doing so, the sintering process time of the ceramic precursor layer can be reduced from several hours to several milliseconds (ms).

In addition, since a single photo-sintering process requires irradiation of a specific range of energy in which the ceramic precursor layer can be sintered, the range of energy may vary greatly depending on the type and production process of the ceramic precursor layer.

For example, since a ceramic material generally requires a larger energy irradiation when sintering than a metallic material, it is necessary to apply a larger energy to the conventional white light irradiation unit.

Therefore, in the case of the conventional white light irradiating unit, since the white light irradiating unit which cannot withstand high energy cannot be used, there is a limitation in the application of the white light irradiating unit, and even in the case of the ceramic precursor layer, the ceramic precursor layer is irradiated with instantaneous high energy. There is a problem that the substrate is destroyed due to a rapid temperature difference between the surface of the precursor layer and the substrate.

However, in the light sintering apparatus according to an embodiment of the present invention, by applying heat energy to a ceramic precursor layer using a heat source (eg, a heater), extreme white light even in an electromagnetic wave range that was previously impossible to be applied as extreme extreme energy Can be investigated.

More specifically, in the light sintering apparatus according to an embodiment of the present invention, when the temperature of the substrate S rises to a target temperature using a heat source (eg, a heater), the light is irradiated with extreme white light to proceed with light sintering. In addition, since sintering is possible with a microwave energy lower than that of a single light sintering process that was previously performed at room temperature, it is possible to sinter the ceramic precursor layer, which was not applicable due to energy dose limitation.

That is, in the light sintering apparatus according to an embodiment of the present invention, even by applying a thermal energy using a heat source to the ceramic precursor layer, even if an extremely short white light energy as low as thermal energy is applied, a high energy is finally applied to the ceramic precursor layer. Therefore, it is possible to exhibit the same effect as the conventional single light sintering process without damaging the substrate.

Therefore, the light sintering apparatus according to an embodiment of the present invention simultaneously performs not only light sintering using ultra-short white light, but also heat sintering using a heat source, thereby enabling a low-temperature sintering process and simultaneously extending the range of application of ultra-short white light energy. You can.

The light sintering apparatus according to an embodiment of the present invention includes a white light irradiator 110 for irradiating white light onto the ceramic precursor layer formed on the substrate S.

The white light irradiator 110 is a component that generates white light and irradiates it in a downward direction, which is the direction of the substrate S. The white light irradiator 110 may have various configurations capable of irradiating white light, but preferably, the white light irradiator 110 may be a Xenon Flash Lamp.

The xenon flash lamp may output extreme white light to the surface of the substrate S, and sinter the ceramic precursor layer formed on the substrate S through irradiation of the extreme white light.

The xenon flash lamp used in the light sintering apparatus according to an embodiment of the present invention is preferably a lamp capable of applying high energy in a short period of less than milliseconds (ms).

According to an embodiment, the white light irradiation unit 110 may include at least one xenon flash lamp, a plurality of xenon flash lamps may be installed in parallel at the same time, it is possible to individually control each xenon flash lamp. A light sintering apparatus according to an embodiment of the present invention including at least one xenon flash lamp will be described with reference to FIGS. 2A and 2B.

The light sintering apparatus according to an embodiment of the present invention includes a reflector 120 that reflects white light emitted from the white light irradiator 110.

It is preferable that the reflector has a mirror surface in order to emit white light emitted from the white light irradiation unit 110 in a completely downward direction.

The light sintering apparatus according to an embodiment of the present invention is disposed under the substrate S and includes a support 130 including a heat source for applying heat to the ceramic precursor layer.

The support part 130 is disposed under the substrate S and is a component that supports the ceramic precursor layer to which the extreme white light emitted from the white light irradiation part 110 is irradiated. The support 130 includes a heat source for applying heat to the ceramic precursor layer formed on the substrate S.

The heat source may be at least one of a contact type and a non-contact type. For example, the heat source may be a hot plate, a heater, and an oven.

Therefore, the light sintering apparatus according to an embodiment of the present invention may include a heat source, so that the temperature of the substrate S on which the ceramic precursor layer is formed can be adjusted to 100 ° C to 700 ° C.

When the temperature of the substrate S is 100 ° C. or less, a high extreme white light energy is required due to insufficient thermal energy, and when the temperature of the substrate exceeds 700 ° C., the film shrinks excessively at the interface between the ceramic precursor layer and the substrate. There is a problem that separation occurs and phase change occurs.

That is, in the light sintering apparatus according to an embodiment of the present invention, a ceramic precursor layer may be heated to a target temperature by placing a heat source near the substrate S on which the ceramic precursor layer to be sintered is formed.

Therefore, the photo-sintering apparatus according to an embodiment of the present invention can use a heat source to sinter the ceramic precursor layer at a lower energy than photo-sintering at room temperature, and reduce the heat load applied to the ceramic precursor layer. Therefore, damage to the ceramic precursor layer can be reduced.

In addition, the light sintering apparatus according to an embodiment of the present invention, by using a heat source, during light sintering, at least two or more pulse cycles can be adjusted to a low-energy pulse cycle and a high-energy pulse cycle.

More specifically, the light sintering apparatus according to an embodiment of the present invention uses a heat source to apply thermal energy to a substrate S on which a ceramic precursor layer is formed using a heat source while simultaneously irradiating pulses from low energy to high energy. Since the photo-sintering process can be performed, the temperature of the substrate S on which the ceramic precursor layer is formed is gradually increased, thereby minimizing damage due to a temperature difference between the ceramic precursor layer and the substrate S.

For example, if the target temperature of the substrate S is set to 500 ° C., and when the extreme white light is to be irradiated, if the temperature increase time at which the temperature of the substrate S is raised to 500 ° C. is too short, Damage to the ceramic precursor layer is caused by a rapid temperature change.

Therefore, in the case of the photo-sintering apparatus according to an embodiment of the present invention, the substrate S on which the ceramic precursor layer is formed can be heated to 1 ° C to 10 ° C.

In addition, the support unit 130 of the light sintering apparatus according to an embodiment of the present invention may further include a slider (slider) 140 for moving the substrate (S) in the horizontal direction.

The slider 140 is connected to the support 130 to move the support 130 in a horizontal direction. Therefore, the slider 140 may move the support 130 to the lower portion of the white light irradiation unit 110 when the substrate S reaches a target temperature. The target temperature of the substrate S may be 100 ° C to 700 ° C.

More specifically, the light sintering apparatus according to an embodiment of the present invention uses a heat source in a state in which the slider 140 is fixed (before or after the light sintering process) in a region other than the lower portion of the white light irradiator 110. After heating the substrate S on which the precursor layer is formed, when the substrate S on which the ceramic precursor layer is formed reaches a target temperature, the slider 140 is horizontally moved to the lower portion of the white light irradiation unit 110 to proceed with the light sintering process. You can.

More specifically, since FIG. 1A is a view showing a moment when light sintering is performed in the light sintering apparatus according to an embodiment of the present invention, the slider 140 is a white light irradiator 110 for the substrate S on which the ceramic precursor layer is formed. ).

On the other hand, Figure 1b is a view showing before or after the light sintering in the light sintering apparatus according to an embodiment of the present invention, the slider 140 is a white light irradiation unit 110 for the substrate (S) on which the ceramic precursor layer is formed ) Away from the bottom.

Therefore, in the light sintering apparatus according to an embodiment of the present invention, by heating the substrate S on which the ceramic precursor layer is formed in a region other than the lower portion of the white light irradiation unit 110, the white light irradiation unit 110 or other device due to the heat source To prevent damage.

The light sintering apparatus according to an embodiment of the present invention includes a power supply 150 that supplies power to the white light irradiator 110. The power supply 140 generates voltage and current, and transmits the generated voltage and current to the white light irradiator 110.

In addition, the light sintering apparatus according to an embodiment of the present invention may include at least one power supply 150. Preferably, the power supply 150 may include a Simmer triggering control circuit, a first power supply, and a second power supply therein.

The first power supply and the second power supply may be formed separately in the power supply 150, or each power supply 150 may be separately formed.

The light sintering apparatus according to an embodiment of the present invention includes capacitors 161 and 162 connected to the power supply 150 to supply instantaneous high power to the white light irradiator 110. The capacitors 161 and 162 accumulate and store charges, and when sparks are generated between both electrodes of the white light irradiation unit 110, the stored charges are transferred to the white light irradiation unit 110.

That is, the capacitors 161 and 162 can instantaneously deliver high power within a very short time to cause pulse formation.

Accordingly, when voltage and current are input from the power supply 140 to the white light irradiator 110, the electric charges accumulated from the capacitors 161 and 162 are applied to generate arc plasma within the white light irradiator 110. Then, extreme white light may be output from the white light irradiation unit 110 to the surface of the substrate S on which the ceramic precursor layer is formed.

In addition, the light sintering apparatus according to an embodiment of the present invention may include at least one or more capacitors 161 and 162.

The light sintering apparatus according to an embodiment of the present invention includes a controller 170 that controls white light emitted from the white light irradiator 110 to be irradiated with at least two or more pulse cycles. The controller 170 is a component that applies power to the white light irradiator 110 to process the process.

The controller 170 may apply power to the white light irradiator 110 in a pulse form, and the controller 170 may apply pulses having different heights according to a change in time or mix two or more pulses. Thus, pulses having more various height changes can be applied.

More specifically, at least two or more pulse cycles have different pulse parameters, and the pulse parameters may be at least one of pulse intensity, pulse gap, pulse width, and number of pulses.

That is, the photo-sintering apparatus according to an embodiment of the present invention may sinter the ceramic precursor layer using a super cycle, and the super cycle includes at least two pulse cycles having different pulse parameters.

The at least two or more pulse cycles include a first pulse cycle applying a pulse intensity of relatively lower energy and a longer pulse gap than the second pulse cycle, and a second pulse applying a pulse pulse of relatively higher energy than the first pulse cycle and a short pulse gap. Including a cycle, it may be a super cycle that can minimize damage to the ceramic precursor layer. However, at least two or more pulse cycles are not limited thereto, and the first to third pulse cycles may be included, and a technique including the first to third pulse cycles will be described with reference to FIG. 1D.

In addition, the first pulse cycle included in the super cycle proceeds to gradually increase the sintering temperature so as to reach the sintering temperature for photo-sintering the ceramic precursor layer, and the second pulse cycle completely sinters the ceramic precursor layer. (Substantial photo-sintering).

For example, the first pulse cycle for gradually increasing the sintering temperature so that the ceramic precursor layer can reach the sintering temperature is a pulse intensity of 50 J / cm ² , a pulse width of 10 ms, a pulse gap of 100 ms and a pulse of 6 The second pulse cycle, which allows the ceramic precursor layer to be substantially photo-sintered, can be adjusted to have a pulse intensity of 100 J / cm ² , a pulse width of 10 ms, a pulse gap of 10 ms and a pulse number of 6 The first pulse cycle and the second pulse cycle may be super cycles having a pulse gap of 1000 ms.

Therefore, the light sintering apparatus according to an embodiment of the present invention applies thermal energy to a substrate on which a ceramic precursor layer is formed using a heat source, and at the same time, applies white light in a super cycle, thereby reducing the energy of the ultra-short white light applied to the white light irradiation unit. At the same time, the degree of sintering of the ceramic precursor layer can be improved.

In addition, the photo-sintering apparatus according to an embodiment of the present invention, during photo-sintering, by controlling at least one of the pulse intensity, pulse gap, pulse width and pulse number between each pulse or pulse cycle, during the photo-sintering process, the ceramic precursor It is possible to control the temperature of the layer from rising. Therefore, the light sintering apparatus according to an embodiment of the present invention can minimize the thermal shock due to the temperature difference between the ceramic precursor layer and the substrate (thermal shock) while maximizing the light sintering effect.

The pulse intensity of the pulses included in at least two or more pulse cycles may be 50 J / cm ² to 200 J / cm ² .

For example, a ceramic-based material has a very high melting point compared to a metal-based material, and thus, when performing heat sintering, a very high temperature of 1000 ° C or higher is required. In addition, even if the ceramic-based material is photo-sintered, in order to exhibit a similar sintering degree to heat sintering, a strong pulse strength corresponding to the heat sintering temperature is required. However, the light sintering apparatus according to an embodiment of the present invention simultaneously performs heat sintering using a heat source and light sintering using extreme white light, thereby performing light sintering with a pulse intensity of 50 J / cm ² to 200 J / cm ² . High sintering degree can be exhibited even if it progresses.

The pulse gap of a pulse included in at least two or more pulse cycles may be from 0.1 ms to 300 ms.

The pulse width of a pulse included in at least two or more pulse cycles may be 0.01 ms to 50 ms.

The pulse number of the pulses included in at least two or more pulse cycles may be 1 to 100.

Also, a pulse gap between at least two or more pulse cycles may be 10 ms to 1 min. Preferably, the pulse gap between at least two or more pulse cycles may be 10 ms to 1000 ms.

In addition, the controller 170 may change pulse parameters of at least two or more pulse cycles according to the material of the ceramic precursor layer.

Preferably, the ceramic precursor layer may include a ceramic precursor, and the ceramic precursor may include at least one of a zirconia precursor and a ceria precursor material.

More preferably, the ceramic precursor is yttria stabilized zirconia (YSZ: (ZrO ₂ ) _1-x (Y ₂ O ₃ ) _x (0.08 = x≤ = 0.13)), scandia stabilized zirconia (ScSZ: (ZrO ₂ ) _{1 -x} (Sc ₂ O ₃ ) x (0.09 = x≤ = 0.10)), Scania stabilized zirconia with ceria (CeO ₂ ) as an additive (ScCeSZ: (ZrO ₂ ) _1-x (CeO2) 0.01 (Sc ₂ O ₃ (0.09 = x)), Samarium doped ceria (SDC: SmxCe _1-x O ₂ (0.1 = x≤ = 0.2)), Galdorinium doped ceria (GDC: SmxCe _1-x O ₂ (0.1 = x≤ = 0.2)) and yttria doped ceria (YDC: (Y ₂ O ₃ ) _x Ce _1-x O ₂ (0.1 = x≤ = 0.2)).

In addition, the controller 170 may change pulse parameters of at least two or more pulse cycles according to components of the ceramic precursor.

Therefore, when the ceramic precursor is composed of the first constituent component and the second constituent component, the first constituent component is more sintered by the first pulse cycle, and the second constituent component can be more sintered by the second pulse cycle. have.

That is, in the first component, the degree of sintering by the first pulse cycle is greater than the degree of sintering by the second pulse cycle, and in the second component, the degree of sintering by the second pulse cycle is greater than that by the first pulse cycle. It can be big.

Therefore, by controlling the pulse parameter of the pulse cycle in the controller 170, it is possible to prevent the thermal shock of the ceramic precursor layer while improving the sintering degree.

Accordingly, the light sintering apparatus according to an embodiment of the present invention uses a super cycle to gradually increase the temperature in the first pulse cycle and proceeds to light sintering in the second cycle, which is the main cycle, to prevent thermal shock and relatively The sintering potential can be increased by increasing the exposure time at high temperatures.

The device connection structure of the optical sintering apparatus according to an embodiment of the present invention will be described with reference to FIG. 1C.

1C is a device connection diagram of an optical sintering apparatus according to an embodiment of the present invention.

At least two or more pulse cycles using the photo-sintering apparatus according to an embodiment of the present invention may include a first pulse cycle and a second pulse cycle, and the first pulse cycle includes a first power supply and a first capacitor 161 The second pulse cycle may be performed through the second power supply and the second capacitor 162.

The power supply 150 of the light sintering apparatus according to an embodiment of the present invention may include a Simmer triggering control circuit, a first power supply, and a second power supply therein.

Accordingly, the optical sintering apparatus according to an embodiment of the present invention may configure the first set to which the first power supply and the first capacitor 161 are connected to adjust the first pulse cycle, the second power supply, and The second pulse cycle may be adjusted by configuring a second set to which the second capacitor 162 is connected. Also, the first set and the second set may be connected to each other.

In addition, when the first pulse cycle is emitted through the first set to which the first power supply and the first capacitor 161 are connected, the second power supply and the second capacitor 162 according to the embodiment of the present invention ) Connected to the second set may perform preparation for charging and emitting extreme white light energy to emit a second pulse cycle.

Therefore, the photo-sintering apparatus according to an embodiment of the present invention can prepare a second pulse cycle while photo-sintering with a first pulse cycle, thereby reducing the photo-sintering process time and simultaneously sintering the ceramic precursor layer completely without thermal shock. You can.

1D is a schematic diagram showing a pattern of a super cycle using a light sintering apparatus according to an embodiment of the present invention.

The controller included in the light sintering apparatus according to an embodiment of the present invention may control a super cycle, and at least two or more pulse cycles may include first to third pulse cycles.

The first pulse cycle may be repeatedly irradiated such that pulses of lower energy than the second pulse cycle have the same pulse intensity to gradually increase the temperature of the ceramic precursor layer, and the second pulse cycle irradiates strong ultra-short white light to the ceramic precursor layer. In order to sinter the ceramic precursor layer, pulses of energy stronger than the first pulse cycle may be repeatedly irradiated with the same pulse intensity, and the third pulse cycle may be repeatedly irradiated by gradually decreasing the pulse intensity to gradually decrease the sintering temperature. You can.

Therefore, the light sintering apparatus according to an embodiment of the present invention can improve the sintering degree of the ceramic precursor layer by using a super cycle and prevent thermal shock.

For example, when 6 pulses are applied with an on time of 10 ms and an off time of 10 ms in the first pulse cycle, the energy of each pulse is 10 J / cm ² It is possible to gradually increase the temperature of the ceramic precursor layer by applying an energy of about 60 J / cm ² to 90 J / cm ^{2 in} total of about 15 J / cm ² .

Thereafter, when the on time is 10 ms in the second pulse cycle and the off time is about 10 ms, when 6 pulses are applied, the energy of each pulse is 20 J / cm ² to 30 J / cm ^2, so a grand total 120 J / cm ² to 180 given the degree of J / cm ² energy can be light sinter the ceramic precursor layer.

In the last third pulse cycle, when the on time is 10 ms and the off time is about 100 ms, when applying 6 pulses, the energy of each pulse is 20 J / cm ² , 15 J / cm ² , 10 J / cm ² , 5 J / cm ² , 3 J / cm ² and 1 J / cm ² are applied to gradually decrease the energy to gradually reduce the temperature of the ceramic thin film (or ceramic precursor layer), thereby causing thermal shock ( thermal shock).

2A and 2B are schematic views showing a light sintering apparatus according to an embodiment of the present invention including a plurality of white light irradiation units, and FIG. 2C is light sintering according to an embodiment of the present invention including a plurality of white light irradiation units It is a device connection diagram of the device.

More specifically, Figure 2a is a schematic diagram showing a light sintering apparatus according to an embodiment of the present invention during light sintering, Figure 2b is a light according to an embodiment of the present invention before / after the light sintering is in progress It is a schematic diagram showing a sintering apparatus.

2A to 2C are the same as in FIGS. 1A and 1B except for including a plurality of white light irradiation units, and thus description of the same components will be omitted.

The light sintering apparatus according to an embodiment of the present invention may include first and second white light irradiation units 111 and 112.

The first and second white light irradiation units 111 and 112 are components that generate white light and irradiate it in a downward direction, which is the direction of the substrate S. The first and second white light irradiators 111 and 112 may have various configurations capable of irradiating white light, but preferably, the first and second white light irradiators 111 and 112 are Xenon Flash Lamps ) Can be used.

The xenon flash lamp may output extreme white light to the surface of the substrate S, and sinter the ceramic precursor layer formed on the substrate S through irradiation of the extreme white light.

The xenon flash lamp used in the light sintering apparatus according to an embodiment of the present invention is preferably a lamp capable of applying high energy of 100J or more in a short period of less than milliseconds (ms).

When the light sintering apparatus according to an embodiment of the present invention includes a plurality of white light irradiation units, a first set connected to a first power supply, a first capacitor 161 and a first white light irradiation unit 111 is removed. One pulse cycle may be adjusted, and a second set connected to the second power supply, the second capacitor 162, and the second white light irradiation unit 112 may adjust the second pulse cycle. Also, the first set and the second set may be connected to each other.

Therefore, the light sintering apparatus according to an embodiment of the present invention includes a plurality of white light irradiation units 111 and 112 to alternately irradiate a pulse cycle to the first white light irradiation unit 111 and the second white light irradiation unit 112. Therefore, pulse cycle conditions that cannot be used in a single white light irradiation unit can be used.

3A and 3B are schematic views showing a light sintering apparatus according to another embodiment of the present invention including a plurality of white light irradiation units.

Since the light sintering apparatus according to another embodiment of the present invention includes the same configuration as the light sintering apparatus according to an embodiment of the present invention, except that a conveyor belt is used as the support 130, a description of the same components It will be omitted.

In the light sintering apparatus according to another embodiment of the present invention, a conveyor belt for moving the substrate S in the horizontal direction to the support 130 may be used.

The conveyor belt is located under the substrate S to move the substrate S in the horizontal direction and can rotate itself.

In addition, the conveyor belt includes a heat source for applying heat to the ceramic precursor layer formed on the substrate S.

Accordingly, the light sintering apparatus according to another embodiment of the present invention may include a heat source, so that the temperature (target temperature) of the substrate S on which the ceramic precursor layer is formed can be adjusted to 100 ° C to 700 ° C.

More specifically, the light sintering apparatus according to another embodiment of the present invention applies a heat energy to a substrate S on which a ceramic precursor layer is formed using a heat source while simultaneously performing a light sintering process of irradiating pulses from low energy to high energy. By doing so, the temperature of the substrate S on which the ceramic precursor layer is formed is gradually increased, thereby minimizing damage due to a temperature difference between the ceramic precursor layer and the substrate S.

For example, if the target temperature of the substrate S is set to 500 ° C., and when the extreme white light is to be irradiated, if the temperature increase time at which the temperature of the substrate S is raised to 500 ° C. is too short, the substrate S Damage to the ceramic precursor layer is caused by a rapid temperature change.

Therefore, in the case of the light sintering apparatus according to another embodiment of the present invention using a conveyor belt, the substrate S on which the ceramic precursor layer is formed on the conveyor is moved, and at the same time, the target is step by step so that the temperature is reached for each region to reach the temperature. Can be set.

For example, when forming the temperature of the upper part of the conveyor for each region at a temperature of 100 ° C, 200 ° C, 300 ° C, 400 ° C, and 500 ° C, the substrate S on which the ceramic precursor layer is formed is added at 100 ° C. When the 500 ° C section is reached, light sintering using extreme white light may proceed.

More specifically, the light sintering apparatus according to another embodiment of the present invention gradually heats the substrate S on which the ceramic precursor layer is formed in a region other than the lower portion of the white light irradiation unit 110, and then the substrate on which the ceramic precursor layer is formed When (S) reaches the target temperature, the substrate S on which the ceramic precursor layer is formed is horizontally moved to the lower portion of the white light irradiation unit 110 so that the light sintering process may be performed.

More specifically, Figure 3a is a diagram showing the moment the light sintering proceeds in the light sintering apparatus according to another embodiment of the present invention, the conveyor belt is a white light irradiation unit 110 of the substrate (S) on which the ceramic precursor layer is formed Moved to the bottom.

On the other hand, Figure 3b is a diagram showing before or after the light sintering in the light sintering apparatus according to another embodiment of the present invention, the conveyor belt is a substrate (S) formed with a ceramic precursor layer of the white light irradiation unit 110 Moved away from the bottom.

Therefore, the light sintering apparatus according to another embodiment of the present invention by heating the substrate S on which the ceramic precursor layer is formed in a region other than the lower portion of the white light irradiation unit 110, the white light irradiation unit 110 or other device due to the heat source To prevent damage.

Figure 4 is a flow chart showing a light sintering method using a light sintering apparatus according to an embodiment of the present invention.

The photo-sintering method includes disposing a substrate including a ceramic precursor layer on a support portion including a heat source (S110), heating a substrate including the ceramic precursor layer to a target temperature (S120), and heating the heated ceramic precursor layer. The step of moving the substrate including the white light irradiation unit (S130), the step of irradiating the white light on the substrate containing the heated ceramic precursor layer to sinter (S140, S150) and the substrate containing the sintered ceramic precursor layer to be carried out Step S160 is included.

Hereinafter, a technique for photo-sintering a ceramic precursor layer using a photo-sintering apparatus according to an embodiment of the present invention in which a slider is formed under a support is described, but is not limited thereto.

The photo-sintering method using the photo-sintering apparatus according to an embodiment of the present invention proceeds to a step (S110) of disposing a substrate including a ceramic precursor layer on a support portion including a heat source.

The substrate can be used by selecting various materials capable of supporting. In particular, since the photo-sintering method is capable of a low-temperature sintering process, a substrate material having poor thermal stability may also be used.

For example, a nitrogen compound-based ceramic material such as boron nitride (BN), aluminum nitride (AlN), aluminum oxide (Al ₂ O ₃ ), zirconium oxide (ZrO ₂ ), yttria stabilized zirconia (YSZ), and oxidation as substrates An insulating layer such as an oxygen compound ceramic such as titanium (TiO ₂ ) or other ceramic material may be used. In addition, an organic substrate may be used as the substrate.

Preferably, the substrate may include at least one of silicon (Si), silicon oxide (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), yttria stabilized zirconia (YSZ) and titanium oxide (TiO ₂ ). .

The ceramic precursor layer formed on the substrate may be formed on the substrate using at least one of a precursor solution containing a precursor material, a precursor ink, and a precursor paste.

For example, the ceramic precursor layer may be formed by coating a ceramic solution containing a ceramic precursor, the ceramic solution may be prepared by adding a ceramic precursor to an organic solvent, and the ceramic precursor may include at least one of zirconia precursor and ceria precursor materials. It can include any one.

More preferably, the ceramic precursor is yttria stabilized zirconia (YSZ: (ZrO ₂ ) _1-x (Y2O ₃ ) _x (0.08 = x≤ = 0.13)), scandia stabilized zirconia (ScSZ: (ZrO ₂ ) _1-x (Sc ₂ O ₃ ) x (0.09 = x≤ = 0.10)), Scania stabilized zirconia with ceria (CeO ₂ ) as an additive (ScCeSZ: (ZrO ₂ ) _1-x (CeO2) 0.01 (Sc ₂ O ₃ ( 0.09 = x)), Samarium doped ceria (SDC: SmxCe _1-x O ₂ (0.1 = x≤ = 0.2)), Galdolinium doped ceria (GDC: SmxCe _1-x O ₂ (0.1 = x≤ = 0.2)) and yttria doped ceria (YDC: (Y ₂ O ₃ ) _x Ce _1-x O ₂ (0.1 = x≤ = 0.2)).

As the solvent, an organic solvent including at least one of methanol, ethanol, acetic acid, and acetyl acetate may be used.

According to an embodiment, the ceramic solution may further include a binder. The binder may include at least one of acrylic, epoxy, and urethane binders.

In particular, an acrylic binder may be used as the binder, and the acrylic binder has good mixing properties with a ceramic precursor such as a metal oxide, and when used in combination with a dispersant, a stable high-concentration ceramic solution can be produced. In addition, since the acrylic binder is a water-soluble polymer, a ceramic solution having good viscosity stability can be prepared, and since it does not contain an inorganic substance, there is no sintering residue, and film-forming properties are good, so that it can be molded to a required thickness.

The ceramic precursor layer may be formed on a substrate by a non-vacuum method, and preferably, the ceramic precursor layer may be processed by at least one of a sol-gel method, an organic metal solution deposition method, a dip coating method, a screen printing method, and a spray coating method.

Conventionally, vacuum deposition methods such as physical vapor deposition (PVD), atomic film deposition (ALD), or chemical vapor deposition (CVD) have been performed to form a ceramic precursor layer. There is a drawback that it takes a lot of time, and there is a drawback that a process cost for applying a vacuum is consumed a lot.

However, in the photo-sintering method, by simultaneously performing heat sintering and photo-sintering, even if a non-vacuum method such as a sol-gel method or a spray coating method is used, a high-quality ceramic thin film can be produced even under normal temperature and pressure conditions.

In addition, in the photo-sintering method, the ceramic precursor layer formed on the substrate may be a thin film structure formed by a non-vacuum method, or a patterned structure formed by a non-vacuum method and then subjected to a patterning process.

The photo-sintering method proceeds to a step (S120) of heating the substrate including the ceramic precursor layer to a target temperature.

Since the light sintering apparatus according to an embodiment of the present invention includes a heat source in the support, the substrate may be heat-treated before light sintering the ceramic precursor layer using a white light irradiation unit.

The target temperature of the substrate on which the ceramic precursor layer is formed may be 100 ° C to 700 ° C.

When the temperature of the substrate is 100 ° C or less, a high extreme white light energy is required due to insufficient thermal energy, and when the temperature of the substrate exceeds 700 ° C, the film shrinks excessively at the interface between the ceramic precursor layer and the substrate, resulting in peeling and There is a problem that a phase change occurs.

Therefore, the light sintering method can prevent the white light irradiation unit or other devices from being damaged by a heat source by heating the substrate on which the ceramic precursor layer is formed before irradiating the extreme white light, and the moisture contained in the ceramic precursor layer is removed. Can be.

The thickness of the ceramic precursor layer formed on the substrate may be 100 nm to 5 μm. In the photo-sintering method, a ceramic precursor layer having a thin thickness of 100 nm to 5 μm is formed by using a solution-based non-vacuum method that is densely stacked, thereby manufacturing a ceramic thin film having a dense structure.

In the light sintering method, a step (S140) of moving the substrate including the heated ceramic precursor layer to the lower portion of the white light irradiation unit proceeds.

In the light sintering apparatus according to the embodiment of the present invention, since a slider is formed under the support portion, when the substrate on which the ceramic precursor layer is formed reaches a target temperature, the slider is used to light sinter the ceramic precursor layer to the bottom of the white light irradiation portion. It can be moved horizontally.

Therefore, in the light sintering method, since the substrate on which the ceramic precursor layer is formed reaches a target temperature and then horizontally moves to the lower portion of the white light irradiation unit, it is possible to prevent the white light irradiation unit or other devices from being damaged by the heat source.

In the light sintering method, a step (S140) of sintering by irradiating white light on a substrate including a heated ceramic precursor layer is performed.

The extreme white light may be microwave light. For example, the extreme white light may be an arc plasma generated by applying a high current to a xenon flash lamp.

More specifically, the extreme white light may be irradiated on the ceramic precursor layer heated by the xenon flash lamp. Therefore, the energy is applied for a short time in milliseconds (ms) to a local area where sintering is required in a normal temperature environment by a xenon flash lamp, thereby minimizing damage and / or deformation of the substrate, processing time and Process costs can be reduced.

On the other hand, when a ceramic precursor layer is manufactured using a single heat sintering, the perovskite crystal structure is formed at a temperature of 700 ° C. or more, so that the substrate on which the ceramic precursor layer is formed is exposed to a high temperature environment of 700 ° C. or more for a long time.

Particularly, in the case of a ceramic precursor layer containing a ceramic precursor, since it is more sensitive to external changes relative to a bulk, it takes a lot of time to create a high temperature environment for sintering. In addition, the amount of energy wasted is very large because energy lost to the outside is greater than energy consumed for sintering the ceramic precursor layer. In addition, since a considerable amount of energy is applied to the substrate on which the ceramic precursor layer is formed in a high temperature environment for a long time, damage and / or deformation of the substrate occurs.

Therefore, the single heat sintering process for sintering the ceramic precursor layer has limitations in application to a flexible substrate such as plastic.

However, in the light sintering method, by irradiating extreme white light to the heated ceramic precursor layer using a xenon flash lamp, a perovskite crystal structure is formed, and the heated ceramic precursor layer is sintered to produce a ceramic thin film. Therefore, energy is applied to the local area where sintering is required in a room temperature environment for a short time in milliseconds, thereby minimizing substrate damage and / or deformation and processing time.

Therefore, the photo-sintering method can sinter the ceramic precursor layer without limitation of the substrate.

In the step (S140) of sintering by irradiating white light on the substrate including the heated ceramic precursor layer, the white light is irradiated in at least two or more pulse cycles.

The pulse intensity of the pulses included in at least two or more pulse cycles may be 50 J / cm ² to 200 J / cm ² .

The pulse gap of a pulse included in at least two or more pulse cycles may be from 0.1 ms to 300 ms.

The pulse width of a pulse included in at least two or more pulse cycles may be 0.01 ms to 50 ms.

The pulse number of the pulses included in at least two or more pulse cycles may be 1 to 100.

Also, at least two or more pulse cycles may have different pulse parameters, and the pulse parameters may be at least one of pulse intensity, pulse gap, pulse width, and pulse number.

For example, a pulse parameter of a pulse included in each pulse cycle of at least two or more pulse cycles may be different, or a pulse parameter between at least two or more pulse cycles may be different.

The pulse gap between at least two or more pulse cycles may be 10 ms to 1 min. Preferably, the pulse gap between at least two or more pulse cycles may be 10 ms to 1000 ms.

In addition, in the light sintering method, the step of sintering by irradiating white light on the substrate including the heated ceramic precursor layer (S140), performs a first pulse cycle to sinter the ceramic precursor layer (S141) and the second pulse It may include a step of performing a cycle to sinter the ceramic precursor layer (S142).

The step of performing the first pulse cycle to sinter the ceramic precursor layer (S141) may be controlled by the first power supply and the first capacitor, and performing the second pulse cycle to sinter the ceramic precursor layer ( S142) may be adjusted by the second power supply and the second capacitor.

Also, the pulse parameters of the first pulse cycle and the second pulse cycle may be changed according to the material of the ceramic precursor layer.

For example, the ceramic precursor layer may include a first ceramic material and a second ceramic material, the first ceramic material may be sintered by a first pulse cycle, and the second ceramic material by a second pulse cycle. Can be sintered.

Therefore, in the step of sintering by irradiating white light on the substrate including the heated ceramic precursor layer (S140), the ceramic precursor layer is sintered by applying heat to the ceramic precursor layer using a heat source and irradiating extreme white light, A perovskite crystal structure may be formed in the ceramic precursor layer.

More specifically, in the step of sintering by irradiating white light on the substrate including the heated ceramic precursor layer (S140), the extreme white light is irradiated to the ceramic precursor layer, so that the perovskite crystal structure can be formed in the ceramic precursor layer. have. That is, by irradiating the ceramic precursor layer with extreme white light, a perovskite crystal is grown in the ceramic precursor layer, and the ceramic precursor layer is sintered to produce a ceramic thin film.

The ceramic thin film may be a porous thin film in which pores are formed by perovskite crystals formed in a ceramic precursor layer.

Therefore, when a ceramic thin film is used as an electrolyte thin film, oxygen ions (O ^2- ) and electrons are easily moved through pores, so that the ion conductivity and electrical conductivity of the battery can be improved. In particular, oxygen ions (O ^2- ) are easily transferred to the electrode through pores formed in the ceramic thin film, and efficiently react with hydrogen ions (H ⁺ ) or carbon ions (C ⁴⁺ ) introduced from the electrodes. can do.

If the ceramic thin film is used as an electrode, the ceramic thin film is a porous thin film formed of pores due to the perovskite crystal structure, and thus oxygen (O ² ) gas introduced into the electrode from the outside is reduced and generated. Oxygen ions (O ^2- ) can be efficiently transferred to the electrolyte foil through pores formed in the electrode.

The photo-sintering method proceeds to step S150 of carrying out the substrate including the sintered ceramic precursor layer.

The photo-sintering method can be carried out by horizontally moving a slider equipped with a substrate including a sintered ceramic precursor layer.

[Production Example 1]

After printing uniformly the ceramic solution containing LSC (lanthanum strontium cobaltite) on a silicon wafer by spin coating, and drying at 100 ° C. for 30 minutes using a heater, a ceramic precursor of 200 nm A layer was formed.

Then, the silicon precursor (Silicon wafer) uniformly coated with a ceramic precursor layer was heated to 300 ° C. using a heater, and then the slider was moved to the bottom of the xenon flash lamp.

A first pulse cycle (preheating) and 10 ms of a pulse width of 10 ms, a number of pulses of 30, a pulse gap of 100 ms, and a light intensity of 300 J / cm 2 in total on a silicon wafer coated with a ceramic precursor layer uniformly The second pulse cycle (main sintering) of the pulse width, the number of pulses of 5 times, the pulse gap of 10 ms and the total light intensity condition of 60 J / cm 2 was investigated, and the pulse pulse gap of 1 min for the first and second pulse cycles It was investigated to have.

[Production Example 2]

After the ceramic solution containing lanthanum nickelate (LNO) is uniformly printed on a silicon wafer by spin coating, it is dried and preheated for 1 hour using a heater at 500 ° C to perform the ceramic precursor. A layer was formed.

Thereafter, the ceramic precursor layer was uniformly coated and heated to 500 ° C. using a heater under the silicon wafer, and then the slider was moved to the bottom of the xenon flash lamp.

Pulse width of 30ms, pulse number of 6 times, pulse gap of 80ms and energy density conditions of 60J / cm2, 80J / cm2, 100J / cm2, 120J / cm2 and 130J / cm2, respectively, on a silicon wafer coated with a ceramic precursor layer uniformly The pulse cycle was investigated.

[Comparative Example 1]

Experiments were conducted in the same manner as in [Production Example 2-1], except that the silicon wafers with the ceramic precursor layer uniformly coated were heated to 800 ° C and 900 ° C, respectively, and only heat sintering was performed.

[Production Example 3]

A ceramic precursor layer of 250 nm was formed by uniformly printing a ceramic solution containing LSM (lanthanum strontium manganese) on a silicon wafer by electrostatic spray deposition.

Then, the silicon precursor (Silicon wafer) uniformly coated with a ceramic precursor layer was heated to 500 ° C. using a heater, and then the slider was moved to the bottom of the xenon flash lamp.

The silicon wafer coated with the ceramic precursor layer was examined for pulse widths of 10 ms, width of 6 pulses, pulse gap of 10 ms, and energy cycle conditions of 70 J / cm 2, 100 J / cm 2 and 130 J / cm 2, respectively.

[Comparative Example 2-1]

In [Production Example 3-2], light sintering was performed by irradiating light with an energy density of 40 J / cm 2.

[Comparative Example 2-2]

The sintering was performed in the same manner as in [Production Example 3], except that only the thermally sintering of the silicon wafer on which the ceramic precursor layer was uniformly coated was performed.

5A and 5B show a scanning electron microscope (SEM) measurement image of a ceramic thin film sintered using a single heat sintering.

FIG. 5A heat-sintered the ceramic precursor layer at a temperature of 200 ° C, and FIG. 5B heat-sintered the ceramic precursor layer at a temperature of 300 ° C.

6A and 6B show a scanning electron microscope (SEM) measurement image of a ceramic thin film sintered using a single light sintering.

6A and 6B light-sintered the ceramic precursor layer with a pulse intensity of 60 J / cm 2.

7A and 7B show a scanning electron microscope (SEM) measurement image of a sintered ceramic thin film using an optical sintering apparatus according to an embodiment of the present invention that simultaneously performs thermal sintering and light sintering.

FIG. 7A is a main sintering ceramic precursor layer with a pulse strength of 60 J / cm 2 at a temperature of 200 ° C. using the photo sintering apparatus according to an embodiment of the present invention, and FIG. 7B is a photo sintering apparatus according to an embodiment of the present invention. The ceramic precursor layer was main sintered with a pulse strength of 60 J / cm 2 at a temperature of 300 ° C.

5A to 7B, the ceramic thin film sintered using the light sintering apparatus according to the embodiment of the present invention has a smaller thermal shock and improved sintering degree than the ceramic thin film sintered using a single heat sintering and single photo sintering. You can see that

8 is a graph showing sheet resistance of a ceramic precursor layer depending on the presence or absence of a heater.

Referring to FIG. 8, when light sintering is performed using a light sintering device (w / o heater) that does not include a heater, the smallest sheet resistance value is measured at a pulse strength of 80 J / cm 2, whereas the heater When the light sintering device according to an embodiment of the present invention (w / heater 200 ° C and w / heater 300 ° C) undergoes light sintering, a small resistance value at a lower pulse strength increases as the temperature of the heater increases. It can be seen that it is measured.

Therefore, it can be seen that the sintering of the ceramic precursor layer proceeds even when white light is irradiated with a lower pulse intensity as the temperature of the heater increases.

9A to 9E are SEM images showing the surface of the ceramic precursor layer according to the intensity of the irradiated extreme white light.

9A to 9E are ceramic precursors when irradiated with ultra-short white light to the ceramic precursor layer with the light intensity of 60J / cm 2, 80J / cm 2, 100J / cm 2, 120J / cm 2 and 130J / cm 2, respectively, for Preparation Example 2 SEM image showing the surface of the layer.

9A to 9E, it can be seen that the sintering pattern of the ceramic precursor layer is different according to the light intensity.

Specifically, the stronger the intensity of the extreme white light irradiated to the ceramic precursor layer is, the more grain develops to block pores, thereby increasing the density of the ceramic precursor layer and improving the sintering degree of the ceramic precursor layer. Can be confirmed.

10 is an XRD graph of the surface of the ceramic precursor layer subjected to photo-sintering and the ceramic precursor layer subjected to heat sintering.

10 is a ceramic precursor after irradiating extreme white light to the ceramic precursor layer with light intensity of 60J / cm2, 80J / cm2, and 100J / cm2 after pre-heating the temperature at the bottom of the substrate to 500 ° C for Preparation Example 2, respectively. It is the result of XRD analysis of the surface of the layer and the result of XRD analysis of the surface of the ceramic precursor layer according to Comparative Example 1 in which only heat sintering was performed.

10, each of ^{60J / cm 2, 80J / cm} 2 , and Preparative Example 2 was conducted to the light sintering to 100J / cm ² is one wherein the control proceeds only be opened by sintering at 700 ℃ after fixing the substrate temperature to 500 ℃ It can be confirmed that the crystallinity was developed as in Example 1.

That is, in Preparation Example 2, in which the photo-sintering was performed after the preliminary heat treatment, it was confirmed that the ceramic precursor layer was successfully sintered as in Comparative Example 1, in which only the heat-sintering was performed.

11 is a graph showing the electrical conductivity of the ceramic precursor layer before and after light sintering.

11 is a graph showing electrical conductivity before and after light sintering of Preparation Example 2 according to On-time 30 ms, Off-time 80 ms, and Pulse # 6.

Referring to FIG. 11, before proceeding to light sintering with respect to Preparation Example 2, it can be seen that the resistance is infinite (∞) and thus does not exhibit electrical conductivity.

In addition, it can be seen that after performing the light sintering with respect to the manufacturing example 2, the resistance is rapidly decreased, and thus it has excellent electrical conductivity.

In addition, in Production Example 2, the photo-sintering energy was excessively large, and it was confirmed that the photo-sintering temperature increased to just before the point where the secondary phase was to be generated (ie, 120 J / cm ² ), resulting in a slight decrease in electrical conductivity.

In addition, in the light intensity of 120 J / cm 2, the resistance increased sharply again with respect to Production Example 2, and at a light intensity of 120 J / cm 2 or more, a secondary phase was formed on the ceramic precursor layer, and the electrical properties of the ceramic precursor layer were lowered. It can be confirmed.

Therefore, it can be seen that it is desirable to proceed with light sintering at a light intensity of less than 120 J / cm 2 when forming the ceramic precursor layer using the light sintering device according to the embodiment of the present invention.

At this time, the 80J / cm ² the resistance of the ceramic precursor layer is small at first, 120J / cm ² or more can be confirmed that again the resistance of the ceramic precursor layer increases sharply.

This is because the structure changes due to the formation of the secondary phase of the LNO material due to excessive energy.

In addition, according to the results of FIG. 11, the light sintering apparatus according to the embodiment of the present invention can effectively perform light sintering even with a low energy density (ie, low light intensity).

12 is a graph showing the resistivity according to the thickness of the ceramic precursor layer when performing light sintering at the same light intensity.

12, the light intensity (energy density) of the substrate temperature is fixed to 500 ℃ 80J / ㎠, on-time (On-time) 30ms, off-time (Off-time) 80ms, the number of pulses (Pulse #) It shows the resistance according to the thickness of the ceramic precursor layer when the light is irradiated to Preparation Example 2 under the condition of 6 to proceed with light sintering.

12, when the thickness of the ceramic precursor layer of Preparation Example 2 is 250nm, it can be seen that it has the lowest resistivity (10.27x10 ^-4 Ωcm) and has the highest electrical conductivity.

FIG. 13 is a graph showing ATR FT-IR (attenuated total reflectance Fourier transformed infra-red) of the ceramic precursor layer, respectively, performing heat sintering and light sintering.

13, the heat sintering, only the control example carried out with respect to the column 2-2 and the sintering temperature 500 ℃ 600 ℃ 851cm ^-1, 1388cm ^-1, metal bore by a peak expression at 1470cm ^-1 - organic bond ( It can be confirmed that the ceramic precursor layer was not sintered because the metal-organic bond) was not broken.

However, in the heat sintering temperature 700 ℃ relative to the Control Example 2-2 performed only by heat sintering 851cm ^-1, 1388cm ^-1, 1470cm ^-1 in the bore that a peak is not observed metals - see that the organic binder is disconnected heat sintering Can.

Preparative Example 3 with respect to the fixed after the substrate temperature to 500 ℃ intensity of light (that is, the energy ^{density) 40J / ㎠ 851cm -1, 1388cm} -1, a peak is seen to have been expressed in metal 1470cm ^-1 - organic bond ( It can be seen that the ceramic precursor layer was not sintered because the metal-organic bond) was not broken.

However, in the above Production Example 3 with respect to intensity of the light 70J / ㎠ 851cm ^-1, 1388cm ^-1, 1470cm ^-1 in the bore that is not a peak is observed metals - can be confirmed that the organic binder is broken ceramic precursor layer are sintered .

Therefore, in Preparation Example 3, since the ceramic precursor layer may be sintered even after only heat sintering after heat-treating the substrate at a temperature lower than that of Comparative Example 2-2 where only heat sintering was performed at 700 ° C, it is lower than the conventional heat sintering process. It can be seen that the ceramic precursor layer can be sintered at a temperature.

14A to 14C are SEM images showing a surface according to the intensity of light irradiated to the ceramic precursor layer including LSM.

14A to 14C show a result of performing light sintering by irradiating light to the ceramic precursor layer for Preparation Example 3 at an intensity of 70 J / cm 2, 100 J / cm 2, or 130 J / cm 2 after fixing the substrate lower temperature to 500 ° C. SEM image showing the surface of the ceramic precursor layer.

14A to 14C, it can be seen that the sintering degree of the ceramic precursor layer is different according to the intensity of light irradiated to the ceramic precursor layer according to Preparation Example 3.

Particularly, it can be seen that as the intensity of light was increased in the order of 70 J / cm 2, 100 J / cm 2, and 130 J / cm 2, the crystallinity of the ceramic precursor layer of Preparation Example 3 was developed to increase the degree of sintering.

15 is a graph of XRD analysis of the surface of the ceramic precursor layer after thermal sintering or photo sintering the ceramic precursor layer including LSM.

15 shows the results of XRD analysis of the surface of the ceramic precursor layer subjected to light sintering by irradiating with light intensity of 70J / cm 2, 100J / cm 2, and 130J / cm 2 with respect to Preparation Example 3, and Comparative Example 2-2. The results of XRD analysis of the surface of the ceramic precursor layer are shown.

Referring to FIG. 15, it can be confirmed that the ceramic precursor layer of Comparative Example 2-2 only performing thermal sintering and the ceramic precursor layer of Preparation Example 3 performing light sintering have the same intensity for the same x-axis value.

From this, it can be confirmed that the ceramic precursor layer was successfully sintered because the crystallinity was developed as in Comparative Example 2-2 in which only the thermal sintering was performed in Production Example 3 in which the photo-sintering was performed.

Therefore, the present invention can be seen that the ceramic precursor layer can be photo-sintered in the same manner as in the prior art, even at a relatively lower temperature than the conventional heat sintering process, without the need for heat sintering at a high temperature as before.

On the other hand, the embodiments of the present invention disclosed in the specification and drawings are merely presented as specific examples to aid understanding, and are not intended to limit the scope of the present invention. It is apparent to those skilled in the art to which the present invention pertains that other modified examples based on the technical idea of the present invention can be implemented in addition to the embodiments disclosed herein.

110: white light irradiation unit 111: the first white light irradiation unit
112: second white light irradiation unit 120: reflector
130: support 140: slider
150: power supply 160: capacitor
161: first capacitor 162: second capacitor
170: controller S: board

Claims (11)

White light irradiation unit for irradiating white light on the ceramic precursor layer formed on the substrate;
A reflector reflecting white light emitted from the white light irradiation unit;
A support portion disposed under the substrate and including a heat source for applying heat to the ceramic precursor layer;
A power supply supplying power to the white light irradiation unit;
A capacitor connected to the power supply to supply high power to the white light irradiation unit; And
A controller that controls white light emitted from the white light irradiation unit to be irradiated with at least two pulse cycles
Light sintering device comprising a.
According to claim 1,
The at least two or more pulse cycles have different pulse parameters,
The pulse parameter is a pulse sintering device, characterized in that at least one of the pulse intensity, pulse gap, pulse width and number of pulses.
According to claim 1,
The at least two or more pulse cycles include a first pulse cycle and a second pulse cycle,
The first pulse cycle is performed through a first power supply and a first capacitor, and the second pulse cycle is performed through a second power supply and a second capacitor.
According to claim 2,
The controller,
And a pulse parameter of the pulse cycle according to the material of the ceramic precursor layer.
According to claim 4,
The ceramic precursor layer includes a ceramic precursor,
The controller, the optical sintering apparatus characterized in that to change the pulse parameter of the pulse cycle according to the component of the ceramic precursor.
According to claim 1,
The pulse sintering device between the two or more pulse cycles is characterized in that 10ms to 1min.
According to claim 1,
The heat source is a heating plate, a heater (heater) or an optical sintering device, characterized in that the oven.
According to claim 1,
The target temperature of the substrate is a photo-sintering device, characterized in that 100 ℃ to 700 ℃.
According to claim 1,
The support unit further comprises a slider (slider) for moving the substrate in the horizontal direction, characterized in that the light sintering device.
The method of claim 9,
The slider is a light sintering device characterized in that when the substrate reaches a target temperature, the substrate is moved to the lower portion of the white light irradiation unit.
According to claim 1,
The support portion is a light sintering device, characterized in that the conveyor belt for moving the substrate in the horizontal direction.

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