KR20160037670A - Apparatus for film deposition and method for preparing thermoelctric device using the same - Google Patents

Abstract

Provided are a film deposition apparatus capable of manufacturing a thermoelectric device, requiring selective deposition, using aerosol deposition, and a method for manufacturing a thermoelectric device using the same. The film deposition apparatus according to the present invention comprises: a process chamber which includes a stage transferring a target in a state of supporting the target; a vacuum pump which is connected and combined with the process chamber, and forms a vacuum condition; an aerosol chamber which accommodates powder; a carrier gas container which stores carrier gas; a carrier gas supply pipe which connects the carrier gas container with an interior of the aerosol chamber so as to introduce the carrier gas into the interior of the aerosol chamber; an aerosol transport pipe which guides aerosol, including the powder mixed with the carrier gas, to an interior of the process chamber; a nozzle which is provided at one end of the aerosol transport pipe, and sprays the aerosol onto the target; and a selective deposition blocking unit which is interposed between the nozzle and the target.

Description

[0001] The present invention relates to a film deposition apparatus and a method of manufacturing a thermoelectric element using the same,

The present invention relates to a film deposition apparatus and a device manufacturing method using the same, and more particularly, to a film deposition apparatus using aerosol deposition and a method of manufacturing a thermoelectric device using the same.

The difference in the concentration of electrons (or holes) having heat dependence due to the temperature difference at both ends of the solid material occurs at both ends, and this is caused by an electric phenomenon, that is, a thermoelectric phenomenon. Such a thermoelectric phenomenon can be classified into a thermoelectric power generating electric energy and a thermoelectric cooling / heating which causes a temperature difference at both ends by electric power supply. Thermoelectric materials exhibiting thermoelectric properties have many advantages because they do not emit pollutants during power generation and cooling and are environmentally friendly and sustainable.

The heat transfer coefficient of the thermoelectric material is generally 200 μV / K, and it is necessary to connect several p-type and n-type thermoelectric materials in series for the desired power. In order to efficiently manufacture a thermoelectric module having a high degree of integration, methods such as sputtering, ion beam deposition, and screen printing have been proposed. However, in the conventional sputtering or ion beam deposition method, the deposition rate is low and the production efficiency is poor.

When the film thickness is thin, the power generation amount is small and is insufficient as a power source for small electronic apparatuses. In order to ensure a sufficient film thickness, there is a method of slurry formation and screen printing followed by degreasing and sintering, but it is difficult to form a p-type and n-type island or stripe film on the same substrate. Therefore, there is a problem that a separate pattern forming step is required. Further, if the degreasing is insufficient, there is a problem that the impurities remain and deteriorate the performance.

In the field of thermoelectric device manufacturing, there is an attempt to use an aerosol deposition apparatus. Generally, an aerosol deposition apparatus is capable of coating or depositing a thin film of a micro-ceramic powder on an electronic part or a mechanical part. In the aerosol deposition, the carrier gas flows into the aerosol chamber containing the ceramic powder, the micro-ceramic powder floating in the aerosol generator is transported into the vacuum chamber, and the micro-ceramic powder is transported through the nozzle to the deposition chamber To form a ceramic coating layer on the target.

The aerosol deposition method is capable of dense ceramic coating at room temperature, thereby preventing softening and oxidation of targets such as plastics and metals. In addition, the aerosol deposition method is applied by spraying a ceramic powder as a raw material. Since the chemical change rarely occurs in the ceramic powder during the process, the chemical composition of the raw material is directly maintained in the coating layer.

Such a conventional aerosol deposition apparatus is a continuous scanning type deposition using a nozzle, which forms a ceramic powder coating layer on the entire surface on a target such as a substrate, but is difficult to selectively deposit in a localized region. In addition, when a film having a pattern is deposited by reducing the width of a nozzle or the like, there is a disadvantage in that a low-resolution pattern in which the edge portion of the deposited film is not smooth is formed. Accordingly, it is difficult to apply the present invention directly to a thermoelectric device requiring selective deposition such as a thermoelectric module in which a p-type and an n-type island or stripe film is formed on the same substrate. Therefore, there is a high need for an apparatus and a method for manufacturing a thermoelectric device using aerosol deposition with high deposition rate and high production efficiency.

SUMMARY OF THE INVENTION The present invention provides a film deposition apparatus capable of manufacturing a device such as a thermoelectric device requiring selective deposition using aerosol deposition, and a method of manufacturing a thermoelectric device using the film deposition apparatus.

According to an aspect of the present invention, there is provided a film deposition apparatus including: a process chamber having a stage capable of moving in a state in which a target is supported; a vacuum pump communicating with the process chamber to form a vacuum; A carrier gas supply pipe connected to the carrier gas storage container and the aerosol generator to allow the carrier gas to flow into the aerosol generator, An aerosol transfer tube for guiding the aerosol into the process chamber, a nozzle disposed at one end of the aerosol transfer tube for spraying the aerosol onto the target, and a selective vapor deposition shield disposed between the nozzle and the target.

And a control valve installed in the aerosol transfer pipe to adjust an aerosol supply amount.

The stage may be a three-axis moving stage that is moved in three axes by a driving source, and a fixing means for fixing the target may be provided. Additionally, the stage may be provided with temperature control to improve the quality of the deposited film. To this end, the stage may include a heating unit and a cooling unit capable of temperature control.

Preferably, the shield may partially or temporarily block the delivery of the aerosol sprayed from the nozzle to the target to deposit and / or impart directionality only to a desired area.

The shield may be a mask in which an opening is formed to allow the aerosol ejected from the nozzle to reach only a partial area on the target to form a patterned film. At this time, the powder in the mask and the aerosol may be charged with equal charge, and the deposition of the powder on the mask may be prevented by the repulsive force between each other. The mask may be formed such that a side wall defining the opening is inclined. The mask may be formed such that a partition protrudes downward on a side wall defining the opening.

The shield may be a collimator that imparts straightness to the aerosol to improve the uniformity of the film being grown. The collimator may include a plurality of passageways through which the aerosol moves to a path that is perpendicular to the target.

The nozzle may be provided with a spiral groove on a pipe wall of the inner pipe through which the aerosol passes and the powder in the aerosol passing through the inner pipe is transmitted while rotating along the groove.

A method of manufacturing a thermoelectric device according to the present invention includes: preparing a material for charging a thermoelectric material powder into an aerosol generator, fixing a target to a stage, supplying a carrier gas into the aerosol generator, mixing the thermoelectric material powder and a carrier gas, A spraying step of spraying an aerosol generated inside the aerosol generator to the target using a nozzle, wherein the aerosol is sprayed from the nozzle and then reaches a target through a selective vapor deposition shield; And a film forming step of forming a film of thermoelectric material on the target.

The method of manufacturing a thermoelectric device according to the present invention can be performed by using the film deposition apparatus according to the present invention.

In the film formation step, the target or the nozzle may be moved to form a patterned film.

The film deposition apparatus according to the present invention includes the selective vapor deposition shielding, so that it is easy to form a patterned film without using a lithography and etching process or the like. Therefore, the present invention can be applied to fields requiring selective film formation such as semiconductor devices, piezoelectric devices, and thermoelectric devices.

In particular, the film deposition apparatus according to the present invention facilitates the fabrication of thermoelectric elements requiring selective deposition. it becomes easier to form a p-type and n-type island-shaped or stripe-like film on the same substrate, and thus a separate pattern formation step is not required. Therefore, aerosol deposition with high deposition rate and high production efficiency can be used for the manufacture of thermoelectric elements.

According to the method for manufacturing a thermoelectric element according to the present invention, it is possible to form a thick film of a thermoelectric material, and thus a large amount of power is generated and a power source of a small electronic apparatus is sufficient.

1 is a schematic view of a film deposition apparatus according to the present invention.
Fig. 2 shows examples of nozzles included in the film deposition apparatus according to the present invention.
3 is an embodiment of a stage included in the film deposition apparatus according to the present invention.
4 is a cross-sectional view of an embodiment of a mask capable of being provided with a shielding apparatus provided in a film deposition apparatus according to the present invention.
5 is a cross-sectional view of a mask according to another embodiment.
6 is a cross-sectional view of a mask according to another embodiment.
7 to 9 are plan views of a mask according to an embodiment.
Fig. 10 is a cross-sectional view of a collimator capable of being provided with a shield provided in a film deposition apparatus according to the present invention, and Fig. 11 is a plan view.
12 is a cross-sectional view of one embodiment of a nozzle included in the film deposition apparatus according to the present invention.
13 is a flowchart of a method of manufacturing a thermoelectric device using a film deposition apparatus according to the present invention.
FIGS. 14 and 15 are schematic diagrams for forming an island-shaped or stripe-like pattern using the film deposition apparatus according to the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. It is provided to let you know. It should be noted that the embodiments described in the present specification and the configurations shown in the drawings are only the most preferred embodiments of the present invention and are not intended to represent all of the technical ideas of the present invention so that various equivalents And variations are possible.

1 is a view schematically showing a film deposition apparatus according to the present invention.

The film deposition apparatus 100 according to the present invention comprises a carrier gas storage vessel 10, an aerosol generator 30, a process chamber 40, a nozzle 50, a stage 70, and the like.

Specifically, the film deposition apparatus 100 includes a process chamber 40 provided with a stage 70 capable of moving while supporting a target 60, and a process chamber 40 in communication with the process chamber 40, A vacuum pump 80 for forming a vacuum inside the vacuum chamber 40, an aerosol generator 30 for receiving the powder, and a carrier gas storage vessel 10 in which the carrier gas is stored and injected. A carrier gas supply pipe 20 communicates the carrier gas storage container 10 and the inside of the aerosol generator 30 to guide the carrier gas into the inside of the aerosol generator 30, And an aerosol delivery pipe 25 provided at one end of the aerosol delivery pipe 25 for spraying the aerosol via the aerosol delivery pipe 25 to the target 60 And a nozzle 50 for spraying. Although the target 60 is fixed to the upper surface of the stage 70 in the figure, the target 60 may be fixed to the lower surface of the stage 70, depending on the configuration of the process chamber 40, You may.

The carrier gas storage vessel 10 may be a means such as a gas cylinder that houses a gas. The carrier gas storage vessel 10 is connected to the aerosol generator 30 through a carrier gas supply pipe 20. Carrier gas is stored in the carrier gas storage container 10. The carrier gas may be air, oxygen (O ₂ ), nitrogen (N ₂ ), helium (He), argon (Ar)

The aerosol generator 30 receives the carrier gas through the carrier gas supply pipe 20 and disperses the powder contained therein and guides the aerosol composed of the powder and the carrier gas to the aerosol transfer pipe 25 do. The aerosol generator 30 can maximize the floating of the powder by the application of vibration. The shape and structure of the aerosol generator 30 can be variously modified depending on the structure of the equipment. For example, a plurality of aerosol generators 30 may be provided, and the types of powder stored therein may be configured differently for each aerosol generator 30. In this case, each of the aerosol generators 30 may be provided with an aerosol transfer pipe 25. The aerosol transfer pipe 25 may be connected to the nozzle 50 or may be connected to the nozzle after being connected by a single transfer pipe. For example, when a multi-layered film or a vertically stacked multi-layered film in which the thermoelectric materials of different kinds are separated on the same plane and arranged in an island shape or a stripe shape is formed, or when two or more kinds of thermoelectric materials are mixed to form a film Such a device configuration may be useful.

The carrier gas introduced into the aerosol generator 30 through the carrier gas supply pipe 20 in the carrier gas storage vessel 10 carries the powder to be scattered into the aerosol flow to form an aerosol and the aerosol is supplied only through the aerosol transfer pipe 25, To the nozzle (50). The inflow rate of the carrier gas that can flow into the aerosol generator 30 from the carrier gas storage container 10 can be adjusted within a range of 1 L / min or more, but the inflow rate can be changed according to the size of the nozzle 50.

The process chamber 40 forms a closed space and communicates with the inside of the vacuum pump 80 so that the vacuum pump 80 is in a vacuum state during operation and a vacuum state such as a low vacuum or a vacuum state suitable for the film forming atmosphere is implemented do. For example, the vacuum degree of the process chamber 40 may be a low vacuum of about 100 kPa to 3 kPa, or a vacuum of about 3 kPa to 100 mPa. The vacuum pump 80 may include a rotary pump for generating a vacuum and a vacuum booster.

In the process chamber 40, a nozzle 50 having an opening is provided. The nozzle (50) is in communication with the aerosol delivery pipe (25). The aerosol transfer pipe 25 guides the aerosol containing powder inside the aerosol generator 30 to the nozzle 50. Both ends of the aerosol transfer pipe 25 are connected to the aerosol generator 30 and the nozzle 50 Respectively. The aerosol transfer pipe (25) may be provided with a discharge control valve to control the amount of aerosol discharged. The emission control valve may be a flow control valve (MFC) that regulates the flow rate. These discharge control valves can serve to pass the flow rate determined by the operator's setting. The nozzle 50 is provided at a position spaced upward from the stage 70. The nozzle 50 is fixed in a predetermined position within the process chamber 40 to guide and accelerate the spray direction of the aerosol. The opening width of the nozzle 50 may be, for example, 0.1 to 5 mm, and the opening length of the nozzle 50 may be 5 to 300 mm. The length of the opening may be longer if necessary. The opening of the nozzle 50 may be in the form of a dot having a relatively small width and length (the point may be circular or rectangular in this case), or a line shape (e.g., a slit) It can have a relatively long surface shape. For example, the opening of the nozzle 50 may be a rectangular point type of 2 mm x 5 mm. As another example, the opening of the nozzle 50 may be a rectangular line type of 2 mm x 60 mm. As another example, the opening of the nozzle 50 may be a square surface type of 60 mm x 60 mm. The cross-sectional shape, width and length of the opening of the nozzle 50 can be variously changed depending on the components of the powder, the film thickness to be deposited, and the pattern shape.

The nozzle 50 itself may be of a box type, such as a rectangular parallelepiped, or a curved surface, such as a cylinder or an elliptical column. FIG. 2 shows examples of nozzles included in the film deposition apparatus according to the present invention, in which the body is a box type such as a rectangular parallelepiped. Referring to Fig. 2, (a) shows a case where the nozzle 50 includes a rectangular tube 51a. (b) shows a case in which the nozzle 50 includes a plurality of cylindrical tubes 51b. (c) shows a case in which the nozzle 50 includes the elliptical tube 51c. The rectangular tube 51a, the cylindrical tube 51b, and the elliptical tube 51c may be connected to the nozzle opening as it is, or may be deformed in the middle to form a nozzle opening of a different shape.

The stage 70 is constructed so as to be movable in three axial directions such as up and down Z, forward and backward and leftward and rightward XY, and is drive-controlled. The stage 70 is movable at a speed of approximately 0 to 50 mm / It is possible to dispose the same target 60 so as to have an interval of approximately 1 to 100 mm against the nozzle 50. The three-axis structure of the stage 70 may be a combination of linear motors, a structure applied to a conventional robot arm, or the like. Further, the stage 70 may be provided with fixing means capable of fixing the target 60. The fixing means for fixing the target 60 can be an air chuck or a clamping device. Accordingly, when the powder is injected downward through the nozzle 50 and the target 60 is moved by the movement of the stage 70, A film of a material can be formed.

3 is an embodiment of a stage included in the film deposition apparatus according to the present invention. The stage 70 may be provided with temperature control capable of improving the film quality to be deposited. The stage 70 includes the heating portion 72, so that it is possible to perform heating during film deposition in order to increase the film quality as necessary. In addition, in-situ annealing may be performed for crystallization by heat treatment at the same time as the film deposition. In addition, post-annealing may be performed after the target 60 is further annealed before the target 60 is taken out of the process chamber 40 of the film deposition apparatus 100. The cooling unit 74 functions to help precise temperature control and prevent heat from being transferred to the lower portion of the stage 70. Therefore, it is possible to improve the film quality by performing constant temperature heating through the control of the heating section 72 and the cooling section 74, or to perform crystallization through in-situ annealing or post heat treatment.

On the other hand, in the process chamber 40, a selective vapor deposition shield 90 such as a mask or a collimator is further installed. The shield 90 is to partially or temporarily block the delivery of the aerosol sprayed from the nozzle 50 to the target 60 so as to be deposited only in a desired area and / or to give directionality. For example, it is possible to provide a collimator that improves the uniformity of the grown film by imparting a directivity to the mask or aerosol having the opening of the desired shape formed so that the aerosol ejected from the nozzle 50 reaches only a predetermined region on the target 60 to form a film Do. Preferably, the shield 90 is disposed and fixed between the nozzle 50 and the target 60.

4 is a cross-sectional view of a mask capable of being provided with a shield provided in a film deposition apparatus according to the present invention.

The mask 91 shown in Fig. 4 is a substantially flat plate-shaped member having an opening A at a predetermined position. Only the aerosol passing through the opening portion A of the mask 91 among the aerosols injected from the nozzle 50 is deposited on the target 60 and the aerosol coming on the surface of the mask 91 other than the opening portion A passes through the target 60 ). ≪ / RTI > Accordingly, a film may be formed on the target 60 in a shape corresponding to the opening A at a position corresponding to the opening A. For example, in the case where a pattern of thermoelectric material on an island or a stripe is to be formed, a mask 91 having an island or stripe-shaped opening A is prepared, and the opening size of the nozzle 50 is adjusted to the opening A) size, it is possible to form a striped thermoelectric material film on the target 60 by moving the stage 70 along the stretching direction of the opening A of the mask 91. [ Further, if the opening size of the nozzle 50 is larger than the size of the opening (A) of the mask 91, a selective material film can be formed without a scanning method or a scanning method such as a stage movement.

In the absence of the mask 91, the width of the film formed by the nozzle 50 is approximately equal to or slightly larger than the size of the opening of the nozzle 50 and some control is achieved by adjusting the distance between the nozzle 50 and the target 60 It is possible. However, there is a problem that the resolution of the film is poor and the boundary of the sidewall of the film is not clear. There is a limitation in forming a film smaller than the size of the opening of the nozzle 50. In order to form a pattern having various sizes, There may be a need to replace it frequently. In the present invention, by introducing a shield such as the mask 91, it becomes easier to form a pattern of a desired size and shape. The mask 91 can be fabricated to have openings of various sizes and is more efficient in forming patterns of various sizes because it is an easily replaceable portion. For example, in order to manufacture a small thermoelectric power generator, a film having a width of several tens to several hundreds of micrometers is required. Therefore, even if the nozzle 50 having a unit size of mm is used, the size of the opening A of the mask 91 So that it can be handled easily.

When the mask 91 is repeatedly used over a long period of time, powder is deposited around the opening A of the mask 91 to form a film. In this case, the powder adhering to the inlet side of the opening portion A is less likely to be powdered to the outlet side of the opening portion A, so that it is difficult to maintain a uniform deposition rate. Then, the size of the opening A may be made smaller or the resolution may be lowered over time. Therefore, after a certain period of time, the powder must be deposited and used or discarded through a regeneration process in which the material attached to the surface is removed from the thickened mask 91. When the mask 91 and the powder in the aerosol are charged with the equal charge, the powder can be prevented from accumulating on the mask 91 by the repulsive force between them, and the cycle of regeneration of the mask 91 can be increased.

5 is a cross-sectional view of another mask.

The mask 92 shown in Fig. 5 is formed such that the side wall B defining the opening A is inclined. This shape has the effect of preventing the powder in the aerosol from being deposited on the mask 92. By employing the mask 92 having such a shape, the cycle of regeneration of the mask 92 can be increased.

6 is a cross-sectional view of another mask.

Referring to FIG. 6, a partition C is formed on the side wall defining the opening A of the mask 93 so as to protrude downward. The partition C further imparts straightness to the aerosol passing through the opening A. Thereby, a desired pattern shape can be formed more accurately.

7 to 9 are plan views of a mask according to an embodiment.

Fig. 7 shows a case where the opening portion A of the mask is rectangular, and Fig. 7 (b) shows a case where the opening portion A of the mask is circular. The width p of the opening A or the distance p between the diameter d and the opening A can be controlled if necessary so that the ratio of the distance p / width or diameter d between the openings is 0.1 to 2 The design rule may be determined. This ratio is a suitable ratio for forming a multi-layer film without interference with adjacent patterns.

Fig. 8 is a case suitable for forming a stripe pattern.

Fig. 9 is more suitable for forming a multi-layer film which is separated on the same plane and arranged in an island shape or a stripe shape, and alternately uses a combination in which the openings A of the two masks are in a complementary relationship. 7A is a modification of the mask shown in FIG. 7A, FIG. 7B is a case where the multiple film is a circular island pattern, and FIG. 7B is a cross- (C) is a modified example of the mask shown in Fig. 8 in the case where the multi-layered film is a stripe-shaped pattern. When a pattern of the first material is formed using the first mask on the left side of the mask combination shown in FIG. 9, and then a pattern of the second material is formed by replacing the second mask with the second mask on the right side, It is possible to form a multi-layer film composed of an alternate pattern of the second material.

As described above, the opening A of the mask can have various shapes according to the required pattern shape, has flexibility that can be changed for the formation of the multilayer film, and it is necessary to form a multilayer film such as a semiconductor element, a piezoelectric element, and a thermoelectric element It is very likely to be used in the field.

Fig. 10 is a cross-sectional view of a collimator capable of being provided with a shield provided in a film deposition apparatus according to the present invention, and Fig. 11 is a plan view. 10 corresponds to a cross section taken along the line X-X 'in FIG.

The collimator 94 is a kind of filtering plate that is positioned between the target 60 and the nozzle 50. The collimator 94 is generally uniform in thickness and has a plurality of passages D formed through this thickness. The collimator 94 filters the aerosol above the required angle. The actual amount of filtering performed by a given collimator 94 depends on the aspect ratio of the passage D through the collimator 94. [ In this way, powders traveling in a path approaching the target 60 in a perpendicular direction are deposited on the target 60 through the collimator 94.

The aerosol is deposited on the upper surface of the target 60 by the collimator 94 having a plurality of passages D while keeping the incident angle constant. The collimator 94 has the function of making uniform deposition and adjusting and stabilizing the amount of aerosol. As shown in FIG. 11, the collimator 94 is formed with a plurality of holes having the same diameter in a substantially disc-shaped body to constitute the passage D. Powder passing through the hole is imparted with straightness. The holes may be latticed, honeycombed, or circular.

The mask and the collimator described above may be provided separately or together in the film deposition apparatus according to the present invention.

12 is a cross-sectional view of one embodiment of a nozzle included in the film deposition apparatus according to the present invention.

The directing of the powder is possible by changing the configuration of the nozzle 50 in addition to the configuration of the collimator. For example, as shown in FIG. 12, a spiral groove 54 may be formed in the inner wall of the inner tube 52 through which the powder passes, so that the powder 50 is rotated while spraying the powder. The groove 54 is formed in a helical shape so as to extend into the inner tube 52. After the groove 54 is machined, the powder passing through the inner tube 52 can be uniformly transferred while rotating along the groove 54 have. The greater the number of grooves 54, the higher the rotational speed and the higher the straightness. This is because the rotational force of the powder disperses the air resistance opposite to the traveling direction in various directions to prevent the trajectory from being changed. Therefore, this configuration can be more effective when the vacuum environment is lower than the vacuum atmosphere.

Next, the operation of the film deposition apparatus 100 having the above configuration will be described. The carrier gas storage vessel 10 is opened to introduce helium gas into the aerosol generator 30 through the carrier gas supply pipe 20 at a flow rate of 2.5 L / min, for example, to generate aerosols. At this time, when the powder can be scattered with the aid of a device such as a vibrator, the aerosol can be stably generated. Among the powders in the aerosol, those which are agglomerated to form the secondary powder can not move upward because they are relatively large in weight. In contrast, a relatively small primary powder or a relatively small powder close to the primary powder can travel up to the top in the aerosol generator 30. Therefore, powder having a desired particle diameter can be selected and derived.

The derived aerosol is injected at high speed from the nozzle 50 toward the target 60 through the aerosol transfer pipe 25. The injection speed of the aerosol is determined by the shape of the nozzle 50, the length and the inner diameter of the carrier gas supply pipe 20 and the aerosol transfer pipe 25, the gas pressure of the carrier gas storage vessel 10, the displacement amount of the vacuum pump 80, Respectively. By these controls, for example, if the inner pressure of the aerosol generator 30 is set to tens of thousands Pa and the inner pressure of the process chamber 40 is set to several hundreds of Pa, and a differential pressure is provided therebetween, And can be accelerated to the supersonic range. Powder in the aerosol that is sufficiently accelerated to obtain kinetic energy collides with the target 60 to form a film. At this time, the powder may be finely crushed by the impact energy, and these fine pieces may adhere to the target 60 or may be adhesively bonded to each other to form a dense film.

The shield 90 partially or temporarily blocks the delivery of the aerosol injected from the nozzle 50 to the target 60 to allow deposition and / or orientation to the desired area only. The target 60 may be allowed to perform the reciprocating motion by the stage 70 during the film forming operation, for example. With this control, it is possible to form a film having a deposition thickness of 1 to 100 mu m, for example, a film of 50 mu m thermoelectric material. The movement speed of the stage 70 can be variously changed for the film forming speed and the surface state control. Further, if the film formation time is prolonged, the deposition thickness can be increased in proportion thereto. If necessary, the film may be improved by adding a heating operation during film formation, firing at the same time as the vapor deposition, or firing by adding a heating operation after the film formation, or may be omitted.

Hereinafter, a method of manufacturing a thermoelectric device by forming a film of a thermoelectric material using the film deposition apparatus 100 constructed as above will be described with reference to FIG. 13 is a flowchart of a method of manufacturing a thermoelectric device using a film deposition apparatus according to the present invention.

First, the thermoelectric material powder is charged into an aerosol generator (30 in FIG. 1), and the target 60 is fixed to the stage 70 (step s1). Thermoelectric materials include Bi ₂ Te ₃ , PbTe, Si-Ge, FeSi ₂ , CoSb ₃ , etc., and p-type and n-type can be produced by doping impurities. Fine particles having a submicron particle size can be prepared by pulverizing a powder obtained by a bulk material or a quenching method or the like. Then, a carrier gas is supplied into the aerosol generator 30 to mix the thermoelectric material powder and the carrier gas to generate an aerosol (step s2).

The aerosol generated in the aerosol generator 30 is transferred to the target 60 using the nozzle 50 (step s3). At this time, the aerosol is sprayed from the nozzle 50 and reaches the target 60 through the shield 90.

Thereby, a film of thermoelectric material is formed on the target 60 (step s4).

In step s4, the target 60 can be moved to form a pattern. This will be described with reference to Fig. FIG. 14 is a schematic view of a case where an island-shaped or stripe pattern is formed by using the film deposition apparatus according to the present invention.

First, the first pattern 62 is formed on the target 60 by aerosol injection through the nozzle 50 as shown in FIG. 14 (a). When the size of the nozzle 50 and the size of the opening of the mask 90 are larger than the size of the first pattern 62, the stage 70 is in a fixed state when the first pattern 62 is formed. When the size of the nozzle 50 is smaller than the opening of the mask 90, the stage 70 is moved to form the first pattern 62 so that the nozzle 50 can scan along the extending direction of the opening of the mask 90. After the first pattern 62 is formed, the second pattern 64 may be formed next to the first pattern 62 by moving the stage 70 laterally as shown in the figure. Repeatedly doing this can easily achieve the desired number of patterns on an island or stripe.

15, several desired patterns on the island or stripe may be simultaneously formed through the scanning of the nozzles 50 through the mask 90 having the scanning method and selectivity of the long rectangular nozzles 50 .

In this way, the stage 70 can be moved in three axial directions and the mask 90 can be provided to easily form a desired pattern on the target 60. The fine pattern can be easily formed on the same target, so that the thermoelectric device can be highly integrated. When the target 60 is moved by the movement of the stage 70, various forms of thermoelectric materials can be formed on the upper surface of the target 60 in accordance with the movement direction of the stage 70.

As described above, according to the present invention, it is easy to form a patterned film without using a lithography and etching process or the like. Therefore, it can be used in the field of multi-layer films such as semiconductor devices, piezoelectric devices, and thermoelectric devices.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but many variations and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims. It will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the appended claims.

10 ... Carrier gas storage container 20 ... Carrier gas supply pipe
25 ... aerosol transfer tube 30 ... aerosol generator
40 ... process chamber 50 ... nozzle
60 ... Target 70 ... Stage
80 ... Vacuum pump 90 ... Shield
100 ... film deposition apparatus

Claims (19)

A process chamber having a stage capable of moving in a state supporting the target;
A vacuum pump communicating with the process chamber to form a vacuum;
An aerosol generator in which the powder is received;
A carrier gas storage container in which a carrier gas is stored;
A carrier gas supply pipe communicating the carrier gas storage container and the inside of the aerosol generator to allow the carrier gas to flow into the aerosol generator;
An aerosol delivery pipe for guiding an aerosol composed of the powder mixed with the carrier gas into the process chamber;
A nozzle provided at one end of the aerosol transfer tube for spraying the aerosol onto the target; And
And a selective vapor deposition shield disposed between the nozzle and the target. The film deposition apparatus of claim 1, further comprising a control valve installed in the aerosol transfer pipe to adjust an aerosol supply amount. 2. The film deposition apparatus according to claim 1, wherein the stage is composed of a three-axis moving stage which is moved in three axes by a driving source, and is provided with fixing means for fixing the target. The film deposition apparatus according to claim 1, wherein the stage includes a heating section capable of temperature control and a cooling section. The film deposition apparatus of claim 1, wherein the shield is configured to partially or temporarily block the delivery of the aerosol sprayed from the nozzle to the target to deposit and / or to orient only the desired region. The film deposition apparatus according to claim 1, wherein the shield is a mask having an opening formed therein so that the aerosol ejected from the nozzle reaches only a partial area of the target to form a patterned film. 7. The film deposition apparatus according to claim 6, wherein the powder in the mask and the aerosol are charged with equal charge so that deposition of the powder on the mask is prevented by a repulsive force between each other. The film deposition apparatus according to claim 6, wherein the mask has a side wall that defines the opening and is formed to be inclined. The film deposition apparatus according to claim 6, wherein the mask is formed so that a partition is projected downward on a side wall defining the opening. 10. The film deposition apparatus according to any one of claims 6 to 9, wherein the mask has a ratio of the interval between the openings to the width or diameter of the openings of 0.1 to 2. The film deposition apparatus according to claim 1, wherein the shield is a collimator for imparting a straightness to the aerosol to improve the uniformity of the film to be grown. 12. The film deposition apparatus of claim 11, wherein the collimator includes a plurality of passageways for passing aerosol that travels in a path approaching the target perpendicularly. 12. The film deposition apparatus according to claim 11, wherein a spiral groove is provided in a pipe wall of the inner pipe through which the aerosol passes, and the powder in the aerosol passing through the inner pipe is transferred while rotating along the groove. . A material preparation step of charging the thermoelectric material powder into the aerosol generator and fixing the target to the stage;
A gas supplying step of supplying a carrier gas into the aerosol generator to mix the thermoelectric material powder and the carrier gas to generate an aerosol;
Spraying the aerosol generated in the aerosol generator to the target using a nozzle, spraying the aerosol from the nozzle and reaching the target through the selective vapor deposition shield; And
And a film forming step of forming a film of a thermoelectric material on the target. 15. The method of claim 14, wherein the shield is configured to partially or temporarily block the delivery of aerosols from the nozzles to the target to deposit and / . 15. The method of claim 14, wherein the shield is a mask having an opening for allowing the aerosol ejected from the nozzle to reach only a partial region of the target to form a patterned film. 15. The method of claim 14, wherein the shield is a collimator that imparts straightness to the aerosol to improve the uniformity of the grown film. 15. The method according to claim 14, wherein the target or the nozzle is moved in the film forming step to form a patterned film. Using the film deposition apparatus according to claim 4,
A material preparation step of charging the thermoelectric material powder into the aerosol generator and fixing the target to the stage;
A gas supplying step of supplying a carrier gas into the aerosol generator to mix the thermoelectric material powder and the carrier gas to generate an aerosol;
Spraying the aerosol generated in the aerosol generator to the target using a nozzle, spraying the aerosol from the nozzle and reaching the target through the selective vapor deposition shield; And
And a film forming step of forming a film of a thermoelectric material on the target,
Further comprising the step of heating at a constant temperature through the control of the heating unit and the cooling unit of the stage to improve the quality of the film or to crystallize the film by in-situ annealing or post-heat treatment.

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