JP2011231361A - Vapor deposition apparatus - Google Patents

Abstract

A vapor deposition apparatus capable of controlling the temperature of a substrate with high accuracy in order to control the particle size of fine particles to be deposited to a desired size.
A temperature control unit (32) includes a heat transfer block (34) to which a temperature-controlled liquid or solid heat medium is supplied, and a heat transfer roller (36) held on a surface facing the base material of the heat transfer block. And a gas introduction path 37 for supplying gas to the space between the base material and the heat transfer block, and the heat transfer roller moves down to contact the back surface of the base material and interlocks with the transfer of the base material. Then, while rotating around an axis that intersects this transfer direction, it is possible to move upward by the force from the base material, and the heat transfer roller and heat transfer block The temperature of the substrate is controlled by the propagation of heat through the heat transfer roller and the heat transfer block.
[Selection] Figure 5

Description

  The present invention relates to a vapor deposition apparatus for producing electrode foils such as capacitors and batteries.

  The electrode foil used for a capacitor | condenser and a battery can be formed by vapor-depositing metal microparticles, for example on metal foil.

  Here, as shown in FIG. 13, the conventional vapor deposition apparatus 1 includes a vacuum chamber 2 to which a vacuum pump (not shown) is connected, and a base material 3 is wound in the vacuum chamber 2. 3, a winding roll 4 for feeding 3 in the direction of arrow A, a winding roll 5 for winding the vapor-deposited base material 3, a container 6 for accommodating the vapor deposition raw material, and a supply pipe 7 for supplying the vapor deposition material to this container 6; Is arranged.

  For example, both ends of the container 6 are connected to positive and negative electrodes of a resistance heating power source, and the inside of the container 6 is heated to the boiling point or higher of the vapor deposition material by resistance heating. The vapor deposition raw material evaporates, becomes fine particles, adheres to the surface of the substrate 3, and is laminated.

  Here, depending on the temperature of the base material 3, the activity of the fine particles in the vicinity of the base material 3 changes, and the particle diameter of the fine particles changes, which affects the characteristics of the capacitor or the battery. For example, when the temperature of the base material 3 rises, the fine particles to be laminated are activated, and a plurality of fine particles are combined and enlarged. Therefore, although the mechanical strength of the fine particles is increased, the surface area of the electrode foil is decreased, and the capacitance of the capacitor and the battery capacity of the battery are reduced.

  Therefore, in order to control the temperature of the base material 3 and to control the particle size of the fine particles, a temperature control unit 8 such as a steel belt or other drum controlled to a predetermined temperature is disposed on the back surface side of the base material 3. It is done. In such a vapor deposition apparatus 1, vapor deposition is performed while the base material 3 is transferred along the temperature control unit 8. In FIG. 13, a steel belt is used as the temperature control unit 8.

  When the base material 3 is brought into contact with the temperature control unit 8 in this way, the temperature of the base material 3 can be adjusted by heat exchange with the temperature control unit 8.

  As prior art document information related to the invention of this application, for example, Patent Document 1 is known.

Japanese Patent Laid-Open No. 58-117813

  When the conventional vapor deposition apparatus 1 is used, the temperature control of the base material 3 is insufficient, and there is a problem that it is difficult to control the particle size of the fine particles adhering to the base material 3.

  This is because the adhesion between the substrate 3 and the temperature control unit 8 is low. That is, conventionally, since the base material 3 is aligned with the fixed temperature control unit 8, if the base material 3 has waviness, a gap is formed between the base material 3 and the temperature control unit 8, and heat is efficiently transmitted. I did not. And the temperature control of the base material 3 becomes insufficient, and as a result, the particle size of the fine particles deposited on the base material 3 cannot be controlled.

  Thus, when the particle size of the fine particles changes, the surface area of the electrode foil also changes, which affects the capacity characteristics of the capacitor and battery. Furthermore, when the particle size of the fine particles is non-uniform, the capacity characteristics of the capacitor and the battery are also non-uniform, which causes product variations during mass production.

  Therefore, an object of the present invention is to control the temperature of the substrate with high accuracy and control the particle size of the fine particles to be deposited to a desired size.

  In order to achieve this object, the present invention includes a container that is disposed on the front surface side of the base material and that is supplied with the raw material of the fine particles, and a temperature control unit that is disposed on the back surface side of the base material. The unit includes a heat transfer block to which a temperature-controlled liquid or solid heat medium is supplied, a heat transfer roller held on the surface of the heat transfer block facing the substrate, a substrate and a heat transfer block, A gas introduction path for supplying gas to the space between the heat transfer roller, the heat transfer roller descends and abuts against the back surface of the substrate, and an axis that intersects this transfer direction in conjunction with the transfer of the substrate It can rotate up and down with the force from the base material, and heat can propagate between the base material and the heat medium via the gas, heat transfer roller, and heat transfer block. The temperature of the material was controlled.

  Thereby, this invention can control the temperature of a base material with high precision, and can control the particle size of the microparticles | fine-particles to vapor deposition to a desired magnitude | size.

  The reason is that the contact area between the substrate and the temperature control unit increases, and the gas mediates heat. That is, since the present invention rotates while swinging up and down so that the heat transfer roller contacts the base material, the base material and the heat transfer roller are in contact with each other even if the base material is wavy. Heat exchange between the two.

  In addition, the space between the heat transfer roller and the heat transfer block, and between the base material and the heat transfer roller or heat transfer block also efficiently exchanges heat between the base material and the heat transfer medium. it can.

  Therefore, according to the present invention, the temperature of the substrate can be controlled with high accuracy, and as a result, the particle size of the deposited fine particles can be controlled to a desired size.

The perspective view of the solid electrolytic capacitor in Example 1 of this invention Sectional drawing of the capacitor | condenser element in Example 1 of this invention The schematic diagram of the vapor deposition apparatus in Example 1 of this invention The top view of the temperature control unit in Example 1 of this invention The figure which shows the XX cross section of FIG. Z section enlarged sectional view of FIG. The figure which shows the YY cross section of FIG. The figure which shows the temperature of the base material in Example 1 of this invention SEM photograph of the electrode foil in Example 1 of the present invention having a magnification of 30,000 times The top view of the temperature control unit in Example 2 of this invention The figure which shows the XX cross section of FIG. The top view of the temperature control unit of another example of Example 2 of this invention Schematic diagram of conventional vapor deposition equipment SEM photo of the electrode foil formed with a conventional vapor deposition device with a magnification of 9000

Example 1
Hereinafter, a vapor deposition apparatus for manufacturing an electrode foil will be described in this example. This electrode foil is used, for example, as the anode of the solid electrolytic capacitor 9 shown in FIG.

  For example, as shown in FIG. 1, the solid electrolytic capacitor 9 includes a plurality of stacked capacitor elements 10, and an anode terminal 13 and a cathode terminal from which the anode electrode portion 11 and the cathode electrode portion 12 of the capacitor element 10 are taken out. 14 and an exterior body 15 that covers the anode terminal 13 and the cathode terminal 14 except for a part thereof.

  2, the capacitor element 10 includes an electrode foil 16 formed by the vapor deposition apparatus of the present embodiment, a dielectric film 17 formed on the electrode foil 16, and a dielectric film 17. , An insulating member 18 that separates the electrode foil 16 into an anode electrode portion 11 and a cathode formation portion (not shown), a solid electrolyte layer 19 made of a conductive polymer formed on the dielectric film 17 of the cathode formation portion, A cathode layer 20 composed of a carbon layer and a silver paste layer formed on the solid electrolyte layer 19 is provided. The solid electrolyte layer 19 and the cathode layer 20 constitute the cathode electrode portion 12.

  And as shown in FIG. 3, the vapor deposition apparatus 21 of a present Example introduce | transduces each of inert gas and active gas in this vacuum chamber 22 with the vacuum chamber 22 to which the vacuum exhaust pump (not shown) was connected. A gas pipe (not shown) to be wound, a strip-shaped aluminum foil to be the base material 23 is wound, and an unwinding roll 24 for feeding out in the direction of arrow B, a take-up roll 25 for winding up the deposited base material 23, and vapor deposition A container 26 that contains aluminum as a raw material and a supply pipe 27 that supplies the container 26 with aluminum in a linear form are provided.

  In this embodiment, the base material 23 is an aluminum foil having a width of 100 to 200 mm and a thickness of about 30 to 50 μm, but other copper foils, various metal alloy foils, resin films, and the like can be used. Moreover, although the aluminum wire was used as the vapor deposition material, various metal materials such as lithium and aluminum alloys can be used.

  The container 26 is made of a resistance heating material such as boron nitride, aluminum nitride, or tungsten, and is connected to positive and negative electrodes of a resistance heating power source (not shown) arranged outside the vacuum chamber 22 and is made of a vapor deposition material by resistance heating. Heated above the boiling point of some aluminum.

  When the container 26 is heated in this manner, the aluminum wire melts, boils and evaporates as aluminum fine particles. The fine particles adhere to the surface of the base material 23 and are laminated to form a rough coarse film layer (the number 28 in FIG. 2). The electrode foil 16 is combined with the base material 23.

  Here, in this embodiment, two deflecting rolls 29 and 30 are arranged at a predetermined interval between the unwinding roll 24 and the winding roll 25 in FIG. The base material 23 was kept as horizontal as possible between the deflection rolls 29 and 30.

  In the present embodiment, a container 26 for storing a vapor deposition raw material is disposed between the deflection rolls 29 and 30 on the surface side of the base material 23. Thereby, in the present embodiment, in the vapor deposition region C of the base material 23 (the region where the fine particles are deposited on the surface of the base material 23), the base material 23 becomes horizontal and the area to which the fine particles adhere can be increased. Therefore, even when the deposition rate is low, the deposition time can be extended and the fine particles can be stacked thickly.

  In this embodiment, a shutter 31 is disposed between the base material 23 and the container 26, and the shutter 31 is opened only in a region corresponding to the vapor deposition region C. Thereby, it can prevent that microparticles | fine-particles adhere to the base material 23 of the area | region remove | deviated from the vapor deposition area | region C, the unwinding roll 24, and the winding roll 25. FIG.

  In this embodiment, the temperature control unit 32 is arranged on the back surface side (opposite side of the vapor deposition surface) of the base material 23 that is horizontal in the vapor deposition region C. That is, the temperature control unit 32 and the container 26 are arranged at positions facing each other with the base material 23 therebetween.

  Here, FIG. 4 is a plan view of the temperature control unit 32 as viewed from the surface facing the substrate 23, and FIG. 5 is a view showing a cross section taken along line XX of FIG. FIG. 6 is an enlarged cross-sectional view of a portion Z in FIG. FIG. 7 is a view showing a YY cross section of FIG.

  The temperature control unit 32 of the present embodiment uses cooling water as a heat medium, and as shown in FIG. 5, a rectangular parallelepiped heat transfer block 34 including a pipe 33 to which the cooling water is supplied, and the heat transfer block. A rectangular parallelepiped holding portion 35 joined to the surface of the 34 facing the base material 23, a plurality of heat transfer rollers 36 held by the holding portion 35, and the heat transfer block 34 and the holding portion 35. Gas introduction passage 37.

  In the present embodiment, a gas as a heat medium is introduced from the gas introduction path 37, and the gas is supplied so as to reach the space between the base material 23 and the holding unit 35 or the heat transfer block 34. This gas uses an inert gas such as helium or argon in order to suppress chemical reaction with the fine particles. In this example, helium gas having better thermal conductivity was used. The temperature of the gas was 20 ° C. to 25 ° C., and the flow rate of the gas was appropriately adjusted so that the base material 23 would not float.

  As shown in FIG. 6, the heat transfer roller 36 of the present embodiment descends by its own weight, contacts the back surface of the base material 23, rotates in the direction of arrow D in conjunction with the transfer of the base material 23, and The upward movement is possible by the force from the material 23.

  In the vapor deposition apparatus 21 of this embodiment, the heat transfer roller 36, the holding unit 35, and the heat transfer block 34 in FIG. 5 and FIG. 6 are in contact with each other between the base material 23 and the cooling water (heat medium). As a result, heat propagates sequentially, and the temperature of the substrate 23 is controlled. In this embodiment, since the base material 23 is in line contact with the cylindrical heat transfer roller 36, there is a region where the base material 23 and the heat transfer roller 36 are not in contact at a certain point in time, but the gas introduction path 37. The gas supplied from the medium mediates heat and can efficiently propagate the heat of the base material 23 to the cooling water.

  Here, each of the heat transfer block 34 and the holding unit 35 shown in FIG. 5 is a rectangle having a surface of about 15 cm × 20 cm on the side facing the base material 23 and has a height of about 2 to 3 cm.

  4 and 5, a groove 38 extending in a direction substantially perpendicular to the transfer direction (arrow B) of the base material 23 is formed on the surface of the holding portion 35 facing the base material 23. A plurality of materials 23 are arranged in the transfer direction (arrow B). The groove 38 may penetrate the holding portion 35.

  Heat transfer rollers 36 are held in the grooves 38, respectively. That is, a plurality of heat transfer rollers 36 are arranged in the transfer direction (arrow B) of the base material 23. Although the number of the heat transfer rollers 36 may be one, the use of a plurality of heat transfer rollers 36 increases the contact area between the base material 23 and the heat transfer roller 36 and allows more efficient temperature control. Moreover, the weight of the heat transfer roller 36 per one can be reduced, and the stress load of the base material 23 can be disperse | distributed.

  Each of these heat transfer rollers 36 has a cylindrical shape with a diameter φ of about 5 mm to 15 mm. The inside of the groove 38 is wider than these diameters in order to accommodate the heat transfer roller 36, but the opening of the groove 38 on the side facing the substrate 23 is larger than the diameter of the heat transfer roller 36. Is also designed to prevent the heat transfer roller 36 from falling off.

  Each heat transfer roller 36 is rotatable about an axis E that is substantially orthogonal to the direction of transfer of the substrate 23 (arrow B). The axis E serving as the center of rotation may be a direction that intersects with the transfer direction (arrow B) of the base material 23. The heat transfer roller 36 can be rotated well.

  In this embodiment, the length of the heat transfer roller 36 and the groove 38 in which the heat transfer roller 36 is accommodated is shorter than the width of the base material 23 in the direction of the axis E that is the rotation center of the heat transfer roller 36. It has become. As a result, the inner wall of the groove 38 and the heat transfer roller 36 do not protrude from the outside of the base material 23, so that it becomes difficult for the deposited fine particles to adhere to the inside of the heat transfer roller 36 and the groove 38 in the vapor deposition process. Becomes simple.

  As shown in FIG. 4, the heat transfer roller 36 in the present embodiment is divided into a plurality of pieces each having a length of about 1.5 cm in the axis E direction serving as the center of rotation. Hereinafter, the divided individual heat transfer rollers 36 are referred to as small rollers 39. The heat transfer roller 36 does not have to be divided. However, if the heat transfer roller 36 is divided finely in this way, the individual small rollers 39 swing up and down in accordance with the undulations and wrinkles of the base material 23, and the base material The contact area with 23 can be further increased.

  In addition, as shown in FIG. 6, the heat transfer roller 36 in the present embodiment partially protrudes from the opening of the groove 38 when lowered by its own weight, but is caught in the opening of the groove 38 on the way, The groove 38 is held inside the groove 38 in contact with the inner wall of the groove 38. The heat transfer roller 36 exchanges heat with the holding unit 35 by contacting the inner wall of the groove 38, and the holding unit 35 exchanges heat with the heat transfer block 34.

  In this embodiment, the heat transfer roller 36 rotates in conjunction with the transfer of the base material 23 due to friction with the base material 23. In this embodiment, the transfer direction of the base material 23 is one direction (arrow B in FIG. 3). For example, the transfer is performed in the reverse direction from the take-up roll 25 side to the unwind roll 24 side in FIG. The base material 23 can be reciprocated in the vapor deposition region C. Also in this case, the heat transfer roller 36 rotates about the axis E of FIG.

  In addition, as shown in FIG. 6, the heat transfer roller 36 is maintained in a state where a part of the heat transfer roller 36 is exposed from the opening of the groove 38 due to its own weight in the natural state. Can be pushed inside. Therefore, if the base material 23 has a swell, it receives a force from the base material 23 in accordance with this swell, and the heat transfer roller 36 is pushed up and moves upward, and when the swell disappears, it returns downward due to its own weight. Here, when the heat transfer roller 36 is pushed up and accommodated in the groove 38, the heat transfer roller 36 floats in the air, and the holding portion 35 becomes difficult to contact. That is, the heat transfer roller 36 and the base material 23 are in contact with each other, but the heat transfer roller 36 and the holding unit 35 may not be in contact with each other. However, in this embodiment, since the gas is filled between the heat transfer roller 36 and the holding unit 35 or the heat transfer block 34, heat can be efficiently transferred through the gas.

  In this embodiment, the heat transfer roller 36 is swung up and down by its own weight, but the heat transfer roller 36 and the bottom surface of the groove 38 may be connected by a spring or rubber. In this case, for example, a spring or rubber contracts due to the force from the base material 23, and the heat transfer roller 36 moves upward. When the stress load disappears, the heat transfer roller 36 moves down to the base position by the reaction force of the spring or rubber. However, as in this embodiment, when the heat transfer roller 36 is swung up and down by its own weight without using an elastic member such as a spring or rubber, the heat transfer roller 36 swings more gently and the load on the base material 23 is reduced. it can. Further, since it is not necessary to arrange a complicated mechanism inside the groove 38, the inside of the groove 38 can be easily cleaned.

  Further, in the present embodiment, the plurality of small rollers 39 divided in each groove 38 are not connected to each other in order to freely swing up and down independently, but each small roller 39 may be connected. Is possible. In this case, for example, holes may be formed in the portions of the shaft E that serve as the rotation shafts of the small rollers 39, and shafts thinner than these holes may be connected to these holes. By making the shaft body thinner than the hole in this way, there is a gap between the hole and the shaft body, and each heat transfer roller 36 can swing up and down in a somewhat independent state.

  Furthermore, the material of the heat transfer block 34, the holding part 35, and the heat transfer roller 36 is preferably a material having high thermal conductivity. Accordingly, various materials such as a metal and a high thermal conductive resin can be mentioned. In this example, aluminum was used. Since aluminum has a light mass, even if it contacts the base material 23 by its own weight, the stress load of the base material 23 can be reduced.

  In this embodiment, the tension per width of the base material 23 is 500 g, and the total mass of the heat transfer roller 36 is 100 g to 250 g. Here, the total mass of the heat transfer roller 36 indicates the mass of the heat transfer roller 36 when there is a single heat transfer roller 36, and the total mass when there are a plurality of heat transfer rollers 36. And in the case of the above-mentioned Example, it was possible to deposit the base material 23 without causing wrinkles or scratches. On the other hand, when the heat transfer roller 36 was formed of SUS for comparison and the total mass of the heat transfer roller 36 was 560 g, wrinkles and scratches were generated on the base material 23 in the vapor deposition process.

  From this, it is considered that wrinkles and scratches of the base material 23 in the vapor deposition process can be suppressed by reducing the stress load from the heat transfer roller 36. Also, it has been found through experiments that the total mass of the heat transfer roller 36 is more preferably less than or equal to one-half of the tension per width of the substrate 23.

  In the present embodiment, the cooling water pipe 33 shown in FIG. 5 has a heat medium inlet 40 on one end side of the heat transfer block 34 and a heat medium outlet 41 on the other end side. Cooling water can be introduced from the heat medium inlet 40 and the cooling water can be recovered from the heat medium outlet 41 side. In this embodiment, water is used as a heat medium, but the cooling effect can be enhanced by using a solvent having a low boiling point such as ethylene glycol. The heat medium is not limited to a liquid, and a solid Peltier element may be used and attached to the back surface of the temperature control unit 32. These heat media are controlled at a predetermined temperature.

  Gas for mediating heat is injected from a gas introduction port 42 provided on the back side of the heat transfer block 34, passes through the inside of the heat transfer block 34 and the holding unit 35 through the gas introduction path 37, and is held. It is ejected from a gas outlet 43 provided on the surface side of the portion 35. The gas outlet 43 may be provided on the inner wall of the groove 38.

  In addition, when using gas like a present Example, as shown in FIG. 7, it is a wall in the outer periphery of the area | region where the heat transfer roller 36 was provided on the opposing surface with the base material 23 of the holding | maintenance part 35. 44 may be provided. FIG. 7 shows walls 44 formed on two sides of the holding portion 35 that are parallel to the transfer direction of the base material 23 (arrow B in FIG. 4). In the region surrounded by the wall 44, that is, inside the wall 44, the gas is easily filled. Therefore, by transferring the base material 23 inside the wall 44, heat exchange can be performed more efficiently. Note that the wall 44 is difficult to diffuse outward by tilting the tip inward or by bending it inward.

  Hereinafter, the manufacturing method of the electrode foil 16 using the vapor deposition apparatus 21 of a present Example is demonstrated.

  (1) As shown in FIG. 3, the base material 23 is arrange | positioned in the vacuum chamber 22, and it evacuates from a vacuum exhaust pump (not shown), and is kept at 0.01-0.001 Pa vacuum.

  (2) Argon gas as an inert gas and oxygen gas as an active gas are introduced into the periphery of the base material 23 from a gas pipe (not shown). The flow rate of argon gas was 2 to 4 times that of oxygen gas. As a result, the pressure around the base material 23 is set to 20 to 30 Pa.

  (3) The base material 23 is slowly transferred in the arrow B direction from the unwinding roll 24 to the winding roll 25. The transfer speed is about 0.05 m / min. The direction of the base material 23 is adjusted between the deflecting rolls 29 and 30 so as to be as horizontal as possible in the vapor deposition region C.

  (4) An aluminum wire is supplied from the supply pipe 27 to the container 26, boiled, and fine particles are deposited on the surface of the substrate 23 by vacuum deposition.

  Here, in this embodiment, in the process of depositing fine particles on the surface of the base material 23 as described above, the temperature is controlled to 20 ° C. in advance from the heat medium inlet 40 of the pipe 33 of the temperature control unit 32 as shown in FIG. Cooling water was introduced. Then, the heat of the base material 23 is sequentially propagated to the heat transfer roller 36, the holding unit 35, and the heat transfer block 34, and further the heat transmitted to the heat transfer block 34 is propagated to the cooling water (heat medium). 23 and the cooling water were subjected to heat exchange, and the temperature of the base material 23 was lowered.

  In this embodiment, a gas previously controlled at about 20 ° C. to 25 ° C. is introduced from the gas introduction port 42 of the gas introduction path 37. And in the area | region where the base material 23 is not contacting the heat-transfer roller 36 by deriving | guiding gas from the gas outlet port 43, supplying gas to the space between the base material 23 and the holding | maintenance part 35, and making it fill. Heat can be propagated to the holding unit 35 and the heat transfer block 34. Also, when the heat transfer roller 36 is pushed up into the groove 38 and is in contact with the base material 23, a space is formed between the heat transfer roller 36 and the holding portion 35. Can transmit heat to The number and location of the gas inlets 42 and the gas outlets 43 are not limited to those shown in FIG. 4, and a plurality or one may be provided at appropriate locations.

  FIG. 8 is a result of plotting the temperature of the base material 23 in the vapor deposition region C for each position of the base material 23 in the above-described vapor deposition process. The horizontal axis of the graph indicates the distance (cm) from the measurement location of the substrate 23 and the deflection roll 29. For comparison, the measurement result of the temperature of the substrate 3 in the vapor deposition apparatus 1 using the steel belt 8 of the conventional example shown in FIG. 13 (conventional example shown in FIG. 8) and only cooling water without using gas. The measurement results when the temperature was controlled (comparative example shown in FIG. 8) are shown.

  In the conventional example using the steel belt 8, the temperature of the base material 3 was about 220 ° C. at the peak value due to the latent heat of fine particles and the radiant heat from the container 6. Further, when the cooling water of the comparative example was used, the temperature was controlled by contact with the heat transfer roller 36, and the temperature peak of the base material 23 was lowered to 180 ° C. Further, when the temperature control unit 32 of this example is used, the temperature peak of the base material 23 is about 120 to 130 ° C., about 100 ° C. compared to the conventional example, and about 50 ° C. to 60 ° C. compared to the comparative example. The temperature rise could also be suppressed by ℃.

  As described above, the coarse film layer (the number 28 in FIG. 2) formed by the vapor deposition apparatus 21 of this example has an average particle diameter of about 0.01 μm to 0.15 μm as shown in the SEM photograph of FIG. A coarse structure in which fine particles are randomly stacked from the surface of the substrate 23 and branched into a plurality of branches. When the inside of the coarse film layer 28 of this example was observed by SEM, the mode value of the pore diameter was about 0.01 to 0.15 μm, which was almost the same as the average particle diameter of the fine particles. The pore diameter can be measured by using a mercury intrusion method, and the peak value of the pore diameter distribution used by this is defined as the mode value of the pore diameter. Moreover, the porosity of the rough film layer 28 of this example was 50 to 80%.

  The thickness is 20 μm to 80 μm only at the portion of the rough film layer 28, and is a thick film as compared with, for example, a general deposited film used as an electrode foil of a film capacitor.

  In addition, when forming the rough film layer 28 on both surfaces of the base material 23, after forming the rough film layer 28 on one surface by the above process, the base material 23 is turned over, and the other surface on which the rough film layer 28 is not formed is formed. The rough film layer 28 may be formed by the same process as the surface. In the present specification, the surface on which the fine particles are deposited (that is, the surface facing the container 26) is expressed as the surface of the base material 23.

  The effect of the present embodiment will be described below.

  In the present embodiment, it is possible to increase the uniformity of the rough film layer 28 constituting the electrode foil 16 by suppressing the temperature rise of the base material 23 and controlling the particle diameter of the deposited fine particles to a desired particle diameter.

  This is because the contact area between the heat transfer roller 36 of the temperature control unit 32 and the substrate 23 can be increased, and the gas mediates heat.

  That is, in the configuration of the conventional temperature control unit 8 shown in FIG. 13, since the base material 3 itself is placed along the fixed steel belt 8, when the base material 3 has a swell, this swell In some parts, a gap may be left between the base material 3 and the steel belt 8. When the gap is thus opened, heat exchange is not efficiently performed between the base material 3 and the heat medium, and the temperature of the base material 3 rises and swells as shown in the conventional example of FIG. In the portion, the particle diameter of the deposited fine particles is enlarged.

  FIG. 14 is an SEM photograph of the electrode foil formed by the conventional vapor deposition apparatus 1. Since the heat exchange between the base material 3 and the temperature control unit 8 is not efficiently performed during the vapor deposition process, the temperature of the base material 3 rises and the particle size of some of the fine particles is enlarged, as shown in FIG. Thus, the particle size of the fine particles of the electrode foil became non-uniform.

  In particular, in the vapor deposition process, when the base material 3 is leveled and the fine particles are slowly deposited, each fine particle can be laminated while maintaining the particle shape to form a coarse film layer with many pores. On the other hand, since the time for the base material 3 and the container 6 to face each other is long, it is easy to receive the latent heat of the fine particles and the radiant heat from the container 6, and the particle size of the fine particles tends to be non-uniform. Since the surface area of the coarse film layer in which the fine particles are not uniform varies greatly, the capacitance characteristics cannot be maintained constant when used as the electrode foil of the capacitor.

  In contrast, in this embodiment, the heat transfer roller 36 of FIGS. 5 and 6 rotates while swinging up and down in accordance with the undulation of the base material 23. Therefore, the contact area between each heat transfer roller 36 and the base material 23 increases, and heat propagates through the heat transfer roller 36, the holding portion 35, and the heat transfer block 34, and heat exchange between the base material 23 and the heat medium is performed. It can be done efficiently.

  Further, since the base material 23 is in line contact with the heat transfer roller 36, there is a region where the base material 23 does not come into contact with the heat transfer roller 36 at a certain time point. Heat can be propagated to the heat roller 36. In addition, the heat transfer roller 36 may be pushed up into the groove 38 due to the force from the base material 23 and may not be in contact with the groove 38. In this case as well, the gas mediates heat and heat transfer is performed. The heat of the roller 36 can be efficiently propagated to the holding unit 35.

  Therefore, even if the base material 23 has waviness, the temperature rise can be suppressed, and as a result, the fine particles adhering to the base material 23 can be controlled to a desired particle size.

  In addition, in the vapor deposition process in a present Example, although the base material 23 was moved slowly, even when it raises a transfer speed, the heat exchange efficiency of the base material 23 and a heat medium can be improved.

  In this embodiment, the substrate 23 is cooled in order to suppress the enlargement of the fine particles to be deposited. However, in order to increase the mechanical strength of the fine particles, there is a case where it is desired to enlarge the fine particles to a desired size. In this case, oil or a solvent heated to a predetermined temperature as a heat medium may be introduced into the pipe 33 in FIG. 5 and the heat transfer block 34 may be heated. Further, instead of supplying the heat medium, a heat source such as a nichrome wire heater, a ceramic heater or a lamp heater capable of generating heat at a predetermined temperature may be provided in the heat transfer block 34 to heat the heat transfer block 34. In this case, the direction of heat transfer is reversed from the case where the cooling water is supplied, and the heat from the heat medium or the heat source is sequentially propagated to the heat transfer block 34, the holding unit 35, and the heat transfer roller 36, and the base material 23 Can be heated. Further, heat is propagated through the gas in the regions that do not contact each other.

  As described above, the temperature control unit 32 of the present embodiment can control the temperature of the base material 23 with high accuracy, and thereby can control the particle size of the fine particles deposited on the base material 23 to a desired size. . Moreover, since the temperature unevenness of the base material 23 can be reduced, the uniformity of the particle diameter of the deposited fine particles can be improved.

  Further, in this embodiment, even if the base material 23 has waviness, the heat transfer roller 36 follows the waviness while swinging up and down, so that it becomes difficult for the base material 23 to be wrinkled.

  The shape of the heat transfer roller 36 may be spherical, for example, but by making it cylindrical as in the present embodiment, the contact area with the base material 23 can be made relatively large, and heat exchange is efficiently performed. While being able to do so, it is possible to disperse the stress load on the base material 23 and to suppress the loss of the rough film layer 28.

  In addition, it is preferable to attach R so that the edge part of the heat-transfer roller 36 may be rounded. This is because if the end of the heat transfer roller 36 is angular, the rough film layer (the number 28 in FIG. 2) may be damaged when rotating.

  Furthermore, the surface of the heat transfer roller 36 is preferably mirror-finished. This is because if the heat transfer roller 36 is uneven, the rough film layer 28 may be damaged.

  In this embodiment, the vapor deposition apparatus 21 is exemplified by the resistance heating type vapor deposition apparatus 21 that evaporates the vapor deposition material by resistance heating of the container 26. For example, the vapor deposition material in the container 26 is irradiated with an electron beam. The present invention can also be applied to an electron beam evaporation apparatus that evaporates.

  Further, in this embodiment, the electrode foil 16 is used for the solid electrolytic capacitor 9 laminated, but it can also be used for the solid electrolytic capacitor 9 wound with the electrode foil 16, and also for an electrolytic capacitor using an electrolytic solution as an electrolyte. Available. Further, for example, by using copper as the base material 23 and lithium as the vapor deposition material, it can also be used as the electrode foil 16 of the battery. In this case, the battery capacity of the electrode foil 16 can be efficiently controlled by controlling the particle size of the fine particles to a desired size.

  In the present embodiment, the heat transfer block 34 and the holding unit 35 are independent components and can be disassembled. For example, the heat transfer block 34 is integrated with the holding unit 35 and the heat transfer block 34 itself is integrated. A groove 38 may be formed. In this case, the heat transfer roller 36 is held by the groove 38 formed in the heat transfer block 34.

  When a heat medium is supplied to the heat transfer block 34, heat propagates between the base material 23 and the heat medium through the heat transfer roller 36 and the heat transfer block 34, thereby controlling the temperature of the base material 23. The Further, if a heat source is arranged in the heat transfer block 34, the heat from the heat source is sequentially propagated to the heat transfer block 34 and the heat transfer roller 36, whereby the temperature of the base material 23 is controlled.

  Further, a gas introduction path 37 is provided in the heat transfer block 34, and gas is led out from the opposite surface side of the heat transfer block 34 to the base material 23 or from the inner wall of the groove 38. Gas can be supplied to the space. The gas mediates heat between the heat transfer block 34 and the base material 23 or between the heat transfer roller 36 and the heat transfer block 34, and the temperature of the base material 23 can be efficiently controlled. In this case, the wall 44 shown in FIG. 7 may be provided outside the region where the heat transfer roller 36 is formed on the surface of the heat transfer block 34 facing the base material 23.

  As described above, the heat transfer block 34 and the holding portion 35 may be either an integral type or a divided type. However, the heat transfer block 34 and the holding portion 35 are separated as in the present embodiment. It is easy to arrange so that the heat roller 36 is held inside the groove 38. Further, the temperature control unit 32 can be easily cleaned by disassembling the heat transfer block 34, the holding unit 35, and the heat transfer roller 36.

(Example 2)
The main difference between the present embodiment and the first embodiment is that the temperature control unit 32 is divided as shown in FIGS. The configuration other than the temperature control unit 32 is the same as that of the vapor deposition apparatus 21 of Example 1 shown in FIG.

  In this embodiment, the temperature control unit 32 includes the heat transfer block 34 and the holding unit 35 together with the small unit 45A on the unwinding roll (the number 24 in FIG. 3) and the winding roll (the number 25 in FIG. 3) side. Divided into two small units 45B. In the small unit 45A on the unwinding roll 24 side, a heater (heat source 46) capable of generating heat to a predetermined temperature is disposed, and a gas introduction path 37A is provided inside. In addition, the small unit 45B on the winding roll 25 side is provided with a pipe 33 for supplying cooling water controlled to a predetermined temperature, and a gas introduction path 37B is provided inside. And between the small units 45A and 45B, the clearance gap was opened in order to suppress heat transfer. The gas introduction path 37A and the gas introduction path 37B are independent of each other. Further, the gas outlets 43 of the gas introduction paths 37 </ b> A and 37 </ b> B were provided on the side of the holding portion 35 facing the base material 23. One or more gas outlets 43 may be provided.

  Thus, in this embodiment, in the vapor deposition region C of FIG. 3, the temperature of the base material 23 can be increased during the first half of the vapor deposition process, and the temperature of the base material 23 can be decreased during the second half. When the temperature of the base material 23 is controlled in this way, the base part of the coarse film layer (number 28 in FIG. 2) deposited in the first half has a larger particle size of the fine particles, and the contact area with the base material 23 increases. The adhesion between the material 23 and the rough film layer 28 can be improved. In the surface layer portion of the rough film layer 28 deposited in the latter half, the particle size of the fine particles is reduced, and the surface area can be increased.

  In this example, when the temperature of the substrate 23 is increased to about 300 ° C. in the first half of the vapor deposition process, the particle size of the fine particles can be reduced to about 0.1 to 0.3 μm. When the temperature of the material 23 was lowered to about 150 ° C., the particle size of the fine particles could be controlled to about 0.01 to 0.15 μm.

  Also in the present embodiment, similarly to the first embodiment, the temperature of the base material 23 can be controlled with high accuracy regardless of the presence or absence of the undulation of the base material 23. Therefore, the base material 23 is continuously moved while being moved. Even if vapor deposition is performed, the particle size of the entire substrate 23 can be controlled to a desired particle size, and a uniform film quality can be obtained.

  In this embodiment, the temperature control unit 32 is divided into two, but various division numbers and division positions may be changed in accordance with desired film quality. For example, the temperature control unit 32 shown in FIG. 12 arranges a plurality of grooves 38 in the transfer direction (arrow B) of the base material 23 and the direction orthogonal to the transfer direction, and the heat transfer roller 36 in each groove 38. Is arranged. The temperature control unit 32 is divided into a transfer direction (arrow B) and a direction orthogonal to the transfer direction so that at least one of these heat transfer rollers 36 is arranged, and the small units 47A, 47B, 47C are divided. Forming. Thereby, the vapor deposition region C can be further subdivided and the temperature can be controlled, and for example, it becomes easy to selectively cool only the portion that is susceptible to latent heat from the container 26.

  Hereinafter, descriptions of the same configurations and effects as those of the first embodiment will be omitted.

  The vapor deposition apparatus according to the present invention can control the particle size of the fine particles to be deposited by controlling the temperature of the substrate with high accuracy, and can make the film quality of the electrode foil uniform. Therefore, it is possible to realize a vapor deposition apparatus suitable for mass production and can be applied as a capacitor or battery manufacturing apparatus with stable characteristics.

DESCRIPTION OF SYMBOLS 9 Solid electrolytic capacitor 10 Capacitor element 11 Anode electrode part 12 Cathode electrode part 13 Anode terminal 14 Cathode terminal 15 Exterior body 16 Electrode foil 17 Dielectric film 18 Insulating member 19 Solid electrolyte layer 20 Cathode layer 21 Deposition apparatus 22 Vacuum chamber 23 Base material 24 Winding roll 25 Winding roll 26 Container 27 Supply pipe 28 Coarse film layer 29 Deflection roll 30 Deflection roll 31 Shutter 32 Temperature control unit 33 Piping 34 Heat transfer block 35 Holding part 36 Heat transfer roller 37 Gas introduction path 37A Gas introduction path 37B Gas introduction path 38 Groove 39 Small roller 40 Heat medium inlet 41 Heat medium outlet 42 Gas inlet 43 Gas outlet 44 Wall 45A Small unit 45B Small unit 46 Heat source 47A Small unit 47B Small unit 47C Small unit

Claims (6)

A vapor deposition apparatus that deposits fine particles on the surface of the substrate while moving the substrate in a predetermined direction in a vacuum chamber,
This deposition equipment
A container that is disposed on the surface side of the substrate and to which the raw material of the fine particles is supplied;
A temperature control unit disposed on the back side of the substrate;
This temperature control unit
A heat transfer block supplied with a temperature-controlled liquid or solid heat medium;
A heat transfer roller held on the side of the heat transfer block facing the substrate;
A gas introduction path for supplying gas to the space between the base material and the heat transfer block,
The heat transfer roller is
It moves down and abuts against the back surface of the base material, rotates around an axis that intersects with the transfer direction in conjunction with the transfer of the base material, and can be moved up by force from the base material. ,
The vapor deposition apparatus by which the temperature of the said base material is controlled when heat propagates between the said base material and the said heat medium through the said gas, the said heat-transfer roller, and the said heat-transfer block. A vapor deposition apparatus that deposits fine particles on the surface of the substrate while moving the substrate in a predetermined direction in a vacuum chamber,
This deposition equipment
A container that is disposed on the surface side of the substrate and to which the raw material of the fine particles is supplied;
A temperature control unit disposed on the back side of the substrate;
This temperature control unit
A heat transfer block supplied with a temperature-controlled liquid or solid heat medium;
A holding portion provided on the side of the heat transfer block facing the substrate;
A heat transfer roller held by the holding unit;
A gas introduction path for supplying gas to the space between the base material and the holding unit,
The heat transfer roller is
It moves down and abuts against the back surface of the base material, rotates around an axis that intersects with the transfer direction in conjunction with the transfer of the base material, and can be moved up by force from the base material. ,
A vapor deposition apparatus in which the temperature of the base material is controlled by heat propagating between the base material and the heat medium through the gas, the heat transfer roller, the holding unit, and the heat transfer block. . A vapor deposition apparatus that deposits fine particles on the surface of the substrate while moving the substrate in a predetermined direction in a vacuum chamber,
This deposition equipment
A container that is disposed on the surface side of the substrate and to which the raw material of the fine particles is supplied;
A temperature control unit disposed on the back side of the substrate;
This temperature control unit
A heat transfer block provided with a heat source capable of generating heat at a predetermined temperature;
A heat transfer roller held on the side of the heat transfer block facing the substrate;
A gas introduction path for supplying gas to the space between the base material and the heat transfer block,
The heat transfer roller is
It moves down and abuts against the back surface of the base material, rotates around an axis that intersects with the transfer direction in conjunction with the transfer of the base material, and can be moved up by force from the base material. ,
The vapor deposition apparatus by which the temperature of the said base material is controlled when the heat from the said heat source propagates to the said base material via the said heat-transfer block, the said heat-transfer roller, and the said gas. A vapor deposition apparatus that deposits fine particles on the surface of the substrate while moving the substrate in a predetermined direction in a vacuum chamber,
This deposition equipment
A container that is disposed on the surface side of the substrate and to which the raw material of the fine particles is supplied;
A temperature control unit disposed on the back side of the substrate;
This temperature control unit
A heat transfer block provided with a heat source capable of generating heat at a predetermined temperature;
A holding portion provided on the side of the heat transfer block facing the substrate;
A heat transfer roller held by the holding unit;
A gas introduction path for supplying gas to the space between the base material and the holding unit,
The heat transfer roller is
It moves down and abuts against the back surface of the base material, rotates around an axis that intersects with the transfer direction in conjunction with the transfer of the base material, and can be moved up by force from the base material. ,
The vapor deposition apparatus in which the temperature of the base material is controlled by the heat from the heat source being propagated to the base material through the heat transfer block, the holding unit, the heat transfer roller, and the gas. 2. A wall is provided on a surface of the heat transfer block facing the base material along a transfer direction of the base material, and the base material is transferred in a region surrounded by the wall. Or the vapor deposition apparatus of 3. A wall is provided along a transfer direction of the base material on a surface of the holding portion facing the base material, and the base material is transferred in a region surrounded by the wall. 4. The vapor deposition apparatus according to 4.