JP5260843B2 - Vapor deposition system - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To improve the temperature controllability of a plurality of gas particle generation units having different gas particle generation temperatures in a film deposition apparatus for depositing a film formed of a composite material. <P>SOLUTION: A film deposition apparatus 10 is constituted by arranging a first gas particle generation unit 20, a second gas particle generation unit 21, two partition members 25 arranged between the first and second gas particle generation units 20, 21, and a film deposition unit 30 holding a substrate D to be worked in a vacuum chamber 11. The partition members 25 are cooled with a refrigerant to suppress the temperature rise of the first gas particle generation unit 20 caused by the radiant heat from the second gas particle generation unit 21 on the hot temperature side. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

The present invention relates to a deposition apparatus using a vapor deposition method for depositing a thin film used for a lithium secondary battery or the like, and more particularly to a device having a plurality of gas particle generation units.

  In general, a thin film made of a composite material is often used as an element such as an electrode of a lithium secondary battery, a semiconductor element, or an optical element. And when forming the thin film which consists of composite materials by a vapor deposition method or a sputtering method, a some gas particle production | generation part will be provided. That is, a plurality of gas particle generation units that perform sputtering, evaporation, and the like are installed, and the plurality of gas particles are evaporated and attached to the workpiece.

  4A and 4B are a plan view and a cross-sectional view of a conventional film forming apparatus described in Patent Document 1. FIG. As shown in the figure, in the vacuum chamber 102 forming the processing chamber 101, three sputtering sources 112 having a target 115 and a magnet 116 are arranged concentrically. Then, different materials are sputtered from the three targets 115 while rotating the substrate D to be centered on the virtual circle C around the center axis O of the bearing device 110 of the center mask 111, By generating gas particles and depositing the gas particles on the substrate D to be processed, a film made of a composite material is formed. The substrate D to be processed is taken in and out along the transfer line L.

JP 2000-282230 A

  By the way, the temperature for generating gas particles may differ depending on the material, such as a difference in evaporation temperature when using the vapor deposition method. In that case, when the conventional film forming apparatus is used, the temperature of the low temperature side gas particle generation unit rises due to the influence of the temperature of the high temperature side gas particle generation unit. There is a problem of getting worse.

An object of the present invention is to provide a film forming apparatus using a vapor deposition method with excellent temperature controllability in a gas particle generating apparatus while including a plurality of gas particle generating apparatuses that generate gas particles of a plurality of materials having different generation temperatures. It is in.

A film forming apparatus according to the vapor deposition method of the present invention includes a plurality of gas particle generation units whose temperatures are controlled according to the gas particles of the plurality of materials in order to generate gas particles of the plurality of materials having different generation temperatures, A film forming unit for forming a film on a base material from gas particles of a plurality of materials generated by a plurality of gas particle generating units, a partition member provided between the plurality of gas particle generating units and cooled, One of the gas particle generation units is set to a temperature of 300 ° C. to 500 ° C. to generate P ₂ S ₅ gas particles, and the other is set to a temperature of 900 ° C. to 1300 ° C. to generate Li ₂ S gas particles. Shall be generated.

  Thereby, since the radiant heat of the gas particle production | generation part whose production | generation temperature is a high temperature side is interrupted | blocked by a partition member, the temperature rise of the gas particle production | generation part of a low temperature side is suppressed. Moreover, even if it receives the radiant heat from each gas particle production | generation part, since the temperature rise of the cooling partition member is suppressed, the temperature rise of the low temperature side gas particle production | generation part resulting from the radiant heat from a partition member will be carried out. It is suppressed. Therefore, the temperature controllability of each gas particle generation unit is improved, and the characteristics of the formed film are also improved.

The film forming apparatus according to the vapor deposition method of the present invention has the following limitations, so that additional effects can be obtained.

  Since the partition member has the cooling part through which the refrigerant flows, the temperature rise of the partition member can be further effectively suppressed, and thus the temperature controllability of each gas particle generation part is further improved.

  When at least one of the plurality of materials includes a component that reacts with moisture, the reliability is improved because the refrigerant is a non-aqueous refrigerant.

  Even when a plurality of materials having a large difference in evaporation temperature are evaporated by a plurality of vapor generation units (gas particle generation units) because the formed film is a solid electrolyte formed by vapor deposition, the low-temperature side vapor The temperature controllability of the generation unit can be maintained well.

  In particular, when the solid electrolyte membrane is used as a part of a lithium secondary battery, the controllability of the composition ratio of the membrane is improved, so that it can be used for the production of a lithium secondary battery having excellent characteristics. it can.

  By further providing a cooled anti-adhesion member around the plurality of gas particle generation units, the temperature controllability of the gas particle generation unit is deteriorated due to radiant heat from the anti-adhesion member while having an anti-adhesion function. Can be suppressed.

According to the film forming apparatus using the vapor deposition method of the present invention, it is possible to improve the temperature controllability of each gas particle generating apparatus while including a plurality of gas particle generating apparatuses that generate gas particles of a plurality of materials having different generation temperatures. it can.

(Embodiment)
FIG. 1 is a side view showing a main part of a film forming apparatus 10 by a vapor deposition method in an embodiment of the present invention. As shown in the figure, a film forming apparatus 10 according to the present embodiment includes two first gas particle generation units 20, one second gas particle generation unit 21, and first and first gas generators in a vacuum chamber 11. The two partition members 25 respectively disposed between the two gas particle generation units 20 and 21, the cylindrical protection plate 27 surrounding the gas particle generation units 20 and 21 and the partition member 25 in the lateral direction, and the gas particles A plate-shaped deposition preventing plate 28 provided above the generation units 20 and 21 and the partition member 25, having an opening 28a, and a work substrate D for an electrode of a lithium secondary battery attached to the ceiling surface of the vacuum chamber 11 are provided. The film forming unit 30 that is held is arranged.

The first gas particle generation unit 20 includes a carbon boat 20a and a boat table 20b, and P ₂ S ₅ gas particles (vapor) (generation temperature 350) for forming a solid electrolyte membrane of a lithium secondary battery. Around ° C). The second gas particle generation unit 21 includes a boat 21a and a boat table 21b made of carbon, and Li ₂ S gas particles (vapor) (generation temperature 1000 ° for forming a solid electrolyte membrane of a lithium secondary battery). Around C). Each of the boats 20a and 21a in the present embodiment generates heat by resistance heating, and in this embodiment, a vapor deposition method by resistance heating is adopted. However, the gas particles may be generated using a vapor deposition method using electron beam heating or a sputtering method involving heating. The height of the partition member 25 needs to be equal to or higher than the height of the boats 20a and 21a, and needs to be less than a height at which an appropriate composition ratio of the film made of the composite material cannot be obtained.

The substrate D to be processed held by the film forming unit 30 is obtained by forming a lithium metal thin film on a copper foil. The film forming apparatus 10 of the present embodiment is a solid electrolyte film on a lithium metal thin film. This is an apparatus for forming a certain Li ₂ S—P ₂ S ₅ mixed film.

2A and 2B are a side view of the partition member 25 and a cross-sectional view taken along line II-II. As shown in FIGS. 2A and 2B, the partition member 25 is configured by welding a SUS cooling pipe 25b having a rectangular cross section to a SUS flat plate 25a. A refrigerant flows through the inside. As the refrigerant, for example, a non-aqueous refrigerant such as a trade name Galden (manufactured by Solvay Solexis Co., Ltd.) which is a fluorine-based heat medium is suitable. Since sulfides such as P ₂ S ₅ and Li ₂ S may react with moisture to generate hydrogen sulfide, which is a toxic gas, by using a non-aqueous refrigerant, the refrigerant should be brought into the film forming apparatus. Even if it leaks, such a situation can be avoided. Non-aqueous refrigerants include liquids such as inert gases such as argon and chlorofluorocarbon, glycol, and trade name Fluorinert (manufactured by Sumitomo 3M Limited). In addition, the cooling pipe 25b, the compressor, and the condenser can be connected by refrigerant piping to form a refrigeration circuit, and the refrigerant can be circulated in the refrigeration circuit. In that case, the cooling pipe 25b functions as an evaporator of the refrigeration circuit.

As described above, the generation temperature of the P ₂ S ₅ gas particles (vapor) is around 350 ° C. (300 ° C. to 500 ° C.). The generation temperature of Li ₂ S gas particles (vapor) is around 1000 ° C. (900 ° C. to 1300 ° C.). Then, the characteristics of the lithium secondary _{battery, Li 2 S-P 2 S} 5 mixture composition ratio _Li 2 _{S /} P 2 _{S 5} of the membrane is a solid electrolyte membrane, determined to be about "3" molar ratio It is done.

  Thus, the first gas particle generation unit 20 and the second gas particle generation unit 21 have significantly different gas particle (vapor) generation temperatures (evaporation temperatures). Then, by providing the partition member 25 between the 1st gas particle production | generation part 20 and the 2nd gas particle production | generation part 21, it originates in the radiant heat from the 2nd gas particle production | generation part 21 which is a high temperature side gas particle production | generation part. The temperature rise of the second gas particle generation unit 21 that is the low temperature side gas particle generation unit can be suppressed to some extent. However, when a certain amount of time has passed, the temperature of the partition member 25 rises due to the radiant heat from the second gas particle generation unit 21, so that the temperature of the first gas particle generation unit 20 is caused by the radiant heat from the partition member 25. May rise.

  Here, in this embodiment, since the partition member 25 has the cooling pipe 25b that is a cooling part cooled by the refrigerant, the temperature rise of the partition member 25 is suppressed, and the radiant heat from the partition member 25 is reduced. The temperature rise of the 1st gas particle production | generation part 20 resulting from it can be suppressed. Therefore, the temperature of the 1st gas particle production | generation part 20 can be stored in 300 degreeC-500 degreeC which is an appropriate range.

  In the present embodiment, the partition member 25 is provided with the cooling pipe 25b as a cooling part. However, a part (for example, the lower end part) of the partition member 25 is connected to the heat sink and is cooled by heat conduction with the heat sink. It may be configured. Further, the deposition preventing plates 27 and 28 may have a structure having a cooling part through which a refrigerant flows, or may be structured to cool using heat conduction from a heat sink.

  FIGS. 3A and 3B are top views showing a modification of the structure of the partition member 25 and the first and second gas particle generators 20 and 21. FIG.

  In the modification shown in FIG. 3A, the partition member 25 is constituted by a double pipe and is not shown, but has a structure in which the refrigerant flows inside the double pipe. And the 1st gas particle production | generation part 20 is arrange | positioned outside the partition member 25 which consists of a double tube, and the 2nd gas particle production | generation part 21 is arrange | positioned inside the partition member 25. FIG. In this case, since the first gas particle generation unit 20 and the second gas particle generation unit 21 are installed separately inside and outside the cylinder, individual temperature control of the gas particle generation units 20 and 21 can be easily performed. There is an advantage of becoming.

  In addition, as shown to the broken line of Fig.3 (a), the 1st gas particle production | generation part 20 may be arrange | positioned not only in two places but in multiple places, such as four places and three places, or more. When three or more types of gas particles (such as steam) are generated, a partition member is disposed between each of the three or more gas particle generation units. In that case, among two or more gas particle generation units, when two gas particle generation units with similar or equal generation temperatures are adjacent to each other, no partition member is provided between them, or the partition Even if a member is provided, the structure that the partition member is not cooled may be sufficient. However, a cooling partition member needs to exist between at least two gas particle generation units among all the gas particle generation units.

  In the modification shown in FIG. 3B, the first gas particle generation unit 20 and the second gas particle generation unit 21 are 1 on both sides of the partition member 25 having the structure shown in FIGS. It is arranged one by one. Thus, the number of gas particle generation units may be one at a time.

Example 1
As shown in FIG. 1, by arranging the partition member 25 of the present invention, by setting the control target temperature of the second gas particle generator 21 to _{1000 ° C, Li 2 S-} P 2 S 5 mixture film (solid Electrolyte membrane) was formed. In this embodiment, the adhesion preventing plates 27 and 28 are not cooled. At this time, the temperature of the first gas particle generator 20 can be controlled to 350 ° C, at a deposition rate of 0.02 [mu] m / s, the composition ratio _Li 2 _{S /} P 2 _{S 5} is Li ₂ "3" An S—P ₂ S ₅ mixed film could be formed. The lithium ion conductivity of the formed Li ₂ S—P ₂ S ₅ mixed film (sulfide-based solid electrolyte film) was 1 × 10 ⁻⁴ S / cm.

(Example 2)
As shown in FIG. 1, the control target temperature of the second gas particle generation unit 21 is set to 1200 ° C. in order to arrange the partition member 25 of the present invention and increase the deposition rate of the solid electrolyte membrane. A Li ₂ S—P ₂ S ₅ mixed film (solid electrolyte film) was formed. In this embodiment, since the temperature of the second gas particle generating unit 25 is higher than that of the first embodiment, a structure in which a cooling pipe through which a refrigerant flows is also attached to the adhesion preventing plates 27 and 28 is employed. At this time, the temperature of the first gas particle generator 20 can be controlled to 400 ° C, at a deposition rate of 0.03 .mu.m / s, the composition ratio _Li 2 _{S /} P 2 _{S 5} is Li ₂ "3" An S—P ₂ S ₅ mixed film could be formed. The lithium ion conductivity of the formed Li ₂ S—P ₂ S ₅ mixed film (sulfide-based solid electrolyte film) was 1.2 × 10 ⁻⁴ S / cm.

(Comparative example)
In the configuration shown in FIG. 1, the control target temperature of the second gas particle generation unit 21 is set to 1000 ° C. without cooling the partition member 25, and a Li ₂ S—P ₂ S ₅ mixed film (solid electrolyte film) ) Was formed. At this time, the temperature of the first gas particle generation unit 20 reached 600 ° C. even though the boat was not energized. The composition ratio Li ₂ S / P ₂ S ₅ of the formed Li ₂ S—P ₂ S ₅ mixed film was “1”. The lithium ion conductivity of the formed Li ₂ S—P ₂ S ₅ mixed film (sulfide-based solid electrolyte film) is 1 × 10 ⁻⁶ S / cm, and the target value is 1 × 10 ⁻⁴ S. / Cm could not be achieved.

(Other embodiments)
The structure of the embodiment of the present invention disclosed above is merely an example, and the scope of the present invention is not limited to the scope of these descriptions. The scope of the present invention is indicated by the description of the scope of claims, and further includes meanings equivalent to the description of the scope of claims and all modifications within the scope.

  In the above embodiment, the vacuum vapor deposition equipment by resistance heating is used as the gas particle generating part such as sulfide for film formation, but the vapor deposition method by electron beam melting or the sputtering method other than the vapor deposition method is used. Can adopt the structure.

In the above embodiment, the film deposition apparatus by deposition of the present invention is applied to formation of the solid electrolyte membrane for a lithium secondary battery, the film forming apparatus according to a vapor deposition method of the present _{invention, O} 2, N ₂ The present invention can also be applied to the formation of solid electrolyte membranes such as gas sensors and fuel cells.

  In the above embodiment, the plate-like workpiece D is installed in the film forming unit 30, but the film is continuously formed while the sheet-like base material is fed between the supply roll and the take-up roll. Can also be taken.

The film forming apparatus according to the vapor deposition method of the present invention can be used for forming a solid electrolyte film such as a lithium secondary battery, a gas sensor, and a fuel cell.

It is a side view which shows the principal part of the film-forming apparatus by the vapor deposition method in embodiment of this invention. (A), (b) is the side view of a partition member, and sectional drawing in the II-II line. (A), (b) is a top view which shows the modification of a gas particle production | generation part and a partition member. (A), (b) is the top view and sectional drawing of the conventional film-forming apparatus described in patent document 1. FIG.

DESCRIPTION OF SYMBOLS 10 Film-forming apparatus 11 Vacuum chamber 20 1st gas particle production | generation part 20a Boat 20b Boat stand 21 2nd gas particle production | generation part 21a Boat 21b Boat stand 25 Partition member 25a Flat plate 2bb Cooling pipe 27 Cylindrical adhesion board 28 Plate-like adhesion Plate 28a Opening 30 Deposition part D Substrate

Claims (7)

A plurality of gas particle generation units, the temperatures of which are controlled according to the gas particles of the plurality of materials in order to generate gas particles of the plurality of materials having different generation temperatures;
A film forming unit that forms a film on a substrate from gas particles of a plurality of materials generated by the plurality of gas particle generating units;
A partition member provided between the plurality of gas particle generation units and cooled,
One of the gas particle generation units is assumed to generate P ₂ S ₅ gas particles at a temperature of 300 ° C. to 500 ° C., and the other one is generated at a temperature of 900 ° C. to 1300 ° C. to generate Li ₂ S gas particles. A film forming apparatus using a vapor deposition method . In the film-forming apparatus by the vapor deposition method of Claim 1,
The partition member has a cooling unit through which a refrigerant flows, and is a film forming apparatus using a vapor deposition method . In the film-forming apparatus by the vapor deposition method of Claim 2,
At least one of the plurality of materials includes a component that reacts with moisture;
The film forming apparatus by a vapor deposition method , wherein the refrigerant is a non-aqueous refrigerant. In the film-forming apparatus by the vapor deposition method in any one of Claims 1-3,
The film is a film forming apparatus by vapor deposition , which is a solid electrolyte film formed by vapor deposition. In the film-forming apparatus by the vapor deposition method of Claim 4,
The said solid electrolyte membrane is a film-forming apparatus by a vapor deposition method used as a part of lithium secondary battery. In the film-forming apparatus by the vapor deposition method in any one of Claims 1-5,
The film-forming apparatus by a vapor deposition method further provided with the adhesion prevention member provided around the said several gas particle production | generation part and being cooled. The film-forming method by the vapor deposition method which forms into a film on a base material using the film-forming apparatus by the vapor deposition method in any one of Claims 1-6.

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