JP3242427B2 - Vapor deposition equipment - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vapor deposition method characterized in that a deposition plate is arranged so as to surround a space from an evaporation source to a deposition position where a substrate is located, and a heating means is provided on the deposition plate. Related to the device.

[0002]

2. Description of the Related Art Generally, a vapor deposition apparatus is an apparatus that forms a vapor stream by heating an evaporation source, and applies the vapor stream to a substrate surface to deposit an evaporation source material on the substrate. is there. In the formation of a vapor deposition film by a vapor deposition apparatus, vapor deposition efficiency (amount deposited on a substrate / amount evaporated) is an important issue from the viewpoint of production cost. On the other hand, the uniformity of the film thickness is also important from the viewpoint of the characteristics of the deposited film. In general, the deposition efficiency is
Deposition is determined by the distance between the substrate and the evaporation source and the allowable range of the desired film thickness distribution. The shorter the distance between the substrate and the evaporation source is, the higher the deposition efficiency is. However, on the other hand, a uniform structure is formed by scattering of fine particles from the evaporation source. It is difficult to obtain a deposited film having the same. Further, since the thickness of the deposited film affects the characteristics of the deposited film, the thickness is preferably as uniform as possible. However, if a uniform thickness is to be obtained, the deposition efficiency is reduced. In particular, in radiation image conversion panels, EL panels, LCD panels, etc., which form a deposited film having a uniform film thickness on a substrate having a large area year by year, the two points of uniformity of the film thickness and improvement of the vapor deposition efficiency are compatible. It is difficult, and in the conventional vapor deposition apparatus, it has been a great problem to achieve both the uniformity of the film thickness and the improvement of the vapor deposition efficiency.

[0003] Under such circumstances, the following vapor deposition apparatus has been conventionally known in which the thickness of a vapor deposition film is made uniform. A deposition plate having a slit is fixedly arranged so as to block the space from the evaporation source to the substrate, and while the substrate is reciprocated just above this slit, a vapor deposition film having a uniform thickness is formed by the vapor flow passing through the slit. Vapor deposition apparatus (Japanese Patent Laid-Open No. 63-89660, Japanese Patent Laid-Open No. 2-97)
No. 665). A shielding plate is arranged so as to block the space from the evaporation source to the substrate, and while moving the shielding plate back and forth, a vapor deposition film having a uniform film thickness is formed on the substrate fixedly disposed above the shielding plate. Apparatus (Japanese Patent Publication No. 60-14832).

[0004]

However, the above-mentioned vapor deposition apparatus has the following problems. (1) The vapor deposition efficiency is low because the vapor deposition film is formed using only a part of the vapor flow by the deposition preventing plate or the shielding plate. (2) When performing evaporation by evaporating a large amount of evaporation source,
The time required for removing and collecting the deposits adhered to the deposition-preventing plate or the shielding plate becomes considerably long. In the conventional vapor deposition apparatus, attention has been paid to making the film thickness distribution uniform, but the vapor deposition efficiency has not been positively improved. Therefore, an object of the present invention is to provide a vapor deposition device with improved vapor deposition efficiency. It is a further object of the present invention to provide a vapor deposition apparatus that improves vapor deposition efficiency while maintaining uniform film thickness distribution in vapor deposition on a large-area substrate. It is a further object of the present invention to provide a vapor deposition apparatus that facilitates the work of removing and collecting deposits.

[0005]

In order to achieve the above object, a vapor deposition apparatus according to the present invention is directed to a vapor deposition apparatus in which a substrate is located at a vapor deposition position facing a vapor source and a vapor source material is vapor-deposited on the substrate. A deposition plate is arranged to surround a space from the evaporation source to a deposition position where the substrate is located.
Is provided heating means for the deposition preventing plate, the anti
The mounting plate (8) is composed of a plurality of divided members (8A).
And each member (8A) is arranged so as to be rotatable.
At the start of vapor deposition, each member (8A) was inclined obliquely.
Posture, and the deposited film on the substrate (9) has reached a predetermined thickness.
Occasionally, each member (8A) is erected and provided to the heating means (13).
The deposit of each member (8A) is heated and evaporated.
When each member (8A) is obliquely inclined,
The thickness of the deposit becomes thicker in the portion closer to the substrate (9).
Each member (8A) is raised and heated by using
By being evaporated, the re-evaporated material is formed around the substrate (9).
It is characterized in that it adheres to the sides .

[0006]

The vapor deposition plate is arranged so as to surround the space from the evaporation source to the deposition position where the substrate is located, so that the vapor flow is regulated by the deposition plate, and the deposition of the vapor source material on the inner wall of the apparatus or the like is prevented. Less. Since the heating means is provided on the deposition-preventing plate, the evaporation source material adhering to the deposition-preventing plate re-evaporates and adheres to the substrate, thereby improving the vapor deposition efficiency. Since the evaporation source material adhering to the deposition-preventing plate is re-evaporated and used, the removal and collection of deposits during maintenance of the apparatus can be performed in a short time, and the operation rate of the apparatus is improved. Further, even when the substrate is fixed, the film thickness distribution can be made uniform, and a complicated transport mechanism or the like is not required for a large-sized substrate, so that the cost of the apparatus can be reduced and the vapor deposition operation can be simplified. .

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be specifically described below.
FIG. 1 is a schematic view of a vapor deposition apparatus having a deposition- preventing plate . this
The evaporation apparatus performs evaporation while fixing a substrate and an evaporation source. In FIG. 1, 1 is a bell jar, 2 is a piercing electron gun, 3 is an electron beam, 4 is an evaporation source, 5 is a crucible,
6 is a water cooling pipe, 7 is a film thickness monitor, 8 is an adhesion preventing plate, 9 is a substrate, 10 is a main valve, 11 is an auxiliary valve, 12 is a leak valve, and 13 is a heating means. Main valve 1
0, the auxiliary valve 11 is used to make the inside of the bell jar 1 a predetermined degree of vacuum in conjunction with an exhaust device (not shown).

[0008] An evaporation source 4 is fixedly disposed, for example, in the lower portion of the bell jar 1, and a substrate 9 is fixedly disposed, for example, at a deposition position above the evaporation source 4. Substrate 9 from evaporation source 4
Is disposed so as to surround the space S reaching the vapor deposition position where is located .

A heating means 13 is provided on the protection plate 8. The heating means 13 can be composed of, for example, a resistance heating element and a heating power supply. For example, as shown in FIG.
A heating power source 1 composed of a resistance heating element such as W
4 may be connected, or as shown in FIG. 3 or FIG.
For example, Ta, Mo, W, Pt, Nt
A resistance heating element 15 such as -Cr may be provided, and the heating power supply 14 may be connected thereto. Reference numeral 17 denotes an evaporation source material deposited on the deposition preventing plate 8. During the vapor deposition period, the deposition-preventing plate 8 may be constantly heated by the heating means 13 so that the evaporation source material adhered thereto may be constantly vaporized. The heating of the deposition-preventing plate 8 may be started from the time when the value reaches the value, and the evaporation source material adhering thereto may be evaporated. The heating temperature of the deposition-preventing plate 8 is appropriately set according to the vapor pressure or melting point of the evaporation source material and the material of the deposition-preventing plate 8. Generally, it is selected from the range of 300 to 2000 ° C, more preferably the range of 400 to 1000 ° C.

FIG . 5 is an explanatory view showing a vapor deposition process when the deposition- preventing plate 8 is fixed . The vapor flow from the evaporation source 4 is applied to the substrate 9 and the deposition-preventing plate 8 around the substrate 9. Toward the substrate 9
And the evaporation source material gradually accumulates on the deposition-preventing plate 8,
The evaporation source material 17 attached to the deposition-preventing plate 8 is again evaporated by being heated by the heating means 13, and the vapor flow is directed to the substrate 9. Therefore, the vapor deposition film 16 is formed mainly in the central portion of the substrate 9 by the vapor flow from the evaporation source 4 and in the periphery of the substrate 9 by the vapor flow from the deposition-inhibiting plate 8.

In the absence of the vapor flow from the deposition- preventing plate 8, a vapor-deposited film is formed only by the evaporation source 4 and, as shown by a dotted line in FIG. Although the film thickness tends to be small, in the apparatus having the above configuration, the vapor flow from the deposition-preventing plate 8 contributes to the formation of the vapor deposition film around the substrate 9. The thickness becomes uniform. Further, of the vapor flow from the evaporation source 4 that adheres to the deposition-preventing plate 8 is heated by the heating means 13 and re-evaporated, so that it is used for forming the vapor deposition film 16 on the substrate 9. In addition, the deposition efficiency is improved. Also, since the amount of the evaporation source material attached to the inner wall of the apparatus is reduced,
During maintenance, removal and recovery of the evaporation source material is facilitated, and the operation rate of the apparatus can be increased. This effect is particularly significant when an expensive stimulable phosphor is used as the evaporation source.

In the case of forming a stimulable phosphor deposited film, the distance H from the evaporation source 4 to the surface of the substrate 9 in FIG.
Is usually 300 to 600 mm, the vertical distance T1 from the end of the substrate 9 to the surface of the deposition-inhibiting plate 8 is usually 0 to 300 mm,
The vertical distance T2 from the upper end of the deposition-preventing plate 8 to the lower surface of the substrate 9
Is usually 0 to 100 mm, and the length L of the deposition-inhibiting plate 8 is usually 50 to 600 mm. These distances T1, T2
By appropriately adjusting the length L and the thickness, the thickness of the deposited film can be controlled with a considerably large degree of freedom.

FIG . 6 is an explanatory view showing a main part of a vapor deposition apparatus according to an embodiment of the present invention . In the present invention, the protection plate 8
Is constituted by a plurality of divided members 8A (for example, four), and each member 8A is arranged so as to be rotatable,
At the start of the vapor deposition, each member 8A is in a position inclined obliquely as shown by a dotted line in FIG. 6 , and when the vapor deposition film on the substrate 9 reaches a predetermined film thickness, each member 8A is erected and is shown by a solid line in FIG. With the posture shown, the heating means 13 heats and deposits the deposit on each member 8A. According to such a configuration, in a state where the members 8A are inclined obliquely, the thickness of the deposit becomes thicker in a portion closer to the substrate 9 of each member 8A.
When the substrate is raised and heated to re-evaporate, the re-evaporated substance efficiently adheres to the peripheral portion of the substrate 9, and a vapor deposition film having a more uniform thickness can be obtained.

In the above embodiment , the deposition efficiency can be improved, and the film thickness distribution can be made uniform even when the substrate is fixed. Therefore, a complicated mechanism related to the substrate transfer or the like is not required, and the cost of the apparatus can be reduced and the vapor deposition operation can be simplified.

[0015]

[0016]

As the evaporation source 4 , those conventionally used as evaporation materials can be used, and the type thereof is not particularly limited. For example, when forming a recording layer of an X-ray device, particularly a radiation image conversion panel, a stimulable phosphor is preferably used, and a sublimable one is particularly preferably used. When a stimulable phosphor is used as the evaporation source 4, it is preferable to dissolve the stimulable phosphor uniformly or to charge the stimulable phosphor into a crucible 5 in a form formed by pressing or hot pressing. In this case, it is preferable to perform a degassing process. Note that the evaporation source 4 for forming the stimulable phosphor deposited film is not necessarily the stimulable phosphor itself, and may be a mixture of the raw materials constituting the stimulable phosphor. Good.

At the time of vapor deposition, the substrate 9 may be heated by a heater (not shown). Before starting the vapor deposition, it is preferable to operate the main valve 10 and the like to remove the gas in the bell jar 1 and maintain the degree of vacuum at about 10 ^-4 to 10 ^-6 Torr. At this time, an inert gas such as argon may be mixed into the bell jar 1.

Further, a plurality of crucibles 5 containing different evaporation sources 4 are set in the bell jar 1, and these evaporation sources 4 are sequentially evaporated to perform vapor deposition. A deposited layer made of a phosphor may be formed.

At the time of vapor deposition, the substrate 9 may be cooled if necessary. After the deposition is completed, the deposited film may be subjected to a heat treatment (annealing) as necessary. At the time of vapor deposition, reactive vapor deposition may be performed by introducing a gas such as O ₂ or H ₂ into the bell jar 1 as necessary. As the heating means for the evaporation source 4, a resistance heating means may be employed in addition to the electron beam.

For example, when the recording layer of the radiation image conversion panel is formed of a stimulable phosphor, the film thickness is
Depending on the sensitivity to radiation and the type of stimulable phosphor, etc., the radiation absorption is increased to improve the radiation sensitivity, the image granularity is improved, and the horizontal direction in the stimulable phosphor layer The thickness is preferably 200 μm or more from the viewpoint of preventing the spread of light to the surface and improving the sharpness of the image. The deposition rate of the stimulable phosphor layer used in the radiation image conversion panel varies depending on the type of the stimulable phosphor and the like, but is preferably 0.01 to 1000 μm / min, and particularly preferably 0.1 to 100 μm / min. preferable. Deposition rate is 0.0
When the rate is less than 1 μm / min, the efficiency of forming the stimulable phosphor layer is poor. On the contrary, when the deposition rate exceeds 1000 μm / min, it is difficult to control the deposition rate, which is not preferable.

The stimulable phosphor used in the radiation image conversion panel is subjected to a stimulus such as light, thermal, mechanical, chemical or electrical after the first irradiation with light or high energy radiation. Is a phosphor that exhibits stimulated emission corresponding to the dose of the first light or high-energy radiation upon excitation, but from a practical viewpoint, a phosphor that exhibits stimulated emission by a stimulated excitation light of 500 nm or more. Is preferred.

Examples of such a stimulable phosphor include BaS described in JP-A-48-80487.
O ₄ : AX, SrS described in JP-A-48-80489.
O ₄ : AX, Li ₂ described in JP-A-53-39277.
B ₄ O ₇ : Cu, Ag, etc. Li ₂ described in JP-A-54-47883.
_{O · (B 2 O 2)} x: Cu and Li ₂ O · (B
₂ O ₂ ) _x : Cu, Ag, etc. SrS: Ce, Sm, SrS: Eu, Sm, La ₂ O described in U.S. Pat. No. 3,859,527.
₂ S: Eu, Sm and (Zn, Cd) S: phosphor represented by Mn, it is described in JP-A-55-12142 Zn
S: Cu, Pb phosphor general formula BaO · xAl ₂ O _3: barium aluminate phosphor represented by Eu, the general formula M ^II O · xSiO _2: alkaline earth metal silicate represented by A phosphor, the general formulas described in _{JP-a-55-12143 (Ba 1-xy Mg x} Ca y) FX: eEu alkaline earth fluoride halide phosphor represented by ^2+, JP A phosphor represented by the general formula LnOX: xA described in JP-A-55-12144, and a phosphor represented by a general formula (Ba _1-x M _x ) FX: yA described in JP-A-55-12145. A phosphor represented by general formula BaFX: xCe, yA described in JP-A-55-84389; a general formula M ^II FX described in JP-A-55-160078. XA: activation of a rare earth element represented by yLn 2
Valent metal fluorohalide phosphor, general formula ZnS: A, C
dS: A, (Zn, Cd) S: A, S: A, ZnS:
A, X and CdS: Phosphors represented by A and X; General formula xM ₃ (PO ₄ ) ₂ .NX ₂ : yA and M ₃ (P
O ₄ ) ₂ : a phosphor represented by yA, a general formula nReX _3.
mAX _'2: xEu and nReX ₃ · mAX' _2: x
Eu, phosphor represented by YSM, and the general formula M ^I X ·
aM ^II X ′ ₂ .bM ^III X ″ ₃ : an alkali halide phosphor represented by cA.

In particular, an alkali halide phosphor is preferable since a stimulable phosphor layer can be easily formed by a vapor deposition method.

The stimulable phosphor used in the radiation image conversion panel is not limited to the above-mentioned phosphors, and the stimulable phosphor emits stimulable light when irradiated with stimulating light after irradiation with radiation. Any phosphor as shown may be used. The vapor-deposited film may be a stimulable phosphor layer group including one or two or more stimulable phosphor layers containing at least one of the stimulable phosphors described above. Also, the stimulable phosphor contained in each stimulable phosphor layer may be the same or different.

The material of the substrate 9 is not particularly limited. For example, when used for a radiation image conversion panel, for example, a ceramic plate such as alumina, a glass plate such as chemically strengthened glass and crystallized glass, aluminum, iron, copper , A metal plate having a coating layer of the metal oxide, a plastic film such as a cellulose acetate film, a polyester film, a polyethylene terephthalate film, a polyamide film, a polyimide film, and a polycarbonate film. The thickness of the substrate 9 varies depending on its material and the like, but is generally 80 to 3000 μm when used for a radiation image conversion panel. The surface of the substrate 9 may be a smooth surface, or may be a mat surface for the purpose of improving the adhesion to the stimulable phosphor layer. Further, the surface of the substrate 9 may be an uneven surface as described in JP-A-61-142497, or may be a tiled plate isolated as described in JP-A-61-142498. May be used. Further, a light reflection layer, a light absorption layer, an adhesive layer, and the like may be provided on the substrate 9 as necessary.

It is preferable to provide a protective layer on the surface of the stimulable phosphor layer formed by the vapor deposition apparatus of the present invention for physically or chemically protecting the stimulable phosphor layer. This protective layer may be formed by directly applying a coating solution for the protective layer on the stimulable phosphor layer, or by bonding a separately formed protective layer on the stimulable phosphor layer. Is also good. Further, a resin that is cured by radiation and / or heat as proposed in JP-A-61-176900 may be used. As the material of the protective layer, cellulose acetate, nitrocellulose, polymethyl methacrylate, polyvinyl butyral, polyvinyl formal, polycarbonate, polyester, polyethylene terephthalate, polyethylene, polypropylene, polyvinylidene chloride, nylon,
Polytetrafluoroethylene, polytrifluoroethylene monochloride,
Examples thereof include ethylene tetrafluoride / propylene hexafluoride copolymer, vinylidene chloride / vinyl chloride copolymer, and vinylidene chloride / acrylonitrile copolymer.

This protective layer is made of SiC, SiO ₂ , SiN, Al by a vacuum evaporation method, a sputtering method or the like.
_It may be formed by laminating inorganic substances such as ₂ O ₃ . Also,
What can be formed into a sheet having excellent translucency can be used as a protective layer by closely adhering it on the stimulable phosphor layer or disposing it at a distance. The protective layer desirably exhibits high light transmittance in a wide wavelength range in order to efficiently transmit stimulated excitation light and stimulated emission, and the light transmittance is preferably 80% or more. Examples of such a material include plate glass such as quartz, borosilicate glass, and chemically strengthened glass, and organic polymer compounds such as PET, drawn polypropylene, and polyvinyl chloride. Borosilicate glass is 3
It shows a light transmittance of 80% or more in a wavelength range of 30 nm to 2.6 μm, and quartz glass shows a high light transmittance even at a shorter wavelength.

Further, it is preferable to provide an anti-reflection layer such as MgF _{2 on} the surface of the protective layer because it has the effects of efficiently transmitting stimulating excitation light and stimulating light and reducing a decrease in sharpness. Moreover, the thickness of the protective layer is 50 μm to 5 m.
m, preferably from 100 μm to 3 mm. When the protective layer is disposed at a distance from the stimulable phosphor layer,
It is preferable to provide a spacer between the substrate and the protective layer so as to surround the phosphor layer, and such a spacer is capable of holding the stimulable phosphor layer in a state shielded from the external atmosphere. There is no particular limitation as long as glass, ceramics, metal, plastic, etc. can be used,
The thickness is preferably equal to or greater than the thickness of the stimulable phosphor layer.

[0030]

As described in detail above, according to the vapor deposition apparatus of the present invention, the vapor deposition efficiency can be increased, and resource saving and cost reduction can be achieved. Further, even on a substrate having a large area, the film thickness can be made uniform and the vapor deposition efficiency can be improved. In particular, it is possible even in a state in which the substrate is fixed, and a complicated mechanism such as transport is not required, so that the cost of the apparatus can be reduced and the operation can be simplified. In addition, deposits can be removed and collected during maintenance of the apparatus in a short time, and the operation rate of the apparatus is improved.

[Brief description of the drawings]

FIG. 1 is a schematic view of a vapor deposition apparatus having a deposition prevention plate .

FIG. 2 is an explanatory diagram illustrating an example of a heating unit.

FIG. 3 is an explanatory view showing another example of the heating means.

FIG. 4 is an explanatory view showing still another example of the heating means.

FIG. 5 is an explanatory diagram showing a vapor deposition process.

FIG. 6 is a view showing a main part of a vapor deposition apparatus according to an embodiment of the present invention .
FIG.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Bell jar 2 Pierce type electron gun 3 Electron beam 4 Evaporation source 5 Crucible 6 Water cooling pipe 7 Film thickness monitor 8 Protective plate 8A Protective plate 9 Substrate 10 Main valve 11 Auxiliary valve 12 Leak valve 13 Heating means 14 Heating power supply 15 Resistance heating element 16 Evaporated film 17 Evaporation source material deposited

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-63-121659 (JP, A) JP-A-2-15165 (JP, A) JP-A-2-185965 (JP, A) JP-A-3-3 183778 (JP, A) JP-A-4-66662 (JP, A) Japanese Utility Model Application Sho 63-7156 (JP, U) (58) Fields investigated (Int. Cl. ⁷ , DB name) C23C 14/00-14 / 58

Claims (1)

(57) [Claims] 1. An evaporation apparatus for positioning a substrate at an evaporation position facing an evaporation source and evaporating an evaporation source material on the substrate, wherein the evaporation system surrounds a space from the evaporation source to the evaporation position where the substrate is located. An attachment plate is provided, and the attachment plate is attached to the attachment plate.
Heating means is provided, and the adhesion-preventing plate (8) is divided into a plurality of divided members (8A).
Each member (8A) can rotate individually
When vapor deposition starts, each member (8A) is tilted obliquely.
The deposited film on the substrate (9) has a predetermined thickness.
When it reaches, each member (8A) is raised and the heating means (1
The deposit of each member (8A) is heated and evaporated by 3).
In the state of being obliquely inclined, the substrate (9) of each member (8A) is
Taking advantage of the fact that the thickness of the sediment becomes thicker as it is closer,
Each member (8A) is raised, heated and reevaporated.
As a result, the re-evaporated substance adheres to the peripheral portion of the substrate (9).
Vapor deposition apparatus characterized in that that.