JPH09279346A - Vaporizing method of powder and its device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a vaporizing method of a powder and the device therefor so that a powdery metal compd. can be completely vaporized without producing a nonvaporized component or a modified component by decomposition heat and that a uniform film quality and film thickness, good color tone and film strength can be obtd. without causing no trouble such as production of a condensate or its deposition and clogging or film defects such as spots. SOLUTION: A powdery metal compd. 1 is heated and vaporized at a temp. lower than the thermal decomposition temp. and introduced with a carrier gas to the surface of a substrate 8. The vaporized metal compd. is thermally decomposed on the surface of the substrate 8 and made to react to form a metal or metal compd. film on the substrate surface. In this method, the powdery metal compd. 1 is quantitatively supplied to a flow of a carrier gas (A) which is an inert so as to carry the powdery metal compd. with the carrier gas (A) flow. The carrier gas (A) and the powdery metal compd. are heated from the outside of the tube where the carrier gas is passed so as to vaporize the powdery metal compd. at a temp. lower than the decomposition temp. The vaporized compd. with the carrier gas (A) is introduced to the substrate surface 8 heated to a temp. higher than the decomposition temp.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a metal compound vapor which is a raw material for coating a metal compound film on a substrate by thermally decomposing or reacting a powdery metal compound, and a metal compound vapor. The present invention relates to a powder vaporization method and a device for generating powder.

[0002]

2. Description of the Related Art Conventionally, coating by the so-called CVD method has been carried out industrially or in a laboratory, but the vapor of a metal compound as a raw material of a coating is generally formed by a bubbling method.

In the bubbling method, a carrier gas is blown into a liquid raw material, bubbling is performed to take out vapor together with the carrier gas, and the raw material vapor is discharged depending on the temperature of the liquid and the carrier gas and the flow rate of the carrier gas. Although it is a method of controlling the supply amount and the device has the advantage of being simple and easy to handle, for example, 1) it can be applied only to liquid substances, and 2) to obtain a multi-component vapor, bubbler can be used depending on the number of components. -Is required, and 3) it has drawbacks such as not being able to quantitatively control and grasp the amount of raw material supply.

On the other hand, when a solid material at room temperature is used in the CVD method, the material is powdered and used as a carrier in a fluidized bed.
If gas is sent in, vapor can be generated by a bubbler method like liquid.

As a steam apparatus using such a method, for example, Japanese Patent Laid-Open No. 60-70176 discloses a solid source evaporation cylinder, which is a cylindrical solid source evaporation source. In a cylinder, a hierarchical structure configured to divide the cylinder into a plurality of floors at regular intervals by a perforated plate having a large number of holes, an introducing pipe for introducing a carrier gas, and a carrier gas and a solid source. An evaporative bomb is described that includes a spout that discharges powder.

Further, for example, Japanese Patent Laid-Open No. 7-278818 discloses CV.
D A vaporizer for powder raw material is described, in which an inlet for introducing carrier gas and an outlet for discharging carrier gas are separated by the powder raw material inside the vaporizer main body through which carrier gas passes. It is described that they have a different structure.

Further, for example, Japanese Patent Application Laid-Open No. 3-94066 describes a vaporizer of a CVD raw material for producing an oxide superconductor, which uses chemical vapor deposition using a compound of each element constituting the oxide superconductor. In a device for vaporizing a raw material used in producing an oxide superconductor by the method, a vertical vaporization tower and a carrier joined to the lower part of the vaporization tower-bonded above the joint of a gas introduction pipe A powder supply device, and a transport pipe joined to the reactor by being joined to the upper part of the vaporization tower,
A recovery section for the unvaporized raw material attached to the bottom of the vaporization tower,
And a heating device provided on the outer periphery of the vaporization tower,
It is described that the powder supply device includes a supply cylinder joined to the vaporization tower, an extrusion screw rotatably provided in the supply cylinder, and a hopper for supplying the powder raw material, which is connected to the supply cylinder. Has been done.

Further, for example, Japanese Unexamined Patent Publication No. 5-311446 describes a powder supply device and a vaporization supply device of an organometallic compound, and a powder is quantitatively supplied by vibrating a container filled with the organometallic compound powder. It is described to do.

[0009]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention For example, in the solid source evaporation cylinder described in JP-A-60-70176,
Since it is a method of vaporizing and transferring carrier gas to the powdered raw material of the heated container, it is difficult to maintain a constant vaporization amount due to the decrease of the powdered raw material due to vaporization, and the raw material heated for a long time without vaporization is caused by heat. Continuous stable supply is difficult, such as solidification in a dango shape, and the unvaporized powder raw material is easily mixed in the carrier gas and transferred.

Further, for example, in the vaporizer for CVD powder raw material described in JP-A-7-278818, it is difficult to maintain a constant vaporization amount, it is difficult to generate gas for a long time, and it is difficult to generate gas for a long time. Since the raw material is exposed to high temperature, it causes thermal transformation, and the amount of evaporation changes.

In the solid source evaporation cylinder described in JP-A-60-70176 or the vaporizer for CVD powder raw material described in JP-A-7-278818, 1) the vapor concentration in the gas is 2) The powder is heated for a long time and agglomerated,
3) In the case of general raw materials, the raw materials may be deteriorated by heating for a long time, so it is difficult to use a practical steam generation method except for very special raw materials.

Further, for example, in the vaporization apparatus for CVD raw material for producing oxide superconductor described in Japanese Patent Laid-Open No. 3-94066, powder is fed to the heating vaporization tower by a screw conveyor and carrier gas is fed by an introduction pipe. Since it is a device for obtaining vapor of powder gas, and due to the structure of the vaporizer, unvaporized powder raw material may be transferred together with vaporization, and the raw material utilization efficiency is improved by the accumulation of the unvaporized powder in the lower part of the vaporization tower. Is not high, and the carrier gas introduced cannot be separated from the carrier gas containing the vapor, so the yield of gas relative to the inserted raw material is poor, and sometimes unevaporated powder is discharged together with the carrier gas. In some cases, the vapor composition may not be constant when a plurality of raw materials having different vaporizabilities are vaporized. Furthermore, a raw material such as acetylacetonate cannot be reused because it is thermally metamorphosed.

Further, for example, in the powder supply device and vaporization supply device of the organometallic compound described in Japanese Patent Laid-Open No. 5-311446, the powder is dropped on the heating rotary plate by a vibrator to enclose the rotary plate. It is a device that introduces a carrier gas to obtain steam, and because it is a drop type, there is little heat transfer surface required for vaporization to the plate, gas generation is not stable and unvaporized parts are removed, so utilization efficiency is high. Alternatively, the unvaporized raw material may be mixed and transferred in the carrier gas.

[0014]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and includes a carrier gas containing vapor to be taken out, a carrier gas containing no vapor introduced, and powder. It is an object of the present invention to provide a method and an apparatus for obtaining a high vapor yield and a stable vapor concentration, in which the body is sufficiently separated.

That is, according to the present invention, the powdery metal compound is heated to a temperature not higher than the thermal decomposition temperature, vaporized, guided to the high temperature substrate surface together with the carrier gas, thermally decomposed and reacted on the substrate surface, and the substrate surface In the method of coating a metal or a metal compound on the powdery metal compound, the powdery metal compound is quantitatively sent into a flow of a carrier gas A which is an inert gas, and the powdery metal compound is supplied together with the flow of the carrier gas A. The carrier gas A and the powdery metal compound are heated from the outside of the pipe through which the carrier gas passes, the powdery metal compound is vaporized at a temperature equal to or lower than the decomposition temperature, and the vaporized vapor is transferred to the carrier. -With gas A,
A method for vaporizing powder, characterized in that steam is introduced to the surface of a substrate heated to a decomposition temperature or higher.

Further, the flow of the vapor and the carrier gas A is combined with the flow of the carrier gas B which is an inert gas containing a reactive gas sent from another path so as to dilute the vapor. The method for vaporizing powder as described above, characterized in that

Further, the inert gas is N ₂ , Ar, He,
The above-mentioned powder vaporization method, characterized in that it is Ne or Xe. Further, the above-mentioned powder vaporization method, wherein the reactive gas is a gas containing at least one of oxygen, water vapor, and ammonia.

Further, the heating temperature of the pipe for transferring the carrier gas A and the powdery metal compound is higher than the temperature for transferring the carrier gas A and the vapor. .

Further, as the above-mentioned powdery metal compound,
Organometallic compounds, metal alkoxides, halides, β
-The above-mentioned powder vaporization method, which is a diketone compound or a lantide compound.

The pipe heating temperature is 150 to 350.
The method for vaporizing powder as described above, characterized in that the temperature is ° C. Further, the above-mentioned powder vaporization method, wherein the substrate is glass.

Further, the powdery metal compound is heated to a temperature not higher than the thermal decomposition temperature, vaporized, led to a high temperature substrate surface together with a carrier gas, and thermally decomposed and reacted on the substrate surface.
In a device for coating a metal or a metal compound on the surface of a substrate, a powdery metal compound is quantitatively measured as a carrier gas A.
A device for feeding the carrier gas A for transferring the powdery metal compound, a device for heating the outside of the pipe through which the powdery metal compound and the carrier gas A pass, and the vaporization And a carrier gas A for guiding the vapor to the surface of the substrate heated above the vapor decomposition temperature.

Further, each of the above-mentioned powder vaporizers is characterized in that the outside of the pipe through which the powdery metal compound and the carrier gas A pass is heated by a heated heating medium. .

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION Here, the powdery metal compound is quantitatively fed into a flow of a carrier gas A which is an inert gas, and the powdery metal compound is transferred together with the flow of the carrier gas A. Then, the carrier gas A and the powdery metal compound are heated from the outside of the pipe through which the carrier gas passes, the powdery metal compound is vaporized at a temperature equal to or lower than the decomposition temperature, and the vaporized vapor is used as the carrier gas. As shown in FIG. 1, it was decided to introduce, together with A, to the surface of the substrate heated above the decomposition temperature, thermally decompose and react on the surface of the substrate, and to coat the metal or metal compound on the surface of the substrate. By using a simple powder vaporizer, it is possible to obtain a high vapor yield and a stable vapor concentration, a simple method and efficient, uniform film quality and film thickness, and no defects,
Moreover, it is a useful vaporization method of powder, which is significantly superior to the conventional one, and a device thereof, which can form a film capable of exhibiting desired film characteristics in a well-balanced manner without impairing optical characteristics such as color tone. .

As an example of the vaporizing device for powder, as shown in FIG. 1, a device for feeding carrier gas A2 which is an inert gas for transferring powder raw material 1 which is a powder metal compound. And the flow rate of the carrier gas A2 controlled by the mass flow controller 9 to quantitatively supply the powder raw material 1, which is a powdery metal compound, to the rotation speed of the extrusion screw. With a screw conveyor 4 which controls the supply amount by means of a constant and quantitative feed device, and a temperature controller, a set value of ± 0.
The powder raw material 1 which is the powdery metal compound and the gas transfer pipe 7 which is a pipe through which the carrier gas A2 passes are immersed in a heating bath 5 which is filled with a heating medium 6 whose temperature is controlled to about 5 ° C. And the heat transfer medium 6 from the outside to the gas transfer pipe 7
A device for heating the inside, a vaporized powder raw material 1 which is the powdery metal compound up to the outlet of the device, a vapor composed of the carrier gas A2 and a carrier gas A10
Are mixed with a flow of a carrier gas B3, which is an inert gas containing a reactive gas sent from another path, and are mixed together to dilute the steam, and the above-mentioned steam, the carrier gas A10, and the above are mixed. The vapor composed of the carrier gas B3 and the carrier gases A and B11 are set to a desired set temperature, for example,
Transferring to the spray nozzle 12 (for example, various nozzles such as slits) while keeping the temperature at 150 to 350 ℃, the spray nozzle
12 is a device for vaporizing powder, which is constituted by a device for spraying onto the surface of the substrate 8 which is heated to a temperature not lower than the decomposition temperature of steam.

Means for quantitatively feeding the powder include, for example, the screw conveyor and the like, and a rotary drum provided with a groove in addition thereto, which quantitatively supplies the carrier gas against the pressure thereof. If you can do it,
The means is not particularly limited.

Further, the carrier gas A is introduced into the powder discharge port at a flow rate that allows the powder to be transferred.
The carrier gas A may be blown to the discharge port so as to be blown away, but it is preferable to supply the carrier gas A so that the powder is pushed into the steady flow path because the powder and the gas do not stay.

Further, carrier gas A for transferring the powder
Is designed to pass through the heating device (bath) while maintaining a sufficient flow rate, and at this time, the pipe that guides the gas flow (material powder, heat transfer area, flow rate, clogging, etc. is taken into consideration, shape, size, Although the length and the like are determined, it is preferable to heat from the outside together with the pipe-like one).

Furthermore, in the method of introducing the gas flow for transferring the powder into the heating bath section, the gas flow velocity becomes slow, the powder and the gas flow are separated, and it is difficult to quickly evaporate the powder. Not only that, a gas flow containing no powder or steam is mixed into the gas flow sent to the next step, which makes it difficult to obtain a film of sufficient quality. A method of heating the pipe from the inside is also conceivable, but in this case, for example, it is difficult to secure a sufficient heat transfer area, the gas flow path becomes complicated to secure the heat transfer area, and a scale or the like is formed on the heating member surface. It has drawbacks such as easy accumulation. Generally, when a thermally decomposable raw material powder is heated to evaporate, evaporation and decomposition are likely to occur at the same time, which is how to suppress the decomposition to evaporate, and it is not preferable to have a heating means inside the pipe.

After the reactive gas containing rich vapor is obtained by the above method, it is possible to mix it with the carrier gas B sent from another system and dilute it to the desired concentration. In this case, for example, the steam generator and the steam transport pipe can be designed compactly, and the raw material supply amount and the blowing speed can be separately controlled, so that more preferable film forming conditions can be achieved.

Furthermore, by diluting the steam,
It is also possible to lower the temperature of the reactive gas (the raw material vapor and the carrier gases A and B joined together). By lowering the temperature, it becomes possible to simultaneously transport components that react with each other.

Further, the above-mentioned vapor and carrier gas A10
Of the carrier gas B3, which is an inert gas containing a reactive gas sent from another path, to dilute the vapor,
This is preferable from the viewpoint of film formation efficiency.

Further, as the above-mentioned inert gas,
Examples of the inert gas include N ₂ , Ar, He, Ne, and Xe, and N ₂ gas is preferable, although it depends on the powder raw material, the film to be aimed, or the film forming conditions.

Further, the above-mentioned reactive gas is a gas containing at least one of oxygen, water vapor, and ammonia, and is appropriately selected and used depending on the powder raw material, the film to be aimed, or the film forming conditions.

Furthermore, the heating temperature of the pipe for transferring the carrier gas A and the powdery metal compound is higher than the temperature at the time of transferring the carrier gas A and the vapor. And the temperature at which the vapor is transferred are at least lower than the heating temperature of the pipe for transferring the carrier gas A and the powdery metal compound, and the temperature between the carrier gas B and the spray port of the spray nozzle is the This is because the decomposition reaction of vapor is suppressed and prevented, the decomposition reaction product is prevented from adhering to the inner surface of the tube, and the film formation efficiency is increased.

The above-mentioned powdery metal compound is specifically composed of Al, Cr, Co, Cu, Fe, Ni, Zn, V, In, Ce, Sn, Si, Ti, etc., such as acetylacetone (AcAc ), Dipivaloylmethane (DPM) or hexafluoroacetylacetone (H
FA) and the like, metal alkoxides, halides, β-diketone compounds such as AcAc, DPM or HFA or lantide compounds, or two or more of these compounds selected and used. To be

The heating temperature in the gas transfer pipe is about the evaporation temperature of the powder which is the above-mentioned powdery metal compound, specifically about 150 to 350 ° C. Allow the evaporation to complete while passing through the heated bath. The heat insulation of the gas transfer pipe is 15
If the temperature is lower than 0 ° C, the amount of gas generated is small and a huge device is required to generate the required amount. If the temperature exceeds 350 ° C, a thermal decomposition reaction occurs and a film cannot be formed. The preferable heating and heat retention of the gas transfer pipe is about 180 to 300 ° C.

The substrate may be made of various materials such as organic or inorganic glass, ceramics and metals, and is not particularly limited, but it is particularly glass or inorganic transparent plate glass, which is colorless or colored, and its The type or color tone is not particularly limited, and after being fired, it can be used not only as bent plate glass, but also as various tempered glass, strength-up glass, flat plate or single plate, and can also be used as multi-layer glass or laminated glass. It goes without saying that it can also be appropriately applied to various plate-like bodies, particularly window glasses for construction and automobiles.

Furthermore, as the heated heat medium for heating the gas transfer pipe through which the powdery metal compound and the carrier gas A pass, for example, various oils, barrel thermos (trade name) and the like are used. Can be mentioned.

As described above, in the powder vaporization method and apparatus of the present invention, in the quantitative powder supply, by using a long spiral evaporation tube and keeping the optimum evaporation temperature, the non-vaporized components are removed. It does not come out, and stable gas generation is possible from the total supply.

Further, since the raw material supply section and the gas generating section are separated, it is possible to appropriately improve various problems of the invention described in the above-mentioned prior patent application publication, and no problems related to the raw material supply occur. You can

Further, the N ₂ gas or the like inert gas carrier - by vaporization and the gas, to suppress the oxidation reaction while maintaining a temperature not thermally decomposed so as to gas transport, the further O ₂ minutes required for deposition It can be mixed just before film formation and controlled to an optimum gas concentration.

Furthermore, the stable evaporation condition can be maintained by the structure in which the evaporation pipe is installed in the heat medium bath whose temperature is controlled to be constant, for example, the oil bath. Furthermore, when the raw material is fed, the vaporization temperature and the thermal decomposition temperature are close to each other, for example, in the case of a raw material such as the acetylacetonate metal compound of the present invention, if a low temperature portion is present in a part of the high temperature heating portion, the generated gas is generated. Are condensed and attached. Further, the raw material supply section needs to be maintained at a vaporization temperature or lower in order to prevent thermal denaturation and solidification due to high temperature, but in the case of the present invention, the above problems do not occur due to the continuous heating and conveying system, which is useful. A method for vaporizing powder and an apparatus therefor are provided.

Further, the powder vaporization method and apparatus thereof of the present invention include, for example, a colored film, a film for privacy glass, various heat ray reflective films, an ultraviolet shielding film, a low reflective film, an oxide superconducting film, and a single crystal. It can be used for various functional films such as a film, a water / oil repellent film, an alkali elution preventive film, a protective film, a hard coat film, an antifouling film and an antibacterial film.

[0044]

The present invention will be described below in detail with reference to examples. However, the present invention is not limited to such an embodiment.

Example 1 A float glass substrate having a size of about 100 mm × 200 mm and a thickness of about 3 mm was sequentially washed with a neutral detergent, a water rinse, and an alcohol,
After drying, it was wiped with acetone and heated to about 600 ° C. to obtain a high temperature glass substrate for coating.

In the powder vaporizer X shown in FIG. 1 described above, cobalt III acetylacetonate was used as the powdered organometallic compound, and nitrogen gas was used as the carrier gas A, as shown in Table 1. Carrier-gas A
The flow rate of nitrogen gas is about 4 with a mass flow controller.
In a flow controlled and quantitatively controlled at l / min, cobalt III acetylacetonate, which is a powdered organometallic compound, was supplied at a constant rate of about 2 g / min by screw rotation of a screw conveyor. Send to.

Subsequently, a temperature controller was used to measure about 300.degree.
The cobalt III acetylacetonate and nitrogen gas were further transferred to a gas transfer pipe immersed in a heating bath (oil bath) filled with a heating medium which was an oil whose temperature was controlled to about 0.5 ° C., and then in the gas transfer pipe. By heating, nitrogen gas having a concentration containing about 0.5 g / l of cobalt III acetylacetonate vapor is sent out.

Then, the reaction was sent in which the nitrogen gas containing the cobalt III acetylacetonate vapor was quantitatively supplied from another route by controlling the flow rate of about 10 l / min by a mass flow controller. Combined with a stream of nitrogen gas containing 5% of oxygen, which is an inert gas containing a volatile gas, and the temperature is about 180 ° C.
To about 100 m, while diluting it with nitrogen gas containing about 0.2 g / l of vapor concentration and keeping the temperature by keeping it warm.
Transfer to a spray nozzle with a slit nozzle of about m.

Next, on the surface of the heated glass substrate which moves at a constant speed of about 30 mm / sec, the spray nozzle with the slit-shaped nozzle is moved at a constant moving speed in the width direction at least between the widths of the glass substrate. Spray and guide while scanning,
At the same time, vapor decomposition reaction was performed on the surface of the substrate to coat a cobalt oxide thin film, which was dried and baked to form a film.

The obtained glass substrate with a film was evaluated as follows. [Observation on appearance] 1) Color tone: Measure with Minolta surface color difference meter (CR-200).

2) Optical characteristics: (1) Visible light transmittance, visible light reflectance (380 nm to 780 nm), ultraviolet ray transmittance by 340 type self-recording spectrophotometer (manufactured by Hitachi Ltd.) and JIS Z 8722, JIS R3106.
(320 nm to 400 nm), solar radiation transmittance (320 nm to 400 nm), stimulus purity, dominant wavelength, etc. were determined.

(2) Head meter [Nippon Denshoku Industries Co., Ltd.]
Manufactured by NDH-20D] to measure the haze value. (3) Measure the film surface reflectance with a Minolta surface color difference meter (CR-200). [Measurement of film thickness] Measure with DEKTAK (manufactured by Sloan). [Film strength measurement (wear resistance test)] Wear a wheel with a taper tester (TOYOYOSEIKI ROTARY ABRATION TESTER).
Change in haze value (transmittance) after 100 rotations with CS-10F △ H
I asked. [Film defect] A sensory test judges the degree of cloud unevenness, spots, etc. by visual comparison with a standard sample. [Chemical resistance] (1) Acid resistance: The rate of change in transmittance before and after immersion in HCl (1 standard) for 24 hours (23 ± 3 ° C).

(2) Alkali resistance: 24 (1 standard) NaOH
Percentage change in transmittance before and after immersion in time (23 ± 3 ° C). [Weather resistance] Implemented with a sunshine weather meter. [Others] Water repellency, electrical characteristics, etc. are appropriately evaluated by commonly used measurement methods as necessary.

As a result, as shown in Table 2, the film thickness of the Co ₂ O ₃ thin film in the obtained glass plate with a film was about 60 nm, and it was possible to obtain a predetermined film thickness. It was uniform, had no film defects due to incomplete gas generation, had good color tone and film strength, and was marked with ⊚, which was the intended powder vaporization method and its vaporization apparatus.

Example 2 Using the same high temperature coating glass substrate as in Example 1 and the powder vaporizer X shown in FIG. 1 described above, the powder organometallic compound was changed to chromium III acetylacetonate. Table 1
As shown in FIG.
3.2g / min, heat medium of about 280 ℃ ± 0.5 ℃,
Nitrogen gas having a concentration of about 0.8 g / l of chromium III acetylacetonate vapor was sent out, and then nitrogen gas containing the chromium III acetylacetonate vapor was supplied by a mass flow controller from another route. A flow rate of about 16 l / min was controlled to quantitatively supply and send a flow of nitrogen gas containing 2% of oxygen, which is an inert gas containing a reactive gas, and the temperature was lowered to about 190 ° C. Concentration about 0.2 g / l
It is diluted with nitrogen gas containing about a certain amount and is transferred to a spray nozzle with a slit-shaped nozzle having a nozzle width of about 100 mm while maintaining the temperature by keeping it warm.

Next, in the same manner as in Example 1, the spray nozzle with the slit-shaped nozzle was applied in the width direction on the surface of the heated glass substrate which moved at a constant speed of about 30 mm / sec, at least between the widths of the glass substrate. At the same time, it was sprayed and guided at a constant moving speed, and vapor decomposition reaction was simultaneously performed on the substrate surface, and a chromium oxide thin film was coated and dried and baked to form a film.

The obtained glass substrate with a film was evaluated in the same manner as in Example 1. As a result, as shown in Table 2, the thickness of the Cr ₂ O ₃ thin film in the obtained glass plate with a film was about 40.
Approximately nm, as in Example 1, a predetermined film thickness can be obtained, the film quality and film thickness distribution are uniform, there is no film defect due to incomplete gas generation, and the color tone and film strength are good. That is, the intended vaporization method of powder and its vaporization apparatus.

Example 3 Using the same high temperature glass substrate for coating as in Example 1 and the powder vaporizer X shown in FIG. 1 described above, the powder organometallic compound was changed to iron III acetylacetonate. As shown in Table 1, in the same manner as in Example 1, the supply amount was about 0.8 g.
/ Min, heat medium of about 220 ℃ ± 0.5 ℃, iron II
I Nitrogen gas having a concentration of about 0.2 g / l of acetylacetonate vapor was sent out, and then the nitrogen gas containing the iron III acetylacetonate vapor was mass-flowed from another route.
A flow rate of about 4 l / min was controlled by a controller to quantitatively supply the oxygen gas, which was an inert gas containing a reactive gas and was fed quantitatively, and was combined with a flow of nitrogen gas containing 4% to obtain a temperature of about 160.
The temperature is lowered to about ℃, diluted with nitrogen gas containing about 0.1 g / l of vapor concentration, and the nozzle width is kept at about 10 while maintaining the temperature by keeping it warm.
Transfer to a spray nozzle with a slit-shaped nozzle of about 0 mm.

Next, in the same manner as in Example 1, the spray nozzle with the slit-shaped nozzle was applied in the width direction on the surface of the heated glass substrate which moved at a constant speed of about 30 mm / sec at least between the widths of the glass substrate. At the same time, it was sprayed and guided at a constant moving speed, and the decomposition reaction of vapor was simultaneously performed on the substrate surface, the iron oxide thin film was coated and dried and baked to form a film.

The obtained glass substrate with a film was evaluated in the same manner as in Example 1. As a result, as shown in Table 2, the film thickness of the Fe ₂ O ₃ thin film in the obtained glass plate with a film was about 40.
Approximately nm, as in Example 1, a predetermined film thickness can be obtained, the film quality and film thickness distribution are uniform, there is no film defect due to incomplete gas generation, and the color tone and film strength are good. That is, the intended vaporization method of powder and its vaporization apparatus.

Example 4 The same high temperature glass substrate for coating as in Example 1, the above-described powder vaporizer X shown in FIG. 1, and cobalt III acetylacetonate as a powder metal compound were used. As shown in, the supply amount was about 0.
8g / min, 220 ℃ ± 0.5 ℃ heat medium, iron
III Nitrogen gas having a concentration containing about 0.2 g / l of acetylacetonate vapor is sent out and transferred to a spray nozzle with a slit-shaped nozzle having a nozzle width of about 100 mm while keeping the temperature as it is while keeping it warm.

Next, in the same manner as in Example 1, the spray nozzle with the slit-shaped nozzle was applied in the width direction on the surface of the heated glass substrate which moved at a constant speed of about 30 mm / sec, at least between the widths of the glass substrate. At the same time, it was sprayed and guided at a constant moving speed, and vapor decomposition reaction was simultaneously performed on the substrate surface, and a cobalt oxide thin film was coated and dried and baked to form a film.

The obtained glass substrate with a film was evaluated in the same manner as in Example 1. As a result, as shown in Table 2, the film thickness of the Co ₂ O ₃ thin film in the obtained glass plate with a film was about 20.
The thickness is about nm, which is different from that in Example 1,
Although the film forming speed, that is, the film forming efficiency, is somewhat inferior, the film quality and film thickness distribution are uniform, there are no film defects due to incomplete gas generation, and the color tone and film strength are also good, and the film thickness and color density are stable. Although it can be solved by extending the film time, it is the intended vaporization method of the powder and its intended vaporization device, although it is indicated by a circle.

Comparative Example 1 As shown in Table 1, only carrier gas A was changed to nitrogen gas and oxygen 20%, and other conditions were the same as in Example 4.

The obtained glass substrate with a film was evaluated in the same manner as in Example 1. As a result, as shown in Table 2, Co ₂ O
₃ The thickness of the thin film is about 20 nm, and carrier gas A
Since there is a large amount of O _{2 in} the gas, vaporization and thermal oxidation reaction during gas transfer accumulate, and the decomposed product (oxide) causes spot defects on the film surface during film formation, and further stable gas generation. It is also not possible to say that it is a vaporization method of powder and its vaporization device that aims at the ultimate goal, expressing the adverse effects such as gradually clogging the inside of the pipe and making it feel like it,
It was a mark X.

Comparative Example 2 As shown in Table 1, a conventional powder vaporizer Y was used, the carrier gas A was changed to nitrogen gas and oxygen 5%, and cobalt III acetylacetonate as a powder metal compound was used. The supply rate of nitrogen gas was increased to about 2.0 g / min, and the heating medium was increased to about 250 ° C ± 0.5 ° C, and the concentration of nitrogen gas was increased to contain cobalt III acetylacetonate vapor at about 0.5 g / l. And the others were the same as in Example 4 and Comparative Example 1.

The obtained glass substrate with a film was evaluated in the same manner as in Example 1. As a result, as shown in Table 2, Co ₂ O
_{3 The} film thickness of the thin film is as thin as about 20 nm or less, the gas concentration during evaporation becomes too high, and the carrier gas A contains O ₂ so that thermal oxidation proceeds and decomposed products (oxides) are formed. Occasionally, spot-like defects are generated on the film surface, deposits adhere to the inside of containers (pipes, etc.) as in Comparative Example 1, and stable gas generation is difficult. It could not be said that it was the vaporization method of the body and the vaporization apparatus therefor, and was marked with a cross.

[0068]

[Table 1]

[0069]

[Table 2]

[0070]

As described above, according to the present invention,
Since the powdery metal compound in the inert gas is indirectly heated and vaporized to a temperature at which the powdery metal compound is not thermally decomposed, an unvaporized component is not generated and the oxidation reaction is suppressed. Stable and complete generation of vapor of powdered metal compounds can be transferred without troubles such as condensate and its adhesion and clogging, etc., and further proper dilution can prevent thermal denaturation and solidification due to high temperature, resulting in a predetermined film thickness. A useful powder that can be efficiently formed, has uniform film quality and film thickness distribution, has no film defects due to incomplete gas generation, has good color tone and film strength, and can be used for various functional films. The present invention provides a vaporization method and apparatus therefor.

[Brief description of drawings]

FIG. 1 is an explanatory diagram showing an example of a vaporization apparatus used in Examples 1 to 4 according to a powder vaporization method and apparatus of the present invention.

[Explanation of symbols]

 1 Powder Raw Material 2 Carrier Gas A 3 Carrier Gas B 4 Screw Conveyor 5 Heating Bath 6 Heat Medium 7 Gas Transfer Pipe 8 Substrate 9 Mass Flow Controller 10 Steam and Carrier Gas A 11 Steam and Carrier Gas A and B 12 Spray nozzle

Claims (10)

[Claims] 1. A powdery metal compound is heated to a temperature lower than its thermal decomposition temperature, vaporized, introduced to a high-temperature substrate surface together with a carrier gas, thermally decomposed and reacted on the substrate surface, and a metal on the substrate surface, Alternatively, in the method of coating a metal compound, a powdery metal compound is quantitatively fed into a flow of a carrier gas A which is an inert gas, and the powdery metal compound is transferred together with the flow of the carrier gas A, From the outside of the pipe through which the carrier gas passes, the carrier gas A
And heating the powdery metal compound to vaporize the powdery metal compound at a temperature below the decomposition temperature, and to guide the vaporized vapor together with the carrier gas A to the surface of the substrate heated above the decomposition temperature. A method for vaporizing powder, which is characterized in that 2. The flow of the vapor and carrier gas A,
2. The method for vaporizing powder according to claim 1, wherein the vapor is diluted with a flow of a carrier gas B, which is an inert gas containing a reactive gas, which is sent from another route. . 3. The inert gas is N ₂ , Ar, He, Ne, Xe
The method for vaporizing powder according to claim 1 or 2, wherein 4. The method for vaporizing powder according to claim 1, wherein the reactive gas is a gas containing at least one of oxygen, water vapor, and ammonia. 5. The pipe heating temperature for transferring the carrier gas A and the powdery metal compound is higher than the temperature for transferring the carrier gas A and vapor. Powder vaporization method. 6. The method for vaporizing powder according to claim 1, wherein the powdery metal compound is an organic metal compound, a metal alkoxide, a halide, a β-diketone compound or a lantide compound. 7. The method for vaporizing powder according to claim 1, wherein the heating temperature of the pipe is 150 to 350 ° C. 8. The method for vaporizing powder according to claim 1, wherein the substrate is glass. 9. A powdery metal compound is heated to a temperature lower than its thermal decomposition temperature, vaporized, introduced to a high-temperature substrate surface together with a carrier gas, thermally decomposed and reacted on the substrate surface, and a metal on the substrate surface, Alternatively, in a device for coating a metal compound, a device for quantitatively feeding the powdery metal compound into the flow of the carrier gas A, a device for feeding the carrier gas A for transferring the powdery metal compound, and the powder And a device for heating the outer side of the pipe through which the metal compound and the carrier gas A pass, and a device for guiding the vaporized vapor together with the carrier gas A to the surface of the substrate heated above the decomposition temperature of the vapor. Vaporizer for powder. 10. The apparatus for vaporizing powder according to claim 9, wherein the outside of the pipe through which the powdery metal compound and the carrier gas A pass is heated by a heated heating medium.