JP5990994B2 - A method for producing a glass powder material and a porous vitreous membrane. - Google Patents

Description

  The present invention relates to a powder material for forming a porous glassy film by a thermal spraying method or a spray method, and a method for producing a porous glassy film.

  In recent years, in semiconductor manufacturing processes, organic EL displays, and liquid crystal display manufacturing processes, it is becoming common to undergo plasma processing and the like as dry etching. For the purpose of providing insulation and plasma resistance, It has been proposed to form various functional coatings on ceramic substrates, metal substrates, and the like.

  The method for forming a film on the substrate is selected depending on the material of the film and the type of the substrate. For example, thermal spraying technology is applied as a technology for forming a coating film made of ceramics.

  Patent Document 1 discloses a thermal spray film made of ceramics as a plasma-resistant film that can be used for an electrostatic chuck. Further, in Patent Document 2, a thermal spray film made of insulating alumina or chromium oxide is formed on a substrate mounting table of a plasma CVD apparatus to reduce a contact area between the substrate and the mounting table, which is caused by charging or static electricity during film formation. Suppressing adsorption is disclosed.

However, on the other hand, when the substrate is subjected to plasma processing, a mounting table in which Y ₂ O ₃ having excellent plasma resistance is generally sprayed onto a metal substrate is used. However, Y ₂ O ₃ is more effective than a soda lime glass substrate or Si wafer. Since the hardness of the substrate is high, there is a problem that when the substrate is vacuumed or electrostatically chucked on the Y ₂ O ₃ sprayed film, the substrate is damaged. In Patent Document 3, as a substrate mounting table used in the manufacturing process of a flat panel display, metal aluminum is applied to an Al ₂ O ₃ or AlN ceramic material so as to have a hardness equal to or lower than that of the substrate in order to prevent the substrate from being damaged. The use of a mixed sprayed coating is disclosed. However, in the metal / ceramic composite film, it is difficult to completely prevent scratches due to the presence of ceramic with high hardness locally.

  In addition to the above-described coating, it has been proposed to form a vitreous film for the purpose of imparting insulating properties and plasma resistance (for example, Patent Document 4). One of the common methods for forming a glassy film is a method in which a glass powder material is mixed with an organic vehicle, and a paste-like material is applied and fired on a substrate by screen printing or the like. Since a film can be formed, a useful glassy film can be obtained.

However, a glass powder material for forming a glassy film generally has a lower thermal expansion coefficient than that of the substrate in order to prevent cracking and peeling due to thermal stress generated in the cooling stage after baking onto the substrate. There is a need to. For example, in Patent Document 5, when a glass powder material is baked onto a soda lime glass substrate having a thermal expansion coefficient of 90 × 10 ⁻⁷ / ° C., the glass powder material having a thermal expansion coefficient of 70 to 85 × 10 ⁻⁷ / ° C. Is selected.

JP 2007-217774 A JP 2008-156718 A JP 2011-119326 A JP 2007-268970 A JP 2008-239396 A

  In the organic EL display, liquid crystal display, and semiconductor manufacturing processes, glass substrates, Si wafers, and the like are used. However, the above-described coating made of ceramic has a problem that the substrate is damaged because of its high hardness.

Further, if the glass membrane described above, _Bi 2 _{O 3} based glass, PbO-based glass, _{R 2} O system _{(R 2 O = Li 2 O} , Na 2 O, K 2 O) _glass, P 2 _{O 5} based glass Glasses such as V ₂ O ₅ glass and B ₂ O ₃ —ZnO glass have a softening point of 650 ° C. or lower and are low in the glass, and thus are useful when performing heat treatment such as baking onto a substrate. Furthermore, it is known that the glass has a low hardness, and a glass substrate or a substrate such as a Si wafer is not damaged like a ceramic coating.

  However, these glasses generally have a problem that the thermal expansion coefficient with respect to ceramics or a glass substrate is high, and the formed vitreous film is cracked or peeled off, which is not suitable for use.

  In view of the above-described problems, the present invention has an object to obtain various displays and semiconductors such as an organic EL display and a liquid crystal display, and a film that can be suitably used for manufacturing processes thereof.

As a result of diligent research on the above problems, the present inventors have formed a porous vitreous film using a thermal spraying method or a spray method, and thus, such as a ceramic or metal substrate that forms the vitreous film. It has been found that even when a glass powder material having a higher thermal expansion coefficient than that of the substrate is used , cracks and peeling do not occur in the vitreous film after baking. It is inferred that the porous film quality provided a buffering effect against the stress remaining in the vitreous film. Furthermore, by using this method, it is possible to form a vitreous film on various substrates. It becomes possible.

That is, the present invention relates to Bi ₂ O ₃ glass, PbO glass, SiO ₂ —B ₂ O ₃ —R ₂ O glass (R = Li, Na, K), P ₂ O ₅ glass, V ₂ O _5. system glass, and _B 2 _O 3 and at least one glass powder material selected from the group consisting of -ZnO-based glass, the glass powder material has an average particle diameter of 10 to 30 [mu] m, and a maximum particle diameter of 300μm or less, A glass powder material characterized by being formed on a substrate by a thermal spraying method or a spraying method.

  The maximum particle size and the average particle size of the present invention were measured by a laser diffraction / scattering method using Microtrack MT3000 manufactured by Nikkiso Co., Ltd. In the measurement, after the glass powder material was dispersed in a solvent, laser light was irradiated to obtain scattered / diffracted light, and the particle size distribution was calculated from the light intensity distribution data of the diffracted / scattered light. Note that the scattering phenomenon that occurs when light strikes particles suspended in a solvent varies depending on the size, refractive index, wavelength of incident light, etc., but in this study, the amount of scattered light and the number of occurrences were measured. From the value, the particle size of the particles was calculated according to the program set in the apparatus.

  The average particle size is obtained by multiplying the measured particle size value by the relative particle amount (difference%) and dividing by the total relative particle amount (100%). The average particle diameter is the average particle diameter, and means the particle diameter at an integrated value of 50% (median diameter) in the particle size distribution determined by the laser diffraction / scattering method.

  According to the present invention, it has become possible to obtain various displays such as organic EL displays and liquid crystal displays, semiconductors, and coatings that can be suitably used in those manufacturing processes.

Also, by forming a porous glassy film by thermal spraying or spraying, a glassy film is formed using a glass powder material having a higher thermal expansion coefficient than that of the ceramic or metal substrate that forms the glassy film. It became possible to do. Thereby, it is possible to bake a glass powder material having low hardness on the ceramic without cracking or peeling, and as a result, it is possible to suppress scratches generated on the glass substrate, the Si wafer, and the like.

The glass powder material of the present invention includes Bi ₂ O ₃ glass, PbO glass, SiO ₂ —B ₂ O ₃ —R ₂ O glass (R = Li, Na, K), P ₂ O ₅ glass, V ₂ O ₅ based glass, and consists of at least one of the glass powder material selected from the group consisting of _B 2 _O 3 -ZnO based glass. The glass is classified as a low-melting glass, and generally has a low glass hardness.

In particular, Bi ₂ O ₃ based glass mainly composed of Bi ₂ O ₃ and PbO based glass mainly composed of PbO are known to have low hardness. However, considering the harmfulness to the environment, Bi ₂ O ₃ Based glass is preferred. More preferably, Bi ₂ O ₃ is 40 to 90% by mass, B ₂ O ₃ is 1 to 30% by mass, ZnO is 1 to 30% by mass, and Bi ₂ O ₃ is used in order to obtain a glass having lower hardness. It is good also as 70-90 mass%.

In addition to the above, as the PbO-based glass, PbO 40 to 90 wt%, SiO ₂ 0 to 10 _wt%, B 2 _{O 3} 5 to 30 wt%, _Al 2 _{O 3} is 0 to 5 wt% It is preferable to contain each component so that it may become a range.

_{Further, SiO 2 -B 2 O 3 -R} 2 O -based glass (R = Li, Na, K ) as the, SiO ₂ is 1 to 15 _wt%, B 2 _{O 3} 5 to 20 wt%, ZnO 10 40 mass%, and preferably each component as _{R 2} O is in the range of 5 to 20 wt%.

_As the P 2 _{O 5} based glass, SiO ₂ is 1 to 10 mass%, _Al 2 _{O 3} is 1 to 20 _mass%, containing each component as P 2 _{O 5} is the range of 30 to 55 wt% It is preferable to do.

_As the V 2 _{O 5} based _glass, V 2 _{O 5} is 30 to 50 wt%, ZnO is 5 to 30 _mass%, containing each component as P 2 _{O 5} is in the range of 5 to 30 mass% It is preferable to do.

_As the B ₂ O 3 -ZnO based _glass, B 2 _{O 3} is 20 to 40 wt%, and preferably each component so ZnO is in the range of 60 to 80 wt%.

  The glass powder material preferably has a Vickers hardness of 3 to 5 GPa. The Vickers hardness is a physical property value indicating the hardness of the glass, and by setting it to a low value, it is possible to suppress scratches generated on the glass substrate or the Si wafer in the manufacturing process. In the present invention, the Vickers hardness was measured by a method in which a diamond indenter was pushed into a test piece by the method described in JIS-Z2244. Usually, non-alkali glass is used for the glass substrate used for a liquid crystal display or an organic EL display. For example, Vickers hardness of EAGLE XG (manufactured by Corning) is 6 GPa. Further, the Vickers hardness of the Si wafer used in the semiconductor is 10 GPa. By making the Vickers hardness of the glass powder material lower than these values, the occurrence of scratches in the process can be suppressed. More preferably, it is in the range of 3-4 GPa.

  In the present invention, a glass powder material having an average particle size of 10 to 30 μm and a maximum particle size of 300 μm or less is used. When a glassy film is formed using the spray method, there is a correlation between the particle size and the degree of porosity, and if the average particle size is less than 10 μm, bubbles generated in the glassy film become smaller, so the stress after firing The relaxation effect is reduced. As a result, cracks and peeling may occur in the vitreous film after firing. On the other hand, if the average particle diameter exceeds 30 μm, bubbles in the vitreous film become too large, and the film thickness may be nonuniform. If the maximum particle size exceeds 300 μm, clogging may occur in the spray device.

  In addition, when the thermal spraying method is used, since the glass powder material is conveyed to the thermal spray gun through a pipe such as a tube, if the average particle diameter is less than 10 μm, the glass powder material may be clogged due to re-aggregation of the glass powder material. . On the other hand, if the average particle diameter exceeds 30 μm, the film thickness may become non-uniform, similar to the spray method. If the maximum particle size exceeds 300 μm, clogging may occur in the piping such as a tube. Preferably, the average particle system is 10 to 20 μm, and the maximum particle system is 150 μm or less.

The glass powder material of the present invention can be used for general ceramics and metal substrates, and the kind thereof is not particularly limited. Moreover, it is preferable that the thermal expansion coefficient is such that the ratio of the thermal expansion coefficient of the substrate to the thermal expansion coefficient of the glass powder material is 0.3 or more and 1 or less. For example, a general soda lime glass substrate (90 × 10 ⁻⁷ / ° C.), Al ₂ O ₃ (70 × 10 ⁻⁷ / ° C.), Y ₂ O ₃ (70 × 10 ⁻⁷ / ° C.), ZrO ₂ ( 90 × 10 ⁻⁷ / ° C.), ceramic materials such as SiN, SiC, and AlN, and metal materials such as aluminum, SUS, and titanium. In addition, the thermal expansion coefficient of this invention calculated | required the linear expansion coefficient from the amount of elongation in 30-300 degreeC when it heated up at 5 degree-C / min using the thermal dilatometer.

In the glass powder material of the present invention, the thermal expansion coefficient at 30 ° C. to 300 ° C. is preferably such that the ratio of the thermal expansion coefficient of the substrate to the glass powder material is 0.3 or more and 1 or less. For example, the glass powder material which is 80-140 * 10 < ^-7 > / degreeC among the low melting glass mentioned above is mentioned. If it is in the said range, a crack and peeling can be suppressed by setting it as a porous film, without being restrict | limited to the thermal expansion coefficient of a soda-lime glass substrate or a ceramic substrate. Outside the above range, the Vickers hardness of the glass powder material is increased, the difference in thermal expansion coefficient is increased, and the residual stress cannot be relaxed even in the porous layer, which may cause cracks.

  This invention is a manufacturing method for forming a porous vitreous film | membrane by the thermal spraying method or the spray method using the said glass powder material. The glass powder material of the present invention and the method for producing a porous film by spraying or spraying can be applied well for liquid crystal display, organic EL display, and mounting table overcoat in the semiconductor manufacturing process as previously described. .

  The thermal spraying method transports a glass powder material to a thermal spray gun through piping such as a tube, heats it with a combustion flame or plasma, etc. to make a molten or semi-molten state, and then uses a gas or air on the substrate surface to form a coating. A forming material is sprayed to form a film. In general, as a method for forming a sprayed film, there are methods such as flame spraying, plasma spraying, etc., and the glass powder material of the present invention has a softening point of 700 ° C. or lower, and a temperature equal to or lower than that of a commonly used ceramic material Therefore, any method can be preferably used.

  In the spray method, a glass powder material is dispersed in an organic vehicle, and is formed into a mist using compressed air to form a film on a substrate. After applying to the substrate, a glassy film is formed by heat treatment at a temperature equal to or higher than the softening point of the glass powder material. It is preferable to mix 10-60 mass% of glass powder materials at this time with respect to the total amount with an organic vehicle. Outside the above range, the glass powder material may not be dispersed due to aggregation, sedimentation, or the like.

  Organic vehicles include, for example, N, N′-dimethylformamide (DMF), α-terpineol, higher alcohol, γ-butyllactone (γ-BL), tetralin, butyl carbitol acetate, ethyl acetate, isoamyl acetate, diethylene glycol monoethyl Ether, diethylene glycol monoethyl ether acetate, benzyl alcohol, toluene, 3-methoxy-3-methylbutanol, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether , Tripropylene glycol monobutyl ether, propylene carbonate, dimethyl sulfoxide (DMSO , N- methyl-2-pyrrolidone and the like can be used. In particular, α-terpineol is preferable because it is highly viscous and has good solubility in resins and the like.

  Hereinafter, a description will be given based on examples.

(Formation of porous film)
First, a glass material was produced. First, a glass material was prepared by weighing and mixing various inorganic raw materials so as to have a predetermined composition described in Table 1. This raw material batch was put into a platinum crucible and heated and melted in an electric heating furnace at 1200 ° C. for 1 to 2 hours to obtain a glass having the composition shown in Table 1. The molten glass was partially poured into a mold and made into a block shape (50 mm × 50 mm × 10 mmt) for measurement of thermal properties (thermal expansion coefficient, softening point) and Vickers hardness measurement. The remaining glass was made into flakes with a rapid twin-roll molding machine.

  Each measurement was performed about each glass made into the block shape mentioned above.

  The softening point was measured using a thermal analyzer TG-DTA (manufactured by Rigaku Corporation).

  Moreover, the said thermal expansion coefficient calculated | required the linear expansion coefficient from the amount of elongation at 30-300 degreeC when it heated up at 5 degree-C / min using the thermal dilatometer.

  Further, the Vickers hardness was measured by a method in which a diamond indenter was pushed into a test piece by a method described in JIS-Z2244.

  Next, the glass powder material described in Table 2 was produced using the said glass material, and it was set as Examples 1-5 and Comparative Examples 1-3, respectively. As the glass powder material, the flaky glass obtained above was adjusted to a predetermined particle size by a jet mill grinder.

  The maximum particle size and average particle size of the glass powder material were measured using a laser diffraction type particle size measuring device (Microtrack, manufactured by Nikkiso Co., Ltd.). Measurement is performed by dispersing the glass powder material in water and then irradiating the laser beam to obtain scattered / diffracted light. From the light intensity distribution, the particle size of the glass powder material is determined according to the program set in the device. And the maximum particle size and the average particle size were determined.

Next, 40% by mass of the glass powder material was prepared for each sample and dispersed in 60% by mass of a mixed solvent of terpineol and isopropyl alcohol to prepare a spray liquid. The obtained spray liquid was applied onto a soda lime glass substrate (coefficient of thermal expansion 90 × 10 ⁻⁷ / ° C., Vickers hardness 5.3 Gpa) at a coating pressure of 0.5 MPa using a hand gun type spray device. Thereafter, it was fired at a temperature 20 ° C. higher than the softening point of the glass powder material.

  In Comparative Example 1, the coefficient of thermal expansion was lower than that of the substrate used, but since the Vickers hardness was higher than that of the substrate, no vitreous film was formed because it was not suitable for the present invention.

  Moreover, what performed screen printing using the spray liquid similar to Example 1 was made into the reference example.

  The obtained glassy film was observed with an optical microscope to confirm the presence or absence of cracks, and the results are shown in Table 3.

  As shown in Examples 1 to 5 in Table 3, within the physical property range of the present invention and in coating by the spray method, it had suitable physical properties, and cracks after firing did not occur.

  On the other hand, Comparative Example 2 has both a large average particle size and a maximum particle size, and there are problems that clogging occurs during spray conveyance and that the film thickness becomes uneven. In Comparative Example 3, both the average particle size and the maximum particle size were small, and clogging due to reaggregation occurred during spray conveyance, and a vitreous film could not be formed. Moreover, since the reference example has cracks after firing, it can be said that the present invention is a glass powder material suitable for film formation by a thermal spraying method or a spraying method.

Claims (7)

In a glass powder material for a porous vitreous film formed on a ceramic or metal substrate by a thermal spraying method or a spray method,
The glass powder material is Bi ₂ O ₃ glass, PbO glass, SiO ₂ —B ₂ O ₃ —R ₂ O glass (R = Li, Na, K), P ₂ O ₅ glass, V ₂ O. _And at least one selected from the group consisting of ₅ glass and B ₂ O ₃ —ZnO glass ,
The average particle size is 10-30 μm, the maximum particle size is 300 μm or less,
The glass powder material has a Vickers hardness of 3-5 GPa lower than the substrate;
A glass powder material for a vitreous film , wherein a ratio of a coefficient of thermal expansion of the substrate to a coefficient of thermal expansion of the glass powder material is 0.3 to 1 at a coefficient of thermal expansion from 30 ° C. to 300 ° C. . 2. The glass powder material for vitreous film according to claim 1, wherein a thermal expansion coefficient at 30 ° C. to 300 ° C. is 80 to 140 × 10 ⁻⁷ / ° C. 3. The ceramic or metal substrate is a soda lime glass substrate, Al ₂ O ₃ , Y ₂ O ₃ , ZrO ₂ The glass material according to claim 1 or 2, wherein the glass material is any one of a ceramic material selected from the group consisting of SiN, SiC, and AlN, and a metal material selected from the group consisting of aluminum, stainless steel, and titanium. Glass powder material. The said glassy film is a liquid crystal display, an organic EL display, or the overcoat of the mounting table of the glass substrate or Si wafer in the manufacturing process of a semiconductor, The any one of Claim 1 thru | or 3 characterized by the above-mentioned. Glass powder material for glassy film. The glass powder material is Bi ₂ O ₃ Glass, and the Bi ₂ O ₃ Glass is Bi ₂ O ₃ 40 to 90% by mass, B ₂ O ₃ The glass powder material for a vitreous film according to any one of claims 1 to 4, comprising 1 to 30% by mass of Zn and 1 to 30% by mass of ZnO. The glass powder material according to any one of claims 1 to 5, and heated using a combustion flame or plasma as the heat source, was melted or semi-melting the glass powder material, the substrate surface at high velocity gas stream A method for producing a porous vitreous film by a thermal spraying method , characterized in that a vitreous film is formed on a substrate surface by spraying on the substrate. The glass powder material according to any one of claims 1 to 5, a solution obtained by dispersing an organic solvent, wherein after application to the substrate surface and calcined at a temperature higher than the softening point of the glass powder material using a spray A method for producing a porous vitreous film by a spray method , characterized in that a vitreous film is formed on a substrate surface .