JP2002045779A - Method for forming thin film and method for treating surface of substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To reduce cost at the times of formation of a thin film and surface treatment of a substrate. SOLUTION: Fine particles of the same kind or a different kind are ejected to be allowed to collide with the substrate to form the thin film, wherein the fine particles are fused mutually, on the substrate or to embed the fine particles in the substrate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for forming a thin film and a method for treating a surface of a substrate.

[0002]

2. Description of the Related Art Along with the advancement of information, a number of information video devices have been developed, and devices such as semiconductor devices, display devices, and recording media have been frequently used as key devices constituting these devices. As for the display device, LCD (Liquor
A flat panel display typified by an id Crystal Display is frequently used, and a PDP (Platform Display) is used.
sma Display Panel), FED (Fie
The development and commercialization of next-generation displays such as ld Emission Display) are being actively carried out. In order to protect the global environment, new energy developments are being actively conducted in place of conventional thermal, hydro and nuclear power plants, and solar cells, wind power, tidal power generation, etc. do not place a burden on the environment. As attention has been drawn.

[0003] However, a large amount of resources and energy are consumed in the manufacturing stages of the above-mentioned various devices such as information video equipment and solar cells, and drastic changes in manufacturing methods are desired. In particular, chemical vapor deposition requires a large amount of power and resources in forming metal layers, insulating layers, semiconductor layers, etc., which are indispensable for the manufacture of various information and video equipment.
(CVD method), an evaporation method, a sputtering method, an ion plating method and the like are used. For this reason, development of a new film formation method that is efficient and has less impact on the environment is desired. Table 1 shows that in the solar cell and semiconductor related fields,
Conventionally used film forming methods are summarized.

[0004]

[Table 1]

[0005] Table 2 summarizes film forming methods conventionally used in the field of display devices.

[Table 2]

Further, Table 3 summarizes film forming methods conventionally used in various fields such as tools, molds, fittings, automobiles, and the like.

[Table 3]

[0007] On the other hand, the great expansion of the production and distribution of foods and daily necessities has led to the possibility of rapidly and widely spreading bacterial contamination which could not be imagined hitherto.
In addition, new types of pathogens, such as O-157 and MRSA, which have never existed before, are also occurring, and it is desired to thoroughly implement antibacterial and deodorant measures throughout society in order to realize a safer living environment. . As antibacterial and deodorant products, a wide variety of products have been developed in various fields of life as shown in Table 4, including kitchenware such as cutting boards and kitchen knives, and textile products such as underwear and sheets.

[0008]

[Table 4]

[0009] Antibacterial action of metal ions such as silver (Ag) has been known for a long time, and silver tableware has been prized for a long time. Titanium as another metal antibacterial agent
(Ti), zinc (Zn) and the like are known. Titanium dioxide, which is an oxide of titanium, has a photocatalytic effect, and by absorbing ultraviolet light, the titanium dioxide on the surface exerts an oxidizing power to oxidize and decompose odors and kill various germs.

On the other hand, as organic antibacterial agents used in antibacterial plastics and the like, Thiabendazole (thiabendazole), Carbendazin (carbendazin), Iodocarb
(Iodocarb), Chlorothalonil (chlorothalonil),
Methylsulfonyltetrachloropyridine, Fluorfolpet, Captan, Zinc Pyrithione, Chlorhexidine hydrochloride, chlorhexidine hydrochloride, and Triclosan are known. Other known inorganic antibacterial agents include inorganic and organic hybrid antibacterial agents.

The above-mentioned inorganic and organic antibacterial agents are generally used by being supported on a carrier such as zeolite, silica gel, glass, calcium phosphate, zirconium phosphate, silicate, ceramic and whisker. On the other hand, rubber, plastic, metal and ceramic
By applying deodorant or baking,
Processed products with antibacterial and deodorant effects have already been manufactured. For example, a base in which a silver-based antibacterial agent having a sterilizing effect is kneaded into a plastic has been applied to electric appliances such as a refrigerator / refrigerator and a computer. "Antibacterial aluminum enamel" is a composite ceramic in which a hard and rigid vitreous glaze having a strong antibacterial action is baked on the metal surface of an aluminum-plated steel plate, and has been put to practical use as a panel material.

A method of spraying fine particles on the surface of a glass substrate or a semiconductor substrate to form a film of fine particles on the surface of a workpiece is disclosed in JP-A-2-30752 and JP-A-5-301.
066 publication. The former JP-A-2-30
No. 752 describes a method in which ultrafine particles are introduced into a film formation chamber together with a gas to form an ultrafine particle film on a workpiece. Japanese Patent Application Laid-Open No. Hei 5-301066 describes a method of forming a film of sprayed fine particles by embedding fine particles in the surface of the workpiece.
As a result, the corrosion resistance and wear resistance of the surface of the workpiece can be improved.

[0013]

(1) Low power consumption / low cost / vacuum removal-film formation technology As the most common methods for forming a thin film, vacuum deposition using a vacuum and sputter deposition are known. I have. However, with the increase in the size of the device, an increase in power consumption, an increase in manufacturing cost, and the like have become major issues. In particular, Table 1,
As shown in Tables 2 and 3, a large number of large vacuum devices are used for forming various thin films, which are main processes of solar cells and semiconductors, display devices, and fittings and automobiles. Therefore, it is desired to eliminate the vacuum process in order to reduce the manufacturing cost and environmental load.

(2) Formation of Texture Structure In the field of solar cells, a transparent electrode (Transparent Conductiv) is used to improve power generation efficiency.
e Oxide: TCO) has high transmittance,
It is required to form a texture (fine irregularities on the surface) at the same time as having low resistance characteristics. For forming a transparent electrode having a texture structure, a method of optimizing the sputtering deposition conditions of SnO ₂ having excellent transmittance has conventionally been adopted. However, since the material cost and manufacturing cost of SnO ₂ are higher than that of ITO, development of a method for forming a substrate having a textured TCO at a lower cost is desired.

(3) Formation of junction structure In the display device-related field and the solar cell-related field described above, semiconductors having different conductivity types, metal-semiconductor, conductive film-insulating film,
In many cases, a bonding structure of materials having different properties such as a semiconductor-insulating film is formed. Conventionally, the film forming methods listed in Tables 1 and 2 have been used for forming such a bonding structure.
However, these methods are accompanied by an increase in the size of the device,
An increase in manufacturing costs becomes a problem. Therefore, development of a less expensive method of forming a bonding surface is desired.

For example, monocrystalline or polycrystalline silicon solar cells used for electric power solar cells are expensive and have not been widely used for household power. This is due to the use of a high-priced silicon material for semiconductors and the use of a high-cost film-forming technique for forming the junction structure. Therefore, development of low-cost film-forming technology is desired along with development of low-cost materials. Japanese Patent Application Laid-Open No. Hei 2-30752 discloses a film formation method using fine particles. However, a bonding structure cannot be formed by fusing the fine particles.

(4) Persistence of antibacterial and deodorant effects When an antibacterial and deodorant effect is examined for a product to which an antibacterial and deodorant is added, there is no antibacterial and deodorant effect from the beginning, or if it is used for a long time. It was found that the antibacterial and deodorant effects gradually weakened. The cause is that even if an antibacterial / deodorant is added, the dispersion of the antibacterial / deodorant in rubber, plastic, or ceramic is insufficient, and the antibacterial /
This is because the deodorant is not evenly spread. Actually examining the distribution of antibacterial and deodorant on the substrate surface,
Those having no antibacterial / deodorant effect were found to have no antibacterial / deodorant on the surface of the substrate, and those not having long-lasting properties revealed that the antibacterial / deodorant was exposed on only a part of the surface. Therefore, it is an issue of the antibacterial and deodorant treatment how to concentrate the antibacterial and deodorant near the surface and expose the antibacterial and deodorant in a large amount on the surface of the substrate. JP-A-5-3
Japanese Patent Application Publication No. 01066 discloses a technique for embedding fine particles on the surface of a workpiece such as a glass substrate or a semiconductor substrate. However, the method involves spraying the fine particles on a polymer such as plastic or rubber to form a film. Could not.

(5) Addition process of antibacterial and deodorant In order to add an antibacterial and deodorant, conventionally, it is necessary to knead the antibacterial and deodorant into a base such as plastic or to apply and bake on the surface of a molded article. Was. For this reason, in order to add and completely disperse the antibacterial and deodorant materials from the purification stage of the substrate, a large number of steps are required to knead the antibacterial and deodorant materials, or the manufacturing process of the substrate needs to be changed. Needed. In addition, when applying and baking to a molded product, various problems have arisen such as a need to control the temperature of the substrate, which leads to an increase in cost in the manufacturing process.

(6) Improvement of slidability “Improvement of slidability” means that the surface of the substrate is made to be slippery,
It is to reduce wear. By reducing the sliding resistance, the feeling of use of the processed product is improved, and the slip feeling is increased. The shape of the surface is an important factor in improving such slidability. For example, when very fine irregularities are formed on the fiber surface, it is expected that the texture of the chemical fiber will be improved, the friction will be reduced, and the durability will be improved. However, it is difficult to form fine irregularities on the surface of the conventional chemical fiber due to the manufacturing method, and it has been difficult to realize a soft texture as natural fiber has. The same can be said for almost all substrates such as plastics, ceramics, and metals.

(7) Surface Modification of Plastics and Fibers Fine particles having an average particle radius of about 100 μm
When sprayed onto a substrate of different hardness, such as plastic, metal, ceramic, and fiber, at a speed of m / sec or more, a thermal cycle in which the surface temperature instantaneously becomes 2000 ° C. or more and then returns to room temperature is repeated. For this reason, a fine shape change occurs on the surface of the base, or the fine particles themselves are embedded in the base. However, since the temperature of plastics and fibers rises to 2000 ° C. in about microseconds, the substrate tends to undergo oxidative decomposition. As a result, a change in the color or composition of the substrate surface occurs, and it is difficult to maintain the shape and performance before processing.

[0021]

Thus, according to the present invention, there is provided a method of forming a thin film used as a metal layer, an insulating layer or a semiconductor layer, wherein the same type or different types of fine particles are sprayed together with an inert gas onto a substrate. A method for forming a thin film is provided, wherein the thin film is formed by fusing the fine particles to each other on a substrate to form a thin film. Further, according to the present invention, by injecting the same kind or different kinds of fine particles together with an inert gas to collide with a polymer or fiber substrate,
There is provided a method for treating the surface of a substrate, which comprises embedding fine particles in a surface layer of the substrate.

[0022]

DESCRIPTION OF THE PREFERRED EMBODIMENTS (1) Low Power Consumption / Low Cost / Evacuum-Film Deposition Technique The method of laminating a specific material on a substrate is largely divided into physical vapor deposition and chemical vapor deposition. Can be classified. Representatives of the former are vacuum deposition methods using physical adsorption of materials, MBE
(Molecular beam epitaxy), sputter deposition, ion cluster beam (ICB) deposition, and the like. As the latter, there are a thermal CVD method, a plasma CVD method, a photo-CVD method and the like utilizing chemical adsorption of a material. In these film forming methods, the fine particles are adsorbed on the surface of the substrate in a soft landing state, diffused on the surface of the substrate, and then deposited at the nucleation site. In order to generate fine particles such as molecules and clusters, heat is used in vacuum deposition, and plasma is used in sputter deposition.

Generally, when fine particles are sprayed on the surface of a substrate,
It is known that fine particles behave differently depending on the speed. That is, as shown in FIG. 1A, the low-speed fine particles 101 are adsorbed on the surface of the base 100 at the nucleation site 102 in a soft landing state. Medium speed particulates 10
3 is reflected on the surface of the base as shown in FIG. The high-speed fine particles 104 are embedded in the base as shown in FIG.

In the case of molecules or clusters, plasma is used to give the particles speed. On the other hand, fine particles having an average particle radius of 0.01 μm to 0.2 mm are formed into a 5 m particle by ejecting a high-pressure gas or liquid from a nozzle at a high pressure.
/ Sec or more. The feasibility of film formation was measured using quartz glass as the substrate and Ag as the fine particles. As shown in Table 5, in the case of fine particles having an average particle radius of 200 μm, a speed of 5 m / sec or more was required to form a film. It turned out to be necessary. On the other hand, in the case of Ag microcluster fine particles (an aggregate of about 10 particles), 5 eV
Energy (speed of 950 m / sec) is required, and even a single atom sputter is 5 eV (speed is 3000).
m / sec) was found to be necessary. FIG. 2 shows the relationship between the velocities of various fine particles and the average particle radius that can be formed from these data. FIG.
A region 200 (shaded area) indicates a region where film formation is possible, and a region 201 indicates a region where film formation is not possible.

[0025]

[Table 5]

Here, quartz glass was used as the substrate, but non-alkali glass used in a liquid crystal display device or PDP
It was found that soda lime glass used for the above-described method may be used, and the same film-forming effect can be obtained even on a substrate on which another film is formed. Further, it has been found that the use of metal fine particles such as Ta and Al can be applied to metal film formation in display device-related fields.

Next, regarding the embedding of fine particles in a plastic substrate, the required speed was measured using Ag.
It has been found that a speed of 10 m / sec or more is required to form g particles. On the other hand, Ag microcluster fine particles (aggregate of about 10 particles)
It was found that energy of about V (speed is about 1900 m / sec) was required, and about 20 eV (speed is about 6000 m / sec) was necessary even for single atom sputtering.
FIG. 3 shows the relationship between the velocities of various fine particles and the average particle radius that can be embedded from these data. An area 300 (shaded area) in FIG. 3 indicates an area where embedding is possible, and indicates that embedding is not possible in area 301.

[0028]

[Table 6]

The method of forming a film using high-speed fine particles according to the present invention is, as shown in FIG. 4, simply by injecting a compressed gas containing fine particles 402 from a nozzle 403, and in addition to a special vacuum vessel or a sputtering apparatus. No oscillator for generating plasma is required. Therefore, the amortization cost and power consumption of the device in the manufacturing cost can be significantly reduced. In addition, the film forming material cost, when using fine particles,
Since the cost can be significantly reduced as compared with a large target for a sputter, etc., the production cost can be significantly reduced. Further, the semiconductor layer on the glass substrate provided with the transparent electrode is made of Si having an average particle radius of 1 to 5 μm and 60 to 30 m /.
It can be formed by spraying in seconds.

(2) Formation of Texture Structure In order to form a TCO substrate for a solar cell, an average particle radius of 0.
A SnO ₂ fine particle of 01 to 0.05 μm is fed at a speed of 500 to ₂
It was found that when sprayed onto the substrate surface at 00 m / sec, a fine texture (surface irregularities) was formed on the surface.
The reason why the texture can be formed is that a part of the fine particles is formed while melting by the heat generated by the fine particles colliding with the surface of the base, and a part of the formed film is formed by the high-speed fine particles. It is thought that it is due to being dug up again. In addition, when a film was formed by spraying ITO fine particles in the same manner as the SnO ₂ fine particles, it was found that a similar texture structure was formed. As a result, it was shown that fine texture can be formed by spraying high-speed fine particles onto the surface of the substrate. When a polycrystalline Si solar cell was produced using the substrate, it was found that the light use efficiency was improved by about 20% as compared with a substrate having no texture.

(3) Formation of junction structure As a method of forming a junction structure of a semiconductor, a liquid phase film formation or a gas phase film formation has been conventionally performed. On the other hand, when the fine particles are sprayed onto the substrate at a high speed, the heat generated by the collision of the fine particles generates a high-temperature liquid or gaseous state on the surface of the fine particles. FIG.
(A) to (c) schematically show a process of forming a bonding surface between a semiconductor and a metal. The substrate 50 shown in FIG.
1, a TCO 502 and a P-type Si layer 503 are formed. As shown in FIG. 5B, an N-type S
When the i microparticles 504 collide, a part of the semiconductor on the base is melted. As a result, the surface of the melted semiconductor is in a liquid phase state, and a semiconductor junction 506 is formed. In the figure, reference numeral 505 denotes the molten fine particles.

When the characteristics of the junction thus formed were measured, it showed current-voltage characteristics as shown in FIG. From this result, it was found that a bond was formed by the present method. On the other hand, as shown in FIG. 5C, when forming the AuSn electrode 507 on the P-type semiconductor layer,
When the uSn fine particles 508 were injected, it was found that a good ohmic contact like the current-voltage characteristic shown in FIG. 7 was formed.

(4) Persistence of Antibacterial / Deodorant Effect The antibacterial / deodorant agent has an effect of preventing the propagation of various bacteria generated on the surface of the substrate and sterilizing it. Therefore, it is an issue of the antibacterial and deodorizing treatment how to concentrate the antibacterial and deodorant near the surface and expose a large amount of the antibacterial and deodorant on the surface of the base. It is necessary to embed an antibacterial / deodorant in the surface of the substrate as shown in FIG. 1 (c) of the present invention in order to enhance the effect of the antibacterial / deodorant.

Examples of the antibacterial and deodorant include silver (Ag), titanium (Ti), zinc (Zn) and the like containing these as active ingredients. Further, organic antibacterial and deodorants such as thiabendazole, carbendazine, iodocarb, chlorothalonil, methylsulfonyltetrachloropyridine, fluorophorpet, captan, zinc pyrithione, chlorhexidine hydrochloride, and triclosan can also be used. In addition, inorganic and organic hybrid antibacterial and deodorant agents can be used.

These antibacterial and deodorant agents may be carried on carriers such as zeolite, silica gel, glass, calcium phosphate, zirconium phosphate, silicate, ceramic and whisker. Antibacterial and deodorant,
Although those having an average particle radius of 0.01 μm or less can be produced,
It becomes impractical because the ejection speed becomes too fast. In addition, if the average particle radius is 0.5 mm or more, a coloring problem occurs, so that it cannot be used for general purposes. Therefore, antibacterial particles having an average particle radius of 0.01 μm to 0.5 mm
It is preferred to use deodorants.

On the other hand, regarding the distribution of the antibacterial / deodorant in the depth direction, no effect is exhibited when the antibacterial / deodorant is embedded deep from the surface. When the antibacterial / deodorant is present only on the surface, there is a problem that the effect is not sustained. For this reason, it is preferable that the antibacterial and deodorant be distributed at a depth of 1 mm from the surface. As an example, as an antibacterial agent, a silver-based antibacterial agent (manufactured by Nippon Sheet Glass) Amorculin P-0
5 was injected at a high speed of 20 m / sec in a nitrogen gas atmosphere and embedded in a plastic (substrate). The composition of amolculin is based on the basic components SiO ₂ , B ₂ O ₃ , Na ₂ O, A
In g ₂ O, the Ag content is 0.9 ± 0.1% by weight;
The true specific gravity was about 2.5 g / cm ³ , and the pH of the 1% suspension was 8.8. In addition, the average particle radius of amolculin was 5 μm. When a culture test of fungi and mold was performed on the substrate subjected to the antibacterial treatment, the occurrence of fungi was suppressed to 5 or less, and no occurrence of mold was observed. The antibacterial test and the mold resistance test were performed by the methods shown in Table 7.

[0037]

[Table 7]

Further, in order to examine the antibacterial activity test and the durability of the antibacterial activity, a “water immersion test”, a “lightfastness test”, and a “washing test” were performed, and then a culture test was performed again. In the test, it was suppressed to as low as 10, 5, and 10, and no mold was observed. Here, plastic is used as the base, but fine particles can be similarly embedded in a base such as rubber, ceramic, metal, or fiber.

(5) Process of Adding Antibacterial / Deodorant In the conventional method, it was necessary to knead the antibacterial / deodorant into a substrate such as a plastic or to apply and bake on the surface of a molded article. Therefore, in order to add and completely disperse the antibacterial and deodorant materials from the stage of purification of the substrate, it is necessary to knead the antibacterial and deodorant materials and to change the manufacturing process of the substrate. In addition, when applying and baking to a molded product, various problems have arisen such as a need to control the temperature of the substrate, which leads to an increase in cost in the manufacturing process. This is not necessary in the method of the present invention.

(6) Improvement of Slidability In order to improve the slidability, it is important that the surface shape, particularly the fine irregularities are formed on the surface. Conventional chemical fibers are difficult to form fine irregularities on the surface due to the production method, and it is difficult to realize a soft texture as natural fibers have. The same can be said for almost all substrates such as plastics, ceramics and metals. In the method of the present invention, the unevenness can be easily provided, so that the slidability can be improved.

(7) Surface Modification of Plastics and Fibers When high-speed fine particles are sprayed on plastics and fibers, the substrate is exposed to a high temperature of about 2000 ° C. Causes oxidative decomposition. Therefore, when high-speed fine particles are jetted in an atmosphere of an inert gas such as nitrogen gas or argon, thermal decomposition of the substrate can be avoided. As a result, it has become possible to improve the surface of plastics and fibers, which has been impossible in the past, and the strength, smoothness, abrasion resistance and the like have been improved. When silver, titanium, zinc or the like having an antibacterial and deodorant action is used for the high-speed fine particles, the surface of plastics and fibers is activated, and the antibacterial and deodorant action can be enhanced.

[0042]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below based on embodiments.
However, the present invention is not limited to these examples. <Embodiment 1> FIG. 4 shows a film forming method in this embodiment.
It is a thing. In the present embodiment, using Al fine particles,
The wiring of the liquid crystal cell was formed. The apparatus used for film formation is shown in FIG.
As shown in FIG. _Twoetc
Inert high-pressure gas is introduced and fine particles 402 are
In addition, it has a function of jetting from the nozzle 403.

Fine particles ejected from the nozzle 403 collide with the substrate 404 and are adsorbed and deposited on the substrate 404 to form a film. The substrate 404 used here has a thickness of 1.
1 mm non-alkali glass. The fine particles not deposited on the base 404 are collected and sent to the nozzle 403 again through the valve 405 for reuse. Also,
A fan 40 for agitating the fine particles is provided in the device for injecting the fine particles.
6 and a high-pressure gas filter 407 are provided. The substrate is patterned in advance using a photoresist at a pitch of 5 μm and a width of 300 μm, and an Al wiring is formed on a portion not protected by the resist. A
(1) the average particle radius of the fine particles is 0.01 to 0.05 μm
The nozzle flow rate at the time of ejection is 500 to 200 as shown in Table 5.
m / sec. The nozzle pressure is 6K when the flow velocity is 200m / sec.
At gf / cm ² , the flow rate was found to be proportional to nozzle pressure.

The size of the nozzle opening is 25 × 50 mm
And the distance between the nozzle and the substrate was 10 mm. During film formation, the substrate is fed at a feed pitch of 5 mm / sec for a total of 300 m.
m scans. The thickness of the formed Al wiring is 0.1 to
At 0.5 μm, the film formation time was 1 minute. The specific resistance of this wiring was measured and found to be 5 μΩcm, which was comparable to Al wiring formed by magnetron sputtering.

Although the wiring of this embodiment is made of Al, AuS
Wiring made of n, Ta, Cu, WSi ₂ or the like could be formed in the same manner. Although the substrate used in this example was non-alkali glass, wiring could be formed similarly on a substrate made of another material. When these wirings were observed with a microscope, it was found that the fine particles were fused to each other on the substrate. When the gate wiring of the TFT liquid crystal display device was formed using the above-described Al wiring, it was found that a wiring without disconnection could be formed.
In addition, TCO, P-type polycrystalline Si layer, N
After sequentially laminating the type polycrystalline Si layers, an average particle radius of 0.0
It was found that a solar cell manufactured by laminating 1 to 0.05 μm of AuSn as a wiring by the above method achieved a light utilization efficiency of about 15% and had excellent electrode performance.

<Embodiment 2> FIG. 4 shows a film forming method in this embodiment. In this example, a wiring material for a solar cell was formed using SnO ₂ fine particles. As shown in FIG. 4, the apparatus used for film formation was a high-pressure gas inlet 4
It has a function of introducing an inert high-pressure gas such as He or H ₂ from 01 to eject fine particles 402 from the nozzle 403 together with the high-pressure gas.

The fine particles ejected from the nozzle 403 collide with the substrate 404 and are adsorbed and deposited on the substrate 404 to form a film. The substrate 404 used here has a thickness of 1.
1 mm non-alkali glass. The fine particles not deposited on the base 404 are collected and sent to the nozzle 403 again through the valve 405 for reuse. Also,
A fan 40 for agitating the fine particles is provided in the device for injecting the fine particles.
6 and a high-pressure gas filter 407 are provided.

The substrate is previously patterned using a photoresist at a pitch of 5 μm and a width of 300 μm.
₂ Form wiring. The average particle radius of the SnO ₂ fine particles is 0.01 to 0.05 μm.
And 500 to 200 m / sec. Flow velocity 200m /
It was found that the nozzle pressure in seconds was 6 kgf / cm ² and the flow rate was proportional to the nozzle pressure.

The size of the opening of the nozzle is 25 × 50 mm
And the distance between the nozzle and the substrate was 10 mm. During film formation, the substrate is fed at a feed pitch of 5 mm / sec for a total of 300 m.
m scans. The thickness of the formed SnO ₂ wiring is 0.
The film formation time was 1 minute at 1 to 0.5 μm. The specific resistance of this wiring was measured and found to be 500 μΩcm, which was comparable to SnO ₂ wiring formed by magnetron sputtering.

Although the wiring of this embodiment is made of SnO ₂ ,
Wiring made of TO or the like could be formed similarly. Although the substrate used in this example was non-alkali glass, wiring could be formed similarly on a substrate made of another material. Further, when the surface of the SnO ₂ wiring produced in this example was observed with a microscope, it was found that fine irregularities were formed on the surface, and the fine particles were fused to each other. P-type polycrystalline S
When a solar cell was manufactured by sequentially forming an i-layer, an N-type polycrystalline Si layer, and a metal electrode, the light use efficiency was improved by about 20% as compared with a substrate having SnO ₂ wiring without unevenness.

<Embodiment 3> FIG. 4 shows a film forming method in this embodiment. In this example, a semiconductor junction of a solar cell was formed using Si fine particles. As shown in FIG. 4, the apparatus used for film formation is a high-pressure gas inlet 40.
It has a function of introducing an inert high-pressure gas such as He or H ₂ from 1 to eject fine particles 402 from the nozzle 403 together with the high-pressure gas. The fine particles ejected from the nozzle 403 collide with the substrate 404 and are adsorbed and deposited on the substrate 404 to form a film. The substrate 404 used here is a substrate obtained by forming TCO on non-alkali glass having a thickness of 1.1 mm. The fine particles not deposited on the base 404 are collected and sent to the nozzle 403 again through the valve 405 for reuse. Further, the device for injecting fine particles is provided with a fan 406 for stirring fine particles and a filter 407 for high-pressure gas.

The average particle radius of the Si fine particles is 1 to 5 μm.
The nozzle flow rate at the time of ejection is 60 to 30 m /
Seconds. The nozzle pressure at a flow rate of 60 m / sec is 1.8 kg
At f / cm ² , the flow rate was found to be proportional to the nozzle pressure. The size of the opening of the nozzle was 25 × 50 mm, and the distance between the nozzle and the base was 10 mm. During film formation, the substrate is fed at a feed pitch of 2.5 mm / sec for a total of 300 m.
m scans. The formed Si layer had a P-type conductivity type, a film thickness of 20 to 100 μm, and a film formation time of 2 minutes. Next, N-type Si fine particles were similarly sprayed on the same substrate to form an N-type Si layer having a thickness of 100 μm.

When the Si layer produced in this example was observed with a microscope, it was found that the fine particles were fused to each other. The characteristics of the PN junction of this solar cell showed good characteristics as shown in FIG. From this result, it was found that a semiconductor junction was formed by the present method. On the other hand, as shown in FIG.
In order to form the n-electrode 507, AuSn fine particles 508 are used.
Was injected. It was found that a good ohmic contact was formed between the obtained P-type semiconductor layer and the AuSn electrode 507 as shown in the current-voltage characteristics shown in FIG.

<Embodiment 4> FIG. 4 shows a film forming method in this embodiment. In this example, a structure was prepared in which fine particles were embedded in a plastic (substrate) using Ag fine particles. As shown in FIG. 4, the apparatus used for film formation has a function of introducing an inert high-pressure gas such as nitrogen or argon from a high-pressure gas inlet 401 and ejecting fine particles 402 from a nozzle 403 together with the high-pressure gas. Nozzle 4
The fine particles ejected from 03 collides with the plastic 404 and are embedded in the surface of the plastic 404. The fine particles that have not been embedded in the plastic 404 are collected and sent to the nozzle 403 again through the valve 405 for reuse. Further, the device for injecting fine particles is provided with a fan 406 for stirring fine particles and a filter 407 for high-pressure gas.

The average particle radius of the Ag fine particles used in this example was 0.01 μm to 0.2 mm, and the nozzle flow rate at the time of ejection was 700 to 10 m / sec. When the flow rate was 10 m / sec, the nozzle pressure was 0.3 kgf / cm ² , and it was found that the flow rate was proportional to the nozzle pressure. The size of the opening of the nozzle is 25 × 50 mm, and the distance between the nozzle and the base is 10 m.
m. During film formation, the substrate was scanned at a feed pitch of 5 mm / sec for a total of 300 mm. The distance in the depth direction of the embedded Ag was 0.05 μm to 1 mm.

It was found that fine irregularities were formed on the surface of the plastic, the friction coefficient was reduced by 5 to 50%, and the slidability was improved. It was also found that the abrasion and chemical resistance were improved. Although the substrate used in this example was plastic, the slidability can be similarly improved in a substrate made of ceramic, rubber, metal, or fiber. In the case of a fiber, since irregularities are formed on the surface, it is possible to improve the texture of the chemical fiber and the like, reduce the friction, and improve the durability.

<Embodiment 5> FIG. 4 shows a film forming method in this embodiment. In the present example, a structure in which fine particles were embedded in a plastic (substrate) using TiO ₂ fine particles was manufactured. As shown in FIG. 4, the apparatus used for film formation has a function of introducing an inert high-pressure gas such as nitrogen or argon from a high-pressure gas inlet 401 and ejecting fine particles 402 from a nozzle 403 together with the high-pressure gas. The fine particles ejected from the nozzle 403 collide with the plastic 404 and are embedded in the surface of the plastic 404.
The fine particles that have not been embedded in the plastic 404 are collected and sent to the nozzle 403 again through the valve 405 for reuse. Further, the device for injecting fine particles is provided with a fan 406 for stirring fine particles and a filter 407 for high-pressure gas.

The average particle radius of the TiO ₂ fine particles used in this example was 0.01 μm to 0.2 mm, and the nozzle flow rate at the time of ejection was 700 to 10 m / sec. When the flow rate was 10 m / sec, the nozzle pressure was 0.3 kgf / cm ² , and it was found that the flow rate was proportional to the nozzle pressure. The size of the opening of the nozzle is 25 × 50 mm, and the distance between the nozzle and the base is 10 mm.
mm. During film formation, the substrate is fed at a feed pitch of 5 mm /
A total of 300 mm was scanned in seconds. Embedded TiO
The distance in the depth direction of No. ₂ was 0.05 μm to 1 mm.

Apart from the above, a silver-based antibacterial agent is used as an antibacterial agent.
Amolculin P-5 (manufactured by Nippon Sheet Glass) was injected at a high speed of, for example, 50 m / sec per second in a nitrogen gas atmosphere, and embedded in plastic. The composition of amolcline is the basic component SiO
₂ , B ₂ O ₃ , Na ₂ O, Ag ₂ O, Ag content 0.9 ±
0.1% by weight, true specific gravity of about 2.5 g / cm ³ , 1%
The pH of the suspension was 8.8. In addition, the average particle radius of amolculin was 5 μm. After the antibacterial treatment, the antibacterial activity test and the mold resistance test as shown in Table 7 were performed.
It was found to be superior to the one baked with an antibacterial agent.

<Embodiment 6> FIG. 4 shows a film forming method in this embodiment. In the present example, a structure in which fine particles were embedded in fibers using TiO ₂ fine particles was manufactured. As shown in FIG. 4, the apparatus used for film formation introduces an inert high-pressure gas, such as nitrogen or argon, from a high-pressure gas inlet 401 to form fine particles 402 together with the high-pressure gas in a nozzle 4.
It has the function of squirting from 03. The fine particles ejected from the nozzle 403 collide with the fiber 404 and are embedded in the surface of the fiber 404. The fine particles not embedded in the fiber 404 are collected and sent to the nozzle 403 again through the valve 405 for reuse. Further, the device for injecting fine particles is provided with a fan 406 for stirring fine particles and a filter 407 for high-pressure gas.

The average particle radius of the TiO ₂ fine particles used in this example was 0.01 to 20 μm, and the nozzle flow rate at the time of ejection was 700 to 30 m / sec. When the flow rate was 30 m / sec, the nozzle pressure was 0.9 kgf / cm ² , and it was found that the flow rate was proportional to the nozzle pressure. The size of the nozzle opening is 25
× 50 mm, and the distance between the nozzle and the substrate was 10 mm. During film formation, the substrate was scanned at a feed pitch of 5 mm / sec for a total of 300 mm. The distance in the depth direction of the embedded TiO ₂ was 0.05 μm to 0.1 mm.

Apart from the above, a silver-based antibacterial agent is used as an antibacterial agent.
Amolculin P-5 (manufactured by Nippon Sheet Glass) was injected in a nitrogen gas atmosphere at a high speed of, for example, 50 m / sec, and embedded in the fiber. The composition of amolcline is based on the basic components SiO ₂ and B ₂ O
₃ , Na ₂ O, Ag ₂ O, Ag content 0.9 ± 0.1% by weight, true specific gravity about 2.5 g / cm ³ , p of 1% suspension
H was 8.8. In addition, the average particle radius of amolculin was 5 μm. After the antibacterial treatment, the antibacterial activity test and the mold resistance test as shown in Table 7 were performed. For all the materials, the persistence of the effect of the antibacterial agent was higher than that obtained by kneading the antibacterial agent into fibers. It turned out to be excellent.

<Embodiment 7> FIG. 4 shows a film forming method in this embodiment. In this example, a structure in which fine particles were embedded in a substrate was prepared using fine particles of thiabendazole as an antibacterial agent. As shown in FIG. 4, the apparatus used for film formation has a function of introducing an inert high-pressure gas such as nitrogen or argon from a high-pressure gas inlet 401 and ejecting fine particles 402 from a nozzle 403 together with the high-pressure gas.

The fine particles ejected from the nozzle 403 collide with the substrate 404 and are embedded on the surface of the substrate 404.
The fine particles that have not been embedded in the substrate 404 are collected and reused through the valve 405 to re-use the nozzle 4.
03 is sent. In addition, a device for injecting fine particles includes a fan 406 for stirring fine particles and a high-pressure gas filter 40.
7 are provided. After the antibacterial treatment, the same antibacterial activity test and mold resistance test as in Example 6 were performed. As for each material, the persistence of the effect of the antibacterial agent was superior to that in which the antibacterial agent was incorporated. I understood that.

[0065]

According to the present invention, various films can be formed without using a vacuum process apparatus conventionally used for manufacturing solar cells, semiconductor devices, display devices, and the like.
It is possible to provide a method for manufacturing various inexpensive information and image equipment. In addition, since a large-sized vacuum device is not required, manufacturing cost and environmental load can be reduced. Further, according to the present invention, since a texture structure necessary for improving the power generation efficiency of the solar cell can be formed without using magnetron sputtering, it is possible to provide a less expensive method of manufacturing a solar cell. Further, according to the present invention, it is possible to concentrate the antibacterial and deodorant near the surface of the base and to expose a large amount of the antibacterial and deodorant to the surface of the base, so that the effect of the antibacterial and deodorant can be maintained for a longer time. Can be done.

Further, according to the present invention, there is no need for a large number of steps for kneading the antibacterial and deodorant materials, no change in the manufacturing process of the substrate, and no need for temperature control of the substrate. Thus, it is possible to provide an inexpensive manufacturing method by eliminating various problems that lead to an increase in cost in the manufacturing process. Furthermore, according to the present invention, since very fine irregularities can be formed on the fiber surface, it is possible to expect improvement of the texture of chemical fibers and the like, reduction of friction, and improvement of durability. Further, according to the present invention, it is possible to prevent a color change or a composition change on the surface of the substrate due to oxidative decomposition of the substrate by jetting the fine particles using an inert gas, and to prevent a change in the composition before processing. Shape and performance can be maintained.

[Brief description of the drawings]

FIG. 1 is a diagram showing a relationship between a particle collision speed and a substrate surface treatment.

FIG. 2 is a graph showing a relationship between an average particle radius and an injection speed with respect to the film forming conditions of the fine particles of the present invention.

FIG. 3 is a graph showing a relationship between an average particle radius and an injection speed with respect to a condition for embedding particles of the present invention.

FIG. 4 is a view showing a high-speed injection device of fine particles of the present invention.

FIG. 5 is a diagram showing a process of forming a bonding surface between a semiconductor and a metal according to the present invention.

FIG. 6 is a graph showing characteristics of a Si PN junction obtained by the present invention.

FIG. 7 is a view showing characteristics of a metal ohmic contact obtained by the present invention.

[Explanation of symbols]

 100, 501 Substrate 101 Low-speed fine particles 102 Nucleation site 103 Medium speed fine particles 104 High-speed fine particles 200 Area where film formation is possible 201 Area where film formation is impossible 300 Area where embedding is possible 301 Embedding is impossible Area 401 High-pressure gas inlet 402, 504, 508 Fine particles 403 Nozzle 404 Plastic, fiber or substrate 405 Valve 406 Fan 407 Filter 502 TCO 503 Si layer 505 Melted fine particles 506 Joining 507 Electrode

Claims (8)

[Claims] 1. A method for forming a thin film used as a metal layer, an insulating layer, or a semiconductor layer, wherein fine particles of the same type or different types are sprayed together with an inert gas to collide with a substrate, whereby the fine particles are formed on the substrate. A method for forming a thin film, comprising forming thin films fused to each other. 2. The method according to claim 1, wherein the thin film has fine texture by spraying fine particles onto the surface of the substrate. 3. The method according to claim 1, wherein the fine particles are sprayed onto the substrate to generate a liquid phase or a gaseous phase on the surface of the fine particles, thereby forming a bonding structure with a material constituting the substrate. the method of. 4. The method according to claim 1, wherein the fine particles have an average particle radius of 0.01 μm to 0.2 mm. 5. The electrode is formed by spraying fine particles under conditions such that the relationship between the particle radius and the injection speed is in the range of the hatched portion in FIG.
The method according to any one of Items 1 to 4, wherein 6. The substrate is a plastic having a transparent electrode, and the relationship between the particle radius and the injection speed of the fine particles is shown in FIG.
The method according to any one of claims 1 to 4, wherein the semiconductor layer is formed by being sprayed under conditions such that the range of the hatched portion is satisfied. 7. A method for treating a surface of a substrate, wherein the particles are embedded in a surface layer of the substrate by spraying fine particles of the same type or different types together with an inert gas to collide with a substrate made of a polymer or a fiber. 8. The fine particles are embedded in a surface layer of a substrate having a depth of 1 mm or less, and the fine particles have a thickness of 0.01 μm to 0.5 mm.
The method of claim 7 having an average particle radius of: