JP3057714B2 - Pattern formation method - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a conductive film, a transparent conductive film, a resistive film, an insulating film, and the like used for various electronic components such as a liquid crystal display device, a solar cell, and a high-density integrated circuit. The present invention relates to a pattern forming method for forming a metal oxide film, a metal film, a metal sulfide film or a metal nitride film on a substrate.

2. Description of the Related Art Conventionally, a method of forming a pattern of a metal oxide film, a metal film, a metal sulfide film or a metal nitride film on a substrate includes: (1) vacuum deposition, sputtering, CVD, spraying, etc. (2) A uniform film is formed on a substrate on which a negative pattern is formed with a resist material serving as a mask layer by a vacuum evaporation method or a sputtering method, and then a solvent is formed. The resist material is washed by a method, and at the same time, a pattern is formed by dropping a film-forming portion formed on the resist material, that is, a so-called lift-off method. (3) Thermal decomposition and firing after pattern printing of a metal compound solution directly on a substrate The method of doing so is well known.

Problems to be Solved by the Invention However, in the above-mentioned conventional method (1), wet etching using a strong acid such as aqua regia or nitric acid is mainly performed in the etching step. There is a problem that great care and cost are required for handling, management, waste liquid treatment, and the like. Further, since a metal oxide or the like that is stable to an acid such as a tin oxide film cannot be directly etched, there is a problem that a more complicated process of once performing a reduction treatment and then etching is required. On the other hand, there is a method called dry etching, but in this case, since operation in a vacuum vessel is necessary, productivity is poor, processing of a substrate having a large area is difficult, and equipment cost is expensive. It is used only for special applications such as ultrafine processing on semiconductors. Also, in the film forming process, a high vacuum is required in the case of a vacuum evaporation method, a sputtering method, or the like, so that there is a problem that productivity is inferior, large-area film formation is difficult, and apparatus cost is high.

The method (2) does not include an etching step, but the film forming step is limited to a vacuum evaporation method or a sputtering method that requires a high vacuum, so that productivity is poor, large-area film formation is difficult, and apparatus cost is low. However, there is a problem that the substrate cannot be heated to a temperature higher than the decomposition temperature of an organic resist during film formation.

The method (3) is an effective method in that film formation and patterning can be performed at the same time. However, it is difficult to produce a metal compound ink suitable for pattern printing depending on the metal compound, and the thermal decomposition component during firing is low. Since the gas is scattered as gas from the film, the completed metal oxide film, metal film, metal sulfide film or metal nitride film lacks denseness in the film structure, and is electrically, mechanically and scientifically produced. There is a problem that the characteristics are inferior.

The present invention solves the above-mentioned problems, and provides a method for forming a pattern of a metal oxide film, a metal film, a metal sulfide film or a metal nitride film, which is a simple process, and has a dense and excellent characteristic. It is intended for.

Means for Solving the Problems As a means for solving the above problems, the present invention contains, as a filler, an organic powdery substance that does not decompose or evaporate or remains as a decomposition residue below the firing temperature of the metal compound. After applying the ink composition onto the substrate, drying or curing to form a patterned mask layer, and heating the substrate on which the mask layer is formed at a temperature equal to or higher than the thermal decomposition temperature of the metal compound, A step of spraying a solution of the compound or injecting a gas or a pyrolysis gas of the metal compound to thermally decompose and fire the metal compound on the substrate, and after firing, the mask layer is peeled off from the substrate and patterned on the substrate. Forming a metal oxide film or a metal film.

Effects Therefore, according to the present invention, an ink composition containing, as a filler, an organic powdery substance that does not decompose or evaporate or remains as a decomposition residue at or below the firing temperature of the metal compound is applied to a substrate, and then dried or dried. The substrate with the mask layer formed by curing is heated at a temperature equal to or higher than the thermal decomposition temperature of the metal compound while spraying a solution of the metal compound or spraying a gas or a pyrolysis gas of the metal compound to thermally decompose the metal compound. By baking, the resin binder in the mask layer almost disappears due to thermal decomposition, and the mask layer portion is formed on the remaining filler by any one of a metal oxide film, a metal film, a metal sulfide film, and a metal nitride film. The film is covered or a mixture of the remaining filler and any of metal oxides, metals, metal sulfides, and metal nitrides. This state is in the form of flakes or powder, and the adhesion to the substrate is very weak. Therefore, it can be easily peeled off or dropped off by washing or the like, so that a metal oxide film, a metal film, a metal sulfide film or a metal nitride film can be formed on the necessary parts. It can form a pattern of a material film.

Embodiment Hereinafter, an embodiment of the present invention will be described with reference to FIGS.
This will be described with reference to (b), (c), (d), and (e).

As shown in FIG. 1 (a), a filling made of an organic powdery substance, an inorganic powdery substance, or a mixture thereof, on which a decomposition or evaporation does not occur or a decomposition residue remains below the firing temperature of the metal compound on the substrate 1. The pattern-forming mask layer 3 containing the filler 2 is formed by photolithography after pattern printing and drying or curing of the ink composition contained as the agent 2 or after application and drying or curing.

Next, as shown in FIG. 1 (b), while heating the substrate 1 on which the mask layer 3 is formed at a temperature equal to or higher than the thermal decomposition temperature of the metal compound, a solution 4 of the metal compound is sprayed thereon, When the metal compound is thermally decomposed and fired by injecting the gas or the pyrolysis gas 5, the portion without the mask layer 3 on the substrate 1 as shown in FIG. A formation film 6 of one of a metal sulfide film and a metal nitride film is formed, while a portion of the mask layer 3 is baked, and a metal oxide film, a metal film,
As shown in FIG. 1 (d), the filler 2 and a metal oxide, a metal, a metal sulfide, or a metal nitride are in a state of being coated with any one of the metal sulfide film and the metal nitride film 7. The mixed layer 8 is obtained by mixing the components. When the metal compound solution 4 shown in FIG. 1 (b) is sprayed or the gas of the metal compound or the pyrolysis gas 5 is sprayed, the mask layer 3 already has the resin binder thermally decomposed and the filler 2 It may be a state where only the resin binder remains, before the resin binder is thermally decomposed, or during the thermal decomposition.

After the substrate 1 is baked, it is immersed in water and subjected to ultrasonic cleaning, brush cleaning, or the like to form the filler 2 where the mask layer 3 was provided as shown in FIG. One of a metal oxide film, a metal film, a metal sulfide film, and a metal nitride film 7 or a mixed layer 8 in which a filler is mixed with one of a metal oxide, a metal, a metal sulfide, and a metal nitride The pattern of the formed film 6 of any one of a metal oxide film, a metal film, a metal sulfide film and a metal nitride film is completed at a necessary portion by stripping and dropping.

Next, specific examples of the specific pattern forming method of the present invention will be described.

(Example 1) An ink composition for forming a mask layer 3 containing an inorganic powdery substance having the composition shown in Table 1 as a filler 2 is prepared by kneading with a three-roll mill.

This ink composition is screen-printed on a silica-coated soda glass substrate 1 and cured by heating at 150 ° C. for 30 minutes.
The mask layer 3 was formed. The substrate 1 with the mask layer 3 is
While heating to 0 ° C., a solution containing tin 2-ethylhexanoate and antimony 2-ethylhexanoate (tin / antimony (weight ratio) = 10/1) was further placed under a nitrogen atmosphere for 30 minutes.
When a pyrolysis gas obtained by heating to 0 ° C. is injected and fired, the portion without the mask layer 3 is on the formed film 6 made of an antimony-doped tin oxide film, and the portion of the mask layer 3 is on the filler 2 made of graphite and carbon. Is covered with a film 7 of antimony-doped tin oxide, which is subjected to ultrasonic cleaning in water for 1 minute to coat the film 7 of antimony-doped tin oxide on the filler 2 made of graphite and carbon. The removed portion can be completely removed, and the formation film 6 of antimony-doped tin oxide can be formed accurately. The resistance value of this formation film 6 is 1.6 × 10
^-4 Ω · cm low resistance, high temperature and humidity (60 ℃, 95% R
F) The resistance change is 10% even if left for 1000 hours under the condition.
And mechanical strength is excellent.

(Example 2) Next, an organic powdery substance having the composition shown in Table 2 was used as a filler 2.
Is prepared by kneading the ink composition for forming the mask layer 3 containing as a three-roll mill.

This ink composition was applied on a substrate 1 of silica-coated soda glass, and a mask layer 3 having a pattern with a line gap and a line width of 10 μm was formed by photolithography. While heating the substrate 1 with the mask layer 3 to 450 ° C., a solution containing indium 2-ethylhexanoate and tin 2-ethylhexanoate (indium / tin (weight ratio))
= 95/5) and sprayed and baked, the portion without the mask layer 3 is coated with a tin-doped indium oxide forming film 6, and the portion of the mask layer 3 is coated with a filler 7 made of benzoguanamine resin with a tintope indium oxide film 7 By performing ultrasonic cleaning in water for one minute, the portion of the filler 2 made of a benzoguanamine resin, in which the tin tope indium oxide film 7 is covered, can be completely removed. The formation film 6 of tin top indium oxide having a pattern with a line width of 10 μ can be formed with high precision.
The resistance value of the formed film 6 is as low as 1.2 × 10 ⁻⁴ Ω · cm, and its resistance change is 15% even when left for 1000 hours under the condition of high temperature and high humidity (60 ° C., 95% RH). Within, and excellent in mechanical strength.

In addition to those described in Example 1 or Example 2, the filler 2 may be a non-oxide inorganic powder such as boron nitride or silicon carbide, or a tertiary material such as polyimide resin, phenol resin or xylene resin. It has been confirmed that the same pattern can be formed by using a heat-resistant organic powdery substance such as a powder of a primary crosslinkable thermosetting resin or a fluororesin powder. However, oxides such as silica, alumina, and talc have been confirmed. In the case where the inorganic powder compound is used, fusion with an oxide-based substrate 1 such as glass is likely to occur by firing in the air, and the adhesion to the substrate 1 becomes considerably large after firing, making it difficult to remove the mask layer 3. I found that there was.

Examples of the metal compound usable in the present invention include tin, antimony, and indium such as tin 2-ethylhexanoate, antimony 2-ethylhexanoate, and indium 2-ethylhexanoate shown in Example 1 or Example 2.
-Not only hexanoate but also other organic acid salts, such as acetates, acrylates, propionates, benzoates, p
Organic salts such as toluates, oxalates and the like can likewise be used. In addition, similar effects were obtained by using nitrates, chlorides, fluorides, alkoxides, acetylacetonates, organometallic compounds and the like of these metals. However, it has excellent compound stability, easy handling,
In addition, it was found that the most stable film formation was possible when an organic acid salt was used because of its low toxicity, and it was found that it was suitable for mass production. Further, not only such a soot, antimony, and indium compound, but also decomposed by heating to give a formed film 6 of a target metal oxide film, a metal film, a metal sulfide film, or a metal nitride film. If so, materials other than the above materials can also be used.Silica film and titania film are organic acid salts and alkoxides of silicon or titanium, ruthenium oxide film is ruthenium organic acid salt, and gold film is gold resinate. It was confirmed that a similar pattern could be formed by using this method. In the case of a sulfide film such as a zinc sulfide film or a cadmium sulfide film, a pattern can be formed by using zinc or cadmium mercaptide or thiocarbamate in an atmosphere such as nitrogen, argon, or hydrogen sulfide. Using a mask layer 3 containing boron nitride as a filler 2 for the film, a pyrolysis gas of titanium 2-ethylhexanoate is thermally decomposed and fired while heating the substrate 1 made of sapphire to 1370 ° C. in a nitrogen atmosphere. Can form a pattern.

The binder used in the ink composition for forming the mask layer 3 can be arbitrarily used as long as most of the binder disappears during firing. For example, when firing at a relatively low temperature, a cellulose-based binder is used. When firing at a high temperature of 500 ° C. or higher, a polyimide-based material or the like can be appropriately selected.

As described above, according to the above-described embodiment, a metal oxide film, a metal film, a metal sulfide film, or a metal film having excellent characteristics can be obtained by a simple and good productivity method that does not require expensive equipment and an etching step required for a vacuum system. A pattern of a metal nitride film can be formed.

Effects of the Invention The present invention has the following effects, as is apparent from the above embodiment.

(1) A substrate with a formed film can be produced at low cost by a simple method of only heat treatment and cleaning without using dangerous chemicals such as the etching method and requiring a process requiring great care and cost. it can.

(2) Since film formation is performed by spraying a solution or jetting gas at normal pressure, an expensive device such as a vacuum facility is not required, and therefore, it is possible to easily form a film even on a substrate having a large area at a low cost. A pattern of a metal oxide film, a metal film, a metal sulfide film or a metal nitride film having excellent characteristics can be obtained.

[Brief description of the drawings]

1 (a), (b), (c), (d) and (e) are process diagrams for explaining a pattern forming method in one embodiment of the present invention. DESCRIPTION OF SYMBOLS 1 ... board | substrate 2, ... filler, 3 ... mask layer, 4 ... metal compound solution, 5 ... metal compound gas or pyrolysis gas, 6 ... formed film (metal oxide film, metal film) , A metal sulfide film, or a metal nitride film).

──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Masahiro Ito 1006 Kadoma Kadoma, Kadoma City, Osaka Prefecture Inside Matsushita Electric Industrial Co., Ltd. In-company (72) Inventor Hiroshi Hasegawa 1006 Kadoma Kadoma, Osaka Prefecture Inside Matsushita Electric Industrial Co., Ltd. (72) Inventor Kazuyuki Okano 1006 Okadoma Kadoma, Kadoma City Osaka Pref. References JP-A-61-9471 (JP, A) JP-A-2-61914 (JP, A) JP-A-56-97379 (JP, A) JP-B-47-5292 (JP, B1) (58) Survey Field (Int.Cl. ⁷ , DB name) H01B 13/00 H05K 3/10-3/26

Claims (2)

(57) [Claims] 1. An ink composition containing, as a filler, an organic powdery substance that does not decompose or evaporate or remains as a decomposition residue at a temperature lower than the firing temperature of a metal compound, and is applied on a substrate.
Drying or curing to form a patterned mask layer, and spraying the solution of the metal compound thereon while heating the substrate on which the mask layer is formed at a temperature equal to or higher than the thermal decomposition temperature of the metal compound. Or a step of injecting a gas or a pyrolysis gas of the metal compound to thermally decompose and firing the metal compound on the substrate; and, after firing, peeling off the mask layer from the substrate to form a metal oxide patterned on the substrate. Forming one of a film formed of an oxide film, a metal film, a metal sulfide film, and a metal nitride film. 2. The pattern forming method according to claim 1, wherein the metal compound is an organic acid salt of a metal.