JPH03155005A - Gold pattern forming composition and forming method - Google Patents

Abstract

PURPOSE:To make it possible to form a metallic gold pattern, capable of preventing reduction of the operation rate of a hybrid IC production line, and moreover fitted to mass production, by applying a heat of 250 deg.C or higher to a gold compound having a structure formula of A-O-Au=O. CONSTITUTION:Metallic gold forming component material paste 8 is obtained by adding lead boro-silicated glass to a K-O-Au=O water solution in which gold hydroxide is melted in a potassium hydroxide water solution. Metallic gold 10 is obtained by applying the abovementioned paste 8 to a substrate 3, then heating an irradiated part to 250 deg.C or higher with YAG laser beam 9 irradiated, thereon and lead boric acid glass is melted to act to sufficiently stick deposited metallic gold 10 fast to the substrate 3. This permits prompt response for the mass production even if an electronic circuit pattern is changed, and also the metallic gold 10 having uniformity and high density can be deposited.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a gold pattern forming composition and a method for forming a gold pattern used in the production of electronic circuit boards such as hybrid ICs.

BACKGROUND OF THE INVENTION Electronic circuits in conventional hybrid ICs have been formed on alumina ceramic substrates using a printing method. The basic components of this printing method, as shown in FIG. 4, are a screen 1 and a squeegee 2 with holes provided in a positive relationship with an electronic circuit 5 to be drawn on a substrate 3. This screen 1 is parallel to the substrate 3 and 0.25 mm above the substrate 3.
The screen 1 is held at a position of about 2.0 mm to 2.0 mm, and a conductive paste 4 that becomes an electronic circuit 5 is placed on this screen 1.
This conductive paste 4 is pressed by the moving squeegee 2 while pressing the screen 1, and moves together with the screen 1. As a result, the conductive paste 4 passes through the hole in the screen 1.
is transferred onto the substrate 3, and an electronic circuit 5 is formed on the substrate 3. .

Furthermore, recently it has been proposed to form electronic circuits on a substrate using a drawing method. In this drawing method, as shown in FIG. 5, first, a paste cartridge 7 is filled with conductive paste 4. This paste cartridge 7 has a cylindrical shape, and the lower end is narrowed and a hole with a diameter of about 0.06 to 2 mra is provided.By applying pressure with air or the like to the upper end of the paste cartridge 7, the lower end is A paste 4 having a constant diameter is discharged from the part. By moving the paste cartridge 7 while discharging the paste, an electronic circuit 5 with a constant line width is drawn on the substrate 3.

Problems to be Solved by the Invention However, in the printing method, when the pattern of the electronic circuit to be obtained changes, it is necessary to change the screen. In addition, even if the same electronic circuit pattern is printed, the screen will stretch after a certain number of printings, resulting in misalignment of the printed electronic circuit pattern. The screen needs to be replaced. When replacing the screen, it is not always possible to obtain a uniform screen due to the processing accuracy of the screen frame and the accuracy of attaching the screen to the frame. Therefore, when replacing the screen, it is necessary to make new adjustments such as alignment and parallelism between the board and the screen. However, this adjustment requires at least 30 minutes, reducing the operating rate of the hybrid IC production line.

Furthermore, when designing an electronic circuit and testing it, it takes about four days to produce a screen, which is a cause of prolonging the development period.

Next, in the drawing method, even if the electronic circuit pattern is changed, the program in which the pattern coordinates are input is simply changed, so there is almost no stopping of the hybrid IC production line due to these reasons. However, the hole at the tip of the paste cartridge at this time is limited to a diameter of 0.06 to 2IIIl, and since the electronic circuit is basically formed by wire,
The disadvantage is that productivity is extremely low compared to printing.

Therefore, instead of conventional printing or drawing methods, an electronic circuit forming method has been proposed in which metal is deposited by irradiating energy that is relatively easy to control, such as ultraviolet rays, visible light, or infrared rays.

However, methods for forming gold electronic circuits using energy such as ultraviolet rays, visible light, and infrared rays have not been put to practical use.

Also, known examples of conventional photosensitive gold compounds that can be used in this formation method include chloroauric acid, gold hydroxide, and gold oxide. However, in the case of chloroauric acid, it is acidic itself, and by precipitating metallic gold with light, HAuCe −”Au+HCe +Ce2 (
1) As a result of the reaction shown in (1), hydrochloric acid is generated, which is undesirable because it causes corrosion of other metals.

In addition, the gold oxide and hydroxide combination is extremely unstable, and 4 A u
(OH) →4 A u + 6 H2O+ 30
2 (2) 2 A u O → 4 A u + 302
(3) 3 (2) This is not preferred because it easily causes the reaction shown in (3) and precipitates metallic gold.

Therefore, the purpose of the first invention is to use thermal energy such as a laser to avoid reducing the operating rate of the hybrid IC production line even when obtaining boards with different electronic circuit patterns, and also to be able to cope with mass production. The present invention provides a method for forming metallic gold patterns.

The purpose of the second invention is to provide hybrid I even when obtaining substrates with different electronic circuit patterns by using ultraviolet rays.
The object of the present invention is to provide a metallic gold pattern forming material that does not reduce the operating rate of the C production line and can be used for mass production.

A third object of the seventh invention is to provide a method for forming a metallic gold pattern using the metallic gold pattern forming material of the second invention.

A fourth object of the invention is to provide a method for forming a pattern of metallic gold that can selectively deposit metallic gold at a higher density and a thickness of 20 μm or more using ultraviolet rays.

Means for Solving the Problems The first invention has a structural formula of A-0-Au=O(A:K
.

alkali metals such as Na) at 250°C.
This is a gold pattern forming method characterized by applying heat of the above amount.

The second invention has a structural formula of A-0-Au=0(A:K,N
an alkali metal such as a) and 1,4-naphthoquinone,
A gold pattern forming composition comprising at least one of 1,4-anthraquinone, 9.10-anthraquinone, 1-4-naphthoquinone derivative, 1,4-anthraquinone derivative, and 9.10 anthraquinone derivative. It is a thing.

A third invention is a method for forming a gold pattern, characterized in that the gold pattern forming composition according to claim 2 is irradiated with ultraviolet rays.

The fourth invention is 1,4-naphthoquinone, 1,4 anthraquinone, 9,10-anthraquinone, 1.4-naphthoquinone derivative, 1,4-anthraquinone derivative, 9,10
- After applying a reducing agent paste containing at least one anthraquinone derivative onto a substrate and irradiating the paste with ultraviolet rays to the part where metallic gold is to be deposited, the structural formula is A.
-0-Au=O (A: alkali metal such as K and Na)
This is a gold pattern forming method characterized by contacting with an aqueous solution of a composition.

According to the first invention, A-0-Au=O(A: Na
.

Alkali metals such as K) are thermally decomposed when heated to 250° C. or higher to precipitate metallic gold. A metallic gold pattern is obtained on the substrate by applying this solution onto the substrate and selectively applying heat to it using a laser beam or the like.

According to a third invention using the second invention, 1,4-naphthoquinone, 1,4-anthraquinone, 9,10 anthraquinone, and their derivatives do not exhibit reducing power by themselves and are hydrophobic. When irradiated with ultraviolet rays, for example, in the case of 9,10-anthraquinone, non, and their derivatives themselves do not exhibit reducing power and are hydrophobic, but when irradiated with ultraviolet rays, for example, in the case of 9,10-anthraquinone, 0
A reaction indicated by 0H takes place. That is, 9,10 anthraquinone undergoes a chemical change to 9,10-antradiol when exposed to ultraviolet light. This 9,10-antradiol has reducing power and is a hydrophilic substance.

Therefore, 1,4-naphthoquinone, 1,4-anthraquinone, 9,10-anthraquinone, and their derivatives and A-0-Au=0 (A: Na.

The mixture with alkali metals such as K) remains stable until it is irradiated with ultraviolet light. However, as soon as ultraviolet rays are irradiated, 1,4-naphthoquinone, 1,4-anthraquinone, and 9,10-anthraquinone exhibit reducing power and precipitate metallic gold.

According to the fourth invention, 1,4-naphthoquinone, 1.4-
The reaction shown with anthraquinone, 9,10-anthrachy, occurs. That is, 9,10 anthraquinone chemically changes to 9,1O-antradiol when exposed to ultraviolet light. This 9.10-antradiol has reducing power and is a hydrophilic substance.

Therefore, for example, by applying a thick layer of 9,10-anthraquinone and then selectively irradiating it with ultraviolet rays, the ultraviolet irradiated area changes to 9,10-antradiol. When a metallic gold-forming composition in solution form is applied to this, 9,10-
Because anthradiol is hydrophilic, a metallic gold-forming composition applied over it will penetrate into the interior (without UV exposure), whereas an entire forming composition applied over the IO-anthraquinone will be repelled. As a result, patterned metallic gold can be obtained at high density and at any thickness by changing the thickness of the reducing agent paste.

Embodiments Embodiment 1 FIGS. 1A and 1B are cross-sectional views showing a method for forming a metallic gold pattern according to a first embodiment of the present invention, that is, the first invention.

First, add 5 g of gold hydroxide to 10 m of a 5N aqueous potassium aquatic solution.
f! K − is a metal-all-forming composition by dissolving it in
0-A Ll = O aqueous solution was obtained, to which 20%-
Polyvinyl alcohol aqueous solution with 5me and average particle size of 1μ
m of lead borosilicate glass was added and stirred well to obtain a metal-forming composition paste 8.

This is applied onto the substrate 3 as shown in FIG. 1A, and then the YAG laser beam 9 is irradiated to the area where the metal gold is to be deposited as shown in FIG. By heating to , metallic gold IO is obtained in that part,
In addition, the lead borosilicate glass present in that portion worked to sufficiently adhere the molten and precipitated metal gold IO to the substrate 3. Thereafter, portions where metallic gold was not deposited were removed by washing with water. This enabled the creation of an electronic circuit using metallic gold.

In this example, from the viewpoint of operability when applying the all-metal forming composition onto the substrate 3, a polyvinyl alcohol aqueous solution was added to the all-metal forming composition to increase the viscosity and make it into a paste. If you don't need that thickness, don't make it into a paste. In addition, other polymeric resins such as ethyl cellulose may be used in the case of forming into a paste. Further, washing with water is not particularly necessary, and in this case, it is not necessary to add lead borosilicate glass or the like to increase the adhesion strength between the precipitated metal gold and the substrate 3. Furthermore, although a YAG laser was used as a heat source in this example, CO2
Other heating means may be used, such as another laser such as a laser, or a heated letterpress other than the laser.

Example 2 FIGS. 2A and 2B show a second example of the present invention, that is, a method for forming a metallic gold pattern according to the third invention using the metallic gold pattern forming composition according to the second invention.

First, add 5g of gold hydroxide to 10r of a 5N potassium hydroxide aqueous solution.
It is a metal-all-forming composition that does not dissolve in RL-0
An -Au=O aqueous solution is obtained, to which 5me of a 20% polyvinyl alcohol aqueous solution and 5 g of 9.10-anthraquinone are added to form a metal gold forming paste.

Next, as shown in FIG.
Allow time to dry. Furthermore, as shown in FIG. 1FI2B, the ultraviolet rays emitted from the light source 13 are patterned and irradiated onto the metal gold forming paste 11 using a mask 12 whose portion on which metallic gold is to be deposited is transparent to ultraviolet rays. The 9,10-anthraquinone present in the ultraviolet irradiated area undergoes a chemical change to 9,10-antradiol, and as a result -0-Au=O is reduced to all metal formations present in the ultraviolet irradiated area. Deposit gold. This makes it possible to obtain an electronic circuit using the metal gold 10 on the substrate 3.

In this example, 1,4-naphthoquinone, (1), 4-anthraquinone and their derivatives, or 9,10-anthraquinone derivatives may be used as the substance which becomes a reducing agent upon irradiation with ultraviolet rays. Moreover, although -0-Au=O was used for the entire metal formation, it may be Na-0 to Au=O.

In addition, from the viewpoint of operability when applying the all-metal forming composition onto a substrate, a polyvinyl alcohol aqueous solution was added to the all-metal forming composition to increase the viscosity and form a burst shape. Don't make it into a paste if it's not necessary. Furthermore, when making a paste, other polymeric resins such as ethyl cellulose etc. may be used without causing the paste to deteriorate. In addition, when patterning ultraviolet rays, a mask was used, but the ultraviolet rays were focused into a beam, which was manipulated to irradiate onto the metal gold forming paste, converting 9,10-anthraquinone into 9,10-antradiol. I don't mind if you let me.

Embodiment 3 FIGS. 3A, B, and C show the third embodiment of the present invention, that is, the fourth embodiment.
1 shows a method for forming a metallic gold pattern according to the invention of the present invention.

First, add 5 g of hydroxide to 10 m of 5N potassium hydroxide aqueous solution.
1! K − is a metal-all-forming composition by dissolving it in
An aqueous solution of 0-A u =O is obtained, which is designated as an aqueous solution of the total metal forming composition. Further, a 9,10-anthraquinone paste was prepared by adding 5 g of 9.10-anthraquinone to 5 me of a 20% polyvinyl alcohol aqueous solution.

First, as shown in FIG. 3A, place this 9.10 on the substrate 3.
- Apply anthraquinone paste 14 and heat it at 50°C.
Leave it for 2 hours to dry under the following conditions. Next, as shown in FIG. 3B, the ultraviolet rays emitted from the light source 13 are patterned using a mask 12 whose portion on which metallic gold is to be deposited is transparent to ultraviolet rays, and 9.10-Anthraquinone paste 14 is irradiated with the ultraviolet rays. do. 9 of the ultraviolet irradiation section 15.
10-anthraquinone is chemically transformed to 9,10-antradiol, and this substance is converted into metal-all-forming composition K-0-A.
Metallic gold can be deposited by reducing u = O. This is then immersed in a metallic gold-forming aqueous solution 16 as shown in FIG. 3C. This results in the total metal forming composition i(-0
-A u = O aqueous solution 16 penetrates into this portion 15 and precipitates metal gold 10 because 9,10-antradiol is hydrophilic and has reducing power, but 9,10- Since anthraquinone has no reducing power and is hydrophobic, it makes the total metal forming composition aqueous solution 16 hydrophobic and does not reduce it, so that metallic gold does not precipitate. Through the above steps, an electronic circuit made of metallic gold could be formed.

In this example, 9.10-anthraquinone, which becomes a reducing agent by irradiation with ultraviolet rays, was used as a substance, but in addition to this, 1,4-naphthoquinone, 1,4 anthraquinone, and their derivatives, or 9.10-anthraquinone derivatives were used. You may also use Also, metallic gold formations are -0
-Au=O was used, but Na-0-Au=O may also be used.

In addition, from the viewpoint of operability when applying 9,10-anthraquinone onto a substrate, a polyvinyl alcohol aqueous solution was used.
In addition to anthraquinone, it was made into a paste, but especially 9,1
If no thickness is required for 0-anthraquinone, it is not made into a paste. In addition, other polymeric resins such as ethyl cellulose may be used to form a paste.

In addition, when patterning the ultraviolet rays, a mask was used, but the ultraviolet rays were focused into a beam, and the beam was scanned to irradiate the entire metal forming paste.9. IO-anthraquinone 9,1
It may be changed to 0-antradiol. Furthermore, when reacting a metal gold-forming aqueous solution with a patterned reducing agent, the substrate was immersed in the metal gold-forming aqueous solution, but the whole metal aqueous solution was immersed in a roller equipped with a hydrophilic substance on the outer periphery.
Other methods may be used, such as bringing this into contact with a reducing agent on a patterned substrate.

Effects of the Invention According to the first invention, 250
Metallic gold is precipitated by applying heat above ℃. Therefore, by using a relatively easy-to-control heat source such as a laser,
Heat can be applied selectively. As a result, even if the electronic circuit pattern changes, it can be responded to immediately, and the pattern formation takt time is sufficient for mass production. Furthermore, since the metallic gold formation material was used in the form of an aqueous solution, it was possible to deposit uniform and highly dense metallic gold.

According to the third invention using the composition of the second invention, a mixture of a total metal forming composition and a reducing agent that exhibits reducing power when exposed to ultraviolet light is applied onto the substrate, and the area where metallic gold is to be deposited is coated on the substrate. Metallic gold is obtained by irradiating ultraviolet light, which is relatively easy to control. As a result, even if the electronic circuit pattern changes, it can be responded to immediately, and the pattern formation takt time is sufficient for mass production. Furthermore, unless exposed to ultraviolet rays, this reducing agent has no reducing power and is a hydrophobic substance, so it is very stable before using this material and in the non-ultraviolet irradiated area after pattern formation.

According to the fourth invention, a reducing agent paste that exhibits reducing power and becomes hydrophilic when exposed to ultraviolet rays is applied onto a substrate, and the reducing agent is patterned by irradiating it with ultraviolet rays that are relatively easy to control. Metallic gold is obtained by contacting a metal-all-forming aqueous solution with the metal-forming aqueous solution. As a result, even if the electronic circuit pattern changes, it can be responded to immediately, and the pattern formation takt time is sufficient for mass production. In addition, in the absence of ultraviolet rays, it has no reducing power and is a hydrophobic substance, but the part exposed to ultraviolet rays generates reducing power and becomes a hydrophilic substance, so by applying a thick layer of reducing agent paste on the substrate, It was possible to increase the thickness of the deposited metal gold, and it was possible to deposit it to a thickness of 20 μm or more. Furthermore, with this method, it was possible to increase the density of the reducing agent, so a high-density pattern could be formed and an electronic circuit with a line width of 0.06 mm could be obtained.

[Brief explanation of the drawing]

FIGS. 1(A) and (B) are cross-sectional views showing the metal gold pattern forming method in the first embodiment of the present invention, FIG. 2(A),
(B) is a sectional view showing the gold pattern forming method in the second embodiment of the present invention, and FIGS. 3(A), (B), and (C) are the gold pattern forming method in the third embodiment of the present invention. FIGS. 4 and 5 are simple cross-sectional views respectively showing the printing method and drawing method used in forming metal patterns used in conventional electronic circuits. 3...Substrate, 8...Metal all-forming composition paste, 9...YAG laser beam, 10...
...metallic gold, 11...metal all-forming paste, 12...mask, 13...light source, 1
4...9,10-anthraquinone paste, 1
5... Ultraviolet irradiation part, 16... All metal formed product aqueous solution.

Claims (4)

[Claims] (1) A gold pattern forming method in which a gold compound having the structural formula A-O-Au=O (A: alkali metal such as K, Na, etc.) is heated at 250° C. or higher. (2) A substance whose structural formula is A-O-Au=O (A: alkali metal such as K, Na, etc.), 1,4-naphthoquinone, 1,4-
anthraquinone, 9,10-anthraquinone, 1,4-
naphthoquinone derivatives, 1,4-anthraquinone derivatives,
and at least one 9,10-anthraquinone derivative. (3) A gold pattern forming method comprising irradiating the gold pattern forming composition according to claim 2 with ultraviolet rays. (4) Reducing agent paste containing at least one of 1,4-naphthoquinone, 1,4-anthraquinone, 9,10-anthraquinone, 1,4-naphthoquinone derivative, 1,4-anthraquinone derivative, and 9,10-anthraquinone derivative After coating the paste on a substrate and irradiating the part of the paste with ultraviolet rays where metallic gold is to be deposited, the structural formula is changed to A-O-
A gold pattern forming method in which Au=0 (A: alkali metal such as K, Na, etc.) is brought into contact with an aqueous solution of a composition.