KR101138246B1 - Manufacturing method of paste composition having low temperature coefficient resistance for resistor, thick film resistor and manufacturing method of the resistor - Google Patents

Abstract

PURPOSE: A manufacturing method of a paste composition for a resistor, a thick film resistor using the same, and a manufacturing method thereof are provided to prevent the generation of a blaster using unleaded paste composition. CONSTITUTION: A CaO-B2O3-Al2O3-SiO2-based glass material and a ruthenium-based oxide including CaO 8-60 weight%, B2O3 15-35 weight%, al2O3 2-15 weight%, SiO2 5-25 weight%, RO 0-45 weight% are prepared. The glass material and ruthenium-based oxide are mixed at the rate of 1:9-9:1. The mixture of the ruthenium-based oxide and the glass material is fused through a thermal process. The ruthenium-based oxide-glass composite composition is formed. The ruthenium-based oxide-glass composite powder is formed by crushing the ruthenium-based oxide - glass composite composition. The ruthenium-based oxide-glass composite powder is coated with the metal oxide. The paste composition for a resistor is formed.

Description

Manufacturing method of paste composition having low temperature coefficient resistance for resistor, thick film resistor and manufacturing method of the resistor

The present invention relates to a method for preparing a resistor composition for a resistor, a thick film resistor using the same, and a method for manufacturing the same, and more particularly, to mix and melt a glass raw material and a ruthenium oxide powder to form a ruthenium oxide-glass composite powder. A lead-free paste composition having a low temperature resistance coefficient (TCR) by coating a metal oxide serving as a temperature resistance modifier and mixing with an organic binder to form a paste composition for a resistor. Therefore, it is environmentally friendly, exhibits high adhesion with an aluminum nitride (AlN) substrate, does not generate blisters, and can be applied to a thick film resistor that requires high power and high frequency. A thick film resistor and a method of manufacturing the same.

Ruthenium oxide (RuO ₂ ) -based thick film resistors can realize a wide range of resistance values by controlling the ratio of RuO ₂ and glass components, and have excellent temperature resistance coefficients. It is widely applied to hybrid microcircuits.

Conventional thick film resistors were formed on alumina substrates by screen printing methods, but due to the problem of deteriorating the reliability and lifespan of chips or circuits due to the increase of heat emitted per unit area according to the trend of miniaturization, high frequency, and high power of electronic components. Substrates having excellent thermal properties such as aluminum nitride have been used in place of alumina substrates.

In general, in the thick film resistive material, the glass phase plays a role of enhancing the bonding with the substrate, so it is very important to select an appropriate glass composition. Currently commercially available resistance pastes for alumina substrates use a low melting point glass composition containing lead (Pb).

However, glass containing lead has been recently banned due to environmental regulations, and is known to have poor adhesion to aluminum nitride substrate due to low adhesion and blister generation. When using lead-containing glass, oxides, particularly lead oxide (PbO), may react with aluminum nitride, which is a substrate, which may cause blistering. One of the causes of low adhesion is that the lead oxide in the glass reacts with aluminum nitride upon sintering and is reduced to lead (Pb) to generate nitrogen gas (N ₂ ) (g). Therefore, it is important to select a lead-free glass composition that does not contain lead and has good mutual bonding with aluminum nitride. In addition, it is advantageous to have a low temperature resistance coefficient of ± 150ppm / ℃ to use the thick film resistance as a product. In general, since RuO _{2 has} a high temperature resistance coefficient of 5670 ppm / ° C, efforts to lower the temperature resistance coefficient of the final thick film resistance by adjusting the composition of glass or adding a component having a low resistance temperature coefficient It is necessary to do

On the other hand, since the RuO ₂ powder and the glass powder are generally prepared by simply mixing the resistance paste, it is difficult to obtain a uniform mixing state between the components. As a result, it is difficult to obtain a uniform microstructure after firing in the thick film resistor, and as a result, a change in electrical properties may be large.

The problem to be solved by the present invention is to mix and melt a glass raw material and ruthenium oxide powder to be mixed in a very uniform state of ruthenium oxide and glass powder to prepare a ruthenium oxide-glass composite powder, and serves as a temperature resistance coefficient regulator After coating a metal oxide to form a dispersion composition for the resistor by dispersing it in an organic binder, it shows a stable resistance characteristics, a low temperature resistance coefficient, lead-free paste composition containing no lead, environmentally friendly, nitride The present invention provides a method for producing a paste composition for resistors, which exhibits high adhesion with an aluminum substrate, does not generate blisters, and can be applied to thick film resistors requiring high power and high frequency.

Another object of the present invention is to provide a method for manufacturing a thick film resistor that can be used in a device requiring high power and high frequency.

Another object of the present invention is to provide a thick film resistor that can be used in a device that requires high power and high frequency.

The present invention provides CaO- containing 8 to 60% by weight of CaO, 15 to 35% by weight of B ₂ O ₃ , 2 to 15% by weight of Al ₂ O ₃ , 5 to 25% by weight of SiO ₂ , and 0 to 45% by weight of RO. Preparing a B ₂ O ₃ -Al ₂ O ₃ -SiO ₂ based glass material and a ruthenium oxide, and mixing the glass raw material and the ruthenium oxide in a weight ratio of 1: 9-9: 1; And heat treating the mixture of the glass material and the ruthenium oxide to melt the glass material, quenching the resultant of the melting of the glass material to form a ruthenium oxide-glass composite composition, and ruthenium formed by quenching. Pulverizing the oxide-glass composite composition to form a ruthenium oxide-glass composite powder, coating the ruthenium oxide-glass composite powder with a metal oxide, and the ruthenium oxide-glass composite powder coated with the metal oxide. Mixed with organic binder And forming the cast composition, the RO is ZnO, MnO, material NaO and made of one or more materials that are selected from Na ₂ O, wherein the metal oxide is at least one selected from the group consisting of Mn ₃ O _4, CoO, and NiO It provides a method for producing a paste composition for a resistor having a low temperature resistance coefficient, characterized in that consisting of.

The coating with the metal oxide may include preparing at least one metal acetate selected from manganese acetate, cobalt acetate, and nickel acetate, wherein the ruthenium-based oxide-glass composite powder and the metal acetate are in a weight ratio of 90: 1 to 80:20. Preparing a metal acetate solution by weighing and dissolving the metal acetate in a solvent to prepare a metal acetate solution; and injecting and stirring a ruthenium oxide-glass composite powder into the metal acetate solution, and the ruthenium oxide-glass composite powder Drying the added metal acetate solution and the heat treatment of the dried result may include the step of converting the metal acetate to a metal oxide while the organic component is removed.

The heat treatment is preferably performed for 30 minutes to 12 hours at a temperature of 600 ~ 900 ℃ in an oxidizing atmosphere.

The ruthenium-based oxide is RuO _2, calcium ruthenate carbonate (CaRuO _3), strontium ruthenate carbonate (SrRuO _3), barium ruthenate carbonate (BaRuO _3), thallium ruthenate carbonate (Ta ₂ Ru ₂ O ₇₎ and bismuth ruthenate carbonate (Bi ₂ Ru ₂ O ₇ ) It may be made of one or more conductive oxide powder selected from.

The heat treatment for melting the glass raw material is preferably made of a step of maintaining for 10 minutes to 6 hours at a temperature of 1100 ~ 1500 ℃ to melt the glass raw material.

The organic binder and the ruthenium-based oxide-glass composite powder coated with the metal oxide may be mixed in a ratio of 1: 1 to 1: 9 by weight.

The resin used in the organic binder is ethyl cellulose, ethyl hydroxyethyl cellulose, wood rosin, phenol resin or polymethacrylate, and the solvent used in the organic binder is dihydroterpineol, dihydroacetate, alpha- Terpineol, beta-terpineol, dibutyltalate, butylcarbitor butylcarbitol acetate, hexylene glycol, or texanol, wherein the organic binder is the resin and the solvent in a weight ratio of 1: 3 to 1 :: It may be made of a mixture of 15.

The present invention also provides a method for forming a resistor pattern by printing a resistor paste composition prepared by the above method on a substrate on which an electrode pattern is formed, drying the substrate on which the resistance pattern is formed, and drying the dried substrate. It provides a thick film resistor manufacturing method comprising the step of sintering at a temperature of 1100 ℃ and cooling to form a thick film resistor.

In addition, the present invention is produced by the above-mentioned thick film resistor manufacturing method, ruthenium oxide particles are CaO 8-60% by weight, B ₂ O ₃ 15-35% by weight, Al ₂ O ₃ 2-15%, SiO ₂ 5 It is surrounded by a CaO-B ₂ O ₃ -Al ₂ O ₃ -SiO ₂ -based glass matrix containing ˜25% by weight, RO 0-45% by weight, wherein the CaO-B ₂ O ₃ -Al ₂ O _3- The SiO ₂ based glass matrix provides a thick film resistor having a structure surrounded by a metal oxide.

According to the present invention, a glass material and a ruthenium oxide powder are mixed and melted to form a ruthenium oxide-glass composite powder, coated with a metal oxide serving as a temperature resistance coefficient regulator, and dispersed in an organic binder to prepare a paste composition for resistors. When the glass material is melted and pulverized to form a glass powder, and the glass powder, the ruthetium oxide powder, and the organic binder are mixed to form a resistor paste composition, the sheet resistance is 10 times higher than the temperature. The resistance coefficient (TCR) was low.

The resistor paste composition of the present invention is a lead-free paste composition containing no lead, which is environmentally friendly, exhibits high adhesion to an aluminum nitride substrate, and does not generate blisters.

The thick film resistor manufactured using the resistor paste composition of the present invention has an advantage that it can be applied to a device requiring high power and high frequency.

1A and 1B are scanning electron microscope (SEM) photographs of a ruthenium-based oxide-glass composite powder prepared by melting CaZnBAlSi-1 glass material and RuO ₂ powder shown in Table 1. FIG.
2A and 2B are scanning electron microscope (SEM) photographs of a ruthenium-based oxide-glass composite powder prepared by melting CaZnBAlSi-2 glass material and RuO ₂ powder shown in Table 1. FIG.
3A and 3B are scanning electron microscope (SEM) photographs of a ruthenium-based oxide-glass composite powder prepared by melting CaZnBAlSi-3 glass material and RuO ₂ powder shown in Table 1. FIG.
4A and 4B are scanning electron microscope (SEM) photographs of a ruthenium-based oxide-glass composite powder prepared by melting CaZnBAlSi-4 glass material and RuO ₂ powder shown in Table 1. FIG.
5 illustrates a particle structure of a thick film resistor.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the following embodiments are provided to those skilled in the art to fully understand the present invention, and may be modified in various forms, and the scope of the present invention is limited to the embodiments described below. It doesn't happen.

In order to prepare a paste composition for a resistor according to a preferred embodiment of the present invention, a glass raw material and a ruthenium oxide are prepared.

The ruthenium-based oxide is RuO _2, calcium ruthenate carbonate (CaRuO _3), strontium ruthenate carbonate (SrRuO _3), barium ruthenate carbonate (BaRuO _3), thallium ruthenate carbonate (Ta ₂ Ru ₂ O ₇₎ and bismuth ruthenate carbonate (Bi ₂ Ru ₂ O ₇ ) may be at least one conductive oxide powder selected from.

The glass raw material is CaO-B ₂ O ₃ -Al ₂ O ₃ -SiO ₂ -based raw material, the content of CaO in the total content of the glass raw material is 8 to 60% by weight, the content of B ₂ O ₃ is 15 to 35% by weight The content of Al ₂ O ₃ is 2-15% by weight, the content of SiO ₂ is 5-25% by weight, and the content of RO is 0-45% by weight. The RO is preferably at least one material selected from ZnO, MnO, NaO, and Na ₂ O, more preferably ZnO. More preferably, the content of RO is 0.01 to 41% by weight.

In general, the glass raw material has a low viscosity when the glass transition temperature is exceeded according to an elevated temperature for melting, and promotes sintering of ruthenium oxide particles, which are conductive materials, through the viscous flow, and provides adhesion to the substrate. . At this time, the glass having a relatively low viscosity is easily ruthenium oxide Penetration between the particles promotes the rearrangement of ruthenium oxide, and forms a glass layer between the ruthenium oxide particles. As a result, resistors with low viscosity glass will have higher resistance values at the same heat treatment temperature.

The glass raw material and the ruthenium oxide are mixed in a weight ratio (glass raw material: ruthenium oxide) in a ratio of 1: 9-9: 1, preferably 4: 6. The mixing may use a mixer such as a Turbula mixer.

The mixture of the glass raw material and the ruthenium oxide is heat-treated to cause the glass raw material to melt. In the heat treatment, a mixture of a glass material and ruthenium oxide is contained in a crucible made of alumina or platinum, charged into the furnace such as an electric furnace, and then a heat treatment temperature (eg, a target temperature of the furnace) is used. After heating up to 1100-1500 ° C., the process may be performed for a predetermined time (eg, 10 minutes to 6 hours). At this time, it is preferable that the temperature increase rate of the furnace is about 5 to 50 ° C./min. If the temperature rising rate of the furnace is too slow, it takes a long time and productivity decreases, and if the temperature rising rate of the furnace is too fast, the temperature rises rapidly. Since stress can be applied, it is desirable to raise the temperature of the furnace at a rate of temperature rise in the above range. The target heat treatment temperature is preferably about 1100 ~ 1500 ℃ in consideration of the diffusion of particles, necking (necking) between the particles, if the heat treatment temperature is too high, the physical properties may be reduced due to excessive growth of the particles. In addition, when the heat treatment temperature is too low, the glass material may not be melted, and the physical properties of the ruthenium-based oxide-glass composite composition may not be good due to incomplete melting.

The resultant of the melting of the glass raw material is quenched. The quenching may be a step of quenching in air or the like. By quenching the resultant heat treatment, the internal strength of the ruthenium-based oxide-glass composite composition is enhanced.

The quenched product is ground to form a ruthenium-based oxide-glass composite powder. The grinding may be a planetary mill or a ball mill, which is generally known.

Ruthenium-based oxide-glass composite powder is coated with a metal oxide. The metal oxide may be at least one material selected from Mn ₃ O ₄ , CoO, and NiO. The metal oxide serves to lower the temperature resistance coefficient. The ruthenium-based oxide-glass composite powder may be coated with two or more metal oxides such as Mn ₃ O ₄ and NiO.

It describes a method of coating a metal oxide on the ruthenium-based oxide-glass composite powder.

A solvent such as distilled water is prepared by preparing at least one metal acetate selected from manganese acetate, cobalt acetate and nickel acetate. It is dissolved in to prepare a metal acetate solution, and the ruthenium-based oxide-glass composite powder is added to the metal acetate solution thus prepared and stirred for a predetermined time (for example, 10 minutes to 12 hours).

The metal acetate solution into which the ruthenium-based oxide-glass composite powder is added is dried. The drying may be used, such as a hot air dryer, preferably at a temperature of 80 ~ 150 ℃. By the drying, a solvent such as distilled water is evaporated and removed.

The dried resultant is heat-treated in an oxidizing atmosphere (eg, an oxygen gas atmosphere or an air atmosphere) to remove the organic component and convert the metal acetate into a metal oxide. Through the heat treatment, it is possible to obtain a ruthenium-based oxide-glass composite powder coated with at least one material selected from Mn ₃ O ₄ , CoO, and NiO. The heat treatment is preferably made at a temperature of 600 ~ 900 ℃, when the heat treatment process at a temperature of less than 600 ℃, the oxidation of the metal acetate is not well made and the heat treatment time is long, the temperature exceeding 900 ℃ When the heat treatment process is performed in the high energy consumption is not economical. Preferably, the heat treatment is performed for 30 minutes to 12 hours. If the heat treatment time is less than 30 minutes, the metal acetate may not be sufficiently converted to the metal oxide, and if it exceeds 12 hours, it may not be economical because it takes a long time. It is preferable that the temperature increase rate up to the heat treatment temperature is about 5 to 50 ° C./min. If the temperature increase rate is too slow, the heat treatment takes a long time, so it is not economical. It is preferable to increase the temperature at a temperature rising rate in the above range because thermal stress may be applied to the same.

Cooling of the furnace after the heat treatment may be cooled to a natural state by shutting off the furnace power source, or may be cooled by arbitrarily setting a temperature drop rate (eg, 5 to 15 ° C./min).

The metal oxide-coated ruthenium-based oxide-glass composite powder obtained as described above is mixed with an organic binder to prepare a paste composition for a resistor. The organic binder and the ruthenium oxide-glass composite powder may have a weight ratio (organic binder: metal oxide coated ruthenium oxide-glass composite powder) in a ratio of 1: 1 to 1: 9, preferably 4: 6. Mix with. The organic binder may be formed by mixing a resin and a solvent in a ratio of 1: 3 to 1:15 in a weight ratio (resin: solvent).

Specifically, an organic binder and ruthenium oxide are prepared by mixing a resin such as ethyl cellulose and a solvent such as terpineol in a ratio of a predetermined ratio (for example, 10:90) to prepare an organic binder. The glass composite powder is mixed in a predetermined ratio (for example, 4: 6 by weight) and stirred using a disperser such as a 3-roll mill for uniform dispersion to prepare a paste composition for a resistor. The resin may be a material such as ethyl cellulose, ethyl hydroxyethyl cellulose, wood rosin, phenol resin, polymethacrylate, or a mixture thereof, and the solvent may be dihydroterpineol, di, which can dissolve the resin. Materials such as hydroacetate, alpha-terpineol, beta-terpineol, dibutyltalate, butylcarbitor butylcarbitol acetate, hexylene glycol, texanol or mixtures thereof. The organic binder may further be added a material such as a dispersant and a plasticizer.

After printing the resist paste composition on the substrate on which the electrode pattern is formed by a screen printing method to form a resistance pattern, drying the substrate on which the resistance pattern is formed, and sintering the dried substrate at a temperature of 700 to 1100 ° C. By cooling, a thick film resistor can be produced. For example, the silver paste is first printed on an AlN substrate by screen printing, followed by sintering at a predetermined temperature (for example, 850 ° C.) for a predetermined time (for example, 10 minutes) to form an electrode pattern. The paste composition is printed to form a resistance pattern, held and dried at a predetermined temperature (e.g., 150 ° C) for a predetermined time (e.g., 10 minutes), and predetermined time at a predetermined temperature (e.g., 850 ° C) in a furnace such as an electric furnace. After sintering (for example, 10 minutes), a thick film resistor can be formed through furnace cooling.

As shown in FIG. 5, the thick film resistor includes ruthenium oxide particles 110 having 8 to 60 wt% of CaO, 15 to 35 wt% of B ₂ O ₃ , 2 to 15 wt% of Al ₂ O ₃ , and SiO ₂ 5 to Surrounded by a CaO-B ₂ O ₃ -Al ₂ O ₃ -SiO ₂ based glass matrix 120 comprising 25% by weight, RO 0-45% by weight, CaO-B ₂ O ₃ -Al ₂ O ₃ The SiO ₂ -based glass matrix 120 has a structure surrounded by the metal oxide 130.

When the ruthenium-based oxide the temperature resistance coefficient of RuO ₂ is 3600ppm / ℃ when sintering makil, in the single crystal there is has a value of high positive (positive) to 7000ppm / ℃, the glass to be added to the RuO _2, the value in the RuO ₂ In general, the TCR tends to be opposite to the resistance value.

Hereinafter, examples according to the present invention will be presented in more detail, and the present invention is not limited to the following examples.

≪ Example 1 >

In the present invention, in developing a paste composition for a resistor suitable for AlN substrates, a CaO-B ₂ O ₃ -Al ₂ O ₃ -SiO ₂ -based glass material is selected, and a glass material is selected by varying the content ratio of CaO and ZnO. The effects of the composition of glass, the composition of glass and the mixing ratio of RuO ₂ and glass on the electrical properties and microstructure of thick film resistors were investigated.

As a raw material powder, RuO ₂ , a conductive oxide, was made of Wuhu Haina (China) powder having a purity of 99.95%. RuO ₂ powder was heavily coagulated and used after milling at 200 rpm for 2 hours using a zirconia (ZrO ₂ ) ball with a diameter of 3 mm in planetary mill (Pulverisette 5, Fritsch, Germany).

Glass raw materials used as sintering aids are based on CaO-ZnO-B ₂ O ₃ -Al ₂ O ₃ -SiO ₂ system, and the ratio of CaO and ZnO (CaO / ZnO) is 53/0, 43/10, Four compositions were used, varying from 32.5 / 20.5 to 12/41. Each component of the glass raw material used in this experiment was manufactured by Japan High Purity Co., Ltd. with a purity of 99.9% or more.

The composition of the glass raw material used in the present invention is shown in Table 1.

Glass type constituent content (wt%) CaO ZnO B ₂ O ₃ Al ₂ O ₃ SiO ₂ Total CaZnBAlSi -1 53 0 25 7 15 100 CaZnBAlSi -2 43 10 25 7 15 100 CaZnBAlSi -3 32.5 20.5 25 7 15 100 CaZnBAlSi -4 12 41 25 7 15 100

After mixing the glass raw material and the RuO ₂ powder shown in Table 1 in a ratio of 4: 6 (glass raw material: RuO ₂ powder), the mixture was mixed using a three-dimensional Turbula mixer at 50 rpm for 2 hours. The mixture was placed in an alumina crucible and melted at 1200 ° C. for 1 hour, followed by quenching in air to prepare a ruthenium oxide-glass composite composition.

The ruthenium-based oxide-glass composite composition thus prepared was subjected to 200-mesh sieve through primary coarse grinding in a mortar, and then zirconia balls with a diameter of 3 mm in a planetary mill for fine grinding. Milling was performed for 2 hours at a speed of 200 rpm. The powder thus obtained was sufficiently dried in an oven at 80 ° C. for 24 hours, and passed through a 325 mesh sieve to prepare a ruthenium oxide-glass composite powder.

1A to 4B are scanning electron microscope (SEM) photographs of ruthenium-based oxide-glass composite powders prepared by mixing, melting and pulverizing a glass raw material and RuO ₂ powder as described above. 1A and 1B are scanning electron microscope (SEM) photographs of a ruthenium oxide-glass composite powder prepared by mixing and melting a CaZnBAlSi-1 glass material and RuO ₂ powder shown in Table 1, and FIGS. 2A and 2B are Table 1 A scanning electron microscope (SEM) photograph of a ruthenium-based oxide-glass composite powder prepared by mixing and melting a CaZnBAlSi-2 glass material and a RuO ₂ powder shown in FIGS. 3A and 3B is a CaZnBAlSi-3 glass material shown in Table 1 A scanning electron microscope (SEM) photograph of a ruthenium-based oxide-glass composite powder prepared by mixing and melting RuO ₂ powder, and FIGS. 4A and 4B are prepared by mixing and melting a CaZnBAlSi-4 glass material and RuO ₂ powder shown in Table 1. SEM image of ruthenium-based oxide-glass composite powder.

1a to 4b, the ruthenium-based oxide-glass composite powder obtained by mixing, melting and pulverizing a glass raw material and RuO ₂ powder can be confirmed that RuO ₂ is evenly dispersed in large glass particles having a size of 3 to 5 μm. there was.

A ruthenium-based oxide-glass composite powder prepared by mixing, melting and pulverizing CaZnBAlSi-3 glass material and RuO ₂ powder shown in Table 1 was prepared, and the ruthenium-based oxide-glass composite powder and manganese acetate were 97.5: 2.5, 95: Manganese acetate was weighed and dissolved in distilled water to obtain a weight ratio of 5, 90:10, and 85:15 to prepare a manganese acetate solution. The ruthenium-based oxide-glass composite powder was added to the prepared manganese acetate solution for 2 hours. Stirred.

The manganese acetate solution containing the ruthenium oxide-glass composite powder was dried to allow distilled water to evaporate. The drying was used a hot air dryer.

The dried resultant was heat-treated in an air atmosphere to remove manganese acetate into manganese oxide (Mn ₃ O ₄ ) as organic components were removed. The heat treatment was performed for 1 hour at a temperature of 800 ℃. The temperature increase rate which heated up to the said heat processing temperature was about 10 degree-C / min.

Cooling of the furnace after the heat treatment was to cut the furnace power source to cool in a natural state.

A paste composition for a resistor was prepared by adding an organic binder to a ruthenium-based oxide-glass composite powder coated with manganese oxide (Mn ₃ O ₄ ) at a predetermined ratio. More specifically, after preparing an organic binder by mixing ethyl cellulose and terpineol as a solvent in a ratio of 10:90 by weight, 60 wt% of a ruthenium oxide-glass composite powder coated with manganese oxide (Mn ₃ O ₄ ) % And the organic binder was measured by 40% by weight to prepare a paste composition for resistors using a 3-roll mill for uniform dispersion.

Before forming a thick film resistor using the prepared paste composition for resistance, commercial silver (Ag) paste was first printed by screen printing on an AlN substrate, and then heated to 50 ° C / min, and sintered at 850 ° C for 10 minutes to form an electrode. The resistance pattern was printed on the electrode pattern thus obtained by printing by screen printing so that the width and length were 1 mm x 1 mm, that is, the width and length ratio were 1. At this time, the material of the screen used is 250 mesh stainless steel, the thickness of the fluid film is 20㎛. After the resist pattern was formed and dried at 150 ° C. for 10 minutes, a thick film resistor was formed after sintering at 850 ° C. for 10 minutes at a temperature rising rate of 50 ° C./min using a horizontal rapid heating furnace.

The resistance of the thick film resistor formed by sintering was measured using a multimeter (3457A, Hewlett Packard, manufacturer), and the sheet resistance (R _□ ) (Ω / □) was calculated from Equation 1 below.

Where R is the resistance, W is the longitudinal length of the resistor, and L is the horizontal length of the resistor.

In addition, the value of TCR (ppm / degreeC) which is a temperature resistance coefficient was computed from following formula (2).

Here, R ₂₅ and R ₁₂₅ are resistance values measured at 25 ° C. and 125 ° C., respectively.

Table 2 below shows the measured values of resistance and temperature resistance coefficient. Sample 1 in Table 2 shows a case in which the ruthenium-based oxide-glass composite powder was not coated with manganese oxide.

Sample
Mixing ratio (% by weight) Resistance ((Ω / □) TCR ((ppm / ° C)
Compound powder Manganese Acetate 25 ℃ 125 ℃ One 100 0 547.24 565.17 328 2 97.5 2.5 496.3577 503.1662 137 3 95 5 340.7052 345.9181 153 4 90 10 495.6808 511.6967 323 5 85 15 616.9244 572.9783 -712

In order to more easily understand the physical properties of the above Example 1 presents a comparative example that can be compared with the embodiment of the present invention, Comparative Example 1 to be described later is presented only for comparison as the prior art of the present invention no.

Comparative Example 1

After mixing CaZnBAlSi-3 glass material and RuO ₂ powder shown in Table 1 in a ratio of 4: 6 (glass material: RuO ₂ powder), the 3D Turbula mixer was operated at 50 rpm for 2 hours. The mixture was mixed in an alumina crucible, melted at 1200 ° C. for 1 hour, and quenched in air to prepare a ruthenium oxide-glass composite composition.

The ruthenium-based oxide-glass composite composition thus prepared was subjected to 200-mesh sieve through primary coarse grinding in a mortar, and then zirconia balls with a diameter of 3 mm in a planetary mill for fine grinding. Milling was performed for 2 hours at a speed of 200 rpm. The powder thus obtained was sufficiently dried in an oven at 80 ° C. for 24 hours, and passed through a 325 mesh sieve to prepare a ruthenium oxide-glass composite powder.

The ruthenium-based oxide-glass composite powder, manganese oxide (Mn ₃ O ₄ ) and an organic binder were added at a predetermined ratio to prepare a paste composition for a resistor. More specifically, after preparing an organic binder by mixing ethyl cellulose and terpineol as a solvent in a ratio of 10:90 by weight, 60 wt% of ruthenium oxide-glass composite powder and manganese oxide (Mn ₃ O ₄ ) and The organic binder was weighed at 40% by weight to prepare a paste composition for resistors using a 3-roll mill for uniform dispersion. The ruthenium-based oxide-glass composite powder and manganese oxide (Mn ₃ O ₄ ) were mixed in a weight ratio of 97.5: 2.5, 95: 5, 90:10, and 85:15.

Before forming a thick film resistor using the prepared paste composition for resistance, commercial silver (Ag) paste was first printed by screen printing on an AlN substrate, and then heated to 50 ° C / min, and sintered at 850 ° C for 10 minutes to form an electrode. The resistance pattern was printed on the electrode pattern thus obtained by printing by screen printing so that the width and length were 1 mm x 1 mm, that is, the width and length ratio were 1. At this time, the material of the screen used is 250 mesh stainless steel, the thickness of the fluid film is 20㎛. After the resist pattern was formed and dried at 150 ° C. for 10 minutes, the final thick film resistor was formed through sintering at 850 ° C. for 10 minutes at a temperature rising rate of 50 ° C./min using a horizontal rapid heating furnace.

Table 3 below shows the measured values of the resistance and the temperature resistance coefficient of the thick film resistor prepared according to Comparative Example 1.

Sample
Mixing ratio (% by weight) Resistance ((Ω / □) TCR ((ppm / ° C)
Compound powder Mn ₃ O ₄ 25 ℃ 125 ℃ One 100 0 547.24 565.17 328 2 97.5 2.5 513.3184 525.8341 244 3 95 5 409.5501 421.2021 285 4 90 10 512.8672 529.5211 325 5 85 15 593.6962 570.3756 -393

Comparing the temperature resistance coefficients shown in Table 2 and Table 3, it can be seen that the thick film resistor manufactured according to Example 1 is smaller than the thick film resistor manufactured according to Comparative Example 1.

As mentioned above, although preferred embodiment of this invention was described in detail, this invention is not limited to the said embodiment, A various deformation | transformation by a person of ordinary skill in the art within the scope of the technical idea of this invention is carried out. This is possible.

Claims (9)

CaO 8 ~ 60 _{wt%, B 2 O 3 15 ~} 35 _{wt%, Al 2 O 3 2 ~} 15 wt%, SiO ₂ 5 ~ 25 wt%, RO 0 ~ CaO-B 2 O 3 containing 45 wt% Preparing a -Al ₂ O ₃ -SiO ₂ -based glass material and a ruthenium oxide;
Mixing the glass raw material and the ruthenium oxide in a weight ratio of 1: 9-9: 1;
Heat-treating the mixture of the glass raw material and the ruthenium-based oxide to melt the glass raw material;
Quenching the resultant of melting the glass raw material to form a ruthenium-based oxide-glass composite composition;
Pulverizing the ruthenium-based oxide-glass composite composition formed by quenching to form a ruthenium-based oxide-glass composite powder;
Coating a ruthenium-based oxide-glass composite powder with a metal oxide; And
Mixing the metal oxide coated ruthenium-based oxide-glass composite powder with an organic binder to form a paste composition for a resistor;
The RO is made of one or more materials selected from ZnO, MnO, NaO and Na ₂ O, the metal oxide is made of one or more materials selected from Mn ₃ O ₄ , CoO and NiO,
The ruthenium-based oxide-glass composite powder coated with the organic binder and the metal oxide are mixed in a ratio of 1: 1 to 1: 9 by weight ratio.
The method of claim 1, wherein the coating with the metal oxide comprises:
Prepare at least one metal acetate selected from manganese acetate, cobalt acetate and nickel acetate, and weigh the metal acetate so that the ruthenium-based oxide-glass composite powder and the metal acetate are in a weight ratio of 90: 1 to 80:20 Dissolving in to prepare a metal acetate solution;
Adding a ruthenium-based oxide-glass composite powder to the metal acetate solution and stirring the mixture;
Drying the metal acetate solution into which the ruthenium-based oxide-glass composite powder is added; And
A method of producing a paste composition for a resistor having a low temperature resistance coefficient, comprising the step of converting a metal acetate into a metal oxide while removing the organic component by heat treating the dried resultant.
The method of claim 2, wherein the heat treatment is performed for 30 minutes to 12 hours at a temperature of 600 to 900 DEG C in an oxidizing atmosphere.
The method of claim 1, wherein the ruthenium oxide is RuO ₂ , calcium ruthenate (CaRuO ₃ ), strontium ruthenate (SrRuO ₃ ), barium ruthenate (BaRuO ₃ ), thallium ruthenate (Ta ₂ Ru ₂ O ₇ ) and A method for producing a paste composition for a resistor having a low temperature resistance coefficient, characterized by consisting of at least one conductive oxide powder selected from bismuthruthenate (Bi ₂ Ru ₂ O ₇ ).
The method of claim 1, wherein the heat treatment for melting the glass raw material is a resistor having a low temperature resistance coefficient, characterized in that the step of maintaining for 10 minutes to 6 hours at a temperature of 1100 ~ 1500 ℃ to melt the glass raw material Method for preparing the paste composition.
delete The method of claim 1, wherein the resin used in the organic binder is ethyl cellulose, ethyl hydroxyethyl cellulose, wood rosin, phenol resin or polymethacrylate, and the solvent used in the organic binder is dihydroterpineol, Dihydroacetate, alpha-terpineol, beta-terpineol, dibutyltalate, butylcarbitor butylcarbitol acetate, hexylene glycol or texanol, wherein the organic binder is the resin and the solvent in a weight ratio A method for producing a paste composition for resistors having a low temperature resistance coefficient, which is mixed at a ratio of 1: 3 to 1:15.
Forming a resistance pattern by printing a resistor paste composition prepared by the method of claim 1 on the substrate on which the electrode pattern is formed;
Drying the substrate on which the resistance pattern is formed; And
After sintering the dried substrate at a temperature of 700 ~ 1100 ℃ cooling to form a thick film resistor comprising the step of forming a thick film resistor.
Prepared by the method according to claim 8, the ruthenium oxide particles are CaO 8 to 60% by weight, B ₂ O ₃ 15 to 35% by weight, Al ₂ O ₃ 2 to 15% by weight, SiO ₂ 5 to 25% by weight, Surrounded by a CaO-B ₂ O ₃ -Al ₂ O ₃ -SiO ₂ -based glass matrix comprising 0-45% by weight of RO, the CaO-B ₂ O ₃ -Al ₂ O ₃ -SiO ₂ -based glass matrix Is a thick film resistor having a structure surrounded by a metal oxide.

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