TWI662561B - Lead-free thick film resistor composition, lead-free thick film resistor and production method thereof - Google Patents

Abstract

The invention relates to a lead-free thick film resistor composition, a lead-free thick film resistor, and a manufacturing method thereof. More specifically, the present invention relates to a lead-free thick-film resistor composition, a lead-free thick-film resistor, and a method for manufacturing the same. The lead-free thick-film resistor composition includes a conductive material containing a ruthenium-based composite oxide and a glass component to form a dual network structure. The composite powder makes it possible to improve the temperature characteristics, current noise, overload characteristics and electrostatic discharge characteristics in a wide range of resistance even without the lead component.

Description

   Lead-free thick film resistor composition, lead-free thick film resistor and manufacturing method thereof   

The invention relates to a lead-free thick film resistor composition, a lead-free thick film resistor, and a manufacturing method thereof. More specifically, the present invention relates to a lead-free thick-film resistor composition, a lead-free thick-film resistor, and a method of manufacturing the same. The lead-free thick-film resistor composition includes a ruthenium-based composite oxide and a first glass component. The heat-treated conductive composite powder and a second glass component form a dual network structure, so that even without the lead component, the temperature characteristics, current noise, overload characteristics, and electrostatic discharge characteristics can be improved in a wide resistance range.

The thick film resistor composition is generally composed of a glass component for adjusting the resistance value and imparting bondability, a conductive material, and an organic carrier composed of an adhesive and a solvent. The composition is printed on a substrate and then fired to form a thick film resistor.

Many conventional thick film resistor compositions include lead oxide-based glass as a glass material, and ruthenium oxide or a compound of ruthenium oxide and lead as a conductive material. Therefore, the conventional thick film resistor composition contains lead.

In their thick-film resistor compositions, ruthenium oxide (RuO ₂ ) -based thick-film resistors can achieve a wide range of resistance values by controlling the ratio of RuO ₂ and glass components, and have excellent resistance temperature coefficients. It is widely used in chip resistors and hybrid microcircuits.

Traditional thick film resistors are formed on alumina substrates by screen printing. However, according to the recent trend of miniaturization, high frequency, and high power consumption of electronic components, there is a problem that the reliability and life of a chip or a circuit are deteriorated due to an increase in the amount of heat radiation per unit area. Substrates with excellent thermal properties, such as aluminum nitride substrates, instead of aluminum oxide substrates. In general, since the glass phase in the thick film resistance material is used to increase the bonding with the substrate, it is very important to select a suitable glass composition system. Currently commercialized resistance compositions for alumina substrates have low melting point glass compositions including lead (Pb).

However, recently, leaded glass has been banned due to environmental regulations, and it is known that the mutual bonding properties of leaded glass and aluminum nitride substrates are low due to low adhesion, blister, and the like. When using lead-containing glass, oxides, especially lead oxide (PbO), can react with the aluminum nitride substrate, which can cause blistering. One of the reasons for the low adhesion is that when lead oxide in glass is sintered, lead oxide reacts with aluminum nitride to reduce to lead (Pb), and nitrogen is generated therein. Therefore, it is important to select a lead-free glass composition system that does not include lead and has good mutual bonding properties with aluminum nitride. In addition, since the temperature coefficient of resistance of RuO ₂ is usually as high as 5670 ppm / ° C, it is necessary to strive to reduce the temperature coefficient of resistance of the final thick film resistance by controlling the glass composition or by adding a component having a low temperature coefficient of resistance.

Korean Patent Early Publication No. 10-2006-0056330 (Patent Document 1) discloses a resistor paste that can provide a high resistance value by using a glass material that substantially does not include lead but includes NiO. Low temperature characteristics of resistance value and low short-term overload resistance. Korean Patent Early Publication No. 10-2014-0025338 (Patent Document 2) discloses a composition for thick film resistance by using a ruthenium oxide (RuO ₂ ) powder having a rutile crystal structure and a Thick film resistors with sufficient performance even at low ruthenium content.

When the composition of the glass material is changed or when ruthenium oxide having a rutile crystal structure is used, when the resistance composition is fired, the growth of the particles is suppressed, so that the specific resistance is reduced, and the resistance value of the thick film resistance is reduced. Stability is significantly reduced, and electrical properties such as TCR, current noise (C-Noise), etc. are also reduced. In addition, when preparing a resistance composition, usually, RuO ₂ powder and glass powder are simply mixed, and therefore it is difficult to obtain a uniformly mixed state of the components. Therefore, it is difficult to obtain a uniform microstructure in a thick film resistor after sintering. For this reason, there is still a problem that the stability of the thick film resistor is deteriorated due to an increase in the change in the electrical properties of the thick film resistor.

    [Related technical documents]    

(Patent Document 1) Korean Patent Early Publication No. 10-2006-0056330

(Patent Document 2) Korean Patent Early Publication No. 10-2014-0025338

An object of the present invention is to provide a lead-free thick film resistor composition capable of maintaining the stability of resistance value and the reliability of electrical characteristics. More specifically, one embodiment of the present invention aims to provide a lead-free thick film resistor composition including: a conductive composite powder that is heat-treated by including a ruthenium-based composite oxide and a first glass component, and a second glass ingredient.

The lead-free thick film resistor composition forms a double network structure, so that fine conductive paths are uniformly formed. Therefore, an embodiment of the present invention provides a lead-free thick film resistor composition, which can be used even when lead is not included. In the case of components, it improves temperature characteristics, resistance distribution, current noise, overload characteristics, and electrostatic discharge characteristics over a wide resistance range, and has excellent stability.

In addition, another aspect of the present invention is to provide a method for manufacturing a lead-free thick film resistor.

Further, another aspect of the present invention is to provide a chip resistor, including: a lead-free thick film resistor formed by firing the lead-free thick film resistor composition.

In a general aspect, a lead-free thick film resistor composition is provided, comprising: a conductive composite powder heat-treated by including a ruthenium-based composite oxide and a first glass component; and a second glass component, wherein the first glass component includes SiO ₂ , B ₂ O ₃ , BaO, and Al ₂ O ₃ , and the second glass component includes SiO ₂ , B ₂ O ₃ , and Al ₂ O ₃ .

The conductive composite powder may have a crystalline structure.

The lead-free thick film resistor composition can provide a dual network structure after firing.

Ruthenium composite oxide may be selected from _{3, 3,} mixture CaRuO BaRuO SrRuO _3, and _{(Ca x Sr y Ba z)} RuO ₃ of any one or two or more of those, where the (Ca _x Sr _y Ba _z ) In RuO ₃ , x + y + z = 1, 0 x <1, 0 y <1, 0 z <1, and 0 <x + y 1. The first glass component may further include any one or a mixture of two or more selected from transition metal oxides, alkali metal oxides, and alkaline earth metal oxides, and may have a softening point of 500 ° C to 800 ° C. And the second glass component may further include any one or a mixture of two or more selected from transition metal oxides, alkali metal oxides, and alkaline earth metal oxides, and may have a softening point of 500 ° C to 700 ° C. .

The transition metal oxide may be any one or a mixture of two or more selected from Nb ₂ O ₅ , Ta ₂ O ₅ , TiO ₂ , MnO ₂ , CuO, ZrO ₂ , WO ₃ , and ZnO. The alkali metal is oxidized. The substance may be any one or a mixture of two or more selected from Na ₂ O, K ₂ O, and Li ₂ O, and the alkaline earth metal oxide may be any one selected from SrO, CaO, and MgO or A mixture of two or more.

The conductive composite powder may include 20% to 80% by weight of a ruthenium-based composite oxide and 80% to 20% by weight of a first glass component.

The conductive composite powder and the second glass component may have a weight ratio of 10:90 to 90:10.

The lead-free thick film resistor composition may further include: any one or a mixture of two or more selected from the group consisting of conductive powder and inorganic particles.

The inorganic particles may be selected from the group consisting of Nb ₂ O ₅ , Ta ₂ O ₅ , TiO ₂ , M _n O ₂ , Al ₂ O ₃ , CuO, ZrO ₂ , CoO, BaTiO ₃ , La ₂ O ₃ , Li ₂ TiO ₃ and ZnO. Any one or a mixture of two or more, and the conductive powder is selected from the group consisting of Ag, Au, Pd, Pt, Cu, Ni, W, Mo, Zn, Al, RuO ₂ , IrO ₂ , Rh ₂ O ₃ and Any one or a mixture of two or more AgPd.

The lead-free thick film resistor composition may include 3% to 65% by weight of a conductive composite powder, 1% to 60% by weight of a second glass component, 0.1% to 40% by weight of a conductive powder, and 0.1% to 10% by weight. % By weight of inorganic particles.

In another general aspect, a lead-free thick film resistor formed by using the above-mentioned lead-free thick film resistor composition is provided.

The lead-free thick film resistor is formed by printing the above-mentioned lead-free thick film resistor composition on a substrate and then firing.

The resistance value (Rs) can be 10 ohms / □ to 10 megaohms / □ (MΩ / □), the resistance distribution (CV) can be 5% or lower, and the temperature characteristic (TCR) can be -100ppm / ℃ to 100ppm / ℃, the current noise (C-Noise) characteristic can be 12 dB or lower, and the overload characteristic (STOL) measured at 1/8 watt rated power can be 0.1% or lower.

In another general aspect, a method for manufacturing a lead-free thick film resistor is provided, including: (a) manufacturing a conductive composite powder by heat-treating a ruthenium-based composite oxide and a first glass component; (b) preparing the conductive composite powder including the conductive composite powder and A lead-free thick film resistor composition of a second glass component; and (c) manufacturing a lead-free thick film resistor having a dual network structure by firing the lead-free thick film resistor composition, wherein the first glass component includes SiO ₂ , B ₂ O ₃ , BaO, and Al ₂ O ₃ , and the second glass component include SiO ₂ , B ₂ O ₃ , and Al ₂ O ₃ .

In step (a), the temperature of the heat treatment is higher than 600 ° C. and equal to or lower than 900 ° C., and the conductive composite powder is manufactured by the heat treatment and subsequent grinding.

In step (a), the conductive composite powder may be manufactured by heat-treating 20 to 80% by weight of a ruthenium-based composite oxide and 80 to 20% by weight of a first glass component, and in step (b) In the lead-free thick film resistor composition, the conductive composite powder and the second glass component may have a weight ratio of 10:90 to 90:10.

In step (b), the lead-free thick film resistor composition may further include any one or a mixture of two or more selected from the group consisting of conductive powder and inorganic particles.

The lead-free thick film resistor composition may include 3% to 65% by weight of a conductive composite powder, 1% to 60% by weight of a second glass component, 0.1% to 40% by weight of a conductive powder, and 0.1% to 10% by weight. % By weight of inorganic particles.

In another general aspect, a chip resistor is provided, including: a first electrode, a thick film resistor, and a protective glass, wherein the thick film resistor is a lead-free thick film resistor, which is obtained by combining the lead-free thick film resistors described above. An object is printed on a substrate and then formed by firing.

The lead-free thick-film resistor composition includes a conductive composite powder that is heat-treated by including a ruthenium-based composite oxide and a first glass component, and a second glass component to form a dual network structure, which is similar to a conventional thick film including lead. Compared with resistance, even without including lead, it can still provide excellent thick film resistance with wide resistance value range. In addition, the lead-free thick film resistor composition includes a conductive composite powder, so that the decomposition of the ruthenium-based composite oxide can be suppressed during heat treatment, and the network structure of the conductive composite powder can be uniformly mixed with the second glass component, thereby forming a double Network structure. Therefore, a fine conductive path can be formed more uniformly, thereby providing a feature that has no degradation of characteristics even in a high resistance region, and has very excellent temperature characteristics, current noise, overload characteristics, and electrostatic discharge characteristics, and excellent Stable lead-free thick film resistor compositions and lead-free thick film resistors are possible.

FIG. 1 is an optical microscope image of a printed pattern and a printed geometry of a lead-free thick film resistor composition according to an exemplary embodiment of the present invention.

FIG. 2 is a cross-sectional view of a chip resistor including a lead-free thick film resistor according to an exemplary embodiment of the present invention.

FIG. 3 shows a scanning electron microscope (SEM) image of the surface and cross section of a lead-free thick film resistor according to an exemplary embodiment of the present invention. Figure 3 (a) shows the surface of the resistor, and Figure 3 (b) shows the cross section of the resistor.

FIG. 4 shows an XRD measurement chart of the composite powder 3 in Table 2 according to an exemplary embodiment of the present invention according to the heat treatment temperature and time.

FIG. 5 shows an XRD measurement chart of the composite powder 5 in Table 2 according to an exemplary embodiment of the present invention.

FIG. 6 shows an XRD measurement chart of the composite powder 13 in Table 2 according to an exemplary embodiment of the present invention.

FIG. 7 shows an XRD measurement chart of a dried coating film and a lead-free thick film resistance after firing according to an exemplary embodiment of the present invention.

FIG. 8 is a schematic diagram showing a dual network structure after firing a lead-free thick film resistor composition according to an exemplary embodiment of the present invention.

Hereinafter, preferred exemplary aspects of a lead-free thick film resistor composition, a lead-free thick film resistor, and a manufacturing method thereof, and a method for measuring physical properties will be described in detail. The present invention can be specifically understood through the following examples, and the following examples are intended to provide illustrative illustrations, but not to limit the scope of protection defined by the appended claims of the present invention.

The present inventors have discovered that a lead-free thick film resistor including a conductive composite powder and a second glass component which are heat-treated by including a ruthenium-based composite oxide and a first glass component can be formed, thereby forming a dual network structure and making fine conductive The paths are formed uniformly, so that even if the lead component is removed, the temperature characteristics, current noise, overload characteristics, and electrostatic discharge characteristics can be improved over a wide resistance range, and the stability is excellent, and the present invention has been completed.

As used herein, the term "dual network structure" means that a conductive composite powder obtained by heat-treating a ruthenium-based composite oxide and a first glass component has a primary network structure. This is the first network, and the second glass component is fired. Therefore, a secondary network is formed secondaryly, thereby forming a dual network structure, which means that the conductive path formed is denser than the primary network structure.

As used herein, the term "lead-free" means that the lead content of the thick film resistor is 1000 ppm or less, preferably 500 ppm or less.

Hereinafter, exemplary embodiments of the present invention will be described in detail.

According to an exemplary embodiment of the present invention, the lead-free thick film resistor composition may include a conductive composite powder and a second glass component.

According to an exemplary embodiment of the present invention, the lead-free thick film resistor composition may include a conductive composite powder, a second glass component, a conductive powder, and inorganic particles.

Due to the primary network (the first network of the conductive composite powder) and the second glass component, a stable dual network structure with a secondary network formed therein can be formed, so that fine conductive can be formed uniformly even without including lead Path to provide excellent thick film resistance with a wide range of resistance values.

According to an exemplary embodiment of the present invention, the conductive composite powder may be manufactured by a heat treatment including a ruthenium-based composite oxide and a first glass component. When the traditional ruthenium-based composite oxide is used alone, XRuO ₃ is decomposed into XO and RuO ₂ , the specific resistance is reduced, and the stability of the resistance value of the thick film resistor to be manufactured is significantly reduced, and it is difficult to maintain Such as temperature characteristics (TCR), current noise (C-Noise) and other electrical properties. In XRuO ₃ and XO, X is Ca, Sr, Ba, or the like. In order to solve these problems, it is understood that when a conductive composite powder obtained by heat-treating a ruthenium-based composite oxide having a perovskite structure and a first glass component is used, a stable network structure can be formed.

According to an exemplary embodiment of the present invention, the ruthenium-based composite oxide is not limited as long as it is a ruthenium-based composite oxide having a perovskite crystal structure well known in the art. For example, ruthenium-based composite oxide according to any one selected from calcium ruthenate (CaRuO _3), strontium ruthenate (SrRuO _3), barium ruthenate (BaRuO _3), and _{(Ca x Sr y Ba z)} RuO 3 of Or a mixture of two or more of them, in (Ca _x Sr _y Ba _z ) RuO ₃ , x + y + z = 1, 0 x <1, 0 y <1, 0 z <1, and 0 <x + y 1. For example, (Ca _x Sr _y ) RuO ₃ , (Sr _y Ba _z ) RuO ₃ , or (Ca _x Ba _z ) RuO _{3 may be used} . The first glass component further includes any one or a mixture of two or more selected from transition metal oxides, alkali metal oxides, and alkaline earth metal oxides. In addition, the conductive composite powder can be obtained by including a ruthenium oxide, a conductive metal oxide, and a metal component in addition to the ruthenium-based composite oxide and the first glass component.

A ruthenium-based composite oxide having a perovskite crystal structure is effective because it is used to maintain temperature characteristics (TCR) and overload (STOL) especially at 1 KΩ or higher.

The ruthenium-based composite oxide according to an exemplary embodiment of the present invention may have a specific surface area of 10 square meters / g or more, and more preferably a specific surface area of 10 square meters / g to 80 square meters / gram. , But not limited to this.

The ruthenium-based composite oxide according to an exemplary embodiment of the present invention is not limited, but can be manufactured by the manufacturing method described in Korean Patent No. 10-0840893.

For example, 1) the ruthenium salt aqueous solution can be formed by dissolving a ruthenium metal powder in a strong acid or a strong base or by an alkali fusion of the ruthenium metal powder. 2) The prepared ruthenium salt aqueous solution may be mixed with a dispersant-containing strontium compound aqueous solution to obtain strontium ruthenate hydrate. 3) The obtained strontium ruthenate hydrate can be heat-treated at 300 ° C to 1500 ° C to obtain strontium ruthenate powder. 4) An inorganic acid may be added to the obtained strontium ruthenate powder to remove impurities. However, the preparation of the ruthenium salt aqueous solution is not limited thereto.

More specifically, in order to prepare an aqueous ruthenium salt solution, an oxidizing agent is added to a strong alkaline aqueous solution or a strong acid aqueous solution, and a ruthenium compound is added thereto, followed by stirring, so that ruthenium can be oxidized to obtain a scarlet ruthenate aqueous solution. The ruthenium compound is not limited, but as the ruthenium compound, ruthenium chloride, ruthenium sulfate, or a ruthenium metal sponge can be used, and a ruthenium metal sponge is preferably used.

As the acid, any one or a mixture of two or more selected from hydrochloric acid, nitric acid, and sulfuric acid may be used, or preferably aqua regia including hydrochloric acid and nitric acid in a weight ratio of 3: 1 to 1: 1 ; As the base, sodium hydroxide or potassium hydroxide can be used. The oxidant may be, but is not limited to, sodium hypochlorite or potassium nitrate.

In addition, the ruthenium salt aqueous solution can be obtained even by alkali melting using a basic salt. According to alkali melting, the ruthenium metal sponge is mixed with an aqueous solution in which potassium hydroxide and sodium hydroxide are mixed in a weight ratio of 3: 1 to 1: 3, and heated at 400 ° C to 800 ° C, followed by leaching with a strong acid (leach ) To obtain a ruthenium salt. The ruthenium metal sponge is a ruthenium metal having an equal size between particles and powder, and can be used as a starting material for preparing a ruthenium salt. The ruthenium concentration per liter (L) of the ruthenium acid aqueous solution is suitably less than 50 g / liter, and the temperature for dissolving ruthenium in alkali dissolution is preferably 20 ° C to 100 ° C, but is not limited thereto.

According to an exemplary embodiment of the present invention, the first glass component may include SiO ₂ , B ₂ O ₃ , BaO, and Al ₂ O ₃ . The first glass component having the above combination is effective because it is liable to cause a mismatch with the ruthenium-based composite oxide.

Further, the first glass component may include SiO ₂ , B ₂ O ₃ , BaO, and Al ₂ O ₃ as main components, which is more effective for improving the reactivity with the ruthenium-based composite oxide and making the network structure more densely formed. It is good, and further, it can effectively improve the compatibility with the second glass component when preparing the conductive composite powder. Their main components may be included in the first glass component in an amount of at least 50% by weight, more specifically, 50% to 99% by weight. In particular, the conductive composite powder obtained by the combination of the first glass component containing BaO and the ruthenium-based composite oxide can prevent the formation of ruthenium oxide due to the reaction between the ruthenium composite oxide and the second glass component, and thus can form a more stable Crystal structure. The crystal structure in the present invention includes a Ba-Si-Al-based partial crystal structure or an overall crystal structure. When using a conductive composite powder with a stable crystal structure to prepare a conductive thick film resistor composition, the formation of ruthenium oxide can be controlled by the reaction of the ruthenium-based composite oxide and the second glass component during firing, thereby It is possible to obtain a thick film resistor with more stable electrical properties, because as shown in Fig. 7, the change in the crystal structure due to firing is small.

A specific composition of the first glass component according to an exemplary embodiment of the present invention may include, for example, 10% to 40% by weight of SiO ₂ , 10% to 30% by weight of B ₂ O ₃ , 5% to 40% by weight of BaO, 2% by weight to 15% by weight of Al ₂ O ₃ , 0.1% by weight to 20% by weight of transition metal oxides, and 20% by weight to 60% by weight of alkali metal oxides and alkaline earth metal oxides . Preferably, the first glass component may include 15 to 30% by weight of SiO ₂ , 15 to 30% by weight of B ₂ O ₃ , 10 to 30% by weight of BaO, and 5 to 15% by weight. % Al ₂ O ₃ , 5% to 15% by weight of transition metal oxides, and 20% to 40% by weight of alkali metal oxides and alkaline earth metal oxides, but are not limited thereto. The first glass component having the above range is effective for having excellent reactivity with the ruthenium-based composite oxide and improving electrical properties and durability.

According to an exemplary embodiment of the present invention, the first glass component may include any one or a mixture of two or more selected from transition metal oxides, alkali metal oxides, and alkaline earth metal oxides.

The transition metal oxide in the first glass component may be added to control temperature characteristics (TCR), overload characteristics (STOL), and electrostatic discharge characteristics (ESD), and may include alkali metal oxides and alkaline earth metal oxides to improve and Reactivity of ruthenium-based composite oxides.

According to an exemplary embodiment of the present invention, the transition metal oxide is not limited as long as it is a transition metal oxide well known in the art. The transition metal oxide may be, for example, any one or a mixture of two or more selected from the group consisting of Nb ₂ O ₅ , Ta ₂ O ₅ , TiO ₂ , MnO ₂ , CuO, ZrO ₂ , WO ₃ and ZnO. this.

According to an exemplary embodiment of the present invention, the alkali metal oxide is not limited as long as it is an alkali metal oxide well known in the art. The alkali metal oxide may be any one selected from Na ₂ O, K ₂ O, and Li ₂ O, or a mixture of two or more, but is not limited thereto.

According to an exemplary embodiment of the present invention, the alkaline earth metal oxide is not limited as long as it is an alkaline earth metal oxide well known in the art. The alkaline earth metal oxide may be any one selected from SrO, CaO, and MgO or a mixture of two or more, but is not limited thereto.

According to an exemplary embodiment of the present invention, the first glass component may have a softening point of 500 ° C. to 800 ° C. to form a uniform network. The first glass component having a softening point in the above range is preferable because the reactivity with the ruthenium-based composite oxide can be improved to more uniformly form a primary network, which is the first network and can be formed during heat treatment. A heat-treated conductive composite powder having a partially crystalline structure was produced.

Further, the second glass component may have a softening point of 500 ° C to 700 ° C. When the softening point of the second glass component is in the above range, it is easy to form a dual network at a firing temperature of 700 ° C to 900 ° C, and the surface uniformity of the lead-free thick film resistor can be improved to reduce the coefficient of variation ( CV), which has excellent electrical properties. The different softening points of the first glass component and the second glass component can be controlled according to the presence or absence of barium oxide. Since the second glass component does not include barium oxide, it is possible to prevent the phenomenon of increasing the coefficient of variation (CV) due to the high reactivity with the substrate during the formation of the double network.

According to an exemplary embodiment of the present invention, the conductive composite powder may be granulated by heat-treating a mixture of a ruthenium-based composite oxide and a first glass component at a specific heat treatment temperature range, followed by grinding. The average particle diameter of the conductive composite powder is not limited. For example, when accumulated from small particles to an amount, the particle diameter D50 corresponding to 50% of the total amount may be 2.0 microns or less. Preferably, D50 can be 1.0 micrometer to 2.0 micrometer. Grinding according to the above range is effective because the conductive composite powder can be easily mixed with the second glass component in the thick film resistor composition to provide a uniform composition.

The heat treatment temperature is not limited as long as it is a heat treatment temperature or higher of a thick film resistor composition known in the art, and for example, it is preferably higher than 600 ° C and equal to or lower than 900 ℃, and the heat treatment can be performed within 120 minutes at the heat treatment temperature.

The conductive composite powder formed as described above can form a uniform primary network structure, and the primary network structure is a first network structure. When manufacturing lead-free thick film resistors, the ruthenium-based composite oxide and the first glass component are formed into a primary network of the first network through heat treatment, and the reactivity between the ruthenium-based composite oxide and the second glass component can be suppressed, so Decomposition of the ruthenium-based composite oxide does not occur, thereby forming a more stable dual network structure.

According to an exemplary embodiment of the present invention, the conductive composite powder may include 20 to 80% by weight of a ruthenium-based composite oxide and 80 to 20% by weight of a first glass component, and more preferably 30 to 70% by weight. The ruthenium-based composite oxide is 70% by weight and the first glass component is 70% to 30% by weight. More preferably, the conductive composite powder may include 40% to 60% by weight of a ruthenium-based composite oxide and 60% to 40% by weight of a first glass component.

It is effective when the ruthenium-based composite oxide and the first glass component system are included in the above range, because it can be easily formed into a primary network structure of the first network, and it is easy to control temperature characteristics (TCR), overload characteristics (STOL), And electrostatic discharge characteristics (ESD).

In addition, when the ruthenium-based composite oxide and the first glass component system are included in the above range, a low resistance value can be obtained, the temperature characteristic can be prevented from moving in the (-) direction, and the temperature characteristic of (+) does not appear as conductive The best specific resistance of the material, and the stability of the crystal structure is better maintained.

According to an exemplary embodiment of the present invention, the second glass component may include SiO ₂ , B ₂ O _3, and Al ₂ O ₃ as main components, and may further include a member selected from transition metal oxides, alkali metal oxides, and Any one or a mixture of two or more alkaline earth metal oxides. These main components may be included in the second glass component in an amount of at least 40% by weight, more specifically, 40% to 99% by weight.

According to an exemplary embodiment of the present invention, the specific composition of the second glass component may include, for example, 10% to 30% by weight of SiO ₂ , 10% to 40% by weight of B ₂ O ₃ , 2% by weight To 15% by weight of Al ₂ O ₃ , 0.1% to 10% by weight of transition metal oxides, and 20% to 60% by weight of alkali metal oxides and alkaline earth metal oxides. Preferably, the second glass component may include 10 to 20% by weight of SiO ₂ , 20 to 40% by weight of B ₂ O ₃ , 2 to 10% by weight of Al ₂ O ₃ , and 0.1% by weight. To 10% by weight of transition metal oxides, and 30% to 60% by weight of alkali metal oxides and alkaline earth metal oxides, but are not limited thereto. The second glass component has the above-mentioned components in the above-mentioned content range, can effectively have excellent compatibility and mismatch with the conductive composite powder, and can effectively improve electrical properties and durability.

When the composition of the second glass component has the above range, the stability of the second glass component can be excellent and an increase in the softening point can be prevented. It is better when the stability is excellent, because this can improve the coating film strength of the thick film resistor. The electrical properties of the lead-free thick film resistor can be used to form the first electrode and to protect the chip resistance. The glass process was improved.

Therefore, the second glass composition according to the combination of the above constitutions is effective because it can maintain the density and smooth plastic surface of the lead-free thick film resistor and form a uniform and dense double network structure with the conductive composite powder.

Transition metal oxides can be added to control temperature characteristics (TCR), overload characteristics (STOL), and electrostatic discharge characteristics (ESD), and can include alkaline earth metal oxides to improve reactivity with ruthenium-based composite oxides. In particular, an alkali metal oxide may be added to the second glass component to improve the fluidity of the glass component in combination with other components.

The transition metal oxide according to an exemplary embodiment of the present invention is not limited as long as it is a transition metal oxide well known in the art. The transition metal oxide may be, for example, any one or a mixture of two or more selected from the group consisting of Nb ₂ O ₅ , Ta ₂ O ₅ , TiO ₂ , MnO ₂ , CuO, ZrO ₂ , WO ₃ and ZnO. this.

According to an exemplary embodiment of the present invention, the alkali metal oxide is not limited as long as it is an alkali metal oxide well known in the art. The alkali metal oxide may be any one selected from Na ₂ O, K ₂ O, and Li ₂ O, or a mixture of two or more, but is not limited thereto.

According to an exemplary embodiment of the present invention, the alkaline earth metal oxide is not limited as long as it is an alkaline earth metal oxide well known in the art. The alkaline earth metal oxide may be any one selected from SrO, CaO, and MgO or a mixture of two or more, but is not limited thereto.

According to an exemplary embodiment of the present invention, in the firing temperature of 700 ° C. to 900 ° C. in step (c), the second glass component preferably has a softening point of 500 ° C. to 700 ° C. to form a conductive composite powder. Uniform network and improve the density of thick film resistance, but the softening point is not limited to this.

According to an exemplary embodiment of the present invention, the lead-free thick film resistor composition may include a conductive composite powder and a second glass component in a weight ratio of 10:90 to 90:10, and more preferably 20:80 to 80:20. Weight ratio of the conductive composite powder and the second glass component.

It is effective when the conductive composite powder and the second glass component are included in the above range, because it can easily form a dual network structure, and it is easy to control temperature characteristics (TCR), overload characteristics (STOL), and electrostatic discharge characteristics (ESD) ).

In addition, it is preferable when the conductive composite powder and the second glass component are included in the above range, because the electrical properties of the lead-free thick film resistor prepared by the lead-free thick film resistor composition having the above range can be improved, And can form a uniform lead-free thick film resistor.

To the extent that the physical properties of the lead-free thick film resistor are not impeded, the lead-free thick film resistor composition may further include conductive powder and inorganic particles to increase the conductive path.

The conductive powder is not limited as long as it is a conductive powder well known in the art, for example, it may further include a member selected from the group consisting of Ag, Au, Pd, Pt, Cu, Ni, W, Mo, Zn, Al, RuO _2. Any one or a mixture of two or more of IrO ₂ , Rh ₂ O ₃ and AgPd.

Further, the lead-free thick film resistor composition may further include inorganic particles to control temperature characteristics (TCR), overload characteristics (STOL), and electrostatic discharge characteristics (ESD).

According to an exemplary embodiment of the present invention, the inorganic particles may be selected from Nb ₂ O ₅ , Ta ₂ O ₅ , TiO ₂ , MnO ₂ , Al ₂ O ₃ , CuO, ZrO ₂ , CoO, BaTiO ₃ , La ₂ O _3. Any one or a mixture of two or more of Li ₂ TiO ₃ , ZnO, and WO ₃ , but is not limited thereto.

According to an exemplary embodiment of the present invention, the lead-free thick film resistor composition may include, for example, 3% to 65% by weight of a conductive composite powder, 1% to 60% by weight of a second glass component, 0.1 The conductive powder is from 40% by weight to 40% by weight, and the inorganic particles are from 0.1% to 10% by weight, but each content of the lead-free thick film resistor composition is not limited thereto. Preferably, the lead-free thick film resistor composition may include 25% to 60% by weight of a conductive composite powder, 20% to 60% by weight of a second glass component, 1% to 20% by weight of a conductive powder, and 0.1. Weight percent to 5 weight percent of inorganic particles.

The lead-free thick film resistor composition has the above-mentioned content range, so that a dual network structure can be easily formed. Due to the formation of the dual network structure, excellent resistance distribution (CV) and resistance reproducibility are obtained, and temperature characteristics (TCR), overload characteristics (STOL), and electrostatic discharge characteristics (ESD) are excellent.

According to an exemplary embodiment of the present invention, the lead-free thick film resistor composition may further include a carrier composed of an organic solvent and an adhesive. In order to mix the conductive composite powder and the second glass component and apply the mixture to screen printing, etc., the mixture is used to form a combination of paste, paint, and ink each having suitable rheology. Can be mixed with general carriers. The carrier is not limited as long as it is a carrier well known in the art. For example, the carrier may be a solution mixed with the following components: terpineol, carbitol, butacarbitol, cyperidine, tetriol, or an ester thereof; any one selected from toluene, xylene, and the like One or two or more organic solvents; and any one or two or more selected from the group consisting of ethyl cellulose, nitrocellulose, acrylate polymers, methacrylate polymers, rosin, etc. Binder resin. If necessary, it may further include any one or a mixture of two or more of a plasticizer, a viscosity modifier, a surfactant, an antioxidant, a metal organic compound, and the like.

In addition, the mixing ratio of the carrier is not limited, as long as it is applied to a general thick film resistor composition, and can be controlled according to the application method (such as printing) of the composition.

Furthermore, the viscosity of the lead-free thick film resistor composition can be adjusted by further increasing the organic solvent, and the organic solvent can be the same as or different from the solvent used in the carrier. The organic solvent may further include 10 to 200 parts by weight based on 100 parts by weight of the lead-free thick film resistor composition. More preferably, the organic solvent may further include 30 to 100 parts by weight based on 100 parts by weight of the lead-free thick film resistor composition, but the present invention is not limited thereto.

According to another exemplary embodiment of the present invention, a method for manufacturing a lead-free thick film resistor is provided, including: (a) manufacturing a conductive composite powder by heat-treating a ruthenium-based composite oxide and a first glass component; (b) Preparing a lead-free thick film resistor composition including the conductive composite powder and a second glass component; and (c) manufacturing a lead-free thick film resistor having a dual network structure formed by firing the lead-free thick film resistor composition, wherein The first glass component includes SiO ₂ , B ₂ O ₃ , BaO, and Al ₂ O ₃ , and the second glass component includes SiO ₂ , B ₂ O ₃ , and Al ₂ O ₃ .

According to an exemplary embodiment of the present invention, in step (a), the temperature of the heat treatment is higher than 600 ° C and equal to or lower than 900 ° C, and the conductive composite powder is obtained by the heat treatment and subsequent grinding. Manufacturing. Preferably, in step (a), the temperature of the heat treatment is 800 ° C to 900 ° C, and the conductive composite powder is manufactured by the heat treatment and subsequent grinding.

According to an exemplary embodiment of the present invention, the conductive composite powder may have a partially crystalline structure. Due to the heat treatment, a part of the perovskite-type crystal structure of the ruthenium-based composite oxide may react with the first glass component to be decomposed into a ruthenium oxide, wherein the first glass component may partially crystallize. Therefore, a strong primary network structure that is a first network can be formed by the ruthenium-based composite oxide and the first glass component. The conductive composite powder may have a primary network structure that is a first network by heat treatment. Due to the partial crystallization of, for example, the Ba-Si-Al-based crystals of the first glass component, the glass-ceramic behavior is revealed, and the glass softening point system is significantly increased. Be lowered. As a result, the primary network structure formed by the heat treatment suppresses the reaction with the second glass component during paste firing at 850 ° C, which can suppress the decomposition of the second glass component by the ruthenium-based composite oxide. The role of the reaction.

According to an exemplary embodiment of the present invention, in step (a), the conductive composite powder may include 20% to 80% by weight of a ruthenium-based composite oxide and 80% to 20% by weight of a first glass component. And, more preferably, 30% to 70% by weight of a ruthenium-based composite oxide and 70% to 30% by weight of a first glass component. More preferably, the conductive composite powder can be manufactured by heat-treating 40 to 60% by weight of a ruthenium-based composite oxide and 60 to 40% by weight of a first glass component.

It is effective when the ruthenium-based composite oxide and the first glass component system are included in the above range, because it is easy to form a primary network structure of the first network, and it is easy to control temperature characteristics (TCR), overload characteristics (STOL), And electrostatic discharge characteristics (ESD).

In addition, when the ruthenium-based composite oxide and the first glass component are included in the above range, a low resistance value can be obtained, the temperature characteristics can be prevented from moving in the (-) direction, and the temperature characteristics of (+) are not exhibited as a conductive material. In the case of the best specific resistance, it is better to maintain the stability of the crystal structure.

According to an exemplary embodiment of the present invention, the conductive composite powder may be formed by heat treatment and grinding. The average particle diameter of the conductive composite powder is not limited. For example, when accumulated from small particles to an amount, a particle diameter D50 corresponding to 50% of the total amount may be 2.0 micrometers or less. Preferably, D50 can be 1.0 micrometer to 2.0 micrometer. It is effective when the conductive powder has the above range by grinding, because the conductive powder can be easily mixed with the second glass component in the thick film resistance composition to provide a uniform composition.

The conductive composite powder can be used alone as a thick film resistor composition, but the electrical properties and fluidity may be insufficient, and the smoothness of the thick film resistor to be formed later and the adhesion to the substrate will be significantly reduced. Therefore, it is better to The conductive composite powder is mixed with the second glass component to form a dense secondary network structure.

Therefore, step (b) is a step of mixing the conductive composite powder and the second glass component to prepare a lead-free thick film resistor composition. For example, a lead-free thick film resistor composition can be prepared by including a conductive composite powder, a carrier, and a second glass component, and more preferably by including a conductive composite powder, a carrier, a second glass component, a conductive powder, and an inorganic material. Granules are prepared.

According to an exemplary embodiment of the present invention, the lead-free thick film resistor composition may include a conductive composite powder and a second glass component in a weight ratio of 10:90 to 90:10, and more preferably 20:80 to 80:20. Weight ratio of the conductive composite powder and the second glass component.

In addition, it is preferable to include the conductive composite powder and the second glass component in the above range, because the electrical properties of the lead-free thick film resistor prepared by the lead-free thick film resistor composition having the above range can be improved, and uniformity can be formed. Lead-free thick film resistor.

More specifically, in step (b), the lead-free thick film resistor composition may include a conductive composite powder of 3% to 65% by weight, a second glass component of 1% to 60% by weight, and 0.1% to 40% by weight of conductive powder and 0.1% to 10% by weight of inorganic particles. Preferably, the lead-free thick film resistor composition may include a conductive composite powder of 25% to 60% by weight, a second glass component of 20% to 60% by weight, a conductive powder of 1% to 20% by weight, And 0.1% to 5% by weight of inorganic particles, but each content is not limited to this.

When the conductive composite powder, the second glass component, the conductive powder, and the inorganic particles are included in the above range, a dual network structure can be easily formed, and temperature characteristics (TCR), overload characteristics (STOL), and electrostatic discharge characteristics can be easily controlled. (ESD), and when manufacturing a thick film resistor, the resistance is excellent in smoothness and adhesion to the substrate.

According to another exemplary embodiment of the present invention, a lead-free thick film resistor having a dual network structure is provided. The lead-free thick film resistor composition is screen-printed onto a substrate and then fired. And formed.

In lead-free thick film resistors, the resistance value (Rs) can be 10 ohms / □ to 10 megaohms / □, the resistance distribution (CV) can be 5% or lower, and the temperature characteristic (TCR) can be -100ppm / ℃ to 100ppm / ℃, the current noise (C-Noise) characteristic can be 12 dB or lower, and the overload characteristic (STOL) measured at 1/8 Watt rated power can be 0.1% or lower.

More preferably, in the lead-free thick film resistor, the resistance value (Rs) may be 10 ohms / □ to 500 kohm / □, the resistance distribution (CV) may be 5% or less, and the temperature characteristic (TCR) may be − 50ppm / ℃ to 50ppm / ℃, the current noise (C-Noise) characteristic can be 10dB or lower, and the overload characteristic (STOL) measured at 1/8 Watt rated power can be 0.05% or lower.

In order to achieve the physical properties, the conductive composite powder may preferably include 30% to 70% by weight of a ruthenium-based composite oxide and 70% to 30% by weight of a first glass component. More preferably, the conductive composite powder may include 40% to 60% by weight of a ruthenium-based composite oxide and 60% to 40% by weight of a first glass component.

According to another exemplary embodiment of the present invention, after screen printing, the lead-free thick film resistor can be dried to remove the organic solvent. The drying may be performed at 100 ° C to 200 ° C for 5 minutes to 30 minutes, but is not limited thereto.

As shown in FIG. 8, in a lead-free thick film resistor according to an exemplary embodiment of the present invention, a ruthenium-based composite oxide and a first glass component are heat-treated to form a first network, which is a primary network. The second glass component is mixed with it and fired to form a second network, thereby forming a dual network, which can be confirmed in Figure 3.

Lead-free thick film resistors can have excellent durability even in post-processing such as laser trimming and resistance adjustment, and have excellent electrical stability because of the electrical properties of resistors (such as the resistance according to the resistance size (Rs ), TCR, etc.) will not change.

According to an exemplary embodiment of the present invention, the lead-free thick film resistor-based electronic component can be applied not only to a single-layer circuit board or a multilayer circuit board, but also to an electrode component (such as a capacitor, an inductor, etc.).

A chip resistor according to an exemplary embodiment of the present invention includes: a first electrode, a thick film resistor, and a protective glass, wherein the thick film resistor may be obtained by screen printing the lead-free thick film resistor composition described above to a On the substrate, a lead-free thick film resistor with a dual network structure is formed by firing.

As a specific example, the lead-free thick film resistor of the present invention may be included in a chip resistor as shown in FIG. 2. The chip resistor may include a first electrode, a thick film resistor, and a protective glass.

The first electrode does not include lead, and the composition of the inorganic adhesive can be controlled according to the specifications of the resistance so as not to be affected by the electrical properties (such as temperature characteristics and resistance characteristics).

The inorganic adhesive preferably does not include lead as a glass component, preferably has a softening point of 500 ° C to 700 ° C, and more preferably includes inorganic particles such as TiO ₂ , MnO ₂ , Nb ₂ O ₅ and the like having functions of controlling temperature.

Further, it is preferable to apply protective glass to the resistor to improve the stability in post-processing such as laser trimming and resistance adjustment.

The protective glass does not include lead, has a softening point of 500 ° C. to 600 ° C., and may further include a B ₂ O ₃ component that is not available in the first electrode. When the softening point of the protective glass has the above range, it is preferable because the adhesion to the lead-free thick film resistor is excellent, and the resistance value change at a firing temperature of about 500 ° C is small.

Hereinafter, a preferred exemplary embodiment of a lead-free thick film resistor composition, a lead-free thick film resistor, and a manufacturing method thereof and a method of measuring physical properties will be described in detail.

Measurement of physical properties

1. Evaluation of the coefficient of variation (CV)

The lead-free thick film resistor composition according to the present invention is printed and then fired on an electrode to make 20 resistors, and the resistance value of each resistor is measured by a multimeter. Calculate the average and standard deviation of these resistance values, and divide the standard deviation of the resistance values by the average to derive the resistance distribution (CV), and the resistance distribution is expressed as a percentage.

2. Evaluation of temperature coefficient of resistance (TCR)

The TCR was evaluated by confirming the rate of change in resistance value when the temperature was raised to 125 ° C based on room temperature (25 ° C). Specifically, when the respective resistance values at 25 ° C and 125 ° C are represented by R ₂₅ (Ω / □) and R ₁₂₅ (Ω / □), and TCR is derived by the following equation, it is expressed in ppm / ℃ The results are shown in Table 4.

_{[Equation] TCR = (R 125 -R 25} ) / R 25/100 × 1000000

3. Evaluation of short-term overload characteristics (STOL)

The lead-free thick-film resistor was left for 30 minutes 5 seconds after the test voltage was applied thereto, and the resistance value change rate before and after the voltage application was confirmed. The test voltage is 2.5 times the rated voltage. Rated voltage is , Where R is the resistance value (Ω / □). In addition, for a resistor having a calculated test voltage exceeding 200 V, the test voltage is 200 V, and the results are shown in Table 4.

4. Evaluation of C-Noise

The fired lead-free thick film resistor was mounted in a current noise tester, and the resistance value displayed and the noise value at this time were measured. The results are shown in Table 4.

5. Evaluation of electrostatic discharge characteristics (ESD)

Using an electrostatic discharge tester (ELECTRO STATIC DISCHARGE SIMULATOR ESS-066), a voltage of 1 kV was applied to the fired lead-free thick film resistor 5 times at a speed of several nanoseconds with a speed of 1 second on and 1 second off. The change in resistance between before and after the application of a voltage of 1 kV was calculated. The results are shown in Table 4.

6. Confirmation of crystal structure through XRD

The dried and fired lead-free thick film resistor was horizontally placed on a sample plate in an XRD measuring instrument, and then a 2θ value of 10 ° C to 80 ° C was measured. The results are shown in FIGS. 4 to 6.

[Examples 1 to 24 and Comparative Examples 1 to 9]

Preparation of conductive composite powder

Weigh each component according to the composition content (g) shown in Table 2 below, which includes the first glass component and the second glass component shown in Table 1 below, and mix by a ball mill for 2 hours . Further, the mixture was heat-treated at 800 ° C for 30 minutes to obtain a sintered body. The obtained sintered body was ground by a grinder for 12 hours. The final powder had an average particle size of 1.5 microns, and XRD was measured to confirm the crystal structure.

Preparation of lead-free thick film resistor composition

A lead-free thick film resistor composition having a composition content (g) shown in Table 3 below was used, and 12% by weight of an ethyl cellulose resin as an organic adhesive and 88% by weight of which was in a weight ratio of 3:16 An organic vehicle composed of a mixed organic solvent of tetracarbitol acetate (BCA) and terpineol (TPNL), and a dispersant (BYK-111) is used as an additive. The composition was stirred for 2 hours using a P / L mixer, and then dispersed using a 3-roll mill with 5 releases and 5 compressions. The obtained paste was aged at 65 ° C. for 24 hours, and the viscosity was controlled with an organic solvent (ie, terpineol (TPNL)), and then a filtration procedure was performed.

Manufacturing of lead-free thick film resistors

The Ag-Pd conductor paste was printed on a U-patterns screen to a 96% pure alumina substrate, and dried at 150 ° C. for 10 minutes. The content of Ag is 95% by weight and the content of Pd is 5% by weight. The dried sample was fired at 850 ° C for 10 minutes. The lead-free thick-film resistor composition of the example was printed on a screen of a conductor forming an alumina substrate into a predetermined shape of 1 mm × 1 mm, followed by drying at 150 ° C. for 10 minutes, and firing at 850 ° C. for 10 minutes. Obtain lead-free thick film resistors. The lead-free thick film resistor has a thickness of 8.5 microns, and its physical properties are measured and shown in Table 4 below.

FIG. 3 shows a scanning electron microscope (SEM) image of a surface and a cross section of a lead-free thick film resistor according to an exemplary embodiment of the present invention. Referring to FIG. 3, it can be confirmed that the dual network structure is uniformly formed.

In addition, FIG. 4, FIG. 5, and FIG. 6 are XRD measurement diagrams of the conductive composite powder according to an exemplary embodiment of the present invention and a comparative example.

FIG. 4 shows the XRD measurement chart of the conductive composite powder having the composition 3 of Table 2 after heat treatment according to the heat treatment temperature range of 650 ° C. to 900 ° C .; and FIG. 5 and FIG. 6 show the conductive composite powder having Table 2 XRD measurement chart of 5 and 13.

As shown in FIG. 4, it can be understood that by conducting a heat treatment with a 2θ value of 30 °, the conductive composite powder of the present invention has a stable crystal structure even if the heat treatment is performed at a temperature higher than 600 ° C. In addition, as shown in FIGS. 5 and 6, it was confirmed that the conductive composite powders 5 and 13 also exhibit a stable crystal structure by heat treatment.

Figure 7 shows the XRD pattern of the coating film obtained by drying the paste at 150 ° C for 10 minutes, and the XRD pattern of the coating film obtained by firing at 850 ° C for 10 minutes. The second glass component is prepared by mixing.

As shown in Fig. 6, it can be understood that only when the conductive composite powder of the present invention is applied, it shows a stable crystal structure.

In addition, when the existing conductive composite powder is not included, the crystal structure change after firing is large. On the contrary, it can be understood that when the conductive composite powder according to the present invention is included, compared with the dried coating film, a stable double network structure can be formed after firing without much change in crystal structure.

Further, it can be understood that when a ruthenium-based composite oxide (Ca _x Sr _y Ba _z ) RuO _{3 is} used in the conductive composite powder according to the present invention, the double network structure is uniformly formed after firing without much change in crystal structure. , Where (Ca _x Sr _y Ba _z ) RuO ₃ needs to satisfy x + y + z = 1, 0 x <1, 0 y <1, 0 z <1, and 0 <x + y 1. In addition, the lead-free thick film resistor formed with the lead-free thick film resistor composition thus prepared also exhibits excellent temperature characteristics (TCR), overload characteristics (STOL), and electrostatic discharge characteristics (ESD). Specifically, a ruthenium-based composite oxide that satisfies x = 54 or 80, y = 46 or 20, and z = 0 in Ca _x Sr _y RuO ₃ is used.

As described above, although the preferred embodiments of the present invention have been described, the present invention should be construed to include all changes, modifications, and equivalents, so that the present invention can be modified by appropriately modifying the above-mentioned exemplary embodiments. Equally utilized. Therefore, the foregoing description is not intended to limit the scope of the invention, which is defined by the following limitations of the scope of the patent application.

Claims (15)

A lead-free thick film resistor composition comprising: a conductive composite powder that has been heat-treated by including a ruthenium-based composite oxide of 20% to 80% by weight and a first glass component of 80% to 20% by weight; and A second glass component, wherein the first glass component includes SiO ₂ , B ₂ O ₃ , BaO, Al ₂ O ₃ , and any one selected from transition metal oxides, alkali metal oxides, and alkaline earth metal oxides. Or a mixture of two or more and having a softening point of 500 ° C to 800 ° C, and the second glass component includes SiO ₂ , B ₂ O ₃ , Al ₂ O ₃ , and selected from transition metal oxides, alkali metals Any one or a mixture of two or more oxides and alkaline earth metal oxides, and having a softening point of 500 ° C to 700 ° C, wherein the ruthenium-based composite oxide is selected from CaRuO ₃ , BaRuO ₃ , SrRuO ₃ and mixtures or (Ca _x Sr _y Ba _z) RuO ₃ of any one or more of the two, in which _{(Ca x Sr y Ba z)} RuO 3 , the need to satisfy x + y + z = 1,0 x <1, 0 y <1, 0 z <1, and 0 <x + y 1, and wherein the conductive composite powder and the second glass component have a weight ratio of 10:90 to 90:10. The lead-free thick film resistor composition of claim 1, wherein the conductive composite powder has a crystallized structure. The lead-free thick film resistor composition of claim 1, wherein the lead-free thick film resistor composition has a double network structure after firing. The lead-free thick film resistor composition according to claim 1, wherein the transition metal oxide is selected from the group consisting of Nb ₂ O ₅ , Ta ₂ O ₅ , TiO ₂ , MnO ₂ , CuO, ZrO ₂ , WO ₃ , and ZnO. Or a mixture of two or more, the alkali metal oxide is selected from any one or a mixture of two or more of Na ₂ O, K ₂ O, and Li ₂ O, and the alkaline earth metal oxide is Any one or a mixture of two or more selected from SrO, CaO, and MgO. The lead-free thick film resistor composition according to claim 1, further comprising: any one or a mixture of two or more selected from the group consisting of conductive powder and inorganic particles. The lead-free thick film resistor composition according to claim 5, wherein the inorganic particles are selected from the group consisting of Nb ₂ O ₅ , Ta ₂ O ₅ , TiO ₂ , MnO ₂ , Al ₂ O ₃ , CuO, ZrO ₂ , CoO, BaTiO ₃ , Any one or a mixture of two or more of La ₂ O ₃ , Li ₂ TiO ₃ and ZnO, and the conductive powder is selected from Ag, Au, Pd, Pt, Cu, Ni, W, Mo, Zn, Al , RuO ₂ , IrO ₂ , Rh ₂ O _3, and a mixture of two or more of AgPd. The lead-free thick film resistor composition as claimed in claim 5, wherein the lead-free thick film resistor composition includes 3 to 65% by weight of the conductive composite powder, 1 to 60% by weight of the second glass component, and 0.1% by weight. % To 40% by weight of the conductive powder, and 0.1% to 10% by weight of the inorganic particles. A lead-free thick film resistor is formed by printing the lead-free thick film resistor composition according to any one of claims 1 to 7 on a substrate and then firing. For the lead-free thick film resistor of claim 8, its resistance value (Rs) is 10 ohms / □ to 10 megohms / □ (MΩ / □), resistance distribution (CV) is 5% or less, temperature characteristic (TCR) It is -100ppm / ℃ to 100ppm / ℃, the current noise (C-Noise) characteristic is 12dB or lower, and the overload characteristic (STOL) measured at 1/8 Watt rated power is 0.1% or lower. A method for manufacturing a lead-free thick film resistor includes: (a) manufacturing a conductive composite powder by heat-treating a ruthenium-based composite oxide and a first glass component; (b) preparing a conductive composite powder including the second composite glass and a second glass Composition of a lead-free thick film resistor composition; and (c) manufacturing a lead-free thick film resistor having a dual network structure formed by firing the lead-free thick film resistor composition, wherein the first glass component includes SiO ₂ , B ₂ O ₃ , BaO, Al ₂ O ₃ , and a mixture of any one or two or more selected from transition metal oxides, alkali metal oxides, and alkaline earth metal oxides, and has a temperature of 500 ° C. to 800 ° C. Softening point, and the second glass component includes SiO ₂ , B ₂ O ₃ , Al ₂ O ₃ , and any one or two or more selected from transition metal oxides, alkali metal oxides, and alkaline earth metal oxides. A mixture of many, having a softening point of 500 ° C to 700 ° C, and wherein the ruthenium-based composite oxide is selected from CaRuO ₃ , BaRuO ₃ , SrRuO ₃ , and (Ca _x Sr _y Ba _z ) RuO ₃ Or a mixture of two or more, wherein (Ca _x Sr _y Ba _z ) RuO _{In 3} , x + y + z = 1, 0 x <1, 0 y <1, 0 z <1, and 0 <x + y 1. The manufacturing method of claim 10, wherein in step (a), the temperature of the heat treatment is higher than 600 ° C and equal to or lower than 900 ° C, and the conductive composite powder is subjected to the heat treatment and subsequent grinding ) While manufacturing. The manufacturing method as claimed in claim 10, wherein in step (a), the conductive composite powder is heat-treated by 20 to 80% by weight of the ruthenium-based composite oxide and 80 to 20% by weight of the first The glass component is manufactured, and in step (b), the conductive composite powder and the second glass component in the lead-free thick film resistor composition have a weight ratio of 10:90 to 90:10. The method of claim 10, wherein in step (b), the lead-free thick film resistor composition further comprises a mixture selected from any one or two or more of conductive powder and inorganic particles. The manufacturing method of claim 13, wherein the lead-free thick film resistor composition includes the conductive composite powder in an amount of 3 to 65% by weight, the second glass component in an amount of 1 to 60% by weight, and 0.1 to 40% by weight. % Of the conductive powder, and 0.1% to 10% by weight of the inorganic particles. A chip resistor includes: a first electrode, a thick film resistor, and a glass for overcoating, wherein the thick film resistor is a lead-free thick film resistor, which will be used as described in claims 1 to 7 The lead-free thick film resistor composition of any one is printed on a substrate and then fired to form it.