TW201814727A - Lead-free thick film resistor composition, lead-free thick film resistor and production method thereof - Google Patents

Abstract

The present invention relates to a lead-free thick film resistor composition, a lead-free thick film resistor, and a production method thereof, and more particularly, to a lead-free thick film resistor composition which includes conductive composite powder that contains a ruthenium-based composite oxide and a glass component to form a double network structure, such that temperature characteristic, current noise, overload characteristic and electrostatic discharge characteristic are improved in a wide resistance range even without containing a lead component, a lead-free thick film resistor, and a production method thereof.

Description

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

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. More particularly, 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 comprising by including a lanthanide 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 if the lead component is not contained, temperature characteristics, current noise, overload characteristics, and electrostatic discharge characteristics can be improved over a wide resistance range.

The thick film resistor composition generally consists 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 cerium oxide or lanthanum oxide and lead as a conductive material. Therefore, the conventional thick film resistor composition contains lead.

In these thick film resistor compositions, ruthenium oxide (RuO ₂ ) thick film resistance can be controlled by the ratio of RuO ₂ and glass components to achieve a wide range of resistance values, and has an excellent temperature coefficient of resistance, and is Widely used in chip resistors, hybrid microcircuits, etc.

Conventional thick film resistors are formed on an alumina substrate by screen printing. However, according to recent trends in miniaturization, high frequency, and high power consumption of electronic components, there is a problem that the reliability and life of a wafer or a circuit are deteriorated due to an increase in the amount of heat radiation per unit area, and therefore, A substrate having excellent thermal properties, such as an aluminum nitride substrate, is used instead of the alumina substrate. In general, the selection of a suitable glass composition is very important because the glass phase in the thick film resistor material is used to increase bonding to the substrate. Current commercial resistance compositions for alumina substrates have a low melting point glass composition including lead (Pb).

However, recently, lead-containing glass has been banned due to environmental regulations, and it is known that the bonding property of lead-containing glass and aluminum nitride substrate is low due to low adhesion, blister, and the like. When a glass containing a lead component is used, an oxide, particularly lead oxide (PbO), reacts with the aluminum nitride substrate, which causes foaming. One of the reasons for the low adhesion is that when the lead oxide in the glass is sintered, the lead oxide reacts with the aluminum nitride to be reduced to lead (Pb), in which nitrogen is generated. Therefore, it is important to select a lead-free glass composition 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 reduce the temperature coefficient of resistance of the final thick film resistor by controlling the glass composition or by adding a component having a low temperature coefficient of resistance.

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

When the composition of the glass material is changed or when cerium 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 lowered, and the resistance of the thick film resistor is The stability is significantly reduced, and electrical properties such as TCR, current noise (C-Noise), etc., are also reduced. Further, in the preparation of the electric resistance composition, the RuO ₂ powder and the glass powder are usually simply mixed, and therefore, it is difficult to obtain a uniform mixed state of the components. Therefore, it is difficult to obtain a uniform microstructure in the thick film resistor after sintering. As a result, there is still a problem that the stability of the thick film resistor is deteriorated due to an increase in the electrical property change 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

SUMMARY OF THE INVENTION An object of the present invention is to provide a lead-free thick film resistor composition capable of maintaining the stability of a resistance value and the reliability of electrical characteristics. More specifically, an aspect of the present invention is directed to provide a lead-free thick film resistor composition comprising: a conductive composite powder heat-treated by including a lanthanide composite oxide and a first glass component, and a second glass ingredient.

The lead-free thick film resistor composition forms a dual network structure such that a fine conductive path is uniformly formed, and therefore, an embodiment of the present invention provides a lead-free thick film resistor composition which can be used even without lead In the case of a component, temperature characteristics, resistance distribution, current noise, overload characteristics, and electrostatic discharge characteristics are improved over a wide resistance range, and excellent stability is obtained.

Further, another aspect of the present invention is directed to a method of manufacturing a lead-free thick film resistor.

Further, another aspect of the present invention is directed to a wafer resistor comprising: 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 lanthanide composite oxide and a first glass component; and a second glass component, wherein the first glass component comprises SiO ₂ And 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 electrically conductive composite powder may have a crystalline structure.

The lead-free thick film resistor composition provides 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 , it is necessary to satisfy x+y+z=1,0 x<1,0 y<1,0 z<1 and 0<x+y 1. The first glass component may further comprise a mixture selected from any one or two or more of a transition metal oxide, an alkali metal oxide, and an alkaline earth metal oxide, and may have a softening point of from 500 ° C to 800 ° C. And the second glass component may further comprise a mixture selected from any one or two or more of a transition metal oxide, an alkali metal oxide, and an alkaline earth metal oxide, and may have a softening point of from 500 ° C to 700 ° C. .

The transition metal oxide may be a mixture of any one or 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, alkali metal oxide The material may be any one selected from the group consisting of Na ₂ O, K ₂ O, and Li ₂ O or a mixture of two or more, and the alkaline earth metal oxide may be selected from any one of SrO, CaO, and MgO or a mixture of two or more.

The conductive composite powder may include 20% by weight to 80% by weight of the lanthanoid composite oxide and 80% by weight to 20% by weight of the first glass component.

The electrically 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 comprise: a mixture selected from the group consisting of conductive powder and inorganic particles or a mixture of two or more.

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 of AgPd or a mixture of two or more.

The lead-free thick film resistor composition may include from 3% by weight to 65% by weight of the conductive composite powder, from 1% by weight to 60% by weight of the second glass component, from 0.1% by weight to 40% by weight of the conductive powder, and from 0.1% by weight to 10% 6% by weight of inorganic particles.

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

A lead-free thick film resistor is formed by printing the above-described lead-free thick film resistor composition onto a substrate and then firing.

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

In another general aspect, a method for producing a lead-free thick film resistor is provided, comprising: (a) preparing a conductive composite powder (b) by heat-treating a lanthanide composite oxide and a first glass component to prepare the conductive composite powder and a lead-free thick film resistor composition of a second glass component; and (c) fabricating the lead-free thick film resistor composition to produce a lead-free thick film resistor having a dual network structure, wherein the first glass component comprises 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 the 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 produced by the heat treatment and subsequent grinding.

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

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

The lead-free thick film resistor composition may include from 3% by weight to 65% by weight of the conductive composite powder, from 1% by weight to 60% by weight of the second glass component, from 0.1% by weight to 40% by weight of the conductive powder, and from 0.1% by weight to 10% 6% by weight of inorganic particles.

In another general aspect, a wafer resistor is provided, comprising: a first electrode, a thick film resistor, and a protective glass, wherein the thick film resistor is a lead-free thick film resistor by combining the lead-free thick film resistor described above The object is printed onto a substrate and then fired to form.

The lead-free thick film resistor composition includes a conductive composite powder which is heat-treated by including a lanthanide composite oxide and a first glass component, and a second glass component, thereby forming a dual network structure to be combined with a conventional thick film including lead Compared to resistors, even without lead, it provides excellent thick film resistance over a wide range of resistance values. In addition, the lead-free thick film resistor composition includes a conductive composite powder, so that the decomposition of the lanthanide composite oxide during heat treatment can be suppressed, 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, so that there is no deterioration of characteristics even under a high resistance region, and it has excellent temperature characteristics, current noise, overload characteristics, and electrostatic discharge characteristics as well as excellent A stable lead-free thick film resistor composition and a lead-free thick film resistor are possible.

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.

2 is a cross-sectional view of a wafer resistor including a lead-free thick film resistor in accordance with an exemplary embodiment of the present invention.

Figure 3 shows a scanning electron microscope (SEM) image of the surface and cross section of a lead-free thick film resistor in accordance with 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.

Figure 4 is a graph showing the XRD measurement of the composite powder 3 in Table 2 according to an exemplary embodiment of the present invention, depending on the heat treatment temperature and time.

Figure 5 shows an XRD measurement of Composite Powder 5 in Table 2, in accordance with 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.

Figure 7 is a graph showing the XRD measurement of the dried coating film and the lead-free thick film resistor after firing according to an exemplary embodiment of the present invention.

Figure 8 is a schematic illustration of a dual network structure after firing a lead-free thick film resistor composition in accordance with an exemplary embodiment of the present invention.

Hereinafter, preferred exemplary embodiments regarding a lead-free thick film resistor composition, a lead-free thick film resistor, and a method of manufacturing the same, and a method for measuring physical properties will be described in detail. The invention is specifically understood by the following examples, which are intended to be illustrative, and not to limit the scope of the invention as defined by the appended claims.

The present inventors have found that it is possible to form a lead-free thick film resistor including a conductive composite powder which is heat-treated by including a lanthanide-based composite oxide and a first glass component, and a second glass component, thereby forming a dual network structure, resulting in fine conductive The path is uniformly formed, so that even if the lead component is removed, temperature characteristics, current noise, overload characteristics, and electrostatic discharge characteristics can be improved in a wide resistance range, and the stability is excellent, and thus the present invention has been completed.

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

As used herein, the term "lead-free" means that the lead component 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 conductive composite powder) and the second glass component, a stable dual network structure in which the secondary network is formed can be formed, so that fine conductive can be uniformly formed even without including lead. Path to provide an excellent thick film resistor with a wide range of resistance values.

According to an exemplary embodiment of the present invention, the conductive composite powder can be produced by heat treatment including a lanthanide composite oxide and a first glass component. When the conventional lanthanide composite oxide is used alone, XRuO ₃ is decomposed into XO and RuO ₂ , the specific resistance is lowered, and the stability of the resistance value of the thick film resistor to be manufactured is remarkably lowered and difficult to maintain. For example, electrical properties such as temperature characteristics (TCR) and current noise (C-Noise). 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 lanthanide-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 lanthanide composite oxide is not limited as long as it is a lanthanide 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, in (Ca _x Sr _y Ba _z )RuO ₃ , satisfying 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 also be used. The first glass component further includes a mixture selected from any one or two or more of a transition metal oxide, an alkali metal oxide, and an alkaline earth metal oxide. Further, the conductive composite powder can be obtained by further including a cerium oxide, a conductive metal oxide, and a metal component in addition to the lanthanide composite oxide and the first glass component.

The lanthanide composite oxide having a perovskite crystal structure is effective because it is used for maintaining temperature characteristics (TCR) and overload (STOL) particularly at 1 K? or higher.

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

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

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

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

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

Further, the cerium salt aqueous solution can be obtained even by alkali fusion using an alkaline salt. According to alkali fusion, the base 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 strong acid (leach ) to obtain strontium salts. The base metal sponge has a base metal of equal size among the particles and the powder, and can be used as a starting material for preparing the onium salt. The concentration of the ceric acid aqueous solution per liter (L) is suitably less than 50 gram / liter, and the temperature for dissolving hydrazine in the alkali dissolution is preferably from 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 lanthanide 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 further improving the reactivity with the lanthanide composite oxide to make the network structure denser. Preferably, and further, it is effective to improve compatibility with the second glass component in the preparation of the electrically conductive composite powder. The main components may be included in the first glass component in an amount of at least 50% by weight, more specifically 50% by weight to 99% by weight. In particular, the conductive composite powder obtained by the combination of the first glass component containing BaO and the lanthanoid composite oxide can prevent yttrium oxide from being formed by the reaction of the ruthenium composite oxide with the second glass component, thereby forming a more stable formation. Crystal structure. The crystal structure in the present invention includes a Ba-Si-Al-based partial crystal structure or an overall crystal structure. When a conductive thick film resistor composition is prepared using a conductive composite powder having a stable crystal structure, the formation of niobium oxide can be controlled by the reaction of the lanthanide composite oxide and the second glass component in the firing process, thereby It is possible to obtain a thick film resistor having a more stable electrical property because, as shown in Fig. 7, the crystal structure change due to firing is small.

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

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

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 The reactivity of the lanthanide composite oxide.

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, but not limited to, a mixture 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. 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 the group consisting of 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 the group consisting of 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 lanthanide composite oxide can be modified to form the primary network more uniformly, the primary network being the first network, and during the heat treatment A heat-treated conductive composite powder having a partial crystal structure is produced.

Further, the second glass component may have a softening point of 500 ° C to 700 ° C. It is preferable that the softening point of the second glass component is in the above range because it is easy to form a double 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 lower the coefficient of variation ( CV), thus having excellent electrical properties. The different softening points of the first glass component and the second glass component described above can be controlled depending on the presence or absence of cerium oxide. Since the second glass component does not include ruthenium oxide, it is possible to prevent a phenomenon in which the coefficient of variation (CV) is increased due to high reactivity with the substrate during the formation of the double network.

According to an exemplary embodiment of the present invention, the electrically conductive composite powder may be granulated by heat-treating a mixture of the lanthanide composite oxide and the 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 accumulating from small particles to an amount, the particle diameter D50 corresponding to 50% of the total amount may be 2.0 μm or less. Preferably, D50 can be from 1.0 micron to 2.0 microns. The 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 a higher temperature of a thick film resistor composition well known in the art, and for example, it is preferably higher than 600 ° C and equal to or lower than 900. °C, and heat treatment can be performed in this heat treatment temperature in 120 minutes.

The electrically conductive composite powder formed as above can form a uniform primary network structure which is the first network structure. When the lead-free thick film resistor is manufactured, the lanthanide composite oxide and the first glass component are formed into a primary network of the first network by heat treatment, and the reactivity between the lanthanide composite oxide and the second glass component can be suppressed. The decomposition of the lanthanide composite oxide does not occur, resulting in a more stable dual network structure.

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

When the lanthanide composite oxide and the first glass component are included in the above range, it is effective 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).

Further, when the lanthanide composite oxide and the first glass component are included in the above range, a low resistance value can be obtained, temperature characteristics can be prevented from moving in the (-) direction, and (+) temperature characteristics are not exhibited as conduction. The optimum specific resistance of the material, and preferably maintains the stability of the crystal structure.

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 transition metal oxide, an alkali metal oxide, and Any of alkaline earth metal oxides or a mixture of two or more. The main components may be included in the second glass component in an amount of at least 40% by weight, more specifically 40% by weight 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% by weight to 30% by weight of SiO ₂ , 10% by weight to 40% by weight of B ₂ O ₃ , and 2% by weight. Up to 15% by weight of Al ₂ O ₃ , 0.1% by weight to 10% by weight of the transition metal oxide, and 20% by weight to 60% by weight of the alkali metal oxide and the alkaline earth metal oxide. Preferably, the second glass component may include 10% by weight to 20% by weight of SiO ₂ , 20% by weight to 40% by weight of B ₂ O ₃ , 2% by weight to 10% by weight of Al ₂ O ₃ , 0.1% by weight Up to 10% by weight of the transition metal oxide, and 30% by weight to 60% by weight of the alkali metal oxide and the alkaline earth metal oxide, but are not limited thereto. The second glass component has the above-mentioned components in the above content range, and can effectively have excellent compatibility and mismatch with the conductive composite powder, and can effectively improve electrical properties and durability.

When the constitution of the second glass component has the above range, the stability of the second glass component can be excellent and the increase in the softening point can be prevented. When the stability is excellent, it is preferable because it can improve the coating film strength of the thick film resistance of the coating film, and the electrical properties of the lead-free thick film resistor can be used for forming the first electrode and for protecting the wafer resistance. The process of glass has been improved.

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

A transition metal oxide may be added to control temperature characteristics (TCR), overload characteristics (STOL), and electrostatic discharge characteristics (ESD), and may include an alkaline earth metal oxide to improve reactivity with the lanthanide composite oxide. 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, but not limited to, a mixture 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. 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 the group consisting of 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 the group consisting of 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 the 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 resistors, 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, more preferably 20:80 to 80:20. The conductive composite powder and the second glass component in a weight ratio.

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) ).

Further, when the conductive composite powder and the second glass component are included in the above range, since 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.

In the range where 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, and may, for example, further include a material selected from the group consisting of Ag, Au, Pd, Pt, Cu, Ni, W, Mo, Zn, Al, RuO. ₂ , a mixture of IrO ₂ , Rh ₂ O ₃ and AgPd or a mixture of two or more.

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 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 , La ₂ O ₃ , a mixture of Li ₂ TiO ₃ , ZnO, and WO ₃ or a mixture of two or more, 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% by weight to 65% by weight of the conductive composite powder, 1% by weight to 60% by weight of the second glass component, 0.1 The conductive powder is from 5% by weight to 40% by weight, and from 0.1% by weight to 10% by weight of the inorganic particles, but the respective contents of the lead-free thick film resistor composition are not limited thereto. Preferably, the lead-free thick film resistor composition may include 25% by weight to 60% by weight of the conductive composite powder, 20% by weight to 60% by weight of the second glass component, 1% by weight to 20% by weight of the conductive powder, and 0.1 From 5% by weight to 5% by weight of inorganic particles.

The lead-free thick film resistor composition has the above content range, so that the dual network structure can be easily formed. Due to the formation of the dual network structure, the resistance distribution (CV) and the resistance reproducibility are excellent, and the temperature characteristics (TCR), the overload characteristics (STOL), and the 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 or the like, and use the mixture as a combination for forming a paste, a paint, and an ink each having a suitable rheology. The medium can be mixed with a general carrier. 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 of the following components: terpineol, carbitol, butyl carbitol, celecoxime, dexamethasone, or an ester thereof; selected from any of toluene, xylene, and the like. Or two or more organic solvents; and one or two or more selected from the group consisting of ethyl cellulose, nitrocellulose, acrylate polymers, methacrylate polymers, rosin, and the like. Adhesive resin. If desired, it may further comprise 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.

Further, 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 (for example, printing, etc.) of the composition.

Further, the viscosity of the lead-free thick film resistor composition can be adjusted by further increasing the organic solvent, which may be the same as or different from the solvent used for the carrier. The organic solvent may further be included in an amount of 10 parts by weight to 200 parts by weight based on 100 parts by weight of the lead-free thick film resistor composition. More preferably, 30 parts by weight to 100 parts by weight of the organic solvent may be further included in 100 parts by weight of the lead-free thick film resistor composition, but the 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, comprising: (a) manufacturing a conductive composite powder by heat-treating a lanthanide composite oxide and a first glass component; (b) Preparing a lead-free thick film resistor composition comprising the conductive composite powder and a second glass component; and (c) fabricating 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 the step (a), the temperature of the heat treatment is 600 ° C to 900 ° C, and the conductive composite powder is produced by the heat treatment and the subsequent grinding. Preferably, in the step (a), the temperature of the heat treatment is 800 ° C to 900 ° C, and the conductive composite powder is produced by the heat treatment and the subsequent grinding.

According to an exemplary embodiment of the present invention, the electrically conductive composite powder may have a partially crystalline structure. Due to the heat treatment, a part of the perovskite-type crystal structure of the lanthanide composite oxide may be reacted with the first glass component to be decomposed into a cerium oxide, wherein crystallization may be partially generated in the first glass component. Therefore, a strong primary network structure of the first network can be formed by the lanthanide composite oxide and the first glass component. The electrically conductive composite powder may have a primary network structure that is the first network by heat treatment. Due to, for example, partial crystallization of the Ba-Si-Al-based crystal of the first glass component, the behavior of the glass ceramic is revealed, whereby the glass softening point is significantly increased, and the mutual reactivity between the second glass component and the lanthanide composite product Being lowered. As a result, the primary network structure formed by the heat treatment suppresses the reaction with the second glass component during the paste firing at 850 ° C, which provides inhibition of the decomposition of the second glass component by the lanthanide composite oxide. The role of the reaction.

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

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

Further, when the lanthanide composite oxide and the first glass component are included in the above range, a low resistance value can be obtained, temperature characteristics can be prevented from moving in the (-) direction, and (+) temperature characteristics are not exhibited as a conductive material. The optimum specific resistance is better for maintaining 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 electrically conductive composite powder is not limited. For example, when accumulating from small particles to an amount, the particle diameter D50 corresponding to 50% of the total amount may be 2.0 μm or less. Preferably, D50 can be from 1.0 micron to 2.0 microns. 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 resistor composition to provide a uniform composition.

The conductive composite powder may be used alone as a thick film resistor composition, but 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 may be remarkably lowered, and therefore, it is preferred The electrically conductive composite powder is mixed with the second glass component to form a dense secondary network structure.

Therefore, the 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, the 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 comprises a conductive composite powder, a carrier, a second glass component, a conductive powder, and an inorganic component. Preparation of granules.

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, more preferably 20:80 to 80:20. The weight ratio of the conductive composite powder and the second glass component.

Further, it is preferable that 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 uniform Lead-free thick film resistors.

More specifically, in the step (b), the lead-free thick film resistor composition may comprise from 3% by weight to 65% by weight of the conductive composite powder, from 1% by weight to 60% by weight of the second glass component, and from 0.1% by weight to It is prepared by using 40% by weight of conductive powder and 0.1% by weight to 10% by weight of inorganic particles. Preferably, the lead-free thick film resistor composition may comprise, by weight, from 25% by weight to 60% by weight of the conductive composite powder, from 20% by weight to 60% by weight of the second glass component, from 1% by weight to 20% by weight of the conductive powder, And 0.1% by weight to 5% by weight of inorganic particles are prepared, but the respective contents are not limited thereto.

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 smoothness of the electric resistance and the adhesion to the substrate are excellent.

According to another exemplary embodiment of the present invention, there is provided a lead-free thick film resistor having a dual network structure by screen printing the above lead-free thick film resistor composition onto a substrate, followed by firing And formed.

In the lead-free thick film resistor, the resistance value (Rs) may be 10 ohm/□ to 10 mega ohm/□, the resistance distribution (CV) may be 5% or lower, and the temperature characteristic (TCR) may be -100 ppm/°C to The 100ppm/°C, current noise (C-Noise) characteristic can be 12 dB or less, and the overload characteristic (STOL) measured at 1/8 watt rated power can be 0.1% or less.

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

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

According to another exemplary embodiment of the present invention, after screen printing, a lead-free thick film resistor may be dried to remove the organic solvent. The drying may be carried out 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, the lanthanide composite oxide and the first glass component are heat treated to form a first network, which is a primary network, and then The second glass component is mixed therewith and fired to form a second network, thereby forming a dual network, as evidenced in Figure 3.

Lead-free thick film resistors 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 the resistors (eg, resistance according to the size of the resistors (Rs) ), TCR, etc.) will not change.

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

A wafer 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 can be screen printed by the above-mentioned lead-free thick film resistor composition On the substrate, a lead-free thick film resistor having a dual network structure formed by firing is subsequently performed.

As a specific example, the lead-free thick film resistor of the present invention can be included in the wafer resistor as shown in FIG. 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 specification of the resistance so as not to be affected by electrical properties such as temperature characteristics and resistance characteristics.

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

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

The protective glass does not include lead and has a softening point of 500 ° C to 600 ° C, and may further include a B ₂ O ₃ component which 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 change in the resistance value at the firing temperature of about 500 ° C is small.

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

Measurement of physical properties

1. Evaluation of 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 produce 20 resistors, and the resistance values of the resistors are measured by a multimeter. The average and standard deviation of these resistance values are calculated, and the standard deviation of the resistance values is divided by the average to derive the resistance distribution (CV), and the resistance distribution is expressed as a percentage.

2. Evaluation of the temperature coefficient of resistance (TCR)

The evaluation of the TCR was carried out by confirming the rate of change of the resistance value when the temperature was raised to 125 ° C based on room temperature (25 ° C). Specifically, when 25 ° C and 125 ° C, the respective resistance values are represented by R ₂₅ (Ω/□) and R ₁₂₅ (Ω/□), and the TCR is derived by the following equation, which is in ppm/°C. Indicated, and 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 allowed to stand for 5 minutes after the test voltage was applied thereto for 5 seconds, and the rate of change in resistance value 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/□). Further, for a resistance having a calculated test voltage exceeding 200 V, the test voltage was 200 V, and the results are shown in Table 4.

4. Evaluation of current noise (C-Noise)

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

5. Evaluation of Electrostatic Discharge Characteristics (ESD)

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

6. Confirmation of crystal structure through XRD

The dried and fired lead-free thick film resistor was placed horizontally 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 Figures 4 through 6.

[Examples 1 to 22 and Comparative Examples 1 to 9]

Preparation of conductive composite powder

The ingredients were weighed according to the composition content (g) shown in Table 2 below, including the first glass component and the second glass component shown in Table 1 below, and mixed 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

Using a lead-free thick film resistor composition having a composition content (g) shown in Table 3 below, using 12% by weight of an ethylcellulose resin as an organic binder and 88% by weight of which was 3:16 by weight. An organic vehicle composed of an organic solvent of mixed butyl carbitol acetate (BCA) and terpineol (TPNL), and a dispersing agent (BYK-111) is used as an additive. The composition was stirred for 2 hours using a P/L mixer, followed by dispersion 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 (i.e., terpineol (TPNL)), followed by a filtration procedure.

Manufacturing of lead-free thick film resistors

The Ag-Pd conductor paste was screen-printed U-patterns onto a 96% pure alumina substrate and dried at 150 ° C for 10 minutes. The content of Ag was 95% by weight and the content of Pd was 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 screen-printed into a predetermined shape of 1 mm × 1 mm on an alumina substrate forming a conductor, followed by drying at 150 ° C for 10 minutes, and firing at 850 ° C for 10 minutes. A lead-free thick film resistor is obtained. 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.

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

Further, Fig. 4, Fig. 5, and Fig. 6 are XRD measurement views of the electrically conductive composite powder according to an exemplary embodiment of the present invention and comparative examples.

Figure 4 is a graph showing the XRD measurement 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 Figs. 5 and 6 show the conductive composite powder having the surface of Table 2. XRD measurement plots for 5 and 13.

As shown in Fig. 4, it is understood that the conductive composite powder of the present invention has a stable crystal structure by heat treatment having a 2θ value of 30° even if the heat treatment is carried out at a temperature higher than 600 °C. Further, as shown in Fig. 5 and Fig. 6, it was confirmed that the conductive composite powders 5 and 13 also exhibited a stable crystal structure by heat treatment.

Fig. 7 is an XRD pattern of a coating film obtained by drying a paste at 150 ° C for 10 minutes, and an XRD pattern of a coating film obtained by firing at 850 ° C for 10 minutes, wherein the paste is obtained by using a conductive composite powder and The second glass component is prepared by mixing.

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

Further, 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 electroconductive composite powder according to the present invention is included, a stable double network structure can be formed after firing without much crystal structure change as compared with the dried coating film.

Further, it can be understood that when the lanthanide 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 and there is not much crystal structure change. , in Ca _x Sr _y Ba _z , it is necessary to satisfy x+y+z=1, 0 x<1,0 y<1,0 z<1 and 0<x+y 1. Further, the lead-free thick film resistor formed by the lead-free thick film resistor composition thus prepared also exhibited excellent temperature characteristics (TCR), overload characteristics (STOL), and electrostatic discharge characteristics (ESD). Specifically, an lanthanoid composite oxide satisfying x=54 or 80, y=46 or 20, and z=0 in Ca _x Sr _y RuO ₃ is used.

As described above, the preferred embodiments of the present invention have been described, but the present invention should be construed to include all modifications, modifications, and equivalents, so that the present invention can be modified by appropriately modifying the above-described exemplary embodiments. It is used equally. Accordingly, the above description is not intended to limit the scope of the invention as defined by the scope of the appended claims.

Claims (18)

A lead-free thick film resistor composition comprising: a conductive composite powder heat-treated by comprising a lanthanide composite oxide and a first glass component; and a second glass component, wherein the first glass component comprises 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 .  The lead-free thick film resistor composition of claim 1, wherein the electrically 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 of claim 1, wherein the lanthanide composite oxide is selected from the group consisting of CaRuO ₃ , BaRuO ₃ , SrRuO ₃ , and (Ca _x Sr _y Ba _z )RuO ₃ or two or more. a mixture of many, in Ca _x Sr _y Ba _z , to satisfy x + y + z = 1, 0 x<1,0 y<1,0 z<1 and 0<x+y 1. The first glass component further comprises a mixture selected from the group consisting of transition metal oxides, alkali metal oxides, and alkaline earth metal oxides, or a mixture of two or more, and having a softening point of from 500 ° C to 800 ° C. And the second glass component further comprises a mixture selected from any one or two or more of a transition metal oxide, an alkali metal oxide, and an alkaline earth metal oxide, and has a softening point of from 500 ° C to 700 ° C. The lead-free thick film resistor composition of claim 4, 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 of Na ₂ O, K ₂ O, and Li ₂ O or a mixture of two or more, and the alkaline earth metal oxide system Any one selected from the group consisting of SrO, CaO, and MgO, or a mixture of two or more.  The lead-free thick film resistor composition of claim 1, wherein the conductive composite powder comprises 20% by weight to 80% by weight of the lanthanide-based composite oxide and 80% by weight to 20% by weight of the first glass component.    The lead-free thick film resistor composition of claim 1, 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, further comprising: a mixture selected from the group consisting of conductive powder and inorganic particles or a mixture of two or more.   The lead-free thick film resistor composition of claim 8, 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 the group consisting of Ag, Au, Pd, Pt, Cu, Ni, W, Mo, Zn, Al Any one of RuO ₂ , IrO ₂ , Rh ₂ O ₃ and AgPd or a mixture of two or more.  The lead-free thick film resistor composition of claim 8, wherein the lead-free thick film resistor composition comprises from 3% by weight to 65% by weight of the conductive composite powder, from 1% by weight to 50% by weight of the second glass component, 0.1% by weight From 0.01 to 40% by weight of the conductive powder, and from 0.1% by weight to 10% by weight of the inorganic particles.    A lead-free thick film resistor formed by printing a lead-free thick film resistor composition according to any one of claims 1 to 10 onto a substrate and then firing.    The lead-free thick film resistor of claim 11 has a resistance value (Rs) of 10 ohm/□ to 10 mega ohm/□ (MΩ/□), a resistance distribution (CV) of 5% or less, and a temperature characteristic (TCR). The line-100ppm/°C to 100ppm/°C, the current noise (C-Noise) characteristic is 12 dB or lower, and the overload characteristic (STOL) measured at 1/8 watt rated power is 0.1% or less.   A method for manufacturing a lead-free thick film resistor, comprising: (a) thermally treating a lanthanide composite oxide and a first glass component to produce a conductive composite powder; (b) preparing a conductive composite powder and a second glass a lead-free thick film resistor composition of the composition; and (c) 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 comprises 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 .  The manufacturing method of claim 13, wherein in the 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 (grinding) ) and manufactured.    The manufacturing method of claim 13, wherein in the step (a), the conductive composite powder is heat-treated by 20% by weight to 80% by weight of the lanthanoid composite oxide and 80% by weight to 20% by weight of the first The glass component is manufactured, and in the 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 13, wherein in the step (b), the lead-free thick film resistor composition further comprises a mixture selected from the group consisting of conductive powder and inorganic particles or a mixture of two or more.    The method of claim 16, wherein the lead-free thick film resistor composition comprises from 3% by weight to 65% by weight of the conductive composite powder, from 1% by weight to 60% by weight of the second glass component, from 0.1% by weight to 40% by weight. % of the conductive powder, and 0.1% by weight to 10% by weight of the inorganic particles.    A chip resistor comprising: a first electrode, a thick film resistor, and a glass for overcoating, wherein the thick film resistor is a lead-free thick film resistor, as claimed in claims 1 to 10 The lead-free thick film resistor composition of any one of them is printed on a substrate and then fired to form.