KR101848694B1 - Lead-free thick film resistor, and electronic deivce coprising the same - Google Patents

Abstract

The present invention relates to a lead-free thick film resistor, which comprises: a first network derived from a first glass precursor mixture comprising a silicon oxide, a barium oxide, a boron oxide and an aluminum oxide and a ruthenium complex oxide; and a second network derived from a second glass precursor mixture comprising a silicon oxide, a boron oxide and an aluminum oxide, wherein the first network and the second network are formed to intersect with each other, and to electronic parts containing the same.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a lead-free thick film resistor and an electronic component including the lead-

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lead-free thick film resistor and an electronic component including the lead-free thick film resistor. More particularly, the present invention relates to a lead- Characteristics, current noise, overload characteristics, and antistatic characteristics, and an electronic component including the lead-free thick-film resistor.

The thick-film resistor composition for manufacturing a thick-film resistor generally comprises a glass component for adjusting the resistance value and bonding property, an organic vehicle composed of a conductive material and a binder and a solvent, And then fired to form a thick film resistor.

Conventional thick film resistor compositions contain a lead component such as lead oxide glass and a conductive component such as ruthenium oxide or ruthenium oxide and lead compounds. Among them, RuO ₂ thick film resistors can control the ratio of RuO ₂ and the glass component so that a wide range of resistance values can be realized, and since they have an excellent temperature resistance coefficient, Circuits (hybrid microcircuits) have been widely applied.

However, it is known that lead-containing glass has recently been prohibited from being used due to environmental regulations, and has low adhesiveness to aluminum nitride substrates due to low adhesion and blister generation. In use of lead-containing glass, oxides, especially lead oxide (PbO), react with the substrate aluminum nitride and may cause blistering. In addition, lead oxide in glass reacts with aluminum nitride during sintering to reduce lead (Pb) and generate nitrogen gas, which may be a cause of low adhesion. Therefore, it is important to select a lead-free glass composition that does not contain lead and has good mutual bonding with aluminum nitride. In general, since the temperature coefficient of resistance of RuO ₂ has a high positive temperature coefficient of 5670 ppm / ° C, it is possible to control the composition of the glass component or add a component having a low resistance temperature coefficient, It is necessary to make efforts to lower.

Korean Patent Laid-Open No. 10-2006-0056330 (Patent Document 1) discloses that a glass element containing NiO is used substantially without containing lead, thereby providing a resistor having a high resistance value and a small temperature resistance and short overload Korean Patent Laid-Open Publication No. 10-2014-0025338 (Patent Document 2) discloses a resistor paste using ruthenium oxide (RuO ₂ ) powder having a rutile crystal structure, A composition for a thick-film resistor and a thick-film resistor having sufficient performance even when the thickness is low.

However, when the glass component is changed or rutile oxide having a rutile crystal structure is used as described above, the resistivity of the thick film resistor is lowered due to the suppression of particle growth during firing of the resistor composition, TCR) and C-Noise are remarkably deteriorated. In addition, since the RuO ₂ powder and the glass component are generally simply prepared by mixing at the time of producing the resist composition, it is difficult to obtain a uniform mixture state of the constituent components. As a result, it is difficult to obtain a uniform microstructure after firing in the thick-film resistor, and as a result, the change of the electrical characteristics of the thick-film resistor increases, and the stability of the thick-film resistor remains poor.

Korean Patent Publication No. 10-2006-0056330 Korean Patent Publication No. 10-2014-0025338

In order to solve the above problems, the present invention relates to a first network derived from a first glass precursor mixture and a ruthenium complex oxide comprising silicon oxide, barium oxide, boron oxide and aluminum oxide; And a second network derived from a second glass precursor mixture comprising silicon oxide, boron oxide and aluminum oxide, said first network and said second network being intended to provide a lead free thick film resistor formed crossing each other do.

In addition, since the first network and the second network form a crosslinked structure, the double network structure is formed to uniformly form a fine conductive path, so that the temperature characteristic, resistance scattering, current noise, An object of the present invention is to provide a lead-free thick-film resistor having improved antistatic characteristics.

It is also an object of the present invention to provide an electronic component including the above-described lead-free thick-film resistor.

In order to achieve the above object, a lead-free thick film resistor of the present invention comprises a first network derived from a first glass precursor mixture and a ruthenium complex oxide comprising silicon oxide, barium oxide, boron oxide and aluminum oxide; And a second network derived from a second glass precursor mixture comprising silicon oxide, boron oxide and aluminum oxide, wherein the first network and the second network are formed to intersect with each other.

The second network forms a continuous phase and the first network forms a dispersed phase within the continuous phase, wherein the dispersed phase forms a crosslinked structure.

The first glass precursor mixture and the second glass precursor mixture may further comprise 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 is _{Nb 2 O 5, Ta 2 O} 5, TiO 2, MnO 2, CuO, ZrO 2, WO 3 and a mixture of at least any one or more selected from ZnO, the alkali metal oxides Na ₂ O, K ₂ O and Li ₂ O, and the alkaline earth metal oxide may be any one or a mixture of two or more selected from SrO, CaO and MgO.

The softening point (T ₁ ) of the first glass precursor mixture may be 600 to 800 ° C and the softening point (T ₂ ) of the second glass precursor mixture may be 500 to 700 ° C.

The softening point (T ₁ ) of the first glass precursor mixture and the softening point (T ₂ ) of the second glass precursor mixture may be such that T ₁ -T ₂ is 50 to 150 ° C.

The lead-free thick film resistor may have a diffraction peak in the region of 2? = 27 to 29 degrees and 2? = 30 to 32 degrees in an X-ray diffraction pattern using a CuK? Ray.

The lead-free thick film resistor may have a peak area intensity satisfying the following formula 1 in an X-ray diffraction pattern using a CuK? Ray.

[Equation 1]

In the above formula (1)

Wherein A _2θ0 is the sum of the diffraction peak area intensity of the 2θ = 20 to 36 ° region,

Wherein A is a diffraction peak area _2θ1 strength of 2θ = 27 to 29 ° region,

Wherein A is a diffraction peak area _2θ2 strength of 2θ = 30 to 32 ° area.

The lead-free thick film resistor may have a peak area intensity ratio satisfying the following expression (2) in an X-ray diffraction pattern using a CuK? Ray.

[Formula 2]

In the formula 2,

Wherein A is a diffraction peak area _2θ1 strength of 2θ = 27 to 29 ° region,

Wherein A is a diffraction peak area _2θ2 strength of 2θ = 30 to 32 ° area.

The lead-free thick-film resistor may have a resistance value Rs of 10? /? To 10 M? / ?, and a resistance value spread (CV) of 5% or less.

The lead-free thick film resistor may have 20 or less bubbles having a diameter of 80 mu m or more at an area of 1 mm x 1 mm.

The present invention can be an electronic component including the lead-free thick-film resistor described above.

The electronic component may be a circuit board, a chip resistor, an isolator element, a CR composite element, a module element, a capacitor or an inductor.

The lead-free thick-film resistor according to the present invention is advantageous in that it has a temperature characteristic, a current noise, an overload characteristic, and an anti-static characteristic in a wider range of resistance values than a conventional thick-film resistor including lead.

The lead-free thick-film resistor according to the present invention can provide a resistor having excellent surface uniformity and low resistance value (CV) due to the formation of a double network structure by forming a cross-linked structure in the first network and the second network, .

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a photograph of a lead-free thick-film resistor according to one embodiment of the present invention and one comparative example in which the surface uniformity is observed with an optical microscope. FIG.
2 is a graph of XRD measurement of a lead-free thick film resistor according to an embodiment of the present invention.
3 is a graph of XRD measurement of a lead-free thick film resistor according to one embodiment of the present invention and one comparative example.
4 is a graph showing a comparison XRD measurement of a lead-free thick-film resistor after drying and firing according to one embodiment of the present invention and one comparative example.
5 is a SEM photograph of a surface and a cross section of a lead-free thick film resistor according to an embodiment of the present invention. 5 (a) shows the surface of the resistor, and Fig. 5 (b) shows the surface of the resistor.

Hereinafter, the lead-free thick film resistor and the electronic component including the lead-free thick film resistor according to the present invention will be described in further detail with reference to examples. It should be understood, however, that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the invention.

Unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

The present invention relates to a first network derived from a first glass precursor mixture comprising a silicon oxide, a barium oxide, a boron oxide and an aluminum oxide, and a ruthenium complex oxide; And a second network derived from a second glass precursor mixture comprising silicon oxide, boron oxide and aluminum oxide, said first network and said second network being capable of forming a lead free thick film resistor formed to intersect with each other And completed the present invention.

As used herein, the term " dual network " refers to the formation of a second network by firing a mixture of a conductive composite powder and a second glass precursor having a first network formed by heat-treating a mixture of a ruthenium complex oxide and a first glass precursor, And the second network cross each other to form a more dense conductive path.

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

Hereinafter, one embodiment of the present invention will be described in more detail.

The lead free thick film resistor of the present invention comprises a first network derived from a first glass precursor mixture and a ruthenium complex oxide comprising silicon oxide, barium oxide, boron oxide and aluminum oxide; And a second network derived from a second glass precursor mixture comprising silicon oxide, boron oxide and aluminum oxide, wherein the first network and the second network are formed to intersect with each other. As described above, since the first network and the second network cross each other to form a dual network, a fine conductive path is uniformly formed and the surface uniformity is excellent. Thus, the resistance value dispersion, temperature characteristic, current noise, overload characteristic, It is possible to improve the prevention characteristics.

According to one aspect of the present invention, the second network forms a continuous phase and the first network forms a dispersed phase in the continuous phase, wherein the dispersed phase forms a crosslinked structure. The crosslinked structure may mean that the entire dispersed phase is connected to each other, and a part of the dispersed phase is connected to each other to form a crosslinked structure. For example, all or part of the first network dispersed phase may be connected with the second network to form a crosslinked structure while the dispersed phase, which is the first network, is formed in the continuous phase formed of the second network. The cross-linking structure is preferable because a fine and uniform conductive path can be ensured to further improve resistance value dispersion, temperature characteristics, current noise, overload characteristics, and antistatic characteristics.

According to an embodiment of the present invention, the first network may be formed by being derived from the first glass precursor mixture and the ruthenium complex oxide. The first glass precursor mixture and the ruthenium complex oxide may be heat treated to form a conductive composite powder having a first network. The ruthenium complex oxide is heat-treated with the first glass precursor mixture in one step to form a first network, and then the mixture is mixed with the second glass precursor mixture to form the ruthenium composite oxide in the first glass precursor mixture, 2 glass precursor mixture, the ruthenium composite oxide having the shape of XRuO ₃ is decomposed into XO and RuO ₂ , resulting in a lower resistivity and a remarkable decrease in the resistance value stability of the produced thick-film resistor. In addition, it may cause difficulties in maintaining electrical characteristics such as temperature characteristics and current noise characteristics. The XRuO ₃ And in XO, X is selected from Ca, Sr, Ba and the like.

In order to solve the above problems, a stable network structure is formed by using a conductive composite powder having a first network formed by heat-treating a mixture of a ruthenium complex oxide having a perovskite structure and a first glass precursor.

The conductive composite powder according to an embodiment of the present invention may be mixed with the second glass precursor mixture by heat-treating the mixture of the ruthenium complex oxide and the first glass precursor mixture at a heat treatment temperature in a specific range and then finely grinding the mixture. The average particle diameter of the conductive composite powder is not limited. For example, when the particle size of the conductive composite powder is measured to accumulate the volume from the small particle, the D50 having a particle size corresponding to 50% of the total volume may be 2.0 탆 or less . Preferably 1.0 to 2.0 mu m. As it is pulverized in the above range, it is preferable that the first network having excellent compatibility with the second glass precursor mixture and crossing with the second network can be uniformly formed.

According to an embodiment of the present invention, the heat treatment temperature may be heat treated at 700 to 900 ° C for 10 to 60 minutes to form a dense and uniform first network. Preferably at 700 to 850 DEG C for 10 to 40 minutes, but is not limited thereto.

The conductive composite powder thus formed can form a uniform primary network structure. The ruthenium-based composite oxide is mixed with the first glass precursor mixture and the ruthenium-based composite oxide due to the formation of the first network through heat treatment during the production of the lead- The reactivity with the second glass precursor mixture is suppressed and the ruthenium composite oxide is not decomposed, so that a stable and uniform double network structure can be formed.

When the thick film resistor is prepared singly from the conductive composite powder, there is a problem that the electrical properties are insufficient and the fluidity is insufficient, so that the smoothness of the thick film resistor and the adhesion with the substrate may be significantly lowered. And then fired to form a dense double network structure.

According to an aspect of the present invention, the first free precursor mixture may comprise silicon oxide, barium oxide, boron oxide, and aluminum oxide. The silicon oxide may be silicon dioxide (SiO ₂ ), the barium oxide may be barium oxide (BaO), the boron oxide may be boron trioxide (B ₂ O ₃ ), the aluminum oxide may be aluminum oxide Al ₂ O ₃ ). By including the silicon oxide, barium oxide, boron oxide and aluminum oxide, the reactivity with the ruthenium based composite oxide can be further improved and the first network structure can be formed more densely, which is preferable. Further, the compatibility between the first network and the second network induced by the mixture of the ruthenium complex oxide and the first glass precursor can be improved, which is preferable.

In particular, by incorporating barium oxide into the first glass precursor mixture, it is possible to form a crystal structure in which a more stable first network is formed in the reaction with the ruthenium composite oxide. The crystal structure may be a B-Ba-Si-Al system partial crystal structure. As the partial crystal structure is formed, mutual fusion with the second glass precursor mixture does not occur, and the distinction between the first network structure and the second network is clarified, so that a dual network can be formed. In addition, it is possible to suppress the formation of ruthenium oxide by the reaction between the ruthenium composite oxide and the second glass precursor mixture during the burning process of the lead-free thick-film resistor, thereby obtaining a more stable lead-free thick-film resistor.

According to one embodiment of the present invention, the ruthenium-based complex oxide is not limited as long as it is a ruthenium-based complex oxide having a perovskite-type crystal structure that is well known in the art. It may be, for example, calcium carbonate ruthenate (CaRuO _3), strontium carbonate ruthenate (SrRuO _3), and barium ruthenate carbonate (BaRuO ₃₎ one or a mixture of two or more selected from the. In addition, according to one embodiment of the present invention, the ruthenium composite oxide can be used alone or in combination with other ruthenium composite oxide (Ca _{1 -x- y} Sr _x Ba _y ) RuO ₃ . As one example of the above, (Ca _1-xy Sr _x Ba _y ) RuO ₃ 0 <x <0.8, 0? Y <0.8, and 0 <x + y <0.9.

The ruthenium complex oxides having the perovskite type crystal structure are preferable because they can maintain the temperature characteristics (TCR) and the overload characteristics (STOL) at 1 K? Or more.

According to one embodiment of the present invention, the ruthenium complex oxide is not limited, but a ruthenium complex oxide prepared according to the preparation method of Korean Patent No. 10-0840893 may be used.

For example, 1) a step of preparing a ruthenium salt aqueous solution by dissolving or alkali fusing a ruthenium metal powder in a strong acid or strong base; 2) mixing an aqueous solution of a strontium compound containing a dispersant into the aqueous solution of ruthenium salt prepared in the above step to obtain a hydrate strontium ruthenate; 3) heat treating the hydrate strontium ruthenate obtained in the above step at 320 to 1,000 ° C to obtain strontium ruthenate powder; 4) The strontium ruthenate powder obtained in the above step may be used by removing impurities using inorganic acid, but is not limited thereto.

According to an embodiment of the present invention, the ruthenium composite oxide is preferable because it can form a lead-free thick-film resistor having high electrical resistivity, high resistance, and less than 5% resistance value dispersion without causing structural change during heat treatment and firing .

According to an embodiment of the present invention, the conductive composite powder formed with the first network may include 20 to 80% by weight of the ruthenium composite oxide and 80 to 20% by weight of the first glass precursor mixture, more preferably the ruthenium composite oxide 30 To 70% by weight of the first glass precursor mixture and 70 to 30% by weight of the first glass precursor mixture. More preferably 40 to 60 wt% of the ruthenium based composite oxide and 60 to 40 wt% of the first glass precursor mixture to form the first network.

According to an embodiment of the present invention, when the mixture of the ruthenium composite oxide and the first glass precursor is included in the above-mentioned range, the first network structure is uniformly formed and the temperature characteristic (TCR), the overload characteristic (STOL) (ESD) is remarkably improved. In addition, it is possible to prevent the temperature characteristic from moving in the (-) direction by the conductive material, and it is preferable to maintain the stability of the crystal structure.

According to one aspect of the present invention, the second network may be formed from a second glass precursor mixture. The second glass precursor mixture may be mixed with the conductive composite powder formed with the first network and sintered so that the first network and the second network cross each other to form a double network. As described above, the first network and the second network cross each other to form a dual network, which is excellent in resistance value dispersion (CV) and resistance value reproducibility, and is excellent in temperature characteristics (TCR), overload characteristics (STOL) A lead-free thick-film resistor having excellent characteristics can be obtained.

According to an embodiment of the present invention, the conductive composite powder and the second glass precursor mixture may be contained in a weight ratio of 10:90 to 90:10, more preferably in a weight ratio of 20:80 to 80:20 to form a second network Thereby forming a dual network.

When included in the above range, the electrical characteristics of the lead-free thick-film resistor are improved, and a lead-free thick-film resistor having a uniform surface can be formed.

According to an embodiment of the present invention, the lead-free thick film resistor may have a dual network structure while a second network is formed by mixing a conductive composite powder formed with a first network and a second glass precursor mixture. And a double network structure may be formed by screen printing and then firing a mixture of the conductive composite powder and the second glass precursor mixture, on which the first network is formed, at the time of manufacturing. The substrate may be an alumina substrate, but is not limited thereto.

According to an embodiment of the present invention, the firing temperature can be heat treated at 700 to 900 ° C for 10 to 60 minutes. Preferably 800 to 900 占 폚 for 10 to 40 minutes, but is not limited thereto.

According to an embodiment of the present invention, the first glass precursor mixture and the second glass precursor mixture may contain one or more selected from transition metal oxides, alkali metal oxides, and alkaline earth metal oxides in order to improve reactivity with the ruthenium- Mixture. &Lt; / RTI &gt;

According to an embodiment of the present invention, 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 transition metal oxide may be included in the first glass precursor mixture and the second glass precursor mixture to form a lead-free thick-film resistor, thereby improving the temperature characteristics of the lead-free thick-film resistor.

The alkali metal oxide may be any one or a mixture of two or more selected from Na ₂ O, K ₂ O and Li ₂ O. The alkali metal oxide is preferably included in the first glass precursor mixture and the second glass precursor mixture to control the softening point.

The alkaline earth metal oxide may be any one or a mixture of two or more selected from SrO, CaO, and MgO. The alkaline earth metal oxide can control the reactivity with the ruthenium complex oxide.

A specific composition of the first glass precursor mixture according to an embodiment of the present invention is, for example, SiO ₂ 10 To 40% by weight _, B ₂ O ₃ 10 to 30% by weight, BaO 5 to 40% by weight, Al ₂ O ₃ 2 to 15% by weight of transition metal oxide, 0.1 to 20% by weight of transition metal oxide, and 15 to 40% by weight of alkali metal oxide and alkaline earth metal oxide. Preferably SiO ₂ 15 to 35% by weight, B ₂ O ₃ 15 to 30 wt%, BaO 10 to 30 wt%, Al ₂ O ₃ 4 to 15% by weight of transition metal oxide, 5 to 20% by weight of transition metal oxide, and 15 to 35% by weight of alkali metal oxide and alkaline earth metal oxide. The above composition is preferable because it is excellent in reactivity with the ruthenium composite oxide and can improve the electrical characteristics and durability.

Specific composition of the second glass precursor mixture in accordance with one aspect of the present invention, for example, SiO _2, 5 to 30 wt%, B ₂ O ₃ 10 to 40% by weight, Al ₂ O ₃ 2 to 15% by weight of transition metal oxide, 0.1 to 35% by weight of transition metal oxide, and 20 to 60% by weight of alkali metal oxide and alkaline earth metal oxide. Preferably SiO ₂ 5 to 20% by weight, B ₂ O ₃ 20 to 40% by weight, Al ₂ O ₃ 2 to 10% by weight of transition metal oxide, 2 to 30% by weight of transition metal oxide, and 25 to 60% by weight of alkali metal oxide and alkaline earth metal oxide. Since the composition is composed as described above, it is excellent in compatibility with the conductive composite powder and can be compounded to maintain a density of the lead-free thick film resistor and a smooth fired surface, and to form a uniform and dense double network structure with the conductive composite powder effective.

When the composition of the second glass precursor mixture is included in the composition of the second glass precursor mixture, the stability of the second glass precursor mixture is excellent, so that the coating film strength of the lead-free thick film resistor of the coating film is improved, the softening point is prevented from increasing, So that the characteristics are improved.

According to one aspect of the present invention, the second network may further comprise inorganic particles and conductive powder in the second glass precursor mixture to maintain the density and smooth and uniform surface of the lead free thick film resistor to form a second network.

According to an embodiment of the present invention, the inorganic particles include Nb ₂ O ₅ , Ta ₂ O ₅ , TiO ₂ , MnO ₂ , CuO, ZrO ₂ And ZnO. &Lt; / RTI &gt; The inorganic particles are preferably made of a lead-free thick-film resistor of the first glass precursor mixture and the second glass precursor mixture because electrical properties and fluidity can be improved.

The conductive powder may be any one selected from Ag, Au, Pd, Pt, Cu, Ni, W, Mo, Zn, Al, RuO _{2 ,} IrO ₂ , Rh ₂ O ₃ and AgPd or a mixture of two or more thereof. The conductive powder is included in the first glass precursor mixture and the second glass precursor mixture to form a lead-free thick-film resistor, thereby improving the electrical characteristics of the lead-free thick-film resistor.

More specifically, according to an embodiment, the second network comprises 10 to 65 wt% of conductive composite powder, 10 to 60 wt% of a second glass precursor mixture, 0.01 to 40 wt% of conductive powder and 0.1 to 10 wt% of inorganic particles . But is not limited to, 15 to 60 wt% of the conductive composite powder, 15 to 60 wt% of the second glass precursor mixture, 1 to 20 wt% of the conductive powder and 0.1 to 6 wt% of the inorganic particles . When the conductive composite powder, the second glass precursor mixture, the conductive powder and the inorganic particles are included in the above range, a uniform and dense double network structure is formed, and a temperature characteristic (TCR), an overload characteristic (STOL) ) Is improved and a lead-free thick film resistor having excellent smoothness and adhesion to a substrate can be produced.

According to an aspect of the present invention, a second network may be formed by further including a vehicle composed of an organic solvent and a binder in the second glass precursor mixture. The vehicle should meet rheological properties suitable for screen printing or the like by mixing the conductive composite powder and the second glass precursor mixture. Thus, the second glass precursor mixture can be mixed with a conventional vehicle and applied to paste, paint, or ink formation. But are not limited to, those publicly known in the art as the vehicle, for example, terpineol, carbitol, butyl carbitol, cellosolve, butyl cellosolve and esters thereof; Toluene, xylene, and the like; Ethyl cellulose, nitrocellulose, acrylic acid ester, methacrylic acid ester, rosin, and the like; or a mixture of two or more thereof; Etc. may be used. If necessary, it may further include any one or a mixture of two or more selected from plasticizers, viscosity modifiers, surfactants, antioxidants, metal organic compounds, and the like.

The compounding ratio of the vehicle is not limited as long as it is applied to a conventional lead-free thick-film resistor, and can be adjusted according to application methods such as printing.

The vehicle may preferably further comprise 0.01 to 100 parts by weight based on 100 parts by weight of the conductive composite powder, the second glass precursor mixture, the conductive powder and the inorganic particles. More preferably 0.1 to 50 parts by weight, per 100 parts by weight of the composition.

The organic solvent used in the vehicle may further include an organic solvent to improve the miscibility between the second glass precursor mixture and the conductive composite powder, but the present invention is not limited thereto. The organic solvent may further include 10 to 200 parts by weight, based on 100 parts by weight of the conductive composite powder, the second glass precursor mixture, the conductive powder and the inorganic particles. More preferably 20 to 100 parts by weight.

According to an embodiment of the present invention, the softening point (T ₁ ) of the first glass precursor mixture may be 600 to 800 ° C, and the softening point (T ₂ ) of the second glass precursor mixture may be 500 to 700 ° C. When the first glass precursor mixture has a softening point in the above range, the reactivity with the ruthenium complex oxide is improved, thereby forming the first network more uniformly and having a partial crystal structure during the heat treatment. Also, in the case of the softening point of the second glass precursor mixture in the above range, the firing temperature can be easily formed at 800 to 900 ° C in the second network which intersects with the first network, and the surface uniformity of the lead- It is preferable because it can exhibit excellent electrical characteristics. As described above, it is possible to control the different softening points of the first glass precursor mixture and the second glass precursor mixture depending on whether or not barium oxide is present. Since the barium oxide is not included in the second glass precursor mixture, It is possible to prevent a phenomenon that the resistance value scattering (CV) is increased due to high reactivity with the substrate.

According to an embodiment of the present invention, the softening point (T ₁ ) of the first glass precursor mixture and the softening point (T ₂ ) of the second glass precursor mixture may be such that T ₁ -T ₂ is 50 to 150 ° C. Preferably, T ₁ -T ₂ may be 80 to 110 ° C. When the softening point difference as described above is observed, mutual fusion of the first network and the second network does not occur at the time of firing, so that a dual network in which the first network and the second network cross each other can be formed.

In the present specification, an X-ray diffraction pattern obtained by using a Cu K? Ray includes X-ray diffraction results measured by the? -2? Method at normal temperature and atmospheric pressure and has a scanning rate of 2 占 min Ray diffraction. &Lt; / RTI &gt;

According to one embodiment of the present invention, in the lead-free thick film resistor, an X-ray diffraction pattern using CuK? Ray has diffraction peaks in the region of 2? = 27 to 29 占 and 2? = 30 to 32 占. The diffraction peak of the region is a diffraction peak appearing as a double network of the lead-free thick-film resistor is formed, and the lead-free thick-film resistor having the diffraction peak can exhibit excellent surface uniformity and electrical characteristics.

As shown in FIG. 2, the lead-free thick film resistor of the present invention was formed on a substrate, followed by drying at 150 ° C for 10 minutes and then baking at 850 ° C for 10 minutes to form a double network. When the X-ray diffraction pattern thereof is observed, it can be confirmed that the diffraction peak is located in the region of 2? = 28 占 and 2? = 30 占.

As shown in FIG. 3, in order to compare the lead-free thick-film resistor with the lead-free thick-film resistor according to an embodiment of the present invention, the lead-free thick-film resistor was formed on the substrate and dried at 150 ° C. for 10 minutes. And an X-ray diffraction pattern was observed. Unlike the embodiment of the present invention, in the comparative example, diffraction peaks are not located in the 2θ = 28 ° and 2θ = 30 ° regions, It can be confirmed that a dual network is not formed.

According to one embodiment of the present invention, the lead-free thick film resistor may have a peak area intensity satisfying the following formula 1 in an X-ray diffraction pattern using a CuK? Ray.

[Equation 1]

In the above formula (1)

Wherein A _2θ0 is the sum of the diffraction peak area intensity of the 2θ = 20 to 36 ° region,

Wherein A is a diffraction peak area _2θ1 strength of 2θ = 27 to 29 ° region,

Wherein A is a diffraction peak area _2θ2 strength of 2θ = 30 to 32 ° area.

을 만족할 수 있다.Preferably, the peak area intensity is

Can be satisfied.

When the lead-free thick film resistor of the present invention has a peak area strength satisfying the above-described formula (1), the first network and the second network may intersect with each other to form a double network. As the structure of the dual network is formed, the resistance value dispersion, temperature characteristic, current noise, overload characteristic, and anti-static characteristic of the lead-free thick film resistor are further improved, and a uniform surface can be formed.

According to one embodiment of the present invention, the lead-free thick film resistor may have a peak area intensity ratio satisfying the following expression (2) in an X-ray diffraction pattern using a CuK?

[Formula 2]

In the formula 2,

Wherein A is a diffraction peak area _2θ1 strength of 2θ = 27 to 29 ° region,

Wherein A is a diffraction peak area _2θ2 strength of 2θ = 30 to 32 ° area.

을 만족할 수 있다.Preferably, the peak area intensity ratio is

Can be satisfied.

It can be shown that a more dense and uniformly double network is formed between the first network and the second network when the lead-free thick film resistor of the present invention has the peak area intensity ratio satisfying the above-mentioned formula (2). As the dense and uniform double network structure is formed, it is preferable that the lead-free thick-film resistor can further improve the dispersion of the resistance value, the temperature characteristic, the current noise, the overload characteristic and the anti-static characteristic, and form a uniform surface.

As shown in FIG. 4, when the crystal structure in the drying process and the crystal structure after firing in the process before the formation of the second network after firing are compared with each other, the firing temperature of the lead- And the area intensity of the diffraction peak appears more strongly in the range of -20 to 32 [deg.], It can be confirmed that the second network is formed more densely and uniformly. On the other hand, in the case of the lead-free thick-film resistor fabricated by the comparative example, it is confirmed that even after the double network is fired, the double network connected to the first network and the second network by crossing each other is not formed like the structure of the lead- .

The lead free thick-film resistor of the present invention can be observed with an optical microscope to have a particle size of 80 占 퐉 or more, preferably 20 or less of 70 占 퐉 or more in particle size at an area of 1 mm 占 1 mm. Preferably, the number of bubbles may be 10 or less in the area of 1 mm x 1 mm. More preferably, the number of bubbles may be 5 or less in the area of 1 mm x 1 mm. As the number of bubbles decreases, a lead-free thick film resistor with excellent surface uniformity is produced. As the surface uniformity is better, the resistance value spread (CV) decreases and stable electrical characteristics can be exhibited. As shown in FIG. 1, the lead-free thick-film resistor of the present invention is a lead-free thick-film resistor having low electrical resistance (CV) and stable electrical characteristics by producing lead free thick-film resistor having excellent surface uniformity without bubbles at all .

According to an embodiment of the present invention, the lead-free thick-film resistor may have a resistance value Rs of 10? /? To 10 M? / ?, and a resistance value spread (CV) of 5% or less.

More specifically, the lead-free thick film resistor has a resistance Rs value of 10? /? To 10 M? / ?, a resistance value spread (CV) of 5% or less, a temperature characteristic (TCR) of -100 to 100 ppm / The noise (C-Noise) characteristic is less than 13dB, and the overload characteristic (STOL) measured at 1 / 8W rated power can be less than 0.15%.

More preferably, the lead-free thick film resistor has a resistance value Rs of 10? /? To 10 M? / ?, a resistance value spread (CV) of 5% or less, a temperature characteristic (TCR) of -70 to 70 ppm / The noise (C-Noise) characteristic is less than 12dB, and the overload characteristic (STOL) measured at 1 / 8W rated power can be less than 0.1%. The lead-free thick-film resistor satisfying the above physical properties is excellent in stability of resistance value, and is excellent in smoothness and adhesion to a substrate.

The present invention can include the lead-free thick film resistor described above in an electronic component according to an aspect.

According to an aspect of the present invention, the lead-free thick film resistor may be applied to a single-layer or multi-layer circuit board, a chip resistor, an isolator device, a CR composite device, a module device, a capacitor or an inductor.

Hereinafter, the lead-free thick film resistor and the electronic component including the lead-free thick film resistor according to the present invention will be described in further detail with reference to examples. It should be understood, however, that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the invention.

Unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

In addition, the unit of the additives not specifically described in the specification may be% by weight.

[Measurement of physical properties]

1. Resistance Scatter ( CV , coefficient of variation

Twenty lead-free thick-film resistors of the present invention are fabricated, and the respective resistance values are measured using a multimeter. Calculate mean and standard deviation values for these values, and divide the standard deviation of the resistance value by the average value to derive the resistance value spread (CV). The unit is expressed as a percentage.

2. Resistive  Temperature characteristics TCR , temperature coefficient of resistance

And checking the rate of change of the resistance value when the temperature was changed from 125 占 폚 to 25 占 폚 on the basis of the room temperature. Specifically, the resistance values at 25 ° C and 125 ° C are expressed by R ₂₅ and R ₁₂₅ (Ω / □), respectively, and TCR is derived from the following equation, and the unit is ppm / ° C.

[Mathematical Expression]

3. Short-time overload characteristics (STOL, short-time overload

로 하였다. 여기에서 R은 저항치(Ω/□)이다. 또한, 계산한 시험 전압이 200V를 넘는 저항치를 갖는 저항체에 대해서는, 시험 전압을 200V로 행하였다.The lead-free thick-film resistor was allowed to stand for 30 minutes after the test voltage was applied for 5 seconds, and the rate of change of the resistance value before and after the test was confirmed. The test voltage was 2.5 times the rated voltage. The rated voltage is

Respectively. Here, R is the resistance value (? /?). The test voltage was 200 V for a resistor having a resistance value at which the calculated test voltage exceeded 200 V.

4. Evaluation of Current Noise (C-NOISE)

After the fired lead-free thick-film resistor is mounted in the C-NOISE test equipment, the displayed resistance value and the NOISE value are measured.

5. ESD evaluation

The fired lead-free thick-film resistors are subjected to a voltage of 1 kV at a speed of several nanoseconds, one turn on, one turn off and five times, using an ESD test equipment (ELECTRO STATIC DISCHARGE SIMULATOR ESS-066). After applying a voltage of 1 kV and a resistance value, the change of the resistance value was calculated.

6. XRD  Determination of crystal structure through

The lead-free thick film resistor was placed on the sample plate horizontally using X-ray diffraction Ultima IV manufactured by Rigaku Co., Ltd., and 2θ values were measured from 10 ° to 80 ° under the following conditions. The measurement conditions were a tube voltage of 40 kV, a tube current of 40 mA, and an X-ray: CuK? (Wavelength? = 1. 541 Å). Diffraction peaks were confirmed by X-ray diffraction measurement.

7. Optical microscope  Lead free through Thick film  Check the surface uniformity of the resistor

The lead-free thick-film resistor was quantitatively evaluated by using an optical microscope to determine the number of resistor bubbles formed on the surface at a magnification x50 x100 x500.

[Examples 1-25 and Comparative Examples 1-9]

1) Preparation of a conductive composite powder having a first network

The composition of the first glass precursor mixture or the second glass precursor mixture described in the following Table 1 was mixed with a glass precursor mixture or a second glass precursor mixture to obtain a composition of the content (g) as shown in the following Table 2 Were weighed and mixed with a ball mill for 2 hours. The resultant sintered body was pulverized for 12 hours using a pulverizer to prepare a conductive composite powder having a first network with an average particle diameter of 1.5 μm.

2) Preparation of Lead Free Thick Film Resistance Composition

(G) as described in the Examples and Comparative Examples in the following Table 3, and 12% by weight of an ethyl cellulose resin as an organic binder and 16% by weight of a mixture of BCA (Butyl Carbitol Acetate) 3 and TPNL (Terpineol) An organic vehicle consisting of 88 wt% of solvent was used and a dispersant (BYK-111) was used as an additive. The above composition was stirred for 2 hours using a P / L mixer, and then dispersed using a 3-roll mill for 5 times and 5 times of pressing. The obtained paste-free thick film resist composition was aged at 65 ° C for 24 hours and adjusted by viscosity using an additional organic solvent TPNL (Terpineol), followed by filtration.

3) Manufacture of lead-free thick film resistor

An Ag-Pd conductor paste was screen printed in a U-pattern on an alumina substrate of 96% purity and dried at 150 ° C for 10 minutes. Ag was 95 wt% and Pd was 5 wt%. The dried specimen was fired at 850 ° C for 10 minutes. The lead-free thick film resistor composition according to the embodiment was screen-printed in a predetermined shape of 1 mm x 1 mm on the alumina substrate on which the conductor was formed, dried at 150 ° C for 10 minutes and then baked at 850 ° C for 10 minutes, A lead-free thick-film resistor was prepared.

The first glass precursor mixture The second glass precursor mixture 1G-1 1G-2 1G-3 1G-4 2G-1 2G-2 2G-3 week
castle
minute SiO ₂ 19 20 18 34 16 10 10 B ₂ O ₃ 17 18 16 23 26 23 30 BaO 18 19 17 11 - - - Al ₂ O ₃ 11 12 11 4 9 7 6 Transition metal oxide Nb ₂ O ₅ 5 - 10 - - - - Ta ₂ O ₅ - - - - - - - CuO 3 3 3 - 4 4 - ZrO ₂ 5 5 5 19 4 3 2 ZnO - - - - - - - Alkali metal oxide Na ₂ O 2 2 2 8 2 5 11 K ₂ O One One One One 2 4 - Alkaline earth metal oxide SrO 19 20 - - 20 24 41 CaO - - 17 - 17 20 - Sum 100 100 100 100 100 100 100 Softening point ℃
(Ts) 692 703 718 641 606 568 601

Conductive Composite Powder complex
One complex
2 complex
3 complex
4 complex
5 complex
6 complex
7 complex
8 complex
9 complex
10 complex
11 complex
12 complex
13 Comparison complex Ru-based composite oxide CaRuO ₃ 30 40 50  -  -  - 60 70 80 - - - 50 40 SrRuO ₃  - - - 30 40 50 - - - 60 70  80 - - The first glass precursor mixture 1G-1  70  60  50  -  -  -  40  30  20  -  -  - - - 1G-2  -  -  - 70 60 50 - - - 40 30 20 - - 1G-3 - - - - - - - - - - - - 50 - The second glass precursor mixture 2G-1 - - - - - - - - - - - - - 60

Content (g) conductivity
Composite powder Ruthenium series
Complex oxide Second glass
Precursor mixture Conductive powder Inorganic particle Vehicle Organic solvent Kinds content CaRuO ₃ SrRuO ₃ Kinds content RuO ₂ MnO ₂ Nb ₂ O ₅ Example 1 Compound 1 30 - - 2G-3 24.0 5.0 1.0 - 4.8 35.2 Example 2 Compound 2 26 - - 2G-3 26.5 7.5 - - 4.8 35.2 Example 3 Compound 3 30 - - 2G-3 27.5 2.0 0.5 - 4.8 35.2 Example 4 Compound 4 30 - - 2G-3 25.0 4.0 0.5 0.5 4.8 35.2 Example 5 Compound 5 26 - - 2G-3 28.5 5.0 0.5 - 4.8 35.2 Example 6 Compound 6 25 - - 2G-3 25.2 9.0 0.8 - 24 16 Example 7 Compound 6 25 - - 2G-3 21.5 10 1.5 2 24 16 Example 8 Compound 5 26.5 - - 2G-3 30 3 0.5 - 4.8 35.2 Example 9 Compound 2 29.5 - - 2G-3 21.5 8 1.0 - 4.8 35.2 Example 10 Compound 1 29.5 - - 2G-3 27.5 2 1.0 - 4.8 35.2 Example 11 Compound 7 25 - - 2G-3 33.0 1.0 1.0 - 4.8 35.2 Example 12 Compound 7 30 - - 2G-3 24.0 5.0 1.0 - 4.8 35.2 Example 13 Compound 8 22 - - 2G-3 35.5 2.0 - 0.5 4.8 35.2 Example 14 Compound 8 28 - - 2G-3 21.0 10 0.5 0.5 4.8 35.2 Example 15 Composite 9 26 - - 2G-3 25.5 8.0 0.5 - 4.8 35.2 Example 16 Composite 9 34 - - 2G-3 21.0 4.0 1.0 - 4.8 35.2 Example 17 Compound 10 25 - - 2G-3 23.0 10 1.0 1.0 4.8 35.2 Example 18 Compound 10 30 - - 2G-3 24.5 5.0 0.5 - 4.8 35.2 Example 19 Compound 11 32 - - 2G-3 19.0 8.0 1.0 - 4.8 35.2 Example 20 Compound 11 28 - - 2G-3 27.0 4.0 0.5 0.5 4.8 35.2 Example 21 Compound 12 20 - - 2G-3 34.0 5.0 0.5 0.5 4.8 35.2 Example 22 Compound 12 24 - - 2G-3 30.0 5.0 0.5 0.5 4.8 35.2 Example 23 Compound 1 35 - - 2G-3 25.0 0.0 - - 4.8 35.2 Example 24 Composite 9 25 - - 2G-3 33.0 0.0 1.0 1.0 4.8 35.2 Example 25 Compound 13 30 - - 2G-2 24.0 5.0 1.0 - 4.8 35.2 Comparative Example 1 compare
Compound 1 31 - - 2G-3 24.0 4.0 1.0 - 4.8 35.2 Comparative Example 2 - - 18 - 2G-3 39.0 2 1.0 - 4.8 35.2 Comparative Example 3 - - - 18 2G-3 39.0 2 1.0 - 4.8 35.2 Comparative Example 4 - - 15 - 2G-3 39 5 0.5 0.5 4.8 35.2 Comparative Example 5 - - 20 - 2G-3 29.0 10.0 1.0 - 4.8 35.2 Comparative Example 6 - - 25 - 2G-3 33.0 1.0 1.0 - 4.8 35.2 Comparative Example 7 - - - 22 2G-3 35.0 2.0 0.5 0.5 4.8 35.2 Comparative Example 8 - - - 25 2G-3 27.5 7.0 0.5 - 4.8 35.2 Comparative Example 9 Compound 1 54.0 - - - - 5.0 1.0 - 4.8 35.2

Sheet
Resistance
(Ω / □) TCR
(ppm / DEG C) CV
(%) Current noise
(dB) STOL
(%) surface
Uniformity
(Number of bubbles) Softening point tea
T ₁ -T ₂ Peak location
(°) peak
area
ratio
(Equation 1) peak
area
Intensity ratio
(Equation 2) 2? ₁ 2? ₂ Example 1 90.45K -13 1.11 7.5 0.02 0 91 28.17 30.24 38.86% 1.76 Example 2 9.12 K 50 1.46 2.2 -0.01 0 91 28.18 30.50 39.94% 2.13 Example 3 42.91K 32 3.62 4.6 0.01 0 91 28.17 30.53 38.66% 1.98 Example 4 413.6K -28 3.56 8.2 -0.03 0 91 28.16 30.33 38.43% 2.22 Example 5 15.62K 66 2.86 2.8 0.01 0 91 28.21 30.50 40.12% 1.60 Example 6 2.15K -37 1.6 2.1 0.01 0 91 28.22 30.44 43.34% 1.40 Example 7 13.4K 56 1.7 3.5 0.02 0 91 28.16 30.53 41.89% 1.41 Example 8 159.61K -20 4.27 9.4 -0.04 One 91 28.20 30.33 35.11% 2.16 Example 9 14.54K -38 3.85 3.7 -0.01 0 91 28.21 30.57 38.77% 1.60 Example 10 2.58M -17 3.01 11.8 -0.09 0 91 28.18 30.34 33.46% 1.41 Example 11 450.1K -42 3.55 6.8 0.05 0 102 28.15 30.88 34.21% 1.45 Example 12 180.2K -25 2.16 4.2 -0.04 0 102 28.26 30.23 33.94% 2.04 Example 13 340.7K -47 3.61 5.6 0.02 0 102 28.26 30.75 37.95% 1.44 Example 14 21.6K -21 2.56 3.5 -0.01 0 102 28.07 30.57 42.97% 1.45 Example 15 1.62K 66 4.86 2.8 0.01 One 102 28.17 30.73 45.77% 1.48 Example 16 20.2K -52 4.65 3.9 0.03 One 102 28.25 30.22 38.89% 1.65 Example 17 8.6K -60 3.7 2.5 0.02 0 102 28.21 30.55 40.12% 1.77 Example 18 40.5K -10 2.27 4.4 -0.03 0 102 28.35 30.70 38.01% 1.44 Example 19 18.5K -58 2.95 3.7 -0.04 0 102 28.30 30.21 37.65% 1.65 Example 20 210.5K -27 4.01 6.1 -0.02 Three 102 28.16 30.23 35.68% 1.87 Example 21 80.6K -20 4.5 5.5 0.02 One 102 28.22 30.53 37.98% 1.78 Example 22 60.4K -15 4.45 5.2 0.03 One 102 28.17 30.44 37.76% 1.81 Example 23 9.86M -56 4.25 12.4 -0.02 One 91 28.23 30.53 34.35% 2.12 Example 24 105.4 23.0 3.44 1.5 -0.02 0 102 28.21 30.50 41.66% 1.46 Comparative Example 1 120.4K 45.4 12.5 9.6 0.02 162 5 - - 18.01% - Comparative Example 2 0.7M -149 27.36 11.9 0.05 350 - - - 19.04% - Comparative Example 3 166.73M -312 17.21 45.5 0.25 311 - - - 18.61% - Comparative Example 4 24.5K -120 15.4 5.5 0.01 201 - - - 14.33% - Comparative Example 5 15.2K -50 11.2 3.1 -0.02 154 - - - 15.64% - Comparative Example 6 15.2M -160 12.3 20.9 0.35 177 - - - 18.66% - Comparative Example 7 6.2M -124 9.21 18.5 0.25 130 - - - 16.01% - Comparative Example 8 74.5K -80 7.4 7.8 0.05 88 - - - 17.99% - Comparative Example 9 174.5K -89 15.2 15.1 0.05 200 - - - 15.51% -

As shown in Table 4, it was confirmed that the lead-free thick film resistor of the present invention exhibited remarkably excellent temperature characteristics, current noise, overload characteristics and antistatic characteristics in a wide resistance value range. Further, it was confirmed that the surface uniformity was excellent and the resistance value spread (CV) was low, so that a uniform and dense resistor was produced.

As shown in FIG. 5, the second network is represented by a dark image in a continuous phase, and the first network is represented by a bright image in a dispersed phase within the continuous phase, thereby forming a network structure in which a dispersed phase is formed in the continuous phase, Respectively. As described above, the lead-free thick-film resistor of the present invention having a dual network has improved uniformity of the surface and improved resistance value spread (CV) and electrical characteristics.

In the case of Comparative Examples 1 to 8, since the ruthenium composite oxide does not include the conductive composite powder having the first network formed therein, a double network can not be formed and the ruthenium complex oxide is decomposed, It was confirmed that the stability of the resistance value was remarkably decreased as the surface of the thick-film resistor had an uneven surface, and the temperature characteristics and the property of the current noise were deteriorated. In the case of Comparative Example 9, since the lead-free thick film resistor was manufactured by applying only the conductive composite powder formed with the first network, the flowability was reduced when the lead-free thick-film resistor was formed on the substrate and the uniformity of the surface of the resistor was remarkably decreased, And the stability was deteriorated.

As described above, according to the present invention, the lead-free thick film resistor and the electronic component including the lead-free thick film resistor have been described through the specified matters and the limited embodiments. However, the present invention is only provided for better understanding of the present invention. And various modifications and changes may be made thereto by those skilled in the art to which the present invention pertains.

Accordingly, the spirit of the present invention should not be construed as being limited to the embodiments described, and all of the equivalents or equivalents of the claims, as well as the following claims, belong to the scope of the present invention .

Claims (13)

A first network induced by a one-step heat treatment of a first glass precursor mixture comprising silicon oxide, barium oxide, boron oxide and aluminum oxide and a ruthenium-based complex oxide; And
And a second network further comprising a second glass precursor mixture comprising silicon oxide, boron oxide and aluminum oxide, followed by a two step calcination,
Wherein the second network forms a continuous phase and the first network forms a dispersed phase within the continuous phase, wherein the dispersed phase forms a crosslinked structure,
Wherein the first network and the second network are formed to cross each other. delete The method according to claim 1,
Wherein the first glass precursor mixture and the second glass precursor mixture further comprise any one or a mixture of two or more selected from transition metal oxides, alkali metal oxides and alkaline earth metal oxides. The method of claim 3,
Wherein the transition metal oxide is 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 oxide is any one or a mixture of two or more selected from Na ₂ O, K ₂ O and Li ₂ O,
Wherein the alkaline earth metal oxide is any one or a mixture of two or more selected from SrO, CaO and MgO. The method according to claim 1,
Wherein the softening point (T ₁ ) of the first glass precursor mixture is between 600 and 800 ° C and the softening point (T ₂ ) of the second glass precursor mixture is between 500 and 700 ° C. 6. The method of claim 5,
The first softening point of the glass precursor mixtures (T ₁₎ and a second softening point of the glass precursor mixtures (T ₂₎ is lead-free thick-film resistor, characterized in that T ₁ -T ₂ is 50 to 150 ℃. The method according to claim 1,
Wherein the lead-free thick film resistor has an X-ray diffraction pattern using a CuK? Ray, wherein diffraction peaks in a region of 2? = 27 to 29 degrees and 2? = 30 to 32 degrees are located. 8. The method of claim 7,
Wherein the lead-free thick film resistor has an X-ray diffraction pattern using a CuK? Ray and has a peak area strength satisfying the following formula (1).
[Formula 1]

In the above formula (1)
Wherein A _2θ0 is the sum of the diffraction peak area intensity of the 2θ = 20 to 36 ° region,
Wherein A is a diffraction peak area _2θ1 strength of 2θ = 27 to 29 ° region,
Wherein A is a diffraction peak area _2θ2 strength of 2θ = 30 to 32 ° area.
9. The method of claim 8,
Wherein the lead-free thick film resistor has an X-ray diffraction pattern using a CuK? Ray having a peak area intensity ratio satisfying the following formula (2).
[Formula 2]

In the formula 2,
Wherein A is a diffraction peak area _2θ1 strength of 2θ = 27 to 29 ° region,
Wherein A is a diffraction peak area _2θ2 strength of 2θ = 30 to 32 ° area. The method according to claim 1,
Wherein the lead-free thick-film resistor has a resistance (Rs) value of 10? /? To 10 M? / ?, and a resistance value spread (CV) of 5% or less. The method according to claim 1,
Wherein the lead-free thick-film resistor has an area of 1 mm x 1 mm and the number of bubbles having a diameter of 80 m or more is 20 or less.  An electronic device comprising the lead-free thick film resistor according to any one of claims 1 to 11. 13. The method of claim 12,
Wherein the electronic component is a circuit board, a chip resistor, an isolator element, a CR composite element, a module element, a capacitor or an inductor.

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