WO2018147713A1 - 무연 후막 저항체 및 이를 포함하는 전자부품 - Google Patents

무연 후막 저항체 및 이를 포함하는 전자부품 Download PDF

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WO2018147713A1
WO2018147713A1 PCT/KR2018/001903 KR2018001903W WO2018147713A1 WO 2018147713 A1 WO2018147713 A1 WO 2018147713A1 KR 2018001903 W KR2018001903 W KR 2018001903W WO 2018147713 A1 WO2018147713 A1 WO 2018147713A1
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Prior art keywords
lead
thick film
film resistor
free thick
network
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PCT/KR2018/001903
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English (en)
French (fr)
Korean (ko)
Inventor
우동준
이혜성
김경용
강성학
임종찬
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대주전자재료 주식회사
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Priority to JP2019543789A priority Critical patent/JP6975246B2/ja
Priority to CN201880024662.9A priority patent/CN110494937B/zh
Publication of WO2018147713A1 publication Critical patent/WO2018147713A1/ko

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/14—Conductive material dispersed in non-conductive inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C1/00—Details
    • H01C1/14—Terminals or tapping points or electrodes specially adapted for resistors; Arrangements of terminals or tapping points or electrodes on resistors
    • H01C1/142—Terminals or tapping points or electrodes specially adapted for resistors; Arrangements of terminals or tapping points or electrodes on resistors the terminals or tapping points being coated on the resistive element
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/16—Printed circuits incorporating printed electric components, e.g. printed resistor, capacitor, inductor
    • H05K1/167—Printed circuits incorporating printed electric components, e.g. printed resistor, capacitor, inductor incorporating printed resistors

Definitions

  • the present invention relates to a lead-free thick film resistor and an electronic component comprising the same. More specifically, a lead-free thick film resistor having improved temperature characteristics, current noise, overload characteristics, and antistatic characteristics in a wide range of resistances even though lead components are removed by forming a double network structure in which the first network and the second network cross each other. And it relates to an electronic component comprising the same.
  • Thick film resistor compositions for the manufacture of thick film resistors generally consist of an organic vehicle composed of a glass component, a conductor material, a binder, and a solvent to control resistance and impart bonding properties. After printing on the substrate, the thick film resistor is formed by firing.
  • the conventional thick film resistance composition uses lead, such as glass components, such as lead oxide type glass, and electroconductive materials, such as ruthenium oxide or the compound of ruthenium oxide and lead, and contains lead.
  • lead such as glass components, such as lead oxide type glass
  • electroconductive materials such as ruthenium oxide or the compound of ruthenium oxide and lead
  • ruthenium (RuO 2) based thick film resistor Thiick Film Resistor
  • RuO 2 thick film resistor
  • glass containing lead has been recently banned due to environmental regulations, and is known to be incompatible with the aluminum nitride substrate due to low adhesion and blister generation.
  • oxides especially lead oxide (PbO)
  • PbO lead oxide
  • aluminum nitride which is a substrate
  • Pb lead oxide
  • nitrogen gas is generated, which may cause 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.
  • the temperature resistance coefficient of the final thick film resistance is controlled by adjusting the composition of the glass component or adding a component having a low resistance temperature coefficient. It is necessary to make an effort to lower it.
  • Patent Document 1 provides a resistor having a high resistance value and a low temperature characteristic and a short time overload by using a glass component substantially free of lead and NiO.
  • a resistive paste that can be used is disclosed.
  • Patent Document 2 uses a ruthenium oxide (RuO 2 ) powder having a rutile crystal structure to determine the content of ruthenium.
  • the composition for thick film resistors and thick film resistors which have sufficient performance even if low is disclosed.
  • the glass component is changed or ruthenium oxide having a rutile crystal structure is used as described above, the growth of particles is suppressed during firing of the resist composition, so that the resistivity is lowered and the resistance value stability and temperature characteristics of the thick film resistor ( Electrical characteristics such as TCR) and C-Noise were significantly reduced.
  • the RuO 2 powder and the glass component are generally mixed in the preparation of the resist composition, it is difficult to obtain a uniform mixing state between the components. Because of this, it is difficult to obtain a uniform microstructure after firing in the thick-film resistor, and as a result, the change of the electrical properties of the thick-film resistor increased, so that the stability of the thick-film resistor remained.
  • the present invention comprises a first network derived from the first glass precursor mixture and ruthenium-based composite oxide including silicon oxide, barium oxide, boron oxide and aluminum oxide; And a second network derived from a second glass precursor mixture including silicon oxide, boron oxide, and aluminum oxide, wherein the first network and the second network cross each other to provide a lead-free thick film resistor. do.
  • first network and the second network form a cross-linked structure to form a double network structure, fine conductive paths are uniformly formed so that temperature characteristics, resistance dispersion, current noise, overload characteristics and
  • An object of the present invention is to provide a lead-free thick film resistor having improved antistatic properties.
  • Another object of the present invention is to provide an electronic component including the lead-free thick film resistor described above.
  • the second network may form a continuous phase and the first network may form a dispersed phase in the continuous phase, and the dispersed phase may form a crosslinked structure.
  • the first glass precursor mixture and the second glass precursor mixture may further include any one or a mixture of two or more selected from transition metal oxides, alkali metal oxides and alkaline earth metal oxides.
  • 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, wherein the alkali metal oxide is Na 2 O, a mixture or two or more of any one selected from K 2 O and Li 2 O, 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.
  • 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 50 to 150 °C T 1 -T 2 .
  • the lead-free thick film resistor may have a peak area intensity that satisfies Equation 1 in an X-ray diffraction pattern using CuK ⁇ rays.
  • the lead-free thick film resistor may have a peak area intensity ratio that satisfies Equation 2 in an X-ray diffraction pattern using CuK ⁇ rays.
  • the lead-free thick film resistor has a resistance (Rs) of 10 ⁇ / ⁇ to 10M ⁇ / ⁇ , the resistance value distribution (CV) may be 5% or less.
  • the lead-free thick film resistor may have a number of bubbles of 20 ⁇ m or more in a diameter of 1 mm ⁇ 1 mm or less.
  • the present invention may 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 device, a C-R composite device, a module device, a capacitor, or an inductor.
  • the lead-free thick film resistor according to the present invention has the advantage that the temperature characteristics, current noise, overload characteristics and antistatic properties are remarkably excellent in the range of resistance values wider than the conventional thick film resistors containing no lead.
  • the lead-free thick film resistor according to the present invention has an advantage that the first network and the second network form a cross-linked structure to form a double network structure, thereby providing excellent resistance to surface uniformity and low resistance spread (CV), thereby providing a resistor having excellent stability. There is this.
  • 1 is a photograph of the surface uniformity of the lead-free thick film resistor according to an embodiment and one comparative example of the present invention with an optical microscope.
  • FIG. 2 is an XRD measurement graph of a lead-free thick film resistor according to an embodiment of the present invention.
  • FIG. 3 is an XRD measurement graph of a lead-free thick film resistor according to an embodiment and a comparative example of the present invention.
  • FIG. 4 is a graph of comparative XRD measurement after drying and after baking of a lead-free thick film resistor according to one embodiment and one comparative example of the present invention.
  • Figure 5 shows a SEM photograph of the surface and cross section of the lead-free thick film resistor according to an embodiment of the present invention.
  • Fig. 5A is the resistor surface
  • Fig. 5B is the resistor cross section.
  • the present invention comprises a first network derived from a first glass precursor mixture and a ruthenium-based composite oxide including silicon oxide, barium oxide, boron oxide and aluminum oxide; And a second network derived from a second glass precursor mixture including silicon oxide, boron oxide, and aluminum oxide, wherein the first network and the second network may form a lead-free thick film resistor formed to cross each other.
  • the present invention was completed by finding out.
  • the "dual network” is a heat treatment of the ruthenium-based composite oxide and the first glass precursor mixture to form a second network by firing the conductive composite powder and the second glass precursor mixture on which the first network is formed. And a second network intersecting with each other to form a more dense conductive path.
  • lead-free means a lead component of 1000 ppm or less, preferably 500 ppm or less in the thick film resistor.
  • the lead-free thick film resistor of the present invention comprises a first network derived from a first glass precursor mixture and a ruthenium-based composite oxide including silicon oxide, barium oxide, boron oxide and aluminum oxide; And a second network derived from a second glass precursor mixture including silicon oxide, boron oxide, and aluminum oxide, wherein the first network and the second network may be formed to cross each other.
  • the first network and the second network cross each other to form a double network, the fine conductive paths are uniformly formed and the surface uniformity is excellent, thereby spreading resistance values, temperature characteristics, current noise, overload characteristics, and static electricity in a wide resistance range. Preventive properties can be improved.
  • the second network may form a continuous phase and the first network may form a dispersed phase in the continuous phase, and the dispersed phase may form a crosslinked structure.
  • the crosslinked structure may mean that the entire dispersed phase is connected to each other, and a portion of the dispersed phase may be connected to each other to form a crosslinked structure.
  • the first network distributed phase may be formed in a continuous phase formed of the second network, and all or part of the first network distributed phase may be connected to the second network to form a crosslinked structure. Due to the crosslinked structure, it is preferable to obtain a fine and uniform conductive path, thereby improving resistance distribution, temperature characteristics, current noise, overload characteristics, and antistatic characteristics.
  • the first network may be formed derived from the first glass precursor mixture and the ruthenium-based composite oxide.
  • the first glass precursor mixture and the ruthenium-based composite oxide may be prepared as a conductive composite powder having a first network formed by heat treatment.
  • the ruthenium-based composite oxide is thermally treated with the first glass precursor mixture in one step to form a first network, and then mixed with the second glass precursor mixture, without two-step firing, and the ruthenium-based composite oxide is mixed with the first glass precursor mixture and first.
  • ruthenium-based composite oxides having the shape of XRuO 3 are decomposed into XO and RuO 2 to lower specific resistance and significantly reduce resistance value stability of the manufactured thick film resistor. In addition to this, it may cause difficulty in maintaining electrical characteristics such as temperature characteristics and current noise characteristics.
  • X in XRuO 3 and XO is selected from Ca, Sr, Ba and the like.
  • a ruthenium-based composite oxide having a perovskite structure and a first glass precursor mixture are heat-treated to form a stable network structure by using a conductive composite powder having a first network.
  • the conductive composite powder according to an aspect of the present invention may be mixed with the second glass precursor mixture by heat treatment of the mixture of the ruthenium-based composite oxide and the first glass precursor mixture at a heat treatment temperature of a specific range, followed by pulverization.
  • the average particle diameter of the conductive composite powder is not limited, for example, when the volume is accumulated from the small particles by measuring the particle diameter of each conductive composite powder, a particle size D50 corresponding to a total volume of 50% may be 2.0 ⁇ m or less. . Preferably it may be 1.0 to 2.0 ⁇ m.
  • the second glass precursor mixture is excellent in compatibility with each other, and thus it is preferable to uniformly form the first network intersecting with the second network.
  • 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.
  • the heat treatment may be performed at 700 to 850 ° C. for 10 to 40 minutes, but is not limited thereto.
  • the conductive composite powder formed as described above may form a uniform primary network structure, and as the ruthenium-based composite oxide is formed with the first glass precursor mixture and the first network through heat treatment during manufacture of the lead-free thick film resistor, the ruthenium-based composite oxide and Reactivity with the second glass precursor mixture is suppressed, so that the ruthenium-based composite oxide does not decompose, thereby forming a stable and uniform double network structure.
  • 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 reduced, so that it is mixed with the second glass precursor mixture. It is then desirable to form a dense double network structure by firing.
  • the first glass precursor mixture may include 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 ).
  • the silicon oxide, barium oxide, boron oxide and aluminum oxide it is preferable to further improve the reactivity with the ruthenium-based composite oxide to form the first network structure more densely.
  • the compatibility of the first network and the second network derived from the ruthenium-based composite oxide and the first glass precursor mixture can be improved, which is preferable.
  • the barium oxide in the first glass precursor mixture it is possible to form a crystal structure in which a first network more stable in the reaction with the ruthenium-based composite oxide is formed.
  • the crystal structure may be a B-Ba-Si-Al based partial crystal structure.
  • a fusion between the second glass precursor mixture does not occur and the first network structure and the second network are clearly distinguished, thereby forming a double network.
  • the generation of ruthenium oxide by the reaction of the ruthenium-based composite oxide and the second glass precursor mixture in the process of firing the lead-free thick film resistor can be suppressed, so that a more stable lead-free thick film resistor can be obtained.
  • the ruthenium-based composite oxide is not limited as long as it is a ruthenium-based composite oxide having a perovskite crystal structure 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.
  • the ruthenium-based composite oxide may be used alone or in combination with other ruthenium-based composite oxides (Ca 1-xy Sr X Ba y ) RuO 3 . Examples include the work of (Ca 1-xy Sr y Ba X) in RuO 3 0 ⁇ x ⁇ 0.8, 0 ⁇ y ⁇ 0.8, 0 ⁇ x + y ⁇ 0.9 are satisfied.
  • the ruthenium-based composite oxide having the perovskite crystal structure is particularly preferable because it can play a role of maintaining temperature characteristics (TCR) and overload characteristics (STOL) at 1 K ⁇ or more.
  • Ruthenium-based composite oxide is not limited according to an aspect of the present invention, it may be used a ruthenium-based composite oxide prepared according to the manufacturing method of Korean Patent No. 10-0840893.
  • ruthenium metal powder for example, 1) dissolving ruthenium metal powder in strong acid or strong base or alkali fusion to prepare a ruthenium salt aqueous solution; 2) mixing the aqueous solution of strontium compound containing a dispersant with the aqueous solution of ruthenium salt prepared in the above step to obtain a hydrated 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 to remove impurities using an inorganic acid, but is not limited thereto.
  • the ruthenium-based composite oxide is preferable because it can form a lead-free thick film resistor having high electrical resistance and excellent electrical properties such that no structural change occurs in the heat treatment and sintering process and the resistance distribution is 5% or less. .
  • the conductive composite powder in which the first network is formed may include 20 to 80% by weight of the ruthenium-based composite oxide and 80 to 20% by weight of the first glass precursor mixture, and more preferably, the ruthenium-based composite oxide 30 To 70% by weight and 70 to 30% by weight of the first glass precursor mixture. More preferably, the first network may be formed by including 40 to 60 wt% of the ruthenium-based composite oxide and 60 to 40 wt% of the first glass precursor mixture.
  • the first network structure is uniformly formed, and the temperature characteristic (TCR), the overload characteristic (STOL), and the antistatic characteristic (ESD) is remarkably improved and preferable.
  • TCR temperature characteristic
  • STOL overload characteristic
  • ESD antistatic characteristic
  • the second network may be formed derived from the second glass precursor mixture.
  • the second glass precursor mixture may be mixed with the conductive composite powder having the first network and fired so that the first network and the second network cross each other to form a double network.
  • CV resistance distribution
  • TCR temperature characteristics
  • STOL overload characteristics
  • ESD antistatic characteristics
  • the conductive composite powder and the second glass precursor mixture may be included in a weight ratio of 10:90 to 90:10 and more preferably in a 20:80 to 80:10 weight ratio to form a second network.
  • a weight ratio of 10:90 to 90:10 and more preferably in a 20:80 to 80:10 weight ratio to form a second network.
  • the electrical properties of the lead-free thick film resistor is improved, it is preferable to form a lead-free thick film resistor having a uniform surface.
  • the lead-free thick film resistor may have a dual network structure while forming a second network by mixing a conductive composite powder having a first network and a second glass precursor mixture.
  • a mixture of the conductive composite powder and the second glass precursor mixture having the first network formed thereon may be formed by screen printing on a substrate and then baked to form a double network structure.
  • the substrate may be an alumina substrate, but is not limited thereto.
  • the firing temperature may be heat treated at 700 to 900 ° C. for 10 to 60 minutes.
  • the heat treatment may be performed at 800 to 900 ° C. for 10 to 40 minutes, but is not limited thereto.
  • the first glass precursor mixture and the second glass precursor mixture are any one or two or more selected from transition metal oxides, alkali metal oxides and alkaline earth metal oxides in order to improve reactivity with ruthenium-based composite oxides. It may further comprise a mixture.
  • the transition metal oxide is Nb 2 O 5 , Ta 2 O 5 , TiO 2 , MnO 2 , CuO, ZrO 2 , May be any one or a mixture of two or more selected from WO 3 and ZnO.
  • the transition metal oxide may improve the temperature characteristics of the lead-free thick-film resistor whereby the first glass precursor mixture and the two are included in the glass precursor mixture made of lead-free thick-film resistor It is preferable to make it possible.
  • 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 adjust 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 may control the reactivity with the ruthenium-based composite oxide.
  • the specific composition of the first glass precursor mixture may be, for example, SiO 2 10.
  • SiO 2 to 40% by weight , 10 to 30% by weight of B 2 O 3 , 5 to 40% by weight of BaO, 2 to 15% by weight of Al 2 O 3 , 0.1 to 20% by weight of transition metal oxides and 15 to 20 alkali metal oxides and alkaline earth metal oxides. It may be included in an amount of 40% by weight.
  • the specific composition of the second glass precursor mixture may be, for example, SiO 2 5-30 wt%, B 2 O 3 10-40 wt%, Al 2 O 3 2-15 wt%, transition metal Oxide may be included in an amount of 0.1 to 35% by weight and 20 to 60% by weight of alkali metal oxides and alkaline earth metal oxides.
  • the composition as described above it is excellent in compatibility and compounding with the conductive composite powder to maintain the density and smooth plastic surface of the lead-free thick film resistor and form a uniform and dense double network structure with the conductive composite powder. effective.
  • the stability of the second glass precursor mixture is excellent, so that the film strength of the lead-free thick film resistor of the coating film can be improved, and an increase in the softening point can be prevented.
  • the characteristic is improved and preferable.
  • the second network may further include inorganic particles and conductive powder in the second glass precursor mixture to form a second network in order to maintain the density and smooth and uniform surface of the lead-free thick film resistor.
  • the inorganic particles 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, and ZnO.
  • 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, thereby improving electrical characteristics and fluidity.
  • the conductive powder is Ag, Au, Pd, Pt, Cu, Ni, W, Mo, Zn, Al, RuO 2 , It may be any one or a mixture of two or more selected from IrO 2 , Rh 2 O 3 and AgPd.
  • the conductive powder is included in the first glass precursor mixture and the second glass precursor mixture to be produced as a lead-free thick film resistor, so that the electrical properties of the lead-free thick film resistor can be improved.
  • the second network includes 10 to 65 wt% of the conductive composite powder, 10 to 60 wt% of the second glass precursor mixture, 0.01 to 40 wt% of the conductive powder, and 0.1 to 10 wt% of the inorganic particles.
  • 15 to 60% by weight of the conductive composite powder, 15 to 60% by weight of the second glass precursor mixture, 1 to 20% by weight of the conductive powder, and 0.1 to 6% by weight of the inorganic particles may be derived, but are not limited thereto. .
  • 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, the temperature characteristic (TCR), the overload characteristic (STOL), and the antistatic characteristic (ESD ) Is improved, so that a lead-free thick film resistor having excellent smoothness and adhesion to the substrate can be produced.
  • the second glass precursor mixture may further include a vehicle including an organic solvent and a binder to form a second network.
  • the vehicle must meet suitable rheological properties in order to apply the conductive composite powder and the second glass precursor mixture by screen printing.
  • the second glass precursor mixture may be mixed with a conventional vehicle and applied to paste, paint, or ink formation.
  • the vehicle is not limited as long as it is well known in the art, and examples thereof include terpineol, carbitol, butylcarbitol, cellosolve, butyl cellosolve, and esters thereof; Any one or two or more organic solvents selected from toluene, xylene and the like; Binder resin which is any one or a mixture of two or more selected from ethyl cellulose, nitrocellulose, acrylic acid ester, methacrylic acid ester, rosin and the like; Mixed solutions may be used. If necessary, it may further include any one or a mixture of two or more selected from a plasticizer, a viscosity modifier, a surfactant, an antioxidant, a metal organic compound, and the like.
  • the compounding ratio of the vehicle is also not limited as long as it is a range applied to a conventional lead-free thick film resistor, and may be adjusted according to an application method 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 may be further included, but is not limited thereto.
  • organic solvent may preferably further comprise 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, but may further include 20 to 100 parts by weight, but is not limited thereto.
  • the softening point T 1 of the first glass precursor mixture may be 600 to 800 ° C.
  • the softening point T 2 of the second glass precursor mixture may be 500 to 700 ° C.
  • the reactivity with the ruthenium-based composite oxide may be improved to more uniformly form the first network, and may have a partial crystal structure during heat treatment.
  • the firing temperature is easy to form a second network intersecting with the first network at 800 to 900 ° C., and the surface uniformity of the lead-free thick film resistor is improved, thereby reducing the resistance spread.
  • having a different softening point of the first glass precursor mixture and the second glass precursor mixture can be controlled according to the presence or absence of barium oxide, and the barium oxide is not included in the second glass precursor mixture. It is possible to prevent the phenomenon that the resistance spread value CV becomes high due to high reactivity with the substrate.
  • the first softening point of the glass precursor mixtures (T 1) and a second softening point of the glass precursor mixtures (T 2) may be one of T 1 -T 2 is 50 to 150 °C.
  • T 1 -T 2 may be 80 to 110 °C.
  • the X-ray diffraction pattern obtained using the CuK ⁇ ray includes the X-ray diffraction results measured by the ⁇ -2 ⁇ method at room temperature and normal pressure, and is measured at a scan rate of 2 ° / min. Included X-ray diffraction results.
  • the diffraction peak of the region is a diffraction peak that appears as a double network of the lead-free thick film resistor is formed, and may indicate that the lead-free thick film resistor having the diffraction peak has excellent surface uniformity and electrical characteristics.
  • the lead-free thick film resistor of the present invention was formed on a substrate, dried at 150 ° C. for 10 minutes, and then fired at 850 ° C. for 10 minutes to form a double network.
  • the lead-free thick film resistor may have a peak area intensity that satisfies Equation 1 below in an X-ray diffraction pattern using CuK ⁇ rays.
  • the peak area intensity is Can be satisfied.
  • the lead-free thick film resistor of the present invention has a peak area intensity that satisfies Equation 1, it may represent that the first network and the second network cross each other to form a double network.
  • the double network structure it is preferable to further improve resistance distribution, temperature characteristics, current noise, overload characteristics, and antistatic characteristics of the lead-free thick film resistor, and to form a uniform surface.
  • the lead-free thick film resistor may have a peak area intensity ratio that satisfies Equation 2 below in an X-ray diffraction pattern using CuK ⁇ rays.
  • the peak area intensity ratio is Can be satisfied.
  • the lead-free thick film resistor of the present invention has a peak area intensity ratio that satisfies Equation 2, it may indicate that a double network is formed more densely and uniformly between the first network and the second network.
  • the dense and uniform double network structure it is preferable to further improve resistance distribution, temperature characteristic, current noise, overload characteristic, and antistatic characteristic of the lead-free thick film resistor, and to form a uniform surface.
  • the lead-free thick film resistor of the present invention may be observed in an optical microscope to have a number of bubbles of 80 ⁇ m or more, preferably 70 ⁇ m or more in a 1 mm ⁇ 1 mm area.
  • the number of bubbles in the 1 mm x 1 mm area may be five or less. More preferably, the number of bubbles in the 1 mm x 1 mm area may be zero or less, that is, no bubbles.
  • a lead-free thick film resistor having excellent surface uniformity is prepared, and as the surface uniformity is excellent, resistance spread (CV) is reduced, which is preferable because it can exhibit stable electrical characteristics.
  • the lead-free thick film resistor of the present invention is a lead-free thick film resistor having a stable electrical property with low resistance value dispersion (CV) due to the manufacture of a lead-free thick film resistor having excellent surface uniformity in which bubbles are not generated at all, as shown in FIG. 1. .
  • the lead-free thick film resistor may have a resistance (Rs) of 10 ⁇ / ⁇ to 10 M ⁇ / ⁇ and a resistance distribution (CV) of 5% or less.
  • the lead-free thick film resistor has a resistance (Rs) of 10 ⁇ / ⁇ to 10M ⁇ / ⁇ , resistance spread (CV) of 5% or less, temperature characteristic (TCR) of -100 to 100 ppm / ° C, and 1
  • the overload characteristic (STOL) measured at / 8W rated power can be less than 0.15%.
  • the lead-free thick film resistor has a resistance (Rs) of 10 ⁇ / ⁇ to 10M ⁇ / ⁇ , resistance spread (CV) of 5% or less, temperature characteristic (TCR) of -70 to 70 ppm / ° C, and 1
  • the overload characteristic (STOL) measured at / 8W rated power can be less than 0.1%.
  • the resistance of the lead-free thick film resistor that satisfies the above properties is excellent, and there is an advantage in that smoothness and adhesion to the substrate are excellent.
  • the present invention may include the lead-free thick film resistor described above in an electronic component according to one aspect.
  • the lead-free thick film resistor may be applied to a single layer or a multilayer circuit board, a chip resistor, an isolator element, a C-R composite element, a module element, a capacitor or an inductor as an electronic component.
  • the unit of the additive which is not specifically described in the specification may be wt%.
  • test voltage was applied to the lead-free thick film resistor for 5 seconds, it was left to stand for 30 minutes and confirmed by checking the rate of change of the resistance value before and after.
  • the test voltage was 2.5 times the rated voltage.
  • Rated voltage It was set as. Where R is the resistance value ( ⁇ / ⁇ ).
  • the test voltage was performed at 200V about the resistor whose calculated test voltage exceeded 200V.
  • the fired lead-free thick film resistor is applied with 5 times by applying 1 kV of voltage at a speed of several nano s for 1 second on and 1 second off. Before applying a voltage of 1 kV, the resistance value and the change in resistance value after calculating the voltage were calculated.
  • the lead-free thick film resistors were quantitatively evaluated for the number of resistor bubbles formed on the surface at magnifications x50, x100, and x500 using an optical microscope.
  • the ruthenium-based composite oxide and the first glass precursor mixture or the second glass precursor mixture to have a composition (g) as shown in Table 2, including the composition of the first glass precursor mixture or the second glass precursor mixture shown in Table 1 below.
  • Table 2 Table 2
  • the sintered compact obtained after the heat treatment at 800 ° C. for 30 minutes was pulverized using a grinder for 12 hours to prepare a conductive composite powder having a first network having an average particle diameter of 1.5 ⁇ m.
  • Table 3 it is mixed according to the composition and the content (g) as described in the Examples and Comparative Examples, 12% by weight of the organic cellulose resin ethyl cellulose resin and BCA (Butyl Carbitol Acetate) 3: TPNL (Terpineol) 16 weight ratio organic
  • TPNL Tepineol
  • An organic vehicle consisting of 88% by weight of solvent was used and a dispersant (BYK-111) was used as an additive.
  • the composition was stirred for 2hr using a P / L mixer, and then dispersed 5 times and 5 times using a 3-roll mill.
  • the lead-free thick film resistant composition obtained on the paste was aged at 65 ° C. for 24 hours, and was prepared through a filtration process after viscosity adjustment using an additional organic solvent TPNL (Terpineol).
  • Ag-Pd conductor paste was screen printed with U-pattern on 96% purity alumina substrate and dried at 150 ° C. for 10 minutes. 95 wt% Ag and 5 wt% Pd. The dried specimen was calcined at 850 ° C. for 10 minutes.
  • the lead-free thick film resistance composition according to the embodiment was screen-printed to a predetermined shape of 1 mm x 1 mm on alumina substrate having a conductor, dried at 150 ° C. for 10 minutes, and then baked at 850 ° C. for 10 minutes to have a thickness of 8.5 ⁇ m.
  • a lead-free thick film resistor was prepared.
  • the lead-free thick film resistor of the present invention was remarkably excellent in temperature characteristics, overload characteristics, and antistatic characteristics in a wide range of resistance values.
  • a uniform and dense resistor was prepared because of excellent surface uniformity and low dispersion of resistance value (CV).
  • the lead-free thick film resistor prepared in the embodiment of the present invention had a low current noise compared to the lead-free thick film resistor prepared in the comparative example.
  • the second network is formed in a dark shape in a continuous phase and the first network is represented in a bright shape in a dispersed phase in the continuous phase, thereby forming a network structure in which a dispersed network is formed in the continuous phase. It confirmed that it did.
  • the lead-free thick film resistor of the present invention having a double network as described above was confirmed that the uniformity of the surface is further improved to improve the resistance distribution (CV) and electrical properties.
  • Comparative Examples 1 to 8 since the first network does not include the conductive composite powder and the ruthenium-based composite oxide does not form a double network, the ruthenium-based composite oxide is decomposed and lead-free as shown in FIG. 1. As a result of having a non-uniform surface of the thick film resistor, it was confirmed that the stability of the resistance value was remarkably decreased, thereby deteriorating the physical properties of the temperature characteristic. In addition, in Comparative Example 9, as the lead-free thick film resistor was manufactured by applying only the conductive composite powder having the first network formed thereon, fluidity was decreased during formation on the substrate, thereby significantly decreasing the uniformity of the surface of the resistor, and significantly reducing the adhesion to the substrate. It was confirmed that the stability was poor.

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Non-Adjustable Resistors (AREA)
  • Glass Compositions (AREA)
PCT/KR2018/001903 2017-02-13 2018-02-13 무연 후막 저항체 및 이를 포함하는 전자부품 WO2018147713A1 (ko)

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