CN100590754C - Resistance body ointment, resistance body, and circuit substrate using the resistance body - Google Patents

Resistance body ointment, resistance body, and circuit substrate using the resistance body Download PDF

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Publication number
CN100590754C
CN100590754C CN200610172522A CN200610172522A CN100590754C CN 100590754 C CN100590754 C CN 100590754C CN 200610172522 A CN200610172522 A CN 200610172522A CN 200610172522 A CN200610172522 A CN 200610172522A CN 100590754 C CN100590754 C CN 100590754C
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sub
resistive element
ruo
paste
resistor body
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CN101013617A (en
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佐久间博
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Alps Alpine Co Ltd
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Alps Electric Co Ltd
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Abstract

The present invention is to provides a resistor body paste for forming a resistor body having resistance value with little warp and little temperature coefficient; a resistor body formed with said resistor body paste; and circuit board forming with said resistor body. The resistor body paste according to the invention comprises glass composition not containing plumbic, RuO<SUB>2</SUB>, Ru<SUB>2</SUB>Nd<SUB>2</SUB>O<SUB>7</SUB>, and organic binding agent. Because composing temperature of Ru<SUB>2</SUB>Nd<SUB>2</SUB>O<SUB>7</SUB> is approximate 1100 to 1300 DEG C, said resistor body paste may not decompose at burning temperature, and can for resistor body having resistance value with little warp. In addition, temperature coefficient of Ru<SUB>2</SUB>Nd<SUB>2</SUB>O<SUB>7</SUB> is negative, that of RuO<SUB>2</SUB> is positive, absolute value of temperature coefficient of the resistor body can be suitably and simply reduced by mixing the both.

Description

Resistive element paste, resistive element and used the circuit substrate of described resistive element
Technical field
The present invention relates to be used to form the resistive element paste (paste) of the little and resistive element that absolute value temperature coefficient is little of the deviation of resistance value; The resistive element that uses described resistive element paste to form; And the circuit substrate that uses described resistive element to form.
Background technology
Shown in following patent documentation, the resistive element paste contains glass component, conductive material and vehicle (vehicle).
Resistive element is that described resistive element paste is being printed on the substrate by silk screen printing etc., forms by firing afterwards.
But,, all the time,, developed lead-free resistive element paste for preventing contaminated environment as described in the following patent documentation.
In following patent documentation, use Bi 2Ru 2O 7Or NdBiRu 2O 7Deng as lead-free electric conducting material.
Yet, contain Bi in use 2Ru 2O 7Or NdBiRuO 2O 7The resistive element that forms of resistive element paste in, find that the deviation of resistance value becomes big.This is because because Bi 2Ru 2O 7Or NdBiRu 2O 7Synthesis temperature low (being about 700 ℃～900 ℃), so, then can decompose, fire again if fire described resistive element paste (firing temperature is about 800 ℃～1000 ℃).In addition, think Bi 2Ru 2O 7Or NdBiRu 2O 7The existence of middle Bi also is to cause the deviation of resistance value to become big reason.
In addition, it is also very important to dwindle the absolute value of temperature coefficient (TCR:Temperature Coefficient ofResistance) of resistive element.For example, the multiple conductive material with different temperature coefficients that meets is added in the resistive element paste, realize dwindling the absolute value of described temperature coefficient.For example, because RuO 2Has positive temperature coefficient, so add Nb with negative temperature coefficient 2O 5Or MnO 2Deng.
Yet, present employed conductive material, the control of temperature coefficient is difficulty very, thereby produces deviation easily on the TCR characteristic.
Summary of the invention
Therefore, the objective of the invention is to,, especially provide the resistive element paste of the little and resistive element that absolute value temperature coefficient is little of a kind of deviation that is used to form resistance value for solving above-mentioned existing problem; The resistive element that uses described resistive element paste to form; And the circuit substrate that uses described resistive element to form.
Resistive element paste of the present invention is characterized in that having: lead-free glass component, RuO 2, Ru 2Nd 2O 7, and organic vehicle, RuO 2And Ru 2Nd 2O 7Mixing ratio, calculate RuO with quality % 2: Ru 2Nd 2O 7In 97: 3～50: 50 scope, described Ru 2Nd 2O 7Be synthetic by mixing RuO under 1100 ℃～1300 ℃ synthesis temperature 2Powder and Nd 2O 3Powder and the powder that obtains make.
Because Ru 2Nd 2O 7Synthesis temperature be to be about 1100 ℃～1300 ℃ high temperature, so described resistive element paste can not decompose at firing temperature, can form the little resistive element of deviation of resistance value.In addition, Ru 2Nd 2O 7Temperature coefficient be negative, RuO 2Temperature coefficient for just, by they are mixed, can be suitably and reduce the absolute value of the temperature coefficient of resistive element simply.
In the present invention, preferred RuO 2And Ru 2Nd 2O 7Mixing ratio, calculate RuO with quality % 2: Ru 2Nd 2O 7In 97: 3～50: 50 scope.Thus, can more suitably form the little resistive element of deviation of resistance value.
In addition in the present invention, preferred described glass component contains B 2O 3, CaO, SiO 2And Al 2O 3, B 2O 3-CaO-SiO 2-Al 2O 3The glass component of system is suitable for high temperature sintering.
Resistive element of the present invention in addition is characterized in that having: lead-free glass component, RuO 2, Ru 2Nd 2O 7
Described resistive element obtains by firing described resistive element paste.In the present invention, can be simply and suitably obtain the little resistive element of absolute value of temperature coefficient.
In addition, circuit substrate of the present invention is characterized in that, on the surface of base material or at least one place of the inside of described base material form the resistive element of above-mentioned record.In the present invention, can be simply and suitably obtain having the circuit substrate of the little resistive element of the deviation absolute value little, temperature coefficient of resistance value.
Resistive element paste of the present invention is characterized in that having: lead-free glass component, RuO 2, Ru 2Nd 2O 7, and organic vehicle.
Because Ru 2Nd 2O 7Synthesis temperature be to be about 1100 ℃～1300 ℃ high temperature, so described resistive element paste can not decompose at firing temperature, can form the little resistive element of deviation of resistance value.In addition, Ru 2Nd 2O 7Temperature coefficient be negative, RuO 2Temperature coefficient for just, by they are mixed, can be suitably and reduce the absolute value of the temperature coefficient of resistive element simply.
Description of drawings
Fig. 1 cuts off the low fire ceramic substrate from film thickness direction, represent the profile in its cross section;
Fig. 2 is the chart of deviation of resistance value of the resistive element of expression embodiment;
Fig. 3 is the chart of deviation of resistance value of the resistive element of expression comparative example;
Among the figure:
1-low fire ceramic substrate; The 2-ceramic layer; 4-internal layer distribution conductor; 5-top layer distribution conductor; The 6-resistive element; The 7-chip part
Embodiment
The resistive element paste of present embodiment constitutes, and has: lead-free glass component, RuO 2, Ru 2Nd 2O 7, and organic vehicle.
In described glass component, owing to use B 2O 3-CaO-SiO 2-Al 2O 3System is suitable for high temperature sintering, is preferred therefore.And preferably, B 2O 3Ratio of components x be 1～50 quality %; The ratio of components y of CaO is 10～50 quality %; SiO 2Ratio of components z be 45～70 quality %; Al 2O 3Ratio of components w be 1～30 quality % (, satisfying the relation of ratio of components x+y+z+w≤100 quality %) at this.In addition preferably, in described glass component, can contain Na as the residue composition 2O, K 2At least a among O, the MgO, the ratio of components v that described residue is formed (at this, satisfies the relation of ratio of components x+y+z+w+v=100 quality %) in the scope of 0～10 quality %.
In described organic vehicle, contain organic bond and organic solvent.As described organic bond, can select at least a from ethyl cellulose, nitrocellulose, methacrylate (salt) etc.As described organic solvent, can select at least a in addition from terpineol (terpineol), ethanol, butyl carbitol acetate fiber (butyl carbitol acetate) etc.
In addition, can suitably add dispersant or interfacial agent, plasticizer etc. according to purposes.
Ru 2Nd 2O 7Has negative temperature coefficient, RuO 2Has positive temperature coefficient.
In the present embodiment, preferred RuO 2With Ru 2Nd 2O 7Mixing ratio (RuO 2: Ru 2Nd 2O 7), calculate with quality %, within 97: 3～50: 50 scope.Preferred described mixing ratio is within 95: 5～55: 45 scope, and further preferred range is within 90: 10～55: 45 scope.According to test described later as can be known, by the described mixing ratio of suitable adjustment, can suppress the deviation (3 σ/T (%)) of the resistance value of resistive element effectively.At this σ is standard deviation, and T represents the average electrical resistance.
In addition, described glass component and RuO 2And Ru 2Nd 2O 7Mixing ratio (quality %), carry out suitable adjustment by the resistance value of necessity.If increase mixing ratio as the glass component of insulating material, then can increase the resistance value of described resistive element, on the other hand, if increase RuO 2And Ru 2Nd 2O 7Mixing ratio, then can reduce the resistance value of described resistive element.
Can be on substrate with the described resistive element paste silk screen printing of present embodiment, organic solvent fired back evaporation, thus form resistive element.Described resistive element is used for the surface of circuit substrate, for example low fire ceramic substrate (LTCC:low Temperature Co-fired Ceramic substrate) or inside etc.
Fig. 1 cuts off described low fire ceramic substrate from film thickness direction, represent the part sectioned view in its cross section.
Described low fire ceramic substrate 1 is that stacked a plurality of ceramic layer 2 forms.As shown in Figure 1, at each ceramic layer 2, stamping-out is formed with through hole (via hole) 2a, fills for example path (via) conductor 3 of Ag system at each through hole 2a.
In addition, as shown in Figure 1, between each ceramic layer 2, for example being formed with, Ag is the pattern of the internal layer distribution conductor 4 of conductor.Described internal layer distribution conductor 4 is to form the pattern of described conductor paste by silk screen printing etc. on the surface of raw cook (greensheet) (in this specification, described ceramic layer 2 is meant the state of firing after the described raw cook), and fires formation.
In addition, as shown in Figure 1, on the surface of low fire ceramic substrate 1, for example being formed with, Ag is the pattern of the top layer distribution conductor 5 of conductor.Described top layer distribution conductor 5 is to form the pattern of conductor paste by silk screen printing etc. on the surface of the raw cook that is positioned at the superiors, and fires formation.
Each internal layer distribution conductor 4 and described top layer distribution conductor 5 are electrically connected via described via conductor 3.
As shown in Figure 1, in described low fire ceramic substrate 1, use the resistive element 6 of present embodiment.The pattern that forms described resistive element 6 on the internal layer or the surface of described ceramic substrate 1.
As shown in Figure 1, on the surface of described low fire ceramic substrate 1, chip part 7 is electrically connected on described top layer distribution conductor (electrode) 5.
The resistive element 6 of present embodiment comprises above-mentioned glass component, RuO at least 2And Ru 2Nd 2O 7, the deviation of resistance value is little, and in addition, the absolute value of the temperature coefficient of resistance value (TCR:Temperature Coefficientof Resistance) is little.
In addition, with similarly above-mentioned, RuO 2And Ru 2Nd 2O 7Mixing ratio (RuO 2: Ru 2Nd 2O 7), calculate with quality %, be adjusted at 97: 3～50: 50 scope in, thus, can reduce the deviation (3 σ/T (%)) of the resistance value of described resistive element 6 effectively.In addition, with this mixing ratio, the absolute value that can make described temperature coefficient is below 400ppm/ ℃.
Manufacture method for low fire ceramic substrate 1 shown in Figure 1 describes.Prepare ceramic green sheet at first, respectively, Ag is conductor paste and resistive element paste.
Described resistive element paste has: lead-free glass component, RuO 2, Ru 2Nd 2O 7, and organic vehicle.Ru in the described resistive element paste 2Nd 2O 7Be with RuO 2Powder and Nd 2O 3Powder and being about under 1100 ℃～1300 ℃ the high temperature the synthetic powder that obtains by this mixing makes.
Form through hole on described ceramic green sheet, filling described Ag in described through hole is the conductor paste, and then on the surface of described ceramic green sheet, is that the silk screen printing of conductor paste becomes predetermined pattern with described Ag.In addition, on the surface of described raw cook, the silk screen printing of described resistive element lotion is become predetermined pattern.So, form the described ceramic green sheet that lotion is filled in a plurality of not printings.Described ceramic green sheet becomes ceramic layer shown in Figure 12 after firing, at each raw cook, at the formation position of via conductor shown in Figure 13, internal layer distribution conductor 4, top layer distribution conductor 5 and resistive element 6, carry out the printing of lotion and fill.
And, overlap a plurality of described ceramic green sheets, fire described ceramic green sheet simultaneously, Ag is conductor paste and resistive element paste.Firing temperature is preferably within 800 ℃～1000 ℃ scope.The Ru that in described resistive element paste, contains 2Nd 2O 7Synthesis temperature at 1100 ℃～1300 ℃, so, when ablating work procedure, Ru 2Nd 2O 7Can after decomposing, not fire again, can be suitably and form the little resistive element 6 of deviation of resistance value simply.
In addition, be negative Ru by the mixing temperature coefficient 2Nd 2O 7With temperature coefficient be positive RuO 2, can control temperature coefficient simply, especially, make RuO 2And Ru 2Nd 2O 7Mixing ratio (RuO 2: Ru 2Nd 2O 7), calculate with quality %, in the time of in 97: 3～50: 50 scope, can simply and suitably the absolute value of described temperature coefficient be adjusted to below 400ppm/ ℃.That is, in the present embodiment, can be simply and suitably form the resistive element 6 that deviation is little and absolute value temperature coefficient is little of resistance value.
In addition, the resistive element 6 of present embodiment except being used for high-temperature firing ceramic substrate (HighTemperature Co-fired Ceramic substrate), can be used for base material in addition.
[embodiment]
Fire the resistive element paste that forms with the mixing ratio shown in the following table 1 at 900 ℃, form resistive element, measure the average electrical resistance T of each resistive element and the deviation of resistance value (3 σ/T (%)).σ is a standard deviation.In addition, in each resistive element paste, use the mixture of the terpineol of the ethyl cellulose of organic bond and organic solvent, in glass component, use B as organic vehicle 2O 3-CaO-SiO 2-Al 2O 3System.
[table 1]
As shown in table 1, if mixing ratio (RuO 2: Ru 2Nd 2O 7) be 99: 1 (quality %), 40: 60 (quality %), then because the deviation of resistance value surpasses 50%, so in 97: 3～50: 50 scope, adjust described mixing ratio.In addition, from the experimental result shown in the table 1 as can be known, if described mixing ratio in 95: 5～55: 45 scope, then can be reliably be reduced to the deviation of resistance value less than 50%.In addition, if in 90: 10～55: 45 scope, adjust described mixing ratio, then can be reliably the deviation of described resistance value be reduced to less than 40%.
Then, on base material to lead-free glass component (B 2O 3-CaO-SiO 2-Al 2O 3System), RuO 2, Ru 2Nd 2O 7, and the resistive element paste (embodiment) that contains organic vehicle carry out silk screen printing, in addition,, the Ag conductor paste as electrode is carried out silk screen printing in the both sides of described resistive element paste, fire described resistive element paste and described Ag conductor paste simultaneously.And, formed a plurality of base materials with the resistive element (embodiment) that forms by same composition.
In addition, on base material to containing plumbous glass component (PbO-B 2O 3-SiO 2-Al 2O 3System), RuO 2, Ru 2Pb 2O 6.5, and the resistive element paste (comparative example) that contains organic vehicle carry out silk screen printing, in addition,, the Ag conductor paste as electrode is carried out silk screen printing in the both sides of described resistive element paste, fire described resistive element paste and described Ag conductor paste simultaneously.And, formed a plurality of base materials with the resistive element (comparative example) that forms by same composition.
The condition relevant for manufacture method of embodiment and comparative example (firing temperature etc.) is all identical.
Then, measured the resistance value of each resistive element of embodiment and comparative example.In each embodiment and comparative example, the resistance value of each resistive element of having measured is divided into data interval every 200 Ω, studied the quantity (frequency) of described resistive element with the resistance value in the identical data interval.
Fig. 2 is the experimental result of the resistive element of embodiment, and Fig. 3 is the experimental result of the resistive element of comparative example.From Fig. 2, shown in Figure 3ly can find out clearly that compare with comparative example, the deviation of the resistance value of embodiment is little.

Claims (6)

1. a resistive element paste is characterized in that,
Have: lead-free glass component, RuO 2, Ru 2Nd 2O 7, and organic vehicle,
RuO 2And Ru 2Nd 2O 7Mixing ratio, calculate RuO with quality % 2: Ru 2Nd 2O 7In 97: 3～50: 50 scope,
Described Ru 2Nd 2O 7Be synthetic by mixing RuO under 1100 ℃～1300 ℃ synthesis temperature 2Powder and Nd 2O 3Powder and the powder that obtains make.
2. resistive element paste as claimed in claim 1, wherein,
Described glass component contains B 2O 3, CaO, SiO 2And Al 2O 3
3. resistive element paste as claimed in claim 1, wherein,
RuO 2With Ru 2Nd 2O 7Mixing ratio, calculate RuO with quality % 2: Ru 2Nd 2O 7Within 95: 5～55: 45 scope.
4. resistive element paste as claimed in claim 3, wherein,
RuO 2With Ru 2Nd 2O 7Mixing ratio, calculate RuO with quality % 2: Ru 2Nd 2O 7Within 90: 10～55: 45 scope.
5. a resistive element is characterized in that,
Utilize the described resistive element paste of claim 1 to form described resistive element.
6. a circuit substrate is characterized in that,
On the surface of base material or at least one place of the inside of described base material form the described resistive element of claim 5.
CN200610172522A 2006-01-13 2006-12-26 Resistance body ointment, resistance body, and circuit substrate using the resistance body Expired - Fee Related CN100590754C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2006005502 2006-01-13
JP2006005502A JP2007189040A (en) 2006-01-13 2006-01-13 Resistive paste, resistance object, and circuit board using the same

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CN101013617A CN101013617A (en) 2007-08-08
CN100590754C true CN100590754C (en) 2010-02-17

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JP2008192784A (en) * 2007-02-05 2008-08-21 Sumitomo Metal Mining Co Ltd Resistive paste for forming thermistor
JP7099027B2 (en) * 2018-04-19 2022-07-12 富士電機株式会社 Semiconductor equipment

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JP2002198203A (en) * 2000-12-25 2002-07-12 Tdk Corp Resistor paste, thick-film resistor formed of the same, and circuit board equipped with the thick-film resistor
JP2002367806A (en) * 2001-06-05 2002-12-20 Tdk Corp Resistor paste and method of manufacturing thick film resistor using the same
JP4079669B2 (en) * 2002-02-28 2008-04-23 小島化学薬品株式会社 Thick film resistor paste
JP2007103594A (en) * 2005-10-03 2007-04-19 Shoei Chem Ind Co Resistor composition and thick film resistor

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Address after: Tokyo, Japan, Japan

Patentee after: Alpine Alpine Company

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Patentee before: Alps Electric Co., Ltd.

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