EP3018662A1 - Élément ctp et module de génération de chaleur - Google Patents

Élément ctp et module de génération de chaleur Download PDF

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EP3018662A1
EP3018662A1 EP14819939.1A EP14819939A EP3018662A1 EP 3018662 A1 EP3018662 A1 EP 3018662A1 EP 14819939 A EP14819939 A EP 14819939A EP 3018662 A1 EP3018662 A1 EP 3018662A1
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mass
resistance
base metal
semiconductor ceramic
ptc element
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EP14819939.1A
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German (de)
English (en)
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Kentaro Ino
Takeshi Shimada
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Proterial Ltd
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Hitachi Metals Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • H01C7/02—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • H01C7/02—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient
    • H01C7/021—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient formed as one or more layers or coatings

Definitions

  • the present invention relates to: a PTC element in which an electrode is formed on a semiconductor ceramic composition having a positive temperature coefficient of resistivity; and a heat generating module.
  • PTC characteristic Positive Temperature Coefficient of resistivity
  • semiconductor ceramic compositions in which various semiconductor-forming elements are added to perovskite type compositions represented by BaTiO 3 .
  • the PTC characteristic is a characteristic that a resistance value sharply increases at a high temperature of the Curie point or higher.
  • Semiconductor ceramic compositions having the PTC characteristic are used as PTC elements after electrodes are formed thereon.
  • Patent Document 1 describes, with respect to a PTC element using a non-lead semiconductor ceramic composition and an electrode, that a composition containing 50 to 80% of BaTiO 3 , 3 to 15% of CaTiO 3 , up to 50% of SrTiO 3 and 1 to 2% of SiO 2 is preferred as a semiconductor ceramic composition (see paragraph 0006).
  • the electrode or a partial layer of the electrode is preferably manufactured by a metal deposition method. Examples of the metal deposition method include sputtering, vapor deposition, electrolytic deposition and a chemical deposition.
  • the electrode may be made by baking of a metal paste (see paragraph 0007).
  • Patent Document 2 describes a semiconductor ceramic wherein the ceramic has a Ba m TiO 3 -based composition having a perovskite type structure represented by the general formula A m BO 3 as a main component, a part of Ba constituting the A site is substituted by at least an alkali metal element, Bi and a rare earth element and also the molar ratio m of the A site to the B site is 0.990 ⁇ m ⁇ 0.999, and the ceramic has a good rise characteristic (see paragraph 0026). Also, there is a description of forming an external electrode by plating, sputtering, electrode baking, or the like to thereby obtain a PTC thermistor (see paragraph 0069). In Examples, dry plating is performed to form an external electrode having a three-layer structure of NiCr/NiCu/Ag (see paragraph 0079).
  • a material cost of electrodes and a cost of the production process for forming the electrode occupy a very large proportion.
  • the metal deposition method which is one of methods for forming electrodes has an advantage that the adhesion between the semiconductor ceramic composition and the electrode can be easily enhanced and thus the resistance at the interface between both (hereinafter referred to as “interfacial resistance”) can be easily reduced. Smaller interfacial resistance also reduces the resistance of the PTC element (hereinafter referred to as “element resistance”) and hence it is possible to improve the current efficiency of the PTC element.
  • the metal deposition method has a problem that the production costs are high.
  • the baking is a method of manufacturing an electrode paste in which a metal powder is dispersed in a glass component or an organic component, applying the paste to a semiconductor ceramic composition by printing or the like, and heating the electrode paste to evaporate the glass component or the organic component from it to leave the metal component, thereby forming an electrode.
  • Patent Document 3 discloses a PTC element having at least two ohmic electrodes and a semiconductor ceramic composition in which a part of Ba of BaTiO 3 disposed between the electrodes is substituted by Bi-Na, wherein the semiconductor ceramic composition is represented by a composition formula of [(Bi-Na) x (Ba 1-y- ⁇ R y A ⁇ ) 1-x ]Ti 1-z M z O 3 (where R is at least one kind of rare earth elements, A is at least one kind of Ca and Sr, M is at least one kind of Nb, Ta and Sb), wherein x, y, z, and ⁇ satisfy 0 ⁇ x ⁇ 0.30, 0 ⁇ y ⁇ 0.020, 0 ⁇ z ⁇ 0.010 and ⁇ 0.20, and the ratio of the area where the ohmic component of the electrodes and the semiconductor ceramic composition are not in contact therewith at the interface between the electrodes and the semiconductor ceramic composition is 25% or less.
  • the electrodes contains Ag as a main metal component.
  • metal elements there are those using a noble metal-based electrode paste whose main component is an element such as Ag, Au or Pt and those using a base metal-based electrode paste whose main component is an element such as A1 or Ni.
  • a noble metal-based electrode paste whose main component is an element such as Ag, Au or Pt
  • a base metal-based electrode paste whose main component is an element such as A1 or Ni.
  • a base metal-based electrode paste contains Al, Ni or the like as a main metal component, the paste is very inexpensive. However, it prevents a decrease in resistance since it is easily oxidized.
  • Patent Document 4 discloses an electronic component electrode composed of a metal aluminum and 0.1 to 10 weight % of boron nitride and 0.01 to 5 weight % of glass frit (lead borosilicate glass). It is described that the electrode material can be converted into an electrode having an ohmic property with respect to an ceramic element by firing at 850 to 900°C in the air.
  • An object of the present invention is to provide: a PTC element having sufficiently small interface resistance when a base metal-based electrode is formed on a semiconductor ceramic composition having a perovskite structure composed of a BaTiO 3 type oxide by baking; and a heat generating module.
  • the present invention is directed to a PTC element in which a base metal-based electrode is formed on a semiconductor ceramic composition by baking, wherein the semiconductor ceramic composition has a perovskite structure composed of a BaTiO 3 type oxide, the base metal-based electrode contains, as a main component, at least one kind of Al and Ni as a metal component and also contains at least B, and a low resistance layer having a resistance smaller than that of a matrix phase of the semiconductor ceramic composition is formed on a base metal-based electrode side of the semiconductor ceramic composition.
  • a thickness of the low resistance layer is preferably 0.1 ⁇ m or more.
  • a thickness of the low resistance layer can be 0.4 ⁇ m or more and an interface resistance of the element per unit area (1 cm 2 ) can be 5 ⁇ or less.
  • an element resistance of the element per unit area (1 cm 2 ) can be 10 ⁇ or less.
  • a surface resistance thereof in the PTC element, can be 10 m ⁇ cm or less.
  • a reaction phase mainly including a Ba oxide is preferably present on a semiconductor ceramic composition side of the base metal-based electrode.
  • the base metal-based electrode in the present invention can have a composition containing B in an amount of 3 mass % or more and 25 mass % or less when a total of Al, Ni and B is 100 mass %.
  • the base metal-based electrode in the present invention can contain Si as a metal component and contain B in an amount of 3 mass % or more and 25 mass % or less and Si in an amount of more than 0 mass % and 26 mass % or less when a total of Al, Ni, B and Si is 100 mass %.
  • the base metal-based electrode in the present invention can contain A1 in an amount of 50 mass % or more when a total of Al, Ni, B and Si is 100 mass %.
  • the base metal-based electrode in the present invention can contain Ni in an amount of 5 mass % or more and 40 mass % or less when a total of Al, Ni, B and Si is 100 mass %.
  • an A1 particle having an average particle diameter of 1.2 ⁇ m or more and 10 ⁇ m or less can be dispersed in the base metal-based electrode.
  • the semiconductor ceramic composition in the present invention can have a composition represented by a composition formula of [(BiA) x (Ba 1-y R y ) 1-x ][Ti 1-2 M z ]O 3 (A is at least one kind of Na, Li and K, R is at least one kind of rare earth elements including Y, M is at least one kind of Nb, Ta and Sb), wherein x, y and z satisfy the ranges of 0 ⁇ x ⁇ 0.25, 0 ⁇ y ⁇ 0.052 and 0 ⁇ z ⁇ 0.01 (where y+z>0).
  • the base metal-based electrode in the present invention can be baked at a temperature of 720°C or higher and 850°C or lower in an air atmosphere.
  • a heat generating module includes the PTC element according to any one of the above ones, and the semiconductor ceramic composition generates heat.
  • a PTC element having small interface resistance can be provided.
  • the PTC element can become a PTC element also having small element resistance. Furthermore, it is possible to provide a heat generating module having excellent current efficiency using the PTC element.
  • the present inventors have found that, by incorporating a resistance-decreasing auxiliary agent such as B (boron) as a metal component of a base metal-based electrode using A1 or Ni, a low resistance layer having small resistance with respect to the matrix phase is formed on a base metal-based electrode side of the semiconductor ceramic composition, the layer improves ohmic contact, and accordingly, the interface resistance and the like can be reduced.
  • a resistance-decreasing auxiliary agent such as B (boron)
  • FIG. 1 is an SEM observation photograph of a cross-section of the PTC element showing one example of the present invention and FIG. 2 is a schematic view thereof.
  • FIG. 7 is also an observation photograph of the PTC element cross-section by a scanning spread resistance microscope (SSRM) and FIG. 8 is a schematic view thereof.
  • SSRM scanning spread resistance microscope
  • 1 is a base metal-based electrode
  • 2 is a semiconductor ceramic composition having a perovskite structure composed of a BaTiO 3 type oxide.
  • the interface between the base metal-based electrode 1 and the semiconductor ceramic composition 2 is a broken line part 7 drawn horizontally in the figure, and it is found that a low resistance layer 3 is formed on the base metal-based electrode side of the semiconductor ceramic composition 2.
  • the color tone of the low resistance layer 3 has become darker than the other and thus it is found that the layer has low resistance than the matrix phase.
  • the low resistance layer means a layer that forms a portion having small resistance as compared with the matrix phase of the semiconductor ceramic composition and its resistance value is, for example, 1 ⁇ cm or less. Details thereof will be described later.
  • the low resistance layer 3 Since the low resistance layer 3 has low electric resistance and has many carriers as a semiconductor, the Schottky barrier between the low resistance layer 3 and the base metal-based electrode 1 becomes low and the interface resistance is decreased due to ohmic contact.
  • the low resistance layer 3 need not necessarily be a continuous layer but it is preferable that the layer is formed with being spread throughout the interface and the thickness is suitably 0.1 ⁇ m or more. When the thickness is 0.2 ⁇ m or more, the decrease in the resistance is promoted, so that the case is more preferred.
  • the thickness is further preferably 0.4 ⁇ m or more and most preferably 0.5 ⁇ m or more.
  • the upper limit of the thickness is affected by the B content or baking temperature but the effect of reducing the interface resistance may not be expected so much even when the thickness is beyond 3 ⁇ m. This is because, since the resistance-decreasing auxiliary agent such as B itself has high resistance, there are rather inconveniences such as insulation resistance and a decrease in thermal conductivity when the added amount is excessive.
  • a reaction phase 4 to be formed resulting from the diffusion of Ba to the electrode side is formed thicker as before in the base metal-based electrode 1.
  • the reaction phase 4 includes of an oxide containing Ba as a main component.
  • the reaction phase 4 is formed so as to fill the gap at the interface between the low resistance layer 3 and the electrode 1 or the gap between A1 particles, the contact area therebetween is increased and thus the phase contributes to a decrease in the interface resistance.
  • the reaction phase 4 is further thickened, there is also an effect that the adhesion strength between the semiconductor ceramic composition and the electrode becomes high.
  • the presence or absence of the reaction phase can be determined from the SEM observation photograph, the shape is irregular and the size is difficult to be identified, so that the phase is not defined in a quantitative manner.
  • the reaction phase is also formed. With the thickening of the low resistance layer, the reaction phase also tends to become thicker.
  • the mechanism of the formation of the low resistance layer is not clear, but is considered as follows.
  • a readily oxidizable element such as B is introduced into the base metal-based electrode, B or the like deprives oxygen from the semiconductor ceramic composition during baking to make oxygen defects in the crystal structure. Emitted electrons are generated around the interface and it is considered that the low resistance layer is formed based on them.
  • all the oxygen defects made at this time not necessarily emit electrons and a part of them move from the semiconductor ceramic composition to the electrode side together with cations such as Ba and intend to keep electrical neutrality. It is considered that Ba which has moved at this time reacts with the electrode side to form the reaction phase.
  • B is most preferred but the agent may be a element which expresses the above mechanism and, for example, at least one kind of Zn, Ca, Sb and Sn may be used together with B or solely.
  • the base metal-based electrode contains at least one kind of Al and Ni as a main component, as a whole metal component.
  • the term "containing at least one kind of Al and Ni as a main component” means one in which the content of A1 or Ni is 50 mass % or more or one in which the sum of the contents of Al and Ni is 50 mass % or more.
  • A1 is cheaper in cost than Ni, it is preferable to form an electrode which contains A1 more in amount than Ni.
  • A1 is chemically stable and excellent in reliability and, since oxidation hardly proceeds toward the inside, baking in the air atmosphere is easily conducted. Also in this respect, it is possible to reduce costs.
  • B to be incorporated in the base metal-based electrode may be contained in an amount of 3 mass % or more and 25 mass % or less based on 100 mass % of the total of Al, Ni and B.
  • the incorporation of B enables the formation of a low resistance layer having a thickness of 0.1 ⁇ m or more.
  • the thickness of the low resistance layer can be 0.4 ⁇ m or more and the low resistance layer and the reaction phase can be sufficiently formed, so that it is possible to obtain a PTC element having an interface resistance of 5 ⁇ or less.
  • the electrode may contain Si as described below.
  • the upper limit is preferably 25 mass % or less. More preferred is 5 mass % or more and 17 mass % or less, and at this time, a PTC element having an interface resistance of 1.5 ⁇ or less, an element resistance of about 5 ⁇ or less and a surface resistance of 10 m ⁇ cm or less can be obtained. Furthermore, when the amount is 5 mass % or more and less than 10 mass %, a PTC element also having a surface resistance of 2 m ⁇ cm or less can be obtained.
  • the surface resistance is a measured value of the resistance of the base metal-based electrode itself. When the surface resistance is decreased, there is an effect that an electric field can be uniformly applied to the PTC element.
  • the base metal-based electrode may contain Si as a metal component and contain B in an amount of 3 mass % or more and 25 mass % or less and Si in an amount of more than 0 mass % and 26 mass % or less based on 100 mass % of the total of Al, Ni, B and Si.
  • Si is incorporated in the above range, it is possible to improve moisture resistance and a change in element resistance with time, particularly a change of the PTC element with time under a high temperature and high humidity environment can be decreased.
  • Si is contained, Al particles that are difficult to melt can be easily melted and the ratio of the contact area at the interface between the A1 particles are increased and thus Si also acts on the reduction of the interface resistance.
  • the content of Si is preferably 5.0 mass % or more and 20.0 mass % or less, and more preferably 5.0 mass % or more and 15.0 mass % or less.
  • B in the form of not an oxide but a simple metal.
  • B is added as a stable compound such as an oxide or a nitride thereof, an ability to deprive oxygen from the semiconductor ceramic composition cannot be exhibited or a force to deprive oxygen is weak, so that it becomes difficult to form the low resistance layer.
  • Ba in the semiconductor ceramic composition becomes difficult to move to the electrode side, so that the reaction phase is also hardly formed.
  • the base metal-based electrode preferably one contains Si and contains A1 in an amount of 50 mass % or more based on 100 mass % of the total of Al, Ni, B and Si. The costs of the electrode can be further reduced.
  • the base metal-based electrode may contain Ni in an amount of 5 mass % or more and 40 mass % or less based on 100 mass % of the total of Al, Ni, B and Si.
  • Ni particles remove the oxide layer on the surface of A1 particles at low temperature to facilitate the alloying of the Al particles and the Ni particles, so that it is possible to lower electrode baking temperature.
  • the amount of Ni is 5 mass % or more, the above effect can be sufficiently obtained.
  • the amount of Ni is controlled so as not to exceed 40 mass %, an increase in the resistance of the electrode itself is easily avoided and further, an increase in the material cost of the electrode can be suppressed.
  • the baking temperature can be further lowered and specifically, it becomes possible to perform baking at 700°C.
  • the A1 powder to be used in the base metal-based electrode one having an average particle diameter of 1.2 ⁇ m or more and 10 ⁇ m or less can be suitably used. Furthermore, it is more preferable to use the powder having a particle size distribution that a particle diameter of median diameter d30 is 0.1 ⁇ m or more and less than 1.2 ⁇ m.
  • the A1 particles in the base metal-based electrode is less likely to melt since an oxide film is present on the surface and, as shown in FIG. 2 , remain at about the same size as the size at the time when the particles are contained in the electrode paste before baking. Therefore, a gap 6 is easily generated between the A1 particles and thus the contact area between the semiconductor ceramic composition and the electrode decreases, so that the interface resistance is likely to increase.
  • A1 particles having an average particle diameter of 1.2 ⁇ m or more and 10 ⁇ m or less are appropriate to use.
  • an electrode structure of a particle size distribution containing about 20 to 40% of small particles having an average particle diameter of less than 1.2 ⁇ m there is obtained a form that small A1 particles having an average particle diameter of 0.1 ⁇ m or more and less than 1.2 ⁇ m are filled between Al particles of 1.2 ⁇ m or more and 10 ⁇ m or less, so that the gap at the interface decrease.
  • the ratio of the contact area between the semiconductor ceramic composition and the electrode is increased by the presence of the reaction phase 4 to be formed in a relatively thick state, even when there is formed an electrode in which relatively large A1 particles are dispersed, it is easy to reduce the interface resistance of the PTC element. In addition, the adhesion strength of the electrode becomes high.
  • Ni particles having an average particle diameter smaller than that of A1 particles it is preferable to use Ni particles having an average particle diameter smaller than that of A1 particles. It is easy to achieve a state that the Ni particles are filled into the gap between the A1 particles and the semiconductor ceramic composition and thus the state contributes to the reduction of the interface resistance.
  • the average particle diameter of the Ni particles is preferably 0.1 ⁇ m or more and 5 ⁇ m or less.
  • A1 particles increase a risk of dusk explosion and become difficult to handle as the particle diameter decreases.
  • the particle diameter exceeds 10 ⁇ m, the ratio of the contact area tends to decrease and it tends to be difficult to reduce the interface resistance.
  • a production method in which a semiconductor ceramic composition having a perovskite structure composed of a BaTiO 3 type oxide is first prepared, a base metal-based electrode paste containing, as a metal component, at least one kind of Al and Ni as a main component and containing at least B is applied to the semiconductor ceramic composition in a desired thickness by printing or the like, and the paste is heated in the air atmosphere at a temperature of 720°C or higher and 850°C or lower to bake a base metal-based electrode, can be adopted.
  • the base metal-based electrode even when the baking temperature is as low as about 720°C, the bonding of the semiconductor ceramic composition and the electrode is less likely to be insufficient and an increase in the interface resistance is easily suppressed.
  • the oxidation of the semiconductor ceramic composition and base metal-based electrode can be suppressed by using a base metal-based electrode paste to which B has been added, even when the baking temperature is as high as about 850°C. Thereby, it becomes easy to obtain a PTC element having small element resistance.
  • the baking temperature is preferably 750°C or higher and 830°C or lower and thus a PTC element having an interface resistance of 5 ⁇ or less and an element resistance of 10 ⁇ or less can be obtained. By decreasing the element resistance, it is possible to obtain a PTC element excellent in current efficiency. More preferably, the temperature is 750°C or higher and 800°C or lower.
  • the time for exposure to a temperature of 720°C or higher and 850°C or lower is suitably 10 minutes or more and 5 hours or less.
  • the baking time is preferably 15 minutes or more and 1 hour or less, and more preferably 20 minutes or more and 50 minutes or less.
  • the thickness of the electrode is suitably 5 ⁇ m or more and 50 ⁇ m or less. When the thickness is 5 ⁇ m or more, it becomes easy to suppress uneven application and peeling of the electrode. When the thickness is controlled to 50 ⁇ m or less, the costs of the electrode can be reduced.
  • the thickness is preferably 10 ⁇ m or more and 35 ⁇ m or less, and more preferably 12 ⁇ m or more and 30 ⁇ m or less.
  • the baking temperature can be lowered to 700°C by controlling Ni to 20 mass % or more.
  • a noble metal electrode such as Ag-based one can be also formed as a second-layer electrode on the base metal-based electrode. Furthermore, an electrode structure of three layers or more is also possible, in which other electrode(s) is formed on the noble metal-based electrode.
  • the semiconductor ceramic composition may have a perovskite structure composed of a BaTiO 3 type oxide but, in particular, is preferably a lead-free semiconductor ceramic composition.
  • it preferably has a composition represented by the composition formula of [(BiA) x (Ba 1-y R y ) 1-x ][Ti 1-2 M z ]O 3 (A is at least one kind of Na, Li and K, R is at least one kind of rare earth elements including Y, M is at least one kind of Nb, Ta, and Sb) wherein x, y and z satisfy the ranges of 0 ⁇ x ⁇ 0.25, 0 ⁇ y ⁇ 0.052, and 0 ⁇ z ⁇ 0.01 (where y+z>0).
  • a PTC element having a high temperature coefficient of resistivity ⁇ can be easily obtained as compared with the case of the use of a semiconductor ceramic composition containing Pb as a dopant. Specifically, even in the case of a PTC element having small element resistance (10 ⁇ or less), a PTC element having a temperature coefficient of resistivity ⁇ of 2.5%/°C or more, preferably 3.5%/°C or more is obtained.
  • the semiconductor ceramic composition containing Pb as a dopant tends to have a small temperature coefficient of resistivity ⁇ . It is presumed that this is because the base metal-based electrode paste deprives the oxygen in the grain boundary layer in the semiconductor ceramic composition during baking, the Schottky barrier formed inside the composition is thereby easily lost, and thus the temperature coefficient of resistivity ⁇ is likely to decrease.
  • the semiconductor ceramic composition having the above composition only the oxygen in the surface layer in contact with the electrode in the semiconductor ceramic composition is deprived and the oxygen in the grain boundary phase inside the composition that expresses a jump characteristic is hardly deprived, and as a result, it is possible to maintain a high temperature coefficient of resistivity ⁇ . For such a reason, it is more preferable to use the semiconductor ceramic composition having the above composition and this point is one of new findings obtained in the course of the studies of the present invention.
  • the added amount x of Bi and A is more than 0 and 0.25 or less. In the case where x is more than 0, the Curie temperature can be increased to 130°C or higher.
  • the element resistance becomes large.
  • the elements Bi and A are prone to evaporate during sintering, the number of moles of elements in the Ba site is decreased as compared with the Ti site.
  • the semiconductor ceramic composition becomes Ti-rich, and the Ti-rich phase would precipitate as a different phase. Since a part of the Ti-rich phase melts during sintering, the yield may be deteriorated or a semiconductor ceramic composition having a desired shape may not be obtained.
  • At least one of the added amount y of R and the added amount z of M is essential, that is, y+z>0.
  • the addition of the R element and the M element can increase the temperature coefficient of resistivity ⁇ . However, it is not necessary that both R and M are essential and it is sufficient to use at least one of them.
  • the range of the added amount y of R is 0 or more and 0.052 or less (where y+z>0).
  • y is more than 0.052
  • the temperature coefficient of resistivity that is the PTC characteristic is small and a semiconductor ceramic composition having good heat resistance is not obtained.
  • the temperature necessary for sintering increases, and there is a possibility that the temperature exceeds heat resistance of a sintering furnace, so that the case is not preferred on production.
  • R is at least one or more elements selected from rare earth metals (La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) including Y and particularly, Y and La are preferable since an excellent PTC characteristic is obtained.
  • the range of the added amount z of M is 0 or more and 0.01 or less (where y+z>0).
  • z is more than 0.01, the element resistance increases. Also, mechanical strength of the semiconductor ceramic composition decreases, and breakage is prone to occur when the composition has been formed into a PTC element, so that the case is not preferred on production.
  • M is preferably Nb since an excellent PTC characteristic is obtained.
  • evaluation methods of the individual property values are as follows.
  • Base metal-based electrodes were formed on both main surfaces of a semiconductor ceramic composition to form a PTC element, probes of a current meter and a voltage meter were brought into contact with the base metal-based electrodes at both sides, and element resistance was measured at room temperature (25°C) by 4 terminal method.
  • the element resistance is an element resistance of the entire PTC element, and the element resistance per unit area (1 cm 2 ) can be calculated by dividing the value by the area of the range covered by the electrode (cm 2 ).
  • the element resistance is evaluated when the thickness of the semiconductor ceramic composition is 1 mm and the area is 1 cm 2 , the element resistance can be converted into room temperature resistivity ( ⁇ cm) by multiplying a numerical value of the element resistance by 10.
  • base metal-based electrodes are provided on a semiconductor ceramic composition and the element resistance is measured. Then, the electrodes are once peeled off, the thickness of the semiconductor ceramic composition is decreased to a thickness of 3/4 of the initial thickness, the base metal-based electrodes are again provided, and the element resistance is measured. Similarly, the thickness of the semiconductor ceramic composition is decreased to a thickness of 2/4 or 1/4 of the initial thickness and the element resistance is measured in each case. As shown in FIG. 10 , data are taken by plotting the thickness of the semiconductor ceramic composition on the horizontal axis and the element resistance on the vertical axis. From the data, there is obtained an approximate straight line between the thickness of the semiconductor ceramic composition and the element resistance.
  • this resistance value R 0 when the thickness ⁇ t is 0 on the graph can be calculated for convenience.
  • this resistance value R 0 was regarded to be interface resistance.
  • the interface resistance is interface resistance of the entire PTC element, and the interface resistance per unit area (1 cm 2 ) can be calculated by dividing the value by the area of the range covered by the electrode (cm 2 ).
  • the thickness of the low resistance layer was measured from the SEM observation photograph as shown in FIG. 1 (magnification: 3,000 times) and the mapping (Al) on EDX analysis in the same visual field as shown in FIG. 3 .
  • the mapping (Al) on the EDX analysis a site where A1 was no longer detected was regarded as an interface between the semiconductor ceramic composition and the electrode (indicated by the dotted line 7 in FIG. 2 ).
  • a width having a different color tone was measured arbitrarily at 10 points on the matrix phase side of the semiconductor ceramic composition from the interface, and an average value thereof was taken as the thickness of the low resistance layer.
  • the low resistance layer is darker than the matrix phase and thus is different in color tone.
  • reaction phase is pictured in similar different shades and can be discriminated by a difference in color tone. Since the low resistance layer and the reaction phase are almost simultaneously formed, the presence of both the low resistance layer and the reaction phase can be confirmed if a layer pictured darker than the matrix phase can be visually recognized on the electrode side of the semiconductor ceramic composition in the SEM observation photograph.
  • the surface resistance is a value obtained by measuring the resistance of the base metal-based electrode itself.
  • W was 1 cm
  • L was 1 cm
  • T was aimed at 0.0025 cm.
  • the first m of m ⁇ cm of a unit indicates milli (10 -3 ).
  • the temperature at which resistance twice the room-temperature resistivity at room temperature was shown was taken as the Curie temperature.
  • the temperature coefficient of resistivity ⁇ was calculated by measuring a resistance-temperature characteristic while raising temperature up to 260°C.
  • a change with time is preferably 15% or less, and further preferably 10% or less.
  • the ratio of each element was determined while the total of Al, Ni, B and Si is regarded as 100 mass %.
  • an electron beam microanalyzer manufactured by Shimadzu Corporation: EPMA1610
  • accelerating voltage was 15 kV
  • current was 100 nA
  • the beam diameter was 10 ⁇ m, and an average value of five points was determined.
  • a base metal-based electrode paste was formed by using 100 mass parts of spherical A1 particles having an average particle diameter of 5 ⁇ m, adding 10 mass parts of glass frit and 10 mass parts of B thereto, and further adding an organic binder and an organic solvent.
  • B not an oxide but simple metal B particles were used.
  • B particles those having an average particle diameter of 1 ⁇ m or less were used.
  • the A1 ratio and the B ratio in the base metal-based electrode paste are as shown in No. 1-1 in Table 1.
  • the above base metal-based electrode paste was applied to both sides of the semiconductor ceramic composition by screen printing. After drying of the applied electrode paste at 150°C, in the air, temperature was raised at 30°C/minute, held at 775°C for 10 minutes, and lowered at 30°C/minute to obtain a PTC element on which a baked electrodes were formed.
  • the area of the range covered by the electrodes was 1 cm 2 and the thickness of the electrodes was about 25 ⁇ m.
  • the semiconductor ceramic composition used in Example was produced as follows.
  • Raw material powders of BaCO 3 , TiO 2 and La 2 O 3 were prepared and then blended so as to be (Ba 0.994 La 0.006 )TiO 3 , followed by mixing in pure water.
  • the resulting mixed raw material powder was calcined in the air at 900°C for 4 hours to prepare a first calcined powder.
  • Raw material powders of Na 2 CO 3 , Bi 2 O 3 and TiO 2 were prepared and then weighed and blended so as to be Bi 0.5 N 0.5 TiO 3 , followed by mixing in ethanol.
  • the resulting mixed raw material powder was calcined in the air at 800°C for 2 hours to prepare a second calcined powder.
  • the prepared first calcined powder (Ba 0.994 La 0.006 )TiO 3 and second calcined powder Bi 0.5 Na 0.5 TiO 3 were blended so that the molar ratio became 73:7, thereby obtaining a composition of [(Bi 0.5 Na 0 . 5 ) 0 . 0875 (Ba 0 . 994 La 0 . 006 ) 0 . 9125 ]TiO 3 .
  • Mixing and pulverization were performed by a pot mill using pure water as a medium until the average particle diameter of the mixed calcined powder became from 1.0 to 2.0 ⁇ m, followed by drying.
  • a third calcined powder was subjected to a heat treatment at 1,150°C for 4 hours to obtain a third calcined powder.
  • Y 2 O 3 was added in an amount of 1.0 mol % to the calcined powder obtained, and mixing and pulverization were performed by a pot mill using pure water as a medium until the average particle diameter of the mixed calcined powder became from 1.0 to 2.0 ⁇ m, followed by drying to obtain a mixed calcined powder.
  • PVA was added in an amount of 10 mass % to the pulverized powder of the mixed calcined powder and, after mixing, the resulting powder was granulated by means of a granulating apparatus.
  • the resulting granulated powder was formed on a monoaxial pressing apparatus to make a formed body. After subjected to binder removal at 700°C, the formed body was kept in a nitrogen atmosphere having an oxygen concentration of 0.01% (100 ppm) at 1,400°C for 4 hours and then gradually cooled to obtain a sintered body having a size of 50 mmx25 mmx4 mm.
  • the raw material powders may be mixed in a batch, ground, dried, and then subjected to a heat treatment to obtain a calcined powder (corresponding to the above third calcined powder) without obtaining the first and second calcined powders, Y 2 O 3 may be added thereto, and thereafter, manufacturing may be conducted in the same manner as described above.
  • the above sintered body was processed to prepare sintered bodies of the semiconductor ceramic composition, which were processed into plates having plane dimensions of 10 mmx 10 mm and a thickness dimension of 1.00 mm, 0.75 mm, 0.50 mm, or 0.25 mm, respectively. They were then processed in the same manner to manufacture PTC elements, respectively.
  • FIG. 1 shows the results of observation, by SEM, of the boundary part between the semiconductor ceramic composition and the electrode of the PTC element.
  • FIG. 2 is a schematic view thereof.
  • FIG. 3 is a mapping image of A1 by EDX (energy dispersive X-ray spectroscopy) in the same visual field as that of FIG. 1
  • FIG. 4 is a schematic view of FIG. 3
  • FIG. 5 is a EDX mapping image of Ba in the same visual field as that of FIG. 1
  • FIG. 6 is a schematic view of FIG. 5 .
  • a site at which A1 is no longer detected is regarded as an interface between the base metal electrode 1 and the semiconductor ceramic composition 2 (shown by a dotted line 7 in FIG. 2 and FIG. 4 ). It is found that a low resistance layer 3 having a different color tone is formed on the semiconductor ceramic composition 2 side from the interface and an irregular reaction phase 4 having a different color tone into which Ba is infiltrated is formed also on the base metal electrode 1 side. A degree of infiltration of Ba is not clear but the infiltration is considered to occur to the extent indicated by dots in FIG. 6 .
  • the site that looks primarily spherical in the base metal electrode 1 in FIG. 1 is Al.
  • the Al particles substantially keep the shape at the time when it has been incorporated into the electrode paste in the electrode after baking, but relatively small particles enter between large particles and also particle pieces intervene in the vicinity of the interface.
  • the site that looks black (portion 6 in FIG. 2 ) between the A1 particles is an inner void of the electrode.
  • FIG. 7 is a resistance mapping image of SSRM. It shows that a dark color portion is low in resistance and a light color portion is high in resistance. It is clearly found from FIG. 7 that a dark color layer is formed on the semiconductor ceramic composition 2 side from the interface 7 between the base metal electrode 1 and the semiconductor ceramic composition 2. That is, the layer has a darker color tone than the inner matrix phase and can be said to be a low resistance layer 3 in which the resistance has been decreased. The low resistance layer 3 was confirmed to be coincident with the low resistance layer 3 appearing in the SEM observation image of FIG. 1 .
  • the A1 ratio (mass %), the Ni ratio (mass %), the B ratio (mass %), and the Si ratio (mass %) in the metal component of the electrode thickness of the low resistance layer ( ⁇ m), interface resistance ( ⁇ ), element resistance ( ⁇ ), surface resistance (m ⁇ cm), the Curie temperature (°C), the temperature coefficient of resistivity ⁇ (%/°C) and the change with time (%) were measured.
  • the characteristics other than the interface resistance were measured using a semiconductor ceramic composition having a thickness of 1.00 mm.
  • the obtained evaluation results are shown in Table 1.
  • the thickness of the low resistance layer was 0.5 ⁇ m
  • the reaction phase was also present
  • the interface resistance was 1.1 Q
  • the element resistance was 4.9 ⁇
  • the surface resistance was 0.9 m ⁇ cm
  • the Curie temperature was 160°C
  • the temperature coefficient of resistivity ⁇ was 4.1 %/°C
  • the change with time was 12.5%.
  • the ratios (mass %) of Al, Ni, B and Si shown in Table 1 were observed. Also in the following Examples and Comparative Examples, the ratios of Al, Ni, B and Si in the table indicate values measured by EPMA. The values were the same as the respective content ratios in the electrode paste.
  • Spherical A1 particles having an average particle diameter of 5 ⁇ m and Si particles having an average particle diameter of 5 ⁇ m were mixed so as to be 92:8 by mass ratio and, a total value thereof being regarded as 100 mass parts, glass frit in an amount of 10 mass parts and B in an amount of 3 mass parts, 5 mass parts, 7.5 mass parts, 10 mass parts, 12.5 mass parts, 15 mass parts, 20 mass parts and 25 mass parts, respectively, were added thereto.
  • the A1 ratio, the B ratio and the Si ratio are as shown in Nos. 1-2 to 1-9 of Table 1.
  • the A1 ratio, the B ratio and the Si ratio in the base metal-based electrode pastes were the same as the values shown in Table 1.
  • any of the PTC elements it was able to confirm that there is a low resistance layer having small resistance than that of the matrix phase. Also, the presence of a reaction phase corresponding to the thickness of the low resistance layer was confirmed.
  • the low resistance layer had a thickness of 0.4 ⁇ m or more and the interface resistance was 5 ⁇ or less.
  • the interface resistance was 1.5 ⁇ or less and the element resistance was also about 5 ⁇ or less.
  • the surface resistance of the PTC element was 10 m ⁇ cm or less.
  • the surface resistance was 2 m ⁇ cm or less.
  • Si particles were added in a ratio of 8 mass parts to 92 mass parts of the same A1 particles as in Example 1 so that the total amount was 100 mass parts, and 10 mass parts of glass frit was added thereto, thereby forming a base metal-based electrode paste.
  • Si was added in a ratio of 8 mass parts to 92 mass parts of the same A1 particles as in Example 1 so that the total amount was 100 mass parts, and 10 mass parts of B 2 O 3 or H 3 BO 3 and 10 mass parts of glass frit was added thereto, thereby forming a paste.
  • a base metal-based electrode was formed with changing the baking temperature.
  • Spherical A1 particles having an average particle diameter of 5 ⁇ m and Si particles having an average particle diameter of 5 ⁇ m were mixed so as to be 92:8 by mass ratio and, a total value thereof being regarded as 100 mass parts, glass frit in an amount of 10 mass parts and B in an amount of 10 mass parts were added thereto.
  • a semiconductor ceramic composition there was used one processed into a plate of 10 mm ⁇ 10 mm (plane dimensions)x 1.00 mm (thickness dimension). Moreover, in order to measure the interface resistance, there were also prepared semiconductor ceramic compositions processed into plates of 10 mmx 10 mmx0.75 mm, 10 mmx 10 mmx0.50 mm, and 10 mmx 10 mmx0.25 mm.
  • the above base metal-based electrode paste was applied on both sides of the semiconductor ceramic composition by screen printing. After drying of the applied base metal-based electrode paste at 150°C, in the air, temperature was raised at 30°C/minute, holding temperature was changed to 725°C, 750°C, 775°C, 800°C, 825°C, or 850°C and was held for 10 minutes, and then temperature was lowered at 30°C/minute to obtain PTC elements on which baked electrodes were formed.
  • the area of the range covered by the electrode was 1 cm 2 and the thickness of the electrode was about 25 ⁇ m.
  • the semiconductor ceramic compositions having the above each thickness were similarly converted into PTC elements, respectively.
  • any of the PTC elements it was able to confirm that there is a low resistance layer having small resistance than that of the matrix phase. Also, the presence of a reaction phase corresponding to the thickness of the low resistance layer was confirmed.
  • the thickness of the low resistance layer was as thin as 0.2 ⁇ m and the interface resistance was 6.8 ⁇ .
  • the thickness of the low resistance layer was 0.4 ⁇ m or more and the interface resistance was 5 ⁇ or less.
  • the element resistance was 10 ⁇ or less.
  • the baking temperature is preferably 750°C or higher and 830°C or lower. It has been found that, when the baking temperature is more than 850°C, the semiconductor ceramic composition itself is oxidized and has increased resistance and thus the case is not preferred. [Table 2] No.
  • any of the PTC elements it was able to confirm that there is a low resistance layer having small resistance than that of the matrix phase. Also, the presence of a reaction phase corresponding to the thickness of the low resistance layer was confirmed.
  • Si also has an effect of suppressing the change with time and, when a decrease in resistance is also considered, it can be said that the Si ratio is more preferably 5.0 mass % or more and 15.0 mass % or less.
  • No. Al ratio (mass%) Ni ratio (mass%) B ratio (mass%) Si ratio (mass%) Baking temperature (°C) Thickness of low resistance layer ( ⁇ m) Interface resistance ( ⁇ ) Element resistance ( ⁇ ) Surface resistance (m ⁇ .cm) Curie temperature (°C) Temperature coefficient of resistivity (%/°C) Change with time (%) 3-1 89.1 0 9.1 1.8 775 0.5 1.8 5.5 1.3 160 4.1 13.8 3-2 87.3 0 9.1 3.6 775 0.6 1.6 5.3 1.1 159 4.1 11.5 3-3 85.5 0 9.1 5.5 775 0.7 1.2 4.9 1.4 4.2 8.2 3-4 80.0 0 9.1 10.9 775 1.0 1.0 4.7 2.0 161 4.0 6.1 3-5 7
  • Spherical A1 particles having an average particle diameter of 5 ⁇ m, Si particles having an average particle diameter of 5 ⁇ m and Ni particles having an average particle diameter of 0.2 ⁇ m were mixed so as to be 82.8:7.2:10, 73.6:6.4:20, 64.4:5.6:30, 55.2:4.8:40, 27.6:2.4:70, or 9.2:0.8:90 by mass ratio and, a total value thereof being regarded as 100 mass parts, B in an amount of 10 mass parts was added thereto. Glass frit was 0 mass part.
  • any of the PTC elements it was able to confirm that there is a low resistance layer having small resistance than that of the matrix phase. Also, the presence of a reaction phase corresponding to the thickness of the low resistance layer was confirmed.
  • the interface resistance was such a small value as 2.5 ⁇ or less. Moreover, in No. 4-1, the lowest resistance value was shown. Particularly, in Nos. 4-1 and 4-2 where an Ni ratio was 5 mass % or more and 20 mass % or less, there were obtained PTC elements having an interface resistance of 1 ⁇ or less, an element resistance of 5 ⁇ or less, and a surface resistance of 2.0 m ⁇ cm or less.
  • the Ni ratio is more preferably 20 mass % or less.
  • the addition of glass frit is not always necessary and it is considered that the addition is desired in the case where the baking temperature is more than 800°C.
  • spherical A1 particles having an average particle diameter of 5 ⁇ m, Si particles having an average particle diameter of 5 ⁇ m, and Ni particles having an average particle diameter of 0.2 ⁇ m were mixed so as to be 55.2:4.8:40 by mass ratio and, a total value thereof being regarded as 100 mass parts, B was added thereto in an amount of 5.0 mass parts, 7.5 mass parts and 12.5 mass parts, respectively. Glass frit was 0 mass part.
  • any of the PTC elements it was able to confirm that there is a low resistance layer having small resistance than that of the matrix phase. Also, the presence of a reaction phase corresponding to the thickness of the low resistance layer was confirmed.
  • any of the PTC elements it was able to confirm that there is a low resistance layer having small resistance than that of the matrix phase. Also, the presence of a reaction phase corresponding to the thickness of the low resistance layer was confirmed.
  • compositions in which the ratios of x and y were changed With respect to the composition of the semiconductor ceramic composition, there were manufactured the compositions in which the ratios of x and y were changed.
  • raw material powders of BaCO 3 , TiO 2 , and Ta 2 O 5 were prepared and then blended so as to be Ba(Ti 0.991 Ta 0 . 009 )O 3 , followed by mixing in pure water.
  • the resulting mixed raw material powder was calcined in the air at 900°C for 4 hours to prepare a first calcined powder.
  • any of the PTC elements it was able to confirm that there is a low resistance layer having small resistance than that of the matrix phase. Also, the presence of a reaction phase corresponding to the thickness of the low resistance layer was confirmed.
  • A1 particles having an average particle diameter of 3.8 ⁇ m, A1 particles having an average particle diameter of 2.5 ⁇ m, and A1 particles having an average particle diameter of 1.5 ⁇ m were used in No. 6-1, in No. 6-2, and in Nos. 6-3 and 6-4, respectively.
  • Each of these A1 particles and Si particles were mixed so as to be 92:8 by mass ratio and, a total value thereof being regarded as 100 mass parts, glass frit in an amount of 10 mass parts and B in an amount of 10 mass parts were added thereto.
  • the baking temperature was changed to 750°C.
  • any of the PTC elements it was able to confirm that there is a low resistance layer having small resistance than that of the matrix phase. Also, the presence of a reaction phase corresponding to the thickness of the low resistance layer was confirmed.
  • a semiconductor ceramic composition As a semiconductor ceramic composition, a semiconductor ceramic composition containing Pb was used.
  • the semiconductor ceramic composition containing Pb there was used one in which the composition formula was represented by (Ba 0 . 83 Pb 0.17 )TiO 3 .
  • the other manufacturing methods and evaluation methods of PTC elements were conducted in the same methods as in No. 1-5. The evaluation results obtained are shown in Table 7.
  • FIG. 9 is a schematic view of the heat generating module (PTC heater) according to one embodiment of the present invention.
  • the PTC element described above is sandwiched and fixed between metal-made heat radiating fins 21a, 21b and 21c as shown in FIG. 9 , and then, a heat generating module 20 can be configured.
  • the PTC element 11 includes a base body 1a of a semiconductor ceramic composition and base metal-based electrodes 2a, 2b and 2c, the electrodes 2a and 2c are thermally and electrically closely attached to power supplying electrodes 20a and 20c at positive side, respectively, and the electrode 2b formed on another face is thermally and electrically closely attached to a power supplying electrode 20b at negative side.
  • the power supplying electrodes 20a, 20b and 20c are thermally connected to the heat radiating fins 21a, 21b and 21c, respectively.
  • An insulating layer 2d is provided between the power supplying electrode 20a and the power supplying electrode 20c to electrically insulate both from each other. Heat generated at the PTC element 11 is transmitted to the electrodes 2a, 2b and 2c, the power supplying electrodes 20a, 20b and 20c and the heat radiating fins 21a, 21b and 21c in this order and is mainly radiated from the heat radiating fins 21a, 21b and 21c into the atmosphere.
  • the heat generating module 20 can switch heating capacity depending on load situation of the power source 30c and the desired degree of requirement for rapid or slow heating. By connecting the heat generating module 20 capable of switching the heating capacity to the power source 30c, a heating apparatus 30 can be configured.
  • the power source 30c is a direct-current power source.
  • the power supplying electrode 20a and the power supplying electrode 20c of the heat generating module 20 are connected in parallel to one of the electrodes of the power source 30c through separate switches 30a and 30b and the power supplying electrode 20b is connected as a common terminal to the other electrode of the power source 30c.
  • the heating capacity is small and the load on the power source 30c can be lightened. When both are put on, the heating capacity can be enlarged.
  • the PTC element 11 can be maintained at a constant temperature without equipping the power source 30c with a particular mechanism. That is, when a base body 1a having a large temperature coefficient of resistivity is heated to around the Curie temperature, the resistance value of the base body 1a sharply increases and the flow of current through the PTC element 11 decreases, so that the material is no more heated automatically. Moreover, when the temperature of the PTC element 11 lowers from the vicinity of the Curie temperature, the current is again allowed to flow through the element and the PTC element 11 is heated.
  • the temperature of the PTC element 11 and also the whole temperature of heat generating module 20 can be made constant through repetition of such a cycle, a circuit for regulating the phase and amplitude of the power source 30c and also a temperature detecting mechanism or a mechanism for comparison with a target temperature, a circuit for regulating power for heating and the like are also unnecessary.
  • the heating apparatus 30 can heat air with introducing air between the heat radiating fins 21a to 21c or can heat a liquid such as water with connecting a metal tube for liquid flow among the heat radiating fins 21a to 21c. On this occasion, since the PTC element 11 is also kept at a constant temperature, a safe heating apparatus 30 can be configured.
  • Such a heat generating module is merely one example and changes and modifications such as simplification of the above electrodes into two electrodes can be added.

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  • Electromagnetism (AREA)
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EP14819939.1A 2013-07-02 2014-07-01 Élément ctp et module de génération de chaleur Withdrawn EP3018662A1 (fr)

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