CN107210105A - Semiconductor element and its manufacture method - Google Patents

Semiconductor element and its manufacture method Download PDF

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CN107210105A
CN107210105A CN201680007338.7A CN201680007338A CN107210105A CN 107210105 A CN107210105 A CN 107210105A CN 201680007338 A CN201680007338 A CN 201680007338A CN 107210105 A CN107210105 A CN 107210105A
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particle
ceramic
semiconductor element
sintered bodies
internal electrode
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CN107210105B (en
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深町浩平
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Murata Manufacturing Co Ltd
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Murata Manufacturing Co Ltd
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Abstract

A kind of semiconductor element, it be comprising the ceramic body containing ceramic sintered bodies particle, configuration ceramic body both ends of the surface the first outer electrode and the semiconductor element of the second outer electrode, wherein, ceramic sintered bodies particle is the perovskite-type compounds at least containing Ba and Ti；The average grain diameter of ceramic sintered bodies particle is more than 0.4 μm and less than 1.0 μm；The contact rate of ceramic sintered bodies particle more than 45%, the girth that the ceramic sintered bodies particle being present in a region calculated is observed in a region of the contact rate according to selected in the section with scanning electron microscope to semiconductor element adds up to, the girth in hole that is present in a region is total, the value of the contact length of the outer perimeter in a region and the ceramic sintered bodies particle being present in a region and calculate.

Description

Semiconductor element and its manufacture method
Technical field
The present invention relates to semiconductor element and its manufacture method, more particularly to barium titanate based semiconductor device and its manufacturer Method.
Background technology
Barium titanate based semiconductor porcelain is because with positive temperature characterisitic, so being widely used in positive temperature coefficient thermis (PTC Thermistor) etc. semiconductor element.
For example, recording the manufacture method of temperature characterisitic functional composite particles in patent document 1, it is characterised in that The surfaces of the coatingparticles being made up of the semiconductor particle with nonlinear temperature characteristic it is discontinuous it is scattered be attached with by with the master batch The particle that the metallic of sub- Ohmic contact is constituted.The compound particle that patent document 1 is recorded does not need high temperature sintering, is combined this Particle, which is dispersed in after solvent, to be coated or in the way of powder compact, then by further low-temperature heat, can be as non-linear Temperature characterisitic function element or heater etc. are used.
Positive temperature coefficient thermis has been recorded in patent document 2, it is characterised in that with ceramic insulator substrate, temperature-sensitive electricity Thick film and at least one pair of electrode are hindered, above-mentioned thermistor thick film formation is sintered on ceramic insulator substrate by semiconductive ceramic Body is constituted and shows positive resistance-temperature characteristic, and the above-mentioned electrode of at least one pair of is connected with thermistor thick film and across above-mentioned heat At least a portion of quick resistance thick film and it is relative, the resistivity at room temperature of thermistor thick film is less than 10k Ω cm.Patent text The contact surface between the crystal grain in the semiconductive ceramic for constituting thermistor thick film can be expanded by offering the positive temperature coefficient thermis of 2 records Product, can realize low resistance.
Barium titanate based semiconductor porcelain of the average porcelain particle diameter below 0.9 μm is recorded in patent document 3.In patent Average porcelain particle diameter has been recorded in document 3, and in the barium titanate based semiconductor porcelain of above range, ratio resistance is small at room temperature and has Excellent dieletric strength.Herein below has been recorded in patent document 3：Above-mentioned barium titanate based semiconductor porcelain is existed by particle diameter Less than 0.1 μm, crystalline texture is cubic crystal, and lattice constant is more than 4.020 angstroms, there is the titanium of micro semiconductor agent with solid solution Sour barium dust or using the barium titanate powder be calcined material as material powder, burnt till and be made.
Prior art
Patent document
Patent document 1：Japanese Patent Laid-Open 9-100169 publications；
Patent document 2：No. 2012/111386 publication of International Publication No.；
Patent document 3：Japanese Patent Laid-Open 11-116327 publications.
The content of the invention
The technical problems to be solved by the invention
PTC thermistor is because of the protection to overcurrent, so being used for the electronic equipment of species in extensive range.Along near The high performance of electronic equipment over year, people especially need that the PTC thermistor of high current can be tackled, special with high proof voltage The exploitation of the PTC thermistor element of property is carried out.In order to improve the voltage-resistent characteristic of PTC thermistor, structure is carried out Into the micronized (patent document 3) of the semiconducting ceramic of PTC thermistor.But the result after inventor's research shows：In the presence of Because of micronized, the problem of ratio resistance at room temperature of PTC thermistor increases.
On the other hand, recorded in patent document 2 by expand the intercrystalline contact area in semiconductive ceramic come Realize low resistance.But, the crystal grain described in patent document 2 has the big particle diameter of 2 μm~38 μm of average grain diameter.
The present invention with provide it is a kind of with high voltage-resistent characteristic and show at room temperature low resistivity semiconductor element and Its manufacture method is used as purpose.
Solve the technical scheme that technical problem is used
The present inventor in order to achieve the above object, is conceived to the calcium titanium as the parent material used in manufacture semiconductor element The physical property of ore deposit type compound particles, is studied repeatedly, the result is that being found that by controlling perovskite-type compounds grain The specific surface area of son and the c-axis length of the lattice of perovskite-type compounds particle just can be simultaneous to ratio (regular crystal) c/a of a axial lengths Turn round and look at the micronized of the ceramic sintered bodies particle contained by the ceramic body for constituting semiconductor element and improve ceramic sintered bodies particle Contact rate, and then complete the present invention.
According to the first aspect of the invention there is provided a kind of semiconductor element, it is to include ceramic body, the first outer electrode With the semiconductor element of the second outer electrode,
The ceramic body contains ceramic sintered bodies particle；
First end face of the first outer electrode configuration in the ceramic body；
Second end face of the second outer electrode configuration in the ceramic body；
The ceramic sintered bodies particle is the perovskite-type compounds at least containing Ba and Ti；
The average grain diameter of the ceramic sintered bodies particle is more than 0.4 μm and less than 1.0 μm；
The contact rate of the ceramic sintered bodies particle is more than 45%, and the contact rate is according to scanning electron microscope Observed being present in a region of being calculated in a region selected in a section to the semiconductor element The girth of the ceramic sintered bodies particle adds up to LG, the girth in hole (pore) that is present in a region add up to LNC, it is described The outer perimeter L in one regionSAnd the contact of the ceramic sintered bodies particle being present in a region represented with following formula Length LCValue,
(number 1)
Calculated by following formula,
(number 2)
The contact rate of ceramic sintered bodies particle more fortunately more than 45% and less than 80%.
The semiconductor element can be that more than one first internal electrode and one are configured with the inside of ceramic body The stack-up type semiconductor element of the second internal electrode more than individual.Now, first end face of first internal electrode in ceramic body Electrically connected with the first outer electrode；Second internal electrode is electrically connected in the second end face of ceramic body with the second outer electrode.
First internal electrode and the second internal electrode can be Ni electrodes.
According to the second aspect of the invention there is provided a kind of method, it is the manufacture method of semiconductor element, includes following work Sequence：
The process for modulating the perovskite-type compounds particle at least containing Ba and Ti；
The process for forming the green compact chip containing perovskite-type compounds particle；
By burning till the process that ceramic body is made in green compact chip；And
The process that semiconductor element is made by the both ends of the surface formation outer electrode in ceramic body；
The specific surface area of perovskite-type compounds particle is in 4.0m2/ more than g and 14.0m2/ below g；
The c-axis length of the lattice of perovskite-type compounds particle is to the ratio c/a of a axial lengths more than 1.005 and less than 1.009.
The specific surface area of perovskite-type compounds particle is in 4.0m2/ more than g and 11.0m2/ below g.
In the above-mentioned methods, the process for forming the green compact chip containing perovskite-type compounds particle can include following work Sequence：
The process for making the ceramic green sheet containing perovskite-type compounds particle；
The process of coats internal electrode conductive paste on the main surface of ceramic green sheet；
The process that laminate is made in the ceramic green sheet lamination that multi-disc is coated with into internal electrode conductive paste；And
Configure without coats internal electrode with the ceramic green sheet of conductive paste and crimped above and below laminate, cut Into defined size, the process that green compact chip is made.By such method, it can manufacture in being configured with the inside of ceramic body The stack-up type semiconductor element of portion's electrode.The internal electrode conductive paste can contain Ni metal dusts as electric conductivity powder End.
The effect of invention
The semiconductor element of the present invention is shown with high voltage-resistent characteristic and at room temperature low by being constituted with foregoing Ratio resistance.The manufacture method of the semiconductor element of the present invention can be made with high voltage-resistent characteristic simultaneously by being constituted with foregoing And the semiconductor element of low resistivity is shown at room temperature.
Brief description of the drawings
Fig. 1 is the schematic sectional view of the semiconductor element of an embodiment of the present invention.
Fig. 2 is the schematic sectional view of a variation of the semiconductor element of an embodiment of the present invention.
Fig. 3 is the schematic sectional view of another variation of the semiconductor element of an embodiment of the present invention.
Fig. 4 is the week for showing the ceramic sintered bodies particle being present in SEM viewing areas in a section of ceramic body Long total LGFigure.
Fig. 5 is the total L for the girth for showing the hole being present in SEM viewing areas in a section of ceramic bodyNC's Figure.
Fig. 6 is the outer perimeter L for showing the SEM viewing areas in a section of ceramic bodySFigure.
Embodiment
The semiconductor element of an embodiment of the present invention is illustrated referring to the drawings.But, reality as shown below The purpose for applying mode is to be illustrated, and the invention is not limited in following embodiment.Inscape described below As long as size, material, shape, relative configuration etc. without specific record, then the scope of the present invention is not only defined in by purpose This, only illustrates example.In addition, size, shape, position relationship of inscape shown in each accompanying drawing etc. is present in order that explanation Situation about clearly being exaggerated.The size of all parts is not necessarily correctly to show numerical value as shown below, and with tolerance.
[semiconductor element]
Fig. 1 shows the schematic sectional view of the semiconductor element 1 of embodiment.The semiconductor element 1 of present embodiment is PTC Thermistor.Semiconductor element 1 shown in Fig. 1 comprising ceramic body 2, configuration ceramic body 2 first end face 21 first Outer electrode 31, configuration ceramic body 2 second end face 22 the second outer electrode 32.
(ceramic body)
Ceramic body 2 includes ceramic sintered bodies particle.Ceramic sintered bodies particle in barium titanate by with the addition of donor element Ceramic material constitute.Ceramic sintered bodies particle is the perovskite-type compounds at least containing Ba and Ti.Perovskite-type compounds In addition to containing Ba and Ti, moreover it is possible to contain at least one element selected from the rare earth element in addition to Pm, Tm, Yb and Lu And/or at least one element selected from Nb, W, Sb and Ta.Below by selected from the rare earth element in addition to Pm, Tm, Yb and Lu At least one element is referred to as that " at least one element selected from Nb, W, Sb and Ta is referred to as " element β " by element α ".Element α and member Plain β is to assign ceramic body 2 with the donor (semiconductor agent) of ptc characteristicses.Ceramic sintered bodies particle can contain above-mentioned member Either one of plain α or element β, can also contain both element α and element β.
Ceramic body 2 preferably contains 99.5 moles in the case where Ti and β total molar part is set into 100 molar parts Ba more than part and below 100.5 molar parts.If Ba content is more than 99.5 molar parts and below 100.5 molar parts, pottery The room temperature ratio resistance step-down of porcelain base substrate, can obtain high voltage-resistent characteristic.Ceramic body 2 is in addition to Ba and Ti, before can also containing The element α and/or element β stated.The preferably element α containing ceramic body 2 and element β of ceramic body 2 content is aggregated in 0.020 The element α and/or element β of amount more than molar part and below 0.500 molar part.If element α and element β content are aggregated in More than 0.020 molar part, it can assign ceramic body 2-in-1 suitable PTC (positive temperature coefficient) characteristic.If element α's and element β contains Amount is aggregated in below 0.500 molar part, can reduce the ratio resistance of ceramic body 2.
Ceramic body 2 can also the Si containing the sintering aid chatted after.Ceramic body 2 can also contain to rub relative to 100 The Ti of your part is the Si below 3 molar parts.
Ceramic body 2 can also contain the Zr being unavoidably mixed into manufacturing process.Zr's is mixed into due to chatting ceramics after Slurry uses zirconia ball as caused by crushing and scattered medium when modulating.Ceramic body 2 can contain to rub relative to 100 The Ti of your part is the Zr more than 0.01 molar part and below 1 molar part.
The average grain diameter of ceramic sintered bodies particle contained by ceramic body 2 is more than 0.4 μm and less than 1.0 μm.If flat Equal particle diameter can reach low ratio resistance more than 0.4 μm.If average grain diameter is below 1.0 μm, the energy in semiconductor element 1 Reach high voltage-resistent characteristic.The average grain diameter of ceramic sintered bodies particle with scanning electron microscope (SEM) observation by partly being led Body element cross-section, carries out graphical analysis and calculates.
In the semiconductor element 1 of present embodiment, due to connecing between the ceramic sintered bodies particle contained by ceramic body 2 Tactile area is big, in the case that the average grain diameter of ceramic sintered bodies particle is small, can also reduce the ratio electricity of room temperature (25 DEG C) Resistance.In this manual, as to evaluate the index of area contacted between ceramic sintered bodies particle, ceramic sintered bodies grain is used The contact rate of son.The contact rate of ceramic sintered bodies particle is calculated with steps described below.First, grinding semiconductor element 1, makes Section is exposed, and the section is observed with scanning electron microscope (SEM).Limited for the section observed with SEM without special It is fixed, arbitrary section may be selected.Section for example can be by LT faces (face vertical with W directions) direction by semiconductor element 1 is ground to parallel with LT faces semiconductor obtained from about 1/2W places (W of semiconductor element cuns of approximately half of places) Element cross-section.For being not particularly limited with the SEM regions observed, for example, can be ceramic blank in the section of semiconductor element 1 The region clamped by internal electrode near the central portion of body 2.The size and multiplying power of viewing area are with ceramic in mensuration region It is that the mode of more than about 70 and less than about 200 Zuo You is appropriately configured that the quantity of sintered body particle is countable.By right The SEM pictures of gained carry out graphical analysis, obtain total L of the girth of ceramic sintered bodies particle existing in viewing areaG, see Examine total L of the girth in hole existing in regionNCAnd the outer perimeter L of viewing areaS.The L that will be obtained by graphical analysisG、 LNCAnd LSOne of result represent in Fig. 4~6.Can be by total L of the girth in the hole shown in Fig. 5NCIt is considered as in ceramics burning In the girth of knot body particle not with the length of the part of adjacent ceramic sintered bodies particle contact (hereinafter referred to as " non-contact long Degree ") it is total.As shown in fig. 6, the outer perimeter L of viewing areaSWith positioned at the ceramic sintered bodies particle of viewing area outer most edge Total composition not with the length of ceramic sintered bodies particle contact part existing in viewing area in girth.According to required The L gone outG、LNCAnd LSValue, obtain in viewing area ceramics burning in the girth of existing ceramic sintered bodies particle and adjacent Total L of the length (hereinafter referred to as " contact length ") of the part of knot body particle contactC。LCIt is expressed from the next.
(number 3)
According to calculated LCAnd LNCValue, obtain the contact rate of ceramic sintered bodies particle.Ceramic sintered bodies particles connects The rate of touching is calculated with following formula.
(number 4)
The contact rate of ceramic sintered bodies particle is higher, it is meant that the contact area between ceramic sintered bodies particle is bigger.This In the semiconductor element 1 of embodiment, the contact rate of ceramic sintered bodies particle is more than 45%.If contact rate 45% with On, in the case that the average grain diameter of ceramic sintered bodies particle is small, the ratio resistance of room temperature (25 DEG C) can also be reduced.Ceramics The contact rate of sintered body particle preferably more than 45% and less than 80%.If contact rate is below 80%, high PTC can be reached (positive temperature coefficient) characteristic.
Size for ceramic body 2 is not particularly limited, and can be appropriately configured according to purposes.The size of ceramic body 2 May be, for example, L cuns 2.0mm × W cuns 1.2mm × T cuns of 1.0mm.In this manual, as shown in figure 1, by from the of ceramic body 2 End face 21 is referred to as " L directions " to the direction of second end face 22, and direction vertical with L directions in horizontal plane is referred to as into " W directions ", The direction vertical with W directions with L directions is referred to as in " T directions ".The size in the L directions of ceramic body 2 is referred to as " L cuns ", by W side To size be referred to as " W cun ", the size in T directions is referred to as " T cuns ".
The semiconductor element 1 of present embodiment as shown in Fig. 2 can be configured with the inside of ceramic body 2 one with On the first internal electrode 41 and more than one second internal electrode 42 stack-up type semiconductor element.In this manual, Sometimes the first internal electrode 41 and the second internal electrode 42 are referred to as " internal electrode ".First internal electrode 41 is in ceramic body 2 first end face 21 is electrically connected with the first outer electrode 31；Second internal electrode 42 is in the second end face 22 of ceramic body 2 and Two outer electrodes 32 are electrically connected.
First internal electrode 41 extends from the first end face 21 of ceramic body 2 to second end face 22；Second internal electrode 42 Extend from the second end face 22 of ceramic body 2 to first end face 21.First internal electrode 41 and the second internal electrode 42 are in ceramics The inside of base substrate 2 is alternately arranged relative to one another.In the variation shown in Fig. 2, although in the inside of ceramic body 2 with respective 2 the first internal electrodes 41 and the second internal electrode 42 are configured, but is determined for the endless number of internal electrode, can be according to desired Characteristic suitably set.The quantity (the first internal electrode 41 and the second internal electrode 42 total) of internal electrode for example can be 2 It is individual more than and less than 50 Zuo You.For the distance between adjacent first internal electrode 41 and the second internal electrode 42 without especially Limit, can be appropriately configured according to desired purposes.Between the first adjacent internal electrode 41 and the second internal electrode 42 Distance for example can be more than 10 μm and less than 200 μm.
It is not particularly limited, can be suitably set according to purposes for the composition of internal electrode.First internal electrode 41 and second Internal electrode 42 may, for example, be the Ni electrodes that good ohmic is shown for barium titanate based semiconductor.
In the semiconductor element 1 of present embodiment, as shown in Figure 3, glass can be formed on the surface of ceramic body 2 Layer 5.Glassy layer 5 has the function of improving environmental resistance and component strength.Limited for the composition and thickness of glassy layer 5 without special It is fixed, can suitably it be set according to purposes.In the variation shown in Fig. 3, the first internal electrode is configured with the inside of ceramic body 2 41 and second internal electrode 42, but the semiconductor element 1 of present embodiment is not limited to this composition or without interior The composition of portion's electrode.In the variation shown in Fig. 3, it is formed with the surface of the first outer electrode 31 and the second outer electrode 32 Plating layer 61 and 62 (chatting afterwards), but the semiconductor element 1 of present embodiment is not limited to this composition or without plating The composition of coating.
(outer electrode)
The semiconductor element 1 of present embodiment includes the first outer electrode configured in the first end face 21 of ceramic body 2 31 and configuration ceramic body 2 second end face 22 the second outer electrode 32.First outer electrode 31 and the second external electrical Pole 32 as shown in Figure 1, is formed in the way of the part extension in the side of ceramic body 2.In this manual, it is ceramic " side " of base substrate 2 refers to the face beyond the first end face 21 and second end face 22 of ceramic body 2.In this manual, sometimes First outer electrode 31 and the second outer electrode 32 are referred to as " outer electrode ".The composition and composition of outer electrode can be according to potteries The species of porcelain base substrate 2 or when there is internal electrode according to internal electrode (the first internal electrode 41 and the second internal electrode 42) species is appropriately configured.First outer electrode 31 and the second outer electrode 32 can have for example successively with NiCr, NiCu Alloy and Ag order carry out the sandwich construction of lamination.
In the semiconductor element 1 of present embodiment, as shown in Figure 3, outside the first outer electrode 31 and second The surface of electrode 32 can form plating layer 61 and 62.Plating layer 61 and 62 has the solder wettability and heat resistance when improving assembling Function.The composition of plating layer 61 and 62 can suitably be selected according to the composition of outer electrode, for example, Sn plating layers, Ni plating layers Or their two or more combinations.In the variation shown in Fig. 3, the first external electrical is configured with inside ceramic body 2 The outer electrode 32 of pole 31 and second, but the semiconductor element 1 of present embodiment is not limited to this composition, can be without internal electricity The composition of pole.In addition in the variation shown in Fig. 3, glassy layer 5 is formed with the surface of ceramic body 2, but this embodiment party The semiconductor element 1 of formula is not limited to this composition, can be the composition without glassy layer 5.
[manufacture method of semiconductor element]
One of manufacture method of the semiconductor element of present embodiment is illustrated below, but the present invention is partly led The manufacture method of volume elements part is not limited to method as shown below.The manufacture method of the semiconductor element of present embodiment is comprising as follows Process：
The process for modulating Ca-Ti ore type compound particles；Form the work of the green compact chip containing perovskite-type compounds particle Sequence；By burning till the process that ceramic body is made in green compact chip；It is made by the both ends of the surface formation outer electrode in ceramic body The process of semiconductor element.In the present embodiment, mainly illustratively explanation has the stack-up type PTC thermistor of internal electrode Manufacture method, but the manufacture method of semiconductor element of the present invention is not limited to method as shown below.
First, the perovskite-type compounds particle (hereinafter also referred to " Ca-Ti ore type of raw material of the modulation at least containing Ba and Ti Compound particles ") it is used as the raw material for the ceramic body for constituting semiconductor element.The perovskite-type compounds of raw material are except containing Ba Beyond Ti, moreover it is possible to containing at least one element selected from the rare earth element in addition to Pm, Tm, Yb and Lu and/or selected from Nb, W, Sb and Ta at least one element.Weigh each raw material of perovskite-type compounds particle and constituted the half of final gained to be formed The composition of ceramic sintered bodies particle contained by the ceramic body of conductor element constitutes for target.It is used as the ceramic sintered bodies grain of target The composition of son can be by the ceramic component matrix dissolution containing internal electrode, for example, by ICP-AES (Inductively Coupled Plasma-Atomic Emission Spectrometry) carry out quantitative analysis when each element contain than for Shown in following formula (1) contain than composition：
[changing 1]
In formula, α is at least one element selected from the rare earth element in addition to Pm, Tm, Yb and Lu；β be selected from Nb, W, Sb and Ta at least one element.Ba, α, alpha+beta, Ti+ β containing molar part are set to mBa、mα、m(α+β)、m(Ti+β), by m= (mBa+m(α+β))/m(Ti+β)It is defined as mol ratio.Under this definition, it is set to the feelings of 100 molar parts in Ti and β total molar part Under condition, mBaIt is 99.50≤mBa≤ 100.5, m(α+β)Scope be 0.020≤m(α+β)≤ 0.500, m are 0.995≤m≤1.005.
As the raw material of modulation Ca-Ti ore type compound particles, Ba, Ti, element α and β chlorination can be suitably used Thing, hydroxide, oxide, carbonate, alkoxide etc..As described shown in formula (1), although constitute final obtained semiconductor element Ceramic body contained by ceramic sintered bodies particle contain element α and/or β as donor (semiconductor agent), but raw material Perovskite-type compounds particle can be free of either one for having element α and β, or can be free of by being made and have desired constitute Ceramic sintered bodies particle needed for element α and/or β amount total amount.In these cases, by chatting ceramic slurry after addition The desired amount of element α and/or β chloride, hydroxide, oxide, carbonate, alkoxide, ionization aqueous solution etc. during modulation With regard to desired composition can be adjusted to.
Modulator approach for the perovskite-type compounds particle of raw material is not particularly limited, can be according to desired ratio surface Accumulate synthetic method in the liquid that solid-phase synthesis or hydrothermal synthesis method and Oxalic Acid Method etc. are suitably selected with c/a.The Ca-Ti ore type of raw material Compound particles can also be modulated for example, by steps described below.Each above-mentioned raw material and PSZ for weighing are (partially stabilized The zirconium oxide of change) ball and pure water put into ball milling together.It now can also be properly added SiO2Deng sintering aid.Will with wet type Raw material in ball milling are sufficiently mixed crushing, dry, and mixed powder is made.More than 800 DEG C and at less than 1100 DEG C of temperature By the mixed powder calcination process, the perovskite-type compounds particle of raw material is made as roasting powder.Calcination process temperature according to Suitably set as the specific surface area of the perovskite-type compounds particle of target and c/a value.
The specific surface area preferably 4.0m of the perovskite-type compounds particle of raw material2/ more than g and 14.0m2/ below g.If Specific surface area is in 4.0m2/ more than g, then can be by the ceramic sintered bodies particle in the ceramic body of obtained composition semiconductor element The small particle below 1.0 μm of average grain diameter is made.If specific surface area is in 14.0m2/ below g, can be by the sintering in ceramic body Crystal boundary number between body particle is reduced, and can improve the contact rate of sintered body particle.The result is that：Semiconductor element can be reduced The ratio resistance of room temperature.The specific surface area of perovskite-type compounds particle more preferably 4.0m2/ more than g and 11.0m2/ below g.If Specific surface area is in 11.0m2/ below g, further can reduce the ratio resistance value at room temperature of obtained semiconductor element.Calcium titanium The specific surface area of ore deposit type compound particles can be measured for example, by the gas adsorption method of BET method etc..
The perovskite-type compounds particle of raw material has the high crystalline texture of regular crystal.By using with regular crystal The perovskite-type compounds particle of high crystalline texture, can be by the ratio resistance under the room temperature (25 DEG C) of semiconductor element as raw material Reduction.The c-axis length of the lattice of raw material perovskite-type compounds particle is to the ratio between a axial lengths c/a preferably more than 1.005 and 1.009 Below.If c/a is more than 1.005, the ratio resistance value of the room temperature of semiconductor element can be further reduced.C/a is more preferably 1.006 Above and less than 1.009.If c/a is more than 1.006, the ratio resistance value at room temperature of semiconductor element can be further reduced. The c/a of raw material perovskite-type compounds particle can carry out qualitative analysis by using powder x-ray diffraction device, carry out Rietveld parsings are calculated.Raw material perovskite-type compounds particle contains more than one rare earth element as donor.
Then, the green compact chip containing raw material perovskite-type compounds particle is formed.In product of the manufacture with internal electrode In the case that stratotype PTC thermistor is as semiconductor element, the green compact core containing raw material perovskite-type compounds particle is formed The process of piece includes following process：The process for making the ceramic green sheet containing perovskite-type compounds particle；Internal electrode is used Conductive paste is coated on the process on the main surface of ceramic green sheet；Multi-disc is coated with to the pottery of internal electrode conductive paste The process that laminate is made in porcelain raw cook lamination；And the ceramic green sheet configuration without coats internal electrode conductive paste exists Laminate up and down and crimped, be cut into defined size, the process that green compact chips is made.
First, the ceramic green sheet containing perovskite-type compounds particle is made with step as shown below.By organic Agent, dispersant and water are added in the perovskite-type compounds particle of raw material, and a few hours mixing is carried out together with zirconia ball, system Obtain ceramic slurry.Raw material perovskite-type compounds particle without element α and element β it is any in the case of or Do not contain be made with desired composition ceramic sintered bodies particle needed for element α and/or element β amount total amount feelings Under condition, in the modulation of ceramic slurry, the amount of can specify that addition element α and/or element β chloride, hydroxide, oxidation Thing, carbonate, alkoxide, ionization aqueous solution etc. are used as donor.
The ceramic slurry is configured to by sheet by scraper for coating method, it is dried, ceramic green sheet is made.Ceramic green sheet Preferably more than 10 μm and less than 50 μm of thickness.
Then, the coats internal electrode conductive paste on the main surface of ceramic green sheet.First, by metal dust etc. Electroconductive powder and organic bond are scattered in organic solvent, modulate internal electrode conductive paste.It is used as electric conductivity powder End, can be suitably using metal dust such as Ni metal dusts etc..
The internal electrode is coated on the main surface of ceramic green sheet with conductive paste.Internal electrode conductive paste Coating thickness by the thickness of the internal electrode in final obtained semiconductor element more than 0.5 μm and in the way of less than 2 μm Set.Internal electrode can be carried out with the coating of conductive paste by the method for silk-screen printing etc..
Then, multi-disc is coated with to the ceramic green sheet lamination of internal electrode conductive paste, laminate is made.It is coated with The ceramic green sheet laminated chip number of internal electrode conductive paste can be according to made from final in semiconductor element should have The quantity of portion's electrode is set.
Then, in 20 ceramics without coats internal electrode conductive paste of self-configuring for example each up and down of laminate Raw cook, crimping is cut into defined size in the way of the size after burning till turns into desired value, green compact chip is made.Will The size that green compact chip burns till obtained ceramic body can be such as L cuns 2.0mm × W cuns 1.2mm × T cuns of 1.0mm.
, can be by the way that multi-disc not be had into coats internal electrode in the case of semiconductor element of the manufacture without internal electrode With the ceramic green sheet lamination of conductive paste, after crimping, defined size is cut into, green compact chip is made.
Then, ceramic body is made by burning till green compact chip.First, before burning till, at 300 DEG C under air atmosphere Green compact chip is carried out to above and at less than 450 DEG C of temperature the ungrease treatment of more than 10 hours and less than 15 hours.In H2/N2/ H2O mixed gas, Ar/H2、N2/H2/H2With 0.5 more than 1000 DEG C and at less than 1300 DEG C of temperature under O etc. reducing atmosphere The hour above and the green compact chip burnt till after ungrease treatment for less than 3 hours, are made ceramic body.
It is according to circumstances different, obtained ceramic body can also be subjected to vitreous coating, by under air atmosphere It is heat-treated, while ceramic body glass layer formed on surface, is made pottery with the temperature of more than 600 DEG C and less than 900 DEG C Porcelain base substrate is reoxidized.
Then, in the both ends of the surface formation outer electrode of ceramic body.First, before outer electrode formation, by ceramic blank Body tumbling.The both ends of the surface formation outer electrode of ceramic body after tumbling.Composition and formation to outer electrode Method is not particularly limited, and can suitably be selected according to purpose.For example, outer electrode can by the both ends of the surface in ceramic body according to Cr, NiCu alloy and Ag sequential sputtering are formed.As other methods, outer electrode can also contain resin component by coating With the thickener of metal (Ag etc.), glaze firing at moderate temperatures is formed.It can pass through plating etc. on the surface of the outer electrode of formation Method formation plating layer.The composition of plating layer can suitably be selected according to the composition of outer electrode, but for example, Sn plating layers, Ni Plating layer or their two or more combinations.The semiconductor element of present embodiment is thus made.
Embodiment
Comparative example 1 and 2 and the semiconductor element of embodiment 1~9 are made with step as shown below.Comparative example 1 and 2 with And each of the semiconductor element of embodiment 1~9 is stack-up type PTC thermistor.
[comparative example 1]
BaCO is weighed first3、TiO2And La2O3So as to constitute contained by the ceramic body of final obtained semiconductor element The composition of ceramic sintered bodies particle is the composition shown in following formula (2).In comparative example 1, with α=La, mBa=100, mα=mLa= 0.2nd, m=0.999 mode weighs each raw material.
[changing 2]
Each above-mentioned raw material after weighing puts into ball milling together with PSZ (partially stabilized zirconium oxide) balls and pure water In, the raw material in ball milling are sufficiently mixed by crushing with wet type, it is dried, mixed powder is made.More than 800 DEG C and 1100 By the mixed powder calcination process at temperature below DEG C, the perovskite-type compounds particle of raw material is made as roasting powder.System The specific surface area of the perovskite-type compounds particle of the raw material obtained is 2.1m2/ g, c/a are 1.010.The Ca-Ti ore type chemical combination of raw material The specific surface area of thing particle covers the Macsorb (registration mark) that Tyke (Co., Ltd.'s マ ウ Application テ ッ Network) is made using Co., Ltd. Determined under conditions of 250 DEG C of degassing temperature.The c/a of the perovskite-type compounds particle of raw material is spread out by using X-ray powder Injection device carries out qualitative analysis, carries out Rietveld parsings and obtains.
In the perovskite-type compounds particle that organic bond, dispersant and water are added to obtained raw material, with oxidation Zirconium carries out a few hours mixing together, and ceramic slurry is made.The ceramic slurry is configured to by sheet by scraper for coating method, it is done It is dry, the ceramic green sheet that thickness is 30 μm is made.
Then, it is Ni metal dusts and organic bond is scattered in organic solvent, modulate internal electrode conductive paste Material.The internal electrode is coated on the main surface of ceramic green sheet with conductive paste by silk-screen printing.Internal electrode is with leading The coating thickness of electrical thickener with the thickness of the internal electrode in semiconductor element made from final more than 0.5 μm and 2 μm with Under mode be adjusted.By such ceramic green sheet for being coated with internal electrode conductive paste and without coats internal electricity Accumulated with the ceramic green sheet of conductive paste by comprising 24 internal electrodes and internal electrode spacing in the way of 30 μm pole Layer, is made laminate.In 5 ceramic greens without coats internal electrode conductive paste of self-configuring each up and down of the laminate Piece, crimping cuts size in the way of L cuns 2.0mm × W cuns 1.2mm × T cuns of 1.0mm by the size after burning till, green compact core is made Piece.
The green compact chip is subjected to ungrease treatment in 12 hours at a temperature of 300 DEG C under air atmosphere.Use H2/N2/ H2O mixed gas, burns till 2 hours more than 1000 DEG C and at less than 1300 DEG C of temperature under reducing atmosphere, and ceramic blank is made Body.
Obtained ceramic body is subjected to nature of glass coating, entered by the temperature in less than 800 DEG C under air atmosphere Row heat treatment, while ceramic body glass layer formed on surface, carries out reoxidizing for ceramic body.
The ceramic body tumbling of glassy layer will be formed with.The both ends of the surface of ceramic body after tumbling by by According to Cr, NiCu alloy and Ag sequential sputtering formation outer electrode.By electroplating shape on the surface of the outer electrode formed Into Sn plating layers.The semiconductor element of comparative example 1 is so made.
[comparative example 2 and embodiment 1~9]
Except being used as original using the perovskite-type compounds particle that the specific surface area shown in table 1 and c/a value are chatted after having Beyond material, with the semiconductor element of the step manufacture comparative example 2 and embodiment 1~9 same with comparative example 1.
For comparative example 1 and 2 and each semiconductor element of embodiment 1~9, the average grain of ceramic sintered bodies particle is determined Footpath and contact rate.The average grain diameter of ceramic sintered bodies particle is determined according to following steps.First, it is (vertical with W directions in LT faces Face) semiconductor element is ground to about 1/2W places (W of semiconductor element cuns of approximately half of places) by direction, makes and LT faces Parallel semiconductor element section is exposed.Using scanning electron microscope (Hitachi SU-8040) accelerating potential 1kV, times The section is observed under conditions of 10000 times of rate, SEM image is obtained.By SEM it was observed that region (viewing area) Be sized to the quantity of ceramic sintered bodies particle it is countable be more than 80 and less than 200 size.Use analysis dress Put (Asahi Kasei Corporation's system " A is as monarch ") and graphical analysis is carried out to the SEM image, obtain the ceramics burning in SEM image The area of knot body particle.It regard the homalographic calculated according to calculated area circle equivalent footpath (Heywood footpaths) as ceramic post sintering The particle diameter of body particle.The average value that the particle diameter of the ceramic sintered bodies particle of storage will be completed in viewing area is set to ceramic sintered bodies The average grain diameter of particle.In the present embodiment, although obtained the flat of ceramic sintered bodies particle in aforesaid semiconductor element cross-section Equal particle diameter, but in the case of the average grain diameter obtained in other semiconductor element sections, be also considered as to obtain same The result of sample, is irrespective.
Ceramic sintered bodies particle is determined using the section same with obtaining semiconductor element section used in average grain diameter Contact rate.Using scanning electron microscope (SEM) to the central portion of the ceramic body 2 in semiconductor element section near Observed by the part that internal electrode is clamped.To being not particularly limited with the SEM sections observed, arbitrary section may be selected.Cut Face can (partly be led by the way that semiconductor element 1 is ground into about 1/2W places in LT faces (face vertical with W directions) direction The W of volume elements part cuns of approximately half of place) obtained from the semiconductor element section parallel with LT faces.In semiconductor element 1 Section in, to being not particularly limited with the SEM regions observed, for example, can be internal near the central portion of ceramic body 2 The region of electrode clamping.SEM viewing areas are sized under 10000 times of multiplying power of observation, ceramic sintered bodies particle Quantity is countable be more than 80 and less than 200 size.Use analytical equipment (Asahi Kasei Corporation's system " A pictures Monarch ") graphical analysis is carried out to obtained SEM image, obtain the girth of ceramic sintered bodies particle existing in viewing area Total LG, hole existing in viewing area girth total LNCAnd the outer perimeter L of viewing areaS.Graphical analysis will be passed through Obtain LG、LNCAnd LSOne of result be illustrated respectively in Fig. 4~6.According to calculated LG、LNCAnd LSValue, use following formula Obtain total L of the contact length of ceramic sintered bodies particle existing in viewing areaC。
[number 5]
According to calculated LCValue and LNCValue the contact rate of ceramic sintered bodies particle is obtained using following formula.
[number 6]
For comparative example 1 and 2 and each semiconductor element of embodiment 1~9, room temperature (25 DEG C) is determined by 4 terminal methods Under ratio resistance.Measurement result by more than is shown in Table 1 below.
[table 1]
As known from Table 1：It is 4.0m in the specific surface area of the perovskite-type compounds particle of raw material2/ more than g and 14.0m2/g Hereinafter, during c/a is more than 1.005 and less than 1.009 embodiment 1~9, the ceramics contained by the semiconductor element of gained can be burnt The average grain diameter of knot body particle is formed as more than 0.4 μm and less than 1.0 μm, and can be by the contact rate shape of ceramic sintered bodies particle As more than 45%.On the other hand, raw material perovskite-type compounds particle specific surface area less than 4.0m2/ g, c/a are more than In 1.009 comparative example 1, the average grain diameter of the ceramic sintered bodies particle contained by the semiconductor element of gained is more than 1.0 μm, ceramics The contact rate of sintered body particle is less than 45%.Furthermore, raw material perovskite-type compounds particle specific surface area less than 4.0m2In/g comparative example 2, the contact rate of the ceramic sintered bodies particle contained by the semiconductor element of gained is less than 45%.
As shown in table 1, the average grain diameter of ceramic sintered bodies particle is more than 0.4 μm and less than 1.0 μm and contact rate exists The semiconductor element of more than 45% embodiment 1~9 shows the low resistivity value of below 71 Ω cm at room temperature.In addition, implementing The semiconductor element of example 1~9 has more than 1000V/mm high voltage-resistent characteristic.In addition, the perovskite-type compounds grain of raw material The specific surface area of son is 4.0m2/ more than g and 11.0m2The semiconductor element of/below g embodiment 1~8 shows at room temperature 32 Below Ω cm lower ratio resistance value.On the other hand, the average grain diameter of ceramic sintered bodies particle is more than 1.0 μm and contact rate The semiconductor element of comparative example 1 less than 45% has the low voltage-resistent characteristic less than 1000V/mm.Ceramic sintered bodies particle The semiconductor element of comparative example 2 of the contact rate less than 45% show high specific resistance value at room temperature more than 80 Ω cm.
The possibility utilized in industry
The semiconductor element of the present invention can take into account high voltage-resistent characteristic and low resistivity value at room temperature, be suitable for extensive Purposes.
Symbol description
1 semiconductor element
2 ceramic bodies
The first end face of 21 ceramic bodies
The second end face of 22 ceramic bodies
31 first outer electrodes
32 second outer electrodes
41 first internal electrodes
42 second internal electrodes
5 glassy layers
61 62 plating layers

Claims (8)

1. a kind of semiconductor element, it is the semiconductor element for including ceramic body, the first outer electrode and the second outer electrode,
The ceramic body contains ceramic sintered bodies particle；
First end face of the first outer electrode configuration in the ceramic body；
Second end face of the second outer electrode configuration in the ceramic body；
Characterized in that,
The ceramic sintered bodies particle is the perovskite-type compounds at least containing Ba and Ti；
The average grain diameter of the ceramic sintered bodies particle is more than 0.4 μm and less than 1.0 μm；
The contact rate of the ceramic sintered bodies particle more than 45%, the contact rate according to scanning electron microscope to institute Stating the region selected in a section of semiconductor element, to be observed being present in of being calculated described in a region The girth of ceramic sintered bodies particle adds up to the girth in LG, the hole being present in a region to add up to LNC, a region it is outer Perimeter LSAnd the contact length L of the ceramic sintered bodies particle being present in a region represented with following formulaCValue,
(number 1)
<mrow> <msub> <mi>L</mi> <mi>C</mi> </msub> <mo>=</mo> <mfrac> <mrow> <msub> <mi>L</mi> <mi>G</mi> </msub> <mo>-</mo> <msub> <mi>L</mi> <mrow> <mi>N</mi> <mi>C</mi> </mrow> </msub> <mo>-</mo> <msub> <mi>L</mi> <mi>S</mi> </msub> </mrow> <mn>2</mn> </mfrac> </mrow>
Calculated by following formula,
(number 2)
2. semiconductor element as claimed in claim 1, it is characterised in that the contact rate of the ceramic sintered bodies particle is 45% Above and less than 80%.
3. semiconductor element as claimed in claim 1 or 2, it is characterised in that the semiconductor element is in the ceramic blank The inside of body is configured with the stack-up type semiconductor element of more than one first internal electrode and more than one second internal electrode Part；
First internal electrode is electrically connected in the first end face of the ceramic body with first outer electrode；
Second internal electrode is electrically connected in the second end face of the ceramic body with second outer electrode.
4. semiconductor element as claimed in claim 3, it is characterised in that first internal electrode and second inside electricity Pole is Ni electrodes.
5. a kind of method, it is the manufacture method of semiconductor element, includes following process：
The process for modulating the perovskite-type compounds particle at least containing Ba and Ti；
The process for forming the green compact chip containing the perovskite-type compounds particle；
By burning till the process that ceramic body is made in the green compact chip；And
The process that semiconductor element is made by the both ends of the surface formation outer electrode in the ceramic body；
The specific surface area of the perovskite-type compounds particle is in 4.0m2/ more than g and 14.0m2/ below g；
The c-axis length of the lattice of the perovskite-type compounds particle is to the ratio c/a of a axial lengths more than 1.005 and less than 1.009.
6. method as claimed in claim 5, it is characterised in that the specific surface area of the perovskite-type compounds particle exists 4.0m2/ more than g and 11.0m2/ below g.
7. the method as described in claim 5 or 6, it is characterised in that formed containing the perovskite-type compounds particle The process of green compact chip includes following process：
The process for making the ceramic green sheet containing the perovskite-type compounds particle；
The process of coats internal electrode conductive paste on the main surface of the ceramic green sheet；
The process that laminate is made in the ceramic green sheet lamination that multi-disc is coated with into the internal electrode conductive paste；And
Configure without the coating internal electrode with the ceramic green sheet of conductive paste and crimped above and below the laminate, Defined size is cut into, the process that green compact chip is made.
8. method as claimed in claim 7, it is characterised in that the internal electrode conductive paste contains Ni metal dusts It is used as electroconductive powder.
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CN1274932A (en) * 1999-05-20 2000-11-29 株式会社村田制作所 Barium titanate semiconductor ceramic powder and stacked semiconductor device
CN1482628A (en) * 2002-08-13 2004-03-17 ������������ʽ���� Method of producing laminated ptc thermistor
CN102459127A (en) * 2009-06-05 2012-05-16 株式会社村田制作所 Barium titanate semiconductor ceramic composition and barium titanate semiconductor ceramic element

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