CN107210105B - Semiconductor element and its manufacturing method - Google Patents
Semiconductor element and its manufacturing method Download PDFInfo
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- CN107210105B CN107210105B CN201680007338.7A CN201680007338A CN107210105B CN 107210105 B CN107210105 B CN 107210105B CN 201680007338 A CN201680007338 A CN 201680007338A CN 107210105 B CN107210105 B CN 107210105B
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Abstract
A kind of semiconductor element, it is comprising the ceramic body containing ceramic sintered bodies particle, configuration in the first external electrode of the both ends of the surface of ceramic body and the semiconductor element of the second external electrode, wherein, ceramic sintered bodies particle is at least perovskite-type compounds containing Ba and Ti；The average grain diameter of ceramic sintered bodies particle is 0.4 μm or more and 1.0 μm or less；The contact rate of ceramic sintered bodies particle 45% or more, the contact rate adds up to according to the perimeter for being observed the ceramic sintered bodies particle being present in a region calculated with a region selected in a section of the scanning electron microscope to semiconductor element, the perimeter 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
Technical field
The present invention relates to semiconductor element and its manufacturing methods, in particular to barium titanate based semiconductor device and its manufacturer
Method.
Background technique
Barium titanate based semiconductor porcelain is because having positive temperature characterisitic, so being widely used in positive temperature coefficient thermis (PTC
Thermistor) etc. semiconductor element.
For example, recording the manufacturing method of temperature characterisitic functional composite particles in patent document 1, which is characterized in that
The surface for the coatingparticles being made of the semiconductor particle with nonlinear temperature characteristic it is discontinuous dispersion be attached with by with the master batch
The particle that the metallic of sub- Ohmic contact is constituted.Compound particle described in Patent Document 1 does not need high temperature sintering, keeps this compound
Particle is coated after being dispersed in solvent or in a manner of powder compact, then by further low-temperature heat, can be used as non-linear
Temperature characterisitic function element or heater etc. use.
Positive temperature coefficient thermis is described in patent document 2, it is characterised in that there is ceramic insulator substrate, temperature-sensitive electricity
It hinders thick film and at least a pair of electrodes, above-mentioned thermistor thick film is formed on ceramic insulator substrate, is sintered by semiconductive ceramic
Body constitutes and shows that positive resistance-temperature characteristic, at least a pair of above-mentioned electrode are connect and across above-mentioned heat with thermistor thick film
At least part of quick resistance thick film and it is opposite, the resistivity at room temperature of thermistor thick film is less than 10k Ω cm.Patent text
Offer 2 records positive temperature coefficient thermis can expand constitute thermistor thick film semiconductive ceramic in crystal grain between contact surface
Product, is able to achieve low resistance.
Average porcelain partial size is recorded in patent document 3 in 0.9 μm of barium titanate based semiconductor porcelain below.In patent
Average porcelain partial size is described in document 3, and in the barium titanate based semiconductor porcelain of above range, specific resistance is small at room temperature and has
Excellent dieletric strength.Record the following contents in patent document 3: above-mentioned barium titanate based semiconductor porcelain is existed by partial size
0.1 μm hereinafter, crystalline texture is cubic crystal, lattice constant is 4.020 angstroms or more, has the titanium of micro semiconductor agent to be dissolved
Sour barium dust or using the barium titanate powder roasting made of material as raw material powder, be burnt into and be made.
The prior art
Patent document
Patent document 1: Japanese Patent Laid-Open 9-100169 bulletin；
Patent document 2: No. 2012/111386 bulletin of International Publication No.；
Patent document 3: Japanese Patent Laid-Open 11-116327 bulletin.
Summary 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 type in extensive range.Along with close
The high performance of electronic equipment over year, people especially need to cope with the PTC thermistor of high current, have high proof voltage special
The exploitation of the PTC thermistor element of property is carrying out.In order to improve the voltage-resistent characteristic of PTC thermistor, structure is being carried out
At the micronized (patent document 3) of the semiconducting ceramic of PTC thermistor.But inventor research after the result shows that: exist
Because of micronized, the problem of specific resistance at room temperature of PTC thermistor increases.
On the other hand, record in patent document 2 by expand semiconductive ceramic in intercrystalline contact area come
Realize low resistance.But crystal grain documented by patent document 2 has 2 μm~38 μm of average grain diameter of big partial size.
The present invention with provide a kind of semiconductor element for showing low resistivity with high voltage-resistent characteristic and at room temperature and
Its manufacturing method is as a purpose.
Technical scheme applied to solve the technical problem
The present inventor in order to achieve the above object, is conceived to the calcium titanium as parent material used in manufacture semiconductor element
The physical property of mine type compound particles, is studied repeatedly, as a result, having found by controlling perovskite-type compounds grain
The c-axis of the lattice of the specific surface area and perovskite-type compounds particle of son is long can be simultaneous to ratio (regular crystal) c/a of a axial length
It cares for the micronized for constituting ceramic sintered bodies particle contained by the ceramic body of semiconductor element and improves ceramic sintered bodies particle
Contact rate, and then complete the present invention.
According to the first aspect of the invention, a kind of semiconductor element is provided, it is comprising ceramic body, the first external electrode
With the semiconductor element of the second external electrode,
The ceramic body contains ceramic sintered bodies particle；
First end face of the first external electrode configuration in the ceramic body；
Second end face of the second external electrode configuration in the ceramic body；
The ceramic sintered bodies particle is at least perovskite-type compounds containing Ba and Ti；
The average grain diameter of the ceramic sintered bodies particle is 0.4 μm or more and 1.0 μm or less；
The contact rate of the ceramic sintered bodies particle is 45% or more, 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 perimeter of the ceramic sintered bodies particle adds up to LG, the perimeter 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 for the ceramic sintered bodies particle of following formula expression being present in a region
Length LCValue,
(number 1)
It is calculated by following formula,
(number 2)
The contact rate of ceramic sintered bodies particle more fortunately 45% or more and 80% or less.
The semiconductor element can be in the inside of ceramic body configured with more than one first internal electrode and one
The stack-up type semiconductor element of a the second above internal electrode.At this point, first end face of first internal electrode in ceramic body
It is electrically connected with the first external electrode；Second internal electrode is electrically connected in the second end face of ceramic body with the second external electrode.
First internal electrode and the second internal electrode can be Ni electrode.
According to the second aspect of the invention, a kind of method is provided, it is the manufacturing method of semiconductor element, includes following work
Sequence:
The process of the modulation at least perovskite-type compounds particle containing Ba and Ti；
The process for forming the green compact chip containing perovskite-type compounds particle；
The process that ceramic body is made by firing green compact chip；And
The process that semiconductor element is made in external electrode is formed by the both ends of the surface in ceramic body；
The specific surface area of perovskite-type compounds particle is in 4.0m2/ g or more and 14.0m2/ g or less；
The long ratio c/a to a axial length of the c-axis of the lattice of perovskite-type compounds particle is 1.005 or more and 1.009 or less.
The specific surface area of perovskite-type compounds particle is in 4.0m2/ g or more and 11.0m2/ g or less.
In the above-mentioned methods, the process for forming the green compact chip containing perovskite-type compounds particle may 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 in 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 internal electrode conductive paste；And
The ceramic green sheet of no coats internal electrode conductive paste is configured above and below laminate and is crimped, and is cut
At defined size, the process that green compact chip is made.By such method, it can manufacture in the inside of ceramic body configured with interior
The stack-up type semiconductor element of portion's electrode.The internal electrode uses conductive paste that can contain Ni metal powder as electric conductivity powder
End.
The effect of invention
Semiconductor element of the invention is by having high voltage-resistent characteristic and showing at room temperature low with aforementioned composition
Specific resistance.The manufacturing method of semiconductor element of the invention has high voltage-resistent characteristic simultaneously by that can be made with aforementioned composition
And the semiconductor element of low resistivity is shown at room temperature.
Detailed description of the invention
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 area in a section of ceramic body
Long total LGFigure.
Fig. 5 is the total L for showing the perimeter in the hole being present in SEM viewing area in a section of ceramic bodyNC's
Figure.
Fig. 6 is the outer perimeter L for showing the SEM viewing area in a section of ceramic bodySFigure.
Specific 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 to the following embodiments and the accompanying drawings.Constituent element described below
As long as size, material, shape, relative configuration etc. recorded without specific, the scope of the present invention is not only defined in by purpose
This, only illustrates example.In addition, size, shape, positional relationship of each constituent element shown in the drawings etc. exist to make to illustrate
The case where defining and being exaggerated.The size of all parts is not centainly correctly to show numerical value as shown below, and have 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 include ceramic body 2, configuration ceramic body 2 first end face 21 first
Second external electrode 32 of external electrode 31, the second end face 22 configured in ceramic body 2.
(ceramic body)
Ceramic body 2 includes ceramic sintered bodies particle.Ceramic sintered bodies particle in barium titanate by being added to for element of volume
Ceramic material constitute.Ceramic sintered bodies particle is at least perovskite-type compounds containing Ba and Ti.Perovskite-type compounds
Other than 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.It below will be selected from the rare earth element in addition to Pm, Tm, Yb and Lu
At least one element is known as " element α ", and at least one element selected from Nb, W, Sb and Ta is known as " element β ".Element α and member
Plain β is the donor (semiconductor agent) in order to assign ceramic body 2 with ptc characteristics.Ceramic sintered bodies particle can contain above-mentioned member
Either 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 total molar part of Ti and β is set to 100 molar part
Part or more and 100.5 molar parts Ba below.If the content of Ba is more than 99.5 molar parts and 100.5 molar parts are hereinafter, pottery
The room temperature specific resistance of porcelain billet body is lower, and can obtain high voltage-resistent characteristic.Ceramic body 2 is other than Ba and Ti, before can also containing
The element α and/or element β stated.The content of the preferably element α containing ceramic body 2 and element β of ceramic body 2 is aggregated in 0.020
More than molar part and the element α and/or element β of 0.500 molar part amount below.If the content of element α and element β are aggregated in
More than 0.020 molar part, ceramic body 2 suitable PTC (positive temperature coefficient) characteristic can be assigned.If element α's and element β contains
Amount is aggregated in 0.500 molar part hereinafter, the specific resistance of ceramic body 2 can be reduced.
Si of the ceramic body 2 also containing the sintering aid chatted after.Ceramic body 2 can also contain to rub relative to 100
The Ti of your part is 3 molar parts Si below.
Ceramic body 2 can also contain mixed Zr inevitable in manufacturing process.Zr's is mixed into due to chatting ceramics after
Slurry uses zirconia ball as caused by crushing and dispersion medium when modulating.Ceramic body 2 can contain to rub relative to 100
The Ti of your part is 0.01 molar part or more and 1 molar part Zr below.
The average grain diameter of ceramic sintered bodies particle contained by ceramic body 2 is 0.4 μm or more and 1.0 μm or less.If flat
Equal partial size can reach low specific resistance at 0.4 μm or more.If average grain diameter at 1.0 μm hereinafter, in semiconductor element 1 energy
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 image analysis and calculates.
In the semiconductor element 1 of present embodiment, connecing between the ceramic sintered bodies particle as contained by ceramic body 2
The area of touching is big, even if can also reduce the ratio electricity of room temperature (25 DEG C) in the case where the average grain diameter of ceramic sintered bodies particle is small
Resistance.In the present specification, the index as the area contacted between evaluation ceramic sintered bodies particle, uses ceramic sintered bodies grain
The contact rate of son.The contact rate of ceramic sintered bodies particle is calculated with steps described below.Firstly, grinding semiconductor element 1, makes
Section is exposed, is observed with scanning electron microscope (SEM) the section.The section observed with SEM is limited without special
It is fixed, arbitrary section may be selected.Section for example can be by the face LT (face vertical with the direction W) direction by semiconductor element
1 is ground to semiconductor parallel with the face LT obtained from the place about 1/2W (W cuns of approximately half of place of semiconductor element)
Element cross-section.In the section of semiconductor element 1, the region observed with SEM is not particularly limited, such as can be ceramic blank
The region clamped by internal electrode near the central portion of body 2.The size and multiplying power of viewing area are with the ceramics in measurement region
The countable mode for being about 70 or more and about 200 or less Zuo You of the quantity of sintered body particle is appropriately configured.By right
Resulting SEM picture carries out image analysis, finds out total L of the perimeter of ceramic sintered bodies particle existing in viewing areaG, see
Examine total L of the perimeter in hole existing in regionNCAnd the outer perimeter L of viewing areaS.The L that will be found out by image analysisG、
LNCAnd LSResult an example indicate in Fig. 4~6.It can be by total L of the perimeter in hole shown in fig. 5NCIt is considered as and is burnt in ceramics
Not length (hereinafter referred to as " the non-contact long with the part of adjacent ceramic sintered bodies particle contact in the perimeter of knot body particle
Degree ") it is total.As shown in fig. 6, the outer perimeter L of viewing areaSPositioned at the ceramic sintered bodies particle of viewing area outer most edge
Not total composition with the length of ceramic sintered bodies particle contact part existing in viewing area in perimeter.According to required
L outG、LNCAnd LSValue, find out in viewing area in the perimeter of existing ceramic sintered bodies particle and adjacent ceramics burnt
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, find out the contact rate of ceramic sintered bodies particle.Ceramic sintered bodies particle connects
Touching rate 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 45% or more.If contact rate 45% with
On, even if also the specific resistance of room temperature (25 DEG C) can be reduced in the case where the average grain diameter of ceramic sintered bodies particle is small.Ceramics
The contact rate of sintered body particle preferably 45% or more and 80% or less.If contact rate is 80% hereinafter, can reach high PTC
(positive temperature coefficient) characteristic.
The size of ceramic body 2 is not particularly limited, can be appropriately configured depending on the application.The size of ceramic body 2
It may be, for example, L cuns 2.0mm × W cuns 1.2mm × T cuns of 1.0mm.It in the present specification, as shown in Figure 1, will be from the of ceramic body 2
One end face 21 is known as " direction L " to the direction of second end face 22, and direction vertical with the direction L in horizontal plane is known as " direction W ",
The direction vertical with the direction L and the direction W is known as " direction T ".The size in the direction L of ceramic body 2 is known as " L cuns ", by the side W
To size be known as " W cun ", the size in the direction T is known as " T cuns ".
The semiconductor element 1 of present embodiment as shown in Fig. 2, can be the inside of ceramic body 2 configured with one with
On the first internal electrode 41 and more than one second internal electrode 42 stack-up type semiconductor element.In the present specification,
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 external electrode 31；Second internal electrode 42 is in the second end face 22 of ceramic body 2 and
The electrical connection of two external electrodes 32.
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 green body 2 is alternately arranged relative to one another.In 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 fixed for the endless number of internal electrode, it 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 may be, for example, 2
It is a above and 50 or less Zuo You.For the distance between adjacent first internal electrode 41 and the second internal electrode 42 without especially
It limits, can be appropriately configured according to desired purposes.Between adjacent the first internal electrode 41 and the second internal electrode 42
Distance may be, for example, 10 μm or more and 200 μm or less.
The composition of internal electrode is not particularly limited, can be suitably set depending on the application.First internal electrode 41 and second
Internal electrode 42 may, for example, be the Ni electrode 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.Composition and thickness for glassy layer 5 is without special limit
It is fixed, it can suitably set depending on the application.In variation shown in Fig. 3, the first internal electrode is configured in 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, is also possible to not have interior
The composition of portion's electrode.In variation shown in Fig. 3, it is formed on the surface of the first external electrode 31 and the second external electrode 32
Plating layer 61 and 62 (is chatted) afterwards, but the semiconductor element 1 of present embodiment is not limited to this composition, is also possible to do not have plating
The composition of coating.
(external electrode)
The semiconductor element 1 of present embodiment includes first external electrode of the configuration in the first end face 21 of ceramic body 2
31 and configuration ceramic body 2 second end face 22 the second external electrode 32.First external electrode 31 and the second external electrical
Pole 32 as shown in Figure 1, is formed in such a way that a part in the side of ceramic body 2 extends.In the present specification, ceramic
The first end face 21 and the face other than second end face 22 that " side " of green body 2 refers to ceramic body 2.In the present specification, sometimes
First external electrode 31 and the second external electrode 32 are referred to as " external electrode ".The composition and composition of external electrode can be according to potteries
The type of porcelain billet body 2 or when there are internal electrode according to internal electrode (the first internal electrode 41 and the second internal electrode
42) type is appropriately configured.First external electrode 31 and the second external electrode 32 can have for example successively with NiCr, NiCu
The sequence of alloy and Ag carry out multilayered structure made of lamination.
In the semiconductor element 1 of present embodiment, as shown in Figure 3, outside the first external electrode 31 and second
The surface of electrode 32 can form plating layer 61 and 62.Plating layer 61 and 62 has solder wettability and heat resistance when improving assembly
Function.The composition that plating layer 61 and 62 can be suitably selected according to the composition of external electrode, for example, Sn plating layer, Ni plating layer
Or their two or more combinations.In variation shown in Fig. 3, the first external electrical is configured with inside ceramic body 2
Pole 31 and the second external electrode 32, but the semiconductor element 1 of present embodiment is not limited to this composition, can be and does not have internal electricity
The composition of pole.In addition in variation shown in Fig. 3, glassy layer 5 is formed on 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.
[manufacturing method of semiconductor element]
An example of the manufacturing method of the semiconductor element of present embodiment is illustrated below, but of the invention is partly led
The manufacturing method of volume elements part is not limited to method as shown below.The manufacturing method of the semiconductor element of present embodiment includes 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；The process that ceramic body is made by firing green compact chip；External electrode is formed by the both ends of the surface in ceramic body to be made
The process of semiconductor element.In the present embodiment, mainly illustratively illustrate the stack-up type PTC thermistor with internal electrode
Manufacturing method, but the manufacturing method of semiconductor element of the invention is not limited to method as shown below.
Firstly, the modulation at least perovskite-type compounds particle (hereinafter also referred to " Ca-Ti ore type of raw material containing Ba and Ti
Compound particles ") as constitute semiconductor element ceramic body raw material.The perovskite-type compounds of raw material are in addition to containing Ba
Other than Ti, moreover it is possible to containing selected from rare earth element in addition to Pm, Tm, Yb and Lu at least one element and/or selected from Nb,
W, at least one element of Sb and Ta.Each raw material of perovskite-type compounds particle is weighed to be formed and be constituted final resulting half
The group of ceramic sintered bodies particle contained by the ceramic body of conductor element is formed as target.Ceramic sintered bodies grain as 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 each element when quantitative analysis containing than for
Shown in following formula (1) containing 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,
At least one element of Sb and Ta.The molar part that contains of Ba, α, alpha+beta, Ti+ β are set to mBa、mα、m(α+β)、m(Ti+β), by m=
(mBa+m(α+β))/m(Ti+β)It is defined as molar ratio.Under this definition, it is set to the feelings of 100 molar parts in total molar part of Ti and β
Under condition, mBaIt is 99.50≤mBa≤ 100.5, m(α+β)Range 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, the chlorination of Ba, Ti, element α and β can be suitably used
Object, hydroxide, oxide, carbonate, alkoxide etc..As shown in the formula (1), although constituting final semiconductor element obtained
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, which can be free of, either element α and β, or can be free of and be made of obtained with desired
Ceramic sintered bodies particle needed for element α and/or β amount total amount.In these cases, by chatting ceramic slurry after addition
The chloride of the desired amount of element α and/or β, hydroxide, oxide, carbonate, alkoxide, ionization aqueous solution etc. when modulation
It can be adjusted to desired composition.
The modulator approach of the perovskite-type compounds particle of raw material is not particularly limited, it can be according to desired specific surface
Long-pending and c/a suitably selects synthetic method in the liquid of solid-phase synthesis or hydrothermal synthesis method and Oxalic Acid Method etc..The Ca-Ti ore type of raw material
Compound particles can also be modulated for example, by steps described below.Weighed above-mentioned each raw material and PSZ are (partially stabilized
The zirconium oxide of change) ball and pure water put into ball milling together.It can also be properly added SiO at this time2Deng sintering aid.It will with wet type
Raw material in ball milling are sufficiently mixed crushing, dry, and mixed powder is made.Under 800 DEG C or more and 1100 DEG C of temperature below
By the mixed powder calcination process, the perovskite-type compounds particle of raw material is made as roasting powder.Calcination process temperature according to
The specific surface area of perovskite-type compounds particle and the value of c/a as target are suitably set.
The specific surface area preferably 4.0m of the perovskite-type compounds particle of raw material2/ g or more and 14.0m2/ g or less.If
Specific surface area is in 4.0m2/ g or more, then can be by the ceramic sintered bodies particle in the ceramic body obtained for constituting semiconductor element
1.0 μm of small particles below of average grain diameter are made.If specific surface area is in 14.0m2/ g is hereinafter, 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.As a result, semiconductor element can be reduced
The specific resistance of room temperature.The specific surface area of perovskite-type compounds particle more preferably 4.0m2/ g or more and 11.0m2/ g or less.If
Specific surface area is in 11.0m2/ g is hereinafter, can further reduce the specific resistance value at room temperature of semiconductor element obtained.Calcium titanium
The specific surface area of mine type compound particles can be measured for example, by the gas adsorption method of BET method etc..
The crystalline texture that the perovskite-type compounds particle of raw material has regular crystal high.By using with regular crystal
The perovskite-type compounds particle of high crystalline texture, can be by the specific resistance under the room temperature (25 DEG C) of semiconductor element as raw material
It reduces.The c-axis of the lattice of raw material perovskite-type compounds particle is long to the ratio between a axial length c/a preferably 1.005 or more and 1.009
Below.If c/a can further decrease the specific resistance value of the room temperature of semiconductor element 1.005 or more.C/a is more preferably 1.006
Above and 1.009 or less.If c/a can further decrease the specific resistance value at room temperature of semiconductor element 1.006 or more.
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 parsing calculates.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.There is the product of internal electrode in manufacture
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 of ceramic green sheet of the production containing perovskite-type compounds particle；Internal electrode is used
Conductive paste is coated on the process in 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 of no coats internal electrode conductive paste is existed
Laminate up and down and crimped, be cut into defined size, be made green compact chip process.
Firstly, making the ceramic green sheet containing perovskite-type compounds particle with step as shown below.By organic
Agent, dispersing agent 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.The perovskite-type compounds particle of raw material without element α and element β it is any in the case where or
The feelings of the total amount of amount without containing element α and/or element β needed for the ceramic sintered bodies particle with desired composition is made
Under condition, in the modulation of ceramic slurry, the chloride of the amount of can specify that addition element α and/or element β, hydroxide, oxidation
Object, carbonate, alkoxide, ionization aqueous solution etc. are used as donor.
The ceramic slurry is configured to sheet by scraper for coating method, is made it dry, ceramic green sheet is made.Ceramic green sheet
Preferably 10 μm or more and 50 μm or less of thickness.
Then, the coats internal electrode conductive paste in the main surface of ceramic green sheet.Firstly, by metal powder etc.
Electroconductive powder and organic bond dispersion in organic solvent, modulate internal electrode conductive paste.As electric conductivity powder
Metal powder such as Ni metal powder etc. can be suitably used in end.
The internal electrode is coated in the main surface of ceramic green sheet with conductive paste.Internal electrode conductive paste
Coating thickness in such a way that the thickness of the internal electrode in final semiconductor element obtained is below at 0.5 μm or more and 2 μm
It is set.The coating of internal electrode conductive paste can be carried out 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
In the ceramic green sheet lamination the piece number of internal electrode conductive paste can should have according to final semiconductor element obtained
The quantity of portion's electrode is set.
Then, in self-configuring 20 ceramics without coats internal electrode conductive paste for example each up and down of laminate
Raw cook, crimping are cut into defined size in such a way that the size after being burnt into becomes desired value, green compact chip are made.It will
The size that green compact chip is burnt into ceramic body obtained can be such as L cuns 2.0mm × W cuns 1.2mm × T cuns of 1.0mm.
It, can be by the way that multi-disc not be had coats internal electrode in the case where manufacturing the semiconductor element without internal electrode
With the ceramic green sheet lamination of conductive paste, after crimping, it is cut into defined size, green compact chip is made.
Then, ceramic body is made by firing green compact chip.Firstly, before firing, at 300 DEG C under air atmosphere
Green compact chip is carried out 10 hours or more and ungrease treatment below in 15 hours above and at 450 DEG C of temperature below.In H2/N2/
H2O mixed gas, Ar/H2、N2/H2/H2With 0.5 under 1000 DEG C or more and 1300 DEG C of temperature below under the reducing atmosphere of O etc.
Hour or more and 3 hours or less firing ungrease treatment after green compact chip, be made ceramic body.
It is according to circumstances different, obtained ceramic body can also be subjected to vitreous coating, by under air atmosphere
With 600 DEG C or more and 900 DEG C of temperature below are heat-treated, and while ceramic body glass layer formed on surface, are made pottery
Porcelain billet body reoxidizes.
Then, external electrode is formed in the both ends of the surface of ceramic body.Firstly, before external electrode formation, by ceramic blank
Body tumbling.The both ends of the surface of ceramic body after tumbling form external electrode.Composition and formation to external electrode
Method is not particularly limited, and can suitably be selected according to purpose.For example, external electrode can by the both ends of the surface in ceramic body according to
The sequential sputtering of Cr, NiCu alloy and Ag are formed.As other methods, external electrode can also contain resin component by coating
With the thickener of metal (Ag etc.), glaze firing is formed at moderate temperatures.Plating etc. can be passed through on the surface of the external electrode of formation
Method forms plating layer.The composition of plating layer can suitably be selected according to the composition of external electrode, but for example, Sn plating layer, Ni
Plating layer or their two or more combinations.The semiconductor element of present embodiment is thus made.
Embodiment
The semiconductor element of comparative example 1 and 2 and Examples 1 to 9 is made with step as shown below.Comparative example 1 and 2 with
And each of semiconductor element of Examples 1 to 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 semiconductor element obtained
The group of ceramic sintered bodies particle becomes to be formed shown in following formula (2).In comparative example 1, with α=La, mBa=100, mα=mLa=
0.2, the mode of m=0.999 weighs each raw material.
[changing 2]
Above-mentioned each raw material after weighing puts into ball milling together with PSZ (partially stabilized zirconium oxide) ball and pure water
In, the raw material in ball milling are sufficiently mixed by crushing with wet type, are made it dry, mixed powder is made.At 800 DEG C or more and 1100
By the mixed powder calcination process at DEG C temperature below, 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 1.010.The Ca-Ti ore type chemical combination of raw material
The specific surface area of object particle covers the Macsorb (registered trademark) of Tyke (Co., Ltd.'s マ ウ Application テ ッ Network) system using Co., Ltd.
It is measured 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 parsing and finds out.
Organic bond, dispersing agent and water are added in the perovskite-type compounds particle of raw material obtained, with oxidation
Zirconium carries out a few hours mixing together, and ceramic slurry is made.The ceramic slurry is configured to sheet by scraper for coating method, keeps it dry
It is dry, the ceramic green sheet with a thickness of 30 μm is made.
Then, in organic solvent by Ni metal powder and organic bond dispersion, internal electrode conductive paste is modulated
Material.The internal electrode is coated in 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 final semiconductor element obtained 0.5 μm or more 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
The ceramic green sheet of pole conductive paste is accumulated by comprising 24 internal electrodes and in a manner of internal electrode spacing is 30 μm
Laminate is made in layer.In self-configuring each up and down 5 ceramic greens without coats internal electrode conductive paste of the laminate
Green compact core is made in piece, crimping, the cutter size in such a way that the size after being burnt into is L cuns 2.0mm × W cuns 1.2mm × T cuns of 1.0mm
Piece.
Under air atmosphere 300 DEG C at a temperature of by the green compact chip carry out ungrease treatment in 12 hours.Use H2/N2/
H2O mixed gas is burnt into 2 hours under 1000 DEG C or more and 1300 DEG C of temperature below under reducing atmosphere, and ceramic blank is made
Body.
Obtained ceramic body is subjected to nature of glass coating, by under air atmosphere in 800 DEG C of temperature below into
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 are by pressing
External electrode is formed according to the sequential sputtering of Cr, NiCu alloy and Ag.Pass through plating shape on the surface for be formed by external electrode
At Sn plating layer.The semiconductor element of comparative example 1 is made in this way.
[comparative example 2 and Examples 1 to 9]
In addition to use have after chat the perovskite-type compounds particle of specific surface area shown in table 1 and the value of c/a as original
Other than material, with the semiconductor element of step the manufacture comparative example 2 and Examples 1 to 9 same as comparative example 1.
For each semiconductor element of comparative example 1 and 2 and Examples 1 to 9, the average grain of ceramic sintered bodies particle is measured
Diameter and contact rate.The average grain diameter of ceramic sintered bodies particle measures according to the following steps.Firstly, (vertical with the direction W in the face LT
Face) semiconductor element is ground to the place about 1/2W (W of semiconductor element cuns of approximately half of places) by direction, makes and the face LT
Parallel semiconductor element section is exposed.Using scanning electron microscope (Hitachi SU-8040) acceleration voltage 1kV, times
The section is observed under conditions of 10000 times of rate, obtains SEM image.The region (viewing area) observed by SEM
Be sized to ceramic sintered bodies particle quantity it is countable be 80 or more and 200 sizes below.It is filled using analysis
It sets (Asahi Kasei Corporation's system " A is as monarch ") and image analysis is carried out to the SEM image, the ceramics found out in SEM image are burnt
The area of knot body particle.Ceramic post sintering will be used as according to homalographic circle equivalent diameter (Heywood diameter) of calculated area calculating
The partial size of body particle.The average value for the partial size that the ceramic sintered bodies particle of storage is completed in viewing area is set to ceramic sintered bodies
The average grain diameter of particle.In the present embodiment, although having found out the flat of ceramic sintered bodies particle in aforesaid semiconductor element cross-section
Equal partial size, but even if found out in other semiconductor element sections average grain diameter in the case where, also think to obtain same
Sample as a result, being irrespective.
Ceramic sintered bodies particle is measured using section same as semiconductor element section used in average grain diameter is found out
Contact rate.Using scanning electron microscope (SEM) to the central portion of the ceramic body 2 in semiconductor element section near
It is observed by the part that internal electrode clamps.The section observed with SEM is not particularly limited, arbitrary section may be selected.It cuts
Face for example can be (is partly led by the way that semiconductor element 1 is ground to the place about 1/2W in the face LT (face vertical with the direction W) direction
The W of volume elements part cuns of approximately half of place) obtained from the semiconductor element section parallel with the face LT.In semiconductor element 1
Section in, the region observed with SEM is not particularly limited, such as can be internal near the central portion of ceramic body 2
The region of electrode clamping.SEM viewing area is sized under 10000 times of multiplying power of observation, ceramic sintered bodies particle
Countable quantity is 80 or more and 200 sizes below.Use analytical equipment (Asahi Kasei Corporation's system " A picture
Monarch ") image analysis is carried out to obtained SEM image, find out the perimeter of ceramic sintered bodies particle existing in viewing area
Total LG, hole existing in viewing area perimeter total LNCAnd the outer perimeter L of viewing areaS.Image analysis will be passed through
Find out LG、LNCAnd LSAn example of result be illustrated respectively in Fig. 4~6.According to calculated LG、LNCAnd LSValue, use following formula
Find out 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 found out using following formula.
[number 6]
For each semiconductor element of comparative example 1 and 2 and Examples 1 to 9, room temperature (25 DEG C) are measured by 4 terminal methods
Under specific resistance.Above measurement result is shown in Table 1 below.
[table 1]
As known from Table 1: being 4.0m in the specific surface area of the perovskite-type compounds particle of raw material2/ g or more and 14.0m2/g
Hereinafter, c/a is that can burn ceramics contained by resulting semiconductor element in 1.005 or more and 1.009 Examples 1 to 9 below
The average grain diameter of knot body particle is formed as 0.4 μm or more and 1.0 μm hereinafter, and can be by the contact rate shape of ceramic sintered bodies particle
As 45% or more.On the other hand, in the specific surface area of the perovskite-type compounds particle of raw material less than 4.0m2/ g, c/a are greater than
In 1.009 comparative example 1, the average grain diameter of ceramic sintered bodies particle contained by resulting semiconductor element is greater than 1.0 μm, ceramics
The contact rate of sintered body particle is less than 45%.Furthermore the specific surface area of the perovskite-type compounds particle of raw material less than
4.0m2In the comparative example 2 of/g, the contact rate of ceramic sintered bodies particle is less than 45% contained by resulting semiconductor element.
As shown in table 1, the average grain diameter of ceramic sintered bodies particle is 0.4 μm or more and 1.0 μm or less and contact rate exists
The semiconductor element of 45% or more Examples 1 to 9 shows 71 Ω cm low resistivity value below at room temperature.In addition, implementing
The semiconductor element of example 1~9 has the high voltage-resistent characteristic of 1000V/mm or more.In addition, the perovskite-type compounds grain of raw material
The specific surface area of son is 4.0m2/ g or more and 11.0m2The semiconductor element of/g Examples 1 to 8 below shows at room temperature 32
Ω cm lower specific resistance value below.On the other hand, the average grain diameter of ceramic sintered bodies particle is greater 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 at room temperature more than the high specific resistance value of 80 Ω cm.
A possibility that being utilized in industry
Semiconductor element of the invention can take into account high voltage-resistent characteristic and low resistivity value at room temperature, 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 external electrodes
32 second external electrodes
41 first internal electrodes
42 second internal electrodes
5 glassy layers
61 62 plating layers
Claims (4)
1. a kind of semiconductor element, it is the semiconductor element comprising ceramic body, the first external electrode and the second external electrode,
The ceramic body contains ceramic sintered bodies particle；
First end face of the first external electrode configuration in the ceramic body；
Second end face of the second external electrode configuration in the ceramic body；
It is characterized in that,
The ceramic sintered bodies particle is at least perovskite-type compounds containing Ba and Ti；
The average grain diameter of the ceramic sintered bodies particle is 0.4 μm or more and 1.0 μm or less；
The contact rate of the ceramic sintered bodies particle 45% or more, the contact rate according to scanning electron microscope to institute
Stating a region selected in a section of semiconductor element, to be observed being present in of being calculated described in a region
The perimeter of ceramic sintered bodies particle adds up to LG, the perimeter in hole that is present in a region add up to LNC, the region it is outer
Perimeter LSAnd the contact length L for the ceramic sintered bodies particle of following formula expression being present in a regionCValue,
(number 1)
It is calculated by following formula,
(number 2)
2. semiconductor element as described in claim 1, which is characterized in that the contact rate of the ceramic sintered bodies particle is 45%
Above and 80% or less.
3. semiconductor element as claimed in claim 1 or 2, which is characterized 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 external electrode；
Second internal electrode is electrically connected in the second end face of the ceramic body with second external electrode.
4. semiconductor element as claimed in claim 3, which is characterized in that first internal electrode and second inside electricity
Pole is Ni electrode.
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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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| JPH07220902A (en) * | 1994-02-07 | 1995-08-18 | Murata Mfg Co Ltd | Barium titanate semiconductor ceramic |
| JP2001326102A (en) * | 2000-05-15 | 2001-11-22 | Murata Mfg Co Ltd | Laminated semiconductor ceramic device and method of manufacturing the same |
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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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107210105A (en) | 2017-09-26 |
| JPWO2016125520A1 (en) | 2017-09-14 |
| WO2016125520A1 (en) | 2016-08-11 |
| JP6739353B2 (en) | 2020-08-12 |
| DE112016000618T5 (en) | 2017-11-02 |
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