CN103813997A - Silicon nitride sintered body and method for producing same - Google Patents

Silicon nitride sintered body and method for producing same Download PDF

Info

Publication number
CN103813997A
CN103813997A CN201380003146.5A CN201380003146A CN103813997A CN 103813997 A CN103813997 A CN 103813997A CN 201380003146 A CN201380003146 A CN 201380003146A CN 103813997 A CN103813997 A CN 103813997A
Authority
CN
China
Prior art keywords
silicon nitride
heat
raw material
material powder
manufacture method
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201380003146.5A
Other languages
Chinese (zh)
Inventor
有马峻
松村保范
梶野仁
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsui Mining and Smelting Co Ltd
Original Assignee
Mitsui Mining and Smelting Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsui Mining and Smelting Co Ltd filed Critical Mitsui Mining and Smelting Co Ltd
Publication of CN103813997A publication Critical patent/CN103813997A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B35/63416—Polyvinylalcohols [PVA]; Polyvinylacetates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3427—Silicates other than clay, e.g. water glass
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3852—Nitrides, e.g. oxynitrides, carbonitrides, oxycarbonitrides, lithium nitride, magnesium nitride
    • C04B2235/3873—Silicon nitrides, e.g. silicon carbonitride, silicon oxynitride
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3852—Nitrides, e.g. oxynitrides, carbonitrides, oxycarbonitrides, lithium nitride, magnesium nitride
    • C04B2235/3873—Silicon nitrides, e.g. silicon carbonitride, silicon oxynitride
    • C04B2235/3878—Alpha silicon nitrides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5445—Particle size related information expressed by the size of the particles or aggregates thereof submicron sized, i.e. from 0,1 to 1 micron
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6562—Heating rate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6567—Treatment time
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/658—Atmosphere during thermal treatment
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/76—Crystal structural characteristics, e.g. symmetry
    • C04B2235/767—Hexagonal symmetry, e.g. beta-Si3N4, beta-Sialon, alpha-SiC or hexa-ferrites
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
    • C04B2235/787—Oriented grains
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/80—Phases present in the sintered or melt-cast ceramic products other than the main phase
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/80—Phases present in the sintered or melt-cast ceramic products other than the main phase
    • C04B2235/85—Intergranular or grain boundary phases
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Products (AREA)

Abstract

This silicon nitride sintered body has substantially non-oriented crystallization, a 100 W/mK or higher thermal conductivity, and 500 MPa or higher room-temperature three-point bending strength measured in accordance with JIS R1601. The sintered body is preferably produced by a method comprising: an ageing step for holding a raw powder material comprising silicon nitride powder at a constant temperature between 1400-1750 DEG C over 1-100 hours; a temperature increasing step for increasing the temperature at a rate of 1-100 DEG C/h from the temperature of the ageing step; and a firing step for firing at a constant temperature between 1800-2000 DEG C over 30-60 hours.

Description

Silicon nitride sinter and manufacture method thereof
Technical field
The present invention relates to silicon nitride sinter.In addition the invention still further relates to, the manufacture method of silicon nitride sinter.
Background technology
In recent years, in the field for driving solar power generation and the wind-power electricity generation etc. of expressing the field of the hybrid electric vehicle of very high concern and the electric motor of electromobile and attract attention as sustainable energy, from the viewpoint that improves Energy efficiency and save the energy, power semiconductor becomes important technology essential factor.Because the thermal value of power semiconductor is large, so its circuit substrate must have high heat-conduction coefficient in order to dispel the heat.In the time adopting the substrate of insulativity as this substrate, in recent years to using silicon nitride to carry out various research (with reference to patent documentation 1 and 2) as the technology of this substrate.This be because: silicon nitride is to have high theoretical heat-conduction coefficient, good mechanical characteristics and the material of high electric insulation.
In patent documentation 1, record: if in silicon nitride particles residual O, Al, Ca and Fe, the phonon in silicon nitride particles propagate hindered, result make silicon nitride sinter heat-conduction coefficient decline.In addition, in the document, also record: by making the direction of silicon nitride particles to any one party to orientation, propagate and can not stagnate at the inside phonon of the party, can realize thus high heat conductivity.In addition, in the document, also record: more than the short shaft diameter of silicon nitride particles is defined as to 2 μ m, also can improve the heat-conduction coefficient of silicon nitride sinter.
In patent documentation 2, having recorded by the heat-conduction coefficient of thickness direction is the substrate that more than 1.2 silicon nitride sinters forms with respect to the ratio of the heat-conduction coefficient of real estate direction.According to the record of the document, think by giving anisotropy to heat-conduction coefficient, in the time carrying the element of the heatings such as circuit or IC at substrate surface, be formed at the heat producing in the lip-deep circuit of a side of substrate or element compared with side, can propagate to the inside efficiently, can not emit heat to face direction to thickness direction, thereby can improve thermal diffusivity, so can prevent the rising of the temperature of circuit or element.In order to give anisotropy to the heat-conduction coefficient of the substrate being formed by silicon nitride sinter, the manufacture method below adopting in the document.That is to say, by forming containing the raw material powder that β type alpha-silicon nitride powders as crystal seed, further contains alpha-form si nitride powder, make β type alpha-silicon nitride powders orientation in magnetic field.If then burnt till, can manufacture β type silicon nitride particles after being orientated and be kind, alpha-form si nitride particle dissolves and separate out and carry out grain growing, substrate in thickness direction c-axis orientation with column.
Prior art document
Patent documentation 1: TOHKEMY 2001-19555 communique
Patent documentation 2: TOHKEMY 2002-121076 communique
Summary of the invention
, the electric power of power semiconductor processing is in recent years increasing, and current density is also more and more higher in addition.The silicon nitride sinter of recording for patent documentation 1 and 2, become be difficult to fully corresponding with so large electrification and high current densityization.
So problem of the present invention is to provide a kind of silicon nitride sinter and manufacture method thereof that solves the many disadvantages that above-mentioned conventional art has.
The invention provides a kind of crystal of silicon nitride in fact without the silicon nitride sinter being orientated.The heat-conduction coefficient of this silicon nitride sinter is more than 100W/mK, and the normal temperature three-point bending strength of measuring according to JIS R1601 is more than 500MPa.
In addition,, as the preferred manufacture method of described silicon nitride sinter, the invention provides a kind of manufacture method of the silicon nitride sinter that is included in the operation of under nitrogen atmosphere, the raw material powder that contains alpha-silicon nitride powders being burnt till.Described operation possesses: described raw material powder is kept under the steady temperature between 1400～1750 ℃ to aging (ageing) operation of 1～100 hour; The heating process that temperature from aging process heats up with the heat-up rate of 1～100 ℃/h; And under the steady temperature between 1800～2000 ℃, burn till the firing process of 30～60 hours.
Embodiment
Silicon nitride in silicon nitride sinter of the present invention can be any one in α type and β type.If α type and β type are compared, by inference: β type has simple crystalline structure, be therefore difficult to produce phon scattering, heat-conduction coefficient improves.So preferred nitrogen SiClx is β type.
One of feature of silicon nitride sinter of the present invention is: have high heat-conduction coefficient, have high strength simultaneously.About heat-conduction coefficient, silicon nitride sinter of the present invention has high heat-conduction coefficient more than 100W/mK, preferably there is the heat-conduction coefficient of 100～150W/mK, more preferably there is the heat-conduction coefficient of 100～140W/mK, further preferably there is the heat-conduction coefficient of 100～135W/mK.There is so silicon nitride sinter of the present invention of high heat-conduction coefficient, be particularly suitable as the substrate of the power semiconductor that for example requires high-cooling property or the roller of various aluminium molten metal parts and iron and steel producing apparatus etc.When this heat-conduction coefficient is for example tabular at silicon nitride sinter of the present invention, as long as meeting, the either direction in its X-direction, Y direction and Z-direction just can, preferably 2 directions in these 3 directions meet, and particularly most preferably all meet in these 3 directions.Heat-conduction coefficient can be measured according to JIS R1611 and by for example laser flash method.
About intensity, it is high strength more than 500MPa that silicon nitride sinter of the present invention has normal temperature three-point bending strength, preferably has the intensity of 500～900MPa, more preferably has the intensity of 500～800MPa, further preferably has the intensity of 500～700MPa.Having so high-intensity silicon nitride sinter of the present invention and above-mentioned high heat-conduction coefficient mutually combines, in the time that this sintered compact is used as to the substrate of for example power semiconductor, when operation in the manufacturing process of device, become and be not easy breakage, also effectively prevented the crackle easily producing because of the thermal cycling of device.In addition, the effect of the thermal stresses owing to can reduce shock heating quenching time is large, so be also useful as heat shock resistance member.When this intensity is for example tabular at silicon nitride sinter of the present invention, if either direction in its X-direction, Y direction and Z-direction just meet can, preferably 2 directions in these 3 directions are satisfied, particularly most preferably all meet in these 3 directions.Normal temperature three-point bending strength can be measured according to R1601.
For silicon nitride sinter of the present invention, in order to have above-mentioned heat-conduction coefficient and intensity, it is important that the crystal grain of the silicon nitride particles in this sintered compact is essentially without orientation.In the silicon nitride sinter of known up to now high heat-conduction coefficient, by crystal being given to orientation, phonon propagation is not obstructed, thereby improves heat-conduction coefficient.The crystal grain that on the other hand, can obtain silicon nitride is to be unknown up to now very brand-new idea without orientation and the idea of the present invention with the silicon nitride sinter of high heat-conduction coefficient.About the suitable method being essentially for the crystal grain that obtains silicon nitride without the silicon nitride sinter of orientation, will narrate in the back.
About the degree of the orientation of the crystal grain of the silicon nitride in silicon nitride sinter of the present invention, can judge from the mensuration of utilizing X-ray diffraction method of this sintered compact.Specifically, in the time that silicon nitride is β type, according to the diffractogram of measuring by powder X-ray diffractometry, the height that mensuration comes from (200) face of silicon nitride and the peak value of (002) face is I 200and I 002.Then, to ND(Normal Direction) and RD(Rolling Direction) the two ratio that calculates these peak heights is I 002/ I 200.Be without orientation at the crystal grain of silicon nitride, in theory, for ND and RD the two, described ratio I 002/ I 200value be 1.Thereby in the present invention, in the scope that the value of ND and the two above-mentioned ratio calculating of RD is to 0.6～3, in 0.6～1.5 scope, be especially in 0.6～1.3 scope time, judge that the crystal grain of the silicon nitride in this silicon nitride sinter is essentially without orientation.So-called " in fact " means that not only the value at above-mentioned ratio is at 1 o'clock, and is also judged as without orientation in the time that the value of above-mentioned ratio departs from 1 above-mentioned scope.Moreover, come from the peak height I of (002) face 002in the case of the crystallinity of silicon nitride is high, be divided into α 1and α 2observe, so in such cases, I 002from I 002=(2 α 1+ α 2)/3 calculate.
For silicon nitride sinter of the present invention, its bulk specific gravity is preferably 3.0～4.0, is particularly preferably 3.4～3.5.In addition its specific heat is preferably 0.1～1(J/kgK), be particularly preferably 0.5～0.7(J/kgK).Its reason be because: because heat-conduction coefficient ［ k ］ represents with heat-conduction coefficient ［ k ］=bulk specific gravity × specific heat × thermal diffusivity, thus bulk specific gravity and specific heat more high heat-conduction coefficient more improve.The linear expansivity of silicon nitride sinter of the present invention is preferably 3.0～4.0 × 10 the scope of 20～400 ℃ in addition -6/ K, is particularly preferably 3.2～3.3 × 10 -6/ K.
The bulk specific gravity of silicon nitride sinter can be controlled by particle diameter and the firing condition etc. of raw material powder.Bulk specific gravity can be measured by Archimedes's method according to JIS Z8807.The specific heat of silicon nitride sinter and linear expansivity can be controlled by the kind of raw material powder etc.Specific heat can be according to JISR1611, for example measure with laser flash method.Linear expansivity can be measured according to JIS R3102 and by for example TMA method.
Silicon nitride sinter of the present invention is using silicon nitride as principal constituent, and further contains the element as the compound of sintering aid.As sintering aid, can adopt those identical with the sintering aid that used up to now in this technical field.The element that forms sintering aid is mainly present in the crystal boundary in silicon nitride sinter.Particularly, preferably use Yb 2o 3, SiO 2and at least one in MgO is as sintering aid.Crystal boundary can form crystallization phases, or also can be glassy phase.When both are compared, crystallization phases is difficult to produce phon scattering compared with glassy phase, consequently: heat-conduction coefficient improves compared with glassy phase.From then on viewpoint is set out, and it is favourable that crystal boundary forms crystallization phases.In the time adopting above-mentioned material as sintering aid, form the element of this sintering aid for example with Yb 2si 3n 4o 3or Yb 2si 3n 2o 7, Yb 2si 2o 7state Deng the crystallization phases of compound is mainly present in crystal boundary.In these crystallization phases compounds, the more simple heat-conduction coefficient of crystalline structure is higher, is therefore preferred.For example Yb 2si 3n 4o 3or Yb 2si 3n 2o 7deng element nitride crystal and Yb 2si 2o 7compare Deng oxide crystal, general covalency is high, and therefore heat-conduction coefficient improves.From then on viewpoint is set out, and preferably uses Yb 2si 3n 4o 3or Yb 2si 3n 2o 7on nitride as crystallization phases compound.
Then, the suitable manufacture method of silicon nitride sinter of the present invention is described.This manufacture method is included in the operation of under nitrogen atmosphere, the raw material powder that contains alpha-silicon nitride powders being burnt till.As alpha-silicon nitride powders contained in raw material powder, can adopt any in the silicon nitride of α type and β type.Preferably adopt the alpha-silicon nitride powders of α type, be preferably transformed into the silicon nitride of β type by burning till under condition described later.The median size of alpha-silicon nitride powders is preferably 0.3～1.5 μ m, is particularly preferably 0.3～1 μ m.Median size can be measured according to JIS R1629 and by laser diffraction and scattering method.Alpha-silicon nitride powders shared ratio in raw material powder is preferably 70～99 quality %, is particularly preferably 85～99 quality %.
In raw material powder, except alpha-silicon nitride powders, preferably contain the powder of sintering aid.As sintering aid, as previously mentioned, can adopt those identical with the sintering aid that used up to now in this technical field.Particularly, as sintering aid, preferably pass through Yb 2o 3, SiO 2and at least one in MgO, especially, pass through Yb 2o 3and SiO 2combination or Yb 2o 3with the combination of MgO, in the time burning till according to firing condition described later, be preferred without being orientated on this aspect in fact at the crystal grain that can easily make silicon nitride.Sintering aid shared ratio in raw material powder is preferably 1～30 quality %, is particularly preferably 1～15 quality %.
Use above-mentioned raw materials powder, by according to the several different methods of its shape, can manufacture the silicon nitride sinter as target.For example, in the case of the sintered compact as target be tabular, manufacture body by press molding, and this molding burnt till.On the other hand, in the situation that base material has 3D shape, manufacture body by casting forming, and this molding is burnt till.Except these methods, can also use as required for example extrusion molding.
In the case of manufacturing tabular sintered compact, as long as by above-mentioned raw material powder and tackiness agent, dispersion agent and solvent, modulation slurry, and use spray-drying process by this slurry granulation, by Press forming machine by this shaping particles established practice shape that formalizes.As tackiness agent and dispersion agent, can use those identical with the tackiness agent that used up to now and dispersion agent in this technical field.As tackiness agent, can use such as polyvinyl alcohol, polyacrylic resin, cellulose-based resin, polyvinyl butyral acetal etc.As dispersion agent, can use such as toxilic acid, poly carboxylic acid ammonium salt, ammonium polyacrylate salt etc.As solvent, according to the kind of tackiness agent and dispersion agent, can use the organic solvents such as such as water and methyl alcohol, propyl alcohol, ethanol, butanols etc.About the concentration of the raw material powder in slurry (alpha-silicon nitride powders and sintering aid), preference, as being defined as 10～100 quality %, is particularly preferably defined as 30～50 quality %.
By to burning till by molding obtained above, can obtain the silicon nitride sinter as target.This manufacture method has a feature aspect firing condition.At length say, in packing described molding into firing furnace after, be first warmed up to the high temperature of regulation, keep specified time to carry out aging this temperature.Aging object is to make fine alpha-form si nitride particle to the phase transformation of β type silicon nitride particles.In this is aging, preferably 1400～1750 ℃, more preferably 1400～1700 ℃, further preferably 1400～1600 ℃, further preferably under the steady temperature between 1500～1600 ℃, preferably keep 1～100 hour, more preferably keep 1～10 hour.
After aging end, will in firing furnace, heat up, reach the firing temperature as target.Firing temperature is preferably 1800～2000 ℃, more preferably 1800～1900 ℃.Heat-up rate while being warmed up to till this firing temperature from aging temperature is preferably set to 1～100 ℃/h, more preferably 1～30 ℃/h, more preferably 3～30 ℃/h.If adopt the heat-up rate of this scope, the particle of silicon nitride is easily with columnar growth.This result is, easily makes the crystal grain of silicon nitride in fact without orientation, is therefore preferred.Consequently, can easily the heat-conduction coefficient of silicon nitride sinter and normal temperature three-point bending strength be set in above-mentioned scope.Particularly, can easily the heat-conduction coefficient of silicon nitride sinter be set in above-mentioned scope.
Heat up with described heat-up rate, after the firing temperature reaching as target, maintain this firing temperature, preferably will burn till and carry out 30～60 hours, more preferably will burn till and carry out 30～50 hours, further preferably will burn till and carry out 30～48 hours.If firing time is shorter than this scope, be not easy to make the crystal of silicon nitride in fact without orientation.
In above operation, nitrogen atmosphere will be defined as in firing furnace.About the pressure (absolute pressure of the nitrogen in firing furnace.Below, in the time relating to the pressure of nitrogen, refer to absolute pressure.), until in the way of aging process and then its heating process, be all preferably defined as 1～92kPa, be particularly preferably defined as 10～92kPa.Then, the later half of heating process and and then in its firing process, for improving the pressure of nitrogen, be preferably defined as 92～920kPa, be more preferably defined as 65～920kPa.Like this, the stage of burning till by basis makes the pressure change of nitrogen, becomes while holding one's breath hole at ventilate, is difficult in this holds one's breath hole, catching the nitrogen that is present in the high pressure in hole of holding one's breath, and can obtain highdensity sintered body, is therefore preferred.
The silicon nitride sinter so obtaining be silicon nitride crystal grain in fact without orientation silicon nitride sinter, become thus and there is high heat-conduction coefficient and there is high-intensity silicon nitride sinter.So this silicon nitride sinter is particularly suitable for the insulated substrate of for example power semiconductor.In addition,, except this insulated substrate, can also be applicable to utilize the various structure units of high thermal conductivity.Particularly the effect of the thermal stresses owing to can reduce shock heating quenching time is remarkable, so be useful as heat shock resistance member.Also be useful as various aluminium molten metals by parts and iron and steel producing apparatus roller class used in addition.
Embodiment
Below, illustrate in greater detail the present invention by embodiment.But scope of the present invention is not limited to these embodiment.Only otherwise special instruction, " % " just means for " quality % ".
(embodiment 1)
(1) modulation of slurry
As raw material powder, preparation median size is that alpha-form si nitride powder 85%, the median size of 0.7 μ m is the Yb of 1 μ m 2o 3powder 13%, median size are the SiO of 0.8 μ m 2powder 2%.In addition, use polyvinyl alcohol as tackiness agent, use toxilic acid based copolymer as dispersion agent.They are packed into and are equipped with in the resin container of resin balls that diameter is 10mm, reinstall water, then sealing.This resin container is arranged on jar mill, mixes 24 hours, modulation slurry.The ratio of the raw material powder in slurry is 63.4%, and the ratio of tackiness agent is 2%, and the ratio of dispersion agent is 1.5%.
(2) manufacture of molding
By spray-drying process by after the slurry granulation obtaining, this particle is formed with oil pressure forming mill, obtain that 60mm is square, the molding of thick 7mm.Be shaped and press as 100MPa.
(3) burn till
The molding obtaining is rested in firing furnace.In firing furnace, make nitrogen circulation by the pressure of 92kPa.To in firing furnace, be warmed up to rapidly 1500 ℃ from room temperature, at 1500 ℃ aging 2 hours.Then, heat up with the heat-up rate of 5 ℃/h, make to reach 1900 ℃ in firing furnace.In the way of heating up, make the pressure rise of the nitrogen in firing furnace to 920kPa.Then, the pressure of the nitrogen in firing furnace is remained on to this value.Then, at 1900 ℃, will burn till and carry out 48 hours.So, obtain silicon nitride sinter.
(embodiment 2 and comparative example 1 and 2)
As raw material powder, adopt the raw material powder with the composition shown in following table 1.In addition,, as firing condition, adopt the condition shown in following table 1.In addition, according to the step identical with embodiment 1, obtain silicon nitride sinter.
(evaluation)
To the silicon nitride sinter obtaining by embodiment and comparative example, heat-conduction coefficient and normal temperature three-point bending strength are measured by above-mentioned method.In addition obtained I for ND and RD by powder X-ray RD mensuration (gamma ray source: Cuk α, θ-2 θ method) 002/ I 200ratio of peak.In addition, bulk specific gravity, specific heat and linear expansivity have been measured by above-mentioned method.The results are shown in following table 1.
Table 1
Figure BDA0000480146720000081
Distinguish from the result shown in table 1: the silicon nitride sinter obtaining by embodiment is compared with the silicon nitride sinter being obtained by comparative example, and heat-conduction coefficient and three-point bending strength are all high.On the other hand, although the silicon nitride sinter three-point bending strength being obtained by comparative example is high, heat-conduction coefficient does not improve.
Moreover though do not illustrate in table, the silicon nitride in the silicon nitride sinter obtaining is β type.In addition,, from the results verification of XRD determining, in the silicon nitride sinter being obtained by embodiment 1, there is Yb at crystal boundary 2si 3n 4o 3crystallization phases, in the silicon nitride sinter being obtained by embodiment 2, there is Yb at crystal boundary 2si 3n 4o 3or Yb 2si 3n 2o 7crystallization phases.
Utilizability in industry
According to the present invention, can provide and there is high heat-conduction coefficient and there is high-intensity silicon nitride sinter.

Claims (11)

1. a silicon nitride sinter, is characterized in that, the crystal of silicon nitride is in fact without orientation, and heat-conduction coefficient is more than 100W/mK, and the normal temperature three-point bending strength of measuring according to JIS R1601 is more than 500MPa.
2. silicon nitride sinter according to claim 1, wherein, is measuring described silicon nitride sinter by powder X-ray diffractometry, and obtaining the height that comes from (200) face of silicon nitride and the peak value of (002) face is I 200and I 002, and calculate and compare I 002/ I 200value time, this compares I 002/ I 200value for ND and RD, the two is 0.6～3.
3. silicon nitride sinter according to claim 1 and 2, wherein, the bulk specific gravity of measuring according to JIS Z8807 is 3.0～4.0.
4. according to the silicon nitride sinter described in any one in claim 1～3, wherein, the specific heat of measuring according to JISR1611 is 0.1～1J/(kgK).
5. according to the silicon nitride sinter described in any one in claim 1～4, wherein, in the scope of 20～400 ℃, be 3.0～4.0 × 10 according to the JISR3102 setting-out line coefficient of expansion -6/ K.
6. a manufacture method for silicon nitride sinter, it is the manufacture method of silicon nitride sinter claimed in claim 1, it is characterized in that, is included in the operation of under nitrogen atmosphere, the raw material powder that contains alpha-silicon nitride powders being burnt till, described operation possesses following operation:
Described raw material powder is kept under the steady temperature between 1400～1750 ℃ to the aging process of 1～100 hour;
The heating process that temperature from aging process heats up with the heat-up rate of 1～100 ℃/h; And
Under the steady temperature between 1800～2000 ℃, burn till the firing process of 30～60 hours.
7. manufacture method according to claim 6, wherein, the operation of under nitrogen atmosphere, the raw material powder that contains alpha-silicon nitride powders being burnt till possesses following operation:
Described raw material powder is kept under the steady temperature between 1400～1750 ℃ to the aging process of 1～10 hour;
The heating process that temperature from aging process heats up with the heat-up rate of 1～30 ℃/h; And
Under the steady temperature between 1800～2000 ℃, burn till the firing process of 30～48 hours.
8. according to the manufacture method described in claim 6 or 7, wherein, described raw material powder contains α-Si 3n 4.
9. according to the manufacture method described in any one in claim 6～8, wherein, described raw material powder further contains sintering aid.
10. manufacture method according to claim 9, wherein, described sintering aid is Yb 2o 3, SiO 2and at least one in MgO.
11. according to the manufacture method described in claim 9 or 10, and wherein, described sintering aid shared ratio in described raw material powder is 1～30 quality %.
CN201380003146.5A 2012-02-13 2013-01-25 Silicon nitride sintered body and method for producing same Pending CN103813997A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2012028550 2012-02-13
JP2012-028550 2012-02-13
PCT/JP2013/051616 WO2013121861A1 (en) 2012-02-13 2013-01-25 Silicon nitride sintered body and method for producing same

Publications (1)

Publication Number Publication Date
CN103813997A true CN103813997A (en) 2014-05-21

Family

ID=48983978

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201380003146.5A Pending CN103813997A (en) 2012-02-13 2013-01-25 Silicon nitride sintered body and method for producing same

Country Status (4)

Country Link
JP (1) JPWO2013121861A1 (en)
KR (1) KR20140095460A (en)
CN (1) CN103813997A (en)
WO (1) WO2013121861A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106132908A (en) * 2014-03-31 2016-11-16 日本精细陶瓷有限公司 The manufacture method of silicon nitrate substrate

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106631040A (en) * 2016-12-27 2017-05-10 郑州源冉生物技术有限公司 High strength ceramic low in expansion coefficient, and preparation method thereof
JP7272370B2 (en) * 2018-11-01 2023-05-12 Ｕｂｅ株式会社 Silicon nitride substrate manufacturing method and silicon nitride substrate

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000128643A (en) * 1998-10-21 2000-05-09 Sumitomo Electric Ind Ltd Highly heat conductive silicon nitride-based sintered compact and its production
JP2003313079A (en) * 2002-04-23 2003-11-06 Hitachi Metals Ltd Silicon nitride-based sintered compact, method of producing the same, and circuit board using the sintered compact

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0987037A (en) * 1995-07-18 1997-03-31 Ngk Spark Plug Co Ltd Silicon nitride-base sintered compact and its production
US7915533B2 (en) * 2005-04-28 2011-03-29 Hitachi Metals, Ltd. Silicon nitride substrate, a manufacturing method of the silicon nitride substrate, a silicon nitride wiring board using the silicon nitride substrate, and semiconductor module

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000128643A (en) * 1998-10-21 2000-05-09 Sumitomo Electric Ind Ltd Highly heat conductive silicon nitride-based sintered compact and its production
JP2003313079A (en) * 2002-04-23 2003-11-06 Hitachi Metals Ltd Silicon nitride-based sintered compact, method of producing the same, and circuit board using the sintered compact

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106132908A (en) * 2014-03-31 2016-11-16 日本精细陶瓷有限公司 The manufacture method of silicon nitrate substrate

Also Published As

Publication number Publication date
KR20140095460A (en) 2014-08-01
JPWO2013121861A1 (en) 2015-05-11
WO2013121861A1 (en) 2013-08-22

Similar Documents

Publication Publication Date Title
Zhou et al. Development of high-thermal-conductivity silicon nitride ceramics
JP6292306B2 (en) Silicon nitride powder, silicon nitride sintered body and circuit board, and method for producing silicon nitride powder
TWI573757B (en) A silicon nitride powder manufacturing method and a silicon nitride powder, and a silicon nitride sintered body and a circuit board using the same
JP3565425B2 (en) Method for producing silicon nitride-based powder and method for producing silicon nitride-based sintered body
JP6714044B2 (en) Silicon nitride sintered body manufacturing method, silicon nitride sintered body and heat dissipation substrate using the same
CN103813997A (en) Silicon nitride sintered body and method for producing same
JP4667520B2 (en) Silicon nitride based composite ceramics and method for producing the same
JP5894288B2 (en) Silicon nitride sintered body, heating device and adsorption device
JP2002293642A (en) Silicon nitride-based sintered compact having high thermal conductivity, method of producing the same, and circuit board
Peng et al. Spark plasma sintered silicon nitride ceramics with high thermal conductivity using MgSiN2 as additives
WO2005049525A1 (en) High thermally conductive aluminum nitride sintered product
KR101959485B1 (en) Sintered body, composition for sintering silicon nitride and preparation method of sintered body
JP4903431B2 (en) Silicon nitride sintered body and manufacturing method thereof, semiconductor manufacturing apparatus member and liquid crystal manufacturing apparatus member using the same
KR20170055639A (en) Manufacturing method of silicon nitride sintered body having high thermal conductivity
JP2004043241A (en) High purity silicon carbide sintered compact and its forming method
JP4089974B2 (en) Silicon nitride powder, silicon nitride sintered body, and circuit board for electronic components using the same
JP4556162B2 (en) Silicon nitride-based sintered body, method for producing the same, and circuit board using the same
KR102003193B1 (en) Manufacturing method of sintered AlN ceramics
JP2006096661A (en) Sintered silicon nitride compact and circuit board using it
JP4123388B2 (en) Zinc antimony compound sintered compact
JP2022153934A (en) Silicon nitride sintered body, circuit board, and manufacturing method of silicon nitride sintered body
JP5265859B2 (en) Aluminum nitride sintered body
Zhou et al. Fabrication and Properties of High Thermal Conductivity Silicon Nitride
CN113614035A (en) Silicon nitride powder, method for producing same, and method for producing silicon nitride sintered body
CN110832650A (en) Thermoelectric material and thermoelectric device including the same

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20140521