CN100441543C - Ceramic film and method of manufacturing the same, semiconductor device, and piezoelectric device - Google Patents

Ceramic film and method of manufacturing the same, semiconductor device, and piezoelectric device Download PDF

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Publication number
CN100441543C
CN100441543C CNB2005100759130A CN200510075913A CN100441543C CN 100441543 C CN100441543 C CN 100441543C CN B2005100759130 A CNB2005100759130 A CN B2005100759130A CN 200510075913 A CN200510075913 A CN 200510075913A CN 100441543 C CN100441543 C CN 100441543C
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raw material
liquid
ceramic membrane
stock liquid
layer
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CN1724381A (en
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名取荣治
古山晃一
田崎雄三
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Seiko Epson Corp
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Seiko Epson Corp
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Abstract

A method of manufacturing a ceramic film includes a step of forming a ceramic film 30 by crystallizing a raw material body 20. The raw material body 20 contains different types of raw materials in a mixed state. The different types of raw materials differ from one another in at least one of a crystal growth condition and a crystal growth mechanism in the crystallization of the raw materials. According to this manufacturing method, a surface morphology of the ceramic film can be improved.

Description

A kind of manufacture method of ceramic membrane
The present patent application is that application number is the dividing an application of the PCT application that enters country's stage of CN01802497.1 (international filing date is June 14 calendar year 2001).
Technical field
The present invention relates to ceramic membrane and manufacture method thereof and semiconductor device and piezoelectric element.
Background technology
Now, as the strong dielectric film that is applicable to semiconductor device (for example strong dielectric memory (FeRAM)), proposed to have the strong dielectric film (for example BiLaTiO system, BiTiO system, SrBiTaO system) of laminated perovskite type structure.Strong dielectric film with this laminated perovskite type structure generally forms by carrying out crystal growth by amorphous state.
Utilizing this formation method to form under the situation of the strong dielectric film with laminated perovskite type structure, strong dielectric film results from crystalline texture, and the axial crystalline growth velocity of c is slower than the axial crystalline growth velocity of a, b.That is to say, in a, the easy crystal growth of b direction of principal axis.Therefore, if adopt above-mentioned formation method, the strong dielectric film that then has laminated perovskite type structure becomes coarse configuration of surface.That is, between the crystal of resulting strong dielectric film, produce gap (for example hole and ditch).
Summary of the invention
The objective of the invention is to, the manufacture method of the ceramic membrane of the configuration of surface that can improve ceramic membrane is provided.
The ceramic membrane that provides the manufacture method of utilizing ceramic membrane of the present invention to obtain is provided.
Other purpose of the present invention is, the semiconductor device and the piezoelectric element that use ceramic membrane of the present invention are provided.
The manufacture method of ceramic membrane
(A) manufacture method of the 1st kind of ceramic membrane of the present invention, contain by thereby starting material body crystallization being formed the operation of ceramic membrane, the state that above-mentioned starting material body exists with mixing contains diverse raw material, and there is different relation mutually in diverse raw material at least one side of the crystal growth condition in the crystallization of raw material and mechanism of crystal growth to each other.
At this, the kind difference of so-called raw material is meant the relation of the stock yard of at least one side who resembles crystal growth condition and mechanism of crystal growth mutually different.That is to say whether different viewpoints judges whether the kind of raw material is different from least one side of crystal growth condition and mechanism of crystal growth.
For crystal growth condition in the crystallization of raw material and mechanism of crystal growth, for example comprise formation temperature, crystal growth temperature, crystalline growth velocity, the formation speed of nucleus, the size of nucleus, the crystallization method of crystallized temperature, nucleus.
In the present invention, the starting material body comprises diverse raw material.That is, the starting material body comprises and is no less than 2 kinds raw material.And diverse raw material is mutual, and there is different relation mutually at least one side of crystal growth condition in the crystallization of raw material and mechanism of crystal growth.Therefore,, for example make other raw materials of a kind of raw material ratio carry out crystallization earlier, can in the gap between the crystal that causes by a kind of raw material, make other material crystalizations by controlling various conditions.That is, utilize the crystallization that causes by other raw materials can be with the gap landfill that produces between the crystal that causes by a kind of raw material.Therefore, can improve the configuration of surface of ceramic membrane.
In addition, by controlling various conditions, also can make a kind of raw material and other raw materials crystallization simultaneously.For example, be replaced as other elements, can adjust crystallized temperature by a part with the metallic element of raw material.Owing to can adjust crystallized temperature, can make the crystallized temperature of diverse raw material roughly approaching each other.If make the crystallized temperature of diverse raw material roughly approaching each other, just can make diverse raw material while crystallization each other.
(B) manufacture method of the 2nd kind of ceramic membrane of the present invention, thereby comprise by making starting material body crystallization form the operation of ceramic membrane, above-mentioned starting material body contains diverse raw material under the state that mixes existence, diverse starting material to each other, there is different relation mutually in the crystalline crystalline structure that is obtained by raw material.
At this, the kind difference of so-called raw material is meant the raw material mutual relation of the crystalline crystalline structure that obtains from raw material different mutually that resemble.That is to say,, judge whether the kind of raw material is different from the whether different viewpoint of the crystalline crystalline structure that obtains by raw material.
For the difference of the crystalline crystalline structure that obtains from raw material, for example comprise that the crystallization that will obtain from raw material is expressed as (Bi 2O 2) 2+(A M-1B aO 3m+1) 2-The time the difference of m.
In the present invention, there is the different relation of crystalline crystalline structure that is caused by raw material each other in diverse raw material.If from the crystalline crystalline structure difference that raw material obtains, then the crystal growth condition of raw material is just different with mechanism of crystal growth.Therefore, can reach the identical action effect of manufacture method with the 1st kind of ceramic membrane of the present invention.
(C) manufacture method of the 3rd kind of ceramic membrane of the present invention, thereby comprise by making starting material body crystallization form the operation of ceramic membrane, above-mentioned starting material body contains diverse raw material under the state that mixes existence, diverse raw material to each other, at least in the crystallization initial stage, crystallization independently of each other.
At this, the kind difference of so-called raw material is meant the mutual relation of raw material of carrying out crystallization at least in the crystallization initial stage independently of one another.
The manufacture method of the 3rd kind of ceramic membrane of the present invention is to make diverse raw material carry out crystallization independently of one another in the crystallization initial stage at least each other.Therefore, in the gap between a kind of crystal of raw material, can make the crystal growth of other raw materials.Its result can be suppressed at the gap takes place between crystal, improves configuration of surface.
The manufacture method of the 1st～3rd kind of ceramic membrane of the present invention can be taked any following at least mode.
(a) above-mentioned ceramic membrane is the mode of strong dielectric.
(b) above-mentioned ceramic membrane is the mode of paraelectrics.
(c) above-mentioned ceramic membrane is that strong dielectric and paraelectrics mix the mode that exists.
(d) aspect the mutual relationship of diverse raw material, in the relation of at least a the two, the crystallized temperature in the crystallization of raw material is a different mode mutually.
(e) aspect the mutual relationship of diverse raw material, in the relation of at least a the two, the formation temperature of the nucleus in the crystallization of raw material is a different mode mutually.
(f) aspect the mutual relationship of diverse raw material, in the relation of at least a the two, the crystal growth temperature in the crystallization of raw material is a different mode mutually.
(g) aspect the mutual relationship of diverse raw material, in the relation of at least a the two, be different mode mutually at the crystalline growth velocity of raw material.
(h) aspect the mutual relationship of diverse raw material, in the relation of at least a the two, the formation speed of the nucleus in the crystallization of raw material is different mode mutually.
(i) aspect the mutual relationship of diverse raw material, in the relation of at least a the two, the size of the nucleus in the crystallization of raw material is a different mode mutually.
(j) aspect the mutual relationship of diverse raw material, in the relation of at least a the two, the crystallization method in the crystallization of raw material is a different mode mutually.
(k) diverse raw material be each other stagger in time ground crystallization mode.
(l) diverse raw material is to stagger in time and form the mode of the nucleus in the material crystalization each other.
(m) diverse raw material is the mode of while crystallization each other.
In addition, if diverse raw material crystallization simultaneously each other will interdict the crystal growth that is caused by other raw materials mutually.Its result can make the crystal micritization that obtains.If crystal micritization, the gap between crystal just become narrow and small, configuration of surface improves.
Moreover, in the diverse raw material occasion of crystallization simultaneously each other, preferably use the different raw material of crystalline structure of the ceramic membrane that obtains.By making the crystalline structure difference, can change crystal growth condition and mechanism of crystal growth in material crystalization simultaneously.
(n) diverse raw material will be expressed as (Bi by the pottery that raw material obtains each other 2O 2) 2+(A M-1B aO 3m+1) 2-The time be mutually different mode of m value.
(o) above-mentioned starting material body is to adopt LSMCD (Liquid Source Misted ChemicalDeposition, fluid supply atomizing electroless plating) method, the mode that forms on matrix.
If adopt the LSMCD method to form the starting material body on matrix, the starting material body is directed on the matrix with vaporific by ultrasonic wave.Thereby it is good that the admixture of diverse raw material becomes.Therefore, in this manner, can access ceramic membrane with micro crystal.
Supply with diverse raw material respectively, can on matrix, form above-mentioned starting material body.
In addition, supply with diverse raw material simultaneously, also can on matrix, form above-mentioned starting material body.
(p) above-mentioned starting material body is the mode that adopts method of spin coating or pickling process to form on matrix.
(q) above-mentioned starting material body is the mode of at least one side in collosol and gel raw material and MOD (Metal OrganicDecomposition, the metal organic decomposition) raw material.
(r) above-mentioned starting material body is the mode that contains collosol and gel raw material and MOD raw material.
In addition, in mode (p) with (q), above-mentioned collosol and gel raw material can be the mode that polycondensation takes place by hydrolysis.
In addition, above-mentioned collosol and gel raw material is that crystalline crystalline structure in this material crystal occasion has the mode of identical or similar crystalline structure.In this manner, can make the collosol and gel material crystalization easily.
Above-mentioned MOD raw material can be the mode of polynuclear coordination compound raw material.
(s) above-mentioned starting material body has diverse collosol and gel raw material, the different mode of composition of degree that diverse collosol and gel raw material is mutual polycondensation each other or metallic element.
(t) above-mentioned starting material body has diverse collosol and gel raw material, and diverse raw material is not carry out the blended mode with atomic level each other.
At this, what is called is mixed with atomic level, for example means that the atom that constitutes raw material mixes mutually.That is, raw material preferably mixes with the state of keeping independent molecule or aggregate.If raw material does not mix with atomic level, just can reach effect of the present invention reliably, and can improve the characteristic of ceramic membrane more.
(D) manufacture method of the 4th kind of ceramic membrane of the present invention comprises by making starting material body generation crystallization form the operation of ceramic membrane, and the crystallization of above-mentioned starting material body carries out in the mode that forms a plurality of phases.
Above-mentioned ceramic membrane can become any following mode.
(a) above-mentioned ceramic membrane is the mode of strong dielectric.
(b) above-mentioned ceramic membrane is the mode of paraelectrics.
(c) above-mentioned ceramic membrane is that strong dielectric and paraelectrics mix the mode that exists.
(E) manufacture method of the 5th kind of ceramic membrane of the present invention, comprise the ceramic raw material liquid crystallization that contains the 1st stock liquid and the 2nd stock liquid by making, thereby form the operation of ceramic membrane, there are diverse relation in above-mentioned the 1st stock liquid and above-mentioned the 2nd stock liquid, above-mentioned the 1st stock liquid is to have the stock liquid that Bi is the strong dielectric of laminated perovskite type structure in order to generate, and above-mentioned the 2nd stock liquid is to be that the ABO of Bi is the stock liquid of oxide compound in order to generate the A position.
Form ceramic membrane by the stock liquid that utilizes pottery of the present invention, for example can be formed in the strong dielectric film that low temperature has predetermined characteristic.In addition, adopt the stock liquid of pottery of the present invention and the ceramic membrane that obtains, configuration of surface is good.
Strong dielectric that generates based on above-mentioned the 1st stock liquid and the ABO that generates based on above-mentioned the 2nd stock liquid are the mol ratio preferably 100: 20～100: 100 of oxide compound.Thus, can be formed on the strong dielectric film that low temperature has predetermined characteristic more reliably.
Above-mentioned the 1st stock liquid is the solution that the metallic compound of the formation metallic element of above-mentioned strong dielectric or metal inorganic compound are dissolved in solvent, and above-mentioned the 2nd stock liquid can be to be the metallic compound of formation metallic element of oxide compound or the solution that metal inorganic compound is dissolved in solvent with above-mentioned ABO.
(F) manufacture method of the 6th kind of ceramic membrane of the present invention, comprise by making the stock liquid crystallization of the pottery that contains the 3rd stock liquid and the 4th stock liquid, thereby form the operation of ceramic membrane, there are diverse relation in above-mentioned the 3rd stock liquid and above-mentioned the 4th stock liquid, above-mentioned the 3rd stock liquid is the stock liquid for the strong dielectric that generates PZT system, and the above-mentioned the 4th stock liquid is to be that the ABO of Pb is the stock liquid of oxide compound in order to generate the A position.
Form ceramic membrane by the stock liquid that utilizes pottery of the present invention, for example can reach the identical action effect of manufacture method with the 5th kind of ceramic membrane of the present invention.
Strong dielectric that generates based on above-mentioned the 3rd stock liquid and the ABO that generates based on above-mentioned the 4th stock liquid are the mol ratio preferably 100: 20～100: 100 of oxide compound.Thus, can be formed on the strong dielectric film that low temperature has predetermined characteristic more reliably.
Above-mentioned the 3rd stock liquid is the solution that the metallic compound of the formation metallic element of above-mentioned strong dielectric or metal inorganic compound are dissolved in solvent, and above-mentioned the 4th stock liquid can be to be the metallic compound of formation metallic element of oxide compound or the solution that metal inorganic compound is dissolved in solvent with above-mentioned ABO.
(G) manufacture method of the 7th kind of ceramic membrane of the present invention, comprise by making the stock liquid crystallization of the pottery that contains the 5th stock liquid and the 6th stock liquid, thereby form the operation of ceramic membrane, above-mentioned the 5th stock liquid is in order to generate the stock liquid of the strong dielectric with strong dielectric that Bi is a laminated perovskite type structure or PZT system, and above-mentioned the 6th stock liquid is to be that the ABO of Ge is the stock liquid of oxide compound in order to generate the B position.
Form ceramic membrane by the stock liquid that utilizes pottery of the present invention, for example can reach the identical action effect of manufacture method with the 5th kind of ceramic membrane of the present invention.
Strong dielectric that generates based on above-mentioned the 5th stock liquid and the ABO that generates based on above-mentioned the 6th stock liquid are the mol ratio preferably 100: 20～100: 100 of oxide compound.Thus, can be formed on the strong dielectric film that low temperature has predetermined characteristic more reliably.
Above-mentioned the 5th stock liquid is the solution that the metallic compound of the formation metallic element of above-mentioned strong dielectric or metal inorganic compound are dissolved in solvent, and above-mentioned the 6th stock liquid can be to be the metallic compound of formation metallic element of oxide compound or the solution that metal inorganic compound is dissolved in solvent with above-mentioned ABO.
(H) manufacture method of the 8th kind of ceramic membrane of the present invention, comprise the operation of raw material body layer of a plurality of raw material layers that formed lamination, and by making above-mentioned raw materials body layer crystallization form the operation of ceramic membrane, the raw material layer of the superiors in above-mentioned raw materials body layer is lower than the raw material layer crystallized temperature of the lower floor that contacts with the raw material layer of these the superiors, and resulting crystal does not have laminate structure.
According to the present invention, the crystal that is generated by the raw material layer of the superiors is as the inculating crystal layer performance function in the crystallization of the raw material layer of this lower floor.In addition, because resulting crystal does not have laminate structure, so the raw material layer of the superiors can seek to improve the configuration of surface of ceramic membrane.
The raw material layer of the lower floor that contacts with the raw material layer of the above-mentioned the superiors makes the 1st raw material layer be arranged on the matrix between the centre, and above-mentioned the 1st raw material layer is compared with the raw material layer of the lower floor that contacts with the raw material layer of the above-mentioned the superiors, can be the low mode of crystallized temperature.Thus, the crystal that generates based on the 1st raw material layer in the crystallization of the raw material layer of the lower floor that contact with the raw material layer of the superiors, is brought into play function as inculating crystal layer.
(I) manufacture method of the 9th kind of ceramic membrane of the present invention, comprise: formation contains the operation with the raw material body layer of the raw material multilayer body of the order lamination of the 1st raw material layer, the 2nd raw material layer and the 3rd raw material layer, and make above-mentioned raw materials body layer crystallization and form the operation of ceramic membrane, above-mentioned the 2nd raw material layer is lower than the crystallized temperature of above-mentioned the 1st raw material layer and above-mentioned the 3rd raw material.
According to the present invention,, play effect as the slicer of the crystalline crystal growth that stops the 1st raw material layer and the 3rd raw material layer based on the crystal that the 2nd raw material layer generates.Therefore, can make the crystalline grain fineness number that generates based on the 1st raw material layer and the 3rd raw material layer little.
Stacked again the 4th raw material layer on above-mentioned the 3rd raw material layer, above-mentioned the 4th raw material layer is compared with above-mentioned the 3rd raw material layer, can be the low mode of crystallized temperature.In the occasion of this mode,, in the crystallization of the 3rd raw material layer, bring into play function as inculating crystal layer based on the crystal that the 4th raw material layer generates.
(J) manufacture method of the 10th kind of ceramic membrane of the present invention, comprise the operation of raw material body layer of a plurality of raw material layers that formed lamination, and make above-mentioned raw materials body layer crystallization and form the operation of ceramic membrane, the raw material layer of the superiors in above-mentioned raw materials body layer, with compare the crystallized temperature height with lower floor's raw material layer of the raw material layer that contacts these the superiors.
According to the present invention, the crystalline mode that can generate with the raw material layer that covers based on its lower floor forms the crystal that the raw material layer based on the superiors generates.
The raw material layer of the superiors in above-mentioned raw materials body layer, resulting crystallization preferably do not have laminate structure.Thus, can improve the configuration of surface of ceramic membrane.
In the manufacture method of the 1st～the 10th ceramic membrane of the present invention,, can repeatedly implement to form the operation of ceramic membrane by making the starting material crystallization.
Ceramic membrane
Ceramic membrane of the present invention is to use the manufacture method of ceramic membrane of the present invention to obtain.
The application examples of ceramic membrane
Semiconductor device of the present invention has the electrical condenser that contains ceramic membrane of the present invention.
Piezoelectric element of the present invention contains ceramic membrane of the present invention.
Brief description of drawings
Figure 1A-C is the sectional drawing of manufacturing process of schematically representing to use the ceramic membrane of the ceramic raw material liquid relevant with embodiment.
Fig. 2 is a sectional drawing of schematically representing ferroelectric memory apparatus.
Fig. 3 schematically represents to use the LSMCD method for form the sectional drawing of the device of starting material body on matrix.
Fig. 4 A, B are the concept maps of schematically representing to use the formation of the starting material body that the device among Fig. 3 obtains.
Fig. 5 A-C is a concept map of schematically representing the manufacturing process of the 1st kind of multilayer ceramic film.
Fig. 6 A-C is a concept map of schematically representing the manufacturing process of the 2nd kind of multilayer ceramic film.
Fig. 7 A-C is a concept map of schematically representing the manufacturing process of the 3rd kind of multilayer ceramic film.
Fig. 8 A, B are the concept maps of schematically representing the manufacturing process of the 4th kind of multilayer ceramic film.
Fig. 9 is the process flow sheet of film process.
Figure 10 is the microphotograph figure of the strong dielectric film that obtains of the mixed solution from main liquid relevant with embodiment 1 and secondary liquid.
Figure 11 is the microphotograph figure of the strong dielectric film relevant with comparative example.
The best mode that carries out an invention
Below, on one side with reference to accompanying drawing, suitable embodiment of the present invention is described on one side.
The 1st embodiment
The manufacture method of ceramic membrane
Below, the manufacture method of the ceramic membrane relevant with embodiment is described.Figure 1A-C is the manufacturing process that schematically represents the ceramic membrane relevant with embodiment.Especially, Figure 1B is the concept map of notion of the mechanism of expression crystallization.
(1) shown in Figure 1A, on matrix 10, forms starting material body 20.As the method that on matrix 10, forms starting material body 20, for example can enumerate coating method, LSMCD method.As coating method, can enumerate method of spin coating, pickling process etc.Starting material body 20 contains collosol and gel raw material and MOD raw material.This collosol and gel material choice is lower than the crystallized temperature of MOD raw material, the formation speed of nucleus and the fast raw material of crystalline growth velocity.
The collosol and gel raw material can resemble particularly and modulate following.At first, mix being not more than 4 metal alkoxides that constitute, be hydrolyzed and polycondensation by carbonatoms.By this hydrolysis and polycondensation, can form the firm key of M-O-M-O.The bond structure of the M-O-M that obtain this moment has the structure near the crystalline texture (perovskite structure) of pottery.At this, M is metallic element (for example Bi, Ti, La, Pb), and O represents oxygen.The ratio of metallic element and metallic element, the pottery that contrast will obtain are selected decision.If exemplify out the pottery of BiLaTiO system (below be called " BLT "), be exactly Bi 3.25La 0.75Ti 3O xRatio.In addition, because of 0 not being the value that finally obtains, so be taken as x.Then, by be hydrolyzed and the resultant that obtains of polycondensation in add solvent, and obtain raw material.Like this, just can be modulated into the collosol and gel raw material.
As the MOD raw material, for example can enumerate the continuous directly or indirectly each other multi-nuclear metal ligand compound raw material that connects of formation element of pottery.The MOD raw material can be enumerated the metal-salt of carboxylic acid particularly.Can enumerate acetate, 2 ethyl hexanoic acid etc. as carboxylic acid.As metal, for example be Bi, Ti, La, Pb.In MOD raw material (multi-nuclear metal ligand compound raw material), the same with the collosol and gel raw material, also have the M-O key.But the M-O key does not resemble and carries out forming the successive key the collosol and gel raw material that polycondensation obtains, and in addition, bond structure is the approximately linear structure also, differs greatly with perovskite structure.
Then, as required, make starting material body 20 dryings.
(2) then, shown in Fig. 1 C,, make starting material body 20 crystallizations, form ceramic membrane 30 by thermal treatment starting material body 20.With collosol and gel raw material and MOD raw material at least in the initial stage of crystal growth process independently of each other under the condition of crystallization, carry out the crystallization of this starting material body 20, form and to result from the 1st crystallization 42 of collosol and gel raw material and the 2nd crystallization 52 of MOD raw material of resulting from.
The concrete example of mechanism of the crystallization of collosol and gel raw material and MOD raw material is described.The collosol and gel raw material is compared with the MOD raw material, and crystallized temperature is low.In addition, the collosol and gel raw material is compared with the MOD raw material, and the formation speed and the crystalline growth velocity of nucleus are fast.Therefore, by controlled temperature etc., the crystallization that just can make the collosol and gel raw material carries out earlier than the crystallization of MOD raw material.Because the crystallization of collosol and gel raw material carries out earlier than the crystallization of MOD raw material, shown in Figure 1B, resulting from the gap of 42 of the 1st crystallizations of collosol and gel raw material residual MOD raw material.Therefore, resulting from the gap of 42 of the 1st crystallizations of collosol and gel raw material, the 2nd crystallization 52 of MOD raw material of resulting from is grown.Like this, crystal growth is carried out in the 1st crystallization 42 and the 2nd crystallization 52 independently of one another.That is, the gap that landfill the 1st crystallization is 42, crystal growth is carried out in the 2nd crystallization 52.In addition, the collosol and gel raw material is compared with the MOD raw material, and crystalline is the direction difference of orientation easily.Therefore, blocking growth mutually, micritization easily.If the crystallization micritization then has the effect that makes the gap smaller between crystal.Its result can form the ceramic membrane 30 that configuration of surface is improved.
Below, the crystallization condition of concrete starting material body is described.
As heat-treating methods, for example can enumerate and utilize RTA (Rapid ThermalAnnealing, rapid thermal annealing) and FA (stove) (Furnace Anneal, smelting furnace annealing), in oxygen atmosphere, carry out the annealed method.
The crystallization condition of starting material body at first, uses RTA under 500～650 ℃ temperature more specifically, and the time of carrying out is short to 5～30 seconds annealing, generates microcrystals.At this moment, generate the nucleus that constitutes by the collosol and gel raw material earlier.In the process of the crystal growth that constitutes by the collosol and gel raw material, the nucleus growth that around it, constitutes by the MOD raw material.Then,, promote crystallization 10-30 minute, obtain ceramic membrane 30 by using FA under 600～650 ℃.
Variation
The manufacture method of the ceramic membrane relevant with above-mentioned embodiment, for example Yi Xia distortion is possible.
(1) raw material combination is not limited to above-mentioned embodiment, and for example Yi Xia combination is possible.
1. can use the different multiple collosol and gel raw material of polycondensation degree.Even identical composition, if the degree difference of polycondensation, it is generally also different that crystal growth is easy to direction.Therefore, if mix the different raw material of degree of polycondensation, then because crystal growth is easy to the direction difference, institute can seek micro-crystallizationization in view of the above so that crystal growth is interdicted mutually.
2. can use the raw material of the different composition of crystalline structure.For example, can use the raw material of following relationship.
To be expressed as (Bi by the pottery that raw material obtains 2O 2) 2+(A M-1BaO 3m+1) 2-The time, can use m different raw material mutually.Example as m=1 can be enumerated Bi 2WO 6, can enumerate Bi as the example of m=2 3TiNbO 9, can enumerate Bi as the example of m=3 4Ti 3O 12These all are strong dielectrics, but the crystalline structure difference.That is, the difference of a separately, b length is few, but the c axle is 16.4 during m=1
Figure C20051007591300121
(1.64nm), be 25.0 during m=2
Figure C20051007591300122
(2.50nm), be 32.8 during m=3
Figure C20051007591300123
(3.28nm).They, because the crystalline structure difference, so it is different with mechanism of crystal growth to generate the mutual crystal growth condition of their each raw material of crystalline.
Also have, in the occasion of using the different constitutive material of crystalline structure, according to following reason, B position element is preferably in the different raw materials common.That is, even crystal growth condition is different with mechanism of crystal growth, different raw materials carries out crystallization to each other independently of each other, also can in long annealing process after this many phase mutual diffusion take place near crystal boundary.This is because in the case, if replace B position element, the tendency of the deterioration in characteristics of pottery is just arranged.
3. can enumerate resulting crystalline crystalline structure is Bi 4Ti 3O 9Raw material (hereinafter referred to as " BTO raw material ") and resulting crystalline crystalline structure be PbTiO 3The combination of raw material (hereinafter referred to as " PTO raw material ").PbTiO 3It is the uhligite of quadrilateral structure.But a axle of PTO and the difference of c axle are little, and the anisotropy of the crystal growth that is caused by crystalline structure is few.In addition, the formation of the nucleus in the PTO raw material is in lower temperature, and generates easily.Therefore, if with few, for example the ratio about 10: 1 is mixed the PTO raw material in the BTO raw material, carries out crystal growth, will interdict other crystal growth separately.Therefore, reach the effect of resulting crystallization micritization.This effect is more remarkable than the crystal with identical lamellated perovskite structure.
4. also can the crystalline material combination of the crystalline raw material and the generation paraelectrics of strong dielectric will be generated.Combined amount decides according to the characteristic of desirable ceramic membrane.
5. can be collosol and gel raw material and MOD raw material combination, also can be the mutual combination of the raw material that differed from one another by the crystalline crystalline structure that separately raw material generates.
6. can be the combination of the mutually different collosol and gel stock yard of the degree of polycondensation, also can be the crystalline crystalline structure combination of different stock yards mutually that is generated by separately raw material.
(2) manufacture method of ceramic membrane of the present invention can be implemented repeatedly, be formed ceramic membrane.In addition, the manufacture method of ceramic membrane of the present invention and the manufacture method of known ceramic membrane can be combined to form ceramic membrane.
(3) adopt the LSMCD method, on matrix, form the method for starting material body, for example can enumerate following method.Fig. 3 schematically represents to adopt the LSMCD method, in order to form the sectional drawing of the device 200 of starting material body on matrix.
The 1st raw material 210 utilizes atomizer 230 to be sent on the sieve 240.The 1st raw material 210 by sieve 240 forms mist 250, supplies on the matrix 10.In addition, also utilize atomizer 232 that the 2nd raw material 220 is delivered on the sieve 240, the 2nd raw material 220 formation mists 250 by sieve 240 supply on the matrix 10.Like this, be deposited on the matrix 10, thereby form the starting material body by mist 250.The particle diameter of mist 250 for example is 10～200nm.
The 1st raw material 210 and the 2nd raw material 220 can supply on the matrix 10 simultaneously.Perhaps the 1st raw material 210 and the 2nd raw material 220 also can alternative supplies.
Under the 1st raw material 210 and the 2nd raw material 220 supplied to situation on the matrix 10 simultaneously, the starting material style was as shown in Fig. 4 A, resulted from the 1st mist 210a of the 1st raw material 210 and the 2nd mist 220a of the 2nd raw material 220 of resulting to be the miscellaneous state.
Under the situation of alternative supply the 1st raw material 210 and the 2nd raw material 220, the starting material body for example shown in Fig. 4 B, results from the 1st mist 210a of the 1st raw material 210 and the 2nd mist 220a of the 2nd raw material 220 of resulting from and constitutes separately one deck.That is, constitute by resulting from the mist of same raw material with one deck.
The 2nd embodiment
The stock liquid of the 1st pottery
The stock liquid of the 1st pottery is that the 1st stock liquid and the 2nd stock liquid are mixed the stock liquid that uses.The stock liquid of the 1st pottery can be to obtain the such stock liquid of ceramic membrane by thermolysis.The 1st stock liquid and the 2nd stock liquid exist the diverse relation of the material that is generated.The the 1st and the 2nd stock liquid for example can be: 1) organometallics (for example metal alkoxide, metal carboxylate) and metal inorganic compound (for example metal nitrate, metal chloride) are dissolved in the liquid in the solvent (for example water, alcohol, ester, aliphatic hydrocarbon, aromatic hydrocarbons, ketone, ether or their mixture); 2) in solvent, make the be hydrolyzed liquid of reaction, polycondensation etc. of metallic compound; 3) sol gel solution that obtains by the hydrolysis of metal alkoxide.
Below, specifically describe the 1st stock liquid and the 2nd stock liquid.
The 1st stock liquid is to be used to generate have the stock liquid that Bi is the strong dielectric of laminated perovskite type structure.As having the strong dielectric that Bi is a laminated perovskite type structure, can enumerate the strong dielectric (SrBi for example of SrBiTaO system 2Ta 2O 9), the strong dielectric of BiLaTiO system (Bi for example 3.25La 0.75Ti 3O 12), the strong dielectric of BiTiO system (Bi for example 4Ti 3O 12).In the 1st stock liquid, contain the metallic element that constitutes strong dielectric.The amount of the formation metallic element of the strong dielectric that contains in the 1st stock liquid, the ratio of the amount by considering desirable strong dielectric and the atomicity of the formation metallic element in the desirable strong dielectric decides.
As the object lesson of the 1st stock liquid,, can enumerate the liquid of solution separately of alkoxide of alkoxide, the tantalum of the alkoxide that in 2-methyl cellosolve, mixes strontium, bismuth in the occasion of the strong dielectric of SrBiTaO system.In the 1st stock liquid, the concentration of the alkoxide of the alkoxide of strontium, the alkoxide of bismuth, tantalum for example can be respectively 0.05mol/l, 0.1mol/l, 1.0mol/l.That is, each concentration can be set at average 1 liter of the 1st stock liquid, generate the SrBi of 0.05mol 2Ta 2O 9Strong dielectric.
The 2nd stock liquid is that to be used to generate the A position be that the ABO of Bi is the stock liquid of oxide compound.If the A position is not Bi, be on the position that will hold Bi of laminated perovskite type structure at Bi, just produce the situation of holding Bi element in addition, often the characteristic to strong dielectric film causes bad influence.As the A position is that the ABO of Bi is an oxide compound, can enumerate BiGeO and be oxide compound (Bi for example 4Ge 3O 12), BiMoO is oxide compound (Bi 2MoO 6), BiVO is oxide compound (Bi 2VO 6), BiCrO is oxide compound (Bi 2CrO 6), BiSiO is oxide compound (Bi 4Si 3O 12), BiWO is oxide compound (Bi 4W 3O 12).Moreover, be the element of the B position of oxide compound by changing ABO, can change crystalline crystallized temperature based on the 2nd stock liquid.In addition, ABO is that oxide compound can be a strong dielectric, also can be paraelectrics.
In the 2nd stock liquid, containing formation ABO is the metallic element of oxide compound.The ABO that contains in the 2nd stock liquid is the amount of the formation metallic element of oxide compound, is that the amount of oxide compound and ratio that desirable ABO is the atomicity of the formation metallic element in the oxide compound decide by considering desirable ABO.
As the object lesson of the 2nd stock liquid, be the occasion of oxide compound at BiGeO, can enumerate the body fluid of solution separately of alkoxide of alkoxide, the germanium of blending bismuth in 2-methyl cellosolve.In the 2nd stock liquid, the concentration of the alkoxide of bismuth, the alkoxide of germanium for example can be respectively 0.20mol/l, 0.15mol/l.That is, each concentration of the alkoxide of the alkoxide of bismuth, germanium can be set at the Bi that average 1 liter of the 2nd stock liquid generates 0.05mol 4Ge 3O 12Oxide compound.
The 1st stock liquid and the 2nd stock liquid preferably are mixed into the strong dielectric that obtains based on the 1st stock liquid and are that the mol ratio of oxide compound is 100: 20～100: 100 based on the ABO that the 2nd stock liquid obtains.Its reason is illustrated in the embodiment item.
The Production Example of ceramic membrane
Utilize the stock liquid of the pottery relevant, for example, resemble and to make ceramic membrane following with present embodiment.Also have,, use Figure 1A-C the samely, the manufacturing processed of ceramic membrane is described with the 1st embodiment as the sectional schematic diagram of the manufacturing process that schematically represents ceramic membrane.
(a) at first, matrix 10 is heat-treated.This thermal treatment is carried out for the moisture on the surface of removing matrix 10.Heat treated temperature for example is 180 ℃.
(b) then, the stock liquid of coating pottery on matrix 10 forms ceramic raw material body layer 20.As this formation method, can enumerate method of spin coating, pickling process, LSMCD method etc.
(c) subsequently, carry out dry heat and handle, make the solvent evaporation in the ceramic raw material body layer 20.The evaporation of this solvent can be carried out under nitrogen atmosphere.Dry heat treated temperature for example is 160 ℃.
(d) then, ceramic raw material body layer 20 is carried out degreasing thermal treatment.By this thermal treatment the organism in the ceramic raw material body layer 20 is decomposed.This organic decomposition can be carried out under nitrogen atmosphere.This heat treated temperature for example is 260 ℃.
(e) subsequently, ceramic raw material body layer 20 is carried out false sintering.In this vacation sintering, form nucleus.False sintering for example under oxygen atmosphere, can adopt RTA to carry out.
(f) then, sintered ceramic raw material body layer 20.This sintering for example under the oxygen atmosphere, can adopt FA (stove) to carry out.
Make operation (a)～(e) be one-period, this cycle can be carried out repeatedly.
Action effect
Below, to using the stock liquid of the pottery relevant with the 2nd embodiment, the action effect during with the ceramic membrane film forming is illustrated.
(1) burns till at the ceramic raw material liquid that will only constitute by the 1st stock liquid, form the occasion of strong dielectric (SBT) film, generally, if not about 700 ℃ firing temperature, in strong dielectric film, just can not get the characteristic (for example remnant polarization effect) of necessary hope.
But, under the state that mixes the 1st stock liquid and the 2nd stock liquid, the 1st ceramic raw material liquid is burnt till, form the occasion of ceramic membrane, as described later, even the firing temperature about 500 ℃ also can access the characteristic of necessary hope in strong dielectric film.That is to say,, at a lower temperature, just can form the strong dielectric film of characteristic with hope according to present embodiment.
(2) material that generates based on the 1st stock liquid is different with the material that generates based on the 2nd stock liquid.Therefore, for example the crystallized temperature of the crystallized temperature of the 1st stock liquid crystallization and the 2nd stock liquid crystallization will be different.Its result can make the crystallization of a side stock liquid, and the crystallization of the opposing party's stock liquid carries out earlier relatively.Therefore, shown in Figure 1B, between crystal 42, can make crystal 52 growths based on the opposing party's stock liquid based on a side stock liquid.That is to say, grow independently, will grow based on the mode between the crystal 42 of a side stock liquid with landfill based on the crystal 52 of the opposing party's raw material based on the crystal 42 of a side stock liquid with based on the crystal 52 of the opposing party's stock liquid.Its result can form the ceramic membrane that improves configuration of surface.
(3) in addition, by making based on the easy differently-oriented directivity of the crystalline of the 2nd stock liquid, will be interdicted by the opposing party's crystalline crystal growth based on the crystalline crystal growth of a side stock liquid with different based on the easy differently-oriented directivity of the crystalline of the 1st stock liquid.Therefore, in this case, can make the crystallization micro-crystallizationization of the ceramic membrane that obtains.Its result can form the ceramic membrane that configuration of surface more is enhanced.
Variation
The 2nd above-mentioned embodiment, it is possible doing following distortion.
(1) manufacturing process of above-mentioned ceramic membrane can be implemented repeatedly to form ceramic membrane.In addition, the manufacturing process of above-mentioned ceramic membrane and the operation of utilizing known ceramic raw material to make ceramic membrane can be made up, form ceramic membrane.
(2) utilize the LSMCD method on matrix, to form the method for starting material body, for example can enumerate following method.Fig. 3 schematically represents to utilize the LSMCD method in order to form the sectional drawing of the device 200 of starting material body on matrix.
The 1st stock liquid 210 utilizes atomizer 230 to deliver on the sieve 240.The 1st stock liquid 210 by sieve 240 forms mist 250, supplies on the matrix 10.In addition, utilize atomizer 232 also the 2nd stock liquid 220 to be delivered on the sieve 240, the 2nd stock liquid 220 formation mists 250 by sieve 240 supply on the matrix 10.Like this, by on matrix 10, piling up mist 250, form the starting material body.The particle diameter of mist 250 for example is 10～200nm.
The 1st stock liquid 210 and the 2nd stock liquid 220 can supply on the matrix 10 simultaneously.Perhaps the 1st stock liquid 210 and the 2nd stock liquid 220 also can alternative supplies.
Under the 1st stock liquid 210 and the 2nd stock liquid 220 supplied to situation on the matrix 10 simultaneously, the starting material style was as shown in Fig. 4 A, resulted from the 1st mist 210a of the 1st raw material 210 and the 2nd mist 220a of the 2nd raw material 220 of resulting to be the miscellaneous state.
Under the situation of alternative supply the 1st raw material 210 and the 2nd raw material 220, the starting material body for example shown in Fig. 4 B, results from the 1st mist 210a of the 1st raw material 210 and the 2nd mist 220a of the 2nd raw material 220 of resulting from and constitutes one deck separately.That is, constitute by resulting from the mist of same raw material with one deck.
The 3rd embodiment
The stock liquid of the 2nd pottery
The stock liquid of the 2nd pottery is that the 3rd stock liquid and the 4th stock liquid are mixed the stock liquid that uses.The stock liquid of the 2nd pottery can be to obtain the such stock liquid of ceramic membrane by thermolysis.The 3rd stock liquid and the 4th stock liquid exist the diverse relation of the material that is generated.The the 3rd and the 4th stock liquid for example can be: 1) organometallics (for example metal alkoxide, metal carboxylate) and metal inorganic compound (for example metal nitrate, metal chloride) are dissolved in the liquid in the solvent (for example water, alcohol, ester, aliphatic hydrocarbon, aromatic hydrocarbons, ketone, ether or their mixture); 2) in solvent, make the be hydrolyzed liquid of reaction, polycondensation etc. of metallic compound; 3) sol gel solution that obtains by the hydrolysis of metal alkoxide.
Below, specifically describe the 3rd stock liquid and the 4th stock liquid.
The 3rd stock liquid is the stock liquid that is used to generate the strong dielectric of PZT system.As the strong dielectric of PZT system, can enumerate the strong dielectric (PbZr for example of PbZrTiO system yTi 1-yO 3), the strong dielectric of PbLaZrTiO system (Pb for example 1-xLa xZr yTi 1-yO 3).In the 3rd stock liquid, contain the metallic element that constitutes strong dielectric.The amount of the formation metallic element of the strong dielectric that contains in the 3rd stock liquid, the ratio of the amount by considering desirable strong dielectric and the atomicity of the formation metallic element in the desirable strong dielectric decides.
As the object lesson of the 3rd stock liquid,, can enumerate the liquid that in 1-methoxyl group-2-propyl alcohol, contains lead acetate trihydrate, zirconium alkoxide, titanium alkoxide if example goes out the strong dielectric of PbZrTiO system.The usage quantity of lead acetate trihydrate, zirconium alkoxide, titanium alkoxide, the ratio of the atomicity by considering the formation metallic element in the desirable strong dielectric and the amount of desirable strong dielectric decide.
The 4th stock liquid is that to be used to generate the A position be that the ABO of Pb is the stock liquid of oxide compound.If the A position is not Pb, be on the position that will hold Pb of oxide compound then at PZT, produce the situation of holding Pb element in addition, often the characteristic to strong dielectric causes bad influence.As the A position is that the ABO of Pb is an oxide compound, and can enumerate PbGeO is oxide compound (Pb 5Ge 3O 11), PbMoO is oxide compound (Pb 2MoO 5), PbVO is oxide compound (Pb 2VO 5), PbCrO is oxide compound (Pb 2CrO 5), PbSiO is oxide compound (Pb 5Si 3O 11), PbWO is oxide compound (Pb 2WO 5), PbSnO is oxide compound (PbSnO 3), PbGeSiO is oxide compound (Pb 5Ge 2SiO 11).Moreover, be the element of the B position of oxide compound by changing ABO, can change crystalline crystallized temperature based on the 2nd stock liquid.In addition, ABO is that oxide compound can be a strong dielectric, also can be paraelectrics.
As the object lesson of the 4th stock liquid, be oxide compound if example goes out PbGeO, can enumerate the liquid that in 1-methoxyl group-2-propyl alcohol, dissolves germanium alkoxide and plumbous alkoxide.The usage quantity of germanium alkoxide and plumbous alkoxide, the ratio and the desirable oxide amount of the atomicity of the formation metallic element by considering desirable oxide compound decide.
The 3rd stock liquid and the 4th stock liquid preferably are mixed into the strong dielectric that obtains based on the 3rd stock liquid and are that the mol ratio of oxide compound is 100: 20～100: 100 based on the ABO that the 4th stock liquid obtains.
The Production Example of the 2nd kind of ceramic membrane
The film of the stock liquid of the 2nd pottery can be in the method shown in the 2nd embodiment.
Action effect
Below, about using the stock liquid of the pottery relevant with the 3rd embodiment, the action effect when carrying out the ceramic membrane film forming is illustrated.
(1) uses the ceramic raw material liquid relevant with present embodiment, form the occasion of strong dielectric film only burning till the 3rd stock liquid, under the firing temperature that is lower than for the necessary firing temperature of characteristic that produces regulation, can form the strong dielectric film of characteristic with regulation.That is to say,, under lower temperature, just can form strong dielectric film with desirable characteristic according to present embodiment.
(2) material that generates based on the 3rd stock liquid is different with the material that generates based on the 4th stock liquid.Therefore, for example the crystallized temperature of the crystallized temperature of the 3rd stock liquid crystallization and the 4th stock liquid crystallization will be different.Its result, same with the 2nd embodiment, can form the ceramic membrane that improves configuration of surface.
The 3rd embodiment can adopt in the variation shown in the 2nd embodiment.
The 4th embodiment
The stock liquid of the 3rd pottery
The stock liquid of the 3rd pottery is that the 5th stock liquid and the 6th stock liquid are mixed the stock liquid that uses.The stock liquid of the 3rd pottery can be to obtain the such stock liquid of ceramic membrane by thermolysis.There are the diverse relation of the material that is generated in the 5th stock liquid and the 6th stock liquid.The the 5th and the 6th stock liquid for example can be: 1) organometallics (for example metal alkoxide, metal carboxylate) and metal inorganic compound (for example metal nitrate, metal chloride) are dissolved in the liquid in the solvent (for example water, alcohol, ester, aliphatic hydrocarbon, aromatic hydrocarbons, ketone, ether or their mixture); 2) in solvent, make the be hydrolyzed liquid of reaction, polycondensation etc. of metallic compound; 3) sol gel solution that obtains by the hydrolysis of metal alkoxide.
Below, specifically describe the 5th stock liquid and the 6th stock liquid.
The 5th stock liquid is the stock liquid that is used to generate the strong dielectric with strong dielectric that Bi is a laminated perovskite type structure or PZT system.As having the strong dielectric that Bi is a laminated perovskite type structure, can use at the stock liquid shown in the stock liquid of the 1st pottery.Strong dielectric as PZT system can use at the stock liquid shown in the stock liquid of the 1st pottery.Object lesson as the 5th stock liquid, has the occasion that Bi is the strong dielectric of laminated perovskite type structure, the object lesson of the 1st stock liquid (the 2nd embodiment) can be used,, the object lesson of the 3rd stock liquid (the 3rd embodiment) can be used in the occasion of the strong dielectric of PZT system.
The 6th stock liquid is the stock liquid that is used to generate the oxide compound of AGeO system.The B position is the oxide compound of Ge, because fusing point is low to moderate near 700 ℃, therefore can seek the low temperatureization of process.As the A position in the oxide compound of AGeO system, for example can enumerate alkaline-earth metal, rare earth element (especially Ce), Zr, Sr, Bi etc.As the oxide compound of ZrGeO system, for example can enumerate ZrGeO 4As the oxide compound of SrGeO system, for example can enumerate Sr 5Ge 3O 11As the object lesson of the 6th stock liquid,, can use the object lesson of the 2nd stock liquid (the 2nd embodiment) in the occasion of the oxide compound of BiGeO system.The oxide compound of AGeO system can be a paraelectrics, also can be strong dielectric.
The 5th stock liquid and the 6th stock liquid preferably are mixed into the strong dielectric that obtains based on the 5th stock liquid and are that the mol ratio of oxide compound is 100: 20～100: 100 based on the ABO that the 6th stock liquid obtains.
The Production Example of the 3rd kind of ceramic membrane
The film of the stock liquid of the 3rd pottery can be in the method shown in the film of the stock liquid of the 1st pottery.
Action effect
Below, about using the stock liquid of the pottery relevant with the 4th embodiment, the action effect when carrying out the ceramic membrane film forming is illustrated.
(1) uses the stock liquid of the pottery relevant with present embodiment, form the occasion of strong dielectric only burning till the 5th stock liquid, under the firing temperature that is lower than for the necessary firing temperature of characteristic that produces regulation, can form strong dielectric film with predetermined characteristic.That is to say,, under lower temperature, can form the strong dielectric film of characteristic with hope according to present embodiment.
(2) material that generates based on the 5th stock liquid is different with the material that generates based on the 6th stock liquid.Therefore, for example the crystallized temperature of the crystallized temperature of the 5th stock liquid crystallization and the 6th stock liquid crystallization will be different.Its result and the 2nd embodiment are same, can form the ceramic membrane that improves configuration of surface.
(3) in addition, by making based on the easy differently-oriented directivity of the 6th stock liquid crystalline, interdicted by the opposing party's crystalline crystal growth based on the crystalline crystal growth of a side stock liquid with different based on the easy differently-oriented directivity of the crystalline of the 5th stock liquid.Therefore, in the case, can make the crystallization micro-crystallizationization of resulting ceramic membrane.Its result can form the ceramic membrane that improves configuration of surface more.
The 4th embodiment can adopt in the variation shown in the 2nd embodiment.
The 5th embodiment
Below, the Production Example of the multilayer ceramic film relevant with the 5th embodiment is described.
The Production Example of the 1st kind of multilayer ceramic film
Below, the Production Example of the 1st kind of multilayer ceramic film is described.Fig. 5 A-C is a sectional drawing of schematically representing the manufacturing processed of the 1st kind of multilayer ceramic film.
At first, shown in Fig. 5 A, utilize coating method on matrix 10, to form in order to generate the main liquid layer 312 of strong dielectric.As the material of main liquid layer 312, can enumerate the 1st stock liquid in the 2nd embodiment, the 3rd stock liquid in the 3rd embodiment.
Then, on main liquid layer 312, form in order to generate the secondary liquid layer 322 of strong dielectric and paraelectrics.The material of secondary liquid layer 322 is selected the also low material of crystallized temperature than the material of main liquid layer 312.In addition, as the material of secondary liquid layer 322, after the selective freezingization, generate the such material of oxide compound do not have laminate structure.As the material of secondary liquid layer 322, different and different with the material of main liquid layer 312, but when making main liquid layer 312 crystallizations, at the occasion of the strong dielectric that generates SBT system, the material of secondary liquid layer 322, for example be that BiGeO system, BiSiO system, SrGeO are.
Then,, shown in Fig. 5 C, make main liquid layer 312 and secondary liquid layer 322 crystallizations, form the ceramic membrane 300 that constitutes by primary crystallization layer 310 and secondary crystallizing layer 320 by thermal treatment.
Production Example according to the 1st kind of multilayer ceramic film can reach following action effect.
Secondary liquid layer 322 is selected the material lower than the crystallized temperature of main liquid layer 312.Therefore, in the initial stage of crystallization, shown in Fig. 5 B, secondary liquid layer 322 preferentially carries out crystallization with respect to main liquid layer 312.Its result, the crystal that generates in secondary liquid layer is brought into play function as seed crystal in the crystallization of main liquid layer 312.Therefore, the crystallization of main liquid layer 312 will carry out from secondary liquid layer 322 sides and matrix 10 sides.Thereby the crystalline grain fineness number in the main liquid layer 312 is diminished.
In addition, the material that as the material of secondary liquid layer 322, use behind crystallization, generation does not have the such oxide compound of laminate structure.Therefore, in secondary liquid layer 322, crystal isotropically carries out crystal growth.Its result forms the secondary crystallizing layer 320 that has an even surface, and can improve the configuration of surface of ceramic membrane 300.
Moreover, as shown in Figure 6A, make secondary liquid layer 322 between matrix 10 and main liquid layer 312, also can form the ceramic membrane 300 that constitutes by primary crystallization layer 310 and secondary crystallizing layer 320,330.
The Production Example of the 2nd kind of multilayer ceramic film
Below, the Production Example of the 2nd kind of multilayer ceramic film is described.Fig. 7 A-C is a sectional drawing of schematically representing the manufacturing processed of the 2nd kind of multilayer ceramic film.
The Production Example of the 2nd kind of multilayer ceramic film is making secondary liquid layer 422 on this aspect between the main liquid layer 412,432, different with the Production Example of the 1st kind of multilayer ceramic film.
That is, on matrix 10, stack gradually main liquid layer 412, secondary liquid layer 422, main liquid layer 432 and secondary liquid layer 442.Then, by making these layers crystallization, form the ceramic membrane 400 that constitutes by primary crystallization layer 410,430 and secondary crystallizing layer 420,440.
Secondary liquid layer 422,442 is the same with the Production Example of the 1st kind of multilayer ceramic film, from than selecting the low material of the crystallized temperature of main liquid layer 412,442.
Like this, by making secondary liquid layer 422 between main liquid layer 412,432, the crystal that generates in secondary liquid layer 422 plays the effect as the suppressor that stops the crystalline crystal growth in the main liquid layer 412,432.Therefore, the crystalline particle diameter of the primary crystallization layer 410,430 of the both sides that are in secondary crystallizing layer 420 is diminished.
The Production Example of the 3rd kind of multilayer ceramic film
Below, the Production Example of the 3rd kind of multilayer ceramic film is described.Fig. 8 A, B are the sectional drawings of schematically representing the manufacturing processed of the 3rd kind of multilayer ceramic film.
The Production Example of the 3rd kind of multilayer ceramic film, the material of main liquid layer 512 be than low this aspect of material of the crystallized temperature of the material of secondary liquid layer 522 on, different with the Production Example of the 1st kind of multilayer ceramic film.
In this occasion,, can enumerate the 1st stock liquid in the 2nd embodiment and the 3rd stock liquid in the 3rd embodiment as the material of main liquid layer 512.Material at main liquid layer 512 is the occasion that generates the strong dielectric of PZT system, and the material of secondary liquid layer 522 can be PbWO system, PbMoO system.
By making this main liquid layer 512 and secondary liquid layer 522 crystallizations, can form the ceramic membrane that configuration of surface improves.It is the reasons are as follows.The material of main liquid layer 512 is made of the low material of crystallized temperature than the material of secondary liquid layer 522.Therefore, the crystallization of secondary liquid layer 522, for main liquid layer 512, hysteresis is carried out, and under the prerequisite of the primary crystallization layer 510 that forms, generates crystal based on secondary liquid layer 522 based on main liquid layer 512 in covering.And the crystal based on this pair liquid layer 522 generates does not have laminate structure, thereby isotropically grows based on the crystal of secondary liquid layer 522.Therefore, form the secondary crystallizing layer 520 of flattening surface.Its result tails off at the concave-convex surface of ceramic membrane 500, can improve the configuration of surface of ceramic membrane 500.
In the Production Example of the 1st～3rd kind of above-mentioned multilayer ceramic film, based on the crystal grain and the situation about spreading of main liquid layer based on the oriented different mutually crystallizing layer of the crystal grain of secondary liquid layer.In addition, exist the formation metallic element in the main liquid layer to spread, or the formation metallic element in the secondary liquid layer is to the situation of main liquid layer diffusion to secondary liquid layer.Therefore, the interface of primary crystallization layer that forms based on main liquid layer and the secondary crystallizing layer that forms based on secondary liquid layer indefinite situation that becomes.
The 6th embodiment
Semiconductor device
Below, the semiconductor device that uses the ceramic membrane that the manufacture method according to ceramic membrane of the present invention obtains is described.In the present embodiment, as semiconductor device, the example of ferroelectric memory apparatus is shown.Fig. 2 is a sectional drawing of schematically representing ferroelectric memory apparatus.
The capacitor area R2 that ferroelectric memory apparatus 5000 has CMOS (complementary type Metal-oxide-semicondutor) region R 1 and forms on this CMOS region R 1.That is the CMOS region R 1 element separated region 2 and MOS (metal-oxide semiconductor (MOS)) transistor 3 and the interlayer insulating film 4 that have semiconductor chip 1, on this semiconductor chip 1, form.Capacitor area R2 has the electrical condenser C100 that is made of lower electrode 5, strong dielectric film 6 and upper electrode 7, the wiring layer 8a that is connected with lower electrode 5, the wiring layer 8b that is connected with upper electrode 7 and insulation layer 9.Strong dielectric film 6 among the electrical condenser C100 is to adopt the manufacture method of ceramic membrane of the present invention to form.The lower electrode 5 of the impurity diffusion layer 3a of MOS transistor 3 and formation electrical condenser 5 connects by the contact layer 11 that is made of many silicon or tungsten.
Below, the action effect of strong dielectric device is described.
(1) forming the occasion of strong dielectric film, considering that ditch and hole generate, from the short circuit that prevents upper electrode and lower electrode need consider, must make the thickness thickening of strong dielectric film.Is material (Ir, IrO at upper electrode by iridium 2) when constituting, the short circuit of this upper electrode and lower electrode takes place significantly.But in the present embodiment, the strong dielectric film 6 of strong dielectric device 5000 is to adopt the manufacture method of ceramic membrane of the present invention to form.Therefore, the configuration of surface of strong dielectric film 6 improves.Its result, only the configuration of surface of strong dielectric film 6 improves, and just can make the thickness attenuation of strong dielectric film 6.Therefore, if utilize this strong dielectric device 5000, just can seek highly integrated.
In addition, according to present embodiment, just can use iridium as the material of upper electrode 7 is material, thereby can enlarge the thickness scope of strong dielectric film 6.That is to say,, can use the material of iridium system, can reduce the boundary of the minimal thickness of strong dielectric film 6 as the material of upper electrode 7.
(Pt) compares with platinum, and the material of iridium system has the advantage of hydrogen potential barrier and material of excellent fatigue characteristics.
(2) if corrode strong dielectric film to produce concavo-convex state on the surface of strong dielectric film, then on the surface of the lower electrode of the substrate of strong dielectric film, will duplicate the concaveconvex shape on strong dielectric film surface, make the configuration of surface deterioration of lower electrode.If the configuration of surface deterioration of lower electrode then between the wiring layer and lower electrode that will be connected with lower electrode, comes in contact condition of poor.
But in the present embodiment, the configuration of surface of strong dielectric film 6 improves.Therefore, after with strong dielectric film 6 corrosion, just can suppress the deterioration of the configuration of surface of lower electrode 5.Its result just can be electrically connected wiring layer 8a reliably with lower electrode 9.
Variation
Can use the semiconductor device of the ceramic membrane that the manufacture method according to ceramic membrane of the present invention obtains, be not limited to strong dielectric memory, can be applicable to various semiconductor devices, for example DRAM.Specifically, ceramic membrane of the present invention can be applicable to the dielectric film in the electrical condenser of DRAM.In this occasion, consider that from the viewpoint of the high capacity of seeking electrical condenser dielectric film can be made of the paraelectrics of the such high-k of BST.
In addition, the ceramic membrane according to manufacture method of the present invention obtains is not only applicable to semiconductor device, and can be applicable to other purposes, the piezoelectrics of the piezoelectric element that for example uses in power element.
Most preferred embodiment
Then, enumerate embodiment, illustrate in greater detail the present invention.In the scope that does not exceed main points of the present invention, the present invention is not subjected to the restriction of following embodiment.
Embodiment 1
Main liquid resembles and obtains following.With the concentration of 2 ethyl hexanoic acid bismuth is that the concentration of toluene solution 1100ml, the 2 ethyl hexanoic acid strontium of 0.1mol/l is that the concentration of the toluene solution 400ml of 0.1mol/l, tantalum alkoxide is that toluene solution 1000ml, the 2 ethyl hexanoic acid 100g of 0.1mol/l mixes the modulation mixed solution.Under nitrogen atmosphere, 120 ℃ with this mixed solution reflux 1 hour, normal pressure heats up in a steamer and desolvates.To wherein adding toluene, make as Sr 0.8Bi 2.2Ta 2O x(SBT) oxide concentration is 0.1mol/l, obtains main liquid.
On the other hand, resemble and obtain secondary liquid following.Concentration at the 2 ethyl hexanoic acid bismuth is among the toluene solution 2000ml of 0.1mol/l, and the concentration of mixing the germanium alkoxide is toluene solution 1500ml and the 2 ethyl hexanoic acid 100g of 0.1mol/l.Under nitrogen atmosphere, 120 ℃ with this vlil 1 hour, normal pressure heats up in a steamer and desolvates.To wherein adding toluene, make as Bi 4Ge 3O 12Oxide concentration be 0.1mol/l, obtain secondary liquid.
The main liquid and the secondary liquid that obtain are mixed, obtain mixed volume than 7 kinds of different mixed solutions.The mixed volume ratio of the main liquid of mixed solution and secondary liquid is 100: 1,100: 10,100: 20,100: 50,100: 100,100: 150,100: 200.
By these 7 kinds of mixed solutions with each self-forming strong dielectric film of solution of main liquid is only arranged.
Film carries out according to method shown in Figure 9.The series of processes of pre-treatment heating process, solution coat operation, dry heat treatment process, degreasing heat treatment step and false sintering circuit is carried out 2 times.And, carry out sintering, film forming at last.Concrete condition is shown below.The pre-treatment heating process was carried out 30 seconds at 180 ℃.The coating of mixed solution uses rotary coating machine (2100rpm) to carry out 30 seconds.Dry heat is handled, under nitrogen atmosphere, carried out 1 minute at 160 ℃.The degreasing heat treatment step is under nitrogen atmosphere, carried out 4 minutes at 260 ℃.False sintering carried out under oxygen atmosphere 30 seconds.False agglomerating temperature is carried out under the sintering temperature shown in the table 1.Sintering carried out under oxygen atmosphere 60 minutes.The agglomerating temperature is carried out under the sintering temperature shown in the table 1.In addition, film forming thickness is 50nm.
Measure the Pr (remnant polarization value) of strong dielectric film separately.The measurement result of Pr is shown in table 1.The unit of Pr is μ C/cm 2
Table 1
Figure C20051007591300251
" ND " means and can not detect
Making SBT is the occasion of the ferroelectric memory device of strong dielectric, if firing temperature be not≤600 ℃, just be difficult to make the ferroelectric memory device of integrated level to a certain degree.In addition, in the ferroelectric memory device, the Pr of ferro-electric materials capacitor preferably has and is not less than 7.In table 1, during in firing temperature≤600 ℃, Pr has 〉=and the mixed volume of 7 data is than (main liquid: secondary liquid) be 100: 20～100: 100.Therefore, the mixed volume of main liquid and secondary liquid ratio, be preferably in 100: 20～100: 100 scope in.
Also have, generate the Sr of 0.1mol by per 1 liter of main liquid 0.8Bi 2.2Ta 2O xModulate main liquid like that.In addition, also generate the Bi of 0.1mol by per 1 liter of secondary liquid 4Ge 3O 12Modulate secondary liquid like that.For this reason, the mixed volume of main liquid and secondary liquid is than the Sr that represents simultaneously to generate based on main liquid 0.8Bi 2.2Ta 2O xWith the Bi that generates based on secondary liquid 4Ge 3O 12Mol ratio.Therefore, preferably according to the Sr that generates based on main liquid 0.8Bi 2.2Ta 2O xWith the Bi that generates based on secondary liquid 4Ge 3O 12Mol ratio be to mix main liquid and secondary liquid in 100: 20～100: 100 like that.
In addition, in the occasion that only constitutes by main liquid, if firing temperature be not 〉=700 ℃, the characteristic that does not just obtain stipulating about Pr.On the other hand, by in main liquid, mixing secondary liquid,, also obtain the characteristic of stipulating about Pr even firing temperature is about 500 ℃.Hence one can see that, carries out film forming if mix secondary liquid in main liquid, just can seek low temperatureization.
Embodiment 2
Main liquid resembles and obtains following.In the 2-methyl cellosolve of 1000ml, add 85.3g titanium isopropoxide and 139.2g butoxy bismuth.Under nitrogen atmosphere, this 2-methyl cellosolve reflux after 1 hour, is returned room temperature at 125 ℃.To wherein adding 23.7g isopropoxy lanthanum, stirring at room 2 hours.Add 1.3g water again, after 1 hour, add 2-methyl cellosolve, be modulated into Bi in stirring at room 3.25La 0.75Ti 3O 12Oxide concentration is 0.07mol/l, and obtains main liquid.
On the other hand, secondary liquid resembles and obtains following.In the 2-methyl cellosolve of 1000ml, add 75.9 oxyethyl group germanium and 171.3g butoxy bismuth.Under nitrogen atmosphere, this 2-methyl cellosolve reflux after 1 hour, is returned room temperature at 125 ℃.To wherein adding 1.3g water, after 1 hour, add 2-methyl cellosolve in stirring at room, be modulated into Bi 4Ge 3O 12Oxide concentration is 0.07mol/l, and obtains secondary liquid.
The main liquid and the secondary liquid that obtain are mixed, obtain 7 kinds of different mixed solutions of ratio of mixture.The main liquid of mixed solution and the ratio of mixture of secondary liquid are 100: 1,100: 10,100: 20,100: 50,100: 100,100: 150,100: 200.
By these 7 kinds of mixed solutions with each self-forming strong dielectric film of solution of main liquid is only arranged.Film is identical with embodiment 1.
In embodiment 2,, the tendency identical with embodiment 1 arranged also about Pr.
Embodiment 3
Main liquid resembles and obtains following.In the dimethylbenzene of 100ml, add 81.2g ethoxy-tantalum and 170g2-thylhexoic acid,, stirred 2 hours, heat up in a steamer the ethanol of removal xylene, generation, remaining 2 ethyl hexanoic acid at 180 ℃ of normal pressures at 120 ℃ to wherein adding 20.6g isopropoxy strontium.To the concentration that wherein adds 2 ethyl hexanoic acid is the xylene solution 200ml of 1.0mol/l.After this, add dimethylbenzene and modulate, so that SrBi 2Ta 2O xOxide concentration is 0.2mol/l.Add butylacetate again, be modulated into SrBi 2Ta 2O xOxide concentration is 0.1mol/l, and obtains main liquid.
Secondary liquid resembles and obtains following.Concentration at the 2 ethyl hexanoic acid bismuth is among the xylene solution 1000ml of 0.1mol/l, and the concentration of mixing oxyethyl group tungsten is xylene solution 500ml and the 2 ethyl hexanoic acid 100g of 0.1mol/l.Under nitrogen atmosphere, 120 ℃ with this mixing solutions reflux after 1 hour, the air distillation solvent.To wherein adding dimethylbenzene, modulate so that Bi 2WO 6Oxide concentration is 0.1mol/l, and obtains secondary liquid.
The main liquid and the secondary liquid that obtain are mixed, obtain mixed volume than 7 kinds of different mixed solutions.The mixed volume ratio of the main liquid of mixed solution and secondary liquid is 100: 1,100: 10,100: 20,100: 50,100: 100,100: 150,100: 200.
By these 7 kinds of mixed solutions with each self-forming strong dielectric film of solution of main liquid is only arranged.Film is identical with embodiment 1.
In embodiment 3,, the tendency identical with embodiment 1 arranged also about Pr.
Embodiment 4
Main liquid resembles and obtains following.In the 1-of 100ml methoxyl group-2-propyl alcohol, add 37.93g lead acetate trihydrate, 19.95g butoxy zirconium, 13.64g titanium isopropoxide, under nitrogen atmosphere, carry out 1 hour reflux at 120 ℃.After this, add 4.5g methyl ethyl diketone and 1.1g water, normal pressure heats up in a steamer and desolvates.To wherein adding 1-methoxyl group-2-propyl alcohol, be modulated into Pb (Zr 0.52Ti 0.48) O 3Oxide concentration is 0.3mol/l, and obtains main liquid.
On the other hand, secondary liquid resembles and obtains following.With the concentration of oxyethyl group germanium is that the 1-methoxyl group-2-propanol solution 200ml of 0.5mol/l and the concentration of butoxy lead are 1-methoxyl group-2-propanol solution 250ml mixing of 0.5mol/l.Under nitrogen atmosphere, this mixing solutions reflux after 1 hour, is returned room temperature at 120 ℃.After this, add 4.1g methyl ethyl diketone and 1.0g water, normal pressure heats up in a steamer and desolvates.To wherein adding 1-methoxyl group-2-acetone, be modulated into Pb 5Ge 3O 11Oxide concentration is 0.15mol/l, and obtains secondary liquid.
The main liquid and the secondary liquid that obtain are mixed, obtain mixed volume than 7 kinds of different mixed solutions.The mixed volume ratio of the main liquid of mixed solution and secondary liquid is 100: 1,100: 10,100: 20,100: 50,100: 100,100: 150,100: 200.
By these 7 kinds of mixed solutions with each self-forming strong dielectric film of solution of main liquid is only arranged.Film is identical with embodiment 1.
In embodiment 4,, the tendency identical with embodiment 1 arranged also about Pr.
Experimental example about configuration of surface
The experimental result of relevant configuration of surface then, is described.
Figure 10 is the microphotograph figure of the strong dielectric film that obtains of the mixed solution by main liquid relevant with embodiment 1 and secondary liquid.Figure 11 is the microphotograph figure of the strong dielectric film relevant with comparative example.
The strong dielectric film relevant with embodiment 1 in Figure 10, the mixed volume ratio that is main liquid and secondary liquid is 100: 100 a strong dielectric film.The strong dielectric film relevant with comparative example according to the film of embodiment 1, will only have the solution of the main liquid shown in the embodiment 1 to carry out film forming to obtain.The thickness of the strong dielectric film of embodiment and comparative example all is 50nm.
As shown in Figure 10 and Figure 11 as can be known, relevant with embodiment strong dielectric film is than relevant strong dielectric film has improved configuration of surface extraordinarily with comparative example.
The present invention can carry out all changes in the scope that does not exceed above-mentioned embodiment.

Claims (6)

1. the manufacture method of a ceramic membrane, this method comprises:
On matrix, form the operation of the starting material body that contains perovskite typed collosol and gel raw material and multi-nuclear metal ligand compound raw material, and the operation that makes above-mentioned starting material body crystallization.
2. the manufacture method of ceramic membrane according to claim 1, the crystallized temperature of above-mentioned perovskite typed collosol and gel raw material is lower than the crystallized temperature of above-mentioned multi-nuclear metal ligand compound raw material.
3. the manufacture method of ceramic membrane according to claim 1, the nucleus formation speed of above-mentioned perovskite typed collosol and gel raw material and crystalline growth velocity are faster than the nucleus formation speed and the crystalline growth velocity of above-mentioned multi-nuclear metal ligand compound raw material.
4. the manufacture method of ceramic membrane according to claim 1, above-mentioned multi-nuclear metal ligand compound raw material is the metal-salt of carboxylic acid.
5. the manufacture method of ceramic membrane according to claim 1 in the above-mentioned operation that makes starting material body crystallization, at first, is carried out 5～30 seconds annealing under 500～650 ℃ temperature, carry out 10～30 minutes annealing then under 600～650 ℃.
6. the manufacture method of ceramic membrane according to claim 1, above-mentioned starting material body forms by coating method or liquid source atomizing chemical deposition.
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