CN1318506C - Composite organic-inorganic material and its production process - Google Patents
Composite organic-inorganic material and its production process Download PDFInfo
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- CN1318506C CN1318506C CNB031027164A CN03102716A CN1318506C CN 1318506 C CN1318506 C CN 1318506C CN B031027164 A CNB031027164 A CN B031027164A CN 03102716 A CN03102716 A CN 03102716A CN 1318506 C CN1318506 C CN 1318506C
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Abstract
A method of producing an organic-inorganic composite material formed from an organic polymer and a metal alkoxide, comprising the steps of polycondensating the metal alkoxide through hydrolysis until the unreacted metal alkoxide is reduced to 3 vol. % or less, and mixing it with the organic polymer to form the organic-inorganic composite material. By laminating such organic-inorganic composite materials, the resulting laminate is provided with a concentration gradation wherein the metal element of the metal alkoxide is increased or decreased from one side to the other side of the laminate.
Description
Technical field
The present invention relates to make the method for the composite organic-inorganic material that forms by organic polymer and metal alkoxide, the composite organic-inorganic material that adopts this method to make, and stacking material.
Technical background
Inorganic materials such as metal and pottery have good thermotolerance, physical strength, electrical property, optical property, chemical stability or the like, utilize these performances to be extensive use of industrial the acquisition.Yet, the general fragility height of these materials, rigidity is also high, owing to when being processed into the shape of requirement, need at high temperature process or mechanical treatment, and its application is restricted.
On the other hand, organic polymer has good processing characteristics and flexibility, therefore is easy to be processed into the shape of requirement.Yet the thermotolerance of organic polymer and chemical stability aspect are not as inorganic materials.
Therefore, in recent years, comprise inorganic materials and organic materials and attract much attention with the composite organic-inorganic material that possesses these two kinds of material properties.
Used the matrix material of organic polymer and inorganic materials in various fields, they are inorganic materials is dispersed in the inorganic materials in the organic polymer material with fiber or powder type matrix materials.In recent years, people in the organic and inorganic zone of broad research with nano level or molecular level blended organic-inorganic nanocomposite (being also referred to as organic-inorganic hybrid material).
Because organic and inorganic zone can nano level or the dispersion of molecular level, organic-inorganic nanocomposite can be used as the material of used for electronic device or the material that mechanical part is used.And the organic or inorganic zone of this material can be designed to less than light wavelength, makes photoabsorption and scattering very low thus.Therefore, studying always and providing optical transparency to it, as the material of usefulness such as optical waveguides, optical fiber with organic-inorganic nanocomposite.
People such as Motoyuki Toki, at " poly-(vinyl pyrrolidone)-SiO 2 hybrid thing " PolymerBulletin 29, people such as 653-660 (1990) and Jen Ming Yang, " organic inorganic hybridization thing sol material; 1 ", disclosed the method for preparing composite organic-inorganic material in Die Angewandte Makromolekulare Chemi 251 (1997) the 49-60 documents such as (Nr.4356).
Yet the problem that the preparation method of these document descriptions exists is to obtain the good composite organic-inorganic material of optical transparency.
When organic-inorganic nanocomposite is used as optical waveguides, generally on base material, form its light-transmitting layer.In this case, base material and light-transmitting layer is bonding very important.
Be to improve binding property, making great efforts to form the material with Gradient distribution is provided always by continuously changing material.
For example, a kind of matrix material of silicon-dioxide/polycarbonate-base has been proposed in Japanese patent gazette flat-34413 (2000), wherein, by on base material, applying the organic coating solution different of many layers in succession, continuously change concentration of silicon dioxide with the composition of inorganic component.
And, in Japanese patent gazette flat-336281 (2000), proposed on organic substrate, to apply coating solution by organic polymer and the energy hydrolysis formation metallic compound of metal oxide, heat drying forms Gradient distribution then, this Gradient distribution simultaneously is that organic constituent content is higher at base material, and higher at the content of near surface inorganic component.
But the problem that the method that proposes in above-mentioned two communiques exists is fully to improve the binding property of light-transmitting layer and base material.
Summary of the invention
First purpose of the present invention provides the manufacture method that can make the good composite organic-inorganic material of optical transparency, and the composite organic-inorganic material that obtains in this way.
Second purpose of the present invention provides has the light transmission structure of having improved with the light-transmitting layer of substrate adherence.
The method of this method of the present invention composite organic-inorganic material that to be a kind of manufacturing formed by organic polymer and metal alkoxide, this method comprises the following steps: to come the polycondensation metal alkoxide by hydrolysis, reduce to 3% (volume) or still less up to the unreacted metal alkoxide, the metal alkoxide of polycondensation is mixed with organic polymer, form composite organic-inorganic material.
Among the present invention, metal alkoxide is by hydrolytie polycondensation, reduces to 3% (volume) or still less up to the unreacted metal alkoxide, and the metal alkoxide of polycondensation is mixed the formation composite organic-inorganic material with organic polymer.The optical transparency of the composite organic-inorganic material that is obtained is good.Therefore, according to the present invention, can make and be suitable as the material that optics such as optical waveguides or optical fiber are used.
The metal alkoxide that uses among the present invention comprises the alkoxide such as Si, Ti, Zr, Al, Sn and Zn metal.Especially preferably use the alkoxide of Si, Ti or Zr.Therefore, better use organoalkoxysilane, pure titanium and pure zirconium, particularly use organoalkoxysilane.Organoalkoxysilane comprises tetraethoxysilane, tetramethyl oxidation base silane, four positive propoxy silane, tetraisopropoxysilan, four n-butoxy silane, tetraisobutoxy-silicane alkane, phenyl triethoxysilane, 3-methanoyl propyl-triethoxysilicane and 3-methanoyl propyl trimethoxy silicane.
Organic polymer among the present invention there is not any restriction, as long as can form composite organic-inorganic material with metal alkoxide.Organic polymer comprises: for example, and Polyvinylpyrolidone (PVP), polycarbonate, polymethylmethacrylate, polymeric amide, polyimide, polystyrene, polyethylene, polypropylene, Resins, epoxy, phenol resins, vinylformic acid (class) resin, urea resin, melmac etc.Consider from forming the good composite organic-inorganic material of optical transparency, should use polyvinylpyrrolidone, polycarbonate, polymethylmethacrylate, polystyrene or their mixture as organic polymer.
The hydrolysis of metal alkoxide should be carried out under the sour existence condition of water that is used for hydrolysis and the catalyzer of using as hydrolysis.Water that hydrolysis is used and the mol ratio of metal alkoxide (water/metal alkoxide) are relatively good to be 1.0-3.0, more preferably 1.5-2.5.Acid as hydrolyst comprises mineral acid example hydrochloric acid, nitric acid and sulfuric acid and organic acid, preferably uses hydrochloric acid.The mol ratio of hydrochloric acid and metal alkoxide (hydrochloric acid/metal alkoxide) is relatively good to be 0.001-0.5,0.001-0.01 more preferably, preferably 0.002.
The amount of unreacted metal alkoxide is that the methods such as the available gas-chromatography of amount of residual metal alkoxide are measured.Decide residual metal alkoxide amount to drop to reaction times by hydrolysis metal alkoxide under conditions such as preset temperature, concentration in advance smaller or equal to 3% (volume); With this reaction times of determining, with metal alkoxide hydrolysis and polycondensation, mix with organic polymer then, form composite organic-inorganic material.Perhaps, when forming matrix material, measure unreacted metal alkoxide amount at every turn.
The characteristics of composite organic-inorganic material of the present invention are to prepare by aforesaid method of the present invention.Composite organic-inorganic material of the present invention for example can be to prepare the metal alkoxide of hydrolysis and polycondensation and the mixing solutions of organic polymer, applies this mixing solutions then and forms.Such coating solution is applied on the base material, on base material, forms composite organic-inorganic material.The base material that can use organic or metallic substance formation is as this base material.When composite organic-inorganic material of the present invention is used as optical material, can on transparent substrate, form composite organic-inorganic material.
When composite organic-inorganic material thickness of the present invention was 10 microns, this material was that the light of 600-1000nm shows 90% transmission to wavelength.Metal content in the composite organic-inorganic material of the present invention is preferably 0.1-46% (weight), more preferably 5-37% (weight).
The distribution of the composite organic-inorganic material that stacking material of the present invention has method for preparing of the present invention stacked.For example, the multiple mixtures that metal alkoxide content is different apply from level to level, just can be formed on the different stacking material of each layer metal alkoxide content.
The stacking material of first aspect present invention has the concentration gradient that a metal element content from the one side of stacking material to the another side metal alkoxide increases or descends.Generally, can change the specific refractory power of composite organic-inorganic material by metallic element concentration in the change composite organic-inorganic material.Therefore, the stacking material of first aspect present invention provides a Gradient distribution, is to make metallic element concentration form gradient, thereby specific refractory power is increased or decline from one side to the another side of stacking material.Stacking material with this Gradient distribution can be used as the material that optical element such as optical waveguides and optical fiber are used.
The metallic element that the stacking material of second aspect present invention has from the one side of stacking material to the another side metal alkoxide at first increases, then the concentration gradient of Xia Jianging.Therefore, the stacking material of second aspect present invention provides a kind of Gradient distribution that at first descends and increase then to the another side specific refractory power from the stacking material one side.
The metallic element of the stacking material of third aspect present invention from the one side of stacking material to the another side metal alkoxide at first descends, then the concentration gradient of Zeng Jiaing.Therefore, the stacking material of third aspect present invention provides a kind of at first increases the Gradient distribution that descends then from the stacking material one side to the another side specific refractory power.
The same with the stacking material of first aspect, the stacking material of the second aspect and the third aspect can be used as the material that optical element such as optical waveguides or optical fiber are used, as long as these materials have above-mentioned index distribution in gradient.
Light transmission structure of the present invention comprises a metal base, the metal oxide layer on this base material and the light-transmitting layer that is made of the composite organic-inorganic material that is provided on the metal oxide layer.
Among the present invention, metal oxide layer is between the light-transmitting layer of base material and composite organic-inorganic material formation.This metal oxide layer has been arranged, can improve the binding property of light-transmitting layer and base material.
Base material among the present invention there is not any restriction, as long as base material is to be made of metal, the base material that example has Si, Al, Ge, Cu, Fe, Ni, Zr, Sn, Zn or Ti to constitute.
Metal oxide layer better is the oxide skin that contains contained at least a element in the base material.For example, when base material was silicon or silicon alloy base material, metal oxide layer was advisable for the Si oxide skin.
The metal oxide layer thickness is preferably 5 nanometers to 20 micron, more preferably 50 nanometers to 5 micron.If metal oxide layer is too thin, can not reach the fusible effect of abundant raising, if metal oxide layer is too thick, because the stress that produces when forming metal oxide layer itself, binding property descends on the contrary.
The method that forms metal oxide layer among the present invention includes but not limited to: reactive vapour deposition, sputter, CVD and PVD.Also can pass through sol-gel method or the wet method such as the anodizing of heated oxide, hydrolysis and polycondensation metal alkoxide, form metal oxide layer.The base material long-term exposure can also be formed metal oxide layer in air or oxygen.
Light-transmitting layer of the present invention is made of the composite organic-inorganic material that organic polymer and metallic compound form.Light-transmitting layer thickness is preferably the 4-500 micron, more preferably the 5-50 micron.
When forming composite organic-inorganic material by organic polymer and metal alkoxide, metal alkoxide passes through hydrolytie polycondensation, is reduced to less than up to the unreacted metal alkoxide to equal 3% (volume), mixes with organic polymer then, forms composite organic-inorganic material.So just can form the good composite organic-inorganic material of optical transparence.Methods such as use gas-chromatography can be measured the amount of unreacted metal alkoxide.By hydrolysis metal alkoxide under conditions such as preset temperature, concentration, decision residual metal alkoxide amount drops to the reaction times smaller or equal to 3% (volume) in advance; With this reaction times of determining, with metal alkoxide hydrolysis and polycondensation, mix with organic polymer then, form composite organic-inorganic material.Also can when forming matrix material, measure unreacted metal alkoxide amount at every turn.Or can also in metal alkoxide hydrolysis and polycondensation, measure remaining metal alkoxide amount, and in case dropping to, this amount is equal to or less than 3% (volume), metal alkoxide is mixed with organic polymer.
Metal element content is preferably 0.1-46% (weight) in the composite organic-inorganic material, more preferably 5-37% (weight).Measuring method that composite organic-inorganic material forms comprises secondary ion mass spectrometry (SIMS) (SIMS) method, x-ray photoelectron spectroscopy (XPS) method and observes with electro-probe micro analyzer (EPMA) or transmission type microscope (TEM).
The specific refractory power of composite organic-inorganic material can be controlled by metallic element amount in the change composite organic-inorganic material.For example, when metallic element is silicon, increases this metallic element amount specific refractory power is descended, can increase specific refractory power and reduce this metallic element amount.
When the metallic element that composite organic-inorganic material comprises was Si, metal oxide layer better was a silicon oxide layer.In composite organic-inorganic material and metal oxide layer, use same metallic element, can further improve the binding property between metal oxide layer and the composite organic-inorganic material.
The accompanying drawing summary
Figure 1 shows that the reaction times that shows the metal alkoxide hydrolysis and the curve of residual metal alkoxide magnitude relation.
Figure 2 shows that the curve that shows specific refractory power and Si relation with contents in the composite organic-inorganic material of the present invention.
Fig. 3 is the synoptic diagram that shows an example of first aspect present invention stacking material.
Figure 4 shows that the curve that shows that the Si concentration of element changes in the first aspect present invention stacking material.
Figure 5 shows that the curve of the variations in refractive index that shows the first aspect present invention stacking material.
Figure 6 shows that the optical waveguides validation test device of first aspect present invention stacking material.
Fig. 7 is the schematic section that shows an example of second aspect stacking material.
Fig. 8 is the schematic section that shows an example of third aspect stacking material.
Figure 9 shows that the curve that shows that the Si concentration of element changes in the second aspect present invention stacking material.
Figure 10 shows that the curve that shows that the Si concentration of element changes in the third aspect present invention stacking material.
Figure 11 shows that the curve of the variations in refractive index that shows the third aspect present invention stacking material.
Figure 12 shows that the optical waveguides validation test device of third aspect present invention stacking material
Figure 13 shows that in the area size that shows film and the solution A curve of relation between the remaining TESO amount.
Figure 14 shows that and show in the film size removed and the solution A curve of relation between the remaining TESO amount.
Figure 15 is the schematic section that shows an example of light transmission structure of the present invention.
Figure 16 is the schematic section that shows another example of light transmission structure of the present invention.
Figure 17 is the schematic section that shows another example of light transmission structure of the present invention.
Figure 18 confirms optical waveguides test schematic representation of apparatus.
The better description of embodiment
Below, describing the present invention in detail in conjunction with some embodiment, these embodiment do not constitute limitation of the scope of the invention.
[preparation metal alkoxide solution]
Use tetraethoxysilane (TEOS) as metal alkoxide.Tetraethoxysilane and solvent Virahol (IPA) and 0.05N hydrochloric acid are pressed the listed mixed of table 1, preparation metal alkoxide solution (solution A).In the solution A, (mol ratio of water/TEOS) is 2.0 for water and metal alkoxide.
Table 1
| Solution A | Weight % |
| TEOS | 39.6 |
| IPA | 53.6 |
| 0.05N HCl | 6.8 |
Solution A remains in 26 ℃ in beaker, stir the TEOS in hydrolysis and the polycondensation solution A.Take a sample from solution A with predetermined time interval, adopt gas chromatographic analysis, measure the amount of unreacted TEOS, the amount of remaining TEOS among the ie in solution A.
Figure 1 shows that and show the curve that concerns between remaining TEOS amount and the hydrolysis time.The amount of remaining TEOS descended with the reaction times as shown in Figure 1.By the curve of Fig. 1 as can be known, when the reaction times reached 12 hours or is longer, remaining TEOS amount dropped to and is equal to or less than 3% (volume).
[preparation organic polymer soln]
Use polyvinylpyrrolidone (PVP) as organic polymer.PVP is dissolved among the solvent IPA preparation organic polymer soln (solution B) according to the listed ratio of table 2.
Table 2
| Solution A | Weight % |
| PVP | 17.5 |
| IPA | 82.5 |
[relation in the evaluation solution A between remaining TEOS amount and the transmittance]
Shown in table 3 data, mix with solution B with each solution A that scheduled time reaction makes remaining TEOS amount reduce to 1% (volume), 3% (volume), 5% (volume), 10% (volume) and 20% (volume) respectively, thereby make 5 kinds of coating solutions.12.3 gram solution B are mixed with 37.7 gram solution A obtain 50 and restrain coating solutions.
By rotary coating, 5 kinds of coating solutions that make are applied on the thick silica glass base material of 1mm separately, in about 110 ℃ of electric ovens dry 1 hour then, form the composite organic-inorganic material film of 10 micron thickness.Film on the photoirradiation base material of using the 630nm wavelength perpendicular to this base material direction is measured its transmittance.Measurement result is listed in table 3.
Table 3
| Remaining TEOS amount (volume %) in the |
1 | 3 | 5 | 10 | 20 |
| Reaction times (hour) | 19 | 12 | 8 | 3 | 1.5 |
| Film transmittance (%) | 97-95 | 95-90 | 85-80 | 80-70 | 80-70 |
The result of table 3 confirms, remaining TEOS amount reduces to 3% (volume) or more hour in solution A, can reach high transmittance and shows good optical transparency.
[estimating the relation between the remaining TEOS amount in thin film region domain sizes and the solution A]
According to above-mentioned identical mode, change the reaction times, prepare the solution A that remaining TEOS amount reduces to 1% (volume), 3% (volume), 5% (volume), 10% (volume), 20% (volume) and 30% (volume) respectively, each solution A is mixed with solution B then, prepares 6 kinds of coating solutions.12.3 the gram solution B is mixed with 37.3 gram solution A, obtains 50 gram coating solutions.
By rotary coating, 6 kinds of coating solutions that make are applied on the silica glass base material separately, on this base material, form the composite organic-inorganic material film.Measure the area size in each film.This zone is the zone one by one of organic materials or inorganic materials.By remaining TEOS amount is the film that the solution A of 1 or 3% (volume) is made, because its area size is less, observes under electron microscope and measures its area size.By remaining TEOS amount be the film made of the solution A of 5,10,20 or 30% (volume) because its area size is bigger, under opticmicroscope, observe the area size that measures them.Curve shown in Figure 13 has shown the relation between the remaining TEOS amount in area size and the solution A.Owing in the film multiple area size is arranged, so the straight line between the minimum value of Figure 13 shows that and the maximum value.
As shown in Figure 13, the amount that reduces remaining TEOS in the solution A is to being equal to or less than 3% (volume), and area size can be reduced to 0.1 micron or littler.Therefore, can reduce area size, make the unlikely optical transmission that influences the wavelength that uses in the optical communication as 400-1600nm.
[relation in film size of estimating and peeling off and the solution A between the remaining TEOS amount]
According to above-mentioned identical mode, change the reaction times, prepare the solution A that remaining TEOS amount reduces to 1% (volume), 3% (volume), 5% (volume), 10% (volume), 20% (volume) and 30% (volume) respectively, prepare 6 kinds of coating solutions according to each solution A of above-mentioned use then.
According to above-mentioned identical mode, being applied to each coating solution long and wide respectively is on the glass baseplate of 2.5cm, to form the composite organic-inorganic material film of 10 micron thickness.After each film leaves standstill 10 days, measure the area size of each film.The area that mensuration is peeled off down from the base material upper film.Measurement result is shown in Figure 14.
Figure 14 confirms, TEOS amount remaining in the solution A is reduced to is equal to or less than 3% (volume), can obtain the good adhesive property of film and base material.
[preparation solution C, solution D and their mixing coating solution]
With the mixed that solvent acetone and 0.05N hydrochloric acid and TEOS list according to table 4, preparation solution C.
Table 4
| Solution C | Weight % |
| TEOS | 39.6 |
| Acetone | 53.6 |
| 0.05N HCl | 6.8 |
With the mixed that polymethylmethacrylate (PMMA) is listed according to table 5 as organic polymer and solvent acetone, the preparation solution D.
Table 5
| Solution D | Weight % |
| PMMA | 17.5 |
| Acetone | 82.5 |
The solution C that solution D and remaining TEOS amount are 3% (volume) is mixed preparation blended coating solution.In this preparation process, 5.4 gram solution D are mixed with 16.6 gram solution C.According to above-mentioned identical mode, should mix coating solution and be applied on the silica glass base material, form the film of 10 micron thickness, measure the transmittance of this film to the 630nm wavelength light, the result is 95-90%.
[preparation solution E, solution F and their mixing coating solution]
Use phenyl triethoxysilane as metal alkoxide.With the mixed that phenyl triethoxysilane and solvent N-N-methyl-2-2-pyrrolidone N-(NMP) and 0.05N hydrochloric acid are listed according to table 6, preparation solution E.
Table 6
| Solution E | Weight % |
| Phenyl triethoxysilane | 39.6 |
| NMP | 53.6 |
| 0.05N HCl | 6.8 |
With the mixed that PMMA and solvent NMP list according to table 7, preparation solution F.
Table 7
| Solution F | Weight % |
| PMMA | 17.5 |
| NMP | 82.5 |
With solution F and remaining TEOS amount is that the solution E of 3% (volume) is mixed, prepares the blended coating solution.In this preparation process, 4.4 gram solution F mix with 15.6 gram solution E.
According to above-mentioned identical mode, should mix coating solution and be applied on the silica glass base material, form the composite organic-inorganic material film of 10 micron thickness, with this film of 630nm wavelength light irradiation, measure its transmittance.Transmittance is 95-90%.
[the different coating solution of preparation Si content, the specific refractory power of mensuration composite organic-inorganic material]
With the mixed that solution A and solution B are listed according to table 8, the different coating solution 1 to 5 of preparation Si content.The solution A of using is to make remaining TEOS amount be reduced to the solution of 1% (volume) by hydrolysis and polycondensation.
Table 8
| Coating solution | Solution A (gram) | Solution B (gram) | Si content in the composite organic- |
| 1 | 43 | 7 | 37 |
| 2 | 38 | 12 | 31 |
| 3 | 30 | 20 | 23 |
| 4 | 22 | 28 | 16 |
| 5 | 7 | 43 | 5 |
According to above-mentioned identical mode, coating solution 1 to 5 is applied to respectively on the silica glass base material, form the composite organic-inorganic material film of 2 micron thickness.Measure the specific refractory power of the film that forms.
Figure 2 shows that the specific refractory power of each film that forms by coating solution 1-5.Fig. 2 shows the relation between specific refractory power and the composite organic-inorganic material Si content.
As shown in Figure 2, specific refractory power descends with the increase of Si content.
Below, the stacking material of first aspect present invention is described in conjunction with some embodiment.
Fig. 3 is the schematic section according to an example of first aspect present invention stacking material.Try Fig. 3, film 2a, the 2b, 2c and the 2d that constitute composite organic-inorganic material are layered on the base material 1.Stacking material 2 is made of film 2a-2d.In film 2a, 2b, 2c and 2d, metallic element is according to the order increasing or decreasing of film.For example, when using organoalkoxysilane as metal alkoxide, the film 2a to 2d of formation should make Si content progressively increase according to the order of film 2a to 2d or reduce.Therefore, stacking material 2 has the concentration gradient that 2 surfaces increase or reduce from base material 1 to stacking material.
As seen from Figure 2, the specific refractory power of film reduces with the increase of Si content.Therefore, when stacking material 2 has the concentration gradient that 2 surperficial Si content increase from base material 1 to stacking material, then form the Gradient distribution of the specific refractory power that 2 surfaces reduce from base material 1 to stacking material.On the other hand, when stacking material 2 has the concentration gradient that 2 surperficial Si content descend from base material 1 to stacking material, then form the Gradient distribution of the specific refractory power that 2 surfaces increase from base material 1 to stacking material.
With above-mentioned coating solution 5,4,3,2 and 1 according to shown in order be applied on the silica glass base material stacking material that forms 5 layers of film that constitutes by each composite organic-inorganic material stacked.Apply each coating solution by rotary coating.Each layer thickness of predetermined dry back is 2 microns.Speed of rotation by base material in the rotary coating step is controlled each layer thickness.Apply each coating solution, in about 110 ℃ of electric ovens dry 1 hour then.Because stacked 5 layer films, sample in electric oven dry 5 times altogether.
Fig. 4 is the curve that the Si concentration of element changes in the stacking material that forms in the manner described above.Measure the Si concentration of element by secondary ion mass spectrometry (SIMS) (SIMS).Among Fig. 4, be depicted as distance on the X-coordinate apart from substrate surface.Fig. 4 confirms that in the stacking material of embodiment 1, Si concentration of element surface from the base material to the stacking material increases.
Crackle does not take place in the stacking material surface of embodiment 1.With making comparisons, on the silica glass base material, only apply coating solution 3, dry back thickness is 10 microns.Compare film surface at this crackle has taken place.In the stacking material of embodiment 1, the concentration gradient that has the Si concentration of element to increase to the surface, therefore the stress when this concentration gradient can alleviate the form layers laminate materials can prevent the crackle on surface.Thereby, form such concentration gradient at stacking material, also can improve binding property with base material.
According to the mode identical with embodiment 1, with coating solution 5,4,3,2 and 1 according to shown in order be applied to the silica glass base material (specific refractory power: 1.46), the form layers laminate materials.Yet, in embodiment 2,20,10,5,3 and 22 microns respectively of the thickness of each of formation layer.
Figure 5 shows that embodiment 2 stacking materials are by its change of refractive curve of thickness direction.
As shown in Figure 5, this stacking material has the Gradient distribution that specific refractory power descends to the stacking material surface gradually from base material.
As shown in Figure 6, this stacking material can be used as graded index type planar optical waveguide.Try Fig. 6, stacking material 4 places on the silica glass base material 3.Laser 5 enters the end surfaces of the specific refractory power of close base material 3 in the stacking material 4 than substratum.With the end surfaces that enters laser 5 opposing the end surfaces of stacking material 4 near, place an optical system 6, and a screen 7 and optical system 6 predetermined distance of being separated by arranged.The laser 5 that feeds 4 one end surfaces of stacking material is radiated on the screen 7 by this optical system 6.Irradiate a luminous point clearly on screen 7, the stacking material of expression embodiment 2 has the function as planar optical waveguide.
Below, the stacking material of the second aspect present invention and the third aspect is described in conjunction with some embodiment.
Fig. 7 is the schematic section of second aspect present invention stacking material.Try this figure, stacked composite organic-inorganic material film 9a, 9b, 9c, 9d, 9e, 9f and 9g on base material 8, form layers laminate materials 9.Among the film 9a to 9g, the metal element content of film 9d is the highest.The metal element content of metal alkoxide increases according to the order of 9a, 9b, 9c and 9d, but descends according to the order of 9d, 9e, 9f and 9g.Therefore, the concentration gradient that stacking material 9 has is that the metallic element of metal alkoxide at first increases, and descends then.As mentioned above, specific refractory power descends with the increase of Si content, therefore, forms the Gradient distribution that a specific refractory power at first descends and increases then in stacking material 9 on thickness direction.
Fig. 8 is the synoptic diagram according to an example of third aspect present invention stacking material.Try this figure, composite organic- inorganic material film 11a, 1b, 11c, 11d, 11e, 11f and 11g according to shown in sequential cascade on base material 10.This stacking material is made of film 11a to 11g.In stacking material 11, the metal element content of film 11d is minimum.Metal element content reduces according to the order of 11a, 11b, 11c and 11d, but increases according to the order of 11d, 11e, 11f and 11g.Therefore, in stacking material 11, form the concentration gradient that the metallic element concentration at the thickness direction metal alkoxide at first descends to be increased then.As mentioned above, specific refractory power descends with the increase of Si content, therefore, forms a specific refractory power and at first increase the Gradient distribution that descends then at thickness direction in stacking material 11.
Each coating solution is according to applying with embodiment 1 identical mode and drying.The predetermined dried thickness of each layer is 2 microns.9 stacked layer films form a stacking material altogether.
Fig. 9 is the change curve of Si concentration of element at the stacking material thickness direction, adopts SIMS to measure concentration.As shown in Figure 9, in the centre of this stacking material, the Si concentration of element is the highest, and the concentration of element at first increases then at the stacking material thickness direction and descends.Therefore, specific refractory power at first descends increases then.
As shown in Figure 9, forming zone about 1 micron on the thickness, the Si concentration of element substantially constant in these zones respectively apart from the position of 1,3,5,7,9,11,13,15 and 17 microns of substrate surfaces.And between these zones, Si element continually varying zone is arranged.These zones form to each layer border by the Si Elements Diffusion.
According to the mode form layers laminate materials identical with embodiment 3, difference is, applying each solution, to form dry back thickness be 0.5 micron film.Dry back thickness respectively is 0.5 micron 9 layer films owing to superposeed, and the thickness of this stacking material is 4.5 microns.
Figure 10 is the curve that is changed by Si concentration of element in the stacking material of SIMS mensuration.As shown in figure 10, each layer is very thin in this stacking material, and the Si concentration of element is changed continuously.Middle Si concentration of element at this stacking material is the highest, and is similar with the stacking material of embodiment 3, and forms concentration gradient in stacking material, promptly at first increases then at thickness direction Si concentration of element to descend.Therefore, in stacking material, form the Gradient distribution that specific refractory power at first descends to be increased then.
For comparing, only apply coating solution 3, form dried thickness and be 4.5 microns composite organic-inorganic material.On the film surface of preparation thus, find many crackles.On the other hand, on the stacking material surface of embodiment 3 and 4, do not observe crackle.In embodiment 3 and 4 the stacking material, a Si concentration of element gradient is arranged, this concentration gradient can be eliminated the stress when forming film, thereby prevents the crackle on the film.
Figure 11 is the change curve of specific refractory power on thickness direction of the stacking material made.As shown in figure 11, the highest at this stacking material middle refractive index, and specific refractory power of formation at first increases the Gradient distribution that descends then at thickness direction in stacking material.
According to the mode identical with embodiment 2, the stacking material of having confirmed embodiment 5 has the function as optical waveguides.Figure 12 is an one explanation.As shown in figure 12, form layers laminate materials 13 on base material 12.As shown in figure 11, at intermediate formation one high refractive index layer of stacking material 13.According to embodiment 2 same way as, laser 5 drops into the edge of high refractive index layers.As a result, on screen 7, observe luminous point clearly.Therefore, confirmed that this embodiment stacking material can be used as the function of flat glistening light of waves waveguide.
In the foregoing description, measure the variation of Si concentration of element in the stacking material by secondary ion mass spectrometry (SIMS) (SIMS), but observe by x-ray photoelectron spectroscopy (XPS) with electro-probe micro analyzer (EPMA) or transmission type microscope (TEM), also can measure concentration gradient.
Composite organic-inorganic material of the present invention and its stacking material not only can be used as the used for optical elements material, and can be used as the material that various electronic components are used with material and insulating film with material, various coating with material, mechanical part.
Manufacturing method according to the invention can be made the good composite organic-inorganic material of optical transparence.And the optical transparence of composite organic-inorganic material of the present invention and stacking material thereof is good, can be used as the material that optical element such as optical waveguides and optical fiber are used.And, can also be used as the material that various electronic components are used with material and insulating film with material, various coating.
Below, in conjunction with some embodiment, describe light transmission of the present invention and distribute, but light transmission of the present invention distribution is not subjected to the restriction of these embodiment.
Figure 15 is the schematic section of light transmission structure of the present invention.It on base material 21 metal oxide layer 22.On metal oxide layer 22, form the coating layer 23 that composite organic-inorganic material constitutes, form the light-transmitting layer 24 that composite organic-inorganic material constitutes thereon.On light-transmitting layer 24, form the coating layer 25 that composite organic-inorganic material constitutes.Coating layer 23, light-transmitting layer 24 and coating layer 25 are all formed by composite organic-inorganic material, and be higher relatively but these layers that constitute are specific refractory poweres of light-transmitting layer, and the specific refractory power of coating layer 23 and 25 is relatively low.
Figure 16 is the schematic section of light transmission structure of the present invention.In this example, on base material 21, be metal oxide layer 22, on this layer, form the light-transmitting layer 24 that constitutes by composite organic-inorganic material.The coating layer 25 that is made of composite organic-inorganic material is formed on again on the light-transmitting layer 24.In this example, metal oxide layer 22 is as coating layer.
Figure 17 is the synoptic diagram that another light transmission of the present invention distributes.In this example, on base material 21, be metal oxide layer 22, on this layer, form the light-transmitting layer 24 that constitutes by composite organic-inorganic material.In this example, metal oxide layer 22 is also as coating layer.
In the example shown in Figure 16 and 17, metal oxide layer 22 is as coating layer.When silicon substrate (specific refractory power: 3.5) be used as base material 21, SiO
2(specific refractory power: 1.45) when the metal oxide layer 22, the thickness of metal oxide layer 22 is preferably 2 microns or bigger to layer, with the influence to optical waveguides of the very high refractive index that reduces silicon substrate.
(formation metal oxide layer)
Use silicon substrate as base material.Particularly, use silicon single crystal wafer.By the sputter of RF magnetoelectricity keyholed back plate, on base material, form and return oxide compound as metal oxide layer.Particularly, place base material in the base material fixer in the vacuum chamber of RF magnetron device, in this vacuum chamber, feed argon gas and oxygen as sputter gas.In this step, the dividing potential drop of predetermined argon and oxygen is respectively 1 * 10
-2With 3.5 * 10
-3Torr.On the Si target, apply high-frequency energy (13.56MHz, 200W), the reaction of the Si particle that sputters out and Sauerstoffatom, forming thickness on base material is the silicon oxide layer of 100nm.
(preparation metal alkoxide solution)
Use tetraethoxysilane (TEOS) as metal alkoxide.Tetraethoxysilane and solvent Virahol (IPA) and 0.05N mixed in hydrochloric acid, the weight ratio of TEOS: IPA: HCl (0.05N) is 39.6: 53.6: 6.8, preparation metal alkoxide solution (solution A).
(preparation organic polymer soln)
Use polyvinylpyrrolidone (PVP) as organic polymer, IPA mixes with solvent, forms 17.5% (weight) solution (solution B) of this organic polymer in IPA.
(preparation forms the coating solution of composite organic-inorganic material)
Solution A is hydrolyzed and polycondensation, reduces to 1% (volume) up to the amount of remaining TEOS, then with solution B its mixing with it.Amount with the remaining TEOS of gas Chromatographic Determination.
20 gram solution B are mixed with 30 gram solution A, make coating solution 1.In addition, 43 gram solution B are mixed preparation coating solution 2 with 7 gram solution A.Si content in the composite organic-inorganic material that is formed by coating solution 1 is 23% (weight), and the Si content in the composite organic-inorganic material that is formed by coating solution 2 is 5% (weight).
On glass baseplate, apply coating solution 1 and 2 respectively,, form the composite organic-inorganic material of 2 micron thickness then about 110 ℃ of electric oven inner dryings 1 hour.Measure the specific refractory power of the film that forms.The specific refractory power of the film that is formed by coating solution 1 is about 1.47, and the specific refractory power of the film that is formed by coating solution 2 is about 1.50.
By rotary coating, have on the silicon substrate of silicon oxide layer coating coating solution 1, in about 110 ℃ of electric ovens dry 1 hour then, form the composite organic-inorganic material of 5 micron thickness thereon.This film is a low-index layer, as coating layer.Then, by rotary coating, coating coating solution 2 on this film, drying is 1 hour in about 110 ℃ of electric ovens, forms the composite organic-inorganic material film of 10 micron thickness.This film is a high refractive index layer, as light-transmitting layer.
Comparative example 1
For comparing, according to using coating solution 1 and 2, not to form silicon oxide layer, but directly form coating layer and light-transmitting layer that this is two-layer to constitute by composite organic-inorganic material on silicon substrate with embodiment 6 identical modes.
(evaluation binding property)
(above-mentioned materials is as the evaluation of optical waveguides)
Sample is as the function of optical waveguides among the evaluation embodiment 6.Figure 18 is described.In embodiment shown in Figure 180 6 samples, on base material 21, form silicon oxide layer 22, form the light-transmitting layer 24 that the coating layer 23 that is made of composite organic-inorganic material and composite organic-inorganic material constitute thereon.Laser 26 is injected the end surfaces of light-transmitting layer 24.With injecting laser 26 end surfaces opposing light-transmitting layer 24 end surfaces near, place an optical system 27, and have a screen 28 separated by a distance with optical system 27.The laser 26 of injecting 24 1 end surfaces of light-transmitting layer impinges upon on the screen 28 by this optical system 6.Irradiate a luminous point clearly on screen 28, the sample of expression embodiment 6 has the function as planar optical waveguide.
In the foregoing description, polyvinylpyrrolidone is used as organic polymer, but has confirmed to use polycarbonate or polymethylmethacrylate also can obtain identical effect as organic polymer.
In the above-described embodiments, use tetraethoxysilane as metal alkoxide, but confirmed to use phenyl triethoxysilane also can obtain identical effect.
According to the present invention, on metal base, provide in the light transmission distribution of the light-transmitting layer that constitutes by composite organic-inorganic material, improved the binding property of light-transmitting layer and base material.Therefore, light transmission of the present invention distribute to optical element such as optical waveguides, be used for liquid-crystal display light guiding plate etc. all useful.And, the light transmission of the present invention distribution that the distribution that can use as electronic component and optical element mechanical part are outward used that distributes.
Claims (14)
1. make the method for composite organic-inorganic material by organic polymer and metal alkoxide for one kind, this method comprises the following steps:
Make the metal alkoxide polycondensation by hydrolysis, reduce to 3% volume or still less up to the unreacted metal alkoxide,
To mix with organic polymer through the metal alkoxide of polycondensation, form composite organic-inorganic material.
2. the method for manufacturing composite organic-inorganic material as claimed in claim 1 is characterized in that described metal alkoxide is an organoalkoxysilane.
3. the method for manufacturing composite organic-inorganic material as claimed in claim 1 is characterized in that described organic polymer is polyvinylpyrrolidone, polycarbonate, polymethylmethacrylate or their mixture.
4. the method for manufacturing composite organic-inorganic material as claimed in claim 1 is characterized in that described composite organic-inorganic material forms on transparent substrate.
5. method of making stacking material, described method comprises the stacked composite organic-inorganic material layer of being made by the described method of claim 1, so that have the concentration gradient that the metallic element in the metal alkoxide increases or reduces to another side from the stacking material one side in the described stacking material.
6. a manufacturing comprises the method for the optical waveguides of stacking material, described method comprises that stacked composite organic-inorganic material layer by the described method manufacturing of claim 1 makes stacking material, so that have the concentration gradient that the metallic element in the metal alkoxide increases or reduces from stacking material one side to another side in the described stacking material, there is specific refractory power to pass through the concentration gradient of metallic element and the Gradient distribution that descends or increase to another side from the stacking material one side in the described stacking material.
7. a manufacturing comprises the method for the optical waveguides of stacking material, described method comprises the stacked composite organic-inorganic material layer of being made by the described method of claim 1, so that the metallic element that has in the described stacking material in the metal alkoxide at first increases the concentration gradient that reduces then from stacking material one side to another side, there is specific refractory power to pass through the concentration gradient of metallic element and the Gradient distribution that at first descends and increase then to another side from the stacking material one side in the described stacking material.
8. a manufacturing comprises the method for the optical waveguides of stacking material, described method comprises the stacked composite organic-inorganic material layer of being made by the described method of claim 1, so that have metallic element in the metal alkoxide in the described stacking material, there is specific refractory power to pass through the concentration gradient of metallic element in the described stacking material and at first increases the Gradient distribution that reduces then to another side from the stacking material one side from the concentration gradient that stacking material one side to another side at first descends and increases then.
9. method of making the light transmission structure comprises:
Arrange metal oxide layer at metal base, and
Light-transmitting layer is provided on metal oxide, and it is made of the composite organic-inorganic material of the described method manufacturing of claim 1.
10. method as claimed in claim 9 is characterized in that described metal oxide layer is the oxide skin that contains at least a contained element in the base material.
11. method as claimed in claim 9 is characterized in that contained element is Si in the base material.
12. method as claimed in claim 9 is characterized in that the metal oxide layer thickness is 5 nanometers to 20 micron.
13. method as claimed in claim 9 is characterized in that described light-transmitting layer thickness is the 4-500 micron.
14. method as claimed in claim 9 is characterized in that described metal oxide layer forms by vapour deposition.
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| JP20029994 | 2002-01-18 | ||
| JP2002009994 | 2002-01-18 | ||
| JP2002-9994 | 2002-01-18 | ||
| JP2002022744A JP2003222745A (en) | 2002-01-31 | 2002-01-31 | Optical propagation structure |
| JP200222744 | 2002-01-31 | ||
| JP2002-22744 | 2002-01-31 |
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| KR100793597B1 (en) * | 2005-06-02 | 2008-01-10 | 주식회사 엘지화학 | Coating composition for ultraviolet-curable film type and film prepared from it |
| AU2006286016B2 (en) * | 2005-08-30 | 2011-10-27 | Jgc Catalysts And Chemicals Ltd. | Composite polymer, thermosetting coating composition, and molded article |
| CN112230334B (en) * | 2020-11-13 | 2022-06-28 | 西安高强绝缘电气有限责任公司 | Optical waveguide composite material and manufacturing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0972809A2 (en) * | 1998-07-17 | 2000-01-19 | Orient Chemical Industries, Ltd. | Organic-inorganic hybrid polymer materials with compositional gradient, and processes for preparing the same |
| EP0997497A1 (en) * | 1997-07-15 | 2000-05-03 | Asahi Kasei Kogyo Kabushiki Kaisha | Alkoxysilane/organic polymer composition for thin insulating film production and use thereof |
| JP2000248065A (en) * | 1999-02-26 | 2000-09-12 | Orient Chem Ind Ltd | Production of organic-inorganic component-gradient component composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0997497A1 (en) * | 1997-07-15 | 2000-05-03 | Asahi Kasei Kogyo Kabushiki Kaisha | Alkoxysilane/organic polymer composition for thin insulating film production and use thereof |
| EP0972809A2 (en) * | 1998-07-17 | 2000-01-19 | Orient Chemical Industries, Ltd. | Organic-inorganic hybrid polymer materials with compositional gradient, and processes for preparing the same |
| JP2000248065A (en) * | 1999-02-26 | 2000-09-12 | Orient Chem Ind Ltd | Production of organic-inorganic component-gradient component composite material |
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