CN102401910A - Method for preparing optical coating material and optical coating material - Google Patents
Method for preparing optical coating material and optical coating material Download PDFInfo
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- CN102401910A CN102401910A CN2010102870608A CN201010287060A CN102401910A CN 102401910 A CN102401910 A CN 102401910A CN 2010102870608 A CN2010102870608 A CN 2010102870608A CN 201010287060 A CN201010287060 A CN 201010287060A CN 102401910 A CN102401910 A CN 102401910A
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Abstract
The invention relates to a method for preparing an optical coating material. The method includes providing a mixture containing at least titanium dioxide and lanthanum sesquioxide; and lanthanum is added into the mixture, and the mixture is processed in vacuum under a temperature from 2,000 DEG C to 3,000 EDG C so as to obtain the optical coating material. Compared with the prior art, the method has the advantages of low raw material cost, relatively simple manufacture process, and the like. In addition, the invention also relates to the optical coating material.
Description
Technical field
The present invention is about a kind of preparation method of optical filming material, especially in regard to a kind of with high temperature to containing titania (TiO
2), lanthanum sesquioxide (La
2O
3) and the potpourri of lanthanum (La) handle, to make the method for optical filming material.
Background technology
Optical coating refers to change the plated film of the optical property of optical module, and its purpose can be antireflection, anti-dazzle, optical filtering ... or the like, and according to the difference of purpose, optical module manufacturer need select for use material different to carry out plated film.
For example, the Taiwan patent announcement discloses a kind of manufacturing approach of deposition material for No. 588113, and it can be used for preparing the optical coating with high refraction and low absorption.In this method, the potpourri that contains titania, titanium and lanthanum sesquioxide is to carry out sintering with the low pressure condition, and then obtains aforesaid deposition material.
Generally speaking, in the optical filming material of numerous kinds, metal oxide is often be used a kind of.For instance, the oxide of lanthanum, titanium, particularly anoxic lanthanium titanate just are usually used in the film-plating process of the anti-reflecting layer of camera lens, projector lens.
Be different from lanthanium titanate (LaTiO
3), the anoxic lanthanium titanate refers to that chemical formula is LaTiO
xThe compound of (x is less than 3).Because its oxygen content is lower than lanthanium titanate, presents the undersaturated state of oxygen, so its processing procedure is also more difficult than lanthanium titanate.
At present known a kind of anoxic lanthanium titanate preparation method directly with Titanium with lanthanoid metal carry out atmosphere melting and oxidation it; Right this kind practice has following shortcoming: one, the unit price of cost costliness-Titanium and lanthanoid metal is all quite high, so the raw materials cost of this method of use is expensive; Two, processing procedure wayward-because the oxidation activity difference of Titanium and lanthanoid metal is very big, in oxidizing process and be difficult for stable its degree of oxygen deficiency of control, to such an extent as to cause the tolerance of overflowing in the follow-up film-plating process unstable easily, and the fraction defective of increase product.
At present known another kind of anoxic lanthanium titanate preparation method makes oxygen-saturated lanthanium titanate with the oxide of lanthanum, titanium earlier, carries out the high-temperature vacuum reduction afterwards again and obtains the anoxic lanthanium titanate.Compared to aforementioned oxidizing process,, still have shortcomings such as processing procedure power consumption and product degree of oxygen deficiency are low though this kind processing procedure raw materials cost is lower.
Summary of the invention
Shortcoming thoughts on known technology; The inventor exhausts the concentrated research of its intelligence then; Be engaged in the experience that this industry is accumulated for many years with it; And then develop a kind of optical filming material preparation method of novelty, its innovation part is titania, lanthanum sesquioxide and the lanthanum of special ratios are carried out pyroprocessing, to obtain can be used for the material of optical coating processing procedure.Compared to known technology, optical filming material preparation method of the present invention has at least that raw materials cost is low, processing procedure is simple relatively, oxygen deficit is stable, the density advantages of higher.Particularly, when the prepared optical filming material of processing procedure of the present invention was applied to film-plating process, it had relatively low excessive tolerance.
In view of this, one of the object of the invention is to provide a kind of method for preparing optical filming material, and its step comprises at least: a kind of potpourri that comprises titania and lanthanum sesquioxide at least is provided; And lanthanum is added in this potpourri, and under vacuum, handle with 1500 ℃ to 3000 ℃ temperature, to make optical filming material.
In aforesaid method, titania that potpourri is contained and lanthanum sesquioxide have 1: 1 to 1: 3 part by weight, and lanthanum is 1: 3 to 1: 7 to the part by weight of this potpourri.In addition, in aforesaid method, the part by weight of titania powder and lanthanum sesquioxide powder is preferably 1: 1 to 1: 2, and the part by weight of lanthanum and mixture of powders is preferably 1: 4 to 1: 6.
In aforesaid method; Preferably carry out following steps: before lanthanum is added into potpourri,, and place in the reservoir vessel of low temperature earlier with this potpourri extrusion forming; For example temperature is lower than 15 ℃ refrigerator or freezing tank; Afterwards again with potpourri by taking out in this reservoir vessel, and handle, like sintering with the temperature more than 1200 ℃.
A purpose more of the present invention is to provide a kind of method for preparing optical filming material, may further comprise the steps: the mixed weight ratio is 1: 1 to 1: 3 titania powder and a lanthanum sesquioxide powder; With the mixture of powders extrusion forming is size between 1 to 5 millimeter granular or block mixture; With this granular or block mixture of 1200 ℃ to 1800 ℃ temperature sintering; Add 1/7 to 1/3 lanthanum that weight is about this granular or block mixture to this in the granular or block mixture, and mix; And this granular or block mixture that contains lanthanum with 1500 ℃ to 3000 ℃ temperature melting.
In aforesaid method, between extrusion forming and sintering step, the temperature that granular or block mixture is preferable over below 15 ℃ is preserved; In addition, the part by weight of titania powder and lanthanum sesquioxide powder is preferably 1: 1 to 1: 2, and the part by weight of lanthanum and mixture of powders is preferably 1: 4 to 1: 6.
Through preceding method, can make and contain anoxic lanthanium titanate LaTiO
xOptical filming material, and wherein x behind sintering before the melting preferably between 2.7 to 2.8, and x after melting preferably between 1.5 to 2.7.
Another purpose of the present invention is to provide a kind of optical filming material that gets through aforesaid prepared in various methods.
In addition, the present invention also provides a kind of optical filming material, and it comprises the potpourri through vacuum melting, and this potpourri comprises the lanthanum sesquioxide of 100 parts by weight of titanium oxide, 100 to 300 weight portions and the lanthanum of 30 to 130 weight portions before vacuum melting.
Description of drawings
Fig. 1 is the first embodiment process flow diagram of optical filming material processing procedure of the present invention;
Fig. 2 is the second embodiment process flow diagram of optical filming material processing procedure of the present invention;
Fig. 3 is the 3rd embodiment process flow diagram of optical filming material processing procedure of the present invention;
Fig. 4 is the 4th embodiment process flow diagram of optical filming material processing procedure of the present invention;
The glass lens that Fig. 5 A, 5B, 5C are respectively sample one, two, three carries out the photo behind the plated film;
Fig. 6 A, 6B, 6C are respectively the photo of glass lens after the plated film strength test is handled of sample one, two, three.
[primary clustering symbol description]
12, the step of 14,16,18 process flow diagrams
Embodiment
For proving absolutely the object of the invention, characteristic and effect; Make and have common knowledge the knowledgeable under the present invention in the technical field and can understand content of the present invention and can implement according to this; The accompanying drawing that at present cooperates through following concrete embodiment, to the present invention do one specify as after.
Please earlier referring to Fig. 1, it is the first embodiment process flow diagram of optical filming material processing procedure of the present invention.The processing procedure of first embodiment mainly comprises two steps; At first, step 12 is that a kind of potpourri is provided earlier, and it comprises titania powder and lanthanum sesquioxide powder; And wherein titania and lanthanum sesquioxide have 1: 1 to 1: 3 part by weight, preferred 1: 1 to 1: 2.Secondly, step 18 is added into lanthanum in this potpourri, and carries out pyroprocessing; Wherein, lanthanum is 1: 3 to 1: 7 to the part by weight of this potpourri, is preferably 1: 4 to 1: 6, and high-temperature step is handled with 1500 ℃ to 3000 ℃ temperature under vacuum.Generally speaking, high-temperature step can be carried out in vacuum melting furnace, and the pressure in the stove is about 10
-3Millibar is not so as limit.
Please again referring to Fig. 2, the second embodiment process flow diagram of its optical filming material processing procedure of the present invention.Compared to first embodiment; Second embodiment is in behind the potpourri that titania and lanthanum sesquioxide are provided and add before lanthanum carries out pyroprocessing; More comprise and carry out step 14, promptly potpourri is carried out extrusion forming, making it is like cake or cylinder even-granular or bulk by powder compacting; And then raising density, can increase the homogeneity of coating film thickness when being subsequently applied to plated film and improve the yield of optical module in order to it.In addition, the influence that under atmosphere, is vulnerable to aqueous vapor owing to cake after the extrusion forming or cylinder etc. is hydrolyzed into powder, and step 14 more comprises the reservoir vessel that the cake after the extrusion forming or cylinder is placed a low temperature.For instance, can the cake after the extrusion forming or cylinder be preserved with the temperature below 15 ℃ earlier, as place below 5 ℃ containers such as refrigerator or freezing tank, to avoid the generation of hydrolysis situation.
Please again referring to Fig. 3, it is the 3rd embodiment process flow diagram of optical filming material processing procedure of the present invention.Compared to first embodiment, the 3rd embodiment more comprises and carry out step 16 in behind the potpourri that titania and lanthanum sesquioxide are provided and add before lanthanum carries out pyroprocessing, promptly potpourri carried out pyroprocessing in advance.In present embodiment, the pyroprocessing of step 16 is carried out under the temperature more than 1200 ℃, and is preferable under 1200 ℃ to 1800 ℃ the temperature and carries out, and the time can be 1 to 5 hour, looks handled potpourri amount and decides.For instance, step 16 can be that the potpourri to titania and lanthanum sesquioxide carries out sintering processes, and like vacuum-sintering or atmosphere sintering, and it is preferable in the vacuum sintering furnace and carries out.After step 16, can potpourri be smashed into graininess, this moment, granular potpourri was difficult for by the aqueous vapor hydrolysis in the atmosphere, and can then in step 18, add lanthanum again and evenly carry out pyroprocessing again after the mixing.
Compared to the pyroprocessing of step 18, it is the deoxygenation step of phase one that the high temperature processing step of step 16 can be regarded as, and after the pyroprocessing via step 16, preferably contains LaTiO in the potpourri
x, and x is between 2.7 to 2.8.
In addition, carry out step 16 the following advantage that can not expect also can be provided.At first,, can shorten the processing time of subsequent step 18 through the carrying out of step 16, and under some situation, even can the processing time of step 18 be foreshortened to 1/5.In addition, after carry out step 16, can be bonded to each other between powder, not splash or the unequal problem of ratio so when the subsequent optical plated film, more can not produce.
At last, see also Fig. 4, it is the 4th embodiment process flow diagram of optical filming material processing procedure of the present invention.As shown in the figure, the processing procedure of present embodiment mainly comprises four steps altogether.At first, step 12 provides the potpourri that comprises titania powder and lanthanum sesquioxide powder, and wherein the part by weight of titania and lanthanum sesquioxide is as previously mentioned.Secondly, as the practice of second embodiment, step 14 pair potpourri carries out extrusion forming promoting its density, and places a cryogenic storage container to avoid hydrolysis cake after the extrusion forming or cylinder.Afterwards then as the practice of the 3rd embodiment, carry out pyroprocessing in advance removing the oxygen of part through step 16 pair potpourri, and make between powder and be bonded to each other.At last, step 18 item adds lanthanum with aforesaid ratio, and the pyroprocessing of carrying out another time.
In present embodiment, aforementioned processing procedure preferably can produce and contain LaTiO
xFinished product; It is silver-colored black under visual inspection, and x is suitable for as optically coated material between 1.5 to 2.7; Can be in order to make the anti-reflecting layer of camera lens, projector lens etc. or all kinds of eyeglass, prism, spectroscope, cold mirror etc., so not as limit.
In addition, the prepared optical filming material of the present invention can carry out plated film in the following manner.At first, import material in the crucible in the deposition unit and insert in the electron-beam evaporator of deposition unit.Desiring the base material of plated film, like 25 millimeters of diameters, thick 1 millimeter quartz-glass disc, is to be placed on the substrate holder in the deposition unit in clean, drying.Because the framework of deposition unit belongs to the known technology of this area, so locate to repeat no more.
Then, be evacuated to 10
-5Millibar is heated to about 300 ℃ with base material.Make oxygen get into deposition unit and reach 10 up to pressure via operation valve
-4To 2 * 10
-4Millibar.Coating Materials is fused under the electron-beam evaporator barrier and is heated to 2200 ℃ of evaporating temperatures.After arriving this evaporating temperature, open barrier, base material is by the optical layers of plating specific thicknesses.After cooling, take out base material from deposition unit, and measure penetrance with spectrometer through plating.Can know that by breakthrough curve in the refractive index of 500 nano wave lengths be 2.20, and the thickness of optical layers is 267 nanometers.
In addition, for further specifying the difference of processing procedure of the present invention and optical filming material and prior art, below be through the plated film strength test presentation of results it.
As shown in Figure 5; It is respectively the photo after glass lens carries out plated film; Wherein Fig. 5 A is the photo of the glass lens (sample one) that is coated with optical filming material of the present invention, and the person is then for being coated with the glass lens through the sintering optical filming material (sample two, sample three) that contains titania, titanium and lanthanum sesquioxide at least shown in 5B, the 5C figure.By all slightly being green (figure does not show) before can observing glass lens and behind plated film, test among the figure, and all there is not obvious obscission.
Afterwards, test according to following program: (1) joins 800 gram water and 100 gram salt in the heating tank, and heats with 1000 watts electrical bar, seethes with excitement up to water; (2) after the water boiling, sample one, two, three is put in the salt solution of boiling, continued heating simultaneously, after 3 minutes, sample is taken out; (3) after the taking-up sample is placed drying,, observe whether rete comes off and colour of lens changes with microscopic examination rete adhesion condition; (4) repeat twice of abovementioned steps (1)-(3), sample is cleaned and spectral measuring with clear water afterwards in the baking back.
Result after sample is handled in step (1)-(3) is as shown in Figure 6, and wherein Fig. 6 A, 6B, 6C are respectively the photo of sample one, two, three.After handling, still present green (figure does not show) by the eyeglass that can be observed sample one among Fig. 6 A, and rete does not have and comes off.In comparison, shown in Fig. 6 B, though the rete of sample two situation that the rete full wafer comes off occurred still for green (figure does not show).In addition, three in sample is not observed out tangible obscission though had by microscope shown in Fig. 6 C, and rete becomes aubergine (figure does not show) by green.
In view of the above, can know after handle step (1)-(3), be coated with the sample one of optical filming material of the present invention, no matter all be superior to sample two and sample three on the plated film intensity or on the optical stability.In addition, the spectrum (figure does not show) that measures in step (4) back can find that the spectrum of sample two and sample three all has obvious variation before handling, and the spectrum of sample one does not then have significant skew, is demonstrating the stability of optical filming material of the present invention.
The present invention describes with preferred embodiment hereinbefore, and right this area has common knowledge the knowledgeable and it should be understood that this embodiment only is used to describe the present invention, and should not be read as restriction scope of the present invention.For example, though the employed material of processing procedure of the present invention mainly comprises titania, lanthanum sesquioxide and lanthanum, under the optically coated quality of excessive influence not, also can add other material.In addition, it should be noted that equivalent with this embodiment such as variation and displacement all should be regarded as being covered by in the category of the present invention.Therefore, protection scope of the present invention when with hereinafter claims were defined is as the criterion.
Claims (9)
1. method for preparing optical filming material comprises:
One potpourri is provided, and it comprises titania and lanthanum sesquioxide; And
Lanthanum is added in this potpourri, and under vacuum, handles with 1500 ℃ to 3000 ℃ temperature, to make optical filming material, wherein:
In this potpourri, titania is 1: 1 to 1: 3 to the part by weight of lanthanum sesquioxide;
Lanthanum is 1: 3 to 1: 7 to the part by weight of this potpourri.
2. the method for claim 1 is characterized in that, more comprises:
Before adding lanthanum,, and place in the reservoir vessel with the temperature that is lower than 15 ℃ and preserve this potpourri extrusion forming.
3. preparation method as claimed in claim 2 is characterized in that, more comprises:
Before adding lanthanum, this potpourri by taking out in this reservoir vessel, and is handled with the temperature more than 1200 ℃.
4. method for preparing optical filming material comprises:
The mixed weight ratio is 1: 1 to 1: 3 titania powder and a lanthanum sesquioxide powder;
With the mixture of powders extrusion forming is size between 1 to 5 millimeter granular or block mixture;
With this granular or block mixture of 1200 ℃ to 1800 ℃ temperature sintering;
Add 1/7 to 1/3 lanthanum that weight is about this granular or block mixture to this in the granular or block mixture, and mix; And
This granular or block mixture that contains lanthanum with 1500 ℃ to 3000 ℃ temperature meltings.
5. preparation method as claimed in claim 4 is characterized in that, more comprises:
After the mixture of powders extrusion forming is granular or block mixture, preserve this granular or block mixture with the temperature below 15 ℃.
6. preparation method as claimed in claim 4 is characterized in that, wherein the part by weight of titania powder and lanthanum sesquioxide powder is 1: 1 to 1: 2, and lanthanum and this part by weight granular or block mixture are 1: 4 to 1: 6.
7. preparation method as claimed in claim 4 is characterized in that wherein optical filming material comprises LaTiO
x, and x is less than 3.
8. preparation method as claimed in claim 7 is characterized in that, wherein x behind sintering before the melting between 2.7 to 2.8, and x after melting between 1.5 to 2.7.
One kind according to each described method preparation in the claim 1 to 8 optical filming material.
10 1 kinds of optical filming materials comprise the potpourri through vacuum melting, and this potpourri comprises the lanthanum sesquioxide of 100 parts by weight of titanium oxide, 100 to 300 weight portions and the lanthanum of 30 to 130 weight portions before vacuum melting.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102870608A CN102401910A (en) | 2010-09-17 | 2010-09-17 | Method for preparing optical coating material and optical coating material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102870608A CN102401910A (en) | 2010-09-17 | 2010-09-17 | Method for preparing optical coating material and optical coating material |
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| CN102401910A true CN102401910A (en) | 2012-04-04 |
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| CN2010102870608A Pending CN102401910A (en) | 2010-09-17 | 2010-09-17 | Method for preparing optical coating material and optical coating material |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4208811A1 (en) * | 1992-03-19 | 1993-09-23 | Merck Patent Gmbh | EVAPORATION MATERIAL FOR PRODUCING HIGHLY BREAKING OPTICAL LAYERS |
| DE10065647A1 (en) * | 2000-12-29 | 2002-07-04 | Merck Patent Gmbh | Deposition material for the production of high refractive index optical layers and method for the production of the vapor deposition material |
| CN1532161A (en) * | 2003-03-24 | 2004-09-29 | 上海新沪玻璃厂 | High refractivity lanthanum optical glass LaSF010 |
| CN101701357A (en) * | 2009-11-18 | 2010-05-05 | 上海特旺光电材料有限公司 | Growth method of lanthanum titanate crystal coated material |
-
2010
- 2010-09-17 CN CN2010102870608A patent/CN102401910A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4208811A1 (en) * | 1992-03-19 | 1993-09-23 | Merck Patent Gmbh | EVAPORATION MATERIAL FOR PRODUCING HIGHLY BREAKING OPTICAL LAYERS |
| DE10065647A1 (en) * | 2000-12-29 | 2002-07-04 | Merck Patent Gmbh | Deposition material for the production of high refractive index optical layers and method for the production of the vapor deposition material |
| CN1532161A (en) * | 2003-03-24 | 2004-09-29 | 上海新沪玻璃厂 | High refractivity lanthanum optical glass LaSF010 |
| CN101701357A (en) * | 2009-11-18 | 2010-05-05 | 上海特旺光电材料有限公司 | Growth method of lanthanum titanate crystal coated material |
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Application publication date: 20120404 |