CN1365956A - 生产高折射率光学涂层的气相沉积材料和该气相沉积材料的生产方法 - Google Patents
生产高折射率光学涂层的气相沉积材料和该气相沉积材料的生产方法 Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 52
- 230000003287 optical effect Effects 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title abstract description 9
- 239000007792 gaseous phase Substances 0.000 title 2
- 239000011247 coating layer Substances 0.000 title 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 46
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000000203 mixture Substances 0.000 claims abstract description 38
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000010936 titanium Substances 0.000 claims abstract description 23
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 18
- 238000000576 coating method Methods 0.000 claims description 49
- 239000011248 coating agent Substances 0.000 claims description 46
- 238000000151 deposition Methods 0.000 claims description 43
- 239000012071 phase Substances 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 17
- 238000005245 sintering Methods 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000012808 vapor phase Substances 0.000 claims description 13
- 238000009834 vaporization Methods 0.000 claims description 6
- 230000008016 vaporization Effects 0.000 claims description 6
- 238000010894 electron beam technology Methods 0.000 claims description 5
- 238000005516 engineering process Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
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- 230000010748 Photoabsorption Effects 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
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- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- BAQNULZQXCKSQW-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[Ti+4].[Ti+4] BAQNULZQXCKSQW-UHFFFAOYSA-N 0.000 claims 1
- 238000007740 vapor deposition Methods 0.000 abstract description 3
- 229910003087 TiOx Inorganic materials 0.000 abstract 1
- 239000000470 constituent Substances 0.000 abstract 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 abstract 1
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 abstract 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 11
- 230000008021 deposition Effects 0.000 description 7
- 230000008033 biological extinction Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 241000588731 Hafnia Species 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 5
- 230000031700 light absorption Effects 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- 239000005083 Zinc sulfide Substances 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 description 3
- 241000894007 species Species 0.000 description 3
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910001936 tantalum oxide Inorganic materials 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical group [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
- C09C1/0021—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a core coated with only one layer having a high or low refractive index
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
- C03C17/245—Oxides by deposition from the vapour phase
- C03C17/2456—Coating containing TiO2
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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- C03C2217/00—Coatings on glass
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- C03C2217/212—TiO2
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Abstract
一种在减压下生产氧化钛、钛和氧化镧的高折射率光学涂层的气相沉积材料,由一种烧结混合物组成,其组成为TiOx+z×La2O3,这里x=1.5-1.8,z=10-65重量%,以混合物的总重量为基准。该混合物的组成为19-65重量%范围内的氧化镧,38-74重量%范围内的氧化钛和2-7重量%范围内的钛。
Description
本发明涉及一种在减压下生产氧化钛、钛和氧化镧的高折射率光学涂层的气相沉积材料,并涉及该气相沉积材料的生产方法。
氧化物涂层在工业中广泛应用,特别是在光学领域中,作为防护涂层或者用于光学功能目的。它们用于防腐蚀和防止机械损坏,或者用于涂敷光学器件和仪器的表面,如透镜、反射镜、棱镜、物镜等。此外,为了增加或减少反射,氧化物涂层用于生产高、中、低折射率的光学涂层。最重要的应用领域是生产眼镜透镜和照相机透镜的防反射涂层,用于双目镜和光学器件以及激光技术的光学***。其它用途是生产具有特定折射率和/或某些吸光性能的涂层,例如用于干涉镜、分光器、热防护滤光器和冷光镜。
DE 42 08 811 A1公开了一种气相沉积材料,用于在减压下通过基板的气相沉积涂敷生产高折射率光学涂层。该材料是一种分子式为La2Ti2O7-x的化合物,其中,x=0.3-0.7,特别是一种分子式为La2Ti2O6.5的化合物。这种气相沉积材料通过以相应的化学计量比混合镧和钛的氧化物以及金属钛,并在高真空中在低于熔点的温度烧结该混合物来生产。
德国专利1 228 489公开了一种生产用于光学用途的实际上在可见光范围内无吸收的薄氧化物涂层的方法,特别是在减压下通过氧化的和/或可氧化的物质的气相沉积在玻璃基板上生产。如果希望,气相沉积可以在氧化气氛存在下进行。把选自由稀土元素,包括钇、镧和铈组成的组中的一种或多种元素与氧化的和/或可氧化的物质一起气相沉积。这里的起始物质作为一种混合物来蒸发,或者相互独立蒸发。所用的氧化的和/或可氧化的物质尤其是钛和/或氧化钛。
对于光折射率约为2的高折射率涂层的生产,合适的起始材料的选择受到限制。可能的用于此目的的起始材料主要是钛、锆、铪和钽的氧化物及其混合体系。一种用于高折射率涂层的优选的起始材料是二氧化钛。
除了氧化钛以外,现有技术还使用氧化钽、氧化锆、氧化铪和硫化锌等化合物及其混合物,例如,氧化锆和氧化钛,氧化钛和氧化镨,氧化钛和氧化镧。
这些物质的优点是,例如,二氧化钛具有高折射率,氧化铪和氧化锆具有低吸光率。这些已知物质的缺点是气体放出强烈和二氧化钛的分解,在氧化钽Ta2O5的情况下和在氧化钛与氧化镨的混合物的情况下吸光率较高,氧化锆、氧化铪以及氧化锆和二氧化钛的混合物的不完全熔化,还有例如在硫化锌的情况下硬度低。在氧化钛和氧化镧的混合物中,获得了低吸光率、没有气体放出和没有飞溅以及熔化较好的优点。然而,这种混合物的折射率明显低于氧化钛和硫化锌混合的情况。从实际工艺的观点出发,这些物质具有高熔点和高沸点也是不利的,此外,它们互相之间相当接近。为了保证均匀充分的蒸发速度,气相沉积材料在明显蒸发开始前应该完全熔化。为了能够在待气相沉积涂敷的物体上形成均匀一致的厚涂层,这个条件是必须的。然而,对于锆和铪的氧化物和在钛/锆混合氧化物体系的情况下,在实际应用条件下,不是这种情况。所述物质在典型的工作条件下不熔化或不完全熔化,它们难以全部蒸发,在气相沉积涂层中产生厚度变化。现有技术中的目的是通过合适的添加剂来降低基础材料的熔点,这里,这些添加剂还在一定限度内改变所得涂层的折射率,确定折射率为特定值。为此目的选择的合适的添加剂受不吸光的要求的限制。所以,适用于相应的添加剂最好的金属氧化物是那些在可见光谱区域内以及近紫外波长范围内(即最高约320纳米)不吸光的金属氧化物。
作为起始材料,所述氧化物在可见光波长范围内不吸光或者仅仅轻微吸光,这是相应的光学用途的基本要求。然而,在高真空蒸发过程中发生氧的损失和氧含量不足化学计量的氧化钛涂层的沉积。这意味着,如果没有专门的预防措施,用这些材料通过真空蒸发生产薄涂层导致涂层在可见光范围内具有高的吸光率。根据上述德国专利1228489,在具有5×10-5-<5×10-4毫巴的某一残余氧压力的真空中进行蒸发,即建立一种氧化气氛,解决了这个问题。解决该问题的另一种可能性在于使所得的涂层在氧气或空气中进行后处理。
即使通过添加剂的合适选择或者相应物质混合物的选择可以解决上述问题,但是,在真空气相沉积技术中,混合体系的使用本身不是优选的。原因是混合体系一般蒸发不一致,即它们在蒸发过程中改变其组成。沉积的涂层的组成也相应变化。如果混合体系由没有材料变化而蒸发和重新冷凝的分立的化合物组成,可以避免这个问题。
本发明的目的是提供一种开始时描述的类型的气相沉积材料,用这种气相沉积材料,可以生产具有可能最高的折射率和低吸光率,这里,该气相沉积材料表现出非常好的熔化和蒸发性能,可以蒸发而不放出气体或分解。
根据本发明,该材料是一种组成为TiOx+z×La2O3的烧结混合物,达到了这一目的,其中,x=1.5-1.8,z=10-60重量%,以混合物的总重量为基准。
在本发明的一种实施方案中,该混合物包含19-65重量%的氧化镧,38-74重量%的氧化钛和2-7重量%的钛。在本发明的一种特定实施方案中,混合物由58.9重量%的氧化镧、37.9重量%的氧化钛和3.2重量%的钛组成。同样提出了一种实施方案,其中,混合物由63.2重量%的氧化镧、33.9重量%的氧化钛和2.9重量%的钛组成。
在本发明的一种实施方案中,氧化钛TiO2与钛之间的比例决定在氧化钛TiOx(x=1.5-1.8)中氧的化学计量比。这里,氧化钛∶氧化镧的重量比可以通过氧化镧与氧化钛和钛的混合物混合来确定。通过减压烧结,保证混合物关于氧的化学计量比不变。根据本发明的气相沉积材料与具有精确化学计量组成的基础化合物钛酸镧相比,在上述给出的分子式定义中存在氧不足。由于在根据本发明的气相沉积材料中故意建立氧不足,首先,在减压蒸发过程中,不会发生导致熔融气相沉积材料飞溅的氧气进一步释放。其次,选择的氧不足范围使得可以在真空蒸发法中,在通常的工作条件下,自动形成不吸光的涂层。研究表明,即使相当少的氧化镧加入量也可以改善熔化和蒸发过程中的性能。根据本发明的混合物可以在电子束蒸发器中蒸发,通过确定关于氧的最佳化学计量比,而没有飞溅和气体放出。这里发现,所得涂层的光学性质最终不受减压蒸发过程中的残余氧压力变化的影响。通过对比,在氧化钛(IV)TiO2的情况下和在钛的低价氧化物如TiO1.7、Ti3O5或Ti4O7的情况下,不能完全防止熔化过程中的飞溅。用根据本发明的气相沉积材料生产的涂层的折射率只比纯氧化钛涂层的情况略低。特别地,该折射率明显高于氧化钛、氧化锆、氧化铪或氧化物混合物如氧化锆和氧化钛、氧化钛和氧化镨、氧化钛和氧化镧的涂层的情况。良好的熔化性能能为气相沉积材料的蒸发建立并保持平整的熔化表面。这能够在待涂敷基板上确定均匀可重复的涂层厚度分布。这特别在使用熔融性能较差的材料时是非常困难的,甚至是不可能的,例如氧化铪、氧化锆、或氧化锆和氧化钛的混合物。
本发明的另一个目的是提供一种能够生产气相沉积材料的方法,该气相沉积材料可以转变为高折射率的光学涂层,而没有分解且没有气体放出。通过下列方法达到了该目的,即均匀混合组成为TiOx+z×La2O3的氧化钛、钛和氧化镧的混合物,其中,x=1.5-1.8,z=10-65重量%,以混合物的总重量为基准,造粒或者压片达到1-4毫米的颗粒尺寸,随后减压烧结。在进行该方法时,在1×10-4毫巴的真空下,在1500-1600℃的烧结温度下进行烧结,烧结时间为5.5-6.5小时。
另一个目的是提供一种能从气相沉积材料生产高折射率且基本不吸光的光学涂层的方法。通过下列方法达到了这一目的,即把待涂敷的基板清洗、干燥并安装在气相沉积装置中的基板夹具上,把气相沉积装置抽真空到1×10-5毫巴,把基板加热到280-310℃,使氧气进入气相沉积装置,直到压力达到1-2×10-4毫巴,在通过隔板密封的气相沉积装置中的电子束蒸发器中熔化气相沉积材料,加热到其蒸发温度2200-2300℃,打开隔板后,使基板涂敷气相沉积材料达到预定厚度。获得对于500纳米波长的折射率为2.15-2.25,特别是2.20的气相沉积材料的光学涂层。这种光学涂层是用途广泛的,用作眼镜透镜、光学仪器透镜、激光技术的光学器件的防反射涂层,并用于分光器、干涉镜、冷光镜和热防护滤光镜的具有特定高折射率和/或吸光性能的涂层。
使用本发明的气相沉积材料,可以在合适的基板上生产具有强结合性且特别是抗机械和化学影响的具有均匀层厚的均匀薄涂层。正如所提到的,这些涂层具有高折射率,且一般在从近紫外,即约360纳米波长,通过可见光区域,到波长约7000纳米的近红外的波长范围内具有高透过率。这些光学涂层在可见光波长范围内基本没有吸收。
下面参考两个实施例更详细地解释本发明,但是这些实施例绝不限制本发明的范围。
实施例1
均匀混合58.9重量%氧化镧、37.9重量%氧化钛和3.2重量%钛的混合物,造粒到约1-4毫米的颗粒尺寸,在1500℃减压烧结6小时。烧结产物是深黑色的。
为了生产光学涂层,把烧结产物引入到气相沉积装置的钼坩埚中并***到装置的电子束蒸发器中。把待涂敷的基板,例如直径25毫米,厚1毫米的石英玻璃圆盘,清洗并干燥,安装在气相沉积装置的基板夹具上。气相沉积装置是现有技术中已知的装置,既没有在附图中表示,也没有详细描述。在抽真空到1×10-5毫巴的压力后,把基板加热到约300℃的温度。然后使氧气通过控制阀进入气相沉积装置,直到压力达到1-2×10-4毫巴。在电子束蒸发器的隔板下面熔化气相沉积材料,并加热到2200℃的蒸发温度。一旦达到该蒸发温度,打开隔板,基板被涂敷了希望厚度的光学涂层。冷却后,从气相沉积装置中取出涂敷的基板。使用分光光度计测量涂层的透光率。从透光率曲线上确定在500纳米波长的折射率为2.20。涂层厚度为267纳米。
实施例2
均匀混合63重量%氧化镧、34重量%氧化钛和3重量%钛的混合物,造粒到约1-4毫米的颗粒尺寸,在1500℃减压烧结6小时。烧结产物是深黑色的。
用与实施例1所述的相同方法生产该烧结气相沉积材料的光学涂层。这些光学涂层在500纳米波长下的折射率为2.16。光学涂层的厚度为271纳米。该涂层在可见光区域内且最高到900纳米波长下表现出没有吸收。
Claims (11)
1.在减压下生产氧化钛、钛和氧化镧的高折射率光学涂层的气相沉积材料,特征在于所述材料是一种烧结混合物,组成为TiOx+z×La2O3,这里x=1.5-1.8,z=10-65重量%,以混合物的总重量为基准。
2.根据权利要求1的气相沉积材料,特征在于所述混合物包含19-65重量%氧化镧,38-74重量%氧化钛和2-7重量%钛。
3.根据权利要求2的气相沉积材料,特征在于所述混合物由58.9重量%氧化镧、37.9重量%氧化钛和3.2重量%钛组成。
4.根据权利要求2的气相沉积材料,特征在于所述混合物由63重量%氧化镧、34重量%氧化钛和3重量%钛组成。
5.根据权利要求1的气相沉积材料,特征在于氧化钛TiO2与钛之间的比例决定氧化钛TiOx中氧的化学计量比为x=1.5-1.8。
6.根据权利要求1的气相沉积材料,特征在于氧化钛∶氧化镧的重量比可以通过混合氧化镧和氧化钛与钛的混合物来确定。
7.根据权利要求1-4的气相沉积材料,特征在于所述气相沉积材料的光学涂层对于500纳米波长的折射率为2.15-2.25,特别是2.20。
8.生产根据权利要求1-7的气相沉积材料的方法,特征在于均匀混合组成为TiOx+z×La2O3的氧化钛、钛和氧化镧的混合物,其中x=1.5-1.8,z=10-65重量%,以混合物的总重量为基准,造粒或压片到颗粒尺寸为1-4毫米,随后减压烧结。
9.根据权利要求8的方法,特征在于所述烧结在10-4毫巴的真空中,在1500-1600℃的温度下进行,烧结时间为5.5-6.5小时。
10.生产根据权利要求1-7的气相沉积材料的光学涂层的方法,特征在于把待涂敷的基板清洗、干燥并安装在气相沉积装置的基板夹具上,把气相沉积装置抽真空到1×10-5毫巴,把基板加热到280-310℃,使氧气进入气相沉积装置,直到压力达到1-2×10-4毫巴,在通过隔板密封的气相沉积装置中的电子束蒸发器中熔化气相沉积材料,加热到其蒸发温度2200-2300℃,打开隔板后,使基板涂敷气相沉积材料达到预定厚度。
11.根据权利要求10生产的光学涂层作为眼镜透镜、光学仪器透镜、激光技术的光学器件的防反射涂层的用途以及作为用于分光器、干涉镜、冷光镜和热防护滤光镜的具有预定的高折射率和/或吸光性能的涂层的用途。
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CN102692657A (zh) * | 2011-03-25 | 2012-09-26 | 江苏双仪光学器材有限公司 | 光学零件多层镀膜新工艺 |
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JP5266466B2 (ja) * | 2009-04-01 | 2013-08-21 | 東海光学株式会社 | 光学部材、眼鏡用プラスチックレンズ及びそれらの製造方法 |
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CN102062881B (zh) * | 2010-11-25 | 2012-07-04 | 福州阿石创光电子材料有限公司 | 一种高折射率蒸发材料钛酸镧混合物的制备方法 |
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CN114133226A (zh) * | 2021-12-30 | 2022-03-04 | 苏州晶生新材料有限公司 | 一种光学镀层基材及使用方法 |
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CA2366177A1 (en) | 2002-06-29 |
JP5008807B2 (ja) | 2012-08-22 |
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