CN104446458A - Method for preparing yttrium-oxide-stabilized hafnium oxide vacuum coating material - Google Patents
Method for preparing yttrium-oxide-stabilized hafnium oxide vacuum coating material Download PDFInfo
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- CN104446458A CN104446458A CN201410725109.1A CN201410725109A CN104446458A CN 104446458 A CN104446458 A CN 104446458A CN 201410725109 A CN201410725109 A CN 201410725109A CN 104446458 A CN104446458 A CN 104446458A
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- hafnia
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- yttrium oxide
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Abstract
The invention relates to a method for preparing an yttrium-oxide-stabilized hafnium oxide vacuum coating material. The method is characterized by comprising the following steps: 1) evenly mixing raw materials (hafnium oxide and yttrium oxide powder), wherein a molar ratio of hafnium oxide to yttrium oxide is (73-98): (2-27); adding a polyvinyl alcohol binder so that the powder materials are agglomerated and granulating to obtain granular material; (2) pre-sintering the granular material at a pre-sintering temperature of 1260 DEG C; and (3) sintering in a vacuum sintering furnace at the vacuum degree of 1*10<-2>-1*10<-4> Pa and the heating speed of 3-8 DEG C/min; when the temperature reaches 1700-2280 DEG C, carrying out heat preservation for more than 150 minutes, and then naturally cooling to room temperature. By the method, the problems of instability and non-uniform refractive index during the coating of traditional hafnium oxide coating material can be solved and meanwhile, the damage threshold of a hafnium oxide film is increased.
Description
Technical field
The invention belongs to technical field of vacuum plating, specifically a kind of method for making of stabilized with yttrium oxide hafnia vacuum coating material.
Background technology
Prepare the laser film of high damage threshold, at visible and near-infrared band, high-index material aspect then subjected to from TiO
2(n=2.4), Ta
2o
5(n=2.1) to ZrO
2(n=2.1), HfO
2(n=2.0) change transformed.Therefore when people's design with when preparing the higher high performance optical thin film element of threshold requirement, usually tend to adopt HfO
2/ SiO
2combination.
At UV wave band, current people mainly concentrate on excimer laser wavelength 351nm (XeF) to the research of ultraviolet film material, 308nm (XeCl), 248nm (KrF), 193nm (ArF) and Nd ?the frequency tripling of YAG laser and quadruple (355nm and 266nm), wavelength is shorter, and available mould material is fewer.
HfO
2it is high that Coating Materials has specific refractory power, and uptake factor is low, and good thermostability and physical strength and high resisting laser damage characteristic, becomes preferred laser film Coating Materials at present.
HfO
2have high specific inductivity K ~ 25, have wide band gap 5.68ev, at 550nm place, specific refractory power is about 2.0.HfO
2material has three kinds of crystalline phases, exists under room temperature with monoclinic phase, exists mutually under high temperature with Tetragonal with tiltedly square.At 1700 DEG C, monoclinic phase changes Tetragonal into, and phase transformation is along with 3.8% stereomutation.Monoclinic phase is stable existence at room temperature, is heated to 1700 DEG C and changes Tetragonal into, when cooling, reversible transformation occurs.Because along with 3.8% volume change between monocline and tetragonal structure change, this can make hafnium oxide material destroy, so HfO
2film undergoes phase transition generation splash in coating process, makes evaporation line be not easy to control, is difficult to the stability ensureing coating process.Produce a large amount of defect in the film, under the irradiation of laser, this defect becomes absorbent core simultaneously, and produce heat accumulation, temperature raises rapidly and film is damaged at short notice.The specific refractory power of hafnia film has obvious ununiformity in addition, and along with thickness increases, specific refractory power reduces, and due to the above shortcoming of hafnia, causes the film prepared often cannot reach optical property and the resisting laser damage performance of expection.
Summary of the invention
The object of this invention is to provide a kind of vacuum coating material of stabilized with yttrium oxide hafnia, solve the instability in conventional oxidation hafnium Coating Materials coating process and refractive index inhomogeneity problem, improve the damage threshold of hafnia film simultaneously.
Object of the present invention is realized by following technical solution:
A preparation method for the vacuum coating material of stabilized with yttrium oxide hafnia, comprises the following steps:
1. with hafnia and yttrium oxide powder for raw material is by certain molar ratio Homogeneous phase mixing, then add polyvinyl alcohol bonding agent and powder reunited, granulation;
2. carry out pre-burning to particulate material, calcined temperature is 1260 DEG C;
3. then sinter in vacuum sintering furnace, vacuum tightness is 1 × 10
-2~ 1 × 10
-4handkerchief, temperature rise rate is 3 ~ 8 DEG C/min, and be incubated when arriving 1700 ~ 2280 DEG C, soaking time is more than 150 minutes, and then naturally cooling is cooled to room temperature.
The mol% of described raw material is: hafnia 73 ~ 98, yttrium oxide 2 ~ 27.
Described granulated pellet size is about 1mm, so that plated film uses.
The invention has the advantages that:
Stabilized with yttrium oxide hafnium oxide material of the present invention, due to adding of yttrium oxide, Y
3+hf in displacement Hf dot matrix
4+and form binary solid solution, inhibit structure distortion, inhibit HfO
2phase transformation, makes HfO
2high-temperature-phase (Tetragonal or Emission in Cubic) directly remains into room temperature, eliminates HfO
2volume effect, thus ensure that the stable of stabilized with yttrium oxide hafnium oxide material use procedure.This just decreases the probability that defect produces to a great extent, improves the damage threshold of hafnia film, eliminates instability and the refractive index inhomogeneity problem of hafnia film.
Specific implementation method
Embodiment 1: after 98%:2% mixes in molar ratio by hafnia and yttrium oxide, add polyvinyl alcohol bonding agent, by shaping for the powder after mixing, pre-burning, calcined temperature is 1260 DEG C, then vacuum sintering.The vacuum tightness of vacuum sintering is 1 × 10
-4handkerchief, most high sintering temperature is 1700 DEG C, and soaking time is 150 minutes.The hafnia vacuum coating material of stable fine and close stabilized with yttrium oxide is obtained after cooling.By XRD analysis, form sosoloid, hafnia exists with tetragonal structure.By hafnia vacuum coating material evaporation unitary film in BK7 substrate of glass of stabilized with yttrium oxide, stable refractive index, vacuum chamber electron beam gun line is stablized.
Embodiment 2: after 98%:2% mixes in molar ratio by hafnia and yttrium oxide, add polyvinyl alcohol bonding agent, by shaping for the powder after mixing, pre-burning, calcined temperature is 1260 DEG C, then vacuum sintering.The vacuum tightness of vacuum sintering is 1 × 10
-4handkerchief, most high sintering temperature is 2200 DEG C, and soaking time is 150 minutes.The hafnia vacuum coating material of stable fine and close stabilized with yttrium oxide is obtained after cooling.By XRD analysis, form sosoloid, hafnia exists with tetragonal structure.By hafnia vacuum coating material evaporation unitary film in BK7 substrate of glass of stabilized with yttrium oxide, stable refractive index, vacuum chamber electron beam gun line is stablized.
Embodiment 3: after 98%:2% mixes in molar ratio by hafnia and yttrium oxide, add polyvinyl alcohol bonding agent, by shaping for the powder after mixing, pre-burning, calcined temperature is 1260 DEG C, then vacuum sintering.The vacuum tightness of vacuum sintering is 1 × 10
-4handkerchief, most high sintering temperature is 2000 DEG C, and soaking time is 150 minutes.The hafnia vacuum coating material of stable fine and close stabilized with yttrium oxide is obtained after cooling.By XRD analysis, form sosoloid, hafnia exists with tetragonal structure.By hafnia vacuum coating material evaporation unitary film in BK7 substrate of glass of stabilized with yttrium oxide, stable refractive index, vacuum chamber electron beam gun line is stablized.
Embodiment 4: after 90%:10% mixes in molar ratio by hafnia and yttrium oxide, add polyvinyl alcohol bonding agent, by shaping for the powder after mixing, pre-burning, calcined temperature is 1260 DEG C, then vacuum sintering.The vacuum tightness of vacuum sintering is 1 × 10
-4handkerchief, most high sintering temperature is 1700 DEG C, and soaking time is 150 minutes.The hafnia vacuum coating material of stable fine and close stabilized with yttrium oxide is obtained after cooling.By XRD analysis, form sosoloid, hafnia exists with tetragonal structure.By hafnia vacuum coating material evaporation unitary film in BK7 substrate of glass of stabilized with yttrium oxide, stable refractive index, vacuum chamber electron beam gun line is stablized.
Embodiment 5: after 90%:10% mixes in molar ratio by hafnia and yttrium oxide, add polyvinyl alcohol bonding agent, by shaping for the powder after mixing, pre-burning, calcined temperature is 1260 DEG C, then vacuum sintering.The vacuum tightness of vacuum sintering is 1 × 10
-4handkerchief, most high sintering temperature is 2200 DEG C, and soaking time is 150 minutes.The hafnia vacuum coating material of stable fine and close stabilized with yttrium oxide is obtained after cooling.By XRD analysis, form sosoloid, hafnia exists with tetragonal structure.By hafnia vacuum coating material evaporation unitary film in BK7 substrate of glass of stabilized with yttrium oxide, stable refractive index, vacuum chamber electron beam gun line is stablized.
Embodiment 6: after 90%:10% mixes in molar ratio by hafnia and yttrium oxide, add polyvinyl alcohol bonding agent, by shaping for the powder after mixing, pre-burning, calcined temperature is 1260 DEG C, then vacuum sintering.The vacuum tightness of vacuum sintering is 1 × 10
-4handkerchief, most high sintering temperature is 2000 DEG C, and soaking time is 150 minutes.The hafnia vacuum coating material of stable fine and close stabilized with yttrium oxide is obtained after cooling.By XRD analysis, form sosoloid, hafnia exists with tetragonal structure.By hafnia vacuum coating material evaporation unitary film in BK7 substrate of glass of stabilized with yttrium oxide, stable refractive index, vacuum chamber electron beam gun line is stablized.
Embodiment 7: after 75%:25% mixes in molar ratio by hafnia and yttrium oxide, add polyvinyl alcohol bonding agent, by shaping for the powder after mixing, pre-burning, calcined temperature is 1260 DEG C, then vacuum sintering.The vacuum tightness of vacuum sintering is 1 × 10
-4handkerchief, most high sintering temperature is 1700 DEG C, and soaking time is 150 minutes.The hafnia vacuum coating material of stable fine and close stabilized with yttrium oxide is obtained after cooling.By XRD analysis, form sosoloid, hafnia exists with tetragonal structure.By hafnia vacuum coating material evaporation unitary film in BK7 substrate of glass of stabilized with yttrium oxide, stable refractive index, vacuum chamber electron beam gun line is stablized.
Embodiment 8: after 75%:25% mixes in molar ratio by hafnia and yttrium oxide, add polyvinyl alcohol bonding agent, by shaping for the powder after mixing, pre-burning, calcined temperature is 1260 DEG C, then vacuum sintering.The vacuum tightness of vacuum sintering is 1 × 10
-4handkerchief, most high sintering temperature is 2200 DEG C, and soaking time is 150 minutes.The hafnia vacuum coating material of stable fine and close stabilized with yttrium oxide is obtained after cooling.By XRD analysis, form sosoloid, hafnia exists with tetragonal structure.By hafnia vacuum coating material evaporation unitary film in BK7 substrate of glass of stabilized with yttrium oxide, stable refractive index, vacuum chamber electron beam gun line is stablized.
Embodiment 9: after 75%:25% mixes in molar ratio by hafnia and yttrium oxide, add polyvinyl alcohol bonding agent, by shaping for the powder after mixing, pre-burning, calcined temperature is 1260 DEG C, then vacuum sintering.The vacuum tightness of vacuum sintering is 1 × 10
-4handkerchief, most high sintering temperature is 2000 DEG C, and soaking time is 150 minutes.The hafnia vacuum coating material of stable fine and close stabilized with yttrium oxide is obtained after cooling.By XRD analysis, form sosoloid, hafnia exists with tetragonal structure.By hafnia vacuum coating material evaporation unitary film in BK7 substrate of glass of stabilized with yttrium oxide, stable refractive index, vacuum chamber electron beam gun line is stablized.
Claims (2)
1. a method for making for the vacuum coating material of stabilized with yttrium oxide hafnia, is characterized in that, comprises the following steps:
1. with hafnia and yttrium oxide powder for raw material, hafnia in molar ratio: yttrium oxide=73 ~ 98:2 ~ 27, Homogeneous phase mixing, then adds polyvinyl alcohol bonding agent and powder is reunited, granulation;
2. carry out pre-burning to particulate material, calcined temperature is 1260 DEG C;
3. then sinter in vacuum sintering furnace, vacuum tightness is 1 × 10
-2~ 1 × 10
-4handkerchief, temperature rise rate is 3 ~ 8 DEG C/min, and be incubated when arriving 1700 ~ 2280 DEG C, soaking time is more than 150 minutes, and then naturally cooling is cooled to room temperature.
2. the method for making of the vacuum coating material of stabilized with yttrium oxide hafnia according to claim 1, it is characterized in that described granulated pellet size be 0.5 ?1.5mm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109503149A (en) * | 2018-11-27 | 2019-03-22 | 北京富兴凯永兴光电技术有限公司 | A kind of high refractive index optical filming material and preparation method, optical anti-reflective film |
| CN112794640A (en) * | 2021-01-05 | 2021-05-14 | 长飞光纤光缆股份有限公司 | Pretreatment method of multi-component powder raw material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1696328A (en) * | 2005-06-08 | 2005-11-16 | 中国科学院上海光学精密机械研究所 | Yttria-stabilized zirconia vacuum coating material and preparation method thereof |
| CN101081735A (en) * | 2005-10-07 | 2007-12-05 | 苏舍美特科（美国）公司 | Optimized high temperature thermal heat barrier |
-
2014
- 2014-12-03 CN CN201410725109.1A patent/CN104446458A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1696328A (en) * | 2005-06-08 | 2005-11-16 | 中国科学院上海光学精密机械研究所 | Yttria-stabilized zirconia vacuum coating material and preparation method thereof |
| CN101081735A (en) * | 2005-10-07 | 2007-12-05 | 苏舍美特科（美国）公司 | Optimized high temperature thermal heat barrier |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109503149A (en) * | 2018-11-27 | 2019-03-22 | 北京富兴凯永兴光电技术有限公司 | A kind of high refractive index optical filming material and preparation method, optical anti-reflective film |
| CN112794640A (en) * | 2021-01-05 | 2021-05-14 | 长飞光纤光缆股份有限公司 | Pretreatment method of multi-component powder raw material |
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Application publication date: 20150325 |