CN116462418A - Combined treatment method for fused quartz element surface for improving laser damage resistance - Google Patents
Combined treatment method for fused quartz element surface for improving laser damage resistance Download PDFInfo
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- CN116462418A CN116462418A CN202310510158.2A CN202310510158A CN116462418A CN 116462418 A CN116462418 A CN 116462418A CN 202310510158 A CN202310510158 A CN 202310510158A CN 116462418 A CN116462418 A CN 116462418A
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 239000005350 fused silica glass Substances 0.000 title claims abstract description 122
- 238000000034 method Methods 0.000 title claims abstract description 55
- 239000008367 deionised water Substances 0.000 claims abstract description 61
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 61
- 238000004140 cleaning Methods 0.000 claims abstract description 54
- 238000001020 plasma etching Methods 0.000 claims abstract description 53
- 238000005530 etching Methods 0.000 claims abstract description 52
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000000137 annealing Methods 0.000 claims abstract description 31
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 12
- 239000000428 dust Substances 0.000 claims abstract description 9
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 23
- 230000005684 electric field Effects 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000007547 defect Effects 0.000 abstract description 25
- 230000008569 process Effects 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 20
- 239000012535 impurity Substances 0.000 description 13
- 238000012876 topography Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- 238000007789 sealing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 238000000992 sputter etching Methods 0.000 description 2
- 230000007847 structural defect Effects 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000866 electrolytic etching Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000007730 finishing process Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
Classifications
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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
- C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B25/00—Annealing glass products
-
- 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
- C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
- C03C23/0075—Cleaning of glass
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Cleaning Or Drying Semiconductors (AREA)
Abstract
The invention discloses a fused quartz element surface joint treatment method for improving laser damage resistance, which comprises the following steps: ultrasonically cleaning the fused quartz element in ethanol to remove dust and oil stains on the surface, and then ultrasonically cleaning the fused quartz element in deionized water; placing the cleaned fused quartz element in a parallel plate discharge etcher for reactive ion etching, cleaning the surface of the element by adopting inorganic acid after etching, and then cleaning and airing by using deionized water; placing the cleaned fused quartz element in a high-temperature annealing furnace for high-temperature annealing treatment; placing the fused silica component after the high-temperature annealing treatment at H 2 O 2 Performing secondary etching in the etcher; and cleaning the etched fused quartz element by deionized water and ethanol. The invention has better method by combined etchingThe defect of the surface of the fused quartz element is repaired, and meanwhile, the surface quality is improved, so that the laser damage threshold of the surface of the fused quartz element is effectively improved.
Description
Technical Field
The invention belongs to the technical field of optical material post-treatment, and particularly relates to a fused quartz element surface combined treatment method for improving laser damage resistance.
Background
Fused silica has been a key element for many important optical components in high-energy laser systems due to its excellent properties, but the optical property degradation caused by laser-induced damage has created a great impediment to the development of the high-energy density science fields such as inertial confinement fusion, high-energy laser, and the like.
The currently measured laser induced damage threshold of fused quartz is often less than one tenth of the intrinsic threshold, and the root cause is that the element introduces surface defects in the cold working processes of early grinding, polishing and the like. In general, various surface finishing processes introduce damage defects such as scratches or pits in the subsurface layer that lead to a higher probability of laser-induced damage. Meanwhile, contamination defects in the form of impurity elements (e.g., ce, fe, etc.) introduced through a polishing process or environmental pollution may cause enhanced laser absorption, thereby lowering a laser damage threshold. In addition, chemical structural defects such as non-bridging oxygen centers (NBOHCs) and oxygen vacancy centers (ODCs) are also associated with the occurrence of laser damage to fused silica glass. These defects are extremely vulnerable to laser pulse irradiation, and the damage scale increases rapidly as the number of irradiation times increases. Subsurface defects can cause degradation or even failure of optical functions of elements, severely limit the loading capacity of a laser driving system and greatly increase the operation and maintenance burden of the system.
Various surface treatment processes and surface treatment methods have been developed to eliminate these surface defects. For example, reactive Ion Etching (RIE) is an etching process combining physical bombardment and chemical etching, and generates active groups by discharging fluorine-containing gas, and interacts with the surface of a fused quartz material to anisotropically remove surface and subsurface defects of the material, such as the polishing redeposited layer rich in photosensitive impurity elements such as Ce and Zr and the subsurface damage layer composed of broken cracks, scratches and the like, thereby greatly improving the damage resistance of the element. However, with the increase of etching depth, chemical structural defects (ODC, NBOHC, etc.) and densification of materials, and contamination impurities such as F element introduced at the near surface during etching, become important reasons for further limiting the improvement of the laser damage resistance of the fused silica element.
Therefore, single reactive ion etching cannot meet the actual engineering needs, and it is highly desirable to explore a surface post-treatment method capable of effectively improving the laser damage resistance of the fused silica element to solve the above technical problems.
Disclosure of Invention
It is an object of the present invention to address at least the above problems and/or disadvantages and to provide at least the advantages described below.
To achieve these objects and other advantages and in accordance with the purpose of the invention, there is provided a fused silica component surface joint treatment method for improving resistance to laser damage, comprising the steps of:
firstly, ultrasonically cleaning a fused quartz element in ethanol to remove dust and oil stains on the surface, and then ultrasonically cleaning the fused quartz element in deionized water to further remove impurities on the surface of the fused quartz element;
step two, placing the cleaned fused quartz element in a parallel plate discharge etcher for reactive ion etching, cleaning the surface of the element by adopting inorganic acid after etching, dissolving metal impurity pollution possibly remained in the reactive ion etching process, and then cleaning and airing by deionized water;
step three, placing the fused quartz element cleaned in the step two in a high-temperature annealing furnace, and performing high-temperature annealing treatment to converge the residual subsurface physical structure defect after the reactive ion etching treatment, eliminate residual stress and densify, and simultaneously migrate the impurity element of the subsurface layer to the near surface;
fourthly, placing the fused quartz element subjected to the high-temperature annealing treatment in the third step in H 2 O 2 Performing secondary etching in an etcher to completely eliminate a subsurface defect layer of the fused quartz element and passivate the optical surface so as to realize effective and controllable removal of surface defects of the fused quartz element;
and fifthly, cleaning the etched fused quartz element by deionized water and ethanol, wherein the operation steps are the same as those of the first step.
Preferably, the ethanol solution used in the first and third steps is absolute ethanol.
Preferably, in the first step, the ultrasonic cleaning of the ethanol solution is carried out by sequentially using the frequencies of 20kHz, 28kHz, 45kHz, 60kHz, 80kHz, 100kHz and 135kHz, and the working time of each frequency is 2-5 min.
Preferably, in the first step, when the deionized water is subjected to ultrasonic cleaning, the ultrasonic cleaning is divided into two periods, and ultrasonic auxiliary cleaning of 20kHz, 28kHz, 45kHz, 60kHz, 80kHz, 100kHz and 135kHz is sequentially used for 2-5 min to form a period, and deionized water in the rinsing tank is replaced after the cleaning of each period is finished; after the last cleaning, the surface of the fused silica component is washed by flowing deionized water to remove residual moisture and particles.
Preferably, in the second step, CHF is used for reactive ion etching 3 Ar mixture, etching rate 2 μm/h, etching time 80min.
Preferably, in the second step, during the inorganic acid cleaning process, the total immersion volume ratio of the sample is 2: HNO of 1 3 And H 2 O 2 In the mixed inorganic acid of (2), the treatment time is 80min, and HNO 3 70% by mass, 40% H 2 O 2 The mass fraction of (2) is 40%.
Preferably, in step four, H 2 O 2 The mass fraction of (2) is 5-50%.
Preferably, in the second step, the frequency of the high-frequency electric field for performing the reactive ion etching is 12-25 MHz.
Preferably, in the second step, CHF in the reaction chamber for performing reactive ion etching 3 And Ar is controlled to be 0.2-0.9:1.5 or 0.25-0.85:1.
Preferably, in the second step, the Ar inlet flow rate in the reaction chamber for performing the reactive ion etching is selected to be 50cm 3 /min～200cm 3 /min or 65cm 3 /min～180cm 3 /min。
Preferably, in the third step, the atmosphere in the annealing chamber is dry air or nitrogen, the annealing temperature is 400-2000 ℃, and the annealing time is 1-20 h.
The invention at least comprises the following beneficial effects: provides a convenient and quick post-treatment process with controllable quality, which is used for reacting ion etching, high-temperature annealing and H 2 O 2 Etching combined fused quartz element surface combined treatment method. Firstly, removing surface defects of a fused quartz element by reactive ion etching, cleaning, then carrying out high-temperature annealing treatment on the element to converge the residual subsurface physical structure defects after the reactive ion etching treatment, eliminate residual stress and densify, and meanwhile, transferring subsurface impurity elements to the near surface, and then cleaning and drying; then pass through H 2 O 2 Etching the surface of the element to further remove near-surface pollution type defects and passivate the surface of the element.
Wherein, because the high temperature annealing process can converge and reduce the residual defect layer, the time of the previous step of reactive ion etching can be shortened, the dosage of harmful fluorine-containing gas can be reduced, the material can be prevented from being removed in a large amount, and the high temperature annealing process can remove the densification and residual stress of the material caused by the pretreatment on the subsurface of the elementThe method eliminates the factor limiting the laser damage resistance of the fused quartz component, and simultaneously innovatively uses the high-temperature annealing treatment to migrate the pollution type defects remained on the subsurface of the component to the near surface of the component, thereby greatly reducing the next step H 2 O 2 Burden of etching, finally by H 2 O 2 Etching completely eliminates surface defects and passivates the surface, thereby realizing effective and controllable removal of the surface defects of the fused quartz element. Compared with the prior single technology and other combined technologies, the combined treatment method provided by the invention is more economical, clean and environment-friendly, and because the last procedure uses H 2 O 2 With SiO 2 The etching reaction of (2) converges, and other negative effects are hardly introduced, so that the effect can be improved by more predictable damage than the main flow etching process.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Drawings
FIG. 1 is a schematic process flow diagram of a combined treatment method for improving the laser damage resistance of a fused silica component according to embodiments 1-3;
FIG. 2 is a schematic operation flow chart of a combined treatment method for improving the laser damage resistance of a fused silica component according to the embodiments 1-3;
FIG. 3 is an AFM three-dimensional topography of the surface of the fused silica component after the treatment of example 1 and its corresponding roughness values;
FIG. 4 is an AFM three-dimensional topography of the surface of the fused silica component after the treatment of example 2 and its corresponding roughness values;
FIG. 5 is an AFM three-dimensional topography of the surface of the fused silica component after the treatment of example 3 and its corresponding roughness values;
FIG. 6 is an AFM three-dimensional topography of the surface of the fused silica component after treatment of comparative example 1 and its corresponding roughness values;
FIG. 7 is an AFM three-dimensional topography of the surface of the fused silica component after treatment of comparative example 2 and its corresponding roughness values;
FIG. 8 is an AFM three-dimensional topography of the surface of a fused silica component after treatment of comparative example 3 and its corresponding roughness values;
FIG. 9 is an AFM three-dimensional topography of the surface of an untreated fused silica component and its corresponding roughness values.
Detailed Description
The present invention is described in further detail below with reference to the drawings to enable those skilled in the art to practice the invention by referring to the description.
It will be understood that terms, such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
Example 1
As shown in fig. 1 and 2, the embodiment provides a fused quartz element surface joint treatment method for improving the laser damage resistance, which comprises the following steps:
and step one, ultrasonically cleaning the fused quartz element. Firstly, removing oil stains, dust and the like on the surface of an element by ultrasonic cleaning in absolute ethanol solution, wherein the frequencies used in sequence are 20kHz, 28kHz, 45kHz, 60kHz, 80kHz, 100kHz and 135kHz, and the working time of each frequency is 5 minutes.
The deionized water is rinsed, and the deionized water in the rinsing tank is replaced after the cleaning of each cycle is finished, wherein the deionized water is rinsed in two cycles, namely, the two cycles are sequentially cleaned for 2 minutes by using ultrasonic waves of 20kHz, 28kHz, 45kHz, 60kHz, 80kHz, 100kHz and 135 kHz. After the last cleaning, the surface of the fused silica component is washed by flowing deionized water to remove residual moisture and particles.
Step two, placing the cleaned fused quartz element in a parallel plate discharge etcher to carry out reactive ion etching, wherein the reactive ions adopt CHF 3 Ar mixture, high-frequency electric field frequency of reactive ion etching of 15MHz, CHF 3 And the volume ratio of Ar is controlled to be 0.4:1.5 Ar Inlet flow was chosen to be 70cm 3 And/min, the pressure of the gas outlet is selected to be 0.4Pa, the etching speed is 2 mu m/h, and the etching time is 1h. After etching, the volume ratio of the whole immersed sample is 2:1 of 70% HNO 3 And 40% H 2 O 2 The treatment time was 80 minutes in the mixed inorganic acid of (C). The metal impurities possibly remained in the process of dissolving the reactive ion etching are polluted, and then the solution is washed by deionized water and dried. The fused quartz component is put into a quartz inner tube of a high-temperature annealing furnace for high-temperature annealing treatment, and the quartz inner tube is filled with dry air for sealing and annealed for 2 hours at the temperature of 500 ℃.
Step three, placing the fused quartz component cooled after high-temperature annealing in H with the concentration of 30% 2 O 2 Etching in an etcher for 5 hours to completely eliminate a deteriorated layer generated by a reactive ion etching pretreatment process and simultaneously reduce subsurface defect density to the minimum;
step four, H 2 O 2 The etched fused quartz element is subjected to ultrasonic cleaning, and when the ethanol solution and the deionized water are subjected to ultrasonic cleaning, the frequencies used in sequence are 20kHz, 28kHz, 45kHz, 60kHz, 80kHz, 100kHz and 135kHz, and the working time of each frequency is 5 minutes. The deionized rinsing is divided into two periods, ultrasonic auxiliary cleaning of 20kHz, 28kHz, 45kHz, 60kHz, 80kHz, 100kHz and 135kHz is sequentially used for 2-5 min to form a period, and deionized water in the rinsing tank is replaced after the cleaning of each period is finished.
Example 2
The embodiment provides a fused quartz element surface joint treatment method for improving laser damage resistance, which comprises the following steps:
and step one, ultrasonically cleaning the fused quartz element. Firstly, removing oil stains, dust and the like on the surface of an element by ultrasonic cleaning in absolute ethanol solution, wherein the frequencies used in sequence are 20kHz, 28kHz, 45kHz, 60kHz, 80kHz, 100kHz and 135kHz, and the working time of each frequency is 5 minutes.
The deionized water is rinsed, and the deionized water in the rinsing tank is replaced after the cleaning of each cycle is finished, wherein the deionized water is rinsed in two cycles, namely, the two cycles are sequentially cleaned for 5 minutes by using ultrasonic waves of 20kHz, 28kHz, 45kHz, 60kHz, 80kHz, 100kHz and 135 kHz. After the last cleaning, the surface of the fused silica component is washed by flowing deionized water to remove residual moisture and particles.
Step two, placing the cleaned fused quartz element in a parallel plateReactive ion etching is performed in an electroetching machine, wherein CHF is adopted as the reactive ion 3 Ar mixture, high-frequency electric field frequency of reactive ion etching of 15MHz, CHF 3 And the volume ratio of Ar is controlled to be 0.7:1.5 Ar Inlet flow was chosen to be 70cm 3 And/min, the pressure of the gas outlet is selected to be 0.5Pa, the etching speed is 2 mu m/h, and the etching time is 1.5h. After etching, the volume ratio of the whole immersed sample is 2:1 of 70% HNO 3 And 40% H 2 O 2 The treatment time was 80 minutes in the mixed inorganic acid of (C). The metal impurities possibly remained in the process of dissolving the reactive ion etching are polluted, and then the solution is washed by deionized water and dried. The fused quartz component is put into a quartz inner tube of a high-temperature annealing furnace for high-temperature annealing treatment, and the quartz inner tube is filled with dry air for sealing and is annealed for 4 hours at 600 ℃.
Step three, placing the fused quartz component cooled after high-temperature annealing in H with the concentration of 30% 2 O 2 Etching in an etcher for 5 hours to completely eliminate a deteriorated layer generated by a reactive ion etching pretreatment process and simultaneously reduce subsurface defect density to the minimum;
step four, H 2 O 2 The etched fused quartz element is subjected to ultrasonic cleaning, and when the ethanol solution and the deionized water are subjected to ultrasonic cleaning, the frequencies used in sequence are 20kHz, 28kHz, 45kHz, 60kHz, 80kHz, 100kHz and 135kHz, and the working time of each frequency is 5 minutes. The deionized rinsing is divided into two periods, ultrasonic auxiliary cleaning of 20kHz, 28kHz, 45kHz, 60kHz, 80kHz, 100kHz and 135kHz is sequentially used for 2-5 min to form a period, and deionized water in the rinsing tank is replaced after the cleaning of each period is finished.
Example 3
The embodiment provides a fused quartz element surface joint treatment method for improving laser damage resistance, which comprises the following steps:
and step one, ultrasonically cleaning the fused quartz element. Firstly, removing oil stains, dust and the like on the surface of an element by ultrasonic cleaning in absolute ethanol solution, wherein the frequencies used in sequence are 20kHz, 28kHz, 45kHz, 60kHz, 80kHz, 100kHz and 135kHz, and the working time of each frequency is 5 minutes.
The deionized water is rinsed, and the deionized water in the rinsing tank is replaced after the cleaning of each cycle is finished, wherein the deionized water is rinsed in two cycles, namely, the two cycles are sequentially cleaned for 5 minutes by using ultrasonic waves of 20kHz, 28kHz, 45kHz, 60kHz, 80kHz, 100kHz and 135 kHz. After the last cleaning, the surface of the fused silica component is washed by flowing deionized water to remove residual moisture and particles.
Step two, placing the cleaned fused quartz element in a parallel plate discharge etcher to carry out reactive ion etching, wherein the reactive ions adopt CHF 3 Ar mixture, high-frequency electric field frequency of reactive ion etching of 15MHz, CHF 3 And the volume ratio of Ar is controlled to be 0.8:1.5 Ar Inlet flow was chosen to be 70cm 3 And/min, the etching speed is 2 mu m/h, and the etching time is 3h. After etching, the volume ratio of the whole immersed sample is 2:1 of 70% HNO 3 And 40% H 2 O 2 The treatment time was 80 minutes in the mixed inorganic acid of (C). The metal impurities possibly remained in the process of dissolving the reactive ion etching are polluted, and then the solution is washed by deionized water and dried. The fused quartz component is put into a quartz inner tube of a high-temperature annealing furnace for high-temperature annealing treatment, and the quartz inner tube is filled with dry air for sealing and annealed for 6 hours at 800 ℃.
Step three, placing the fused quartz component cooled after high-temperature annealing in H with the concentration of 30% 2 O 2 Etching in an etcher for 5 hours to completely eliminate a deteriorated layer generated by a reactive ion etching pretreatment process and simultaneously reduce subsurface defect density to the minimum;
step four, H 2 O 2 The etched fused quartz element is subjected to ultrasonic cleaning, and when the ethanol solution and the deionized water are subjected to ultrasonic cleaning, the frequencies used in sequence are 20kHz, 28kHz, 45kHz, 60kHz, 80kHz, 100kHz and 135kHz, and the working time of each frequency is 5 minutes. The deionized rinsing is divided into two periods, ultrasonic auxiliary cleaning of 20kHz, 28kHz, 45kHz, 60kHz, 80kHz, 100kHz and 135kHz is sequentially used for 2-5 min to form a period, and deionized water in the rinsing tank is replaced after the cleaning of each period is finished.
The roughness and laser damage threshold values of the fused silica members treated in examples 1 to 3 were measured, respectively, to obtain the following tables:
example 1-example 3 the surface AFM three-dimensional topography of the treated fused silica element and its corresponding roughness values are shown in fig. 3, 4 and 5, and the surface AFM three-dimensional topography of the untreated fused silica element and its corresponding roughness values are shown in fig. 9.
Comparative example 1
The embodiment provides a fused quartz element surface joint treatment method for improving laser damage resistance, which comprises the following steps:
and step one, ultrasonically cleaning the fused quartz element. Firstly, removing oil stains, dust and the like on the surface of an element by ultrasonic cleaning in absolute ethanol solution, wherein the frequencies used in sequence are 20kHz, 28kHz, 45kHz, 60kHz, 80kHz, 100kHz and 135kHz, and the working time of each frequency is 2min;
the deionized water is rinsed, and the deionized water in the rinsing tank is replaced after the cleaning of each cycle is finished, wherein the deionized water is rinsed in two cycles, namely, the two cycles are sequentially cleaned for 2 minutes by using ultrasonic waves of 20kHz, 28kHz, 45kHz, 60kHz, 80kHz, 100kHz and 135 kHz. After the last cleaning is finished, the surface of the fused quartz element is washed by flowing deionized water to remove residual moisture and particles;
step two, placing the cleaned fused quartz element in a parallel plate discharge etcher to carry out reactive ion etching, wherein the reactive ions adopt CHF 3 Ar mixture, high-frequency electric field frequency of reactive ion etching of 13MHz, CHF 3 And the volume ratio of Ar is controlled to be 0.4:1.5 Ar Inlet flow was chosen to be 60cm 3 And/min, the pressure of the gas outlet is selected to be 0.4Pa, the etching speed is 2 mu m/h, and the etching time is 1h. After etching, the sample is fully immersed into 70% HNO with the volume ratio of 2:1 3 And 40% H 2 O 2 The treatment time was 80 minutes in the mixed inorganic acid of (C). Dissolving metal impurities possibly remained in the reactive ion etching process for pollution, and then cleaning with deionized water and airing;
step (a)3. Placing the fused quartz element after the reactive ion etching in H with the concentration of 30% 2 O 2 Etching for 3h in an etcher to completely eliminate a deteriorated layer generated by a reactive ion etching pretreatment process and simultaneously reduce subsurface defect density to the minimum;
step four, H 2 O 2 The etched fused quartz element is subjected to ultrasonic cleaning, and when the ethanol solution and the deionized water are subjected to ultrasonic cleaning, the frequencies used in sequence are 20kHz, 28kHz, 45kHz, 60kHz, 80kHz, 100kHz and 135kHz, and the working time of each frequency is 2 minutes. The deionized water is rinsed, and the deionized water in the rinsing tank is replaced after the cleaning of each cycle is finished, wherein the deionized water is rinsed in two cycles, namely, the two cycles are sequentially cleaned for 2 minutes by using ultrasonic waves of 20kHz, 28kHz, 45kHz, 60kHz, 80kHz, 100kHz and 135 kHz.
Comparative example 2
The embodiment provides a fused quartz element surface joint treatment method for improving laser damage resistance, which comprises the following steps:
and step one, ultrasonically cleaning the fused quartz element. Firstly, removing oil stains, dust and the like on the surface of an element by ultrasonic cleaning in absolute ethanol solution, wherein the frequencies used in sequence are 20kHz, 28kHz, 45kHz, 60kHz, 80kHz, 100kHz and 135kHz, and the working time of each frequency is 3min;
the deionized water is rinsed, and the deionized water in the rinsing tank is replaced after the cleaning of each cycle is finished, wherein the deionized water is rinsed in two cycles, namely, the two cycles are sequentially cleaned for 3 minutes by using ultrasonic waves of 20kHz, 28kHz, 45kHz, 60kHz, 80kHz, 100kHz and 135 kHz. After the last cleaning is finished, the surface of the fused quartz element is washed by flowing deionized water to remove residual moisture and particles;
step three, placing the cleaned fused quartz element in a parallel plate discharge etcher to carry out reactive ion etching, wherein the reactive ions adopt CHF 3 Ar mixture, high-frequency electric field frequency of reactive ion etching of 15MHz, CHF 3 And the volume ratio of Ar is controlled to be 0.7:1.5 Ar Inlet flow was chosen to be 70cm 3 And/min, the gas outlet pressure is selected to be 0.5Pa, the etching speed is 2 mu m/h, and the etching time is 2h. After etching, the sample is fully immersed in the volume ratio of2:1 70% HNO 3 And 40% H 2 O 2 The treatment time was 80 minutes in the mixed inorganic acid of (C). Dissolving metal impurities possibly remained in the reactive ion etching process for pollution, and then cleaning with deionized water and airing;
step three, placing the fused quartz element subjected to reactive ion etching in H with the concentration of 30% 2 O 2 Etching in an etcher for 4 hours to completely eliminate a deteriorated layer generated by a reactive ion etching pretreatment process and simultaneously reduce subsurface defect density to the minimum;
step four, H 2 O 2 The etched fused quartz element is subjected to ultrasonic cleaning, and when the ethanol solution and the deionized water are subjected to ultrasonic cleaning, the frequencies used in sequence are 20kHz, 28kHz, 45kHz, 60kHz, 80kHz, 100kHz and 135kHz, and the working time of each frequency is 3 minutes. The deionized water is rinsed, and the deionized water in the rinsing tank is replaced after the cleaning of each cycle is finished, wherein the deionized water is rinsed in two cycles, namely, the two cycles are sequentially cleaned for 3 minutes by using ultrasonic waves of 20kHz, 28kHz, 45kHz, 60kHz, 80kHz, 100kHz and 135 kHz.
Comparative example 3
The embodiment provides a fused quartz element surface joint treatment method for improving laser damage resistance, which comprises the following steps:
and step one, ultrasonically cleaning the fused quartz element. Firstly, removing oil stains, dust and the like on the surface of an element by ultrasonic cleaning in absolute ethanol solution, wherein the frequencies used in sequence are 20kHz, 28kHz, 45kHz, 60kHz, 80kHz, 100kHz and 135kHz, and the working time of each frequency is 5 minutes.
The deionized water is rinsed, and the deionized water in the rinsing tank is replaced after the cleaning of each cycle is finished, wherein the deionized water is rinsed in two cycles, namely, the two cycles are sequentially cleaned for 5 minutes by using ultrasonic waves of 20kHz, 28kHz, 45kHz, 60kHz, 80kHz, 100kHz and 135 kHz. After the last cleaning, the surface of the fused silica component is washed by flowing deionized water to remove residual moisture and particles.
Step two, placing the cleaned fused quartz element in a parallel plate discharge etcher to carry out reactive ion etching, wherein the reactive ions adopt CHF 3 Ar mixtures, reactive ion etchingThe frequency of the etched high-frequency electric field is 15MHz and CHF 3 And the volume ratio of Ar is controlled to be 0.8:1.5 Ar Inlet flow was chosen to be 70cm 3 And/min, the gas outlet pressure is selected to be 0.5Pa, the etching speed is 2 mu m/h, and the etching time is 3h. After etching, the volume ratio of the whole immersed sample is 2:1 of 70% HNO 3 And 40% H 2 O 2 The treatment time was 80 minutes in the mixed inorganic acid of (C). The metal impurities possibly remained in the process of dissolving the reactive ion etching are polluted, and then the solution is washed by deionized water and dried.
Step three, placing the fused quartz element subjected to reactive ion etching in H with the concentration of 30% 2 O 2 Etching in an etcher for 5 hours to completely eliminate a deteriorated layer generated by a reactive ion etching pretreatment process and simultaneously reduce subsurface defect density to the minimum;
step four, H 2 O 2 The etched fused quartz element is subjected to ultrasonic cleaning, and when the ethanol solution and the deionized water are subjected to ultrasonic cleaning, the frequencies used in sequence are 20kHz, 28kHz, 45kHz, 60kHz, 80kHz, 100kHz and 135kHz, and the working time of each frequency is 5 minutes. The deionized rinsing is divided into two periods, ultrasonic auxiliary cleaning of 20kHz, 28kHz, 45kHz, 60kHz, 80kHz, 100kHz and 135kHz is sequentially used for 2-5 min to form a period, and deionized water in the rinsing tank is replaced after the cleaning of each period is finished.
The laser damage threshold values of the fused silica elements repaired in examples 1 to 3 were tested respectively, and the test results of the obtained laser damage threshold values are shown in the following table:
comparative example 1-comparative example 3 AFM three-dimensional topography of the surface of the fused silica component after treatment and the corresponding roughness values are shown in fig. 6, 7 and 8.
Comparative example 4
In this comparative example, the time for reactive ion etching of the fused silica member was 1H, and the fused silica member was not subjected to H 2 O 2 Etching was performed in the same manner as in example 3.
Comparative example 5
In this comparative example, the time for reactive ion etching of the fused silica member was 2 hours, and the fused silica member was not subjected to H 2 O 2 Etching was performed in the same manner as in example 3.
Comparative example 6
In this comparative example, the time for reactive ion etching of the fused silica member was 3 hours, and the fused silica member was not subjected to H 2 O 2 Etching was performed in the same manner as in example 3.
Comparative example 7
In this comparative example, the fused silica element was not subjected to reactive ion etching, and the fused silica element was subjected to H 2 O 2 The etching time was 3h, and the rest of the operations were the same as in example 3.
Comparative example 8
In this comparative example, the fused silica element was not subjected to reactive ion etching, and the fused silica element was subjected to H 2 O 2 The etching time was 4h, and the rest of the operations were the same as in example 3.
Comparative example 9
In this comparative example, the fused silica element was not subjected to reactive ion etching, and the fused silica element was subjected to H 2 O 2 The etching time was 5h, and the rest of the operations were the same as in example 3.
The laser damage threshold values of the fused silica elements repaired in comparative examples 4 to 9 were respectively tested, and the test results of the obtained laser damage threshold values are shown in the following table:
as can be seen from the above table and FIGS. 3-9, the laser damage threshold of the surface of the fused silica optical element is affected after the surface of the fused silica optical element is treated by adopting the reactive ion etching method, and the damage threshold is increased along with the gradual increase of etching time, but the reactive ion etching, the high-temperature annealing and the H 2 O 2 After etching is combined, the damage threshold of the fused silica surface is significantly increased. To sum up the results of the examplesIt is shown that the reactive ion etching, the high-temperature annealing and the H are performed by reasonably controlling the process 2 O 2 The combined treatment method combining etching can effectively remove the chemical structure defect on the surface of the fused quartz element, improve the surface quality of the fused quartz element, and further improve the laser damage threshold of the fused quartz element.
The number of equipment and the scale of processing described herein are intended to simplify the description of the present invention. Applications, modifications and variations of the present invention will be readily apparent to those skilled in the art.
Although embodiments of the present invention have been disclosed above, it is not limited to the details and embodiments shown and described, it is well suited to various fields of use for which the invention would be readily apparent to those skilled in the art, and accordingly, the invention is not limited to the specific details and illustrations shown and described herein, without departing from the general concepts defined in the claims and their equivalents.
Claims (10)
1. The combined treatment method for the surface of the fused quartz element for improving the laser damage resistance is characterized by comprising the following steps of:
firstly, ultrasonically cleaning a fused quartz element in ethanol to remove dust and oil stains on the surface, and then ultrasonically cleaning the fused quartz element in deionized water;
step two, placing the cleaned fused quartz element in a parallel plate discharge etcher for reactive ion etching, cleaning the surface of the element by adopting inorganic acid after etching, and then cleaning and airing by using deionized water;
step three, placing the cleaned fused quartz element in a high-temperature annealing furnace for high-temperature annealing treatment;
step four, placing the fused quartz element after the high-temperature annealing treatment in H 2 O 2 Performing secondary etching in the etcher;
and fifthly, cleaning the etched fused quartz element by deionized water and ethanol, wherein the operation steps are the same as those of the first step.
2. The method for combined treatment of a surface of a fused silica component having improved resistance to laser damage according to claim 1, wherein the ethanol solution used in the first and third steps is absolute ethanol.
3. The method for combined treatment of a surface of a fused silica element for improving laser damage resistance according to claim 1, wherein in the first step, the frequencies used in the ultrasonic cleaning of the ethanol solution are 20kHz, 28kHz, 45kHz, 60kHz, 80kHz, 100kHz, 135kHz, and the working time of each frequency is 2 to 5min.
4. The method for combined treatment of a surface of a fused quartz component for improving laser damage resistance according to claim 1, wherein in the first step, when ultrasonic cleaning is performed in deionized water, the ultrasonic auxiliary cleaning of 20kHz, 28kHz, 45kHz, 60kHz, 80kHz, 100kHz and 135kHz is sequentially used for 2-5 min as a period, and deionized water in a rinsing tank is replaced after the cleaning of each period is finished; after the last cleaning, the surface of the fused silica component is washed by flowing deionized water to remove residual moisture and particles.
5. The method for combined treatment of a surface of a fused silica component having improved resistance to laser damage as recited in claim 1, wherein in step two, CHF is used for reactive ion etching 3 Ar mixture, etching rate 2 μm/h, etching time 80min.
6. The method for combined treatment of a surface of a fused silica component for improving laser damage resistance according to claim 1, wherein in the second step, the sample is immersed in a volume ratio of 2: HNO of 1 3 And H 2 O 2 In the mixed inorganic acid of (2), the treatment time is 80min, and HNO 3 70% by mass, 40% H 2 O 2 The mass fraction of (2) is 40%.
7. The method for combined treatment of a surface of a fused silica component having improved resistance to laser damage according to claim 1, wherein in step four, H 2 O 2 The mass fraction of (2) is 5-50%.
8. The method for combined treatment of a surface of a fused silica element for improving laser damage resistance according to claim 1, wherein in the second step, the frequency of a high-frequency electric field for reactive ion etching is 12-25 MHz; CHF in a reaction chamber for reactive ion etching 3 And Ar is controlled to be 0.2-0.9:1.5 or 0.25-0.85:1.
9. The method for combined treatment of a surface of a fused silica component having improved resistance to laser damage as recited in claim 1, wherein in said step two, the flow rate of Ar inlet in the reaction chamber for performing reactive ion etching is selected to be 50cm 3 /min～200cm 3 /min or 65cm 3 /min～180cm 3 /min。
10. The method for combined treatment of a surface of a fused silica component for improving laser damage resistance according to claim 1, wherein in the third step, the atmosphere in the annealing chamber is dry air or nitrogen, the annealing temperature is 400-2000 ℃, and the annealing time is 1-20 h.
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