CN112899778B - Method for manufacturing deep ultraviolet high-transmittance quartz crystal - Google Patents

Method for manufacturing deep ultraviolet high-transmittance quartz crystal Download PDF

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CN112899778B
CN112899778B CN202110082024.6A CN202110082024A CN112899778B CN 112899778 B CN112899778 B CN 112899778B CN 202110082024 A CN202110082024 A CN 202110082024A CN 112899778 B CN112899778 B CN 112899778B
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temperature
crystal
area
quartz crystal
crystallization
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CN112899778A (en
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张绍锋
张璇
孙志文
姜秀丽
刘巨澜
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Sinoma Intraocular Lens Research Institute Co ltd
Beijing Sinoma Synthetic Crystals Co Ltd
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BRIGHT CRYSTALS Tech Inc
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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/16—Oxides
    • C30B29/18—Quartz
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
    • C30B11/003—Heating or cooling of the melt or the crystallised material
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
    • C30B11/006—Controlling or regulating
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
    • C30B11/14—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method characterised by the seed, e.g. its crystallographic orientation

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  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
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  • Inorganic Chemistry (AREA)
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Abstract

The invention discloses a method for manufacturing a deep ultraviolet high-transmittance quartz crystal. Relates to the technical field of artificial lens. The invention comprises the following steps: selecting a stripe-free quartz crystal seed crystal to be corroded, horizontally suspending and fixing the stripe-free quartz crystal seed crystal on a crystal growth frame, and pasting a film on the upper surface of the seed crystal for shielding; preparing a high-purity quartz block raw material; the inside of the high-pressure kettle is divided into an upper area and a lower area by a throttling clapboard and is sealed by adding a mineralizer; heating; controlling and repeating an initial crystallization interface; keeping the temperature constant; and (5) cooling and taking out. The deep ultraviolet high-transmittance quartz crystal SiO manufactured by the process2The purity is more than 99.999 percent, the internal transmittance T is more than or equal to 95 percent/cm @193nm, the 193nm optical loss is reduced by more than 2/3, the optical uniformity is less than or equal to 5ppm @633nm, the difference in birefringence and the uniformity are less than or equal to 0.2 percent, and the application requirement of a deep ultraviolet optical instrument is met.

Description

Method for manufacturing deep ultraviolet high-transmittance quartz crystal
Technical Field
The invention relates to the technical field of artificial crystals, in particular to a manufacturing method of a deep ultraviolet high-transmittance quartz crystal.
Background
The quartz crystal (commonly known as crystal) has the advantages of wide light transmission range (170nm-2500nm), good optical uniformity, high transmittance and the like, is used for manufacturing optical elements such as a light transmission window, an optical wave plate, an optical rotation plate and the like, and is widely applied to the fields of high-resolution camera shooting, optical instruments, optical fiber communication and the like. Is one of the widely used optical materials.
With the development of deep ultraviolet light sources, 193nm excimer laser light sources have been widely used in the most advanced fields of current lithography systems, ophthalmic surgery, and the like. Ultraviolet quartz materials, which are one of the few optical materials capable of being applied to deep ultraviolet at present, are widely used at 193nm wavelength due to their extremely low optical loss and extremely high damage threshold, and among them, quartz crystal materials are receiving attention so as not to generate fluorescence under high power conditions.
The crystal crystallization process is a impurity removing process, and the artificial quartz crystal SiO2The purity can reach more than 99.99 percent, and the visible light internal transmittance is about 90 percent/cm. Due to the influences of factors such as short wavelength, poor transmission capability, lattice defects, low material purity and the like of the deep ultraviolet light source, the transmittance of the quartz crystal in 193nm waveband optics is only 85%/cm, and the application requirements of high-transmission and high-power laser beams in the waveband cannot be met. Taking a domestic 28nm photoetching machine illumination system as an example, the transmittance of a quartz crystal at 193nm needs to meet the requirements that T is more than or equal to 95%/cm, optical uniformity is less than or equal to 5ppm @633nm, the difference in birefringence and uniformity are less than or equal to 1%, and the application requirements of deep ultraviolet optical instruments are met. The method puts higher requirements on the purity (N is more than or equal to 99.999%) and lattice matching of the quartz crystal, and puts more strict requirements on seed crystals, equipment and processes in the growth process.
However, the quartz crystal growth is in a high-temperature high-pressure closed environment, the growth period is long, the process is invisible, and factors such as seed crystal defects, raw material purity, equipment pollution, unstable convection and the like cause that tiny defects exist in the crystal and optical loss is increased. For visible light to infrared bands, the influence of lattice distortion caused by submicron inclusions and interstitial ions on optical loss is weak (as specified in IEC 60758: 2016: OPT I-grade optical quartz crystal, the allowable existence of 10-100 μm and not more than 10/100 cm3) In the deep ultraviolet band light beam, the defects have obvious influence, and the internal transmittance is rapidly reduced from more than 95%/cm of visible light to less than 90%/cm. Therefore, the common artificial quartz crystal cannot meet the requirements of a deep ultraviolet optical system on transmittance, a laser damage threshold value and the like in a 193nm wave band.
Therefore, how to provide a manufacturing method of a deep ultraviolet high transmittance quartz crystal is a problem that needs to be solved by those skilled in the art.
Disclosure of Invention
In view of the above, the present invention provides a method for manufacturing a deep ultraviolet high transmittance quartz crystal. From the application requirement, a new quartz crystal growth process is developed through a cocrystal orientation cultivation thinking mode, and the applicable deep ultraviolet high-transmittance quartz crystal material is obtained. Specifically, the artificial quartz crystal material meeting the use requirement of a deep ultraviolet optical system is prepared by using a crystal growth mode of applying isomorphous crystal orientation to crystals, horizontally suspending and downwards unidirectionally crystallizing, filling a high-temperature calcined high-purity quartz block raw material and mineralizers containing components such as KOH + NaOH and the like, controlling a set rate to stably grow in a multiple lattice matching process at the initial stage of crystallization, and thus obtaining the artificial quartz crystal material meeting the use requirement of the deep ultraviolet optical system.
In order to achieve the purpose, the invention adopts the following technical scheme:
a manufacturing method of a deep ultraviolet high-transmittance quartz crystal comprises the following steps:
1) selecting a stripe-free quartz crystal seed crystal to be corroded, horizontally suspending and fixing the stripe-free quartz crystal seed crystal on a crystal growth frame, and pasting a film on the upper surface of the seed crystal for shielding;
2) crushing the purified quartz crystal or quartz glass lump material with the purity of not less than 99.995 percent, and preparing a high-purity quartz block-shaped raw material by washing, acid washing, alkali washing neutralization, washing, calcination and cooling;
3) the inside of the high-pressure kettle is divided into an upper area and a lower area by a throttling clapboard: a crystallization zone and a dissolution zone; high-purity quartz block raw materials are put into the dissolving area; a crystal growth frame with suspended seed crystals is placed in the crystallization area, and a mineralizer is added for sealing;
4) and (3) heating: heating the autoclave to 240-270 ℃ under the condition of 90-100% of rated power, keeping the temperature for 3.5-4.5 h, and then heating to 350-360 ℃ under the condition of 70-80% of rated power, keeping the temperature for 4-8 h;
5) controlling an initial crystallization interface: the temperature of the crystallization zone is reduced to 310-330 ℃, the temperature of the dissolution zone is kept at 350-360 ℃, and the crystallization is carried out for 20-30 hours at constant temperature; then adjusting the temperature of the crystallization area to 350-360 ℃, the temperature of the dissolution area to 370-380 ℃, and keeping the temperature of the crystallization area and the dissolution area constant for 4-8 h;
6) repeating the step 5) for 2-5 times;
7) and (3) constant temperature: then adjusting the temperature of the crystallization area to 330-350 ℃ and keeping the temperature constant, and keeping the temperature of the dissolution area constant at 370-380 ℃, wherein the temperature difference between the crystallization area and the dissolution area is kept at 20-40 ℃, the growth pressure is controlled at 100-130 MPa, and the constant temperature and the constant pressure grow for 60-150 days;
8) cooling: and after the growth period is finished, controlling the cooling rate to be 30-50 ℃/day until the temperature of the dissolution zone is lower than 100 ℃, and taking out.
Has the advantages that: step 2) washing with water to remove stains such as surface floating soil; acid washing to remove residual metal or metal oxide on the surface; alkali washing neutralization and water washing are carried out to avoid influence of residual acidic components on the pH value of the solution; residual water and crystal water in the previous process are removed through calcination, OH is reduced, and ultraviolet band-OH is weakened to excite fluorescence so as to reduce transmittance;
step 4), the solubility of the quartz crystal in a mineralizer is increased along with the temperature rise, the partial dissolution of the surface of the seed crystal is beneficial to removing the surface roughness, the lattice matching is optimized, the temperature of 240-270 ℃ is used as the inflection point of a temperature rise curve, the dissolution rate is controlled, and the penetrating defect caused by too small thickness of the seed crystal is avoided;
step 5) desalting the difference of optical uniformity of the epitaxial part and the original seed crystal area in the seed crystal cultivation and amplification process;
step 6) the uniformity difference can be reduced to the maximum extent by repeating for multiple times;
step 7) keeping constant temperature, temperature difference and pressure is beneficial to stable crystallization and uniform growth of the quartz crystal, the content of trace elements can be accurately controlled, and the breeding of defects is avoided;
and 8) taking out the solution below the boiling point of water, so that the operation safety of equipment can be guaranteed, and the internal stress caused by sudden pressure drop on the surface of the crystal when the kettle is opened is avoided, thereby generating stress stripes and influencing the uniformity and the transmittance.
Further: the window element needs to remove the + x and-x areas (the area part exceeding the original seed crystal width) of the quartz crystal for use; the wave plate element needs to be used by removing a z-direction extension region (a part exceeding the width region of the original seed crystal) of the quartz crystal, and the uniformity of birefringence is less than or equal to 0.2 percent
Preferably: cutting the seed crystal in the step (1) into a [0001] or [11-20] crystal direction, wherein the width direction is the [11-20] crystal direction or the [0001] crystal direction, and the length direction is the [10-10] crystal direction;
wherein the [0001] crystal direction of the seed cutting type is z, 1.0-1.5 mm;
the [11-20] crystal direction of the seed cutting type is x, 1.0-1.5 mm;
the crystal orientation in the width direction [11-20] is x;
the width direction [0001] crystal direction is specifically z;
the crystal orientation in the length direction [10-10] is specifically y.
Preferably: the corrosion process in the step (1) is to use saturated NH at normal temperature4F, soaking for 2-3 h.
Has the advantages that: the concentration of saturated NH4F is controllable, the corrosion rate is uniform, and the surface roughness is removed in the purpose of corrosion.
Preferably: crushing the mixture to blocks of 30-50 mm;
the acid-washing solution is HCl with the mass concentration of 10-20%, and is used at normal temperature for 30 min;
and heating the mixture to 150-550 ℃ during calcination, and keeping the temperature constant for 1-2 hours.
Preferably: the aperture ratio of the throttling partition plate in the step (3) is 7-10%;
the mineralizer comprises the following components: 0.2 to 1.2mol/L NaOH, 0 to 1mol/L KOH, 0.02 to 0.1mol/L LiOH, 0.02 to 0.1mol/L NaNO2(ii) a The solution fullness is 76-82%.
Has the advantages that: the addition of KOH can reduce the content of trace element Na in the crystal, and the radius of K is larger than that of Si, so that the trace element Na is more difficult to enter crystal lattices compared with Na; the addition of Li can reduce Al entering crystal lattices; NO2-Can strengthen Li+The desorption effect of the catalyst can reduce the content of-OH.
Preferably: and (4) setting the rated power to be 14-20 kW.
Further: the specification of the autoclave is 250mm of inner diameter.
The invention also provides the deep ultraviolet high-transmittance quartz crystal prepared by the preparation method.
The invention also provides application of the quartz crystal in preparation of crystal wave plates or detection equipment.
According to the technical scheme, compared with the prior art, the method for manufacturing the deep ultraviolet high-transmittance quartz crystal SiO disclosed by the invention has the technical effect that the deep ultraviolet high-transmittance quartz crystal SiO manufactured by the process disclosed by the invention2The purity is more than 99.999 percent, the internal transmittance T is more than or equal to 95 percent/cm @193nm, compared with the common optical quartz crystal, the 193nm optical loss is reduced by more than 2/3, and the optical uniformity is less than or equal to5ppm @633nm, and the difference and uniformity of birefringence is less than or equal to 0.2 percent, thereby meeting the application requirements of deep ultraviolet optical instruments.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a schematic view of the crystal orientation provided by the present invention.
FIG. 2 is a schematic view of a z-cut seed crystal according to the present invention.
FIG. 3 is a schematic view of an x-cut seed crystal according to the present invention.
Fig. 4 is a schematic view of the horizontal suspension of the seed crystal provided by the invention, wherein the left drawing is a side view and the right drawing is a bottom view.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment of the invention discloses a method for manufacturing a deep ultraviolet high-transmittance quartz crystal.
Example 1
A manufacturing method of a deep ultraviolet high-transmittance quartz crystal comprises the following steps:
1) selecting a stripe-free quartz crystal seed crystal to be corroded, horizontally suspending and fixing the stripe-free quartz crystal seed crystal on a crystal growth frame, and pasting a film on the upper surface of the seed crystal for shielding;
2) crushing the purified quartz crystal (the total impurity content is less than 40ppm), and preparing a high-purity quartz block raw material through water washing, acid washing, alkali washing neutralization, water washing, calcination and cooling;
3) the inside of the high-pressure kettle is divided into an upper area and a lower area by a throttling clapboard: a crystallization zone and a dissolution zone; high-purity quartz block raw materials are put into the dissolving area; placing a crystal growth frame with suspended seed crystals in the crystallization area, and adding a mineralizer for sealing;
4) and (3) heating: heating the autoclave to 240 ℃ under the condition of 90% of rated power, keeping the temperature for 3.5h, then heating to 350 ℃ under the condition of 70% of rated power, and keeping the temperature for 4 h;
5) controlling an initial crystallization interface: the temperature of the crystallization zone is reduced to 310 ℃, the temperature of the dissolution zone is kept at 350 ℃, and crystallization is carried out for 20 hours; then adjusting the temperature of the crystallization area to be raised to 350 ℃, the temperature of the dissolution area to be raised to 370 ℃, and keeping the temperature of the crystallization area and the dissolution area constant for 4 hours;
6) repeating the step 5) for 2 times;
7) and (3) constant temperature: then regulating the temperature of the crystallization area to 330 ℃ for constant temperature, and keeping the temperature of the dissolution area at 370 ℃ unchanged, wherein the temperature difference between the crystallization area and the dissolution area is kept at 20 ℃, the growth pressure is controlled at 100MPa, and the crystal grows for 60d at constant temperature and constant pressure;
8) cooling: after the growth period is finished, controlling the cooling rate to be 30 ℃/day, and taking out until the temperature of the dissolution zone is 80 ℃.
In order to further optimize the technical scheme: the cutting type of the seed crystal in the step (1) is [0001], the width direction is [11-20] crystal direction, and the length direction is [10-10] crystal direction;
wherein the [0001] crystal direction of the seed cutting type is z, 1.0 mm;
the crystal orientation in the width direction [11-20] is x;
the crystal orientation in the length direction [10-10] is specifically y.
In order to further optimize the technical scheme: the corrosion process in the step (1) is to use saturated NH at normal temperature4F, soaking for 2-3 h.
In order to further optimize the technical scheme: crushing the mixture to blocks of 30-50 mm;
the acid-washing solution is HCl with the mass concentration of 10%, and is at normal temperature for 30 min;
the temperature of the calcination is raised to 150 ℃, and the temperature is kept constant for 1 h.
In order to further optimize the technical scheme: the aperture ratio of the throttling partition plate in the step (3) is 7 percent;
the mineralizer comprises the following components: 0.2mol/L NaOH, 0.1mol/L KOH, 0.02mol/L LiOH, 0.02mol/L NaNO2(ii) a The solution was 76% full.
In order to further optimize the technical scheme: the rated power of the step (4) is 14 kW.
Example 2
A manufacturing method of a deep ultraviolet high-transmittance quartz crystal comprises the following steps:
1) selecting a stripe-free quartz crystal seed crystal to be corroded, horizontally suspending and fixing the stripe-free quartz crystal seed crystal on a crystal growth frame, and pasting a film on the upper surface of the seed crystal for shielding;
2) crushing quartz glass lump materials with the purity of not less than 99.995%, and preparing high-purity quartz lump materials through water washing, acid washing, alkali washing neutralization, water washing, calcination and cooling;
3) the inside of the high-pressure kettle is divided into an upper area and a lower area by a throttling clapboard: a crystallization zone and a dissolution zone; high-purity quartz block raw materials are put into the dissolving area; placing a crystal growth frame with suspended seed crystals in the crystallization area, and adding a mineralizer for sealing;
4) and (3) heating: heating the autoclave to 250 ℃ under the condition of 95% of rated power, keeping the temperature for 4 hours, then heating to 355 ℃ under the condition of 75% of rated power, and keeping the temperature for 6 hours;
5) controlling an initial crystallization interface: the temperature in the crystallization area is reduced to 320 ℃, the temperature in the dissolution area is kept at 355 ℃, and crystallization is carried out for 25 hours; then regulating the temperature of the crystallization area to be increased to 355 ℃, the temperature of the dissolution area to be increased to 375 ℃, and keeping the temperature of the crystallization area and the dissolution area constant for 6 hours;
6) repeating the step 5) for 4 times;
7) and (3) constant temperature: then regulating the temperature of the crystallization area to 340 ℃, keeping the temperature constant, and keeping the temperature of the dissolution area at 375 ℃, wherein the temperature difference between the crystallization area and the dissolution area is kept at 30 ℃, the growth pressure is controlled at 120MPa, and the crystal grows for 80d at constant temperature and constant pressure;
8) cooling: after the growth period is finished, controlling the cooling rate to be 40 ℃/day, and taking out until the temperature of the dissolution zone is 80 ℃.
In order to further optimize the technical scheme: cutting the seed crystal in the step (1) into a [11-20] crystal direction, wherein the width direction is the [11-20] crystal direction, and the length direction is the [10-10] crystal direction;
wherein the [11-20] crystal direction of the seed cutting type is x, 1.2 mm;
the crystal orientation in the width direction [11-20] is x;
the crystal orientation in the length direction [10-10] is specifically y.
In order to further optimize the technical scheme: the corrosion process in the step (1) is to use saturated NH at normal temperature4F, soaking for 2.5 h.
In order to further optimize the technical scheme: crushing the mixture to blocks of 30-50 mm;
the acid-washing solution is HCl with the mass concentration of 15%, and is at normal temperature for 30 min;
the temperature of the calcination is raised to 350 ℃, and the temperature is kept constant for 1.5 h.
In order to further optimize the technical scheme: the aperture ratio of the throttling partition plate in the step (3) is 8 percent;
the mineralizer comprises the following components: 0.6mol/L NaOH, 0.5mol/L KOH, 0.05mol/L LiOH, 0.025mol/L NaNO2(ii) a The solution was 78% full.
In order to further optimize the technical scheme: the rated power of the step (4) is 16 kW.
Example 3
A manufacturing method of a deep ultraviolet high-transmittance quartz crystal comprises the following steps:
1) selecting a stripe-free quartz crystal seed crystal to be corroded, horizontally suspending and fixing the stripe-free quartz crystal seed crystal on a crystal growth frame, and pasting a film on the upper surface of the seed crystal for shielding;
2) crushing the purified quartz crystal (the total impurity content is less than 40ppm), and preparing a high-purity quartz block raw material through water washing, acid washing, alkali washing neutralization, water washing, calcination and cooling;
3) the inside of the high-pressure kettle is divided into an upper area and a lower area by a throttling clapboard: a crystallization zone and a dissolution zone; high-purity quartz block raw materials are put into the dissolving area; placing a crystal growth frame with suspended seed crystals in the crystallization area, and adding a mineralizer for sealing;
4) and (3) heating: heating the autoclave to 270 ℃ under the condition of 100 percent of rated power, keeping the temperature for 4.5 hours, and then heating to 360 ℃ under the condition of 80 percent of rated power, keeping the temperature for 8 hours;
5) controlling an initial crystallization interface: the temperature of the crystallization zone is reduced to 330 ℃, the temperature of the dissolution zone is maintained at 360 ℃, and crystallization is carried out for 30 hours; then adjusting the temperature of the crystallization area to be increased to 360 ℃, the temperature of the dissolution area to be increased to 380 ℃, and keeping the temperature of the crystallization area and the dissolution area constant for 8 hours;
6) repeating the step 5) for 5 times;
7) and (3) constant temperature: then adjusting the temperature of the crystallization area to 350 ℃ and keeping the temperature constant, and the temperature of the dissolution area is not changed at 380 ℃, wherein the temperature difference between the crystallization area and the dissolution area is kept at 40 ℃, the growth pressure is controlled at 130MPa, and the crystals grow for 150d at constant temperature and constant pressure;
8) cooling: after the growth period is finished, controlling the cooling rate to be 50 ℃/day, and taking out until the temperature of the dissolution zone is 85 ℃.
In order to further optimize the technical scheme: the cutting type of the seed crystal in the step (1) is a [0001] crystal direction, the width direction is a [11-20] crystal direction, and the length direction is a [10-10] crystal direction;
wherein the [0001] crystal direction of the seed cutting type is z, 1.5 mm;
the crystal orientation in the width direction [11-20] is x;
the crystal orientation in the length direction [10-10] is specifically y.
In order to further optimize the technical scheme: the corrosion process in the step (1) is to use saturated NH at normal temperature4F, soaking for 3 hours.
In order to further optimize the technical scheme: crushing the mixture to blocks of 30-50 mm;
the acid-washing solution is HCl with the mass concentration of 20%, and is at normal temperature for 30 min;
the temperature of the calcination is raised to 550 ℃, and the temperature is kept constant for 2 hours.
In order to further optimize the technical scheme: the aperture ratio of the throttling partition plate in the step (3) is 10 percent;
the mineralizer comprises the following components: 1.2mol/L NaOH, 1mol/L KOH, 0.1mol/L LiOH, 0.1mol/L NaNO2(ii) a The solution was 82% full.
In order to further optimize the technical scheme: and (4) the rated power of the step (4) is 20 kW.
The optical quartz crystal windows prepared in the embodiments 1 to 3 are detected, and all the requirements are met:
trace element analysis quartz crystal SiO2The purity is more than 99.999 percent, the internal transmittance T is more than or equal to 95 percent/cm @193nm,the 193nm optical loss is reduced by more than 2/3, and the optical uniformity is less than or equal to 5ppm @633 nm.
Comparative test
Comparative example 1
The main differences from the present invention are in the raw material, the suspension mode, the process, e.g. cooling mode, and the mineralizing agent composition.
1) Use [0001] as]Crystal orientation (z, 1.5mm) quartz crystal seed crystal (non-strip), the seed crystal cut is that the length direction is<10-10>Crystal direction (y, 200mm), width direction [ 11-20%]Crystal orientation (x, 80mm), seed crystal is corroded (normal temperature, saturated NH)4F, 2h), and vertically suspending and fixing on a crystal growth frame.
2) A30-50 mm natural quartz block raw material (the total impurity content is 52.41ppm, wherein the Al content is 24.71ppm) is washed with water, alkali (1.5mol/L NaOH at normal temperature, pH is 7.5) and water, and then is put into a dissolving area at the lower part of an autoclave.
3) The autoclave is divided into an upper area and a lower area by a throttling clapboard (the opening rate is 6.94%): a crystallization zone and a dissolution zone. 2) raw materials are put in a dissolving area, a crystal growing frame with suspended seed crystals is put in a crystallization area, and mineralizer NaOH (1.1mol/L) + Na2CO3(0.1mol/L)+LiOH(0.05mol/L)+NaNO2(0.05mol/L), the solution fullness degree is 82%, sealing.
4) And (3) heating: the power is controlled at 90 percent of rated power (13.5kW), and the temperature inflection point is 250 ℃. The rated power of the crystallization area is 80 percent, and the temperature is raised to 335 ℃; the rated power of the dissolving zone is 90 percent, and the temperature is raised to 365 ℃.
5) And (3) constant temperature: keeping the temperature of the crystallization zone at 335 ℃, the temperature of the dissolution zone at 365 ℃, the temperature difference at 30 ℃ and the pressure at 130MPa, and growing at constant temperature and constant pressure.
6) Cooling: the growth period is 100 days, the temperature is naturally reduced, and the mixture is taken out when the bottom temperature is 80 ℃.
7) Removing + x and-x regions (the region part exceeding the original seed crystal width) of the quartz crystal to prepare an optical quartz crystal window, and analyzing the quartz crystal SiO by trace elements2The purity is 99.9961%, the internal transmittance T is 86.28%/cm @193.368nm, and the optical uniformity is 76.95ppm @633 nm.
Comparative example 2
The difference from the invention mainly lies in the change of raw materials and processes such as lack of calcination into drying, cooling mode and mineralizer composition.
1) Taking and using<0001>Quartz crystal seed crystal (non-stripe) with crystal orientation (z, 1.5mm), the seed crystal cut is a length direction of [10-10]]Crystal direction (y, 200mm), width direction [ 11-20%]Crystal orientation (x, 80mm), seed crystal is corroded (normal temperature, saturated NH)4F, 2h), horizontally suspending and fixing on a crystal growth frame, and pasting a film on the upper surface of the seed crystal for shielding.
2) A purified quartz block raw material (the total impurity content is 39.27ppm, wherein the Al content is 11.52ppm) with the thickness of 30-50 mm is subjected to water washing, acid washing, alkali washing neutralization (1.5mol/L NaOH at normal temperature), water washing (the pH value is 7.2), drying (120 ℃ and 2 hours), and then the raw material is placed in a dissolving area at the lower part of an autoclave.
3) The inside of the autoclave is divided into an upper area and a lower area by a throttling clapboard (the opening rate is 7.89%): a crystallization zone and a dissolution zone. 2) raw materials are put in a dissolving area, a crystal growing frame with suspended seed crystals is put in a crystallization area, and mineralizer NaOH (1.2mol/L) + LiOH (0.05mol/L) + NaNO2(0.05mol/L), the solution fullness degree is 80%, and sealing.
4) And (3) heating: the power is controlled at 100 percent of rated power (15kW), and the temperature inflection point is 250 ℃. The rated power of a crystallization area is 70 percent, and the temperature is raised to 335 ℃; the rated power of the dissolving zone is 90 percent, and the temperature is raised to 365 ℃.
5) And (3) constant temperature: keeping the temperature of the crystallization zone at 335 ℃, the temperature of the dissolution zone at 365 ℃, the temperature difference at 30 ℃, the pressure at 120MPa, and growing at constant temperature and constant pressure.
6) Cooling: the growth period is 100 days, the temperature is naturally reduced, and the mixture is taken out when the bottom temperature is 80 ℃.
7) Removing + x and-x regions (the region part exceeding the original seed crystal width) of the quartz crystal to prepare an optical quartz crystal window, and analyzing the quartz crystal SiO by trace elements2The purity is 99.9984%, the internal transmittance T is 96.14%/cm @193.368nm, and the optical uniformity is 34.05ppm @633 nm.
Comparative example 3
The main difference from the present invention is the raw material and 2) step process variation.
1) Taking a quartz crystal seed crystal (without stripe) with a z-crystal orientation, corroding the seed crystal (normal temperature, saturated NH)4Solution FAnd 2h), horizontally hanging and fixing the seed crystal on a crystal growth frame, and pasting a film on the upper surface of the seed crystal for shielding.
2) A30-50 mm purified quartz block raw material (total impurity content 39.27ppm, wherein the Al content is 11.52ppm) is subjected to water washing, alkali washing (1.5mol/L NaOH at normal temperature, pH 7.2) and water washing, and then is placed in a dissolution zone at the lower part of an autoclave.
3) The autoclave is divided into an upper area and a lower area by a throttling clapboard (the opening rate is 6.94%): a crystallization zone and a dissolution zone. 2) raw materials are placed in a dissolving area, a crystal growing frame with suspended seed crystals is placed in a crystallization area, and mineralizers of NaOH (0.6mol/L) + KOH (0.6mol/L) + LiOH (0.05mol/L) + NaNO are placed in a crystallization area2(0.05mol/L), the solution fullness degree is 80%, and sealing.
4) And (3) heating: the power is controlled to be 90 percent of rated power (13.5kw), the temperature is kept for 6 hours at 245 ℃, the temperature is raised to be 350 ℃ by controlling 80 percent of rated power, and the temperature is kept for 6 hours.
5) Controlling an initial crystallization interface: the temperature of the crystallization area is reduced to 315 ℃, the temperature of the dissolution area is unchanged, and crystallization is carried out for 24 hours; the temperature of the crystallization zone is increased to 350 ℃, the temperature of the dissolution zone is increased to 380 ℃, and the temperature is kept constant for 4 hours.
6) And (3) constant temperature: the temperature of the crystallization zone is controlled to be 340 ℃, the temperature of the dissolution zone is 375 ℃, the temperature difference between the crystallization zone and the dissolution zone is kept at 35 ℃, the growth pressure is controlled to be 120MPa, and the growth is carried out at constant temperature and constant pressure.
7) Cooling: the growth cycle is 100 days, the cooling rate is controlled to be 50 ℃/day, and the materials are taken out when the bottom temperature is 80 ℃.
Removing the + x and-x regions (the part exceeding the width region of the original seed crystal) of the quartz crystal to prepare a deep ultraviolet high-transmittance optical quartz crystal window, and analyzing the SiO of the quartz crystal by trace elements2The purity is 99.9979%, the internal transmittance T is 93.16%/cm @193.368nm, and the optical uniformity is 16.75ppm @633 nm.
Comparative example 4
The main difference with the present invention is the raw material and mineralizer variation.
1) Taking a Z-direction quartz crystal seed crystal (without stripes), corroding the seed crystal (at normal temperature, saturated NH4F solution, 2h), horizontally suspending and fixing the seed crystal on a crystal growth frame, and covering the upper surface of the seed crystal by a film.
2) A purified quartz block raw material (the total impurity content is 24.93ppm, wherein the Al content is 8.04ppm) with the thickness of 30-50 mm is subjected to water washing, acid washing, alkali washing neutralization (1.5mol/L NaOH at normal temperature), water washing (the pH value is 7.2), calcination (350 ℃, 2 hours) and then placed in a dissolution area at the lower part of an autoclave.
3) The autoclave is divided into an upper area and a lower area by a throttling clapboard (the opening rate is 6.94%): a crystallization zone and a dissolution zone. 2) raw materials are put in a dissolving area, a crystal growing frame with suspended seed crystals is put in a crystallization area, and mineralizer NaOH (1.0mol/L) + Na2CO3(0.1mol/L)+LiOH(0.05mol/L)+NaNO2(0.05mol/L), the solution fullness degree is 80%, and sealing.
4) And (3) heating: the power is controlled at 100 percent of rated power (15kW), the temperature is kept at 245 ℃ for 6h, the temperature is raised to 350 ℃ by controlling 70 percent of rated power, and the temperature is kept for 6 h.
5) Controlling an initial crystallization interface: the temperature of the crystallization area is reduced to 315 ℃, the temperature of the dissolution area is unchanged, and crystallization is carried out for 24 hours; the temperature of the crystallization zone is increased to 350 ℃, the temperature of the dissolution zone is increased to 380 ℃, and the temperature is kept constant for 4 hours.
6) And (3) constant temperature: the temperature of the crystallization zone is controlled to be 340 ℃, the temperature of the dissolution zone is 375 ℃, the temperature difference between the crystallization zone and the dissolution zone is kept at 35 ℃, the growth pressure is controlled to be 120MPa, and the growth is carried out at constant temperature and constant pressure.
7) Cooling: the growth cycle is 100 days, the cooling rate is controlled to be 50 ℃/day, and the materials are taken out when the bottom temperature is 80 ℃.
Removing the + x and-x regions (the part exceeding the width region of the original seed crystal) of the quartz crystal to prepare a deep ultraviolet high-transmittance optical quartz crystal window, and analyzing the SiO of the quartz crystal by trace elements2The purity is 99.9988%, the internal transmittance T is 91.04%/cm @193.368nm, and the optical uniformity is 25.87ppm @633 nm.
Comparative example 5
The difference from the invention mainly lies in the process changes of raw materials, temperature rise and interface regulation.
1) Taking a quartz crystal seed crystal (without stripe) with a z-crystal orientation, corroding the seed crystal (normal temperature, saturated NH)4And F, solution, 2h), horizontally suspending and fixing on a crystal growth frame, and covering the upper surface of the seed crystal by a film.
2) A purified quartz block raw material (the total impurity content is 24.93ppm, wherein the Al content is 8.04ppm) with the thickness of 30-50 mm is subjected to water washing, acid washing, alkali washing neutralization (1.5mol/L NaOH at normal temperature), water washing (the pH value is 7.2), calcination (350 ℃, 2 hours) and then placed in a dissolution area at the lower part of an autoclave.
3) The autoclave is divided into an upper area and a lower area by a throttling clapboard (the opening rate is 6.94%): a crystallization zone and a dissolution zone. 2) raw materials are placed in a dissolving area, a crystal growing frame with suspended seed crystals is placed in a crystallization area, and mineralizers of NaOH (1.0mol/L) + KOH (0.6mol/L) + LiOH (0.05mol/L) + NaNO are placed in a crystallization area2(0.05mol/L), the solution fullness degree is 80%, and sealing.
4) And (3) heating: the power is controlled to be 90 percent of rated power (13.5kW), the temperature is kept at 245 ℃ for 6h, the temperature is raised to 350 ℃ by controlling 75 percent of rated power, and the temperature is kept for 6 h.
5) And (3) constant temperature: adjusting the temperature of the crystallization area to 340 ℃, and keeping the temperature constant; the temperature in the dissolution zone was adjusted to 375 deg.C and maintained at a constant temperature. The temperature difference between the crystallization area and the dissolution area is kept at 35 ℃, the growth pressure is controlled at 120MPa, and the growth is carried out at constant temperature and constant pressure.
6) Cooling: the growth cycle is 100 days, the cooling rate is controlled to be 50 ℃/day, and the materials are taken out when the bottom temperature is 80 ℃.
Removing the + x and-x regions (the part exceeding the width region of the original seed crystal) of the quartz crystal to prepare a deep ultraviolet high-transmittance optical quartz crystal window, and analyzing the SiO of the quartz crystal by trace elements2The purity is 99.9995%, the internal transmittance T is 98.04%/cm @193.368nm, and the optical uniformity is 19.26ppm @633 nm.
The results show that the window performance of the optical quartz crystal prepared by the comparative example is lower than that of the optical quartz crystal prepared by the invention after the raw materials or the process steps are changed.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (7)

1. A method for manufacturing a deep ultraviolet high-transmittance quartz crystal is characterized by comprising the following steps:
1) selecting a stripe-free quartz crystal seed crystal to be corroded, horizontally suspending and fixing the stripe-free quartz crystal seed crystal on a crystal growth frame, and pasting a film on the upper surface of the seed crystal for shielding;
2) crushing the purified quartz crystal or quartz glass lump material with the purity of not less than 99.995 percent, and preparing a high-purity quartz block-shaped raw material by washing, acid washing, alkali washing neutralization, washing, calcination and cooling;
3) the inside of the high-pressure kettle is divided into an upper area and a lower area by a throttling clapboard: a crystallization zone and a dissolution zone; high-purity quartz block raw materials are put into the dissolving area; a crystal growth frame with suspended seed crystals is placed in the crystallization area, and a mineralizer is added for sealing;
4) and (3) heating: heating the autoclave to 240-270 ℃ under the condition of 90-100% of rated power, keeping the temperature for 3.5-4.5 h, and then heating to 350-360 ℃ under the condition of 70-80% of rated power, keeping the temperature for 4-8 h;
5) controlling an initial crystallization interface: the temperature of the crystallization zone is reduced to 310-330 ℃, the temperature of the dissolution zone is kept at 350-360 ℃, and the crystallization is carried out for 20-30 hours at constant temperature; then adjusting the temperature of the crystallization area to 350-360 ℃, the temperature of the dissolution area to 370-380 ℃, and keeping the temperature of the crystallization area and the dissolution area constant for 4-8 h;
6) repeating the step 5) for 2-5 times;
7) and (3) constant temperature: then adjusting the temperature of the crystallization area to 330-350 ℃ and keeping the temperature constant, and keeping the temperature of the dissolution area constant at 370-380 ℃, wherein the temperature difference between the crystallization area and the dissolution area is kept at 20-40 ℃, the growth pressure is controlled at 100-130 MPa, and the constant temperature and the constant pressure grow for 60-150 days;
8) cooling: after the growth period is finished, controlling the cooling rate to be 30-50 ℃/day until the temperature of the dissolution zone is lower than 100 ℃, and taking out;
the mineralizer comprises the following components: 0.2 to 1.2mol/L NaOH, 0 to 1mol/L LKOH, 0.02 to 0.1mol/L LiOH, 0.02～0.1mol/LNaNO2。
2. The method for manufacturing a deep ultraviolet high transmission quartz crystal according to claim 1, wherein the etching process in step 1) is performed at normal temperature by using saturated NH4F, soaking for 2-3 h.
3. The method for manufacturing a deep ultraviolet high transmission quartz crystal according to claim 1, wherein the step 2) is carried out to crush the quartz crystal into blocks of 30-50 mm;
the acid-washing solution is HCl with the mass concentration of 10-20%, and is used at normal temperature for 30 min;
and heating the calcination to 150-550 ℃, and keeping the temperature for 1-2 hours.
4. The method for manufacturing the deep ultraviolet high-transmittance quartz crystal according to claim 1, wherein the aperture ratio of the throttling partition plate in the step 3) is 7-10%; the solution fullness is 76-82%.
5. The method for manufacturing a deep ultraviolet high transmission quartz crystal according to claim 1, wherein the rated power in the step 4) is 14 to 20 kW.
6. The deep ultraviolet high transmission quartz crystal produced by the production method according to any one of claims 1 to 5.
7. Use of the quartz crystal according to claim 6 for the production of crystal waveplates or detection devices.
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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1414145A (en) * 2002-07-17 2003-04-30 刘盛浦 Growing technology of optical grade low corrusion tunnel density quartz crystal
CN101319375A (en) * 2008-05-08 2008-12-10 刘盛浦 Optical-level quartz crystal temperature-variable temperature difference method growth technique
CN101319374A (en) * 2008-05-08 2008-12-10 刘盛浦 Optical-level single-sided long quartz crystal growth technique
JP2009132592A (en) * 2007-11-03 2009-06-18 Nippon Dempa Kogyo Co Ltd Method of producing artificial quartz for optical member, artificial quartz for optical member, method of producing radiation-proof artificial quartz, and radiation-proof artificial quartz
CN103938264A (en) * 2014-04-29 2014-07-23 三明市港乐水晶电子有限公司 Method for growing optical crystal
CN106917142A (en) * 2017-03-14 2017-07-04 浙江博达光电有限公司 The growing method of high purity quartz crystal
CN109112629A (en) * 2018-09-06 2019-01-01 浙江博达光电有限公司 Single side grows quartz crystal and its growing method
CN111472041A (en) * 2019-10-18 2020-07-31 辽宁省交通高等专科学校 Piezoelectric type force sensor XY crystal group processing method
CN112176408A (en) * 2020-09-18 2021-01-05 烁光特晶科技有限公司 Low-corrosion tunnel density artificial quartz crystal seed crystal cultivation method

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1414145A (en) * 2002-07-17 2003-04-30 刘盛浦 Growing technology of optical grade low corrusion tunnel density quartz crystal
JP2009132592A (en) * 2007-11-03 2009-06-18 Nippon Dempa Kogyo Co Ltd Method of producing artificial quartz for optical member, artificial quartz for optical member, method of producing radiation-proof artificial quartz, and radiation-proof artificial quartz
CN101319375A (en) * 2008-05-08 2008-12-10 刘盛浦 Optical-level quartz crystal temperature-variable temperature difference method growth technique
CN101319374A (en) * 2008-05-08 2008-12-10 刘盛浦 Optical-level single-sided long quartz crystal growth technique
CN103938264A (en) * 2014-04-29 2014-07-23 三明市港乐水晶电子有限公司 Method for growing optical crystal
CN106917142A (en) * 2017-03-14 2017-07-04 浙江博达光电有限公司 The growing method of high purity quartz crystal
CN109112629A (en) * 2018-09-06 2019-01-01 浙江博达光电有限公司 Single side grows quartz crystal and its growing method
CN111472041A (en) * 2019-10-18 2020-07-31 辽宁省交通高等专科学校 Piezoelectric type force sensor XY crystal group processing method
CN112176408A (en) * 2020-09-18 2021-01-05 烁光特晶科技有限公司 Low-corrosion tunnel density artificial quartz crystal seed crystal cultivation method

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