CN115821387B - Growth method of ultra-high melting point rare earth doped hafnium oxide optical single crystal - Google Patents
Growth method of ultra-high melting point rare earth doped hafnium oxide optical single crystal Download PDFInfo
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Abstract
The invention discloses a sheetThe method for growing the ultra-high melting point rare earth doped hafnium oxide optical single crystal belongs to the technical field of crystal thin films, and comprises the following steps: s1, increasing the heating temperature of an optical floating zone furnace; s2, preparing a ceramic material rod: weighing, mixing, stirring, drying, preparing a material rod, pumping air, isostatic pressing and sintering; s3, crystal growth: alignment, butt joint, necking, shoulder expansion, constant diameter and ending; s4, crystal processing: annealing, cutting and polishing; hfO in the present invention 2 The silicon dioxide serving as a high dielectric constant material can replace silicon dioxide serving as a gate insulating layer of a core device of the current silicon-based integrated circuit, so that the effective capacitance thickness is minimized; the addition of praseodymium oxide and lutetium oxide can stabilize hafnium oxide crystals, and has good structural stability; because the melting point of hafnium oxide is extremely high, a hafnium oxide single crystal cannot be grown by a common method, and the invention adopts an optical floating zone method to grow the high-quality ultrahigh-melting point rare earth doped hafnium oxide optical single crystal.
Description
Technical Field
The invention belongs to the technical field of monocrystalline films, and particularly relates to a method for growing an ultra-high melting point rare earth doped hafnium oxide optical monocrystal.
Background
The application of the high-energy high-power solid laser to high-energy strong laser weapons and Inertial Confinement Fusion (ICF) is a technology which is needed at present, and the preparation of high-temperature resistant, high-laser damage threshold, high-quality laser crystals with excellent laser performance, thermal stability and mechanical performance are key to achieving the aim, so that the ultra-high-melting-point rare earth doped hafnium oxide crystals are ideal candidates.
Hafnium oxide is a metal oxide with ultra-high melting point (the melting point is up to 2800-2900 ℃), and has higher hardness, better compression resistance, lower thermal expansion coefficient, higher density, wider band gap (Eg approximately 5.5-5.9 eV) and higher dielectric constantｋAbout 25), larger refractive indexn2.0-2.15); hfO within the wavelength range of 220 nm-10 [ mu ] m 2 Has very high transmittance and low reflectivity, has good stability of thermal property and chemical property, and has important application in the aspects of optics, microelectronics, control rods of atomic reactors, fast ion conductor fuel cells, oxygen sensors, refractory materials, coatings of oxygen insulating materials and the like.
Hafnium oxide (HfO) 2 ) The optical crystal has good light transmittance from near ultraviolet (220 nm) to mid infrared (10 mu m), is an optical crystal which can be applied to ultraviolet bands in very few, and pushes the laser energy density born by an optical element to the limit, hfO, along with the continuous increase of the output power requirement of a high-power laser and the miniaturization of a device 2 The high-refractive-index and high-laser-damage-resistance wide-value (LIDT) material is a first-choice high-refractive-index material for preparing high-power lasers, is widely applied in the field of strong lasers, and is commonly used for designing and preparing high-power laser films 2 And low refractive index silica (SiO 2 ) The composition is used for preparing various optical films such as a high-reflection film, an antireflection film, a polarizing film, an optical filter and the like.
Hafnium atoms have a high density, a high atomic number, a large absorption coefficient for radiation, and hafnium oxide has optical isotropy, which makes hafnium oxide an ideal material for producing scintillation crystals.
Hafnium oxide has important applications in microelectronics, hafnium oxide being considered one of the most promising new insulating dielectrics, silicon transistor fabrication has now approached physical limits, when the feature size of the core device metal-oxide-semiconductor (MOS) transistor of a silicon-based integrated circuit is less than 0.1 μm, the source and drain are very close, the drain-to-gate leakage current and the drain-to-source leakage current increase, by leakageHigh power consumption and Wen Wenti by current are urgent to be solved, and most people consider that silicon-based electronic chips are difficult to maintain moore's law in the future, while HfO 2 Thin film technology becomes critical to solve this problem.
The lutetium oxide stabilized hafnium oxide crystal has good structural stability (stable cubic structure from room temperature to melting point), good chemical stability and thermal stability, excellent optical performance and mechanical performance, is one of the most hot matrix materials in luminescent materials, and has great scientific significance and application value when being applied to the fields of optics, microelectronics, control rods of atomic reactors, fast ion conductor fuel cells, oxygen sensors, refractory materials, coatings of oxygen insulating materials and the like.
Disclosure of Invention
Aiming at the situation, the invention provides a method for growing an ultra-high melting point rare earth doped hafnium oxide optical single crystal to overcome the defects of the prior art, and aims to solve the problems of the prior SiO in the prior MOS 2 Development limit problem of Si Structure, hfO in the present invention 2 Gate-insulating silicon dioxide (SiO) as a high dielectric constant material for replacing the MOS core devices of current silicon-based integrated circuits 2 ) Realizing the minimization of the effective capacitance thickness (CET), meeting the requirement of increasing integration level by using HfO 2 Film instead of SiO 2 The CPU chip can effectively reduce the electric quantity of leakage and enhance the calculation performance as a gate insulating layer of a core device MOS of the CPU chip, thereby reducing the energy consumption; the praseodymium oxide and the lutetium oxide are added to stabilize hafnium oxide crystals, so that the hafnium oxide crystals have good structural stability (stable cubic structure from room temperature to melting point), have good chemical stability and thermal stability, have excellent optical performance and mechanical performance, and are one of the most-good hot matrix materials in luminescent materials; because the melting point of the hafnium oxide is extremely high (the melting point is up to 2800-2900 ℃), the hafnium oxide monocrystal can not be grown by a common method, the invention adopts an optical floating zone method for growing the high-quality ultrahigh-melting-point rare earth doped hafnium oxide optical monocrystal, and the optical floating zone method is generalA section of melting zone exists between the overgrown crystal and the polycrystalline material rod, the surface tension of the melting zone is larger than gravity, and the melting zone moves from bottom to top to realize crystallization.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: the invention provides a growth method of an ultra-high melting point rare earth doped hafnium oxide optical single crystal, which comprises the following steps:
s1, increasing the heating temperature of an optical floating zone furnace;
s2, preparing a ceramic material rod: weighing, mixing, stirring, drying, preparing a material rod, pumping air, isostatic pressing and sintering;
s3, crystal growth: alignment, butt joint, necking, shoulder expansion, constant diameter and ending;
s4, crystal processing: annealing, cutting and polishing.
Further, in the step S1, the heating temperature is 4 high-power xenon lamps, and the power of each xenon lamp reaches 3KW; the xenon lamp is used for adjusting a focusing system, so that the light of 4 xenon lamps is focused on the center position of the same horizontal section of the material rod; the focusing system adopts a high-power water cooler and an exhaust fan to cool.
Further, in the step S2, the preparation of the ceramic material rod includes the following steps:
weighing: taking high-purity nano hafnium oxide, lutetium oxide, ytterbium oxide, holmium oxide, terbium oxide, thulium oxide and neodymium oxide as raw materials, and weighing raw material powder with required mass by using an electronic balance;
mixing: putting the weighed raw materials into a 250ml beaker, mixing, and pouring a proper amount of alcohol;
stirring: placing the beaker on a magnetic stirrer, and stirring for 20-30 hours to uniformly mix the beaker;
and (3) drying: placing the sample into a drying box, wherein the temperature is set to 80-90 ℃ and the duration is 20-30 hours until the sample is completely dried;
and (3) manufacturing a seasoning rod: grinding the dried sample into fine powder, adding the powder into long rubber balls by using a small spoon for a small number of times, compacting the powder rancour by using a glass rod, wherein a feeding rod is generally 8 cm-15 cm, and a discharging rod is generally 3 cm-6 cm;
and (3) air extraction: placing the balloon with the material rod into an air pump, and pumping air to enable the material rod to be more compact, wherein the duration time is about 15-20 min;
isostatic pressing: tightly binding a balloon port after the air is pumped, putting the balloon port into an isostatic pressing machine, and carrying out static pressure for 15-25 min under the pressure of 60-70 mpa;
punching: punching one end of the prepared ceramic material rod, and straightening small holes as much as possible, so that the material rod is hung when crystals grow later, and the alignment of the feeding rod and the blanking rod is ensured;
sintering: cutting off the balloon on the surface of the ceramic material rod, taking out the material rod, punching a small hole at the top end of the material rod, then putting the material rod into a muffle furnace, sintering for 10-15 h at 1450-1550 ℃, and cooling along with furnace cooling to obtain the compact ceramic material rod.
Further, in S2, the mass of the raw material:
98.47-103.90 g of hafnium oxide; 4.24 g-16.52 g of lutetium oxide; 0.41-6.31 g of ytterbium oxide; 0.10 g-6.05 g of holmium oxide; terbium oxide 0.18 g-11.41 g; 0.41-6.17 g of thulium oxide; 0.35-5.42 g of neodymium oxide.
Further, the purity of the hafnium oxide is 99.99%; the purity of the lutetium oxide is 99.99%; the purity of the ytterbium oxide is 99.9%; the purity of the holmium oxide is 99.9%; the purity of terbium oxide is 99.99%; the purity of the thulium oxide is 99.99%; the purity of the neodymium oxide was 99.99%.
Further, in S3, the crystal growth includes the steps of:
alignment: before the xenon lamp is opened, a platinum wire penetrates into small holes of long material rods and is tied on an upper rod, a short material rod is fixed on a lower rod by a nickel wire, the upper rod and the lower rod are arranged in opposite directions, the rotating speeds are the same, and the tips of the two material rods are aligned;
docking: oxygen is selected as a growth atmosphere, the flow speed is 2L/min-6L/min, a xenon lamp is opened, a power curve is set, the upper and lower material bars are turned to be left and right, the rotating speed is 5 rpm-10 rpm, then the upper and lower material bars are slowly moved to the center of a melting zone, after the tips of the two material bars are fully melted into spheres, the butt joint is completed, the upper and lower bars simultaneously move downwards, and the part of the melt leaving the melting zone starts to crystallize;
necking: after the melting area tends to be stable, necking to 1.5 mm-3 mm;
shoulder expanding: after the necking process is stable, starting to expand the shoulder until the descending speed of the upper rod and the lower rod is 5 mm/h-10 mm/h;
equal diameter: the power of the grown crystal is kept unchanged in the constant diameter process, and the real-time growth condition is closely concerned;
ending: when the feeding rod is left for about 5 mm-10 mm, entering a ending stage, reducing the descending speed of an upper rod, reducing power while the descending speed of the lower rod is unchanged, and gradually narrowing the width of a melting zone until the melting zone is disconnected; setting a power curve, and ending the crystal growth process after the power is finally reduced to 0 according to a certain rate.
Further, in S4, the crystal processing includes the steps of:
annealing: putting the crystal into a muffle furnace, and annealing at 1450-1550 ℃;
cutting: cutting the crystal into a wafer with the thickness of 1.5 mm-2.0 mm by using a diamond crystal cutting machine;
polishing: and (3) polishing the two sides of the cut crystal wafer, wherein the thickness of the polished sample is 1.0 mm-1.5 mm.
Further, the length of the rare earth doped hafnium oxide optical single crystal is more than 120mm, and the diameter is 2 mm-7 mm.
The beneficial effects obtained by the process are as follows:
(1) The invention provides a method for growing an ultra-high melting point rare earth doped hafnium oxide optical monocrystal, which aims to solve the problem of traditional SiO in the prior MOS 2 Development limit problem of Si Structure, hfO in the present invention 2 Gate-insulating silicon dioxide (SiO) as a high dielectric constant material for replacing the MOS core devices of current silicon-based integrated circuits 2 ) Realizing the minimization of the effective capacitance thickness (CET), meeting the requirement of increasing integration level by using HfO 2 Film instead of SiO 2 As a gate insulating layer of a core device MOS of a CPU chip, the CPU chip can effectively reduce the electric leakage,the calculation performance is enhanced, so that the energy consumption is reduced;
(2) The praseodymium oxide and the lutetium oxide are added to stabilize hafnium oxide crystals, so that the hafnium oxide crystals have good structural stability (stable cubic structure from room temperature to melting point), have good chemical stability and thermal stability, have excellent optical performance and mechanical performance, and are one of the most-good hot matrix materials in luminescent materials;
(3) The invention provides a growth method of high-melting-point hafnium oxide optical single crystal, which has high growth speed, short period and low energy consumption, and can be used for growing a high-quality ultrahigh-melting-point rare earth doped hafnium oxide optical single crystal by adopting an optical floating zone method, wherein the high-melting-point hafnium oxide optical single crystal cannot be grown by adopting a general method due to the extremely high melting point of hafnium oxide (the melting point is up to 2800-2900 ℃), and the optical floating zone method is characterized in that a section of melting zone exists between the grown crystal and a polycrystalline material rod, and the surface tension of the melting zone is larger than gravity, so that the melting zone moves from bottom to top to realize crystallization;
(4) The invention solves the problems of crystal cracking and the like in the process of growing hafnium oxide single crystals;
(5) A method for uniformly doping rare earth activated ions in hafnium oxide is provided;
(6) Successfully grows the rare earth doped lutetium oxide stabilized hafnium oxide optical monocrystal with high quality, crystal clear and gorgeous color;
(7) The invention adopts a high-power optical floating zone furnace to grow a series of high-quality ultra-high melting point rare earth doped lutetium oxide stabilized hafnium oxide optical single crystals, and the crystals have the characteristics of high temperature resistance, high laser damage threshold, excellent laser performance, thermal stability, mechanical performance and the like, and peculiar photoelectric performance, and can be applied to laser gain crystals, up-conversion luminescent crystals, optical elements, microelectronics, control rods of atomic reactors, high-temperature structural materials, temperature sensors, oxygen sensors, insulating materials, fast ion conductor fuel cells and the like.
Drawings
FIG. 1 is a diagram of a holmium, ytterbium and lutetium co-doped hafnium oxide single crystal;
FIG. 2 is a rare earth doped hafnium oxide crystal;
FIG. 3 is a diagram of a neodymium and lutetium co-doped hafnium oxide single crystal;
FIG. 4 is a schematic illustration of ytterbium and lutetium co-doped hafnium oxide single crystals;
FIG. 5 is a diagram of erbium and lutetium co-doped hafnium oxide single crystals;
FIG. 6 is a diagram of erbium, ytterbium and lutetium co-doped hafnium oxide single crystals;
FIG. 7 is a diagram of terbium and lutetium co-doped hafnium oxide single crystals;
FIG. 8 is a diagram of a single crystal of hafnium oxide co-doped with thulium and lutetium;
FIG. 9 is an emission spectrum of ytterbium doped lutetium oxide stabilized hafnium oxide crystals of different concentrations under excitation of light with wavelength 916 nm;
FIG. 10 is an emission spectrum of a neodymium-doped lutetium oxide stabilized hafnium oxide single crystal with different concentrations under excitation of light with a wavelength of 590 nm;
FIG. 11 is an upconversion luminescence of erbium and lutetium co-doped hafnium oxide crystals under infrared excitation at wavelength 980 nm;
FIG. 12 is an upconversion luminescence of erbium, ytterbium and lutetium co-doped cubic hafnium oxide crystals under infrared excitation at wavelength 980 nm;
FIG. 13 is an upconversion luminescence of a holmium, ytterbium and lutetium co-doped cubic hafnium oxide crystal under infrared excitation at wavelength 980 nm.
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the embodiments of the invention, serve to explain the invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention; all other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the examples of the present invention, unless specifically indicated, the raw materials or treatment techniques are all conventional commercially available raw materials or conventional treatment techniques in the art.
Example 1
The invention provides a growth method of an ultra-high melting point rare earth doped hafnium oxide optical monocrystal, which takes high-purity hafnium oxide, lutetium oxide, ytterbium oxide and holmium oxide nano powder as raw materials, and uses an electronic balance to weigh the raw material powder according to the following formula: 103.1293g to 103.3872g of hafnium oxide, 4.2490g to 10.1722g of lutetium oxide, 6.2961g to 6.3118g of ytterbium oxide, 0.4025g to 6.0520g of holmium oxide, wherein lutetium oxide acts as a stabilizer for hafnium oxide.
The weighed raw materials are put into a 250ml beaker to be mixed, and the method for growing the ultra-high melting point rare earth doped hafnium oxide optical single crystal comprises the following steps:
s1, increasing the heating temperature of an optical floating zone furnace;
s2, preparing a ceramic material rod: weighing, mixing, stirring, drying, preparing a material rod, pumping air, isostatic pressing and sintering;
s3, crystal growth: alignment, butt joint, necking, shoulder expansion, constant diameter and ending;
s4, crystal processing: annealing, cutting and polishing.
Through the steps, holmium, ytterbium and lutetium co-doped hafnium oxide single crystals are grown, as shown in figure 1.
Example 2
The invention provides a growth method of an ultra-high melting point rare earth doped hafnium oxide optical monocrystal, which takes high-purity hafnium oxide, lutetium oxide, ytterbium oxide, holmium oxide, erbium oxide and terbium oxide nano powder as raw materials, and uses an electronic balance to weigh the raw material powder according to the following formula: 103.1293g to 103.3872g of hafnium oxide, 4.2490g to 10.1722g of lutetium oxide, 6.2961g to 6.3118g of ytterbium oxide, 0.1013g to 3.0153g of holmium oxide, 0.1052g to 1.0658g of erbium oxide, and 0.1860g to 1.9709g of terbium oxide.
The weighed raw materials are put into a 250ml beaker to be mixed, and the method for growing the ultra-high melting point rare earth doped hafnium oxide optical single crystal comprises the following steps:
s1, increasing the heating temperature of an optical floating zone furnace;
s2, preparing a ceramic material rod: weighing, mixing, stirring, drying, preparing a material rod, pumping air, isostatic pressing and sintering;
s3, crystal growth: alignment, butt joint, necking, shoulder expansion, constant diameter and ending;
s4, crystal processing: annealing, cutting and polishing.
Through the steps, rare earth doped lutetium oxide stable hafnium oxide crystals with the length of more than 120mm and the diameter of 2 mm-7 mm are grown, and the rare earth doped lutetium oxide stable hafnium oxide crystals are shown in figure 2.
Example 3
The invention provides a growth method of an ultra-high melting point rare earth doped hafnium oxide optical monocrystal, which takes high-purity hafnium oxide, lutetium oxide and neodymium oxide nano powder as raw materials, and uses an electronic balance to weigh the raw material powder according to the following formula: 103.1142g to 103.9075g of hafnium oxide, 10.6760g to 16.5274g of lutetium oxide, 0.3583g to 5.4164g of neodymium oxide.
The weighed raw materials are put into a 250ml beaker to be mixed, and the method for growing the ultra-high melting point rare earth doped hafnium oxide optical single crystal comprises the following steps:
s1, increasing the heating temperature of an optical floating zone furnace;
s2, preparing a ceramic material rod: weighing, mixing, stirring, drying, preparing a material rod, pumping air, isostatic pressing and sintering;
s3, crystal growth: alignment, butt joint, necking, shoulder expansion, constant diameter and ending;
s4, crystal processing: annealing, cutting and polishing.
Through the above steps, a hafnium oxide single crystal co-doped with neodymium and lutetium is grown, as shown in fig. 3.
Example 4
The invention provides a growth method of an ultra-high melting point rare earth doped hafnium oxide optical monocrystal, which takes high-purity hafnium oxide, lutetium oxide and ytterbium oxide nano powder as raw materials, and uses an electronic balance to weigh the raw material powder according to the following formula: 103.0615g to 103.1108g of hafnium oxide, 10.5942g to 16.5190g of lutetium oxide, 0.4195g to 6.2950g of ytterbium oxide.
The weighed raw materials are put into a 250ml beaker to be mixed, and the method for growing the ultra-high melting point rare earth doped hafnium oxide optical single crystal comprises the following steps:
s1, increasing the heating temperature of an optical floating zone furnace;
s2, preparing a ceramic material rod: weighing, mixing, stirring, drying, preparing a material rod, pumping air, isostatic pressing and sintering;
s3, crystal growth: alignment, butt joint, necking, shoulder expansion, constant diameter and ending;
s4, crystal processing: annealing, cutting and polishing.
Through the above steps, ytterbium and lutetium co-doped hafnium oxide single crystals were grown, as shown in fig. 4.
Example 5
The invention provides a growth method of an ultra-high melting point rare earth doped hafnium oxide optical monocrystal, which takes high-purity hafnium oxide, lutetium oxide and erbium oxide nano powder as raw materials, and uses an electronic balance to weigh the raw material powder according to the following formula: 103.0721g to 103.2698g of hafnium oxide, 10.6105g to 16.5207g of lutetium oxide, 0.4071g to 6.1196g of erbium oxide.
The weighed raw materials are put into a 250ml beaker to be mixed, and the method for growing the ultra-high melting point rare earth doped hafnium oxide optical single crystal comprises the following steps:
s1, increasing the heating temperature of an optical floating zone furnace;
s2, preparing a ceramic material rod: weighing, mixing, stirring, drying, preparing a material rod, pumping air, isostatic pressing and sintering;
s3, crystal growth: alignment, butt joint, necking, shoulder expansion, constant diameter and ending;
s4, crystal processing: annealing, cutting and polishing.
Through the above steps, a hafnium oxide single crystal co-doped with erbium and lutetium was grown, as shown in fig. 5.
Example 6
The invention provides a growth method of an ultra-high melting point rare earth doped hafnium oxide optical monocrystal, which takes high-purity hafnium oxide, lutetium oxide, ytterbium oxide and erbium oxide nano powder as raw materials, and uses an electronic balance to weigh the raw material powder according to the following formula: 103.1250g to 103.3229g of hafnium oxide, 4.2463g to 10.1718g of lutetium oxide, 6.2958g to 6.3079g of ytterbium oxide, 0.4074g to 6.1228g of erbium oxide.
The weighed raw materials are put into a 250ml beaker to be mixed, and the method for growing the ultra-high melting point rare earth doped hafnium oxide optical single crystal comprises the following steps:
s1, increasing the heating temperature of an optical floating zone furnace;
s2, preparing a ceramic material rod: weighing, mixing, stirring, drying, preparing a material rod, pumping air, isostatic pressing and sintering;
s3, crystal growth: alignment, butt joint, necking, shoulder expansion, constant diameter and ending;
s4, crystal processing: annealing, cutting and polishing.
Through the above steps, a hafnium oxide single crystal co-doped with erbium, ytterbium and lutetium is grown, as shown in fig. 6.
Example 7
The invention provides a growth method of an ultra-high melting point rare earth doped hafnium oxide optical monocrystal, which takes high-purity hafnium oxide, lutetium oxide and terbium oxide nano powder as raw materials, and uses an electronic balance to weigh the raw material powder according to the following formula: 98.4755g to 102.7393g of hafnium oxide, 10.1179g to 16.4673g of lutetium oxide, 0.7934g to 11.4067g of terbium oxide.
The weighed raw materials are put into a 250ml beaker to be mixed, and the method for growing the ultra-high melting point rare earth doped hafnium oxide optical single crystal comprises the following steps:
s1, increasing the heating temperature of an optical floating zone furnace;
s2, preparing a ceramic material rod: weighing, mixing, stirring, drying, preparing a material rod, pumping air, isostatic pressing and sintering;
s3, crystal growth: alignment, butt joint, necking, shoulder expansion, constant diameter and ending;
s4, crystal processing: annealing, cutting and polishing.
Through the above steps, terbium and lutetium co-doped hafnium oxide single crystals were grown, as shown in FIG. 7.
Example 8
The invention provides a growth method of an ultra-high melting point rare earth doped hafnium oxide optical monocrystal, which takes high-purity hafnium oxide, lutetium oxide and thulium oxide nano powder as raw materials, and uses an electronic balance to weigh the raw material powder according to the following formula: 103.0691g to 103.2237g of hafnium oxide, 10.6058g to 16.5202g of lutetium oxide, 0.4108g to 6.1705g of thulium oxide.
The weighed raw materials are put into a 250ml beaker to be mixed, and the method for growing the ultra-high melting point rare earth doped hafnium oxide optical single crystal comprises the following steps:
s1, increasing the heating temperature of an optical floating zone furnace;
s2, preparing a ceramic material rod: weighing, mixing, stirring, drying, preparing a material rod, pumping air, isostatic pressing and sintering;
s3, crystal growth: alignment, butt joint, necking, shoulder expansion, constant diameter and ending;
s4, crystal processing: annealing, cutting and polishing.
Through the above steps, a thulium and lutetium co-doped hafnium oxide single crystal is grown, as shown in fig. 8.
Performance testing
Emission spectra of ytterbium-doped lutetium oxide stabilized hafnium oxide single crystals of different concentrations:
the emission spectra of ytterbium-doped lutetium-stabilized hafnium oxide single crystals of different concentrations under excitation by light with wavelength of 916nm were measured, ytterbium ions (Yb 3+ ) The ground state and the excited state of (a) are respectively 2 F 7/2 And 2 F 5/2 they can produce Stark splitting under the action of crystal field to form quasi-three energy level system; laser with wavelength of 916nm is used as pumping source to stabilize Yb in hafnium oxide monocrystal with lutetium oxide 3+ Ions couple well; under the excitation of light with the wavelength of 916nm, yb with different concentrations 3+ The doped lutetium oxide stabilized hafnium oxide monocrystal has at least two transitions, the wavelengths are 970nm and 1040nm respectively, and the emission with the wavelength of 1040nm has larger intensity; in addition, Y 3+ And Yb 3+ Radius is R (Y) 3+ )=0.1019nm and R (Yb) 3+ ) 0.0985nm, which is not very different and can realize Yb 3+ Is a high concentration doping of (a); as can be seen from the results in FIG. 9, with Yb 3+ The increase in doping concentration increases the emission intensity of lutetium oxide stabilized hafnium oxide crystals with a wavelength of 1040 nm.
Emission spectra of different concentrations of neodymium doped lutetium oxide stabilized hafnium oxide single crystals:
the emission spectra of lutetium-doped stable hafnium oxide single crystals with different concentrations of neodymium under the excitation of light with the wavelength of 590nm are measured; neodymium ion (Nd) 3+ ) At least two transitions exist in the emission spectrum of the lutetium oxide stabilized hafnium oxide crystal, the wavelengths are 1068nm and 1130nm respectively, and the emission with the wavelength of 1068nm has larger intensity; as can be seen from the results of fig. 10, with Nd 2 O 3 The increase in concentration increases the emission intensity of lutetium oxide stabilized hafnium oxide crystals.
In summary, the invention adopts a high-power optical floating zone furnace to grow a series of high-quality ultra-high melting point rare earth doped lutetium oxide stabilized hafnium oxide optical single crystals: holmium, ytterbium and lutetium co-doped hafnium oxide single crystals; rare earth doped hafnium oxide single crystals with different diameters; a hafnium oxide single crystal co-doped with neodymium and lutetium; ytterbium and lutetium co-doped hafnium oxide single crystals; erbium and lutetium co-doped hafnium oxide single crystals; erbium, ytterbium and lutetium co-doped hafnium oxide single crystals; terbium and lutetium co-doped hafnium oxide single crystals; a hafnium oxide single crystal co-doped with thulium and lutetium; the crystal has the characteristics of high temperature resistance, high laser damage threshold, excellent laser performance, thermal stability, mechanical performance and the like, and peculiar photoelectric performance, and can be applied to laser gain crystals, up-conversion luminescence crystals, optical elements, microelectronics, control rods of atomic reactors, high-temperature structural materials, temperature sensors, oxygen sensors, insulating materials, fast ion conductor fuel cells and the like.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
The invention and its embodiments have been described above with no limitation, and the invention is illustrated in the figures of the accompanying drawings as one of its embodiments, without limitation in practice. In summary, if one of ordinary skill in the art is informed by this disclosure, a structural manner and an embodiment similar to the technical solution should not be creatively devised without departing from the gist of the present invention.
Claims (9)
1. A method for growing an ultra-high melting point rare earth doped hafnium oxide optical single crystal, which is characterized by comprising the following steps:
s1, increasing the heating temperature of an optical floating zone furnace;
s2, preparing a ceramic material rod:
weighing: taking high-purity nano hafnium oxide, lutetium oxide, ytterbium oxide, holmium oxide, terbium oxide, thulium oxide and neodymium oxide as raw materials, and weighing raw material powder with required mass by using an electronic balance;
mixing: putting the weighed raw materials into a 250ml beaker, mixing, and pouring a proper amount of alcohol;
stirring: placing the beaker on a magnetic stirrer, and stirring for 20-30 hours to uniformly mix the beaker;
and (3) drying: placing the sample into a drying box, wherein the temperature is set to 80-90 ℃ and the duration is 20-30 hours until the sample is completely dried;
and (3) manufacturing a seasoning rod: grinding the dried sample into fine powder, adding the powder into long rubber balls by using a small spoon for a small number of times, compacting the powder rancour by using a glass rod, wherein a feeding rod is generally 8 cm-15 cm, and a discharging rod is generally 3 cm-6 cm;
and (3) air extraction: placing the balloon with the material rod into an air pump, and pumping air to enable the material rod to be more compact, wherein the duration time is about 15-20 min;
isostatic pressing: tightly binding a balloon port after the air is pumped, putting the balloon port into an isostatic pressing machine, and carrying out static pressure for 15-25 min under the pressure of 60-70 mpa;
punching: punching one end of the prepared ceramic material rod, and straightening small holes as much as possible, so that the material rod is hung when crystals grow later, and the alignment of the feeding rod and the blanking rod is ensured;
sintering: cutting off a balloon on the surface of a ceramic material rod, taking out the material rod, punching a small hole at the top end of the material rod, then putting the material rod into a muffle furnace, sintering for 10-15 h at 1450-1550 ℃, and cooling along with furnace cooling to obtain a compact ceramic material rod;
s3, crystal growth: alignment, butt joint, necking, shoulder expansion, constant diameter and ending;
s4, crystal processing: annealing, cutting and polishing.
2. The method for growing an ultra-high melting point rare earth doped hafnium oxide optical single crystal according to claim 1, wherein in S1, the heating temperature is 4 high-power xenon lamps, and the power of each xenon lamp is 3KW.
3. The method for growing the ultra-high melting point rare earth doped hafnium oxide optical single crystal according to claim 2, wherein the xenon lamp is subjected to a focusing system, so that the light of the 4 xenon lamps is focused on the central position of the same horizontal section of the material rod.
4. The method for growing an ultra-high melting point rare earth doped hafnium oxide optical single crystal according to claim 3, wherein the focusing system is cooled by a high-power water cooler and an exhaust fan.
5. The method for growing an ultra-high melting point rare earth doped hafnium oxide optical single crystal according to claim 4, wherein in S2, the mass of the raw materials is as follows:
98.47-103.90 g of hafnium oxide; 4.24 g-16.52 g of lutetium oxide; 0.41-6.31 g of ytterbium oxide; 0.10 g-6.05 g of holmium oxide; terbium oxide 0.18 g-11.41 g; 0.41-6.17 g of thulium oxide; 0.35-5.42 g of neodymium oxide.
6. The method for growing an ultra-high melting point rare earth doped hafnium oxide optical single crystal according to claim 5, wherein the purity of the hafnium oxide is 99.99%; the purity of the lutetium oxide is 99.99%; the purity of the ytterbium oxide is 99.9%; the purity of the holmium oxide is 99.9%; the purity of terbium oxide is 99.99%; the purity of the thulium oxide is 99.99%; the purity of the neodymium oxide was 99.99%.
7. The method for growing an ultra-high melting point rare earth doped hafnium oxide optical single crystal according to claim 1, wherein in S3, the crystal growth comprises the steps of:
alignment: before the xenon lamp is opened, a platinum wire penetrates into small holes of long material rods and is tied on an upper rod, a short material rod is fixed on a lower rod by a nickel wire, the upper rod and the lower rod are arranged in opposite directions, the rotating speeds are the same, and the tips of the two material rods are aligned;
docking: oxygen is selected as a growth atmosphere, the flow speed is 2L/min-6L/min, a xenon lamp is opened, a power curve is set, the upper and lower material bars are turned to be left and right, the rotating speed is 5 rpm-10 rpm, then the upper and lower material bars are slowly moved to the center of a melting zone, after the tips of the two material bars are fully melted into spheres, the butt joint is completed, the upper and lower bars simultaneously move downwards, and the part of the melt leaving the melting zone starts to crystallize;
necking: after the melting area tends to be stable, necking to 1.5 mm-3 mm;
shoulder expanding: after the necking process is stable, starting to expand the shoulder until the descending speed of the upper rod and the lower rod is 5 mm/h-10 mm/h;
equal diameter: the power of the grown crystal is kept unchanged in the constant diameter process, and the real-time growth condition is closely concerned;
ending: when the feeding rod is left for about 5 mm-10 mm, entering a ending stage, reducing the descending speed of an upper rod, reducing power while the descending speed of the lower rod is unchanged, and gradually narrowing the width of a melting zone until the melting zone is disconnected; setting a power curve, and ending the crystal growth process after the power is finally reduced to 0 according to a certain rate.
8. The method for growing an ultra-high melting point rare earth doped hafnium oxide optical single crystal according to claim 1, wherein in S4, the crystal processing comprises the steps of:
annealing: putting the crystal into a muffle furnace, and annealing at 1450-1550 ℃;
cutting: cutting the crystal into a wafer with the thickness of 1.5 mm-2.0 mm by using a diamond crystal cutting machine;
polishing: and (3) polishing the two sides of the cut crystal wafer, wherein the thickness of the polished sample is 1.0 mm-1.5 mm.
9. The method for growing the ultra-high melting point rare earth doped hafnium oxide optical single crystal according to claim 1, wherein the length of the rare earth doped hafnium oxide optical single crystal is more than 120mm, and the diameter is 2 mm-7 mm.
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