CN115821387A - Method for growing ultrahigh-melting-point rare earth doped hafnium oxide optical single crystal - Google Patents
Method for growing ultrahigh-melting-point rare earth doped hafnium oxide optical single crystal Download PDFInfo
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Abstract
The invention discloses a method for growing an ultrahigh-melting-point rare earth doped hafnium oxide optical single crystal in the technical field of single crystal films, 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 → making material rod → pumping → isostatic pressing → sintering; s3, crystal growth: alignment → butt joint → neck → shoulder-expanding → constant diameter → ending; s4, crystal processing: annealing → cutting → polishing; hfO in the invention 2 The silicon dioxide serving as a high dielectric constant material can replace the silicon dioxide of a grid insulation layer of a core device of the current silicon-based integrated circuit, so that the effective capacitance thickness is minimized; praseodymium oxide and lutetium oxide are added to stabilize hafnium oxide crystals, so that the structure stability is good; because of the extremely high melting point of hafnium oxide, the use of hafnium oxide is commonThe method can not grow the hafnium oxide single crystal, and the invention adopts the 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 single crystal films, and particularly relates to a method for growing an ultrahigh-melting-point rare earth doped hafnium oxide optical single crystal.
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 urgently at present, and the preparation of the high-quality laser crystal which is high in high temperature resistance and laser damage threshold and has excellent laser performance, thermal stability and mechanical performance is the key for achieving the goal, so that the ultra-high melting point rare earth doped hafnium oxide crystal is an ideal candidate.
The hafnium oxide is an ultrahigh melting point metal oxide (the melting point of the hafnium oxide is 2800-2900 ℃), and has high hardness, good compressive property, low thermal expansion coefficient, high density, wide band gap (Eg. About.5.5-5.9eV), and high dielectric constant (Eg. About.5-5.9eV)ｋAbout 25), large refractive index: (nAbout 2.0 to 2.15); hfO within the wavelength range of 220nm to 10 mu m 2 The coating has high transmittance and low reflectivity, has good thermal property and chemical property stability, 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 transmission from near ultraviolet (220 nm) to intermediate infrared (10 mu m), is a very few optical crystal which can be applied to an ultraviolet band, and pushes the laser energy density born by an optical element to the limit with the continuous increase of the output power requirement of a high-power laser and the miniaturization of a device, hfO 2 Has high refractive index and higher laser damage resistance (LIDT), is a preferred high-refractive index material for preparing a high-power laser, is widely applied in the field of strong laser, and is often frequently used as HfO in the design and preparation of a high-power laser film 2 And low refractive index silicon dioxide (SiO) 2 ) The composition is used for preparing various optical films such as high-reflection films, antireflection films, polarizing films, optical filters 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 make hafnium oxide an ideal material for preparing scintillation crystals.
Hafnium oxide is considered to be one of the most promising novel insulating dielectrics in the field of microelectronics, silicon transistor manufacturing is approaching to the physical limit at present, when the characteristic size of a core device metal-oxide-semiconductor (MOS) transistor of a silicon-based integrated circuit is smaller than 0.1 μm, a source electrode and a drain electrode are close to each other, a gate-down leakage current and a source-drain leakage current are increased, high power consumption and high temperature problems caused by the leakage current are urgently needed to be solved, most people consider that the moore's law is difficult to maintain in the future for silicon-based electronic chips, and HfO is considered to be one of the most promising novel insulating dielectrics 2 Thin film technology becomes the key to solving this problem.
The lutetium oxide stabilized hafnium oxide crystal has good structural stability (a stable cubic structure from room temperature to a melting point), good chemical stability and thermal stability, and excellent optical performance and mechanical performance, is one of the most popular host materials in luminescent materials, has excellent growth performance, is a rare earth element doped lutetium oxide stabilized cubic hafnium oxide single crystal, and has important scientific significance and application value in 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, in order to overcome the defects of the prior art, the invention provides a method for growing an ultrahigh-melting-point rare earth doped hafnium oxide optical single crystal, aiming at solving the problemsSolving the conventional SiO in the current MOS 2 Extreme problems in the development of the/Si structure, hfO in the present invention 2 As a high dielectric constant material, the silicon dioxide (SiO) can replace the grid insulation layer of the MOS core device of the silicon-based integrated circuit 2 ) To minimize effective capacitor thickness (CET) and meet the increasing demand for integration, using HfO 2 Film replacing SiO 2 The grid electrode insulating layer is used as a grid electrode insulating layer of an MOS (metal oxide semiconductor) of a core device of a CPU (Central processing Unit) chip, and the CPU chip can effectively reduce the leakage quantity and enhance the calculation performance, thereby reducing the energy consumption; praseodymium oxide and lutetium oxide can stabilize hafnium oxide crystals, have good structural stability (a stable cubic structure from room temperature to a melting point), have good chemical stability and thermal stability, and have excellent optical performance and mechanical performance, and are one of the most hot-handable matrix materials in luminescent materials; because the melting point of the hafnium oxide is extremely high (the melting point is as high as 2800-2900 ℃), a hafnium oxide single crystal cannot be grown by using a common method.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: the invention provides a growth method of an ultrahigh-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 → making material rod → pumping → isostatic pressing → sintering;
s3, crystal growth: alignment → butt joint → neck → shoulder-expanding → constant diameter → ending;
s4, crystal processing: annealing → cutting → polishing.
Further, in the step S1, 4 high-power xenon lamps are adopted for heating temperature, and the power of each xenon lamp reaches 3KW; the xenon lamp is used for adjusting a focusing system, so that the lights of 4 xenon lamps are all focused on the central position of the same horizontal section of the material rod; the focusing system adopts a high-power water cooling fan and an exhaust fan for cooling.
Further, in S2, the preparation of the ceramic material rod includes the following processes:
weighing: weighing raw material powder with required mass by using high-purity nano hafnium oxide, lutetium oxide, ytterbium oxide, holmium oxide, terbium oxide, thulium oxide and neodymium oxide as raw materials and using an electronic balance;
mixing materials: putting the weighed raw materials into a 250ml beaker for mixing, and pouring a proper amount of alcohol;
stirring: placing the beaker on a magnetic stirrer, and stirring for 20h-30h to mix uniformly;
drying: putting the sample into a drying box, setting the temperature to be 80-90 ℃, and setting the duration to be 20-30h until the sample is completely dried;
manufacturing a material bar: grinding the dried sample into fine powder, adding the powder into a long rubber ball by a small spoon for a plurality of times, and compacting the powder by a glass rod, wherein a feeding rod is generally made into 8-15cm, and a discharging rod is generally made into 3-6 cm;
air extraction: placing the balloon filled with the charge rod into an air extracting pump, and extracting air to enable the charge rod to be more compact, wherein the duration is about 15min to 20min;
isostatic pressing: tightening the balloon opening after air pumping, putting the balloon opening into an isostatic pressing machine, and carrying out static pressure at the pressure of 60Mpa to 70Mpa for 15min to 25min;
punching: punching a hole at one end of the prepared ceramic material rod, and straightening small holes as much as possible so as to hang the material rod when crystals grow subsequently and ensure that the upper material rod and the lower material rod can be aligned;
and (3) sintering: cutting off a balloon on the surface of the ceramic material rod, taking out the material rod, drilling a small hole at the top end of the material rod, then putting the material rod into a muffle furnace, sintering at 1450-1550 ℃ for 10h to 15h, and cooling along with the furnace to obtain a compact ceramic material rod.
Further, in S2, the mass of the raw material:
98.47g to 103.90g of hafnium oxide; lutetium oxide 4.24g to 16.52g; ytterbium oxide 0.41g to 6.31g; 0.10g to 6.05g of holmium oxide; terbium oxide 0.18g to 11.41g; 0.41g to 6.17g of thulium oxide; 0.35g to 5.42g of neodymium oxide.
Further, the purity of the hafnium oxide is 99.99%; the lutetium oxide has a purity of 99.99%; the purity of the ytterbium oxide is 99.9%; the purity of the holmium oxide is 99.9%; the purity of the terbium oxide is 99.99 percent; the purity of the thulium oxide is 99.99%; the purity of the neodymium oxide is 99.99%.
Further, in S3, the crystal growth includes the following steps:
alignment: before starting the xenon lamp, a platinum wire penetrates into a small hole of the long material rod and is bound on the upper rod, the short material rod is fixed on the lower rod by a nickel wire, the upper rod and the lower rod are set to rotate in opposite directions at the same rotating speed, and the tips of the two material rods are aligned;
butt joint: selecting oxygen as a growth atmosphere, setting the flow rate to be 2L/min-6L/min, starting a xenon lamp, setting a power curve, setting the upper and lower material rods to be turned to the upper left and the lower right, setting the rotation speed to be 5 rpm-10rpm, then slowly moving the material rods to the center of a melting zone, completing butt joint after the tips of the two material rods are fully melted into a spherical shape, simultaneously moving the upper and lower rods downwards, and starting crystallization of a part of a melt leaving the melting zone;
necking: after the molten zone tends to be stable, necking down to 1.5 mm-3 mm;
shoulder expanding: after the necking process is stable, the shoulder expanding is started until the descending speeds of the upper rod and the lower rod are 5 mm/h-10 mm/h;
and (3) constant diameter: keeping the power of the growing crystal unchanged in the process of constant diameter, and paying close attention to the real-time growth condition;
ending: when the material feeding rod is left at about 5 mm-10mm, entering a final stage, reducing the descending speed of an upper rod, keeping the speed of a lower rod unchanged, reducing power, and gradually narrowing the width of a molten zone until the molten zone is disconnected; setting a power curve, and finally reducing the power to 0 according to a certain speed, and ending the crystal growth process.
Further, in S4, the crystal processing includes the following steps:
annealing: putting the crystal into a muffle furnace, and annealing at 1450-1550 ℃;
cutting: cutting the crystal into a wafer with the thickness of 1.5mm to 2.0mm by using a diamond crystal cutting machine;
polishing: and (3) performing double-sided polishing on the cut crystal wafer, wherein the thickness of the polished sample is 1.0-1.5 mm.
Furthermore, the rare earth doped hafnium oxide optical single crystal has a growth length of more than 120mm and a diameter of 2mm to 7mm.
The invention has the following beneficial effects by adopting the process:
(1) The invention provides a method for growing a rare earth doped hafnium oxide optical single crystal with an ultrahigh melting point, aiming at solving the problem of the traditional SiO in the existing MOS 2 Extreme problems in the development of the/Si structure, hfO in the present invention 2 As a high dielectric constant material, the silicon dioxide (SiO) can replace the grid insulation layer of the MOS core device of the silicon-based integrated circuit 2 ) To minimize effective capacitor thickness (CET) and meet the increasing demand for integration, using HfO 2 Film replacing SiO 2 The grid electrode insulating layer is used as a grid electrode insulating layer of an MOS (metal oxide semiconductor) of a core device of a CPU (Central processing Unit) chip, and the CPU chip can effectively reduce the leakage quantity and enhance the calculation performance, thereby reducing the energy consumption;
(2) Praseodymium oxide and lutetium oxide can stabilize hafnium oxide crystals, have good structural stability (a stable cubic structure from room temperature to a melting point), have good chemical stability and thermal stability, and have excellent optical performance and mechanical performance, and are one of the most hot-handable matrix materials in luminescent materials;
(3) The invention provides a method for growing a high-melting-point hafnium oxide optical single crystal, which has the advantages of high growth speed, short period and low energy consumption, wherein the hafnium oxide optical single crystal can not be grown by a common method due to the extremely high melting point of the hafnium oxide (the melting point is as high as 2800-2900 ℃), the invention adopts an optical floating zone method to grow a high-quality ultrahigh-melting-point rare earth doped hafnium oxide optical single crystal, the optical floating zone method adopts a section of melting zone between the grown crystal and a polycrystalline material rod, the surface tension of the melting zone is greater than the gravity, and 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 the hafnium oxide single crystal;
(5) Provides a method for uniformly doping rare earth active ions into hafnium oxide;
(6) Successfully grows the rare earth doped lutetium oxide stable hafnium oxide optical single crystal with high quality, crystal clearness and bright color;
(7) The invention adopts a high-power optical floating zone furnace to grow a series of high-quality ultrahigh-melting-point rare earth doped lutetium oxide stable hafnium oxide optical single crystals, 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 hafnium oxide single crystal co-doped with holmium, ytterbium and lutetium;
FIG. 2 is a rare earth doped hafnium oxide crystal;
FIG. 3 is a single crystal of hafnium oxide co-doped with neodymium and lutetium;
FIG. 4 is a single crystal of ytterbium and lutetium co-doped hafnium oxide;
FIG. 5 is a single crystal of hafnium oxide co-doped with erbium and lutetium;
FIG. 6 is a single crystal of erbium, ytterbium and lutetium co-doped hafnium oxide;
FIG. 7 is a single crystal of terbium and lutetium co-doped hafnium oxide;
FIG. 8 is 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 varying concentrations under excitation with light of wavelength 916 nm;
FIG. 10 is an emission spectrum of a single crystal of neodymium-doped lutetium oxide-stabilized hafnium oxide at different concentrations under excitation by light of wavelength 590 nm;
FIG. 11 is a graph of the upconversion luminescence of erbium and lutetium co-doped hafnium oxide crystals excited by infrared light having a wavelength of 980 nm;
FIG. 12 is a graph of the up-converted luminescence of erbium, ytterbium and lutetium co-doped cubic hafnium oxide crystals excited by infrared light at a wavelength of 980 nm;
fig. 13 is an upconversion luminescence of holmium, ytterbium and lutetium co-doped cubic hafnium oxide crystals excited by infrared light having a wavelength of 980 nm.
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.
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.
In the examples of the present invention, unless otherwise specified, it is understood that the raw materials and the treatment techniques are all conventional and commercially available raw materials and conventional treatment techniques in the art.
Example 1
The invention provides a method for growing a rare earth doped hafnium oxide optical single crystal with an ultrahigh melting point, 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 and 0.4025g to 6.0520g of holmium oxide, wherein lutetium oxide is used as a stabilizer of hafnium oxide.
The weighed raw materials are put into a 250ml beaker for mixing, and the growth method of 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 → making material rod → pumping → isostatic pressing → sintering;
s3, crystal growth: alignment → butt joint → neck → shoulder-expanding → constant diameter → ending;
s4, crystal processing: annealing → cutting → polishing.
Through the steps, a holmium, ytterbium and lutetium codoped hafnium oxide single crystal is grown, and is shown in figure 1.
Example 2
The invention provides a method for growing a super-high melting point rare earth doped hafnium oxide optical single crystal, 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 for mixing, and the growth method of 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 → making material rod → pumping → isostatic pressing → sintering;
s3, crystal growth: alignment → butt joint → neck → shoulder-expanding → constant diameter → ending;
s4, crystal processing: annealing → cutting → polishing.
Through the steps, rare earth doped lutetium oxide stable hafnium oxide crystals with the length of more than 120mm and the diameter of 2mm-7mm are grown, and are shown in figure 2.
Example 3
The invention provides a growth method of a super-high melting point rare earth doped hafnium oxide optical single crystal, 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 and 0.3583g to 5.4164g of neodymium oxide.
The weighed raw materials are put into a 250ml beaker for mixing, and the growth method of 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 → making material rod → pumping → isostatic pressing → sintering;
s3, crystal growth: alignment → butt joint → neck → shoulder-expanding → constant diameter → ending;
s4, crystal processing: annealing → cutting → polishing.
Through the steps, a hafnium oxide single crystal with neodymium and lutetium being codoped is grown, as shown in fig. 3.
Example 4
The invention provides a method for growing an ultrahigh-melting-point rare earth doped hafnium oxide optical single crystal, 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 and 0.4195g to 6.2950g of ytterbium oxide.
The weighed raw materials are put into a 250ml beaker for mixing, and the growth method of 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 → making material rod → pumping → isostatic pressing → sintering;
s3, crystal growth: alignment → butt joint → neck → shoulder-expanding → constant diameter → ending;
s4, crystal processing: annealing → cutting → polishing.
Through the steps, a hafnium oxide single crystal co-doped with ytterbium and lutetium is grown, as shown in fig. 4.
Example 5
The invention provides a method for growing a super-high melting point rare earth doped hafnium oxide optical single crystal, 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 and 0.4071g to 6.1196g of erbium oxide.
The weighed raw materials are put into a 250ml beaker for mixing, and the growth method of 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 → making material rod → pumping → isostatic pressing → sintering;
s3, crystal growth: alignment → butt joint → neck → shoulder-expanding → constant diameter → ending;
s4, crystal processing: annealing → cutting → polishing.
Through the steps, the hafnium oxide single crystal doped with erbium and lutetium is grown, as shown in fig. 5.
Example 6
The invention provides a method for growing a super-high melting point rare earth doped hafnium oxide optical single crystal, 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 and 0.4074g to 6.1228g of erbium oxide.
The weighed raw materials are put into a 250ml beaker for mixing, and the growth method of 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 → making material rod → pumping → isostatic pressing → sintering;
s3, crystal growth: alignment → butt joint → neck → shoulder-expanding → constant diameter → ending;
s4, crystal processing: annealing → cutting → polishing.
Through the steps, the hafnium oxide single crystal doped with erbium, ytterbium and lutetium is grown, as shown in fig. 6.
Example 7
The invention provides a method for growing a super-high melting point rare earth doped hafnium oxide optical single crystal, 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 and 0.7934g to 11.4067g of terbium oxide.
The weighed raw materials are put into a 250ml beaker for mixing, and the growth method of 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 → making material rod → pumping → isostatic pressing → sintering;
s3, crystal growth: alignment → butt joint → neck → shoulder-expanding → constant diameter → ending;
s4, crystal processing: annealing → cutting → polishing.
Through the steps, a hafnium oxide single crystal with terbium and lutetium codoped is grown, as shown in fig. 7.
Example 8
The invention provides a method for growing a super-high melting point rare earth doped hafnium oxide optical single crystal, 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 and 0.4108g to 6.1705g of thulium oxide.
The weighed raw materials are put into a 250ml beaker for mixing, and the growth method of 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 → making material rod → pumping → isostatic pressing → sintering;
s3, crystal growth: alignment → butt joint → neck → shoulder-expanding → constant diameter → ending;
s4, crystal processing: annealing → cutting → polishing.
Through the steps, a hafnium oxide single crystal with thulium and lutetium co-doped is grown, as shown in fig. 8.
Performance test
The emission spectra of the lutetium oxide stabilized hafnium oxide single crystals with different ytterbium concentrations:
measured under the excitation of light with the wavelength of 916nmEmission spectra of hafnium oxide single crystals stabilized with lutetium oxide and ytterbium ions (Yb) of different concentrations 3+ ) Respectively in the ground and excited states of 2 F 7/2 And 2 F 5/2 they can generate Stark splitting under the action of a crystal field to form a quasi-three-level system; yb in the lutetium oxide stabilized hafnium oxide single crystal by using laser with the wavelength of 916nm as a pumping source 3+ The ions are well coupled; different Yb concentrations under the excitation of light with the wavelength of 916nm 3+ The doped lutetium oxide stabilized hafnium oxide single crystal has at least two transitions, respectively 970nm and 1040nm in wavelength, wherein the emission at 1040nm has a greater intensity; in addition, Y 3+ And Yb 3+ Radius is R (Y) 3+ ) =0.1019nm and R (Yb) 3+ ) =0.0985nm, with little phase difference, yb can be realized 3+ High-concentration doping; as can be seen from the results in FIG. 9, with Yb 3+ The increase of the doping concentration increases the emission intensity of the lutetium oxide stabilized hafnium oxide crystal with the wavelength of 1040 nm.
Emission spectra of different concentrations of neodymium-doped lutetium oxide stabilized hafnium oxide single crystals:
measuring the emission spectra of the neodymium-doped lutetium oxide stabilized hafnium oxide single crystals with different concentrations under the excitation of light with the wavelength of 590 nm; neodymium ion (Nd) 3+ ) At least two transitions are provided in the emission spectrum of the lutetium oxide stabilized hafnium oxide crystal, the wavelengths are 1068nm and 1130nm, respectively, wherein the emission with the wavelength of 1068nm has greater intensity; from the results of FIG. 10, it can be seen that with Nd 2 O 3 The increase in concentration increases the emission intensity of the lutetium oxide stabilized hafnium oxide crystals.
In conclusion, the invention adopts the high-power optical floating zone furnace to grow a series of high-quality ultrahigh-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 with neodymium and lutetium co-doped; a hafnium oxide single crystal co-doped with ytterbium and lutetium; a hafnium oxide single crystal co-doped with erbium and lutetium; erbium, ytterbium and lutetium co-doped hafnium oxide single crystals; a hafnium oxide single crystal co-doped with terbium and lutetium; a single crystal of hafnium oxide co-doped with thulium and lutetium; 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.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
The present invention and its embodiments have been described above, and the description is not intended to be limiting, and what is shown in the drawings is only one embodiment of the present invention, and the practical application is not limited thereto. In summary, those skilled in the art should appreciate that they can readily use the disclosed conception and specific embodiments as a basis for designing or modifying other structures for carrying out the same purposes of the present invention without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A growth method of an ultrahigh melting point rare earth doped hafnium oxide optical single crystal 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 → mixing → stirring → drying → making material rod → pumping → isostatic pressing → sintering;
s3, crystal growth: alignment → butt joint → neck → shoulder-expanding → constant diameter → ending;
s4, crystal processing: annealing → cutting → 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, 4 high-power xenon lamps are used as the heating temperature, and the power of each xenon lamp reaches 3KW.
3. The method as claimed in claim 2, wherein the xenon lamp is adjusted to focus the light from 4 xenon lamps at the center of the same horizontal section of the rod.
4. The method for growing an ultrahigh 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 cooling fan 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 1, wherein in the step S2, the preparation of the ceramic material rod comprises the following steps:
weighing: weighing raw material powder with required mass by using high-purity nano hafnium oxide, lutetium oxide, ytterbium oxide, holmium oxide, terbium oxide, thulium oxide and neodymium oxide as raw materials and using an electronic balance;
mixing materials: putting the weighed raw materials into a 250ml beaker for mixing, and pouring a proper amount of alcohol;
stirring: placing the beaker on a magnetic stirrer, and stirring for 20h-30h to mix uniformly;
drying: putting the sample into a drying box, setting the temperature to be 80-90 ℃, and setting the duration to be 20-30h until the sample is completely dried;
manufacturing a material bar: grinding the dried sample into fine powder, adding the powder into a long rubber ball by a small spoon for a plurality of times, and compacting the powder by a glass rod, wherein a feeding rod is generally made into 8-15cm, and a discharging rod is generally made into 3-6 cm;
air extraction: placing the balloon with the material rod into an air extraction pump, and extracting air to enable the material rod to be more compact, wherein the duration is about 15min to 20min;
isostatic pressing: tightening the balloon opening after air pumping, putting the balloon opening into an isostatic pressing machine, and carrying out static pressure at the pressure of 60Mpa to 70Mpa for 15min to 25min;
punching: punching a hole at one end of the prepared ceramic material rod, and straightening small holes as much as possible so as to hang the material rod when crystals grow subsequently and ensure that the upper material rod and the lower material rod can be aligned;
and (3) sintering: cutting off a balloon on the surface of the ceramic material rod, taking out the material rod, drilling a small hole at the top end of the material rod, then putting the material rod into a muffle furnace, sintering at 1450-1550 ℃ for 10h to 15h, and cooling along with the furnace to obtain a compact ceramic material rod.
6. The method for growing an ultra-high melting point rare earth doped hafnium oxide optical single crystal according to claim 5, wherein in S2, the mass of the raw material is as follows:
98.47g to 103.90g of hafnium oxide; 4.24g to 16.52g of lutetium oxide; ytterbium oxide 0.41g to 6.31g; 0.10g to 6.05g of holmium oxide; terbium oxide 0.18g to 11.41g; 0.41g to 6.17g of thulium oxide; 0.35g to 5.42g of neodymium oxide.
7. The method for growing an ultra-high melting point rare earth doped hafnium oxide optical single crystal as claimed in claim 6, wherein the purity of the hafnium oxide is 99.99%; the purity of the lutetium oxide is 99.99 percent; the purity of the ytterbium oxide is 99.9%; the purity of the holmium oxide is 99.9%; the purity of the terbium oxide is 99.99%; the purity of the thulium oxide is 99.99%; the purity of the neodymium oxide is 99.99%.
8. The method as claimed in claim 1, wherein in step S3, the crystal growth comprises the following steps:
aligning: before starting the xenon lamp, a platinum wire penetrates into a small hole of the long material rod and is bound on the upper rod, the short material rod is fixed on the lower rod by a nickel wire, the upper rod and the lower rod are set to rotate in opposite directions at the same rotating speed, and the tips of the two material rods are aligned;
butt joint: selecting oxygen as a growth atmosphere, setting the flow rate to be 2L/min-6L/min, starting a xenon lamp, setting a power curve, turning upper and lower charge bars to be arranged at the upper left and the lower right, and setting the rotation speed to be 5 rpm-10 rpm, then slowly moving the charge bars to the center of a melting zone, completing butt joint after the tips of the two charge bars are fully melted into a sphere, simultaneously moving the upper and lower charge bars downwards, and starting crystallization of a part of a melt leaving the melting zone;
necking: after the molten zone tends to be stable, necking down to 1.5 mm-3 mm;
shoulder expanding: after the necking process is stable, the shoulder expanding is started until the descending speeds of the upper rod and the lower rod are 5 mm/h-10 mm/h;
and (3) constant diameter: keeping the power of the growing crystal unchanged in the process of constant diameter, and paying close attention to the real-time growth condition;
ending: when the material feeding rod is left at about 5 mm-10mm, entering a final stage, reducing the descending speed of an upper rod, keeping the speed of a lower rod unchanged, reducing power, and gradually narrowing the width of a molten zone until the molten zone is disconnected; setting a power curve, and finally reducing the power to 0 according to a certain speed, and ending the crystal growth process.
9. The method as claimed in claim 8, wherein in step S4, the crystal processing comprises the following steps:
annealing: putting the crystal into a muffle furnace, and annealing at 1450-1550 ℃;
cutting: cutting the crystals into round slices with the thickness of 1.5mm to 2.0mm by using a diamond crystal cutting machine;
polishing: and (3) performing double-side polishing on the cut crystal wafer, wherein the thickness of the polished sample is 1.0-1.5 mm.
10. The method for growing the ultra-high melting point rare earth-doped hafnium oxide optical single crystal as claimed in claim 1, wherein the length of the rare earth-doped hafnium oxide optical single crystal is more than 120mm, and the diameter of the rare earth-doped hafnium oxide optical single crystal is 2mm to 7mm.
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| CN108130591A (en) * | 2017-12-07 | 2018-06-08 | 同济大学 | One kind mixes dysprosium luteium oxide visible waveband laser crystal and preparation method thereof |
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| CN108130591A (en) * | 2017-12-07 | 2018-06-08 | 同济大学 | One kind mixes dysprosium luteium oxide visible waveband laser crystal and preparation method thereof |
| CN110359092A (en) * | 2019-06-24 | 2019-10-22 | 南京同溧晶体材料研究院有限公司 | A kind of scintillation crystal preparation method and application of luteium oxide matrix |
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