CN104099665A - Yttrium lithium fluoride composite crystal and preparation method thereof - Google Patents
Yttrium lithium fluoride composite crystal and preparation method thereof Download PDFInfo
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- CN104099665A CN104099665A CN201410325773.7A CN201410325773A CN104099665A CN 104099665 A CN104099665 A CN 104099665A CN 201410325773 A CN201410325773 A CN 201410325773A CN 104099665 A CN104099665 A CN 104099665A
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Abstract
The invention discloses an yttrium lithium fluoride composite crystal and a preparation method thereof, and belongs to the technical field of laser crystal preparation. According to the method, an yttrium lithium fluoride crystal on a c-axis crystal orientation is pre-boned at the end part of a doped yttrium lithium fluoride crystal on an a-axis crystal orientation with a direct bonding technology, and a first intermediate product is obtained; the intermediate product is subjected to pressure treatment in the direction perpendicular to the bonding surface of the first intermediate product, and a second intermediate product is obtained; and finally, under the vacuum condition, the second intermediate product is subjected to hot isostatic pressure treatment, and the yttrium lithium fluoride composite crystal is obtained. The prepared yttrium lithium fluoride composite crystal doesn't have the axial matching problem and has a low heat effect, thermally induced depolarization loss of the crystal is reduced, and the output power and the beam quality of a laser are improved.
Description
Technical field
The present invention relates to laser crystals preparing technical field, particularly a kind of lithium yttrium fluoride composite crystal and preparation method thereof.
Background technology
Lithium yttrium fluoride (LiYF
4, be called for short YLF) and be a kind of good laser host crystalline material, there is good spectroscopy and laser performance, infrared to visible ray at room temperature realizing, UV-light multi-wavelength's Laser output.More particularly, lithium yttrium fluoride has anti-ultraviolet radiation and is suitable for many doping characteristics, mix wherein the doping lithium yttrium fluoride that different active ions prepare and at room temperature can launch the laser of different wave length, because nonlinear refractive index is little, can be as superpower intensity laser device vibrator and prime amplifier operation material.Yet under high power levels, the heat effect of crystal is very outstanding, therefore, obtain high-power Laser output, the heat effect of crystal in the time of need weakening laser operation as much as possible.
At present, the heat effect of crystal while conventionally utilizing bonding crystal that crystal bonding technology prepares to weaken laser operation, can be improved working-laser material thermal characteristics, reduces working-laser material temperature, be improved laser output power and efficiency by the bonding between crystal.Conventional laser crystals bonding techniques mainly comprises: melting bonding techniques, cryogenic vacuum thermal bonding technology, direct growth bonding techniques and bonding technique.
First melting bonding techniques is proposed in 1985 by Lasky, this technology main process is two steps: first, by two crystal process chemical treatments that surface finish is good, at ambient temperature two polished surfaces are pasted together, by the molecular film of surface adsorption, set up hydrogen bond and connect, complete pre-bonding.Then, by the crystal of pre-bonding is carried out to the high temperature anneal, make the arrangement of bonded interface atom that restructuring and fusion mutually occur, form firmly covalent linkage and connect, this process is exactly melting bonding.This technology is had relatively high expectations to the planeness of plane of crystal and roughness, is not suitable for the metal object device that bonding contains aluminium, is mainly used in making the bonding of III-V family material under resistant to elevated temperatures SOI material, laser crystal material and moderate temperature.
The cryogenic vacuum bonding techniques auxiliary bonding techniques of ion that is otherwise known as is a kind of of characteristics of Direct Wafer Bonded.Before crystal bonding, first use plasma activated surfaces, under vacuum and low temperature condition, just can realize higher differing materials and there is different physical propertys, such as mobility, optical absorption characteristic, thermal conductivity and mechanical characteristics etc.For a certain application, a kind of material often can not meet desired whole optical characteristics, therefore two or more materials need to be integrated.In the past few decades, people are exploring a kind of method that differing materials can be integrated always, thereby produce device with better function, performance is more superior.Based on this, various material integrated technologies in time in the past, have been there are, wherein crystal bonding technology has shown great superiority, by this technology can obtain firmly, level and smooth, optically transparent bonded interface, this interface not only can be in the integrated middle acquisition widespread use of photoelectricity, for the innovation of optical device, also has and important meaning.
The advantage of direct growth bonding is that its composite crystal intensity of preparing is high, but the method efficiency is low, and bonding face loss is large, and cost is high and technique is unstable, becomes flat rate low, at present can not be for scale operation.
The advantages such as it is simple that bonding technique has technique, and requirement on machining accuracy is low, but composite crystal prepared by this method, compound bonding area loss is excessive, and bond strength is low, is difficult to bear high power density.
For lithium yttrium fluoride composite crystal, prior art utilizes melting bonding techniques that a kind of lithium yttrium fluoride composite crystal is provided, this lithium yttrium fluoride composite crystal comprises: working medium and matrix, described matrix is bonded in respectively the two ends that described working medium is relative, wherein, working medium be a axialite to doping ylf crystal, matrix be a axialite to ylf crystal.
Contriver finds that prior art at least exists following problem:
The lithium yttrium fluoride composite crystal that prior art provides cannot guarantee that crystal orientation strictly mates, and has birefringence effect, causes the loss of lithium yttrium fluoride composite crystal, is unfavorable for improving the output efficiency of laser apparatus.
Summary of the invention
Embodiment of the present invention technical problem to be solved is, a kind of crystal orientation matching problem that do not exist is provided, and reduces lithium yttrium fluoride composite crystal of birefringence effect and preparation method thereof.Described technical scheme is as follows:
On the one hand, the embodiment of the present invention provides a kind of lithium yttrium fluoride composite crystal, comprising: working medium and matrix, and described matrix is bonded in described working medium end, described working medium be a axialite to doping ylf crystal, described matrix is the ylf crystal in c-axis crystal orientation.
Further, in described doping ylf crystal doped with rare earth element.
Particularly, described rare earth element is selected from least one in thulium, holmium, neodymium, erbium, praseodymium.
As preferably, in described doping ylf crystal, the atomicity percentage composition of described rare earth element is greater than 0at% and is less than or equal to 50at%.
On the other hand, the embodiment of the present invention provides a kind of preparation method of lithium yttrium fluoride composite crystal, comprising:
Step a, by characteristics of Direct Wafer Bonded, by the ylf crystal in c-axis crystal orientation be bonded in advance respectively a axialite to the end of doping ylf crystal, obtain the first intermediate product;
Step b, in the direction of the bonding face perpendicular to described the first intermediate product, to the processing of exerting pressure of described the first intermediate product, obtain the second intermediate product;
Step c, described the second intermediate product is carried out to hip treatment, obtain described lithium yttrium fluoride composite crystal.
Further, described method also comprises: before described step a, to the bonding face of the ylf crystal in described c-axis crystal orientation and described a axialite to the bonding face of doping ylf crystal carry out polished finish, make the smooth finish of described bonding face be more than or equal to 10-5, roughness is less than or equal to 10 dusts.
Further, described method also comprises: before described step a, and after described polished finish, to the ylf crystal in described c-axis crystal orientation and described a axialite to doping ylf crystal carry out activation treatment.
Particularly, described activation treatment is: by the ylf crystal in described c-axis crystal orientation and described a axialite to doping ylf crystal in active washing lotion, soak 30-120min, described active washing lotion comprises at least one in sherwood oil, toluene, chloroform, acetone.
Particularly, described step a comprises: use the bonding face of ylf crystal in acetone and/or two described c-axis crystal orientation of ethanol and described a axialite to the bonding face of doping ylf crystal, then pass through characteristics of Direct Wafer Bonded, make two described c-axis crystal orientation ylf crystal bonding face respectively with described a axialite to the bonding face of doping ylf crystal carry out pre-bonding, obtain described the first intermediate product.
Particularly, in described step a, in described doping ylf crystal doped with rare earth element.
Particularly, described rare earth element is selected from least one in thulium, holmium, neodymium, erbium, praseodymium.
As preferably, in described doping ylf crystal, the atomicity percentage composition of described rare earth element is greater than 0at% and is less than or equal to 50at%.
Particularly, described step b comprises: in the direction of the bonding face perpendicular to described the first intermediate product, utilize the pressure of 1-10MPa to exert pressure and process 6-24 hour described the first intermediate product, obtain described the second intermediate product.
Particularly, described step c comprises: described the second intermediate product is carried out to hip treatment, obtain described lithium yttrium fluoride composite crystal, the operating parameters of described hip treatment is: operating pressure is 5-200MPa, temperature is 480-750 ℃, and the time is 2-24 hour.
Further, described method also comprises steps d: the described lithium yttrium fluoride composite crystal that described step c is obtained carries out vacuum annealing processing.
Particularly, the operating parameters that described vacuum annealing is processed is: pressure is 0.001-10Pa, and the time is 2-72 hour, and temperature is 400-650 ℃.
The beneficial effect that the technical scheme that the embodiment of the present invention provides is brought is:
On the one hand, the embodiment of the present invention provides a kind of lithium yttrium fluoride composite crystal, by make a axialite to doping ylf crystal and the ylf crystal in c-axis crystal orientation carry out bonding, because c-axis is optical axis, so there is not axial matching problem in prepared lithium yttrium fluoride composite crystal, and there is not birefringence effect in the ylf crystal in c-axis crystal orientation, reduced the loss of lithium yttrium fluoride composite crystal, be beneficial to the output efficiency that improves laser apparatus.
On the other hand, the embodiment of the present invention also provides a kind of preparation method of lithium yttrium fluoride composite crystal, by characteristics of Direct Wafer Bonded, by the ylf crystal in c-axis crystal orientation be bonded in advance respectively a axialite to the end of doping ylf crystal, obtain the first intermediate product; Then in the direction of the bonding face perpendicular to described the first intermediate product, to the processing of exerting pressure of described the first intermediate product, obtain the second intermediate product; Finally, under vacuum condition, described the second intermediate product is carried out to hip treatment, obtain lithium yttrium fluoride composite crystal.The method that the embodiment of the present invention provides is by above-mentioned processing, and problem is thrown off in the thermal expansion easily existing while overcoming disalignment to crystal bonding, prepares and does not have crystal orientation matching problem, and reduced the lithium yttrium fluoride composite crystal of birefringence effect.The method is simple to operation, is convenient to large-scale industrial application.
Accompanying drawing explanation
In order to be illustrated more clearly in the technical scheme in the embodiment of the present invention, below the accompanying drawing of required use during embodiment is described is briefly described, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skills, do not paying under the prerequisite of creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Fig. 1 is the structural representation of the lithium yttrium fluoride composite crystal that provides of the embodiment of the present invention;
Fig. 2 is the lithium yttrium fluoride composite crystal preparation method schema that further embodiment of this invention provides;
Fig. 3 is the lithium yttrium fluoride composite crystal preparation method schema that further embodiment of this invention provides.
Wherein, Reference numeral represents respectively:
1 working medium;
2 matrix.
Embodiment
For making the object, technical solutions and advantages of the present invention clearer, below in conjunction with accompanying drawing, embodiment of the present invention is described further in detail.
First aspect, the embodiment of the present invention provides a kind of lithium yttrium fluoride composite crystal, comprising: working medium 1 and matrix 2, and matrix 2 is bonded in the end of working medium 1, working medium 1 be a axialite to doping ylf crystal, matrix 2 is the ylf crystal in c-axis crystal orientation.
The embodiment of the present invention by make a axialite to doping ylf crystal and the ylf crystal in c-axis crystal orientation carry out bonding, because c-axis is optical axis, so there is not axial matching problem in prepared lithium yttrium fluoride composite crystal, and the ylf crystal in c-axis crystal orientation has low heat effect, be beneficial to and reduce the loss of crystal thermal depolarization, and improve output rating and the beam quality of laser apparatus.
Wherein, " a axialite to " and " c-axis crystal orientation " to refer to the crystallographic axis of crystal be a axle or c-axis.
" matrix is the ylf crystal in c-axis crystal orientation " refers to pure that matrix 2 is c-axis crystal orientation, the ylf crystal of any active ion that undopes.
Be understandable that, in the lithium yttrium fluoride composite crystal that the embodiment of the present invention provides, matrix 2 can be bonded in one end of working medium 1, also can be bonded in the two ends that working medium 1 is relative.For instance, the structure of this lithium yttrium fluoride composite crystal is comprised of three parts, and wherein, two skins are matrix 2; Middle layer is working medium 1, between two skins.
The structure of the lithium yttrium fluoride composite crystal that more specifically, the embodiment of the present invention provides can be selected from column, sheet, taper or other three-dimensional arrangement.
For instance, the structure of the lithium yttrium fluoride composite crystal that the embodiment of the present invention provides can be as shown in Figure 1, and in this lithium yttrium fluoride composite crystal, matrix is positioned at the both sides of working medium 1.Due to any active ion that do not adulterate in the matrix 2 at working medium 1 two ends, matrix 2 is not subject to tension force impact, neither can produce deformation, can not rupture yet, and can play the requirement that improves beam quality and output reliability.And, undope active ion matrix 2 have a design that is beneficial to laser apparatus, the part system of laser apparatus is arranged in matrix 2, whole like this working medium 1 is when work, can all be subject to cooling system effect, effectively guarantee that working medium 1 can be because crystal heating is affected; And matrix 2 two ends have coated surface, in coated surface and laser apparatus, be subject to like this face isolation of thermal stresses maximum separately, effectively prevent that temperature sensitive rete from changing, improve resisting laser damage and the destructiveness of laser rete.Visible, matrix 2 has heat sink effect, is beneficial to the heat radiation of lithium yttrium fluoride composite crystal.
And, the lithium yttrium fluoride composite crystal that the embodiment of the present invention provides, by a axialite to doping ylf crystal and the bonding between the ylf crystal in c-axis crystal orientation (being the bonding between differing materials), reduced lattice mismatch defect, even if there is lattice mismatch, the dislocation defects of its generation is only confined to bonding battery limit (BL), and other positions can't produce lattice dislocation defect.
Further, in above-mentioned doping ylf crystal doped with rare earth element.Particularly, this rare earth element is selected from least one in thulium, holmium, neodymium, erbium, praseodymium.For example, this rare earth element is selected from thulium or holmium or neodymium or erbium or praseodymium; This rare earth element can also be selected from thulium and holmium, thulium and neodymium, erbium and praseodymium, thulium and erbium and praseodymium or thulium, holmium, neodymium, erbium, praseodymium.The different rare earth element that adulterates obtains different optical maser wavelength, for example: mix the optical maser wavelength that thulium can obtain 1.91 μ m and 1.96 μ m; Mix holmium and can obtain the optical maser wavelength of 2.05 μ m; Neodymium-doped can obtain the optical maser wavelength of 1.053 μ m and 1.047 μ m; Er-doped can obtain the optical maser wavelength of 1.7 μ m and 2.8 μ m; Mixing praseodymium can obtain as visible waveband.
Further, in above-mentioned doping ylf crystal, the atomicity percentage composition of rare earth element is greater than 0at% and is less than or equal to 50at%.For example, the atomicity percentage composition of rare earth element is 2at%, 3at%, 5at%, 7at%, 10at%, 12at%, 15at%, 18at%, 21at%, 25at%, 30at%, 35at%, 38at%, 40at%, 43at%, 46at%, 50at% etc.Particularly, for general laser crystal, didymum doping content is 0-1.5at%, and holmium and thulium doping content are 0-10at%, and erbium doping content is 0-50at%.
Second aspect, the embodiment of the present invention provides a kind of preparation method of lithium yttrium fluoride composite crystal, the schema that accompanying drawing 2 is the method.As shown in Figure 2, the method comprises:
Step 101, by characteristics of Direct Wafer Bonded, by the ylf crystal in c-axis crystal orientation be bonded in advance a axialite to the end of doping ylf crystal, obtain the first intermediate product.
Step 102, in the direction perpendicular to the bonding face of the first intermediate product in step 101, to the processing of exerting pressure of this first intermediate product, obtain the second intermediate product.
Step 103, the second intermediate product in step 102 is carried out to hip treatment, obtain the lithium yttrium fluoride composite crystal of expectation.
The method that the embodiment of the present invention provides is by above-mentioned processing, especially hip treatment, while having overcome disalignment to crystal bonding, easily problem is thrown off in the thermal expansion of existence, prepares and does not have crystal orientation matching problem, and reduced the lithium yttrium fluoride composite crystal of birefringence effect.The method is simple to operation, is convenient to large-scale industrial application.
In step 101, preferably the bonding face of the ylf crystal in c-axis crystal orientation and a axialite to the bonding face size shape of doping ylf crystal all identical.
The ylf crystal that above-mentioned " pre-bonding " refers to c-axis crystal orientation and a axialite to doping ylf crystal be in contact with one another, dependence Intermolecular Forces combines.Should " pre-bonding " realize by use characteristics of Direct Wafer Bonded.
Be understandable that, the first intermediate product refers to the lithium yttrium fluoride composite crystal that relies on Intermolecular Forces to combine; The second intermediate product is after processing through exerting pressure, in conjunction with lithium yttrium fluoride composite crystal more firmly; The lithium yttrium fluoride composite crystal of expectation is after hip treatment, realizes the lithium yttrium fluoride composite crystal of atom level mortise.
Further, the embodiment of the present invention also provides a kind of preparation method of preferred lithium yttrium fluoride composite crystal, the schema that accompanying drawing 3 is the method.As shown in Figure 3, the method comprises:
Step 201, to the bonding face of the ylf crystal in two c-axis crystal orientation and a axialite to the bonding face of doping ylf crystal carry out polished finish, make the smooth finish of each bonding face be more than or equal to 10-5, roughness is less than or equal to 10 dusts.
Wherein, above-mentioned " each bonding face " refer to the bonding face of ylf crystal in c-axis crystal orientation and a axialite to the bonding face of doping ylf crystal.
Before step 201, can by blank crystal is carried out directional cutting obtain the ylf crystal in c-axis crystal orientation and a axialite to doping ylf crystal.In directional cutting process, by x ray direction finder, realize the high orientation accuracy of crystal, a axle orientation and the c-axis of realizing crystal are directed.
Because the pattern of plane of crystal has determined the effect of Direct Bonding, when plane of crystal poor flatness, surface irregularity are high, the surface undulation between two wafers may produce cavity, rises and falls excessively even can complete pre-bonding, also just can not realize bonding.Therefore the embodiment of the present invention requires the smooth finish of each bonding face to be more than or equal to 10-5 (being one-level smooth finish), and roughness is less than or equal to 10 dusts, thereby realizes effective Direct Bonding.
Further, in order to obtain the output of different wave length laser, in doping ylf crystal, doped with rare earth element, particularly, this rare earth element is selected from least one in thulium, holmium, neodymium, erbium, praseodymium; In this doping ylf crystal, the atomicity percentage composition of rare earth element is greater than 0 and be less than or equal to 50at%.
Step 202, to the ylf crystal in above-mentioned two c-axis crystal orientation and a axialite to doping ylf crystal carry out activation treatment.
In order to improve bond strength, the embodiment of the present invention is carried out activation treatment to above-mentioned crystal.For example, this activation treatment can utilize chemical solution to form wetting ability or water repellent surface, or utilizes plasma body to carry out surface etch, to improve the surface energy of bonding face, and then improves bond strength.The embodiment of the present invention selects to utilize active washing lotion to clean, and makes the bonding face of crystal form hydrophilic surface, activates the bonding face of crystal, makes crystal bonding face form the dangling bonds of certain activity, utilizes dangling bonds to realize the atom level combination of crystal bonding face.
Particularly, above-mentioned activation treatment is: by the ylf crystal in two c-axis crystal orientation and a axialite to doping ylf crystal in active washing lotion, soak 30-120min, preferred 30min.Wherein, active washing lotion comprises at least one in sherwood oil, toluene, chloroform, acetone.
The above-mentioned active washing lotion that the embodiment of the present invention is selected not only has the effect of activation crystal bonding face, also has the effect of clean bonding face.Because the plane of crystal after polishing exists a large amount of organism (paraffin, paint etc.), metallic particles (iron, copper etc.), inorganic impurity particle (dust of absorption, gas molecule, abrasive grain etc.).These impurity form and pollute on polishing crystal surface, easily cause bonded interface to produce cavity, bubble, the equal defect of impurity.So the embodiment of the present invention not only activates each bonding face by active washing lotion, also by active washing lotion, reach the object of clean bonding face simultaneously.The bonding face of processing by active washing lotion must be without washmarking, without obviously cut and other impurity are residual.
Step 203, the bonding face of ylf crystal that uses two c-axis crystal orientation after acetone and/or ethanol activation treatment and a axialite to the bonding face of doping ylf crystal, then pass through characteristics of Direct Wafer Bonded, make two c-axis crystal orientation ylf crystal bonding face respectively with a axialite to the pre-bonding of bonding face of doping ylf crystal, obtain the first intermediate product.
Herein, the bonding face of the first intermediate product needs without obvious bubble, and the ylf crystal in c-axis crystal orientation and a axialite to doping ylf crystal be difficult for departing from.
In step 203, above-mentioned " characteristics of Direct Wafer Bonded " be optical cement bonding preferably.The use of optical cement bonding, can not only make the bonding face of ylf crystal in c-axis crystal orientation and a axialite to the bonding face of doping ylf crystal rely on Intermolecular Forces effectively to combine, and have simple to operate, the advantage of saving the energy.
Step 204, in the direction of the bonding face perpendicular to the first intermediate product, the pressure that utilizes 1-10MPa is exerted pressure and is processed 6-24 hour described the first intermediate product, obtains the second intermediate product.
In follow-up hot isostatic pressing treating processes, for prevent the ylf crystal in the c-axis crystal orientation in the lithium yttrium fluoride composite crystal after pre-bonding and a axialite to doping ylf crystal depart from, the embodiment of the present invention is in the direction of the bonding face perpendicular to the first intermediate product, utilize 1-10MPa, preferably the pressure of 5MPa is exerted pressure and is processed 6-24 hour this first intermediate product, preferably 12 hours, the second intermediate product that obtains more combining closely.
Step 205, in hot isostatic pressing stove, the second intermediate product is carried out to hip treatment, obtain lithium yttrium fluoride composite crystal, the operating parameters of this hip treatment is: operating pressure is 5-200MPa, temperature is 480-750 ℃, the time is 2-24 hour.
In order to make to realize atom level combination between the bonding face of lithium yttrium fluoride composite crystal, guarantee its bond strength, the embodiment of the present invention is at 480-750 ℃, preferably at the temperature of 580 ℃, the second intermediate product is executed to 5-200MPa, the preferably pressure of 100MPa, and lasting this pressure 2-24 hour, preferably 4 hours, carry out hip treatment.Thereby under hot conditions, make polymerization reaction take place between the crystal of bonding, change original hydrogen bond into strong covalent bond, complete powerful bonding.This atom level has good electric and photoelectric characteristics in conjunction with the device that not only makes to utilize this lithium yttrium fluoride composite crystal to prepare, enough bond strengths are also provided, this lithium yttrium fluoride composite crystal can equally be carried out cleavage and cut the mechanical processing process such as polishing with single crystalline material.
When preventing pyroprocessing, crystal bonding emaciated face is opened, or forms cavity, destroys bonding process, and the embodiment of the present invention is carried out hip treatment.Between the bonding face of the lithium yttrium fluoride composite crystal obtaining after hip treatment, without bubble, bond strength is high.
Step 206, the lithium yttrium fluoride composite crystal that step 205 is obtained carry out vacuum annealing processing.
In order to discharge the stress between the bonding face of prepared lithium yttrium fluoride composite crystal, further improve the performance of this composite crystal, the embodiment of the present invention is carried out vacuum annealing processing to prepared lithium yttrium fluoride composite crystal.
In order to improve vacuum annealing treatment effect, the operating parameters that the embodiment of the present invention is processed above-mentioned vacuum annealing is defined as: pressure is 0.001-10Pa, preferred 10Pa, and the time is 2-72 hour, preferably 24 hours, temperature was 400-650 ℃, preferably 500 ℃.
Visible, the method that the embodiment of the present invention provides is simple to operate, has reduced the integrated difficulty of crystal, and yield rate is high and cost is low, can carry out large-scale production.
Below will the present invention be described further by embodiment particularly.
Embodiment 1
Step 1, the ylf crystal of getting two c-axis crystal orientation and a axialite to doping ylf crystal, respectively the bonding face of these three crystal is carried out to polished finish, make the smooth finish of each bonding face be greater than 10-5, roughness is less than 10 dusts.Wherein, a axialite to doping ylf crystal in doped with the thulium ion of 2.0at%.
Step 2, above-mentioned three crystal after polished finish are soaked to 30min in active washing lotion.Wherein, active washing lotion is sherwood oil.
The bonding face of above-mentioned three crystal after step 3, use acetone wiping activation treatment, then pass through characteristics of Direct Wafer Bonded, make two c-axis crystal orientation ylf crystal bonding face respectively with a axialite to the relative bonding face of doping ylf crystal carry out pre-bonding, obtain the first intermediate product.
Step 4, in the direction of the bonding face perpendicular to the first intermediate product, the pressure that utilizes 5MPa is exerted pressure and is processed 12 hours described the first intermediate product, obtains the second intermediate product.
Step 5, in hot isostatic pressing stove, the second intermediate product is carried out to hip treatment, obtain lithium yttrium fluoride composite crystal, the operating parameters of this hip treatment is: operating pressure is 100MPa, temperature is 580 ℃, the time is 4 hours.
Step 6, at pressure, be 10Pa, temperature is, under the condition of 500 ℃, the lithium yttrium fluoride composite crystal in step 5 to be carried out to vacuum annealing and process 24 hours, obtains the lithium yttrium fluoride composite crystal of expectation.
Under white light or He-Ne Lasers, with the naked eye observe the bonding face position of this lithium yttrium fluoride composite crystal, result shows that prepared lithium yttrium fluoride composite crystal, without bubble, without cracking, without scattering, is beneficial to the heat effect that reduces the generation in the use procedure of lithium yttrium fluoride composite crystal.
Embodiment 2
Step 1, the ylf crystal of getting two c-axis crystal orientation and a axialite to doping ylf crystal, respectively the bonding face of these three crystal is carried out to polished finish, make the smooth finish of each bonding face reach 10-5, roughness reaches 9 dusts.Wherein, a axialite to doping ylf crystal in doped with the holmium ion of 5.0at%.
Step 2, above-mentioned three crystal after polished finish are soaked to 40min in active washing lotion.Wherein, active washing lotion comprises toluene and chloroform.
The bonding face of above-mentioned three crystal after step 3, use acetone and/or ethanol activation treatment, then pass through characteristics of Direct Wafer Bonded, make two c-axis crystal orientation ylf crystal bonding face respectively with a axialite to the relative bonding face of doping ylf crystal carry out pre-bonding, obtain the first intermediate product.
Step 4, in the direction of the bonding face perpendicular to the first intermediate product, the pressure that utilizes 3MPa is exerted pressure and is processed 15 hours described the first intermediate product, obtains the second intermediate product.
Step 5, in hot isostatic pressing stove, the second intermediate product is carried out to hip treatment, obtain lithium yttrium fluoride composite crystal, the operating parameters of this hip treatment is: operating pressure is 200MPa, temperature is 500 ℃, the time is 2 hours.
Step 6, at pressure, be 0.001Pa, temperature is, under the condition of 650 ℃, the lithium yttrium fluoride composite crystal in step 5 to be carried out to vacuum annealing and process 2 hours, obtains the lithium yttrium fluoride composite crystal of expectation.
Under white light, with the naked eye observe the bonding face position of this lithium yttrium fluoride composite crystal, result shows that prepared lithium yttrium fluoride composite crystal, without bubble, without cracking, without scattering, is beneficial to the heat effect that reduces the generation in the use procedure of lithium yttrium fluoride composite crystal.
Embodiment 3
Step 1, the ylf crystal of getting two c-axis crystal orientation and a axialite to doping ylf crystal, respectively the bonding face of these three crystal is carried out to polished finish, make the smooth finish of each bonding face to 10-5, roughness to 10 dust.Wherein, a axialite to doping ylf crystal in doped with the erbium ion of 3.0at%.
Step 2, above-mentioned three crystal after polished finish are soaked to 100min in active washing lotion.Wherein, active washing lotion is acetone.
The bonding face of above-mentioned three crystal after step 3, use acetone and ethanol activation treatment, then pass through characteristics of Direct Wafer Bonded, make two c-axis crystal orientation ylf crystal bonding face respectively with a axialite to the relative bonding face of doping ylf crystal carry out pre-bonding, obtain the first intermediate product.
Step 4, in the direction of the bonding face perpendicular to the first intermediate product, the pressure that utilizes 7MPa is exerted pressure and is processed 6 hours described the first intermediate product, obtains the second intermediate product.
Step 5, in hot isostatic pressing stove, the second intermediate product is carried out to hip treatment, obtain lithium yttrium fluoride composite crystal, the operating parameters of this hip treatment is: operating pressure is 150MPa, temperature is 480 ℃, the time is 24 hours.
Step 6, at pressure, be 3Pa, temperature is, under the condition of 400 ℃, the lithium yttrium fluoride composite crystal in step 5 to be carried out to vacuum annealing and process 72 hours, obtains the lithium yttrium fluoride composite crystal of expectation.
Under He-Ne Lasers, with the naked eye observe the bonding face position of this lithium yttrium fluoride composite crystal, result shows that prepared lithium yttrium fluoride composite crystal, without bubble, without cracking, without scattering, is beneficial to the heat effect that reduces the generation in the use procedure of lithium yttrium fluoride composite crystal.
Embodiment 4
Step 1, the ylf crystal of getting two c-axis crystal orientation and a axialite to doping ylf crystal, respectively the bonding face of these three crystal is carried out to polished finish, make the smooth finish of each bonding face to 10-5, roughness to 10 dust.Wherein, a axialite to doping ylf crystal in doped with the neodymium ion of 1.0at%.
Step 2, above-mentioned three crystal after polished finish are soaked to 30-120min in active washing lotion.Wherein, active washing lotion is the mixing solutions of toluene, chloroform and acetone.
The bonding face of above-mentioned three crystal after step 3, use ethanol activation treatment, then pass through characteristics of Direct Wafer Bonded, make two c-axis crystal orientation ylf crystal bonding face respectively with a axialite to the relative bonding face of doping ylf crystal carry out pre-bonding, obtain the first intermediate product.
Step 4, in the direction of the bonding face perpendicular to the first intermediate product, the pressure that utilizes 10MPa is exerted pressure and is processed 24 hours described the first intermediate product, obtains the second intermediate product.
Step 5, in hot isostatic pressing stove, the second intermediate product is carried out to hip treatment, obtain lithium yttrium fluoride composite crystal, the operating parameters of this hip treatment is: operating pressure is 70MPa, temperature is 600 ℃, the time is 10 hours.
Step 6, at pressure, be 5Pa, temperature is, under the condition of 550 ℃, the lithium yttrium fluoride composite crystal in step 5 to be carried out to vacuum annealing and process 32 hours, obtains the lithium yttrium fluoride composite crystal of expectation.
Under white light or He-Ne Lasers, with the naked eye observe the bonding face position of this lithium yttrium fluoride composite crystal, result shows that prepared lithium yttrium fluoride composite crystal, without bubble, without cracking, without scattering, is beneficial to the heat effect that reduces the generation in the use procedure of lithium yttrium fluoride composite crystal.
Embodiment 5
Step 1, the ylf crystal of getting two c-axis crystal orientation and a axialite to doping ylf crystal, respectively the bonding face of these three crystal is carried out to polished finish, make the smooth finish of each bonding face to 10-5, roughness to 10 dust.Wherein, a axialite to doping ylf crystal in doped with the praseodymium ion of 1.5at%.
Step 2, above-mentioned three crystal after polished finish are soaked to 120min in active washing lotion.Wherein, active washing lotion is chloroform.
The bonding face of above-mentioned three crystal after step 3, use acetone wiping activation treatment, then pass through characteristics of Direct Wafer Bonded, make two c-axis crystal orientation ylf crystal bonding face respectively with a axialite to the relative bonding face of doping ylf crystal carry out pre-bonding, obtain the first intermediate product.
Step 4, in the direction of the bonding face perpendicular to the first intermediate product, the pressure that utilizes 1MPa is exerted pressure and is processed 20 hours described the first intermediate product, obtains the second intermediate product.
Step 5, in hot isostatic pressing stove, the second intermediate product is carried out to hip treatment, obtain lithium yttrium fluoride composite crystal, the operating parameters of this hip treatment is: operating pressure is 5MPa, temperature is 750 ℃, the time is 17 hours.
Step 6, at pressure, be 7Pa, temperature is, under the condition of 490 ℃, the lithium yttrium fluoride composite crystal in step 5 to be carried out to vacuum annealing and process 12 hours, obtains the lithium yttrium fluoride composite crystal of expectation.
Under white light or He-Ne Lasers, with the naked eye observe the bonding face position of this lithium yttrium fluoride composite crystal, result shows that prepared lithium yttrium fluoride composite crystal, without bubble, without cracking, without scattering, is beneficial to the heat effect that reduces the generation in the use procedure of lithium yttrium fluoride composite crystal.
Embodiment 6
What mixing of utilizing respectively that the embodiment of the present invention 1 provides used in thulium lithium yttrium fluoride composite crystal and embodiment 1 mixes thulium ylf crystal as the working medium of laser apparatus, and that within laser resonator, arranges lithium yttrium fluoride composite crystal or same size specification and concentration mixes thulium ylf crystal, pump light source.And this laser apparatus is carried out to performance test, result is as shown in table 1.
Visible, compare and merely use the single thulium ylf crystal of mixing, the lithium yttrium fluoride composite crystal that the embodiment of the present invention provides, due to the matrix that undopes on the two ends bonding working medium (mixing thulium ylf crystal), make the output rating of prepared laser apparatus and output efficiency higher.
The foregoing is only preferred embodiment of the present invention, in order to limit the scope of the invention, within the spirit and principles in the present invention not all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. a lithium yttrium fluoride composite crystal, comprise: working medium and matrix, described matrix is bonded in the end of described working medium, it is characterized in that, described working medium be a axialite to doping ylf crystal, described matrix is the ylf crystal in c-axis crystal orientation.
2. lithium yttrium fluoride composite crystal according to claim 1, is characterized in that, in described doping ylf crystal doped with rare earth element.
3. lithium yttrium fluoride composite crystal according to claim 2, is characterized in that, described rare earth element is selected from least one in thulium, holmium, neodymium, erbium, praseodymium.
4. a preparation method for the lithium yttrium fluoride composite crystal described in claim 1-3 any one, comprising:
Step a, by characteristics of Direct Wafer Bonded, by the ylf crystal in c-axis crystal orientation be bonded in advance a axialite to the end of doping ylf crystal, obtain the first intermediate product;
Step b, in the direction of the bonding face perpendicular to described the first intermediate product, to the processing of exerting pressure of described the first intermediate product, obtain the second intermediate product;
Step c, described the second intermediate product is carried out to hip treatment, obtain described lithium yttrium fluoride composite crystal.
5. method according to claim 4, it is characterized in that, described method also comprises: before described step a, to the bonding face of the ylf crystal in described c-axis crystal orientation and described a axialite to the bonding face of doping ylf crystal carry out polished finish, make the smooth finish of described bonding face be more than or equal to 10-5, roughness is less than or equal to 10 dusts.
6. method according to claim 5, it is characterized in that, described method further comprises: before described step a, and after described polished finish, to the ylf crystal in described c-axis crystal orientation and described a axialite to doping ylf crystal carry out activation treatment;
Described activation treatment is: by the ylf crystal in described c-axis crystal orientation and described a axialite to doping ylf crystal in active washing lotion, soak 30-120min, described active washing lotion comprises at least one in sherwood oil, toluene, chloroform, acetone.
7. according to the method described in claim 4-6 any one, it is characterized in that, described step a comprises: use the bonding face of ylf crystal in acetone and/or two described c-axis crystal orientation of ethanol and described a axialite to the bonding face of doping ylf crystal, then pass through characteristics of Direct Wafer Bonded, make two described c-axis crystal orientation ylf crystal bonding face respectively with described a axialite to the bonding face of doping ylf crystal carry out pre-bonding, obtain described the first intermediate product.
8. method according to claim 4, it is characterized in that, described step b comprises: in the direction of the bonding face perpendicular to described the first intermediate product, utilize the pressure of 1-10MPa to exert pressure and process 6-24 hour described the first intermediate product, obtain described the second intermediate product.
9. method according to claim 4, it is characterized in that, described step c comprises: described the second intermediate product is carried out to hip treatment, obtain described lithium yttrium fluoride composite crystal, the operating parameters of described hip treatment is: operating pressure is 5-200MPa, temperature is 480-750 ℃, and the time is 2-24 hour.
10. method according to claim 4, is characterized in that, described method also comprises steps d: the described lithium yttrium fluoride composite crystal that described step c is obtained carries out vacuum annealing processing;
The operating parameters that described vacuum annealing is processed is: pressure is 0.001-10Pa, and the time is 2-72 hour, and temperature is 400-650 ℃.
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