CN101124163A - Method and structure for non-linear optics - Google Patents
Method and structure for non-linear optics Download PDFInfo
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- CN101124163A CN101124163A CNA2005800158048A CN200580015804A CN101124163A CN 101124163 A CN101124163 A CN 101124163A CN A2005800158048 A CNA2005800158048 A CN A2005800158048A CN 200580015804 A CN200580015804 A CN 200580015804A CN 101124163 A CN101124163 A CN 101124163A
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Abstract
Described are nonlinear optical (NLO) crystals, including aluminum-borate NLO crystals, that have low concentrations of contaminants that adversely affect the NLO crystal's optical properties, such as compounds that contain transition-metal elements and/or lanthanides, other than yttrium, lanthanum, and lutetium. Some NLO crystals with low concentrations of these contaminants are capable of second harmonic generation at very short wavelengths. Also described are embodiments of a method for making these NLO crystals. Some embodiments involve growing a single NLO crystal, such as an aluminum-borate NLO crystal, from a mixture containing a solvent that is substantially free of harmful contaminants. The described NLO crystals can be used, for example, in laser devices.
Description
Cross-reference to related applications
The application requires No. the 60/562nd, 881, U.S. Provisional Application of submitting on April 16th, 2004 and the 60/562nd, No. 626 the right of priority of submitting on April 14th, 2004, and above-mentioned two applications all are incorporated by reference into herein.
The statement of the right of the invention of carrying out about the research subsidized by federal government or exploitation
A part of the present invention is to appropriate funds under the patronage of being afforded for ECS-0114017 number at National Science Foundation to carry out.United States Government enjoys rights more of the present invention.
Tabulate by " sequence table ", form or computer program that CD is submitted to.
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Background of invention
The present invention relates generally to that some has the mixture of optical property.More particularly, for example the invention provides and comprise A
XM
(1-X)Al
3B
4O
12The particular compounds of the electromagnetic radiation wavelength that is used to select, wherein x is more than or equal to 0, and is less than or equal to 0.1, A is selected from Sc, Y, La, Yb and Lu, M is selected from Sc, Y, La, Yb and Lu.For example (but being not limited thereto), described mixture can be used for the electromagnetic radiation that wavelength is equal to or less than 350 nanometers, but should be appreciated that the present invention can be used for using widely.
The unusual part of nonlinear optics (NLO) material is that they can influence the character of light.Well-known example is for example when some material rotates the polarization vector of absorbed light, and these materials can make light polarization.If the influence to the polarization vector of absorbed light is linear, then the light frequency of this material emission is with to be absorbed light frequency identical.The NLO material can influence the polarization vector of absorbed light with non-linear form.Therefore the light frequency of nonlinear optical material emission is affected.
For example when the coherent light beam of the CF that is produced by laser apparatus is propagated the NLO crystalline of suitable orientation of the nonzero component by having secondary (secondorder) tensor of polarizability, this crystal can send the light of different frequency, thereby expands the available frequency range of this laser apparatus.The generation of this light is attributable to for example to produce (DFG) with generation (SFG) frequently, difference frequency and optical parameter is amplified (OPA) process.Use NLO crystalline device to include but not limited to that frequency increases and frequency reduces umformer, optical parametric oscillator, optical rectification device and optical switch.
Frequency in the NLO material produces (frequency generation) normally very important effect.For example, has frequencies omega
1And ω
2Two kinds of monochromatic electromagnetics propagate the light that can produce various frequencies by the NLO crystal of suitable orientation.Regulation by the mechanism of the frequency of the light generation of these two kinds of independent frequency is and generation (SFG) frequently and difference frequency generation (DFG).SFG is a kind of optical frequency of generation
3Be two kinds of incident frequencies and process, i.e. ω
3=ω
1+ ω
2In other words, SFG can be used to long wavelength's light is converted to the light (for example be converted to as seen near infrared, or from as seen being converted to ultraviolet) of shorter wavelength.Special Circumstances that produce with frequency are that second harmonic produces (SHG), wherein ω
3=2 ω
1, when the incident frequency equates, i.e. ω
1=ω
2The time, satisfy this situation.DFG is a kind of light frequency ω of generation
4Be the process of the difference of incident frequency, i.e. ω
4=ω
1-ω
2DFG can be used to the light of shorter wavelength is converted to the light (for example infrared from as seen being converted to) of longer wavelength.The Special Circumstances of DFG are to work as ω
1=ω
2The time, ω
4=0, this situation is called as optical rectification.Optical parametric oscillation (OPO) also is a kind of form of DFG, is used for producing the light of frequency adjustable.
The NLO crystal depends on a large amount of factors for the efficiency of conversion of specific end use, these factors include but not limited to: crystalline effectively non-linear (micromicron/volt [pm/V]), double refraction (Δ n, wherein n is a specific refractory power), phase-matching condition (I type, the II type, non-critical, accurate critical, or it is critical), angular range (angular acceptanceangle) (radian-centimetre), temperature range (temperature acceptance) (K-centimetre), walk-off angle (radian), specific refractory power is with variation of temperature (dn/dT), optical clear scope (nanometer) and optical damage threshold (watt/centimetre
2).Required NLO crystal should have the best of breed of the above-mentioned character that concrete application limits.
Borate crystal has constituted the inorganic NLO material of a big class that is used for various uses, and these purposes for example comprise manufacturing, medical science, hardware and device, communication and the scientific research based on laser.Kai Fa the boric acid alkali NLO crystalline example that is widely used as NLO device (particularly in high power applications) comprises beta-barium borate (BBO: β-BaB in recent years
2O
4), three lithium tetraborate (LBO:LiB
3O
5) and CLBO (CLBO:CsLi (B
3O
5)
2).Listed the character of these crystal of selecting infrared laser to ultraviolet in being suitable for producing in the table 1.
| Character | BBO | LBO | CLBO |
| D eff(micromicron/volt) | 2.2 | 0.8 | 0.9 |
| Light is propagated (nanometer) | 190-3500 | 160-2600 | 180-2750 |
| Angular range (the rice radian-centimetre) | 0.9 | 6.5 | 0.6 |
| Temperature range (K-centimetre) | 55 | 7.5 | 2.5 |
| Walk-off angle (°) | 3 | 0.6 | 1.8 |
| (1,000,000,000 watts/centimetre of damage thresholds 2) | 5 | 10 | 10 |
| Crystal growth character | Fusing or congruent | Fusing (flux) | Congruent (congruent) |
NLO material and character that table 1 is commercially available
BBO has good non-linear (about 2.2 micromicron/volts), and is transparent in the 190-3500 nanometer range, significant double refraction (phase matched institute is essential), and (50 hundred million watts/centimetre of high damage thresholds
2, 1064 nanometers, 0.1 nanosecond pulse width).But its high birefringence has produced less angular range, and this can limit efficiency of conversion and laser beam character.This crystal difficulty grows into large size, and water absorbability slightly.
LBO has light transmission in whole visible electronic wave spectral limit, fully extend to (absorption edge that is fit to is 160 nanometers) in the ultraviolet range, and have (100 hundred million watts/centimetre of high damage thresholds
2, 1064 nanometers, 0.1 nanosecond pulse width).But its intrinsic birefringence is not enough to take place phase matched, to produce far ultraviolet radiation.In addition, LBO is the heterogeneity fusing, therefore must be by the auxiliary crystal growth preparation of flux.These have limited production efficiency, cause making small-crystalline, and production cost are higher.
As if CLBO combines high non-linearity and enough double refractions, therefore can produce UV-light.Crystal also can be made into bigger size.But this crystal often always absorbs moisture often to the moisture tetchiness from air; Therefore the moisture in often must controling environment gingerly is with methanol stress and possible crystal damage.
1981, the Soviet Union reported a kind of NYAB[Nd of being called
xY
(1-x)Al
3B
4O
12] crystal.At Nd
0.2Y
0.8Al
3B
4O
12Realized in the crystal laser from 1320 nanometers be converted to 660 nanometers from frequency-doubled effect, but finding that intrinsic crystal at second harmonic absorbs has limited the practical application that transforms to the laser self-frequency-doubling of 530 nanometers from 1060 nanometers.
Some institutes of China have successfully improved crystal growing process after several years, have made the NYAB crystal with good optical properties and reasonable size.People such as Lu have developed a kind of multi-functional crystal Nd with effective laser self-frequency-doubling's ability to transform
xY
(1-x)Al
3B
4O
12With dye laser to Nd
3+Adulterated laser gain crystal carries out pumping, and the laser beam transformation of 1060 nanometers that will launch at crystals is 530 nanometers (referring to people such as Lu, Chinese Phys.Lett. the 3rd volume, Fig. 2 of the 9th phase (1986)) then.Up to now, NYAB is used as the research crystal that only can be used for visible spectrum.Recently follow the approach identical as the work of self-frequency-doubling laser gain material, just doing very little change aspect operation laser frequency and the wavelength with NYAB about the adulterated YAB of Yb.Laser produces in crystal, and forms the green glow of 520 nanometers from frequency multiplication.(referring to Dekker etc., JOSAB, the 22nd volume, the 2nd phase (2005) 378-384).In addition, its operation and historical preparation method have limited its application in visible and infra-red range.Therefore wish very much to improve the technology that is used for this class mixture that in the ultraviolet region, to bring into play optical function.
In other words, improved the optical property of this class material by the light of nonlinear optics (NLO) material.The improvement of this optical property may be owing to the derivative elementary charge displacement (polarization) as oscillating dipole causes.Oscillating dipole can make material discharge photon.When the polarization of material was linearity, the frequency of the photon of being launched was identical with the light frequency that incides material.If polarization is non-linear, then the light frequency by this material emission can be certain integral multiple of incident light frequency.For example, the net effect of frequency multiplication is that the photon that two frequencies are ω combines photon that frequency is 2 ω of generation.Therefore, the synchronization of ripple (phase matched) is propagated and to be made light generation frequency multiplication.Frequency multiplication is also referred to as second harmonic (SHG) takes place.Find that in 1961 second harmonic can take place the NLO material.Ann.Rev.Mater.Sci.，16：203-43(1986)。
Some NLO materials are well known in the prior art.For example at people's such as Pu Wang Growth AndEvaluation Of Ytterbium-Doped Yttrium Aluminum Borate as a PotentialSelf-Doubling Laser Crystal, J.OF THE OPTICAL SOC.OF AM.B, in January, 1999, disclosed YAl in the 63-69 page or leaf
3(BO
3)
4The NLO crystal, the document is incorporated by reference into herein.YAl
3(BO
3)
4The NLO crystal of NLO crystal and so on has been used to various devices.For example United States Patent (USP) the 5th, 202, described the boric acid neodymium yttrium aluminium NLO crystal that is installed in the laser aid for No. 891.United States Patent (USP) the 4th, 826 has been described for No. 283 another kind of by LiB
3O
5The NLO device that monocrystalline is made.
The NLO material is carried out recrystallization, and the bigger crystal that has uniform crystal structure with formation is known.For example people such as J.Li has disclosed by comprising K
2MoO
4Flux form YAl
3(BO
3)
4The NLO crystal.The Influence of Yb referring to people such as J.Li
3+Concentration on Yb:YAl
3(BO
3)
4, 38 CRYS.RES.TECH.890-895 (2003), the document is incorporated by reference into herein in full.Aluminium-borate NLO crystal by routine techniques growth is limited to usually under greater than the wavelength of 370 nanometers and produces or emission light.
Therefore wish very much to improve the technology that is used for optical composite.
The invention summary
The present invention relates generally to that some has the mixture of optical property.More particularly, for example the invention provides a kind of A that comprises of the electromagnetic radiation that is used for selected wavelength
XM
(1-X)Al
3B
4O
12Particular compounds.X is more than or equal to 0, and is less than or equal to 0.1, and A is selected from Sc, Y, La, Yb or Lu, and M is selected from Sc, Y, La, Yb or Lu.Only as an example, described mixture can be used for the electromagnetic radiation that wavelength is equal to or less than 350 nanometers, but will be appreciated that, the present invention has application widely.
According to an embodiment of the present invention, providing a kind of is used at the mixture that equals and be lower than the device for non-linear optical of 350 nanometers use.This mixture comprises the YAl that comprises that is used for device for non-linear optical
3B
4O
12Material.This mixture do not contain be at least 1000ppm contain molybdenum impurity.
Another embodiment according to the present invention is used for comprising Y being equal to or less than the mixture that uses under 350 nanometers, comprise the device for non-linear optical of the material that is used for device for non-linear optical
(1-X)M
XAl
3B
4O
12X is more than or equal to 0, and is less than or equal to 0.1, and M is selected from Sc, La, Yb or Lu.Described mixture do not contain be at least 1000ppm contain molybdenum impurity.
Another embodiment according to the present invention is used for comprising Yb being equal to or less than the mixture that uses under 350 nanometers, comprise the device for non-linear optical of the material that is used for device for non-linear optical
(1-X)M
xAl
3B
4O
12X is more than or equal to 0, and is less than or equal to 0.1, and M is selected from Sc, Y, La or Lu.Described mixture do not contain be at least 1000ppm contain molybdenum impurity.
Another embodiment according to the present invention is used for comprising Lu being equal to or less than the mixture that uses under 350 nanometers, comprise the device for non-linear optical of the material that is used for device for non-linear optical
(1-X)M
XAl
3B
4O
12X is more than or equal to 0, and is less than or equal to 0.1, and M is selected from Sc, Y, Yb or La.Described mixture do not contain be at least 1000ppm contain molybdenum impurity.
Another embodiment according to the present invention is used for comprising Sc being equal to or less than the mixture that uses under 350 nanometers, comprise the device for non-linear optical of the material that is used for device for non-linear optical
(1-X)M
XAl
3B
4O
12X is more than or equal to 0, and is less than or equal to 0.1, and M is selected from Y, La, Yb or Lu.Described mixture do not contain be at least 1000ppm contain molybdenum impurity.
Another embodiment according to the present invention is used for comprising A being equal to or less than the mixture that uses under 350 nanometers, comprise the device for non-linear optical of the material that is used for device for non-linear optical
XM
(1-X)Al
3B
4O
12X is more than or equal to 0, and is less than or equal to 0.1, and A is selected from Sc, Y, La, Yb or Lu, and M is selected from Sc, Y, La, Yb or Lu.Described mixture do not contain be at least 1000ppm contain molybdenum impurity.
Another embodiment according to the present invention is used for comprising in the preparation method who equals and be lower than the mixture of the device for non-linear optical that uses under 350 nanometers multiple material is provided.Described multiple material comprises and contains lanthanum compound, and the described lanthanum compound that contains can decomposition form lanthanum trioxide at least in heating.In addition, this method comprises at least gets up to form mixture based on the information relevant with predetermined proportion with multiple material mixing, begins crystallisation process in mixture, forms crystal, and crystal is shifted out from mixture, and described crystal comprises lanthanum.
Another embodiment according to the present invention is used for comprising in the preparation method who equals and be lower than the mixture of the device for non-linear optical that uses under 350 nanometers multiple material is provided.Described multiple material comprises and contains yttrium compound, and the described yttrium compound that contains can decomposition form yttrium oxide at least in heating.In addition, this method comprises at least gets up to form mixture based on the information relevant with predetermined proportion with multiple material mixing, begins crystallisation process in mixture, forms crystal, and crystal is shifted out from mixture, and described crystal comprises yttrium.
Many advantages that are better than routine techniques have been obtained by method of the present invention.For example some embodiments of the present invention provide novel preparation method, and this method has been got rid of the pollutent that the borate magnesium calcium carbonate can't be operated in UV spectrum.In addition, develop a kind of preparation method, thereby can form crystal rapidly by enough chemical formulations of the present invention.These methods make it possible to make very big monocrystalline of the present invention, and this big monocrystalline can't obtain in ordinary method up to now.Also developed a kind of preparation method, the starting mixt that this method is used is when being heated to melt temperature, and its volatility is less than the volatility of starting mixt in the ordinary method.
Some embodiment according to the present invention, this paper have been described nonlinear optics (NLO) crystal that wherein causes the compound concentration of negative impact to reduce with respect to known NLO crystal to the crystalline optical property.In conventional NLO crystal, particularly conventional aluminium-borate NLO crystal, comprise these undesirable compounds of various content.Some crystal disclosed herein can be used to the wavelength of conversion incident light (for example light of laser apparatus emission).Some crystal for example disclosed herein can be transformed to the input laser beam of first wavelength outgoing laser beam of second wavelength, certain round values that described second wavelength is an incident wavelength, approximately less than 300 nanometers, usually approximately less than 250 nanometers, usually more preferably from about less than 175 nanometers.
Crystalline volumes more as herein described are approximately greater than 0.1 millimeter
3, usually approximately greater than 1 millimeter
3, even more preferably from about greater than 5 millimeters
3These crystal comprise main raw, also can comprise the secondary materials that one or more are different from main raw.Comprise in the embodiment of secondary materials at some, with respect to the NLO crystal of routine, any can influence with required wavelength produce and/or the concentration of the secondary materials of the light of emission all very low.For example, influence is reducible less than 100 ppm by weight with the concentration of the secondary materials of the light of required wavelength generation and/or emission, usually approximately less than 50 ppm by weight, more preferably from about less than 10 ppm by weight.In other embodiments, described crystal does not contain the secondary materials that can influence with the light of required wavelength generation and/or emission substantially.Influence produces with required wavelength and/or the secondary materials of the light of emission can be for example to comprise the transition metal except that yttrium, lanthanum and lutetium and/or the compound of lanthanon.But the some of them secondary materials, for example tungsten is included in the useful solvent, and the light that produces with certain required wavelength and/or launch is produced limited influence.In some embodiments, can influence in the described crystal produce with required wavelength and/or the content of radiative secondary materials except that Tungstenic compound approximately less than 100 ppm by weight, usually approximately less than 50 ppm by weight, more preferably from about less than 10 ppm by weight.
Described aluminium-borate NLO crystal includes but not limited to have aluminium-borate NLO crystal, for example YAl of the chemical structure that comprises yttrium, lutetium or its combination
3(BO
3)
4, LuAl
3(BO
3)
4And Y
(1-x)Lu
xAl
3(BO
3)
4, wherein x is the integer greater than 0.These materials are when crystallizing to the crystalline size that can be used for optical applications, they are new mixtures, with respect to known crystal, wherein influence with required wavelength and produce and/or the undesirable pollutent of the light of emission is reduced significantly or has been removed basically.
This paper has also described preparation NLO crystal, particularly aluminium-borate NLO crystalline method embodiment.Some embodiments comprise provides precursor material and solvent or main raw and solvent, described solvent does not contain any material that can influence with the light of required wavelength generation and/or emission substantially, this method also comprises makes described main raw crystallization, forms not contain the crystal of any meeting influence with the material of the light of required wavelength generation and/or emission substantially.For example, described solvent and can not contain transition metal and lanthanon except that yttrium, lanthanum and lutetium substantially by the crystal of growing in the solvent.Again for example, described solvent and can not contain molybdenum substantially by the crystal of growing in the solvent.
The embodiment of described method can comprise described precursor material or main raw and solvent, forms mixture, and add crystal seed in mixture.Described crystal seed (for example crystal main raw) may mainly be made up of main raw, can be suspended in this mixture.In some embodiments, the main raw recrystallization is comprised cooling mixture, and from mixture, shift out crystal.Cooling off this mixture can be included in and mixture is cooled to second temperature that is lower than the mixture fusing point from first temperature that is equal to or higher than the mixture fusing point in one section growth time, described growth time is enough to grow the crystal with the desired size that is applicable to effective use, and this growth time is usually approximately greater than 10 hours.Approximately greater than in for some time of 2 hours, this mixture can cool off less than 2 ℃/hour cooling gradient approximately in described growth time.In some embodiments, described second temperature can be the temperature of for example hanging down 5-100 ℃ approximately than mixture fusing point.
Can be aluminium-borate NLO crystal specifically with the embodiment of the described method various NLO crystal of growing, for example have aluminium-borate NLO crystal, for example YAl of the chemical structure that comprises yttrium, lutetium or its combination
3(BO
3)
4, LuAl
3(BO
3)
4And Y
(1-X)Lu
xAl
3(BO
3)
4, x is the integer greater than 0 in the formula.Suitable solvent comprises not containing substantially and can influence produces with required wavelength and/or the material of the light of emission, and it comprises the transition metal that do not contain substantially except that yttrium, lanthanum and lutetium and the solvent of lanthanon, and the solvent that does not contain molybdenum substantially.The example of suitable solvent comprises one or more of following compound: LaB
3O
6, MgB
2O
4Or LiF.In some embodiments, described solvent does not contain transition metal and the lanthanon except that yttrium, lanthanum, lutetium and tungsten substantially.The example of tungstenic solvent is Li
2WO
4, this solvent can with for example B
2O
3Use together, be used for the YAl that grows
3(BO
3)
4Crystal.
Described NLO crystal can be used for comprising in the various devices of laser aid.These devices can be used to for example detect the anomalous structure on the substrate surface, perhaps hole in substrate.
By with reference to following detailed description and accompanying drawing, can more completely understand various other purpose of the present invention, feature and advantage.
The accompanying drawing summary
Fig. 1 is the simplified method for preparing optical composite according to an embodiment of the present invention;
Fig. 2 is the reduced graph of optical composite according to an embodiment of the present invention;
Fig. 3 is the simplified diagram that shows the transmission feature of optical composite according to an embodiment of the present invention;
Fig. 4 is the simplified diagram that shows the frequency transformation of optical composite according to an embodiment of the present invention.
Fig. 5 is presented in the 280-400 nanometer range, with the YAl of tungsten growth
3(BO
3)
4The percent transmittancy of crystal (YAB-W), comprise the YAl of molybdenum
3(BO
3)
4The percent transmittancy of crystal (YAB-Mo) and the YAl that does not contain all transition metal contaminants substantially
3(BO
3)
4The line graph of the percent transmittancy of crystal (YAB-La).
Fig. 6 is the synoptic diagram that NLO crystalline laser aid is housed.
Detailed Description Of The Invention
The present invention relates generally to that some has the mixture of optical property.More particularly, for example, the invention provides and comprise A
XM
(1-X)Al
3B
4O
12The particular compounds that is used for selected wavelength electromagnetic radiation, x is more than or equal to O, and is less than or equal to 0.1, A is selected from Sc, Y, La, Yb or Lu, M is selected from Sc, Y, La, Yb or Lu.Only for example purposes, this mixture can be used for that wavelength equals and less than the electromagnetic radiation of 350 nanometers, but should recognize that the present invention has wideer range of application.
Developed NYAB as the self-frequency-doubling crystal, i.e. optical pumping, and generation fundamental wavelength, and also its second harmonic does not need the independently crystal of frequency-doubling crystal.But because the inherent limitation, possible application is subjected to suitable restriction.At first, described fundamental wavelength often can only be 1060 nanometers and 1300 nanometers.Secondly, because crystalline size often only is several millimeters, often can't obtain having the enough big crystalline size that can be advantageously used in the commerical prod application.
Although made the business-like NYAB of limited quantity one after another, at the commercial YAB that does not make pure state.Conventional manufacture method makes very little crystal, and these small-crystallines comprise a large amount of non-stoichiometric metal pollutants, and its crystalline nature is lower than standard.In addition, used flux can be introduced the pollutent of a large amount of obstruction device valid functions in the ultraviolet range that is lower than 350 nanometers in the ordinary method.
Some embodiment according to the present invention, the borate crystal that comprises metal ions such as one or more rare earth metals that has prepared some kinds, and by (wavelength: 532 nanometers) irradiation has carried out second harmonic test (wavelength: 266 nanometers) to these borate crystals with the Nd:YAG laser of frequency multiplication.Thereby by evidence the NLO material production be lower than the ability of the harmonic light of 350 nanometers.Find thus, can produce the second harmonic of intensive 266 nanometers, and the NLO crystal of the novelty of aluminum yttrium borate form can transmission and produce the uv-radiation that is lower than 350 nanometers by the borate crystal that comprises Y and Al simultaneously.
The purpose of some embodiment of the present invention is that Y is satisfied in preparation and utilization
(1-X)M
XAl
3B
4O
12, and by eliminating or significantly reducing the nonlinear optical material that the method for the pollutent that can hinder the application of device in ultraviolet spectral range is made, wherein M=Sc, La, Yb or Lu, and 0≤x≤0.1.More particularly, in some embodiments of the present invention, do not contain for example metal of the 6th main group in the described device substantially, make this device in the ultraviolet range that is lower than 350 nanometers, to use.
A purpose of some embodiments of the present invention provides the preparation method who satisfies above-mentioned composition and do not have the nonlinear optical material of harmful uv-absorbing.An embodiment comprises the Y source that comprises about 10-30 mole %, the M of about 10-40 mole %, the Al source of about 15-40 mole %, and the mixture of the boron oxide of about 25-50 mole % of forming.If M is Sc, M source Scium trioxide normally then; If M is La, M source lanthanum trioxide normally then; If M is Yb, M source ytterbium oxide normally then; If M is Lu, M source lutecium oxide normally then.This mixture heating up to certain temperature, is heated one period that is enough to form the NLO material.For example heating steps can comprise mixture heating up to being at least 850K, being approximately higher than first temperature of 850K usually.Cool off this mixture then.After the cooling,, be heated to 1300K at least then, be approximately higher than second temperature of 1300K usually this mixture porphyrize (for example grinding to form fine powder) with mortar and pestle.
The another kind of method that forms these crystalline materials can include but not limited to that top shown in Figure 1 adds the seed-solution growth.This method comprises following process:
1. measure high-purity mangesium oxide thing powder and chemical and with suitable mixed.
2. then this mixture is added crucible, place in the process furnace.
3. heat this mixture, make it be melt into liquid.
After a while after, make melt temperature near its zero pour.
5. add cold finger material or crystal seed, to cause crystallization.
6. change and monitoring melt temperature and appointed condition, to promote crystal growth.
7. in suitable, make system reduce to room temperature.
8. crystal is shifted out from system.
For example, can synthesize (Y, La) Al as follows
3B
4O
12Buy purity greater than 99.9% yttrium oxide (Y from the supply and marketing merchant of Aesar and Stanford Materials and so on
2O
3), purity is greater than 99.9% lanthanum trioxide (La
2O
3), purity is greater than 99.9% aluminum oxide (Al
2O
3) and purity greater than 99.9% boron oxide (B
2O
3).Formation comprises the mixture of the boron oxide of the aluminum oxide of the lanthanum trioxide of the yttrium oxide of about 14 weight %, about 30 weight %, about 19 weight % and about 37 weight %.
As mentioned above, some embodiment of the present invention relates to nonlinear optics (NLO) device and electro-optical device, and the use ability of these devices below 350 nanometers.Some embodiments of the present invention relate to and satisfy general formula Y
(1-X)M
XAl
3B
4O
12Do not contain the nonlinear optical material that can hinder the pollutent of using in its ultraviolet (UV) district when (M=Sc, La or Lu, and 0≤x≤0.1 mole %) and preparation at electromagnetic spectrum.
Some embodiments according to the present invention, described nonlinear optical material Y
(1-X)M
XAl
3B
4O
12(M=Sc, La or Lu, and 0≤x≤0.1) is used for the NLO device operated under 350 nanometers being lower than.In another embodiment, described nonlinear optical material uses with the laser source of the device that is used to produce the optical radiation that is lower than 350 nanometers.In another embodiment, described nonlinear optical material uses with the light source of the device that is used to produce the optical radiation that is lower than 350 nanometers.In another embodiment, the nonlinear optical material of described formation is to be used for the following trigonal system of 350 nanometers.In another embodiment, the nonlinear optical material of described formation is to be used for the following R32 spacer of 350 nanometers.
In some embodiments of the present invention, described nonlinear optical material satisfies Yb
(1-X)M
XAl
3B
4O
12(M=Sc, La, or Lu, and 0≤x≤0.1) or Lu
(1-X)M
XAl
3B
4O
12(M=Sc, La or Lu, and 0≤X≤0.1).In some embodiments, described nonlinear optical material Y
(1-X)M
xAl
3B
4O
12, Yb
(1-X)M
XAl
3B
4O
12Or Lu
(1-X)M
XAl
3B
4O
12Ce and/or Nd have mixed.In some embodiments, described nonlinear optical material Y
(1-X)M
XAl
3B
4O
12Or Lu
(1-X)M
XAl
3B
4O
12Ce, Nd and/or Yb have mixed.
As mentioned above, although can provide NYAB, still can't prepare the YAB of pure state in commercialization ground with limited amount.Conventional production method makes and comprises a large amount of non-stoichiometric metal pollutants and the substandard small-crystalline of crystalline nature.In addition, used solvent has been introduced the pollutent that a large amount of obstruction devices are operated in the ultraviolet region that is lower than 350 nanometers.Leonyuk﹠amp; Leonyuk has described a kind of flux (flux) system about the boratory work summary of magnesium calcium carbonate (1995), and this system remained afterwards becomes preparation YAB and series material, i.e. potassium molybdate K
2MoO
4And K
2Mo
3O
10Method.Unfortunately, these solvent formulation have some serious restrictions to extensive crystal growth: a) high flux volatility, b) crystal yield is low, c) comprises a large amount of molybdenum atoms in target boron hydrochlorate magnesium calcium carbonate structure.Therefore, the industrial crystal production of pure YAB also is unrealized, and the NLO crystal is not used for the laser apparatus product as yet yet.
A purpose of some embodiment of the present invention is that A is satisfied in preparation and utilization
XM
(1-X)Al
3B
4O
12(0≤x in the formula≤0.1, A=(Sc, Y, La, Yb, Lu), M=(Sc, Y, La, Yb, Lu) and the nonlinear optical material of making by the method for eliminating or significantly minimizing can hinder the pollutent that device uses in the UV spectrum zone.More particularly, in some embodiments of the present invention, do not contain the metal of the 6th family's metal and so in the described device substantially, make it can be used for being lower than the ultraviolet range of 350 nanometers.Avoid in selected borate magnesium calcium carbonate, comprising the 6th family's impurity of Mo and so on, can extend its ultraviolet light transmission.In addition, owing to do not contain unnecessary metal in the main crystal composition, reduced the overall spectral absorption of crystal in whole transparency range (for example 165-2700 nanometer).By embodiment as herein described, can realize scientific circles' intrinsic light transmission unknown and that do not characterize up to now.
As mentioned above, the target of some embodiments of the present invention provides and satisfies A
XM
(1-X)Al
3B
4O
12(0≤x in the formula≤0.1, A=(Sc, Y, La, Yb, Lu), M=(Sc, Y, La, Yb, Lu)) and do not have the preparation method of the nonlinear optical material of deleterious uv-absorbing.An embodiment comprises the A source that comprises about 10-30 mole %, the M of about 10-40 mole %, the Al source of about 15-40 mole %, and the mixture of the boron oxide of about 25-50 mole % of forming.If A or M are Sc, A source or M Scium trioxide normally then; If A or M are Y, A source or M yttrium oxide normally then; If A or M are La, A source or M lanthanum trioxide normally then; If A or M are Yb, A source or M ytterbium oxide normally then; If A or M are Lu, A source or M lutecium oxide normally then.This mixture heating up to certain temperature, and is heated one period that is enough to form the NLO material.For example, heating steps can comprise mixture heating up to being at least 850K, usually approximately greater than first temperature of 850K.Cool off this mixture then.After the cooling, porphyrization mixture (grinding to form fine powder by for example mortar and pestle) is heated to 1300K at least then, is approximately higher than second temperature of 1300K usually.
As mentioned above, Fig. 1 is the simplification preparation method of optical composite according to an embodiment of the present invention.This diagram only is an example, and the scope to claims does not constitute unsuitable restriction.Those of ordinary skills should recognize, can carry out many changes, substitutions and modifications.Method 100 comprises the process 110 of measuring and mixing the chemical combination product, mixture is transported to the process 120 of crucible and process furnace, the process 130 of this mixture of fusion, the crystallization condition of process furnace is carried out optimized process 140, add crystal seed, beginning crystalline process 150, and the process 160 of cooling system, isolation of crystalline.Although above shown selected procedural order, can carry out manyly substituting, changing and modification.For example, can expand and/or make up some processes.Can in said process, insert other process.According to this embodiment, the certain order of described process can be intercoursed with other alternate process.For example, process 150 is changed into use sporadic nucleation, or use conventional optical crystal growth step, in bath surface, introduce cold finger.Can find the further details of these processes in this manual, will more specifically be described hereinafter.
In process 110, measure some chemical and mix.For example, measure high-purity mangesium oxide thing powder and chemical with suitable ratio, and mix.In process 120, this mixture is transferred in crucible and the process furnace.For example, this mixture is added crucible, and place in the process furnace.In process 130, make the mixture fusion.For example, heat this mixture, and make mixture be melt into liquid.
In process 140, the condition of process furnace is carried out optimization, to carry out crystallization.For example, over time, the temperature that makes melt is near its zero pour.In process 150, add crystal seed, and the beginning crystallization.For example add crystal seed and cause crystallization.In another example, process 150 is changed into and is used the cold finger material to cause crystallization.In another embodiment, process 150 is changed over use sporadic nucleation and cause crystallization.In addition, melt temperature and appointed condition are changed and monitor, to promote crystal growth.In process 160, cool off this system and isolation of crystalline.For example, in suitable, system is reduced to room temperature.Crystal is shifted out from system, be used for test or further processing.
In an example of method 100, Y
(1-X)La
xAl
3B
4O
12Synthetic carry out 0≤x in the formula≤0.1 according to following steps:
In process 110, obtain purity greater than 99.9% yttrium oxide (Y
2O
3), purity is greater than 99.9% lanthanum trioxide (La
2O
3), purity is greater than 99.9% aluminum oxide (Al
2O
3), and purity is greater than 99.9% boron oxide (B
2O
3).For example these chemical are buied by the supply and marketing merchant place of Aesar and Stanford Materials and so on.Formed the Y that comprises about 14 weight %
2O
3, the La of about 30 weight %
2O
3, the Al of about 19 weight %
2O
3, and the B of about 37 weight %
2O
3Mixture.
In process 120, described mixture is added in the crucible, place in the high-temperature heater with atmosphere control device.For example ambiance or inert atmosphere all can satisfy this process.In process 130, in 12 hours, mixture is heated to the other temperature of 1450-1575K by room temperature.Make the melt of gained be incubated about 1-3 days in other temperature.
In process 140, liquid mixture is cooled to temperature near its zero pour with 20K/ hour speed, for example, this temperature is about 1475-1400K.This mixture kept under this temperature about 8 hours.In process 150, by self nucleation or conventional optical crystal growth step, add crystal seed or cold finger to bath surface, when being cooled to the outlet temperature of 1300K with about 1-5K/ days speed, product begins to form.In addition, in process of growth, also randomly change melt temperature and appointed condition, to promote crystal growth by the monitoring of the automation control system on operator and/or the process furnace.
In process 160, then with about 50K/ hour rate of cooling with this system cools to room temperature.Make water white transparency Y
(1-x)La
xAl
3B
4O
12Crystal, 0≤x≤0.1 wherein, and it is shifted out in process furnace.
In another embodiment of method 100, synthesized Lu according to following steps
(1-x)La
xAl
3B
4O
12, 0≤x≤0.1 wherein:
In step 110, obtain purity greater than 99.9% lutecium oxide (Lu
2O
3), purity is greater than 99.9% lanthanum trioxide (La
2O
3), purity is greater than 99.9% aluminum oxide (Al
2O
3), and purity is greater than 99.9% boron oxide (B
2O
3).For example, these chemical are obtained by the supply and marketing merchant place of Aesar and Stanford Materials and so on.Formation comprises the Lu of about 21 weight %
2O
3, about 30 weight % La
2O
3, about 16 weight % Al
2O
3B with about 34 weight %
2O
3Mixture.
In process 120, described mixture is added in the crucible, place in the high-temperature heater of band nitrogen and oxygen atmosphere environment control unit, wherein oxygen partial pressure is more than or equal to 3000ppm.In process 130, in 12 hours, mixture is heated to the other temperature of 1450-1575K by room temperature.Make the melt of gained be incubated about 1-3 days in other temperature.
In process 140, liquid mixture is cooled to temperature near its zero pour with 20K/ hour speed, for example, this temperature is about 1475-1400K.This mixture kept under this temperature about 8 hours.In process 150, by self nucleation or conventional optical crystal growth step, add crystal seed or cold finger to bath surface, when being cooled to the outlet temperature of 1275K with about 1-5K/ days speed, product begins to form.In addition, in process of growth, also randomly change melt temperature and appointed condition, to promote crystal growth by the monitoring of the automation control system on operator and/or the process furnace.
In process 160, with about 50K/ hour rate of cooling with this system cools to room temperature.Make water white transparency Lu
(1-x)La
xAl
3B
4O
12Crystal, 0≤x≤0.1 wherein, and it is taken out in process furnace.
In another embodiment of method 100, by the synthetic Sc of following steps
(1-x)La
xAl
3B
4O
12, 0≤x≤0.1 wherein:
In step 110, obtain purity greater than 99.9% Scium trioxide (Sc
2O
3), purity is greater than 99.9% lanthanum trioxide (La
2O
3), purity is greater than 99.9% aluminum oxide (Al
2O
3), and purity is greater than 99.9% boron oxide (B
2O
3).For example, these chemical are obtained by the supply and marketing merchant place of Aesar and Stanford Materials and so on.Formation comprises the Sc of about 8 weight %
2O
3, about 34 weight % La
2O
3, about 18 weight % Al
2O
3B with about 39 weight %
2O
3Mixture.
In process 120, described mixture is added in the crucible, place in the high-temperature heater with atmosphere control device.For example ambiance or inert atmosphere all can satisfy this process.In process 130, in 12 hours, mixture is heated to the other temperature of 1450-1600K by room temperature.Make the melt of gained be incubated about 1-3 days in this temperature.
In process 140, liquid mixture is cooled to temperature near its zero pour with 20K/ hour speed, for example, this temperature is about 1500-1425K.This mixture kept under this temperature about 8 hours.In process 150, by self nucleation or conventional optical crystal growth step, add crystal seed or cold finger to bath surface, when being cooled to the outlet temperature of 1300K with about 1-5K/ days speed, product begins to form.In addition, in process of growth, also randomly change melt temperature and appointed condition, to promote crystal growth by the monitoring of the automation control system on operator and/or the process furnace.
In process 160, with about 50K/ hour rate of cooling with this system cools to room temperature.Make water white transparency Sc
(1-x)La
xAl
3B
4O
12Crystal, 0≤x≤0.1 wherein, and it is taken out in process furnace.
Fig. 2 is the reduced graph according to the optical composite of one embodiment of the present invention.This figure only is an example, and the scope to claims does not constitute any restriction improperly.Those of ordinary skills should recognize, can carry out many changes, substitute and revise.Described optical composite comprises the Y by aforesaid method 100 preparations
xLa
yAl
3B
4O
12, 0≤x wherein, 0≤y, and x+y≤1.Should be synthetic with yttrium oxide (Y
2O
3), lanthanum trioxide (La
2O
3), aluminum oxide (Al
2O
3) and boron oxide (B
2O
3) be raw material.As shown in Figure 2, this crystal of 6 * 6 * 7 millimeters is enough big, has optically transparent, makes it bring into play function in the laser beam transformation device.
Fig. 3 is the reduced graph of demonstration according to the transmission feature of the optical composite of one embodiment of the present invention.This figure only is an example, should not constitute restriction improperly to the scope of claims.Those skilled in the art should recognize can carry out many changes, alternative and modification.Described optical composite comprises the Y by aforesaid method 100 preparations
(1-x)La
xAl
3B
4O
12, 0≤x in the formula≤0.1.Should be synthetic with yttrium oxide (Y
2O
3), lanthanum trioxide (La
2O
3), aluminum oxide (Al
2O
3) and boron oxide (B
2O
3) be raw material.As shown in Figure 3, curve 300 has shown that percentage transmission is with the wavelength change situation.To between about 175 nanometers, it is constant relatively that percentage transmission keeps in 350 nanometers.
Fig. 4 shows the reduced graph that carries out frequency transformation by optical composite according to an embodiment of the present invention.This figure only is an example, should not cause restriction improperly to the scope of claims.Those of ordinary skills are to be understood that and can carry out many changes, substitute and revise.Described optical composite comprises the Y by aforesaid method 100 preparations
(1-X)La
xAl
3B
4O
12, 0≤x≤0.1 wherein.Should be synthetic with yttrium oxide (Y
2O
3), lanthanum trioxide (La
2O
3), aluminum oxide (Al
2O
3) and boron oxide (B
2O
3) be raw material.For example, described optical composite is a crystal shown in Figure 2.In process of the test, the laser pulse of about 532 nanometers of wavelength is transported to 6 millimeters * 6 millimeters * 7 millimeters Y
(1-X)La
xAl
3B
4O
12The crystal place.This crystal output beam that responds, this output beam is received by the imaging scintillator panel to the uv-radiation sensitivity.As shown in Figure 4, use photographic camera to obtain image, make this photographic camera to 532 not sensitization of nanometer with spectral filter by taking a picture.In this image, on the imaging scintillator panel, observe blue-fluorescence.So Y
(1-X)La
xAl
3B
4O
12Crystal produces UV-light by the SHG process, and is detected by the imaging scintillator panel.In another test, use the dichroscope of light transmission through optimizing especially at 266 nanometers, be placed on Y
(1-x)La
xAl
3B
4O
12Between crystal and the imaging scintillator panel.Also observed with Fig. 4 in similar blue-fluorescence.So Y
(1-x)La
xAl
3B
4O
12Crystal has produced the UV-light of 266 nanometers.
As mentioned above, emphasize further herein that this method can be used to prepare various optical composites.According to one embodiment of the present invention, prepared the mixture that is used for equaling and be lower than the device for non-linear optical that uses under 350 nanometers by method 100.The described mixture of the material that is used for device for non-linear optical that comprises comprises YAl
3B
4O
12This mixture do not contain be at least 1000ppm contain molybdenum impurity.Another embodiment according to the present invention has prepared the mixture that is used for equaling and be lower than the device for non-linear optical that uses under 350 nanometers by method 100.The described mixture of the material that is used for device for non-linear optical that comprises comprises Y
(1-X)M
XAl
3B
4O
12X is more than or equal to 0, and is less than or equal to 0.1, and M is selected from Sc, La, Yb and Lu.This mixture do not contain be at least 1000ppm contain molybdenum impurity.
Another embodiment according to the present invention has prepared the mixture that is used for equaling and be lower than the device for non-linear optical that uses under 350 nanometers by method 100.The described mixture of the material that is used for device for non-linear optical that comprises comprises Yb
(1-X)M
XAl
3B
4O
12X is more than or equal to 0, and is less than or equal to 0.1, and M is selected from Sc, Y, La and Lu.This mixture do not contain be at least 1 000ppm contain molybdenum impurity.Another embodiment according to the present invention has prepared the mixture that is used for equaling and be lower than the device for non-linear optical that uses under 350 nanometers by method 100.The described mixture that comprises the material that is used for device for non-linear optical comprises Lu
(1-X)M
XAl
3B
4O
12X is more than or equal to 0, and is less than or equal to 0.1, and M is selected from Sc, Y, Yb and La.This mixture do not contain be at least 1000ppm contain molybdenum impurity.Another embodiment according to the present invention, a kind of being used for equaling and is being lower than the mixture that uses under 350 nanometers, comprise the device for non-linear optical of the material that is used for device for non-linear optical to comprise Sc
(1-X)M
XAl
3B
4O
12, x is more than or equal to 0, and is less than or equal to 0.1, and M is selected from Y, La, Yb and Lu.This mixture do not contain be at least 1000ppm contain molybdenum impurity.
Another embodiment according to the present invention has prepared the mixture that is used for equaling and be lower than the device for non-linear optical that uses under 350 nanometers by method 100.Described this mixture of the material that is used for device for non-linear optical that comprises comprises A
XM
(1-X)Al
3B
4O
12X is more than or equal to 0, and is less than or equal to 0.1, and A is selected from Sc, Y, La, Yb and Lu, and M is selected from Sc, Y, La, Yb and Lu.This mixture do not contain be at least 1000ppm contain molybdenum impurity.In one embodiment, M is selected from least a among La, Lu, Sc, Y and the Yb.In another embodiment, A is selected from least a among Sc, Y, La, Yb and the Lu.
As mentioned above, according to some embodiment, the various optical composites by method 100 preparation do not contain separately be at least 1000ppm contain molybdenum impurity.For example, described mixture do not contain be at least 500ppm contain molybdenum impurity.In another embodiment, this mixture do not contain be at least 100ppm contain molybdenum impurity.In another embodiment, this mixture do not contain be at least 10ppm contain molybdenum impurity.In another embodiment, this mixture do not contain be at least 1ppm contain molybdenum impurity.In another embodiment, this mixture does not contain molybdenum impurity substantially.Some embodiments according to the present invention, the various optical composites that make by method 100 do not contain the obstruction mixture that is at least 1000ppm separately and are used at any impurity that equals and be lower than the device for non-linear optical that uses under 350 nanometers.For example this mixture does not contain such impurity of any 500ppm of being at least.In another embodiment, this mixture does not contain such impurity of any 100ppm of being at least.In another embodiment, this mixture does not contain such impurity of any 10ppm of being at least.In another embodiment, this mixture does not contain such impurity of any 1ppm of being at least.In another embodiment, this mixture does not contain any such impurity substantially.
As mentioned above, according to some embodiment, the various optical composites volume separately by method 100 preparation is approximately greater than 0.001 millimeter
3For example, the volume of described mixture is approximately greater than 0.01 millimeter
3In another embodiment, the volume of described mixture is approximately greater than 0.1 millimeter
3In another embodiment, the volume of described mixture is approximately greater than 1 millimeter
3
According to some embodiments, the various optical composites by method 100 preparation are used in and equal and be lower than the device for non-linear optical that uses under 350 nanometers.For example, this mixture can be used for about 350-160 nanometer wavelength range.In another embodiment, can be used for about 350-170 nanometer wavelength range.In another embodiment, this mixture can be used for producing the device of the optical radiation that is lower than 350 nanometers.In another embodiment, described device comprises the NLO system, the mixture relevant with laser system, and/or the mixture relevant with light source.
According to some embodiment, this method 100 can be used to prepare the mixture that is used for equaling and be lower than the device for non-linear optical that uses under 350 nanometers.For example described mixture is relevant with the tripartite crystal type that is used to be lower than 350 nanometers, and/or is being lower than the R32 spacer of using under 350 nanometers.In another embodiment, this mixture also comprises doping agent, and described doping agent comprises and is selected from least a of Ce, Nd and Yb.In one embodiment, described nonlinear optical material comprises NYAB.In another embodiment, described nonlinear optical material comprises Yb:YAB.In another embodiment, described nonlinear optical material comprises Ce:YAB.
Another embodiment according to the present invention, a kind of preparation are used for comprising in the method that equals and be lower than the mixture of the device for non-linear optical that uses under 350 nanometers provides multiple material.Described multiple material comprises and contains the lanthanum mixture that the described lanthanum mixture that contains can decompose, and generates lanthanum trioxide at least in heating.In addition, described method comprises at least based on the information relevant with predetermined proportion described multiple material mixing is formed mixture, makes to begin crystallisation process in the mixture, forms crystal, and shift out crystal from mixture, and described crystal comprises lanthanum.For example described multiple material comprises lanthanum trioxide.In a further embodiment, described multiple material also comprises boron oxide.In a further embodiment, described method also comprises described mixture is placed in the process furnace.In another embodiment, described method also comprises first temperature that described mixture heating up is extremely predetermined, and this mixture is cooled to the second predetermined temperature.In another embodiment, beginning crystalline process comprises to bath surface insertion crystal seed.In another embodiment, described crystal comprises A
xM
(1-x)Al
3B
4O
12X is more than or equal to 0, and is less than or equal to 0.1, and A is selected from Sc, Y, La, Yb and Lu, and M is selected from Sc, Y, La, Yb or Lu.In another embodiment, described method is implemented according to method 100.
Another embodiment according to the present invention, a kind of be used for comprising in the preparation method who equals and be lower than the mixture of the device for non-linear optical that uses under 350 nanometers multiple material is provided.Described multiple material comprises and contains yttrium compound that the described yttrium compound that contains can decompose, and generates yttrium oxide at least in heating.In addition, described method comprises at least based on the information relevant with predetermined proportion described multiple material mixing is formed mixture, makes to begin crystallisation process in the mixture, forms crystal, and shift out crystal from mixture, and described crystal comprises yttrium.For example described multiple material comprises yttrium oxide.In a further embodiment, described multiple material also comprises boron oxide.In a further embodiment, described method also comprises described mixture is placed in the process furnace.In another embodiment, described method also comprises first temperature that described mixture heating up is extremely predetermined, and this mixture is cooled to the second predetermined temperature.In another embodiment, beginning crystalline process comprises to bath surface insertion crystal seed.In another embodiment, described crystal comprises A
xM
(1-x)Al
3B
4O
12X is more than or equal to 0, and is less than or equal to 0.1, and A is selected from Sc, La, Yb and Lu, and M is selected from Sc, Y, La, Yb and Lu.In another embodiment, described method is implemented according to method 100.
In the other embodiment below the present invention, use described abbreviation:
Mm: millimeter,
NLO: nonlinear optics
Nm: nanometer
Ppm: 1,000,000/portion
SHG: second harmonic takes place
Also use in following other embodiment giving a definition, these definition only are with helping the reader, rather than the implication that the implication of these terms is become understand than those of ordinary skills is narrow.
Aluminium-borate NLO crystal: chemical formula comprises aluminium and boratory NLO crystal.Aluminium-borate NLO crystalline example comprises: aluminium-borate NLO crystal, for example YAl that comprises yttrium, lutetium or its combination in the chemical structure
3(BO
3)
4, LuAl
3(BO
3)
4And Y
(1-x)Lu
xAl
3(BO
3)
4, x is the integer greater than 0 in the formula.
Laser beam: the photon beam that laser apparatus produces.Laser beam can be for example collimate basically, monochromatic and relevant basically basically.
Molybdate compound: contain the compound of molybdenum in molybdenum or the chemical formula, for example molybdenum oxide.
Non-linear optic crystal: luminous energy responded shows the crystal of nonlinear polarization.These crystal comprise main raw, also can comprise one or more secondary materials.
Main raw: crystalline complex with nonlinear optical property.Main raw forms the main body of lattice in the NLO crystal.Initially synthetic or isolating main raw exists with powder type usually.Described powder main raw must carry out recrystallization, has the suitable dimension of the light that is applicable to the generation and/or required wavelength takes place and the NLO crystal of suitable purity with formation.Perhaps, main raw can be formed by precursor material in crystallisation process.
Precursor material: the material that can be combined to form main raw with other precursor material.For example, Y
2O
3, B
2O
3And Al
2O
3Be to be used for forming YAl
3(BO
3)
4Precursor material.
Secondary materials: contained element except that main raw or compound in the NLO crystal.Secondary materials deliberately (for example doping agent) or by mistake (for example pollutent) incorporated.Secondary materials can become the integral part of lattice, or is present in beyond the lattice.
The compound that comprises transition metal: the element state transition metal perhaps comprises the compound of transition metal, for example transition metal oxide in the chemical formula.
Tungstenic compound: elemental tungsten, or comprise the compound of tungsten in the chemical formula, for example Tungsten oxide 99.999.
Described embodiment relates to non-linear optic crystal, has particularly reduced the non-linear optic crystal of some pollutent (for example can influence the pollutent of the optical property of non-linear optic crystal) content with respect to known non-linear optic crystal.
The embodiment that this paper has described NLO crystalline embodiment and has been used for preparing and using these crystalline methods.Described embodiment can be used for various uses, and these purposes include but not limited to the laser application.
All NLO crystal all have the lattice that comprises at least a main raw.The NLO crystal also can comprise one or more secondary materials.This main raw for example various doping agents that can mix are to change the crystalline optical property.The example of main raw includes but not limited to: YAl
3(BO
3)
4, LuAl
3(BO
3)
4, BaB
2O
4, BaAl
2B
2O
7, K
2Al
2B
2O
7, CaAl
2B
2O
7, SrAl
2B
2O
7, TiOPO
4, KTiOAsO
4, RbTiOPO
4, RbTiOAsO
4, CsTiOAsO
4, LiNbO
3, KNbO
3, AgGaS
2, AgGaSe
2, KH
2PO
4, KD
2PO
4, NH
4PO
4, CsH
2AsO
4, CsD
2AsO
4, LiIO
3And LiTaO
3These NLO materials can be used singly or in combination.
In aluminium-borate NLO crystal, chemical structure comprises aluminium-borate NLO crystal, for example YAl of yttrium, lutetium or its combination
3(BO
3)
4, LuAl
3(BO
3)
4Or Y
(1-x)Lu
xAl
3(BO
3)
4(wherein x is the integer greater than 0), be particularly useful for producing and/or transmitted wave be about less than 300 nanometers, preferred approximately less than 250 nanometers, more preferably from about less than the light of 175 nanometers.
The NLO crystalline that comprises aluminium-borate NLO crystal is used the optical property that mainly is derived from them.For obtaining required optical property, often need growth to have comparatively successive crystalline structure and the seldom monocrystalline of defective.In addition, major applications requires the NLO monocrystalline to have specific size, and it is compatible that for example its size is enough to make the optics of crystal and laser apparatus and so on.Some useful NLO crystalline volumes are approximately greater than 0.1 millimeter
3, preferably approximately greater than 1 millimeter
3, more preferably from about greater than 5 millimeters
3
Before the formation of main raw recrystallization was had the monocrystalline of suitable dimension and purity, described main raw can comprise amorphous material or minimum crystalline powder type exists.Recrystallization process can powder type main raw be raw material, perhaps can be with can being raw material in conjunction with the precursor material that forms main raw.For example, can make precursor material and solvent be combined to form mixture, then by this main raw of this crystalline mixture.Useful precursor material comprises the oxide compound of the various elements in the main raw chemical structure.For example, form YAl
3(BO
3)
4, precursor material can comprise: Y
2O
3, B
2O
3, and Al
2O
3These precursor materials can be buied from the source of for example Sigma-Aldrich (Missouri, USA, St. Louis) and so on.
This paper has described by its form and has been unsuitable for the embodiment that the NLO crystal is used the useful NLO crystalline method of the precursor material of (be primitive form, for example powder type) or main raw growth aluminium-borate NLO crystal and so on.Some embodiments comprise precursor material or main raw and solvent, form mixture.Cool off this mixture then, the NLO crystal is grown along with the cooling of mixture.Solvent provides and has made that the elementary composition of main raw can crystalline form bonded medium.When not using solvent, comprise YAl
3(BO
3)
4And LuAl
3(BO
3)
4Uneven decomposition at high temperature takes place easily at interior many main raws.
But selective solvent, the dissolving by promoting precursor material is to promote crystallisation process.When the precursor material is tart,, can improve solvability if solvent is an alkalescence.Similarly, when the precursor material is alkalescence,, can improve solvability if solvent is acid.Can promote solvability by the pH value of regulating solvent, but high alkalescence or acid meeting bring harmful effect to crystal growth.
Usually be merely the influence of crystallisation process to be come selective solvent according to solvent.Because in crystallisation process, crystal separates with solvent phase, it is believed that the almost not influence or not influence fully of crystal that choice of Solvent produces this process.Curiously, have been found that some element in the conventional solvent can be combined in by in the crystal that grows out in the mixture that comprises these solvents.For example, at K
2MoO
2The YAl of middle growth
3(BO
3)
4Crystal comprises the molybdenum oxide as secondary materials.Have been found that the pollutent that some are such, even content is seldom, the crystalline optical property that also can remarkably influenced grows by the mixture that comprises these solvents.For example, these pollutents can influence the generation and/or the emission of the light of required wavelength.Conventional YAl
3(BO
3)
4Crystal comprise can hinder produce and/or emission wavelength less than the pollutent of the light of 370 nanometers.
By growing crystal in the mixture that does not contain or do not contain at least substantially some pollutent, can make crystal with improved optical property.For example can grow and to produce and/or to launch the aluminium-borate crystal of short wavelength laser that conventional aluminium-borate crystal is beyond one's reach, for example YAl
3(BO
3)
4And LuAl
3(BO
3)
4Crystal, described short wavelength be for example wavelength approximately less than 300 nanometers, usually approximately less than 250 nanometers, more preferably from about less than 175 nanometers.
Some pollutent to the harm of NLO crystal optics character much larger than other pollutent.For example, the generation of some pollutant effect short-wavelength lights and/or emission, described short-wavelength light be for example wavelength approximately less than 300 nanometers, preferably approximately less than 250 nanometers, more preferably from about less than the light of 175 nanometers.Some pollutents can hinder the NLO crystal to absorb short wavelength's light, thereby have suppressed the optical mixing process these short wavelengths.Some pollutents that are combined in the crystal that grows in the conventional solvent are included in the compound that shows the element of charge transfer transition in the ultraviolet electromagnetic spectrum zone.These compounds affect the generation and/or the emission of light of ultraviolet wavelength.For some application, deleterious pollutent comprises: contain the transition metal except that yttrium, lanthanum and lutetium and/or the compound of lanthanon.Table 2 has shown the YAl with conventional solvent growth
3(BO
3)
4The concentration of different elements in the crystal.As shown in the figure, YAl
3(BO
3)
4Crystal comprises the molybdenum of 250 ppm by weight.
| Element | Ppm by weight | Element | Ppm by weight | Element | Ppm by weight |
| H | Do not record | Zn | ≤2 | Pr | 0.11 |
| Li | 0.15 | Ga | ≤1 | Nd | ～6000 |
| Be | ＜0.01 | Ge | ＜0.1 | Sm | 0.1 |
| B | Mainly | As | 0.88 | Eu | 4.0 |
| C | Do not record | Se | ＜0.5 | Gd | 3.0 |
| N | Do not record | Br | ＜0.1 | Tb | 15 |
| O | Mainly | Rb | ＜0.1 | Dy | 0.10 |
| F | ＜0.5 | Sr | 0.37 | Ho | 0.034 |
| Na | 3.0 | Y | Mainly | Er | 0.089 |
| Mg | 5.0 | Zr | 1.1 | Tm | 0.42 |
| Al | Mainly | Nb | 0.079 | Yb | ＜0.1 |
| Si | 15 | |
250 | Lu | 0.37 |
| P | 0.17 | Ru | ＜0.1 | Hf | ＜0.1 |
| S | 4.0 | Rh | ＜0.1 | Ta | ＜10 |
| Cl | 8.0 | Pd | ＜0.1 | W * | 1.2 |
| |
100 | Ag | ＜0.5 | Re | ＜0.1 |
| Ca | 6.0 | Cd | ＜0.5 | Os | ＜0.1 |
| Sc | ＜0.1 | In | ＜0.1 | Ir | ＜0.1 |
| Ti | 0.51 | Sn | ＜0.5 | Pt | 6.5 |
| V | ≤1 | Sb | ＜0.5 | Au | ＜1 |
| Cr | ≤5 | Te | ＜0.1 | Hg | ＜0.1 |
| Mn | 0.37 | I | ＜0.1 | Tl | ＜0.1 |
| Fe | 10 | Cs | ＜0.1 | Pb | ＜0.1 |
| Co | 0.064 | Ba | 0.29 | Bi | ＜0.1 |
| Ni | 0.78 | La | 170 | Th | ＜0.01 |
| Cu | 1.0 | Ce | 0.54 | U | ＜0.01 |
*Uneven
The YAl that table 2 is grown with conventional solvent
3(BO
3)
4Crystalline is formed
In the embodiment that some disclosed, in crystallisation process, use special solvent.These solvents can not contain in the crystal that can be combined in growth substantially, can change the pollutent of these crystalline optical properties.For example these solvents can not contain whole transition metal except that yttrium, lanthanum and lutetium and lanthanon substantially.In some embodiments, these solvents do not contain molybdate compound substantially.In some embodiments, described solvent comprises LaB
3O
6, MgB
2O
4, LiF or their combination.Solvent LaB
3O
6, MgB
2O
4Be specially adapted to form YAl with LiF
3(BO
3)
4Crystal.
Table 3 has shown and is not containing the YAl that grows in the solvent of molybdenum substantially
3(BO
3)
4The concentration of different elements in the crystal.As shown in the figure, YAl
3(BO
3)
4Crystal comprises the molybdenum of 0.15 ppm by weight.
| Element | Ppm by weight | Element | Ppm by weight | Element | Ppm by weight |
| H | Do not record | Zn | ≤2 | Pr | 0.063 |
| Li | 57 | Ga | ≤1 | Nd | 0.15 |
| Be | ＜0.01 | Ge | ＜0.1 | Sm | ＜0.1 |
| B | Mainly | As | ＜0.5 | Eu | ＜0.1 |
| C | Do not record | Se | ＜0.5 | Gd | 0.20 |
| N | Do not record | Br | ＜0.1 | Tb | 0.038 |
| O | Mainly | Rb | ＜0.1 | Dy | 0.29 |
| F | ＜0.5 | Sr | 0.066 | Ho | 0.29 |
| Na | 6.0 | Y | Mainly | Er | 0.23 |
| Mg | 3.0 | Zr | 0.41 | Tm | 0.013 |
| Al | Mainly | Nb | 0.14 | Yb | 1.9 |
| |
75 | Mo | 0.15 | Lu | 0.083 |
| P | 0.81 | Ru | ＜0.1 | Hf | ＜0.1 |
| S | 16 | Rh | ＜0.1 | Ta | ＜10 |
| Cl | 20 | Pd | ＜0.1 | W | 0.55 |
| K | 4.0 | Ag | ＜0.5 | Re | ＜0.1 |
| Ca | 2.5 | Cd | ＜0.5 | Os | ＜0.1 |
| Sc | ＜0.1 | In | ＜0.1 | Ir | ＜0.1 |
| Ti | 0.65 | Sn | ＜0.5 | Pt | 1.5 |
| V | ≤1 | Sb | ＜0.5 | Au | ＜1 |
| Cr | ≤5 | Te | ＜0.1 | Hg | ＜0.1 |
| Mn | 0.28 | I | ＜0.1 | Tl | ＜0.1 |
| Fe | 10 | Cs | ＜0.1 | Pb | ＜0.1 |
| Co | ＜0.1 | Ba | 0.15 | Bi | ＜0.1 |
| Ni | 0.15 | La | Mainly | Th | ＜0.01 |
| Cu | 0.50 | Ce | 0.56 | U | ＜0.01 |
The YAl that table 3 is grown with the solvent that does not contain molybdenum substantially
3(BO
3)
4Crystalline is formed
Some crystal techniques can be used in combination with the solvent of special selection, to make the NLO crystal with required character.In some embodiments, will be by mixing precursor material and solvent, or mix the main raw of original form and mixture heating up that solvent makes to the temperature that is higher than the mixture fusing point.The fusing point of this mixture changes according to the kind and the amount of solvent types and amount and precursor material or main raw.Can change fusing point and other melt property (for example melt viscosity and melt creep) by in mixture, adding various additives.Some useful additives are an alkali metal salt and alkaline earth salt.These salt can be for example oxide compound, fluorochemical or muriate.By select these additives make they can not influence formed crystalline at least a, may be multiple required optical property.For example, by selecting to be used for being formed for the NLO crystalline additive of short wavelength's second harmonic generation, make them can not hinder crystal to absorb these short wavelengths' light.
In some embodiments of growing method, in molten mixture, add crystal seed, make this mixture be cooled to second temperature lentamente then by first temperature.Described crystal seed is the small-crystalline of main raw normally, often has the crystalline structure of even orientation.In some embodiments, when mixture was cooled to second temperature by first temperature, described crystal seed was suspended in the fused mixture.Along with mixture cooling, main raw generation crystallization.Crystallization can be carried out with the uniform crystal orientation that the crystalline orientation with crystal seed is complementary on every side at the crystal seed as monocrystalline.
Most of crystal growths are to be taken place by the growing period that first temperature is cooled to second temperature at mixture.Described first temperature can be near the mixture fusing point or be higher than the temperature of mixture fusing point.Described second temperature can be the temperature that is lower than the mixture fusing point, for example hangs down about 5-100 ℃ temperature than mixture fusing point.The time of process of growth is depended on main raw, solvent and required crystalline size.Usually crystal will with about 0.2-0.3 millimeter/hour the speed growth.Suitable growth time is usually approximately greater than 10 hours.In the portion of time of growth period,, can cool off this mixture with the cooling gradient less than 2 ℃/hour approximately for example approximately greater than in for some time of 2 hours.
Table 4 has been listed some and has been comprised YAl
3(BO
3)
4The example of the mixture of the various combination of (as main raw) and solvent has also been listed the crucial melting characteristic of this mixture.For every kind of mixture, table 4 has been listed fusing point, growth temperature range (i.e. scope between first temperature and second temperature), and the example of suitable growth time.
| Mixture # | Mixture | Fusing point (℃) | Growth temperature range (℃) | Growth time (my god) |
| 1 | YAl 3(BO 3) 4+2LaB 3O 6+LiF | 1085 | 1085-1060 | 15 |
| 2 | YAl 3(BO 3) 4+2LaB 3O 6 | 1155 | 1155-1127 | 15 |
| 3 | YAl 3(BO 3) 4+1.5LaB 3O 6+LiF | 1170 | 1170-1150 | 15 |
| 4 | YAl 3(BO 3) 4+1.5LaB 3O 6 | 1230 | 1230-1200 | 10 |
| 5 | YAl 3(BO 3) 4+LaB 3O 6+2MgB 2O 4 | 1130 | 1130-1110 | 10 |
| 6 | YAl 3(BO 3) 4+3Li 2WO 4+2B 2O 3 | 1010 | 1010-920 | 30 |
Table 4
Some YAl
3(BO
3)
4The melting characteristic of mixture
In the mixture shown in the table 4, the creep that the crystal that is formed by mixture 1-4 shows various degree.Crystal by mixture 5 growths has less creep.
Usually be used for the NLO crystalline growth of short wavelength SHG for expection, preferred selection does not contain the transition metal except that yttrium, lanthanum and lutetium and/or the solvent of lanthanon.Yet some solvents that comprise transition metal can promote the melt uniformity of main raw especially effectively.Therefore in some cases, the potential impact to crystal optics character that may cause in conjunction with harmful element in the NLO crystal should be weighed mutually with the beneficial effect of the solvent that comprises these harmful elements.When the NLO crystal that grows in by solvent does not really want to be used for SHG under the utmost point short wavelength, comprise the solvent particularly suitable of transition metal.For example, when growth is used for wavelength approximately greater than the NLO crystalline of the SHG of 300 nanometers, in some embodiments of growing method, can use the solvent of tungstenic.A kind of can be well suited in YAl
3(BO
3)
4The tungstenic solvent of crystal growth is Li
2WO
4, this solvent can with B
2O
3Be used in combination.Table 4 has been listed the crystal that is grown by mixture 6, and it combines Li
2WO
4And B
2O
3, this crystal has fabulous character.
Table 5 has shown the YAl of growth in the mixture 6 shown in the table 4
3(BO
3)
4The concentration of different elements in the crystal.The amount of institute's bonded tungsten is 550 ppm by weight.
| Element | Ppm by weight | Element | Ppm by weight | Element | Ppm by weight |
| H | Do not record | Zn | 1.5 | Pr | ＜0.1 |
| |
50 | Ga | 0.65 | Nd | ＜0.1 |
| Be | ＜0.01 | Ge | ＜0.5 | Sm | ＜0.1 |
| B | Mainly | As | ＜0.5 | Eu | ＜0.1 |
| C | Do not record | Se | ＜0.1 | Gd | ＜0.1 |
| N | Do not record | Br | ＜0.1 | Tb | ＜0.1 |
| O | Do not record | Rb | ＜0.1 | Dy | ＜0.1 |
| F | ＜0.5 | Sr | Do not record | Ho | ＜0.1 |
| Na | 20 | Y | Mainly | Er | ＜0.1 |
| Mg | 7.5 | Zr | 0.067 | Tm | ＜0.1 |
| Al | Mainly | Nb | ＜0.05 | Yb | ＜0.1 |
| |
50 | Mo | 0.15 | Lu | ＜0.1 |
| P | 1.0 | Ru | ＜0.1 | Hf | ＜0.1 |
| S | 5.0 | Rh | ＜0.1 | Ta | ＜5 |
| |
50 | Pd | ＜0.1 | W | 550 |
| K | 0.90 | Ag | ＜0.5 | Re | ＜0.1 |
| Ca | 7.0 | Cd | ＜0.5 | Os | ＜0.1 |
| Sc | ＜0.5 | In | ＜0.1 | Ir | ＜0.1 |
| Ti | 0.75 | Sn | 0.30 | Pt | ＜0.5 |
| V | 0.55 | Sb | 0.30 | Au | ＜0.5 |
| Cr | 4.0 | Te | ＜0.5 | Hg | ＜0.1 |
| Mn | 0.055 | I | ＜0.1 | Tl | ＜0.1 |
| Fe | 9.0 | Cs | ＜0.1 | Pb | ＜0.1 |
| Co | ＜0.05 | Ba | ＜0.5 | Bi | ＜0.1 |
| Ni | 0.15 | La | Do not record | Th | ＜0.01 |
| Cu | 0.60 | Ce | ＜0.1 | U | ＜0.01 |
Table 5
Use Li
2WO
4And B
2O
3The YAl of growth
3(BO
3)
4Crystalline is formed
Help to estimate the influence of tungsten with reference to Fig. 5 to the NLO crystalline optical property of usefulness tungsten solvent growth.Fig. 5 will be with the YAl of tungsten growth
3(BO
3)
4The percentage transmission of crystal (YAB-W) and the YAl that comprises molybdenum
3(BO
3)
4The percentage transmission of crystal (YAB-Mo) and the YAl that does not contain all transition metal contaminants substantially
3(BO
3)
4The percentage transmission of crystal (YAB-La) compares.As shown in the figure, the wavelength ratio YAB-La crystal that the YAB-W crystal begins extinction begins the wavelength of extinction will be grown, but it is short to begin the wavelength of extinction than YAB-Mo crystal.For many application, the absorbancy under shorter wavelength is favourable.For these application, compare with the YAB-Mo crystal, more preferably YAB-W crystal, but the YAB-W crystal still is inferior to the YAB-La crystal.
After using described method formation crystal, can verify uniform crystalline structure by X-ray diffraction.Can be by placing laser beam to detect the crystalline optical property in these crystal.For example, can detect YAl in this way
3(BO
3)
4Crystal is to confirm the generation of second harmonic light.
The NLO crystal that is formed by methods described herein comprises the NLO crystal of aluminium-borate NLO crystal and so on, this crystal does not contain substantially and/or comprises approximately less than 100 ppm by weight, preferably approximately less than 50 ppm by weight, more preferably from about less than 10 ppm by weight any can the required wavelength of influence the generation of light and/or the element of emission, described required wavelength is for example approximately less than 300 nanometers, preferably approximately less than 250 nanometers, more preferably from about less than the wavelength of 1 75 nanometers.The secondary materials that influences the generation of light of required wavelength and/or emission can be for example transition metal except that yttrium, lanthanum and lutetium and lanthanon.Crystal also can be classified according to the concentration of molybdate compound wherein.Some crystal that form by described method do not contain substantially and/or comprise approximately less than 100 ppm by weight, preferred approximately less than 50 ppm by weight, more preferably from about less than any molybdate compound of 10 weight.
Crystal as herein described has many useful purposes.Aluminium-borate NLO the crystal that for example has the aluminium-borate NLO crystal and so on of the chemical structure that comprises yttrium, lutetium or its combination can be installed in the laser apparatus laser apparatus for example shown in Figure 6.Under certain conditions, these crystal can produce and/or launch short wavelength laser beam.
Laser beam can be used to detect the anomalous structure of the substrate surface that comprises semiconductor chip.This detection can be by for example being directed to laser beam on the surface of substrate with certain pattern (for example grating pattern), and measure catoptrical consistence and carry out.When laser beam ran into anomalous structure (for example particle) on the substrate surface, scattering can take place in reflected light.The laser beam of shorter wavelength can detect less anomalous structure, therefore is particularly useful.This is very important in semi-conductor industry, in semi-conductor industry, along with reducing of component size, can cause the size of the anomalous structure of negative impact also to reduce to device function.
The laser beam of shorter wavelength also can be used to bore the hole of minor diameter in substrate.Compare with the laser beam of longer wavelength, these laser beams can be assembled higher energy in littler area, therefore can give substrate higher energy.The ability of boring small diameter bore in substrate can be used for for example making up component structure on printed circuit board (PCB).
For some embodiment of the present invention, nonlinear optics (NLO) crystal that comprises aluminium-borate NLO crystal has been described, the meeting that comprises lower concentration in these crystal influences the pollutent of NLO crystal optics character, for example comprises the transition metal except that yttrium, lanthanum and lutetium and/or the compound of lanthanon.Second harmonic can take place in some NLO crystal that comprise these pollutents of lower concentration under utmost point short wavelength.The embodiment that is used for preparing these NLO crystalline methods has also been described.Some embodiments comprise by growth NLO monocrystalline, for example aluminium-borate NLO crystal in the mixture that comprises the solvent that does not contain harmful pollutent substantially.Described NLO crystal can be used for for example laser apparatus.
Be to be understood that embodiment described herein and embodiment only are used for explanation, those skilled in the art can propose various modifications or change aspect optics, and these changes are included within the application's the scope of spirit, scope and appended claims.
Claims (103)
1. one kind is used at the mixture that equals and be lower than the device for non-linear optical of using under 350 nanometers, and this mixture comprises the YAl that comprises that is used for device for non-linear optical
3B
4O
12Material; Described mixture do not contain be at least 1000ppm contain molybdenum impurity.
2. mixture as claimed in claim 1 is characterized in that, described mixture do not contain be at least 500ppm contain molybdenum impurity.
3. mixture as claimed in claim 2 is characterized in that, described mixture do not contain be at least 100ppm contain molybdenum impurity.
4. mixture as claimed in claim 3 is characterized in that, described mixture do not contain be at least 10ppm contain molybdenum impurity.
5. mixture as claimed in claim 4 is characterized in that, described mixture do not contain be at least 1ppm contain molybdenum impurity.
6. mixture as claimed in claim 5 is characterized in that, described mixture does not contain molybdenum impurity substantially.
7. mixture as claimed in claim 1 is characterized in that, described application is relevant with the wavelength of about 350-160 nanometer.
8. mixture as claimed in claim 1 is characterized in that, described application is that to be lower than the device of optical radiation of 350 nanometers relevant with generation.
9. mixture as claimed in claim 8 is characterized in that described device comprises the NLO system.
10. mixture as claimed in claim 8 is characterized in that described device comprises the mixture relevant with laser system.
11. mixture as claimed in claim 8 is characterized in that, described device comprises the mixture relevant with light source.
12. mixture as claimed in claim 1 is characterized in that, described mixture with in that to be lower than the trigonal system of using under 350 nanometers relevant.
13. mixture as claimed in claim 1 is characterized in that, described mixture with in that to be lower than the R32 spacer of using under 350 nanometers relevant.
14. mixture as claimed in claim 1 is characterized in that, this mixture also comprises doping agent, doping agent comprise be selected from following at least a: Ce, Nd and Yb.
15. mixture as claimed in claim 14 is characterized in that, described mixture comprises NYAB.
16. mixture as claimed in claim 14 is characterized in that, described mixture comprises Yb:YAB.
17. mixture as claimed in claim 14 is characterized in that, described mixture comprises Ce:YAB.
18. mixture as claimed in claim 1 is characterized in that, the volume of described mixture is approximately greater than 0.001 millimeter
3
19. mixture as claimed in claim 18 is characterized in that, the volume of described mixture is approximately greater than 0.01 millimeter
3
20. mixture as claimed in claim 19 is characterized in that, the volume of described mixture is approximately greater than 0.1 millimeter
3
21. mixture as claimed in claim 20 is characterized in that, the volume of described mixture is approximately greater than 1 millimeter
3
22. one kind is used at the mixture that equals and be lower than the device for non-linear optical of using under 350 nanometers, this mixture comprises the Y that comprises that is used for device for non-linear optical
(1-X)M
XAl
3B
4O
12Material, x is more than or equal to 0, and is less than or equal to 0.1, M is selected from Sc, La, Yb or Lu; Described mixture do not contain be at least 1000ppm contain molybdenum impurity.
23. one kind is used at the mixture that equals and be lower than the device for non-linear optical of using under 350 nanometers, this mixture comprises the Yb that comprises that is used for device for non-linear optical
(1-X)M
XAl
3B
4O
12Material, x is more than or equal to 0, and is less than or equal to 0.1, M is selected from Sc, Y, La or Lu; Described mixture do not contain be at least 1000ppm contain molybdenum impurity.
24. one kind is used at the mixture that equals and be lower than the device for non-linear optical of using under 350 nanometers, this mixture comprises the Lu that comprises that is used for device for non-linear optical
(1-X)M
XAl
3B
4O
12Material, x is more than or equal to 0, and is less than or equal to 0.1, M is selected from Sc, Yb or La; Described mixture do not contain be at least 1000ppm contain molybdenum impurity.
25. one kind is used at the mixture that equals and be lower than the device for non-linear optical of using under 350 nanometers, this mixture comprises the Sc that comprises that is used for device for non-linear optical
(1-X)M
XAl
3B
4O
12Material, x is more than or equal to 0, and is less than or equal to 0.1, M is selected from Y, La, Yb or Lu; Described mixture do not contain be at least 1000ppm contain molybdenum impurity.
26. one kind is used at the mixture that equals and be lower than the device for non-linear optical of using under 350 nanometers, this mixture comprises:
The A that comprises that is used for device for non-linear optical
XM
(1-X)Al
3B
4O
12Material; X is more than or equal to 0, and is less than or equal to 0.1;
Wherein:
A is selected from Sc, Y, La, Yb or Lu;
M is selected from Sc, Y, La, Yb or Lu;
This mixture do not contain be at least 1000ppm contain molybdenum impurity.
27. mixture as claimed in claim 26 is characterized in that, M is La.
28. mixture as claimed in claim 26 is characterized in that, M is Lu.
29. mixture as claimed in claim 26 is characterized in that, M is Sc.
30. mixture as claimed in claim 26 is characterized in that, M is Y.
31. mixture as claimed in claim 26 is characterized in that, M is Yb.
32. mixture as claimed in claim 26 is characterized in that, A is Sc.
33. mixture as claimed in claim 26 is characterized in that, A is Y.
34. mixture as claimed in claim 26 is characterized in that, A is La.
35. mixture as claimed in claim 26 is characterized in that, A is Yb.
36. mixture as claimed in claim 26 is characterized in that, A is Lu.
37. mixture as claimed in claim 26 is characterized in that, this mixture do not contain be at least 500ppm contain molybdenum impurity.
38. mixture as claimed in claim 37 is characterized in that, this mixture do not contain be at least 100ppm contain molybdenum impurity.
39. mixture as claimed in claim 38 is characterized in that, this mixture do not contain be at least 10ppm contain molybdenum impurity.
40. mixture as claimed in claim 39 is characterized in that, this mixture do not contain be at least 1ppm contain molybdenum impurity.
41. mixture as claimed in claim 40 is characterized in that, described mixture does not contain molybdenum impurity substantially.
42. mixture as claimed in claim 26 is characterized in that, described application is relevant with the wavelength of about 350-160 nanometer.
43. mixture as claimed in claim 26 is characterized in that, described application is that to be lower than the device of optical radiation of 350 nanometers relevant with generation.
44. mixture as claimed in claim 43 is characterized in that, described device comprises the NLO system.
45. mixture as claimed in claim 43 is characterized in that, described device comprises the mixture relevant with laser system.
46. mixture as claimed in claim 43 is characterized in that, described device comprises the mixture relevant with light source.
47. mixture as claimed in claim 26 is characterized in that, described mixture with in that to be lower than the trigonal system of using under 350 nanometers relevant.
48. mixture as claimed in claim 26 is characterized in that, described mixture with in that to be lower than the R32 spacer of using under 350 nanometers relevant.
49. mixture as claimed in claim 26 is characterized in that, this mixture also comprises doping agent, doping agent comprise be selected from following at least a: Ce and Nd.
50. mixture as claimed in claim 26 is characterized in that, described application is relevant with the wavelength of about 350-160 nanometer.
51. mixture as claimed in claim 26 is characterized in that, the volume of described mixture is approximately greater than 0.001 millimeter
3
52. mixture as claimed in claim 51 is characterized in that, the volume of described mixture is approximately greater than 0.01 millimeter
3
53. mixture as claimed in claim 52 is characterized in that, the volume of described mixture is approximately greater than 0.1 millimeter
3
54. mixture as claimed in claim 53 is characterized in that, the volume of described mixture is approximately greater than 1 millimeter
3
55. a non-linear optic crystal, its volume are approximately greater than 0.1 millimeter
3, comprise approximately less than having of 100 ppm by weight and suppress that non-linear optic crystal produces and/or transmitted wave is about any element less than the ability of the light of 300 nanometers.
56. non-linear optic crystal as claimed in claim 55 is characterized in that, described non-linear optic crystal is aluminium-borate non-linear optic crystal.
57. non-linear optic crystal as claimed in claim 55 is characterized in that, described non-linear optic crystal is the aluminium-borate non-linear optic crystal that comprises yttrium and/or lutetium.
58. aluminium-borate non-linear optic crystal, its volume is approximately greater than 0.1 millimeter
3, comprise approximately and to comprise the transition metal except that yttrium, lanthanum and lutetium and/or the mixture of lanthanon arbitrarily less than 100 ppm by weight.
59. aluminium as claimed in claim 58-borate non-linear optic crystal is characterized in that, its volume is approximately greater than 1 millimeter
3
60. aluminium-borate non-linear optic crystal, its volume is approximately greater than 0.1 millimeter
3, it comprises approximately any independent molybdate compound less than 100 ppm by weight.
61. YAl
3(BO
3)
4Crystal, its volume are approximately greater than 0.1 millimeter
3, it comprises approximately less than 100 ppm by weight any and has inhibition YAl
3(BO
3)
4Crystal produce and/or emission approximately less than the element of the ability of the light of 300 nano wave lengths.
62. non-linear optic crystal, it comprises the main raw peace treaty has less than 100 ppm by weight any and suppresses that non-linear optic crystal produces and/or transmitted wave is about element less than the ability of the light of 300 nanometers, and described non-linear optic crystal can be used to change the wavelength of the laser beam that laser apparatus produces.
63. non-linear optic crystal as claimed in claim 62 is characterized in that, described non-linear optic crystal is aluminium-borate non-linear optic crystal.
64. non-linear optic crystal as claimed in claim 62 is characterized in that, described non-linear optic crystal is YAl
3(BO
3)
4Crystal.
65. aluminium-borate non-linear optic crystal, its volume is approximately greater than 1 millimeter
3, this crystal can be transformed to the input laser beam of first wavelength outgoing laser beam of second wavelength, and described second wavelength is approximately less than 200 nanometers.
66., it is characterized in that described aluminium-borate non-linear optic crystal is YAl as the described aluminium of claim 65-borate non-linear optic crystal
3(BO
3)
4Crystal.
67. aluminium-borate non-linear optic crystal, its volume is approximately greater than 1 millimeter
3Described aluminium-borate non-linear optic crystal can be transformed to the input laser beam of first wavelength outgoing laser beam of second wavelength, described second wavelength is approximately less than 500 nanometers, and described aluminium-borate non-linear optic crystal also comprises the Tungstenic compound different with main raw.
68. a method for preparing non-linear optic crystal, this method comprises:
Main raw and solvent are provided, described solvent do not contain substantially any have suppress that non-linear optic crystal produces and/or transmitted wave is about element less than the ability of the light of 300 nanometers;
Make the main raw recrystallization form non-linear optic crystal, this crystal do not contain substantially any have suppress that non-linear optic crystal produces and/or transmitted wave is about element less than the ability of the light of 300 nanometers.
69. a method for preparing aluminium-borate non-linear optic crystal, this method comprises:
Main raw and solvent are provided, described solvent do not contain substantially any have suppress that non-linear optic crystal produces and/or transmitted wave is about element less than the ability of the light of 300 nanometers;
Make the main raw recrystallization, form aluminium-borate non-linear optic crystal, this crystal do not contain substantially any have suppress that non-linear optic crystal produces and/or transmitted wave is about element less than the ability of the light of 300 nanometers.
70., it is characterized in that described solvent comprises LaB as the described method of claim 69
3O
6, MgB
2O
4, LiF or their combination.
71., it is characterized in that described solvent does not contain any independent molybdate compound substantially as the described method of claim 69.
72., it is characterized in that described main raw is YAl as the described method of claim 69
3(BO
3)
4
73., it is characterized in that described solvent comprises LaB as the described method of claim 72
3O
6
74., it is characterized in that described main raw is LuAl as the described method of claim 69
3(BO
3)
4
75., it is characterized in that described solvent comprises LaB as the described method of claim 74
3O
6
76., it is characterized in that the recrystallization main raw comprises main raw and solvent, forms mixture, and add crystal seed in this mixture as the described method of claim 69.
77., it is characterized in that described crystal seed mainly is made up of main raw as the described method of claim 76.
78. as the described method of claim 76, it is characterized in that, in mixture, add crystal seed and comprise crystal seed is suspended in the mixture.
79., it is characterized in that the main raw recrystallization also comprises cooling mixture as the described method of claim 76, and from mixture, shift out aluminium-borate non-linear optic crystal.
80. as the described method of claim 79, it is characterized in that, cooling mixture is included in the growth time mixture is cooled to second temperature that is lower than the mixture fusing point from first temperature that is equal to or higher than the mixture fusing point, and described growth time is approximately greater than 10 hours.
81., it is characterized in that described second temperature is approximately than low about 5-100 ℃ of mixture fusing point as the described method of claim 80.
82., it is characterized in that in the portion of time in described growth time, less than 2 ℃/hour cooling gradient cooling mixture, the portion of time in the described growth time is approximately greater than 2 hours with approximately as the described method of claim 80.
83. one kind prepares YAl
3(BO
3)
4The crystalline method, this method comprises:
With YAl
3(BO
3)
4Form mixture with solvent, described solvent does not contain any transition metal except that yttrium, lanthanum and lutetium and/or compound of lanthanon of comprising substantially;
In described mixture, add crystal seed;
In growth time, mixture is cooled to second temperature that is lower than the mixture fusing point from first temperature that is equal to or higher than the mixture fusing point;
After cooling mixture, from mixture, shift out YAl
3(BO
3)
4Crystal, described growth time are approximately greater than 10 hours.
84., it is characterized in that described solvent comprises LaB as the described method of claim 83
3O
6, MgB
2O
4, LiF or their combination.
85. a method for preparing aluminium-borate non-linear optic crystal, this method comprises:
Main raw and solvent are provided, and described solvent comprises tungsten;
With the main raw recrystallization, form and not contain any aluminium-borate non-linear optic crystal that comprises the compound of transition metal except that yttrium, lanthanum, lutetium and tungsten and/or lanthanon substantially.
86., it is characterized in that described main raw is YAl as the described method of claim 85
3(BO
3)
4
87., it is characterized in that described solvent comprises Li as the described method of claim 86
2WO
4.
88., it is characterized in that described solvent also comprises B as the described method of claim 87
2O
3
89. one kind prepares YAl
3(BO
3)
4The crystalline method, this method comprises: YAl is provided
3(BO
3)
4And solvent, described solvent does not contain any independent molybdate compound substantially;
Recrystallization YAl
3(BO
3)
4, form YAl
3(BO
3)
4Crystal, this crystal comprise approximately any independent molybdate compound less than 10 ppm by weight, in molybdenum.
90. one kind prepares the method that is used for equaling and be lower than the mixture of the device for non-linear optical that uses under 350 nanometers, this method comprises:
Multiple material is provided, and described multiple material comprises and contains lanthanum compound, and this contains lanthanum compound and can decompose when heating and generate lanthanum trioxide at least;
At least based on the information relevant described multiple material mixing is got up, form mixture with predetermined proportion;
Crystallization is carried out in beginning in mixture, form crystal;
Crystal is shifted out from mixture, and described crystal comprises lanthanum.
91., it is characterized in that described multiple material comprises lanthanum trioxide as the described method of claim 90.
92., it is characterized in that described multiple material also comprises boron oxide as the described method of claim 91.
93., it is characterized in that this method also comprises described mixture is placed in the process furnace as the described method of claim 90.
94., it is characterized in that this method also comprises as the described method of claim 90:
First temperature that described mixture heating up is extremely predetermined;
Described mixture is cooled to the second predetermined temperature.
95., it is characterized in that beginning crystalline step comprises inserts bath surface with crystal seed as the described method of claim 90.
96., it is characterized in that as the described method of claim 90:
Described crystal comprises A
XM
(1-X)Al
3B
4O
12
X is more than or equal to 0, and is less than or equal to 0.1;
A is selected from Sc, Y, La, Yb or Lu;
M is selected from Sc, Y, La, Yb or Lu.
97. one kind is used in the preparation method who equals and be lower than the mixture of the device for non-linear optical of using under 350 nanometers, this method comprises:
Multiple material is provided, and described multiple material comprises and contains yttrium compound that the described yttrium compound that contains can decompose, and generates yttrium oxide at least when heating;
At least based on the information relevant multiple material mixing is got up, form mixture with predetermined proportion;
In mixture, begin crystallization, form crystal;
Crystal is shifted out from mixture, and described crystal comprises yttrium.
98., it is characterized in that described multiple material comprises yttrium oxide as the described method of claim 97.
99., it is characterized in that described multiple material also comprises boron oxide as the described method of claim 98.
100., it is characterized in that this method also comprises mixture is placed in the process furnace as the described method of claim 97.
101., it is characterized in that this method also comprises as the described method of claim 97:
First temperature that described mixture heating up is extremely predetermined;
Described mixture is cooled to the second predetermined temperature.
102., it is characterized in that described beginning crystallization comprises inserts bath surface with crystal seed as the described method of claim 97.
103., it is characterized in that as the described method of claim 97:
Described crystal comprises A
XM
(1-X)Al
3B
4O
12
X is more than or equal to 0, and is less than or equal to 0.1;
A is selected from Sc, Y, La, Yb or Lu;
M is selected from Sc, Y, La, Yb or Lu.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US56262604P | 2004-04-14 | 2004-04-14 | |
| US60/562,626 | 2004-04-14 | ||
| US60/562,881 | 2004-04-16 |
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| Publication Number | Publication Date |
|---|---|
| CN101124163A true CN101124163A (en) | 2008-02-13 |
Family
ID=39086015
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2005800158048A Pending CN101124163A (en) | 2004-04-14 | 2005-04-14 | Method and structure for non-linear optics |
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| CN102036917A (en) * | 2008-04-11 | 2011-04-27 | 深光子学公司 | Method and structure for nonlinear optics |
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| CN102036917A (en) * | 2008-04-11 | 2011-04-27 | 深光子学公司 | Method and structure for nonlinear optics |
| CN102036917B (en) * | 2008-04-11 | 2014-04-02 | 深光子学公司 | Method and structure for nonlinear optics |
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| CN103194232A (en) * | 2013-03-26 | 2013-07-10 | 上海师范大学 | Wideband ultraviolet-visible light exited near infrared fluorescent emitting material and preparation method and application thereof |
| CN113292080A (en) * | 2020-02-24 | 2021-08-24 | 中国科学院福建物质结构研究所 | Inorganic compound crystal Ba7Sn(BO3)6Preparation method and application thereof |
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