CN114395394A - Near-infrared fluorescent powder and optical device comprising same - Google Patents
Near-infrared fluorescent powder and optical device comprising same Download PDFInfo
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- CN114395394A CN114395394A CN202111539262.1A CN202111539262A CN114395394A CN 114395394 A CN114395394 A CN 114395394A CN 202111539262 A CN202111539262 A CN 202111539262A CN 114395394 A CN114395394 A CN 114395394A
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- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7708—Vanadates; Chromates; Molybdates; Tungstates
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- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
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Abstract
The invention relates to near-infrared fluorescent powder and an optical device comprising the same, wherein the emission peak position of the near-infrared fluorescent powder is positioned at 1270-one 1330 nm. On one hand, the near-infrared fluorescent powder can be excited by blue light and visible light, particularly can be matched with a blue light chip, can enrich the emission coverage band of the near-infrared fluorescent powder, particularly has a wide emission spectrum in the range of 1270-; on the other hand, the near-infrared fluorescent powder has absorption in an infrared region, is suitable for manufacturing ink and is used for anti-counterfeiting materials. In the light-emitting device, on the basis of matching with the near-infrared fluorescent powder, the visible light fluorescent powder with the emission wavelength range of 500-780nm and the near-infrared fluorescent powder with the emission wavelength range of 780-1550nm are simultaneously used, so that the light-emitting device has more high-efficiency near-infrared emission and unique spectrum aiming at the application.
Description
Technical Field
The invention relates to the technical field of luminescent materials, in particular to near-infrared fluorescent powder and an optical device comprising the same.
Background
In recent years, applications of near-infrared light sources in the fields of environmental light sources, medical food detection, water quality detection, semiconductor material alignment detection and the like become an industry focus, and near-infrared LEDs have become an international research focus due to a series of advantages of good directivity, low power consumption, small volume and the like. Currently, only corresponding near-infrared semiconductor chips are available on the market for the above-mentioned applications. However, the near infrared chip has the problems of narrow spectrum (half-height width is less than 40nm), poor tuning performance, high cost, monopoly of foreign countries and the like. In the application field requiring a broadband near-infrared light source, such as the field of semiconductor material alignment detection, the broadband near-infrared light emission with peak positions at 1300nm and 1500nm wave bands is mainly applied, a plurality of near-infrared chips with different emission wave bands need to be compositely packaged, and the technology has high difficulty coefficient in realization: on one hand, the difference of the driving currents of the near-infrared LED chips with different light-emitting wave bands is large, and the large difference of the light attenuation of different chips easily causes the sudden drop of thermal stability, so that the service life of the whole light-emitting device is influenced; on the other hand, the existing long-wave-band chip (>1000nm) technology is immature, especially the chip technology with the emission peak wavelength position located in the 1270-1330nm wave band is difficult to realize, the luminous efficiency is low, the process of packaging by adopting a plurality of chips is complex and uncontrollable, the cost is high, and the application and popularization of the near-infrared LED optical device are limited.
The fluorescence conversion type near-infrared LED is a new near-infrared light source, is realized by adopting a packaging mode of a blue light/visible light chip and high-efficiency near-infrared fluorescent powder, can avoid a short plate of a chip technology, and has the advantages of simple preparation process, low cost, adjustable spectrum and the like, so that the fluorescence conversion type near-infrared LED is widely concerned by the industry. As one of the core materials of the fluorescence conversion type near-infrared LED, the near-infrared fluorescent powder can directly determine the performances of the near-infrared LED device, such as luminous efficiency, spectral continuity and the like, and the application scene. However, the research of the near-infrared phosphor is just beginning, the material variety is deficient, the spectrum coverage range is relatively single, the luminous efficiency is relatively low, and especially, the near-infrared phosphor which emits with high efficiency and the emission peak wavelength position of which is located at the 1270-1330nm wave band is lacking.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides the near-infrared fluorescent powder and the optical device comprising the same, wherein the emission peak position is positioned in the range of 1270-1330 nm. The near-infrared fluorescent powder can be excited by blue light and visible light, and particularly can be matched with a blue light chip, so that the technical problems of the prior art that the near-infrared fluorescent powder is deficient in material types, single in spectrum coverage range, low in luminous efficiency and the like are solved. Another objective of the present invention is to provide a light emitting device containing the near-infrared light emitting material, which can realize efficient visible-near-infrared emission under blue light excitation, so as to solve the problems of the existing infrared chip technology that the longer near-infrared light emitting efficiency is low, especially the chip technology with the emission peak wavelength position located at the 1270-1330nm band is difficult to realize, the light emitting efficiency is low, and the continuity of the emission spectrum of the light emitting device is poor, and widen the application fields of the light emitting device in semiconductor material alignment detection, metal flaw detection, environmental light source, etc.
To achieve the above object, according to one aspect of the present invention, there is provided a near-infrared phosphor, a near-infrared phosphor comprising a composition formula A2-x-d-mSrxDdE1-g-yGgOzyCr, mM inorganic compound, wherein, the A element is one or two of Ca, Ba, Mg and Zn; the D element is one or two of La, Gd, Tb, Y and Lu; the element E is one or two of Hf, Ge and Si; the G element is one or two of Ga, In, Sc, Al, Ce and Bi; m element is one or two of Li, Na and K; wherein 0<x≤0.2，0<d≤0.2，0≤g≤0.1，3.7≤z≤4.3，0<y is less than or equal to 0.1, m is less than or equal to 0 and less than or equal to 0.2, and the near-infrared fluorescent powder has Ca of a cubic crystal system2GeO4A crystal structure. Wherein "comma" indicates an element also contained in the material.
Furthermore, in the molecular formula, the element A is Ca and Ba, the mole percentage of Ba occupying the element A is i, and 0% < i is less than or equal to 10%.
Furthermore, in the molecular formula, x is more than 0 and less than or equal to 0.12.
Furthermore, in the molecular formula, the element E is Hf and Ge, the mole percentage of Hf occupying the element E is j, and j is more than 0% and less than or equal to 8%.
Furthermore, the molecular formula is characterized in that the G element is one of Ce and Bi, and G is more than 0 and less than or equal to 0.1.
Further, in the formula, g is 4/3 y.
Furthermore, in the molecular formula, the element D is one of Y, Gd and Lu, and D is more than 0 and less than or equal to 0.07.
In the formula, M is one of Li, Na and K, and M is d.
The invention provides near-infrared fluorescent powder with an emission peak wavelength position located in the range of 1270-; on the other hand, the near-infrared fluorescent powder has absorption in an infrared region, is suitable for manufacturing ink and is used for anti-counterfeiting materials.
According to another aspect of the present invention, there is provided a light emitting device comprising a light source and a luminescent material comprising a near infrared phosphor as provided hereinbefore in the first aspect of the invention.
Further, the light source is a semiconductor chip with an emission peak wavelength range of 400-460nm or 600-660 nm.
Furthermore, the luminescent material also comprises visible light fluorescent powder with the emission wavelength range of 500-780nm and near-infrared fluorescent powder with the emission wavelength range of 780-1550 nm.
Further, the visible light phosphor is a phosphor with an emission wavelength range of 500-780nm, including but not limited to (Mg, Zn) (Ca, Sr, Ba)3Si2O8:Eu2+、(Ca,Sr,Ba)Si2N2O2:Eu2+、β-SiAlON:Eu2+、(Lu,Y,Gd)3(Al,Ga)5O12:Ce3+,Tb3+、(Lu,Y,Gd)3(Al,Ga)5O12:Ce3+、(La,Y,Lu)3Si6N11:Ce3+、(Ca,Sr,Ba)2Si5N8:Eu2+、(Ca,Sr)AlSiN3:Eu2+、K2(Si,Ge)F6:Mn4+、(Sr,Ca,Ba)4(Al,Sc,Ga,In)14O25:Mn4+、(La,Y,Gd,Lu)3(Al,Ga)(Ge,Si)5O16:Mn4+、CaO·Al2O3·Ga2O3·ZnO·MnO2·Li2O、(Lu,Y,Gd)3(Al,Ga)5O12:Mn4+One or more of.
Further, the near-infrared phosphor is a phosphor with an emission wavelength range of 780-1550nm, including but not limited to (La, Y, Gd, Lu)3(Al,Ga)5(Ge,Si)O14:Cr3+,Yb3+,Er3+、Sc2O3·Ga2O3·(Cr,Yb,Nd,Er)2O3、(La,Lu,Y,Gd)(Sc,Ga,Al,In)3B4O12:Cr3+,Yb3+,Er3+One or more of.
Wherein, in each substance, the term "indicates that the element in parentheses may be a single component or a solid solution containing more than one element, for example: (Ca, Sr) AlSiN3:Eu2+Is represented as CaAlSiN3:Eu2+、SrAlSiN3:Eu2+And Ca1-αSrαAlSiN3:Eu2+(0<α<1) One or more of them. The near-infrared fluorescent powder disclosed by the invention is matched with the fluorescent powder for use, so that a light-emitting device emits light with high luminous efficiency and excellent spectrum continuity, the problems that a longer near-infrared light-emitting efficiency is low in the existing infrared chip technology, especially the chip technology with the emission peak wavelength position located in the 1270 plus-charge 1330nm wave band is difficult to realize, the light-emitting efficiency is low, and the continuity of the emission spectrum of a light-emitting device is poor are solved, and the application requirements of various traditional and novel fields including application fields of semiconductor material alignment detection, metal flaw detection, environmental light source, medical food detection, water quality detection and the like are met.
The technical scheme of the invention has the following beneficial technical effects:
the invention provides near-infrared fluorescent powder with an emission peak wavelength position located in the range of 1270-; on the other hand, the near-infrared fluorescent powder has absorption in an infrared region, is suitable for manufacturing ink and is used for anti-counterfeiting materials. The near-infrared fluorescent powder can be used for preparing a light-emitting device, the light-emitting device can obtain near-infrared emission with the emission peak wavelength position being 1270-1330nm under the excitation of blue light/visible light, particularly under the excitation of the blue light, has the advantage of high luminous efficiency, and can be widely applied to various traditional and novel fields in the application fields of semiconductor material alignment detection, metal flaw detection, environmental light sources, medical food detection, water quality detection and the like. In addition, on the basis of matching with the near-infrared fluorescent powder, the luminescent device simultaneously uses the visible light fluorescent powder with the emission wavelength range of 500-780nm and the near-infrared fluorescent powder with the emission wavelength range of 780-1550nm, so that the luminescent device has more high-efficiency near-infrared emission and unique spectrum aiming at the application, and further widens the application field of the luminescent device.
Drawings
FIG. 1 is a graph showing the absorption spectrum of a near-infrared phosphor sample prepared in example 1;
FIG. 2 is a graph showing an emission spectrum of a near-infrared phosphor sample prepared in example 1;
FIG. 3 is an XRD pattern of a sample of the near infrared phosphor prepared in example 1;
FIG. 4(a) is an SEM photograph of a comparative example; FIG. 4(b) is an SEM photograph of example 1; FIG. 4(c) is an SEM photograph of example 5; FIG. 4(d) is an SEM photograph of example 47;
FIG. 5 is a schematic view of a light-emitting device; wherein 1-luminescent material, 2-semiconductor chip, 3-pin, 4-heat sink, 5-base, 6-glass cover.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings in conjunction with the following detailed description. It should be understood that the description is intended to be exemplary only, and is not intended to limit the scope of the present invention. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present invention.
As described in the background art, the near-infrared chip technology of longer wavelength band in the existing infrared chip technology is immature, the luminous efficiency is low, especially the chip technology of which the emission peak wavelength position is located at the 1270 + 1330nm band is difficult to realize, the luminous efficiency is low, and the research of the existing near-infrared phosphor powder is just started, the material variety is deficient, the spectrum coverage range is single, the luminous efficiency is low, especially the high-efficiency near-infrared phosphor powder of which the emission peak wavelength position is located at the 1270 + 1330nm band is absent, so that the application of the fluorescence conversion type near-infrared LED device is limited, and in order to solve the problem, the application provides a phosphor powder and a light emitting device with the phosphor powder.
According to an embodiment of the present invention, there is provided a near-infrared phosphor including a composition formula A2-x-d-mSrxDdE1-g-yGgOzyCr, mM inorganic compound, wherein, the A element is one or two of Ca, Ba, Mg and Zn; the D element is one or two of La, Gd, Tb, Y and Lu; the element E is one or two of Hf, Ge and Si; the G element is one or two of Ga, In, Sc, Al, Ce and Bi; m element is one or two of Li, Na and K; wherein 0<x≤0.2，0<d≤0.2，0≤g≤0.1，3.7≤z≤4.3，0<y is less than or equal to 0.1, m is less than or equal to 0 and less than or equal to 0.2, and the near-infrared fluorescent powder has Ca of a cubic crystal system2GeO4A crystal structure. The following theoretical explanations are developed on the premise of having the crystal structure of the phosphor.
The A position of the fluorescent powder must contain alkaline earth metal Sr element with larger activity, Sr is the active element, further nucleation and grain growth of the fluorescent powder are facilitated, and experiments prove that Sr element is beneficial to further improving the crystallization property and the single crystal grain size of the fluorescent powder and improving the luminous intensity. Meanwhile, the Sr element is an alkaline earth metal element with a moderate radius, and lattice distortion caused to material lattices after the Sr element and other alkaline earth metal elements are co-doped is small, so that the luminous intensity of the material is favorably and further improved under the condition that the crystal field is not greatly changed, namely, the emission spectrum is almost unchanged. In addition, the D element is one or two of La, Gd, Tb, Y and Lu, and is doped into the A element position. The La, Gd, Tb, Y and Lu elements have larger electronegativity, and can easily form covalent bonds with cations, so that the covalent bonds with stronger covalent bonds are formed, the probability of radiative transition of a luminescence center is increased, and the optical properties of the material, such as luminous intensity and the like, are improved; on the other hand, the La, Gd, Tb, Y and Lu elements have stronger activity, which is beneficial to increasing the probability of radiative transition of the luminescence center and further improving the optical properties of the material, such as luminous intensity and the like. Moreover, the change of the ion radius and electronegativity of La, Gd, Tb, Y and Lu can cause the change of the original ligand position, thereby changing the crystal field intensity and the mass center displacement of the luminescence center, the emission spectrum of the fluorescent powder is easy to move, and the emission waveband of the near-infrared fluorescent powder can be effectively enriched.
Wherein, the A element in the compound is Ca and Ba element, the mole percentage of Ba occupying the A element is i, 0% < i < 10%. The ionic radius of the Ba element is larger than that of the Ca element, so that when the inorganic compound forming the fluorescent powder contains the Ba element, the original ligand site is expanded, the original crystal field environment is weakened, and the light-emitting waveband of the fluorescent powder is moved to a long wave; however, Ba element has a smaller electronegativity than Ca element, so that covalent bonding between cations and oxygen ions is reduced, and the shift of the centroid of the luminescence center can be reduced, thereby shifting the luminescence band of the phosphor to a short wavelength. According to the change of the lattice position and the electronegativity, when the mole percentage of Ba occupying the element A is 0% < i ≦ 10%, the luminescent band of the fluorescent powder hardly moves. On the other hand, the Ba element has higher activity than the Ca element, which is beneficial to the nucleation and grain growth of the fluorescent powder, and experiments prove that when the A element is Ca and Ba elements, the crystallization performance and the single crystal particle size of the fluorescent powder are beneficial to being improved, and the luminous intensity is improved. According to experimental research, when the content of the element Ba is too low, the luminescent intensity is low because the improvement effect of the element Ba on the fluorescent powder is not obvious, and when the content of the element Ba is too high, impurities are possibly generated, the probability of nonradiative transition of the fluorescent powder is increased, the luminescent intensity is also low, so that the mole percentage of the element A occupied by the element Ba is i, and preferably 0% < i ≦ 10%.
Furthermore, under the condition that the A element is Ca and Ba element, the mole percentage of Ba occupying the A element is i, and 0% < i ≦ 10%, the compound must contain Sr element and occupy the site of A lattice. When the element a is Ca and Ba, the difference in radii between Ca and Ba is large, which easily causes lattice mismatch and distortion, resulting in low luminous efficiency. The Sr element with the element radius between the Ca element and the Ba element is put into the lattice site of the A element, so that the conditions of lattice mismatch, distortion and the like can be effectively relieved, and the luminous efficiency of the material is improved. Furthermore, the activity of Sr element is larger than that of Ca element, which is beneficial to further nucleation and grain growth of the fluorescent powder, and experiments prove that Sr element is beneficial to further improving the crystallization property and the single crystal particle size of the fluorescent powder and improving the luminous intensity. According to experimental research, when the content of the Sr element is too low, the Sr element has an unobvious promotion effect on the fluorescent powder, and the luminous intensity is low, and when the content of the Sr element is too high, impurities are possibly generated, so that the probability of nonradiative transition of the fluorescent powder is increased, and the luminous intensity is also low, therefore, 0< x is preferably less than or equal to 0.12.
The element E is one or two of Hf, Ge and Si, wherein Si has a small radius, and silicate has the characteristic of wide absorption band, when Si is doped into a host material, the material can be kept to have effective near infrared emission, and meanwhile, the light-emitting waveband can be shifted to short wave. In another preferred embodiment of the present application, the element E is Hf and Ge, Hf has a larger radius than Ge, and tends to expand the lattice of the material matrix, so that the crystal field intensity is reduced and the emission wavelength band of the phosphor is shifted to a long wavelength. Moreover, the activity of Hf is greater than Ge, which is beneficial to playing a dissolving-assisting effect in the process of synthesizing the near-infrared fluorescent powder, is beneficial to nucleation and grain growth, and improves the luminous intensity. According to experimental research, when the content of the Hf element is too low, the promotion effect of the Hf on the fluorescent powder is not obvious, the luminous intensity is low, when the content of the Hf element is too high, the phenomena of concentration quenching, impurity occurrence, crystal structure change of a target product and the like can be generated, and non-radiative transition enhancement is caused, so that the luminous intensity is also low, and therefore, the mole percentage of the element E occupied by the Hf is j, and j is 0% < j < 8%.
Furthermore, G element is one of Ce and Bi, and the matrix is independently doped with Cr3+Absorption spectrum of (1) covering blue to red lightIn the visible wavelength band. When the G element is one of Ce and Bi, Ce and Bi ions can be doped into the matrix as a sensitizer to show yellow-green light emission, and the emission spectrum and Cr of the yellow-green light emission3+The absorption spectra are overlapped, and Ce and Bi ions can be converted into Cr3+Energy transfer of (3), increase of Cr3+Near infrared luminous intensity. According to experimental research, when the content of the G element is too small, the luminous intensity is also low because the sensitizer is small, the energy transfer effect is not obvious, and the luminous intensity is low, and when the content of the G element is too high, concentration quenching can occur to cause nonradiative transition enhancement, so that 0 is preferred<g is less than or equal to 0.1. Further, the energy transfer effect is best selected according to the most appropriate ratio of the activator (luminescence center) and the sensitizer, preferably g-4/3 y.
Besides, the G element can be one or two of Ga, In, Sc and Al and enters an E lattice site. Ga. The original ligand position can be changed due to different ionic radii and electronegativities of In, Sc and Al elements, so that the crystal field intensity and the mass center displacement of a luminescence center are changed, the emission spectrum of the fluorescent powder is easy to move, and the emission waveband of the near-infrared fluorescent powder can be effectively enriched. Moreover, according to experimental verification, on the premise of ensuring a pure phase structure, g is more than or equal to 0 and less than or equal to 0.1.
The D element is one or two of La, Gd, Tb, Y and Lu, and is doped into the position of the A element. The La, Gd, Tb, Y and Lu elements have larger electronegativity, and can easily form covalent bonds with cations, so that the covalent bonds with stronger covalent bonds are formed, the probability of radiative transition of a luminescence center is increased, and the optical properties of the material, such as luminous intensity and the like, are improved; on the other hand, the La, Gd, Tb, Y and Lu elements have stronger activity, which is beneficial to increasing the probability of radiative transition of the luminescence center and further improving the optical properties of the material, such as luminous intensity and the like. Moreover, the change of the ion radius and electronegativity of La, Gd, Tb, Y and Lu can cause the change of the original ligand position, thereby changing the crystal field intensity and the mass center displacement of the luminescence center, the emission spectrum of the fluorescent powder is easy to move, and the emission waveband of the near-infrared fluorescent powder can be effectively enriched. Further, preferably, the D element is one of Y, Gd and Lu, and enters the A lattice site. Among rare earth elements, Y, Gd, Lu have smaller ionic radiusOn one hand, the method is beneficial to the original ligand site shrinkage, changes the crystal field intensity, easily generates short wave shift in the emission spectrum of the fluorescent powder, and enriches the emission wave band of the near-infrared fluorescent powder; on the other hand, the ionic radius is reduced, so that the distance shrinkage of chemical bonds is facilitated, the material has a more compact spatial structure, and the performances of the material such as luminous intensity and the like are improved. In addition, Y, Gd and Lu have larger electronegativity and are easy to react with O2-The chemical bond with stronger covalent property is formed, and the stronger covalent bond property is favorable for increasing the probability of radiative transition of a luminescence center and further improving the optical properties of the material, such as luminous intensity and the like. And Y, Gd and Lu have stronger activity as rare earth elements, are favorable for the nucleation reaction of the material and improve the luminescence property. In particular, Gd3+Having radiative transitions in the matrix (e.g.:6PJ-8S7/2) The fluorescent powder can provide excitation energy except for an excitation light source for a luminescence center, and is favorable for improving the luminescence intensity of the fluorescent powder. According to experimental research, 0 is preferred<d≤0.07。
Furthermore, the M element is one of Li, Na and K, enters the A lattice position, the Li, Na and K are all metals, the number of electrons on the outermost layer is 1, and the constraint of atomic cores on electrons outside the core on the outermost layer is small, so that the melting point of the raw materials is low, the fluorescent powder is facilitated to melt, the crystallization performance and the single crystal particle size of the fluorescent powder are improved, and the luminous intensity is improved. Further, the A site is a divalent ion site, and after doping with trivalent D ion, it is easy to form minute defects in the phosphor due to charge mismatch, and these defects result in low luminous intensity. Therefore, the doping of the univalent ions Li, Na and K can effectively avoid the defects generated by charge imbalance, carry out charge compensation and fluxing and improve the luminous intensity of the fluorescent powder. From the SEM image, the appearance of the fluorescent powder added with the Li, Na and K additives is greatly improved, the fluorescent powder is similar to a sphere, the appearance is more regular, and the improvement of the luminous intensity of the fluorescent powder is facilitated. In addition, the more regular shape is beneficial to the encapsulation of the fluorescent powder, so that the luminescent device has more excellent optical performance. According to valence equilibrium theory and experimental verification, m-d is preferred.
The compound must contain Sr element and occupy A lattice site. When the element a is Ca and Ba, the difference in radii between Ca and Ba is large, which easily causes lattice mismatch and distortion, resulting in low luminous efficiency. The Sr element with the element radius between the Ca element and the Ba element is put into the lattice site of the A element, so that the conditions of lattice mismatch, distortion and the like can be effectively relieved, and the luminous efficiency of the material is improved. Furthermore, the activity of Sr element is larger than that of Ca element, which is beneficial to further nucleation and grain growth of the fluorescent powder, and experiments prove that Sr element is beneficial to further improving the crystallization property and the single crystal particle size of the fluorescent powder and improving the luminous intensity. According to experimental research, when the content of Sr element is too low, the luminescent intensity is low because the promotion effect of Sr element on the fluorescent powder is not obvious, and when the content of Sr element is too high, impurities can be generated, the probability of nonradiative transition of the fluorescent powder is increased, the luminescent intensity is also low, therefore, 0< x is less than or equal to 0.2 (preferably 0< x is less than or equal to 0.12).
O ions are the only anions in the matrix, and the value range of z is more than or equal to 3.7 and less than or equal to 4.3, so that on one hand, positive and negative charges in the material are balanced, and the material is prevented from generating serious charge imbalance to cause luminescence quenching; on the other hand, oxygen atoms and other cationic elements form polyhedrons in the material, each polyhedron takes the oxygen atoms as a linking point to form a unit cell structure of the whole material, and the appropriate range of O content can ensure the pure phase structure of the material, so that the structure of the material is not collapsed, the performance of the material is ensured, and otherwise luminescence quenching can be caused.
The Cr element is used as a luminescence center, namely an activator, and can enable the material to generate near infrared light, according to experimental verification, the value range of the content is more preferably 0< y and less than or equal to 0.1, when the content of the Cr element is too low, the luminescence intensity is low, and when the concentration of the Cr element is too high, luminescence quenching is easily caused.
The M element can be used as a material for charge compensation and fluxing, so that the material has better crystallinity, and the light effect of the material is improved. For the purpose of assisting experiments, the value range can be 0-m-0.2, and m-d is preferred.
The phosphor described above in the present application can preferably adopt the following preparation method provided in the present application, the preparation method comprising: step 1), taking simple substances selected from A element, D element, E element, G element, M element, Cr element, nitride, oxide or alloy thereof as raw materials, and mixing the raw materials to obtain a mixture; step 2), placing the mixture obtained in the step 1) into a container and roasting the mixture in nitrogen or other non-oxidizing atmosphere to obtain a roasted product, wherein the maximum sintering temperature is 900-1200 ℃, and the heat preservation time is 2-6 hours; and 3) sequentially crushing, washing, sieving and drying the roasted product in the step 2 to obtain the fluorescent powder.
The peak wavelength of the absorption spectrum of the phosphor powder of the inorganic compound with the composition is positioned in the near infrared bands of 400-460nm, 600-660nm and 700-800nm, and the emission peak wavelength covers the interval of 1270-1330 nm.
In another exemplary embodiment of the present application, there is provided a light emitting device including a phosphor and an excitation light source, the phosphor including the above-described phosphor. Because the fluorescent powder has high luminous intensity and the emission spectrum is easy to regulate and control, the working stability of the luminescent device with the fluorescent powder is high, the service life of the luminescent device is long, and the luminescent device is suitable for various different requirements.
In a preferred embodiment, the excitation light source is a semiconductor light emitting diode light source, and further preferably, the emission peak wavelength of the excitation light source is 400-460nm or 600-660 nm.
At present, the commercial LED excitation light source has an excitation wave band within the range, specifically, two excitation light sources are provided, and the light-emitting diode within the wavelength range is beneficial to photoluminescence of fluorescent powder.
In order to further improve the light emitting effect of the light emitting device, it is preferable that the phosphor further comprises other phosphors, including a visible light phosphor having an emission wavelength range of 500-780nm and a near infrared phosphor having an emission wavelength range of 780-1550 nm. The visible light phosphor is a phosphor with an emission wavelength range of 500-780nm, including but not limited to (Mg, Zn) (Ca, Sr, Ba)3Si2O8:Eu2+、(Ca,Sr,Ba)Si2N2O2:Eu2+、β-SiAlON:Eu2+、(Lu,Y,Gd)3(Al,Ga)5O12:Ce3+,Tb3+、(Lu,Y,Gd)3(Al,Ga)5O12:Ce3+、(La,Y,Lu)3Si6N11:Ce3+、(Ca,Sr,Ba)2Si5N8:Eu2+、(Ca,Sr)AlSiN3:Eu2+、K2(Si,Ge)F6:Mn4+、(Sr,Ca,Ba)4(Al,Sc,Ga,In)14O25:Mn4+、(La,Y,Gd,Lu)3(Al,Ga)(Ge,Si)5O16:Mn4+、CaO·Al2O3·Ga2O3·ZnO·MnO2·Li2O、(Lu,Y,Gd)3(Al,Ga)5O12:Mn4+One or more of. The near-infrared fluorescent powder is a fluorescent powder with the emission wavelength range of 780-1550nm, and comprises but is not limited to (La, Y, Gd, Lu)3(Al,Ga)5(Ge,Si)O14:Cr3+,Yb3+,Er3+、Sc2O3·Ga2O3·(Cr,Yb,Nd,Er)2O3、(La,Lu,Y,Gd)(Sc,Ga,Al,In)3B4O12:Cr3+,Yb3+,Er3+One or more of. Wherein, in each substance, the term "indicates that the element in parentheses may be a single component or a solid solution containing more than one element, for example: (Ca, Sr) AlSiN3:Eu2+Is represented as CaAlSiN3:Eu2+、SrAlSiN3:Eu2+And Ca1-αSrαAlSiN3:Eu2+(0<α<1) One or more of them. The near-infrared fluorescent powder is matched with the fluorescent powder for use, so that the light-emitting device emits light with high luminous efficiency and excellent spectrum continuity or special wave bands for special use, the problems that the longer near-infrared luminous efficiency is low in the existing infrared chip technology, particularly the chip technology with the emission peak wavelength position located at the 1270-1330nm wave band is difficult to realize, the luminous efficiency is low, and the light-emitting device emits spectrum with poor continuity are solved, and the requirements of semiconductor material alignment detection, metal flaw detection, environmental light source, medical food detection and water quality detection are metThe application needs of a plurality of traditional and novel fields including application fields such as testing and the like.
The following are specific examples of the present invention, and are only for the purpose of illustrating the near-infrared phosphor and the optical device according to the present invention, but the present invention is not limited to the following examples.
Example 1
The near-infrared phosphor provided in this embodiment comprises a compound with a composition formula of Ca1.79Sr0.2Lu0.01Ge0.94O4.0050.06 Cr. Grinding and mixing the weighed oxide raw materials according to the stoichiometric ratio of the chemical formula to obtain a mixture; grinding and uniformly mixing the mixture, calcining for 5h at 1250 ℃, and cooling to obtain a roasted product; and carrying out post-treatment such as crushing, grinding, grading, screening and washing on the obtained roasted product to obtain the near-infrared fluorescent powder intermediate.
The obtained near-infrared sample was subjected to absorption and emission spectrum measurement using a fluorescence spectrometer, and the absorption and emission spectrum of the near-infrared phosphor sample prepared in example 1 is shown in fig. 1-2. As can be seen from FIG. 1-2, the obtained near-infrared phosphor sample has effective absorption in the near-infrared band ranges of 400-. The results obtained are shown in Table 1.
TABLE 1
The materials and the luminescence property characterization results of the near-infrared phosphors prepared in the above examples 1 to 56 and comparative examples are shown in table 1. Note: the relative luminescence intensity of the examples is the actual luminescence intensity divided by the actual luminescence intensity of the comparative example, multiplied by 100%, based on the luminescence intensity of the comparative example as a reference value of 100%.
By comparing the data of the examples and comparative examples in table 1 above, it can be easily found that: for A2-x-d- mSrxDdE1-g-yGgOzyCr mM inorganic compound, wherein, the A element is Ca and Ba; doping a proper amount of active alkaline earth metal Sr element into the lattice site A, and selecting Gd, Y and Lu rare earth elements with smaller radius and larger electronegativity as D elements to enter the position of the element A; the element E is Hf and Ge; the G element selects proper sensitizers Ce and Bi which can emit in a visible light region; adding univalent elements M which can be used as a charge compensator and a cosolvent and can be Li, Na and K; the above-mentioned methods can realize the regulation and control of the spectral emission peak position in the range of 1270-1330nm and the improvement of the luminous intensity, and obtain more efficient near-infrared broadband emission.
Comparing example 1 with the comparative example, it is found that Sr must be contained in the compound, and the use of rare earth element with smaller ion radius as D element is beneficial to improving the luminous intensity of the near-infrared phosphor. The activity of Sr element is larger than Ca element, which is beneficial to the nucleation growth of phosphor powder, and improves the crystallization property and the single crystal particle size. Meanwhile, the D element is a rare earth element with a smaller radius, and the D element is one of Y, Gd and Lu and enters the A lattice site. In rare earth elements, the ionic radii of Y, Gd and Lu are smaller, so that the contraction of the original ligand site is facilitated, the crystal field intensity is changed, the short-wave movement of the emission spectrum of the fluorescent powder is easy to occur, and the emission band of the near-infrared fluorescent powder is enriched; on the other hand, the ionic radius is reduced, so that the distance shrinkage of chemical bonds is facilitated, the material has a more compact spatial structure, and the performances of the material such as luminous intensity and the like are improved. In addition, Y, Gd and Lu have larger electronegativity and are easy to react with O2-Form more covalentChemical bonds and stronger covalent bond property are favorable for increasing the probability of radiative transition of a luminescence center and further improving the optical properties of the material, such as luminous intensity and the like. And, Gd3+Having radiative transitions in the matrix (e.g.:6PJ-8S7/2) The fluorescent powder can provide excitation energy except for an excitation light source for a luminescence center, and is favorable for improving the luminescence intensity of the fluorescent powder. In addition, Y, Gd and Lu as rare earth elements have stronger activity, are beneficial to nucleation and grain growth of materials, and further improve the luminescence property. As can be seen from the SEM image (fig. 4), the example 1 sample has more regular grain growth, larger grains, and can achieve higher luminous intensity than the comparative example.
Comparing examples 1-6, it can be found that the A elements in the compound are Ca and Ba elements, and the mole percentage of Ba occupying the A element is i, 0% < i ≦ 10%, which is beneficial to the enhancement of the luminous intensity of the material. The ionic radius of the Ba element is larger than that of the Ca element, so that when the inorganic compound forming the fluorescent powder contains the Ba element, the original ligand site is expanded, the original crystal field environment is weakened, and the light-emitting waveband of the fluorescent powder is moved to a long wave; however, Ba element has a smaller electronegativity than Ca element, so that covalent bonding between cations and oxygen ions is reduced, and the shift of the centroid of the luminescence center can be reduced, thereby shifting the luminescence band of the phosphor to a short wavelength. According to the change of the lattice position and the electronegativity, when the mole percentage of Ba occupying the element A is 0% < i ≦ 10%, the luminescent band of the fluorescent powder hardly moves. On the other hand, the Ba element has higher activity than the Ca element, which is beneficial to the nucleation and grain growth of the phosphor, and experiments prove that the A element is Ca and Ba elements, which is beneficial to improving the crystallization property and the single crystal particle size of the phosphor and improving the luminous intensity (fig. 4 shows the SEM images of the embodiment 1 and the embodiment 5). Moreover, according to experimental studies, it is found that when the content of Ba element is too low, the increasing effect of Ba element on the phosphor is not obvious, and the luminous intensity is low, and when the content of Ba element is too high, impurities may be generated, resulting in an increase in the probability of nonradiative transition of the phosphor, and the luminous intensity is also low, so the mole percentage of Ba occupying a element is i, preferably 0% < i ≦ 10% (example 6).
In comparison with examples 6 to 8, it was found that under the condition that the A elements are Ca and Ba elements, Ba occupies the A element in a molar percentage of i, and 0% < i.ltoreq.10%, Sr must be contained in the compound to occupy the A site, and the content of Sr is preferably 0< x.ltoreq.0.12, which is advantageous in increasing the luminous intensity. When the element a is Ca and Ba, the difference in radii between Ca and Ba is large, which easily causes lattice mismatch and distortion, resulting in low luminous efficiency. The Sr element with the element radius between the Ca element and the Ba element is put into the lattice site of the A element, so that the conditions of lattice mismatch, distortion and the like can be effectively relieved, and the luminous efficiency of the material is improved. Furthermore, the activity of Sr element is larger than that of Ca element, which is beneficial to further nucleation and grain growth of the fluorescent powder, and experiments prove that Sr element is beneficial to further improving the crystallization property and the single crystal particle size of the fluorescent powder and improving the luminous intensity. According to experimental research, when the content of the Sr element is too low, the Sr element has no obvious effect on the phosphor, and the luminous intensity is low, and when the content of the Sr element is too high, impurities are possibly generated, the probability of nonradiative transition of the phosphor is increased, and the luminous intensity is also low, so that 0< x < 0.12 is preferred (example 8).
By comparing examples 9-15, it can be seen that the E elements are Hf and Ge elements, and preferably the mole percentage of Hf to the E element is j, and that 0% < j ≦ 8% is favorable for increasing the luminous intensity of the near-infrared phosphor. Hf has larger radius than Ge element, so it is easy to expand the material matrix lattice, and the crystal field strength is reduced, and the fluorescent powder emission wave band moves to long wave. Moreover, the activity of Hf is greater than Ge, which is beneficial to playing a dissolving-assisting effect in the process of synthesizing the near-infrared fluorescent powder, is beneficial to nucleation and grain growth, and improves the luminous intensity. According to experimental research, when the content of the Hf element is too low, the promotion effect of the Hf on the fluorescent powder is not obvious, the luminous intensity is low, when the content of the Hf element is too high, the phenomena of concentration quenching, impurity appearance, crystal structure change of a target product and the like can be generated, and the non-radiative transition is enhanced, so that the luminous intensity is also low, and therefore, the mole percentage of the element E occupied by the Hf is j, and j is 0% < j ≦ 8% (example 15).
Comparison of examples 16-28 shows that the G element is one of Ce and Bi, which is beneficial to further improving the luminous efficiency of the phosphor. Matrix alone doped with Cr3+Covers the visible wavelength range from blue to red. When the G element is one of Ce and Bi, Ce and Bi ions can be doped into the matrix as a sensitizer to show yellow-green light emission, and the emission spectrum and Cr of the yellow-green light emission3+The absorption spectra are overlapped, and Ce and Bi ions can be converted into Cr3+Energy transfer of (3), increase of Cr3+Near infrared luminous intensity. According to experimental research, when the content of the G element is too small, the luminous intensity is also low because the sensitizer is small, the energy transfer effect is not obvious, and the luminous intensity is low, and when the content of the G element is too high, concentration quenching can occur to cause nonradiative transition enhancement, so that 0 is preferred<g.ltoreq.0.1 (examples 25 to 26). Besides, the G element can be one or two of Ga, In, Sc and Al, and enters an E lattice position to carry out emission spectrum adjustment. Ga. The original ligand position can be changed due to different ionic radii and electronegativities of In, Sc and Al elements, so that the crystal field intensity and the mass center displacement of a luminescence center are changed, the emission spectrum of the fluorescent powder is easy to move, and the emission waveband of the near-infrared fluorescent powder can be effectively enriched. Moreover, according to experimental verification, on the premise of ensuring pure phase, g is more than or equal to 0 and less than or equal to 0.1.
Comparison of examples 29-40 shows that the D element is one or two of La, Gd, Tb, Y and Lu, and the doping into the A element position can carry out emission spectrum adjustment. The La, Gd, Tb, Y and Lu elements have larger electronegativity, and can easily form covalent bonds with cations, so that the covalent bonds with stronger covalent bonds are formed, the probability of radiative transition of a luminescence center is increased, and the optical properties of the material, such as luminous intensity and the like, are improved; on the other hand, the La, Gd, Tb, Y and Lu elements have stronger activity, which is beneficial to increasing the probability of radiative transition of the luminescence center and further improving the optical properties of the material, such as luminous intensity and the like. In addition, the change of La, Gd, Tb, Y and Lu ion radius and electronegativity can cause the original ligand position to change, thereby changing the crystal field intensity and the mass center displacement of the luminescence center, the emission spectrum of the fluorescent powder is easy to move, and the fluorescent powder can haveThe emission band of the near-infrared fluorescent powder is enriched. Preferably, the element D is one of Y, Gd and Lu, enters the lattice A, and can improve the luminous intensity of the material under the condition of adjusting the emission spectrum. In rare earth elements, the ionic radii of Y, Gd and Lu are smaller, so that the contraction of the original ligand site is facilitated, the crystal field intensity is changed, the short-wave movement of the emission spectrum of the fluorescent powder is easy to occur, and the emission band of the near-infrared fluorescent powder is enriched; on the other hand, the ionic radius is reduced, so that the distance shrinkage of chemical bonds is facilitated, the material has a more compact spatial structure, and the performances of the material such as luminous intensity and the like are improved. In addition, Y, Gd and Lu have larger electronegativity and are easy to react with O2-The chemical bond with stronger covalent property is formed, and the stronger covalent bond property is favorable for increasing the probability of radiative transition of a luminescence center and further improving the optical properties of the material, such as luminous intensity and the like. And Y, Gd and Lu have stronger activity as rare earth elements, are favorable for the nucleation reaction of the material and improve the luminescence property. And, Gd3+Having radiative transitions in the matrix (e.g.:6PJ-8S7/2) The fluorescent powder can provide excitation energy except for an excitation light source for a luminescence center, and is favorable for improving the luminescence intensity of the fluorescent powder. According to experimental research, 0 is preferred<d.ltoreq.0.07 (examples 37 to 40).
According to examples 29 to 30 and 53 to 55, it can be seen that the sensitizer has better energy transfer effect to the luminescence center and the phosphor has higher luminescence intensity when g is 4/3 y.
The comparison of examples 41 to 47 shows that the M element is one of Li, Na and K, and enters the A lattice site, so that the crystallinity and the grain size of the material can be further improved, and the luminous intensity is improved. Li, Na and K are all metals, the number of electrons on the outermost layer is 1, and the constraint of atom cores on electrons outside the core on the outermost layer is small, so that the melting point of the raw materials is low, the melting effect of the fluorescent powder is facilitated, the crystallization performance and the single crystal particle size of the fluorescent powder are improved, and the luminous intensity is improved. Further, the A site is a divalent ion site, and after doping with trivalent D ion, it is easy to form minute defects in the phosphor due to charge mismatch, and these defects result in low luminous intensity. Therefore, the doping of the univalent ions Li, Na and K can effectively avoid the defects generated by charge imbalance, carry out charge compensation and fluxing and improve the luminous intensity of the fluorescent powder. From the SEM image, it can be found that the morphology of the fluorescent powder added with the Li, Na and K additives is greatly improved, the fluorescent powder is in a sphere-like shape, the morphology is more regular, and the improvement of the luminous intensity of the fluorescent powder is facilitated (fig. 4). In addition, the more regular shape is beneficial to the encapsulation of the fluorescent powder, so that the luminescent device has more excellent optical performance. According to experimental verification, m ═ d (examples 44 and 46) is preferred.
The following embodiments are light emitting devices made by using the broadband near-infrared phosphor of the present invention as a light emitting material, and take the structure of a light emitting device known in the art as an example, and in some embodiments, as shown in fig. 5, the light emitting device includes a light emitting material 1, a semiconductor chip 2, a lead 3, a heat sink 4, a base 5, and a glass cover 6. The heat sink 4 is fixed on the base 5, the semiconductor chip 2 is fixed on the heat sink 4, the lead pins 3 are led out, the luminescent material 1 covers the semiconductor chip 2, the visible light luminescent material layer 6 covers the near-infrared luminescent material layer 1, and the glass cover 6 covers the outside of the luminescent material 1.
Example 57
The light emitting device described in this embodiment uses a semiconductor chip with a wavelength of 460nm as a light source, and the light emitting material is a near-infrared phosphor having a chemical formula of Ca1.84Sr0.08Lu0.04Ge0.817Hf0.043Bi0.08O3.98:0.06Cr,0.04Na+Accurately weighing raw materials according to a stoichiometric ratio, and grinding and mixing the weighed raw materials to obtain a mixture; calcining the mixture at 1200 ℃ for 5h, and cooling to obtain a calcined product; and (3) carrying out crushing, grinding, grading, screening and washing on the obtained roasted product, and then treating to obtain the near-infrared fluorescent powder. In addition, in this embodiment, La with an emission wavelength range of 500-780nm is selected2.85Si6N11:0.15Ce3+、(Ca0.2Sr0.8)0.95AlSiN3:0.05Eu2+And near infrared fluorescent powder (La, Y, Gd, Lu) with emission wavelength range of 780-1550nm3(Al,Ga)5(Ge,Si)O14:Cr3+,Yb3+,Er3+、Sc2O3·Ga2O3·(Cr,Yb,Nd,Er)2O3. In the embodiment, the mass ratio of the near-infrared luminescent material to the silica gel is 2.8: 1, uniformly mixing, stirring and defoaming to obtain a mixture of the visible light fluorescence conversion layer, covering the mixture on the surface of the LED chip layer in a spraying mode, and baking to solidify the mixture into the visible light fluorescence layer. And then mixing the visible light luminescent material and the silica gel according to the mass ratio of 0.3: 1, uniformly mixing and covering the mixture on the near-infrared fluorescence conversion layer, curing, and packaging to obtain the required LED light-emitting device. The light source (forward voltage 2.683V, forward current 60.0mA) of the optical device provided in each example was turned on with a constant current using a high-precision fast spectral radiometer integrating sphere test system, and the luminous power of the light-emitting device described in this example was 82.10mW as a result of the test.
The performance parameters of the optical device obtained by packaging the near-infrared luminescent material in each embodiment of the invention are shown in table 2.
TABLE 2
From the above table 2, it can be seen from the data in the above table that the phosphor in the optical device of the present invention can be effectively excited by the LED chip, and the dual emission of the visible light in the wavelength band of 500-.
The powder can be applied to the field of semiconductor material alignment detection after being matched with near-infrared fluorescent powder with the peak position of about 1500 nm; the powder provided by the invention is matched with a plurality of devices which are provided with broadband/narrow-band emission fluorescent powder in the red light and 780-1550nm region, and can be used in the fields of medical food detection, water quality detection and the like; the powder disclosed by the invention is matched with a plurality of fluorescent powders which have broadband/narrowband emission in visible light at the wave band of 500-.
It is to be understood that the above-described embodiments of the present invention are merely illustrative of or explaining the principles of the invention and are not to be construed as limiting the invention. Therefore, any modification, equivalent replacement, improvement and the like made without departing from the spirit and scope of the present invention should be included in the protection scope of the present invention. Further, it is intended that the appended claims cover all such variations and modifications as fall within the scope and boundaries of the appended claims or the equivalents of such scope and boundaries.
Claims (10)
1. A near-infrared phosphor is characterized by comprising a composition formula A2-x-d-mSrxDdE1-g- yGgOzyCr, mM of an inorganic compound, wherein,
the element A is one or two of Ca, Ba, Mg and Zn;
the D element is one or two of La, Gd, Tb, Y and Lu;
the element E is one or two of Hf, Ge and Si;
the G element is one or two of Ga, In, Sc, Al, Ce and Bi;
m element is one or two of Li, Na and K;
wherein 0<x≤0.2，0<d≤0.2，0≤g≤0.1，3.7≤z≤4.3，0<y is less than or equal to 0.1, m is less than or equal to 0 and less than or equal to 0.2, and the near-infrared fluorescent powder has Ca of a cubic crystal system2GeO4A crystal structure.
2. The near-infrared phosphor of claim 1, wherein the element a is Ca and Ba, and the molar percentage of Ba in the element a is i, 0% < i ≦ 10%.
3. The near-infrared phosphor of claim 2, wherein 0< x ≦ 0.12.
4. The near-infrared phosphor of claim 1, wherein the elements E are elements Hf and Ge, the mole percentage of Hf to the elements E is j, and 0% < j ≦ 8%.
5. The near-infrared phosphor of claim 3 or 4, wherein the G element is one of Ce and Bi, and G is 0< g.ltoreq.0.1.
6. The near-infrared phosphor of claim 5, wherein g is 4/3 y.
7. The near-infrared phosphor of claim 6, wherein the element D is one of Y, Gd, and Lu, and D is 0< D ≦ 0.07.
8. The near-red phosphor of claim 7, wherein M is one of Li, Na, and K, and M is d.
9. A light-emitting device comprising a light source and a luminescent material, wherein the luminescent material comprises the near-infrared phosphor of any one of claims 1-8.
10. The light-emitting device of claim 9, wherein the light source is a semiconductor chip with an emission peak wavelength range of 400-460nm or 600-660nm, and the light-emitting material further comprises a visible light phosphor with an emission wavelength range of 500-780nm and a near-infrared phosphor with an emission wavelength range of 780-1550 nm.
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