CN101502174A

CN101502174A - Phosphor composition with self-adjusting chromaticity

Info

Publication number: CN101502174A
Application number: CN 200780029803
Authority: CN
Inventors: 李依群; 董翊
Original assignee: Intematix Corp
Current assignee: Intematix Corp
Priority date: 2006-08-10
Filing date: 2007-06-19
Publication date: 2009-08-05

Abstract

Disclosed herein are ''smart'' phosphor compositions capable of regulating the chromaticity of their emission to substantially constant values even with the variations in the excitation radiation they receive to induce photoluminescence. One phosphor of the smart composition demonstrates an increase in emission intensity increases as the wavelength of the excitation radiation is increased. The other phosphor shows a decrease in emission intensity with increasing excitation wavelength. Constant chromaticity in this context is defined as a change in CIE x or y coordinate of less than about five percent over a 10 nm range of excitation wavelengths.

Description

Can adjust the phosphor composition of colourity automatically

The application's case is advocated the U.S. Provisional Patent Application case the 60/837th of application on August 10th, 2006 " can adjust the two-phase yellow phosphor of emission wavelength automatically " by name, No. 178 U.S. patent application case the 11/805th with on May 23rd, 2007 application " can adjust the phosphor composition of colourity automatically " by name, No. 808 right and priority, U.S. Provisional Patent Application case the 60/837th, be incorporated herein by reference with both full text of No. the 11/805th, 808, U.S. patent application case for No. 178.

Technical field

Embodiments of the invention relate to and are comprising light-emitting diode (LED) but or the phosphor composition in the light-emitting device of laser diode and excitation phosphor composition.

Background technology

The appearance of GaN base epitaxial structure has caused the ultraviolet light that is the light-emitting device form and/or the development of blueness (" ultraviolet light/blueness ") radiation source, and described radiation source comprises light-emitting diode and laser, and both are referred to as " LED " in this article.In general, radiation source excitation phosphor or the phosphor composition that comprises two or more phosphor are created in the visible light in redness, green or the blue region of spectrum.Then ruddiness, green glow and blue light can be through combination to form white light.In being called the process of down converted, phosphor is converted to a part of ultraviolet light and/or blue light has more long wavelength's light.For instance, Ri Ya chemical company (Nichia Chemical Company) discloses a kind of method that forms white light, thereby will be from such as Y ₃Al ₅O ₁₂: Ce ³⁺The gold-tinted of the phosphor of (so-called YAG-Ce) with from the combination of the blue light of blue led.

For forming white light, the YAG-Ce phosphor will be converted to gold-tinted from a part of blue light of blue led chip, gold-tinted and the blue light combination that still absorbs without phosphor from described LED.This produce color rendering index (CRI) be about 77 and colour temperature about 6,000K to 8, the white light that the 000K scope is interior.For some application, for the user, will be that more long wavelength's light (and then making up from the light of blue led and the light of being launched by described phosphor) generation white light is comparable from the UV/blue down converted of LED by the use phosphor forms the white light more attractive by direct respectively ruddiness, green glow and the blue light from redness, green and blue led of combination.Described ultraviolet light/blue phosphorescent body device for example, can form wideer available color gamut, and it is outbalance for display and illumination application.Add that to be converted to the wavelength that is different from gold-tinted with the light with ultraviolet light/blue led in the yellow phosphor of inferior company of different phosphor Summer Solstice or the Winter Solstice be known, and therefore, total combined colors of known product light from the LED/ phosphor system can be revised by indivedual phosphors of adjusting in the composition.

The difficulty that usually runs into when producing white lights by these technology is for owing to making the variation of the white light quality that the statistical fluctuation that takes place during the blue/UV LED produces.By on the wafer of semi-conducting material, depositing the LED matrix that multiple material is made blue light-emitting and/or ultraviolet light with layered mode.Handle tens of until making, hundreds of or even the array of thousands of LED to wafer.By the technology that is called cutting it is separated to form indivedual LED " chip " subsequently.But make led chip in this way and cause an intrinsic problem: can not make all led chips just the same, and certainly exist some variation in the led chip that is cut.Described variation can be exported by the color of LED and be shown, for example, and as characterizing by spectral power distribution and peak reflectance wavelength.These quantity can change because of the band gap width fluctuation of the active layer of LED.Another of variable blue/UV output is former because the power of supplying to be used for driving LED during operation also can fluctuate.

At production period, make the actual band gap width of having of certain percentage than the LED of the big or little active layer of the band gap width of wanting.Therefore, the output of the color of described LED departs from the parameter of wanting.In addition, even the band gap of specific LED has the width of wanting, the power that is applied to LED also can change during operation.This also can cause led color output to deviate from the parameter of wanting.Owing to contain blue component by the light of some systems emission, so the output of the color of LED changes also from LED.Significantly depart from color output that the parameter of wanting can cause system and be rendered as non-white (that is, light blue or light yellow).

The solution of past for this problem comprises " classification again (binning) " step, wherein before cutting apart, measure the electroluminescence feature that on wafer, forms each blue/UV LED of array, afterwards according to 1) by the peak emission wavelength of the light of LED emission, 2) by the peak strength and 3 of the light of LED emission) in the forward voltage any one sort out indivedual LED (or " classification ").Again to depend on LED be current device in classification.This light intensity that means by the LED emission is to be regulated by the electric current that is supplied to LED (being called " forward current ").Usually a series connection resistor is placed the circuit of close voltage source: this resistor protect LED makes it avoid the overcurrent overload.The value of forward voltage depends on this series resistance, is supplied to the forward current of wanting (being calculated by want intensity, because light output is directly proportional with forward current) of the voltage of circuit and the LED that flows through.

A kind of typical commercial stage division again comes LED is classified according to any one (depending on the importance of those parameters for manufacturer) in forward voltage, peak emission wavelength and the peak emission intensity after making.Illustrated as mentioned, the voltage decision that the is applied to circuit electric current of diode of flowing through, described electric current then influence are by the light intensity of described device emission.Therefore, support that the variation in the part (especially for that part of the supply power) of the circuit of LED is shown in influence is passed to " series resistance " of electric current of LED active layer.As shown schematically in figure 1, empty wafer, and is classified according to three forward voltages that are generally described as VF1, VF2 and VF3 separating indivedual led circuits through cutting.

The light emitted peak emission wavelength of band gap width decision of LED bonding land, described peak emission wavelength transfers to influence color output and colourity.For arbitrary value of forward current, can observe a series of peak emission wavelengths (for example, color output).This schematically illustrates in Fig. 1.For each group forward voltage values, further classify by LED being arranged in the son group based on emission wavelength.In Fig. 1, at first five are divided into groups through the set of the peak emission wavelength of classification again according to the forward voltage on the LED; Then, in three forward voltage grades each, LED is further sorted out according to peak emission wavelength.In the example of Fig. 1, the peak wavelength grade concentrates on 452.5nm, 455.0nm, 457.5nm, 460.0nm and 462.5nm respectively.Itself can have following scope these grades: less than 450nm, 450nm to 425.5nm, 425.5nm to 455nm, 455nm to 457.5nm, 457.5nm to 460nm with greater than 460nm.

Some manufacturing processes may need the LED further refinement of classifying.For instance, each in those grades described in Fig. 1 (its width is 2.5nm) can be divided into other five grades according to colourity, now obtains 75 grades altogether.Can ad infinitum carry out classification process again.For instance, 75 grades that respectively have a 2.5nm width can further be divided into three groups according to brightness.In the example of Fig. 1, for all led chip current bounds 225 grades altogether surely that are manufactured at first on the imaginary wafer.

Though be desirable in some cases, classification and nonessential wave-length coverage again based on excitaton source.In certain methods, each led chip (or " crystal grain ") is electrically connected to external circuit via two electrodes, and then the LED wafer that is cut is tested with regard to the forward voltage of device or from the optical output power of illuminator.Again the exemplary classification that is classified as four grades according to forward voltage is less than 3 volts, 3.0 volts to 3.2 volts, 3.2 volts to 34 volts and 3.4 volts to 3.6 volts.Perhaps, when classification was based on optical output power again, described graded category can be arranged as less than 8mW, 8mW to 10mW, 10mW to 12mW and 12mW to 14mW.

The light output part of blue/UV LED divides the color output of decision illuminator (mean LED and add phosphor).Provide the hue coordinate index (CIE) of the White LED that exciting radiation produces mainly to be subjected to control by blue GaN based light-emitting diode (LED) to yellow phosphor from the emission wavelength of the light of blue led.Therefore, existence relates to the matching process that makes indivedual led chips and phosphor pairing.At this point, in industry, it is said generally and can corresponding selection emission wavelength to mate the blue led wavelength in about 470nm scope extremely to the yellow phosphor in about 575nm scope at about 450nm at about 550nm.Described coupling has been reached the hue coordinate index of wanting, for example, and CIE (0.300,0.300).But need big grade/sort operation that current blue led chip output is handled in the White LED base luminescent system, it is that part is owing to the variation from blue/UV optical chip wavelength of transmitted light to a great extent.

In this technology, need a kind ofly can proofread and correct or the phosphor composition of " automatically adjust " its photochromism of launching in response to the wavelength/energy changing in the exciting radiation through design.

Summary of the invention

The present invention discloses " intelligent " phosphor composition, and it can be in response to the variation of the excitation wavelength of the right blue/UV led chip of its group and its colourity is adjusted automatically.Combination has constant substantially colourity by the light of phosphor composition emission with the formed illumination product of light of being launched by blue/UV led chip storehouse.Term " constant chromaticity " means each the variation of the x of product illumination and y cie color coordinate and is no more than 5 percent of reference value in this article.

The combination of second phosphor that first phosphor that the emissive porwer that may be defined as " intelligent " phosphor composition reduces along with being used to cause its luminous radiation wavelength increase and emissive porwer increase along with the excitation wavelength increase.The advantage of described phosphor composition comprises under the condition that is implemented in the excitation wavelength variation shows the luminous mechanism of constant chromaticity substantially.The described variation by different blue led chip wavelength of light emitted mainly is to change institute by the manufacturing that takes place to cause during production blue led chip.Make variation and can produce the chip of blue led in batch with a series of band gap width, the result of commercial operation is classification requirement again, and it is a previous described exemplary protocol in this disclosure.

Embodiments of the invention relate to the phosphor composition that can adjust colourity automatically, and described composition comprises first phosphor that is configured to make its emissive porwer increase along with excitation wavelength and increases; Second phosphor that reduces with being configured to make its emissive porwer increase along with excitation wavelength.The variation of colourity in about 10nm excitation wavelength range by the luminescence generated by light of described phosphor composition emission is no more than about 5 percent.Described 10nm excitation wavelength range can extend to about 460nm from about 450nm.

In one embodiment of this invention, first phosphor is for having formula (Sr, A ₁) _x(Si, A ₂) (O, A ₃) _2+x: Eu ²⁺Silicate-based orange phosphors; And A wherein ₁Be 2+ cation, 1+ cation and the cationic combination of 3+, or its combination at least one; A ₂Be 3+, 4+ or 5+ cation; A ₃Be 1-, 2-or 3-anion; And any value of x between 2.5 and 3.5, (comprising 2.5 and 3.5).In this embodiment, A ₁Be Mg, Ca and/or Ba; A ₂Be B, Al, Ga, C, Ge and/or P, and A ₃Be F, Cl and/or Br.The instantiation of silicate-based orange phosphors is Sr ₃Eu _0.06Si _1.02O ₅(F, Gl) _0.18, Sr _2.94Ba _0.06Eu _0.06Si _1.02O ₅(F, Cl) _0.18(Sr _0.9Ba _0.1) _2.76Eu _0.06Si _1.02O ₅(F, Cl) _0.18

In this embodiment, second phosphor can be have formula (Sr, A ₁) _x(Si, A ₂) (O, A ₃) _2+x: Eu ²⁺The silicate-base green phosphor, A wherein ₁Be Mg, Ca, Ba, Zn, K, Na, Li, Bi, Y, La and/or Ce; A ₂Be B, Al, Ga, C, Ge, N and/or P; And A ₃Be F, Cl, Br, N and/or S, and any value of x between 1.5 and 2.5, (comprising 1.5 and 2.5).The instantiation of second phosphor is Sr _0.925Ba _1.025Mg _0.05Eu _0.06Si _1.03O ₄(F, Cl) _0.12, Sr _1.025Ba _0.925Mg _0.05Eu _0.06Si _1.03O ₄(F, Cl) _0.12And Sr _1.125Ba _0.825Mg _0.05Eu _0.06Si _1.03O ₄(F, Cl) _0.12

Fluorine in these compositions (F) is used interchangeably with the agent of chlorine (Cl) halogen doping, because the automatic accommodation property relation of the selection of halogen and phosphor composition is little or irrelevant.

According to the embodiment of the invention, White LED base illuminator comprises the automatic adjustment smart phosphor composition that the blue/UV photo-emission source array with broad is complementary; Described array is wideer than the possible array of conventional phosphors encapsulation.It is 452.5nm to 457.5nm that 5nm excites an example of scope, wherein the colourity of wanting of illuminator can be maintained at x ± 0.01 and y ± 0.01 than in the close limit.The variation of product illumination can be about 0.300 ± 0.01 in the x value on the CIE figure, and the y value is in 0.300 ± 0.01 the scope.At present, each 2.5nm for the blue/UV excitation wavelength changes and need at least 5 grades come those blue led chips are classified; And afterwards, define the needs that will need in addition at least 5 grades to satisfy White LED of the present invention in the CIE zone 5 differences.Current method need must be classified to brightness and voltage in each grade, and is therefore final, and LED encapsulation group has 168 grades.

In another embodiment, can make the White LED wafer by described novel smart phosphor is coated on the blue/UV LED wafer that contains blue/UV led chip array (it can be thousands of or more), the peak emission wavelength scope of described blue/UV led chip array is greater than 5nm (same, as to use exemplary range 452.5nm to 457.5nm).The CIE of the indivedual White LED chips that produce by described wafer (x, y) value can be controlled in the scope of x ± 0.01 and y ± 0.01, equally, the x of CIE figure be 0.300 ± 0.01 and y be in 0.300 ± 0.01 the zone.Expect that technology of the present invention surpasses the situation of about 5nm applicable to the variation of blue/UV on wafer wherein, such as the 10nm variation that in current industry, exists.

Description of drawings

Fig. 1 is the schematic diagram according to the assorting process of forward voltage, brightness and excitation wavelength, wherein export the blue led chip " classification again " that the auto-deposition wafer is cut or classify as different brackets according to spectrum, then make described grade and phosphor coupling and classification again once more, this time classification is to carry out according to the CIE zone of white light output again; Then each CIE grade is classified, obtain 225 grades altogether according to brightness;

Fig. 2 is the emission spectrum according to two indivedual phosphors of the exemplary phosphor composition of the embodiment of the invention; In curve chart for a) exciting the emission of the silicate-based phosphors of the green light that is excited by the blue led at the peak emission wavelength place of 450nm, 455nm and 460nm; B) emission spectrum of the silicate-based phosphors of sending out orange-colored light that excites by three same peak emission wavelengths; And c) the two component silicate-bases that comprise green phosphor and orange phosphors are adjusted the emission spectrum of phosphor composition automatically;

Fig. 3 be by peak emission wavelength in the position of the blue light of the different blue leds emissions of 450nm, 455nm and 460nm place three kinds and the CIE of three positions of the light of when by that 450nm, 455nm and the described smart phosphor composition of 460nm optical excitation, launching by green/orange " smart phosphor " composition scheme; The embodiment of the invention is based on following unexpected observation: respectively pass through same CIE impact point (in the case, having coordinate x=0.300 and y=0.300) by three lines that connect 450nm data, 455nm data and the formation of 460nm data;

Fig. 4 A and Fig. 4 B are the curve chart of the cie color coordinate (being respectively x and y) of the excitation wavelength drafting of reference in 452 to 462 scopes, described data display exemplary smart phosphor composition (0.8) Sr _1.025Ba _0.925Mg _0.05Eu _0.06Si _1.03O ₄(F, Cl) _0.12(0.2) Sr _2.94Ba _0.06Eu _0.06Si _1.02O ₅(F, Cl) _0.18The CIE coordinate constant substantially in this wave-length coverage, the variation of arbitrary coordinate is no more than one of about percentage, and yellow phosphor Sr _1.5Ba _0.45Mg _0.05Eu _0.06Si _1.03O ₄(F, Cl) _0.12Show x be changed to 4 percent and y be changed to 8 percent;

Fig. 5 A is the chart of main emission color that multiple phosphor is provided, and further those phosphors are classified as that emissive porwer increases along with excitation wavelength and the group that increases and emissive porwer increase along with excitation wavelength and the group that reduces (with a kind of show both all increase, neutral and reduce the situation of characteristic);

Fig. 5 B is the chart that is arranged in the same phosphor inventory in row and the row, even, under the situation that changes caused excitation wavelength variation owing to the blue/UV chip manufacturing, also can adjust its phosphor of launching colourity automatically to (or composition) even it also can be described as to obtain under the situation that excitation wavelength changes, showing that still the phosphor of constant chromaticity character is right substantially.

Fig. 6 A and Fig. 6 B are three exemplary silicate-base M ₂SiO ₄: Eu ²⁺Type (Fig. 6 A) green phosphor and three M ₃SiO ₅: Eu ²⁺The orange phosphors of form (Fig. 6 B) is in the set of 400nm to 500nm (Fig. 6 A) and the 400nm excitation spectrum to about 570nm (Fig. 6 B) wave-length coverage;

Fig. 7 A and Fig. 7 B are the set of the excitation spectrum of green phosphor identical with Fig. 6 B with Fig. 6 A and orange phosphors, but draw in the excitation wavelength range of 440nm to 470nm to show that the exemplary phosphor shows emissive porwer from so-called " A organizes phosphor " increases by 15%, same wavelength ranges is interior to reduce by 25% and the representative of " B organizes phosphor " is illustrated in; With

Fig. 8 is the excitation spectrum of commercially available phosphor GP-4, YAG and TAG.

Embodiment

The present invention discloses " intelligent " phosphor composition, and it can change in response to the excitation wavelength with the right blue/UV led chip of its group and adjust himself colourity (therefore producing term " adjusts " automatically) passively.Have by constant substantially colourity with the formed illumination product of various light of launching by the light of combination by blue/UV led chip storehouse or selected works (selection) by described phosphor composition emission.Term " constant chromaticity " means each the variation of the x of product illumination and y cie color coordinate and is no more than 5 percent of reference value in this article.

The general operation principle

The operating principle of " intelligent " phosphor composition can be illustrated by the data of observing among Fig. 2 and Fig. 3.Fig. 2 is the emission spectrum of exemplary smart phosphor composition; Draw together with two component phosphor, one is labeled as " green " and another and is " orange ".Composition is " green+orange ".The peak emission wavelength that the peak emission wavelength that observes composition is positioned at individual green component and orange component is position intermediate slightly.Should be appreciated that term " green " and " orange " are used to represent with respect to higher energy of yellow and lower energy, irrelevant with the actual color of phosphor.In the left side of Fig. 2 is three higher narrower peaks, and each is excited residing three wavelength in three samples of its expression; These peaks concentrate on 450nm, 455nm and 460nm place.

Data display among Fig. 2 is along with the wavelength to the exciting radiation of green phosphor is increased to 460nm from 450nm with the 5nm increment, by the corresponding reduction of light intensity of green phosphor emission.Perhaps, along with being used to excite the light wavelength of orange phosphors to be increased to 460nm, by the corresponding increase of light intensity of orange phosphors emission from 450nm.The combination of gained orange-colored light and green glow meets accident but favourable result: combined transmit not only wavelength increases and increases along with the wavelength of exciting radiation, and the combined transmit light intensity also increases thereupon.

Though do not wish to be bound by any particular theory, but the matching property between the electric energy band gap of the energy of the luminous photon of the characteristic origin self-excitation of individual green that is observed and orange phosphors and phosphor is illustrated; " quality " of described coupling is relevant with the efficient of phosphor luminescence.With respect to the light by the orange phosphors emission, the light of being launched by green phosphor has more high-energy and more short wavelength, and its expression green phosphor has bigger band gap.Therefore, along with peak excitation wavelength increases, the energy of this exciting radiation reduces, and becoming with the coupling of the big band gap of green phosphor more and more is best (with respect to orange), and emissive porwer reduces.On the contrary, the band gap of orange phosphors is less than the band gap of green phosphor, and therefore along with excitation wavelength increases, the energy of photon reduces, and excites coupling with the less band gap of orange phosphors become more and more good (with respect to green).The efficient of orange phosphors emission increases and increases along with the blue led light wavelength, and it represents the more suitable than low band-gap and the more low-yield coupling that excites of orange phosphors.

The combination of second phosphor that first phosphor that the emissive porwer that may be defined as " intelligent " phosphor composition reduces along with being used to cause its luminous radiation wavelength increase and emissive porwer increase along with described excitation wavelength increase.The advantage of described phosphor composition comprises under the condition that is implemented in the excitation wavelength variation shows the luminous mechanism of constant chromaticity substantially.The described variation by different blue led chip wavelength of light emitted mainly is to change institute by the manufacturing that takes place to cause during production blue led chip.Make variation and can produce the chip of blue led in batch with a series of band gap width, the result of commercial operation is classification requirement again, and it is a previous described exemplary protocol in this disclosure.

Referring again to Fig. 2, wherein these notions are with concrete data declaration, can observe the emission spectrum of two indivedual phosphors of exemplary smart phosphor composition.Described curve chart is: a) excited the emission of the silicate-based phosphors of the green light that is excited by the blue led at the peak emission wavelength place of 450nm, 455nm and 460nm; B) emission spectrum of the silicate-based phosphors of sending out orange-colored light that excites by three same peak emission wavelengths; And c) comprises the emission spectrum of two component silicate-base smart phosphor composition of individual green and orange phosphors.Luminescence generated by light in the two component compositions is to bring out in the mode identical with the luminescence generated by light that is used for two individual green and orange phosphors; That is, at 450nm, 455nm and 460nm place.

Referring to Fig. 2, as seen along with excitation wavelength is increased to 460nm from 450nm, the intensity of green phosphor has reduced at least 10%, and wherein the peak emission wavelength of green emission is to concentrate on about 530nm to 540nm.On the contrary, as seen along with excitation wavelength changes equally, the intensity of orange phosphors has increased at least 10%.Complex light is showed along with excitation wavelength increases and emissive porwer has increased approximately 5%, is concentrated in the orange-yellow zone at about 580nm place, even the intensity of green phosphor is higher than the intensity of orange phosphors.

When with the data on the schematic form observation XYZ chromaticity diagram, perhaps can be more clearly understood the advantage of the embodiment of the invention.Show the chromaticity coordinate of drawing at the blue light that different blue/UV LED launched that has different band gap width by three kinds among Fig. 3, wherein three kinds of different band gap width are respectively to be shown by the peak wavelength at the electroluminescence light of 450nm, 455nm and the emission of 460nm place.Also draw the x and the y CIE coordinate of the light of launching by the smart phosphor that under 450nm, 455nm and 460nm, excites among Fig. 3.

Referring again to Fig. 3, article one line on the XYZ chromaticity diagram is to connect x and y coordinate corresponding to the point that is arranged in the yellow area of described figure from the radiative point of the 450nm of blue/UV LED and coordinate.Point in the faint yellow zone of described figure is to launch light and produce after the 450nm optical excitation that is derived from blue chip by " green/orange " smart phosphor composition.Similarly, draw the second line, it connects described line one end and has the point of peculiar x of 455nm blue light and y coordinate and the point that the described line other end is represented the emission of smart phosphor after the 455nm radiation excitation.At last, can draw the 3rd line, it connects from the coordinate of the 460nm blue light of 460nm blue led and coordinate by the light that produced with 460nm optical excitation smart phosphor.The embodiment of the invention is based on following unexpected observation: (article one line connects the 450nm data to these three lines, the second line connects the 455nm data, and the 3rd bar line connects the 460nm data) substantially respectively by the common ground on the CIE figure, in the case, desirable color of object is to have x and y coordinate (0.300,0.300).

Even the remarkable advantage of the embodiment of the invention is have under the situation of improper fluctuation in excitation wavelength, in the phosphor composition scope of broad, still can realize constant substantially colourity.In the advantage of the embodiment of the invention, the blue/UV led chip no longer needs " classification " or " classification again " (reaching its degree before at least), because smart phosphor composition can " be adjusted " colourity of its light output automatically in response to the changeability of LED.In the example of Fig. 3, colourity is constant substantially on the 10nm excitation wavelength changes.Because, therefore will no longer need the blue/UV led chip is carried out any further classification no matter the excitation wavelength in 450nm to the 460nm scope all can be reached identical colourity specification.

Maintain colourity substantially that the ability of steady state value is important, because the track that allegedly is positioned at by the chromaticity coordinate on the curve of (0.3,0.3) peace treaty (0.45,0.4) approximately is positioned on the black body locus (BBL).This is the track of the point that defined by Pu Langkeshi equation (Planck ' s equation):

E(λ)＝Aλ ^-5/(e ^(B/T)-1)。

Herein, E is the emissive porwer of phosphor composition, and λ is an emission wavelength, and T is the colour temperature of black matrix, and A and B are constant.Be positioned on the BBL locus of points or make us the class observer near the hue coordinate generation of described track and feel comfortable white light.Therefore, as shown in Figure 3, composition can keep substantially and BBL curves overlapped or positioned adjacent through being designed to its hue coordinate.This specific character is especially desirable in white-light illuminating is used, and the optical property of using Smalt/ultraviolet light chip at white-light illuminating can change in quite on a large scale.

The displaying present composition is adjusted colourity automatically among Fig. 4 A and Fig. 4 B; Even thereby under the situation that excitation wavelength changes, will colourity maintain the further displaying of the ability of steady state value substantially.Fig. 4 A is that CIE " x " coordinate is to the curve of excitation wavelength (in 452nm to the 462nm scope) for two kinds of different phosphors that are labeled as " SMP " and " yellow phosphor ".The yellow phosphor of being tested has formula Sr _1.5Ba _0.45Mg _0.05Eu _0.06Si _1.03O ₄(F, Cl) _0.12The exemplary smart phosphor (SMP) of this place test is for having formula (0.8) Sr _1.025Ba _0.925Mg _0.05Eu _0.06Si _1.03O ₄(F, Cl) _0.12With (0.2) Sr _2.94Ba _0.06Eu _0.06Si _1.02O ₅(F, Cl) _0.18The admixture of two kinds of phosphor components.In these composites, term " (F, Cl) " be intended to represent just adjust the character of colourity automatically, fluorine (F) is interchangeable with the agent of chlorine (Cl) halogen doping.In other words, the automatic accommodation property relation of the selection of halogen and phosphor composition is little or irrelevant in these compositions.

The x chromaticity coordinate value that yellow phosphor is showed in the check of Fig. 4 A and Fig. 4 B is reduced to 0.288 from about 0.301, or about 4 percent, and the y coordinate is increased to 0.323 from about 0.297, or about 8 percent.On the contrary, the variation of x coordinate in same wavelength ranges of smart phosphor (SMP) is increased to 0.305 less than one of percentage slightly from about 0.303.Similarly, the y coordinate of smart phosphor only reduces slightly, is reduced to 0.292 from about 0.294, and it is also less than one of percentage.

The A group component of smart phosphor and B group component

In general, the phosphor composition that can adjust colourity automatically can produce with the phosphor that what is called " B " is organized (its member shows opposite trend: emissive porwer is along with excitation wavelength increases) by the phosphor of fusion from so-called " A " group (the total emissive porwer of its member increases the common trend that reduces along with excitation wavelength).The example wavelengths scope is 450nm to 460nm.

The opposite trend that is used for the phosphor grouping is being significant instinctively.The emissive porwer of phosphor is relevant with the efficient of its its exciting radiation of absorption, and this efficient then with flux matched relevant from the energy between the band gap width of the photon of exciting radiation and phosphor.In the case, provide exciting radiation from the light of ultraviolet light/blue led to phosphor and in one embodiment, ultraviolet light/blue led provides exciting radiation in the wave-length coverage of 450nm to 460nm.

A group phosphor and B organize division between the phosphor and can be normally carry out with the band gap energy of the photon energy that equals gold-tinted substantially.Therefore, it is said that A group phosphor can be positioned at the higher energy side of yellow phosphor, and comprise blueness, green and yellow-green phosphor.It is said that B group phosphor can be positioned at the more low-yield side of yellow phosphor, and comprise orange-yellow, orange and red-emitting phosphor.In photoluminescent process, phosphor is the photon of being launched by described phosphor with the energy " down converted " of the photonic absorption of self-excitation radiation, described emitted energy is relevant with the phosphor band gap, by described band gap generation electronics tension and relaxation process, this energy difference equals the energy of light emitted son.

Utilize the down converted Billy of its big band gap more effective in the A group phosphor with higher-energy exciting radiation (meaning shorter-wavelength light).Therefore, emissive porwer reduces along with excitation energy and reduces (should remember that it is that energy reduces that excitation wavelength is increased to 460nm from 450nm).

On the contrary, B group phosphor is positioned at yellow orange side, and with respect to A group phosphor emission more low-yield (longer wavelength), this is owing to its less band gap width.In this case, when phosphor during by more and more low energy excitation, in designated wavelength range, down-conversion process takes place more effectively at least.Therefore, the emissive porwer of B group phosphor increases and increases along with excitation wavelength.

Show the principle that can be used for designing automatic adjustment phosphor among Fig. 5 A and Fig. 5 B.As seen Fig. 5 A be the form the selected works of exemplary phosphor sorted out according to the color of phosphor emission (as at form left side four marks that list: green, yellow, orange and red).In the form of Fig. 5 A, also show the feature description (emissive porwer reduces along with the excitation wavelength increase) of A group phosphor or the feature description (emissive porwer reduces along with the excitation wavelength increase) of B group phosphor.The exemplary phosphor of sorting out according to this scheme is listed in left column and is comprised different types of phosphor, comprises commercially available phosphor, the phosphor described in science and/or patent documentation and belongs to present inventor's novel phosphor.Under " EM color " (wherein " EM " expression emission), be labeled as green, yellow, four orange and red row and be meant the color of luminescence generated by light.

Three kinds of phosphors at the left column top are labeled as " G series ", " Y series " and " O series " and are meant that each series is launched respectively substantially by the phosphor composition of present inventor's research and development in green area, yellow area and the orange areas of spectrum.YAG is usually known material yttrium aluminum garnet, and it has formula Y ₃Al ₅O ₁₂: Ce ³⁺And the formula of terbium aluminium garnet TAG is Tb ₃Al ₅O ₁₂: Ce ³⁺YAG and TAG commercially available phosphor in the yellow area of spectrum and orange areas, launching respectively.GP-4 is the YAG phosphor of green light, and it also is commercially available, has formula Y ₃(AlGa) ₅O ₁₂: Ce ³⁺And be similar to YAG and TAG, it also is to be activated by trivalent cerium.

In the Far Left row below those three kinds of phosphors of top is three kinds of sulfide based phosphors, and thereunder is three kinds of phosphors based on silicon nitride and silicon oxynitride.In the sulfide based phosphor, in the spectral region of relative narrower, launch SrGa for two kinds ₂S ₄: Eu launches in green fields, and CaS:Eu launches in red color range.That different with it is sulfide ZnSe _xS _1-x: Cu, it can be configured to comprising colors green, yellow, orange and red launching in than wide spectral range.Silicon nitride and silicon oxynitride also can be launched in relatively large spectral region, wherein when form when changing SrSi aspect the relative quantity of alkaline earth component ₂O ₂N ₂: Eu launches in green and yellow, and (Sr, Ba, Ca) ₂Si ₅N ₈: Eu launches in yellow, orange and red color range.Under at least a situation of the fixing use of alkaline earth component single-element, phosphor is launched in narrower spectral region, mainly launches in the solid color scope.For instance, nitride silicon based phosphor Si ₂Si ₅N ₈: Eu launches in red color range.

Referring again to Fig. 5 A, be that three row of gauge outfit are further labelled by following three kinds of situations with mark " excitation curve (450 to 460nm) ": 1) upwards and the arrow that is tilted to the right, 2 in the rightmost side of form) horizontal line and 3) downwards and the arrow that is tilted to the right.These marks are meant that along with excitation wavelength increases whether specific phosphors shows respectively: 1) emissive porwer increases in 450nm to 460nm scope, 2) and the intensity no change, or 3) the intensity reduction.For instance, the shade grid in the top line of Fig. 5 A means the displaying of G series phosphor along with excitation wavelength increases the emissive porwer reduction below the decline arrow.On the contrary, the shade grid in downward the third line represents that the displaying of O series phosphor increases along with the exciting radiation wavelength increases emissive porwer.This characteristic is organized A group or the B that phosphor classifies as according to the embodiment of the invention just.

Though measurable to a certain extent by the trend that orange phosphors and the green phosphor of Fig. 5 A are showed, the characteristic of yellow phosphor is also non-obvious.Can expect that the yellow phosphorescence body display is in A group mode and the middle pattern of B group mode; That is it shows that emissive porwer is along with excitation wavelength increases no change.This situation can expect that this is because yellow phosphor is smaller to the sensitiveness that excitation energy changes, because these yellow phosphors have the band gap energy in the middle of the scope that is defined by all luminescence generated by light phosphors of launching in visible-range.But since yellow phosphor to belong to the A category sometimes other, it is other to belong to the B category sometimes, and as if characteristic is too complicated and can not sort out sometimes, so situation is really not so.

The example that can classify as the yellow phosphor of B group phosphor is Y series (although it can as mentioned belowly be described as " yellow green " more exactly) and silicon oxynitride SrSi by present inventor's research and development ₂O ₂N ₂: Eu.An example that belongs to the phosphor of A group is phosphor yellow-YAG that highly traditional and commercially available Ce mixes; Another example be the silicon nitride compound (Sr, Ba, Ca) ₂Si ₅N ₈: Eu.The observed result of front can hint that yellow YAG can regard Huang-orange phosphors more accurately as, and the output of silicon nitride can be adjusted by the ratio of alkaline earth element.The sulphide phosphor ZnSe of work in copperization _xS _1-x: Cu has the characteristic that is difficult to explain because its can be configured to colors green, yellow, orange and red in any one in do not show among emission and Fig. 5 A this phosphor classified as particular group.

Especially the benchmark of organizing institute's reference according to other A group/B of ability decidable that regulates colourity automatically is by combination M ₂SiO ₄Type " G series " phosphor and M ₃SiO ₅The composition that type " O series " phosphor is made, wherein in two types silicate M be alkaline earth element and wherein the phosphor of G series and O series be to research and develop by the present inventor.The G series phosphor also can be used in combination with the Y series phosphor that belongs to the present inventor equally, and wherein the Y series phosphor has M ₂SiO ₄Configuration.Launch although the latter is expressed as in yellow in Fig. 5 A, the disclosure about these compounds of previous application provides shows it for " yellow green " but not yellow experimental data, and higher-energy makes it classify as the B group green the composition.Intelligent another right example is the yellow YAG phosphor of G series or Y series phosphor and conventional cerium doped, should remember that the latter shows the characteristic of A group phosphor and therefore can regard " orange-yellow " as.Another smart phosphor is that the combination of B group (G or Y series) phosphor and orange TAG phosphor and its are proved to be really to correct.

As previous hint, be not that A group phosphor all can successfully produce constant chromaticity character with all combinations that B organizes phosphor.With the example (described combination does not produce any significantly " wisdom behavior ") of the A group phosphor of B group phosphor pairing yellow YAG phosphor for commercially available green YAG (also being expressed as GP-4) and cerium doping, in Fig. 5 B with the row headed by " YAG " be labeled as in the row of " GP-4 (green YAG) " and be shown as the shaded cells lattice.

A group characteristic and the B group characteristic opposite according to excitation spectrum

Further specifying A of the present invention group phosphor among Fig. 6 A, 6B, 7A and the 7B organizes phosphor with B and has opposite characteristic about its excitation spectrum.Fig. 6 A and Fig. 6 B excitation spectrum for measuring between 400nm and 500nm, wherein green phosphor G525, G530 and G535 displaying emissive porwer increases (especially being increased to 500nm from about wavelength 450nm) along with excitation wavelength and reduces.On the contrary, the emissive porwer of orange series of phosphors O5446, O5544 and O5742 is increased to about 520nm to 540nm and increases along with exciting from about 450nm usually.Under wavelength, even the emissive porwer of orange series of phosphors increases and reduces along with excitation wavelength greater than 540nm.The composition that is used to produce these exemplary orange phosphors of excitation curve Fig. 6 A, 6B, 7A and 7B is: for O5446, and Sr ₃Eu _0.06Si _1.02O ₅(F, Cl) _0.18For O5544, Sr _2.94Ba _0.06Eu _0.06Si _1.02O ₅(F, Cl) _0.18With for O5742, (Sr _0.9Ba _0.1) _2.76Eu _0.06Si _1.02O ₅(F, Cl) _0.18Equally, to mean these halogens interchangeable for term " (F, Cl) ".

Show the further quantification of A group phosphor and B group phosphor characteristic among Fig. 7 A and Fig. 7 B.This data acquisition system shows that the emissive porwer gathered by the orange type phosphors of the special sign of mark O5742, O5746 and O5544 institute is along with excitation wavelength is increased to 470nm (in the blue region of blue/UV laser exciter) and increases from 440nm.This expression emissive porwer increases by 15% approximately.On the other hand, it is about 25% that the emissive porwer of green type phosphors G530, G535 and G525 reduces, as illustrated among Fig. 7 B.

The excitation spectrum of commercially available phosphor YAG, TAG and GP-4 is provided in Fig. 8.

The particular instance that smart phosphor is right

Except the benchmark of and smart phosphor performance that O series phosphor provided serial, now provide and utilize at least one example commercially available and/or prior art component phosphor by present inventor's G.Right the results are summarized among Fig. 5 B of test phosphor, wherein cell shadow representation particular combination of phosphors is showed self-regulation ability at least to a certain degree.In one embodiment of the invention, smart phosphor comprises that B organizes green YAG phosphor and A organizes orange TAG phosphor.Present inventor's B group Y series phosphor also can be organized orange TAG combination of phosphors with A.

In another embodiment, smart phosphor comprises B and organizes green SrGa ₂S ₄: Eu phosphor and the A group O series phosphor of inventing and before having disclosed by the present inventor.Green SrGa ₂S ₄: the Eu phosphor also can be organized yellow YAG or orange TAG combination of phosphors with A.

In another embodiment of the present invention, by combination A red CaS:Eu phosphor and the G series of coming free present inventor to provide are provided or Y series is green and the yellow green silicate-based phosphors in any one phosphor prepare smart phosphor.Described red CaS:Eu also can organize combination of phosphors with another B, such as green YAG of GP-4 and green SrGa ₂S ₄: the Eu phosphor.

The phosphor ZnSe of work in copperization _xS _1-x: Cu shows slightly different in these examples because its can be configured to four kinds of colors green, yellow, orange and red in any one in launch.These phosphors through special configuration will be called green ZnSe _xS _1-x: Cu, yellow ZnSe _xS _1-x: Cu, orange ZnSe _xS _1-x: Cu and red ZnSe _xS _1-x: Cu.In another embodiment of the present invention, smart phosphor comprises A and organizes red ZnSe _xS _1-x: one or many persons in Cu and B group G or the Y series phosphor.With theoretical consistent, green or yellow ZnSe _xS _1-x: the Cu phosphor can with any one combination in the A group phosphor that is selected from the group that forms by yellow YAG, orange TAG and red CaS:Eu phosphor.

Now turn to silicon oxynitride, B group green (and/or yellow) SrSi ₂O ₂N ₂: the Eu compound can be in one embodiment be selected from by the previous present inventor's who discloses O series silicate-based phosphors, yellow (may for orange-yellow) YAG, orange TAG, red CaS:Eu and red ZnSe _XS _1-xAny one combination in the A group phosphor of the group that phosphor is formed.

Based on described silicon nitride compound (Sr, Ba, Ca) ₂Si ₅N ₈: Eu can design multiple smart phosphor composition.The relative amount of alkaline earth element in this compound can change with the phosphor of construction transmitting green, yellow, orange or red " family " optionally.Therefore, the transmitting green of this phosphor and yellow form are showed B group characteristic; Launch orange and red form and show A group characteristic.Each member of described series can launch color according to it and differentiate: (Sr, Ba, Ca) ₂Si ₅N ₈: Eu, yellow (Sr, Ba, Ca) ₂Si ₅N ₈: Eu, orange (Sr, Ba, Ca) ₂Si ₅N ₈: Eu, redness (Sr, Ba, Ca) ₂Si ₅N ₈: Eu phosphor and its analog.

In some embodiments of the invention, smart phosphor comprise B group green and/or yellow (Sr, Ba, Ca) ₂Si ₅N ₈: Eu silicon nitride phosphor with by previous A group Y series that discloses of present inventor or O series silicate-based phosphors.Perhaps, green and/or yellow (Sr, Ba, Ca) ₂Si ₅N ₈: the Eu phosphor can be organized yellow YAG or the pairing of orange TAG phosphor with A.It also can organize sulfide red CaS:Eu or ZnSe with A _xS _1-x: any one pairing among the Cu.

Green form or the orange form of yellow form and same phosphor or the ability of red form pairing of the common ground of the phosphor composition that can be configured in than wide spectral range, launch for making phosphor, and silicon nitride family (Sr, Ba, Ca) ₂Si ₅N ₈: Eu also is advantageously used in this situation.In this embodiment, and B group green or yellow (Sr, Ba, Ca) ₂Si ₅N ₈: the Eu phosphor be with A group orange or red (Sr, Ba, Ca) ₂Si ₅N ₈: Eu phosphor pairing, therefore, the composition of this embodiment major part be (Sr, Ba, Ca) ₂Si ₅N ₈: Eu.

Also can based on be its A configuration set (Sr, Ba, Ca) ₂Si ₅N ₈: Eu, be appointed as orange (Sr, Ba, Ca) ₂Si ₅N ₈: Eu and redness (Sr, Ba, Ca) ₂Si ₅N ₈: Eu designs smart phosphor.In one embodiment of this invention, by combination A group red (Sr, Ba, Ca) ₂Si ₅N ₈: Eu be selected from by G series silicate-based phosphors, Y series silicate-based phosphors and green SrSi ₂O ₂N ₂: the B group phosphor of the group that the Eu phosphor is formed prepares smart phosphor.

G series and Y series silicate-based phosphors composition

The G series of the embodiment of the invention and describing more widely of Y series phosphor now are provided.The G series phosphor comprises have formula (Sr, A ₁) _x(Si, A ₂) (O, A ₃) _2+x: Eu ²⁺The silicate-base compound, A wherein ₁It is at least a bivalent cation (2+ ion) that comprises magnesium (Mg), calcium (Ca), barium (Ba) or zinc (Zn), or 1+ cation and the cationic combination of 3+, wherein the 1+ cation can comprise K, Na and Li, and wherein the 3+ cation can comprise Cs, Y, Ce, Bi and Li.A ₁The cation component can comprise some 2+ cations and the 1+ cation and the cationic combination of 3+ of equal number substantially.A ₂Be 3+, 4+ or 5+ cation, comprise in boron (B), aluminium (Al), gallium (Ga), carbon (C), germanium (Ge) and the phosphorus (P) at least one.A ₃Be 1-, 2-or 3-anion, comprise fluorine (F), chlorine (Cl), bromine (Br), nitrogen (N) and sulphur (S).Any integer or the non-integer of x value between 1.5 and 2.5, (comprising 1.5 and 2.5).In one embodiment of this invention, x is not 2.Write out described formula and represent A ₁Cation replacement strontium (Sr); A ₂Cation replacement silicon (Si), and A ₃Anion replace oxygen (O).In one embodiment of the invention, A ₃Can be sulphur (S) and can have seldom oxygen or anaerobic existence in compound, therefore described phosphor is substantially sulfide and non-oxidized substance.

As rolling up the 1st phase, institute's teaching in the 1-120 page or leaf, β-Ca in Fei Lipu research report (Philips Research Reports) the 23rd by G. ballas people such as (Blasse) ₂SiO ₄: Eu, Sr ₂SiO ₄: Eu or Ba ₂SiO ₄: Eu composition (Eu wherein ²⁺Concentration be 2 atom %) crystal structure and K ₂SO ₄Similar.Therefore, expect that G series green silicate phosphors of the present invention has similar host lattice.

Except other method, can be by adjusting A ₁The ratio of cation and strontium is controlled the optical property of these G series phosphor, wherein A ₁Can be alkaline earth element or transition metal or its combination.For instance, the wavelength location of peak emission takes place at (Sr _1-xBa _x) ₂SiO ₄The yellow position of 580nm when the green position of the 500nm in the phosphor system during from x=1 (in other words, when alkali metal content is 100%Ba) becomes x=0 (100%Sr).When Ba is increased to approximately 90% the time from 0, show from the conversion efficiency of the same light source at 450nm place to increase continuously.The peak emission wavelength of the 545nm that is obtained when x=0.3 is near the peak emission wavelength of YAG:Ce.

With A ₃Anion is included in present inventor's the peculiar G series green silicate based phosphor multiple mode.In one embodiment, during the liquid phase step of handling, in the liquid phase step process that during sol-gel or co-precipitation processing method, is run into, halogen is added in the phosphor composition.This liquid handling allows to mix on molecular level, makes A ₃Anion can be well-dispersed in the composition before at crystallisation step (for example, sintering) after a while.The present inventor had before found A ₃Anion influences emissive porwer and peak wavelength.Though do not wish to be bound by any particular theory, believe silicate-based phosphors that these phosphors Eu mixes luminous be the Eu of the phosphor that mixes owing to Eu ²⁺In the activator from 4f ⁶5d ¹To 4f ⁷Electron transition.Emission wavelength depends on the crystal field splitting of 5d energy level.Along with crystal field strength increases, emission wavelength increases.The parameter that 5d repels between electronics-electronics in the main influenced crystal of the luminescence peak energy of 4f transition influences; In other words, Eu ²⁺Cation and its be the distance between the anion on every side, and the average distance between cation and the ion.

Liquid handling makes at least some A ₃Anion can be replaced the O of body silicon hydrochlorate ^2-Anion and incorporating in the lattice.Work as A ₃When anion is monovalence,, then in lattice, can form cation vacancy to keep neutral charge as under the situation of halogen.Owing in the room on the cation position average distance between cation and the anion is reduced, so crystal field strength will increase.Therefore, the peak of launching curve will increase and form more cation vacancy and move towards long wavelength more along with content of halogen.Emission wavelength is directly related with the energy gap between the excitation state with the ground state of discussion electronics and and this energy gap is to be determined by crystal field strength.

Under the situation of silicate-based phosphors of the present invention, emission wavelength increases (in the particular range of content of halogen) along with content of halogen and the fact that increases is that halogen is incorporated in the host lattice, is positioned at strong evidence on the oxygen lattice position in the replacement mode probably.In one embodiment of the invention, A ₃Anion is a fluorine or chlorine.It is that phosphorus is A under the situation of G series phosphor at least by when being added into phosphorus (P) in the composition that halogen is incorporated intracell extra evidence into ₂Cationic data provide.Add phosphorus and can't change emission wavelength in fact, and this proves that again phosphorus shows as cation and therefore do not replace oxygen in the main crystal.Therefore, phosphorus adds and does not significantly change Eu ²⁺The crystal field strength of material of main part in the crystalline field (it is made up of the oxygen position basically) around the ion.

The Y series phosphor comprises and has formula A ₂SiO ₄: Eu ²⁺The silicate-base compound of D, wherein A is selected from the divalent metal of the group that is made up of Sr, Ca, Ba, Mg, Zn and Cd at least one, and D is for being present in the electronegative ion in the phosphor with the amount in the scope of about 0.01 mole of % to 20 mole of %.In arbitrary phosphor, can there be more than one divalent metals A.According to the embodiment of the invention, D can be the dopant ion that is selected from the group that is made up of F, Cl, Br and I, but D also can be the element such as N, S, P, As and Sb.Silicate-based phosphors is configured to absorbing wavelength in the exciting radiation of about 280nm to about 520nm scope.

The exemplary Y series phosphor that is configured to the light of emission wavelength in about 460nm to 590nm scope has composition (Sr _1-x-yBa _xCa _yEu _0.02) ₂SiO _4-zD _z, wherein 0＜x≤1.0,0＜y≤0.8 and 0＜z≤0.2.The alternative formula of exemplary Y series phosphor is (Sr _1-x-yBa _xMg _yEu _0.02) ₂SiO _4-zD _z, wherein 0＜x≤1.0,0＜y≤0.2 and 0＜z≤0.2.In an alternate embodiment, the Y series phosphor is (Sr _1-x-yBa _xM _yEu _0.02) ₂SiO _4-zD _z, wherein 0＜x≤1.0, and M are one among Ca, Mg, An and the Cd or many persons.In this embodiment, when M was Ca, condition 0＜y≤0.5 was suitable for; When M was Mg, condition 0＜y≤1.0 were suitable for, and when M was Zn or Cd, condition 0＜z≤0.5 was suitable for.In one embodiment, dopant D is F or Cl, or both, and in this embodiment, a certain at least person among F or the Cl replaces the oxygen in the host lattice.

O series silicate-based phosphors composition

The phosphor of O series comprises have formula (Sr, A ₁) _x(Si, A ₂) (O, A ₃) _2+x: Eu ²⁺The silicate-base compound, A wherein ₁Be at least a bivalent cation (2+ ion) that comprises magnesium (Mg), calcium (Ca), barium (Ba) or zinc (Zn), or 1+ cation and the cationic combination of 3+, A ₂Be 3+, 4+ or 5+ cation, comprise in boron (B), aluminium (Al), gallium (Ga), carbon (C), germanium (Ge) and the phosphorus (P) at least one; And A ₃Be 1-, 2-or 3-anion, comprise fluorine (F), chlorine (Cl), bromine (Br); And any value of x between 2.5 and 3.5, (comprising 2.5 and 3.5).Identical with the G series phosphor, the formula of writing out the Y series phosphor is with expression A ₁Cation replacement silicon (Si), and A ₃Anion replace oxygen (O).

The phosphor of these O series silicate-based phosphors also can be by formula (Sr _1-xM _x) _yEu _zSiO ₅The general description, wherein M is selected from the divalent alkaline-earth metal of the group that is made up of Ba, Mg and Ca at least one, but it also can comprise other diad, such as Zn.The value of x, y and z is followed following relation: 0＜x≤0.5,2.6＜y＜3.3 and 0.001＜z≤0.5.Described phosphor is configured to the light of emission wavelength greater than about 565nm.In certain embodiments, the O series phosphor has formula Sr ₃Eu _zSiO ₅In an alternative embodiment, phosphor can be (Ba _0.05Mg _0.05Sr _0.9) _2.7Eu _zSiO ₅Or (Ba _0.075Mg _0.025Sr _0.9) ₃Eu _zSiO ₅Or (Ba _0.05Mg _0.05Sr _0.9) ₃Eu _zSiO ₅In an alternative embodiment, phosphor has formula (Mg _xSr _1-x) _yEu _zSiO ₅, (Ca _xSr _1-x) _yEu _zSiO ₅(Ba _xSr _1-x) _yEu _zSiO ₅, follow the principles 0＜x≤1 and 2.6＜y＜3.3 of the value of x and y wherein, and wherein the relation between y and the z makes y+z approximate 3.

As being rolled up in Fei Lipu research report (Philips Research Reports) the 23rd by G. ballas people such as (Blasse), the 1st phase, institute's teaching in the 1-120 page or leaf belongs to the MeSiO of system ₅Host lattice in the phosphor of (wherein Me is Ca, Sr or Ba) has crystal structure Cs ₃CoCl ₅(or relevant) with described crystal structure.Therefore, expect that the orange silicate-based phosphors of O series of the present invention has similar host lattice.

For describing the activator content that will measure, the O series phosphor can be by formula (Sr _1-xM _x) _yEu _zSiO ₅General expression, wherein the content of europium activator is by " z " parametric description, and it can be in the scope of about 0.001＜z＜0.5.Can be with the effect that halogen is included in the O series phosphor by having formula (M _1-xEu _x) _ySiO ₅H _6zEmbodiment describe.In this embodiment, H is the halide anion that is selected from the group that is made up of F, Cl and Br, and the halogen quantity that is included in the composition is described by parameter " z " equally.Herein, z is in the scope of 0＜z＜0.1.

The automatic adjustment smart phosphor of constant chromaticity and its related with white lumination system classification again

According to the embodiment of the invention, White LED base illuminator comprises the automatic adjustment smart phosphor composition that the blue/UV photo-emission source array with broad is complementary; Described array is wideer than the possible array of conventional phosphors encapsulation.5nm excite the example of scope be 452.5nm to 457.5nm, wherein the colourity of wanting of illuminator can be maintained at x ± 0.01 and y ± 0.01 than in the close limit.The variation of product on CIE figure illumination can be about 0.300 ± 0.01 in the x value, and the y value is in 0.300 ± 0.01 the scope.At present, each 2.5nm for the blue/UV excitation wavelength changes and need at least 5 grades come those blue led chips are classified; And afterwards, will need other at least 5 grades to satisfy the needs of White LED of the present invention in the CIE zone 5 different defining.Current method need must be classified to brightness and voltage in each grade, and is therefore final, and LED encapsulation group has 168 grades.

Claims

1. the phosphor composition that can adjust colourity automatically, described composition comprises:

First phosphor, it is configured to make its emissive porwer to increase and increase along with excitation wavelength; With

Second phosphor, it is configured to make its emissive porwer to increase and reduce along with excitation wavelength.

2. automatic adjustment phosphor composition as claimed in claim 1, wherein the variation of colourity in about 10nm excitation wavelength range by the luminescence generated by light of described phosphor composition emission is no more than about 5%.

3. automatic adjustment phosphor composition as claimed in claim 1, wherein said 10nm excitation wavelength range are that about 450nm is to about 460nm.

4. automatic adjustment phosphor composition as claimed in claim 1, wherein said first phosphor is for having formula (Sr, A ₁) _x(Si, A ₂) (O, A ₃) _2+x: Eu ²⁺Silicate-based orange phosphors, and wherein:

A ₁Be in 2+ cation, 1+ cation and the cationic combination of 3+ or its combination at least one;

A ₂Be 3+, 4+ or 5+ cation;

A ₃Be 1-, 2-or 3-anion; And

X is between 2.5 and 3.5 and comprises any value of 2.5 and 3.5.

5. automatic adjustment phosphor composition as claimed in claim 4, wherein A ₁Be to be selected from the group that forms by Mg, Ca and Ba; A ₂Be to be selected from the group that forms by B, Al, Ga, C, Ge and P, and A ₃Be to be selected from the group that forms by F, Cl and Br.

6. automatic adjustment phosphor composition as claimed in claim 1, wherein said first phosphor is for having formula (Sr _1-x, M _x) _yEu _zSiO ₅Silicate-based orange phosphors, wherein:

M is selected from the divalent metal of the group that is made up of Ba, Mg, Ca and Zn at least one;

0<x<0.5；

2.6＜y＜3.3; And

0.001<z<0.5。

7. automatic adjustment phosphor composition as claimed in claim 1, wherein said first phosphor is for having formula (M _1-xEu _x) _ySiO ₅: A ₃Silicate-based orange phosphors, wherein:

M is selected from the divalent metal of the group that is made up of Sr, Ca, Ba, Zn and Mg at least one;

0.001<x<0.5

2.6＜y＜3.3; And

A ₃For being selected from the halide anion of the group that forms by F, Cl and Br.

8. automatic adjustment phosphor composition as claimed in claim 1, wherein said first phosphor is for being selected from by Sr ₃Eu _0.06Si _1.02O ₅(F, Cl) _0.18, Sr _2.94Ba _0.0.6Eu _0.06Si _1.02O ₅(F, Cl) _0.18(Sr _0.9Ba _0.1) _2.76Eu _0.06Si _1.02O ₅(F, Cl) _0.18The silicate-based orange phosphors of the group that forms.

9. automatic adjustment phosphor composition as claimed in claim 1, wherein said second phosphor is for having formula (Sr, A ₁) _x(Si, A ₂) (O, A ₃) _2+x: Eu ²⁺The silicate-base green phosphor, and wherein:

A ₁For 2+ cation, 1+ cation and 3+ sun from combination or its combination at least one;

A ₂Be 3+, 4+ or 5+ cation;

A ₃Be 1-, 2-or 3-anion; And

X is between 1.5 and 2.5 and comprises any value of 1.5 and 2.5.

10. automatic adjustment phosphor composition as claimed in claim 6, wherein A ₁Be to be selected from the group that forms by Mg, Ca, Ba, Zn, K, Na, Li, Bi, Y, La and Ce; A ₂Be to be selected from the group that forms by B, Al, Ga, C, Ge, N and P; And A ₃Be to be selected from the group that forms by F, Cl, Br, N and S.

11. automatic adjustment phosphor composition as claimed in claim 1, wherein said second phosphor is for having formula (Sr, A ₁) _x(Si, A ₂) (O, A ₃) _2+x: Eu ²⁺The silicate-base green phosphor, and wherein:

A ₂Be 3+, 4+ or 5+ cation;

A ₃Be 1-, 2-or 3-anion; And

X is between 1.5 and 2.5 and comprises any value of 1.5 and 2.5.

12. automatic adjustment phosphor composition as claimed in claim 1, wherein said second phosphor is for being selected from by Sr _0.925Ba _1.025Mg _0.05Eu _0.06Si _1.03O ₄(F, Cl) _0.12, Sr _1.025Ba _0.925Mg _0.05Eu _0.06Si _1.03O ₄(F, Cl) _0.12And Sr _1.125Ba _0.825Mg _0.05Eu _0.06Si _1.03O ₄(F, Cl) _0.12The silicate-base green phosphor of the group that forms.

13. the phosphor composition that can adjust colourity automatically, described composition comprises:

First phosphor, it is to be selected from by O series phosphor, YAG phosphor, TAG phosphor, CaS:Eu phosphor, ZnSe _xS _1-x: the Cu phosphor, (Sr, Ba, Ca) ₂Si ₅N ₈: Eu phosphor and Sr ₂Si ₅N ₈: the group that the Eu phosphor is formed; With

Second phosphor, it comprises the G series phosphor.

14. the phosphor composition that can adjust colourity automatically, described composition comprises:

Second phosphor, it comprises the Y series phosphor.

15. the phosphor composition that can adjust colourity automatically, described composition comprises:

First phosphor, it comprises the O series phosphor; With

Second phosphor, it is to be selected from by the green YAG phosphor of GP-4, ZnSe _xS _1-x: Cu phosphor, SrGa ₂S ₄: Eu phosphor, SrSi ₂O ₂N ₂: the Eu phosphor and (Sr, Ba, Ca) ₂Si ₅N ₈: the group that the Eu phosphor is formed.

16. the phosphor composition that can adjust colourity automatically, described composition comprises:

First phosphor, it comprises the YAG phosphor; With

Second phosphor, it is to be selected from by SrGa ₂S ₄: Eu phosphor, ZnSe _xS _1.x: Cu phosphor, SrSi ₂O ₂N ₂: the Eu phosphor and (Sr, Ba, Ca) ₂Si ₅N ₈: the group that the Eu phosphor is formed.

17. the phosphor composition that can adjust colourity automatically, described composition comprises:

First phosphor, it comprises the TAG phosphor; With

Second phosphor, it is to be selected from by the green YAG phosphor of GP-4, SrGa ₂S ₄: Eu phosphor, ZnSe _xS _1-x: Cu phosphor, SrSi ₂O ₂N ₂: the Eu phosphor and (Sr, Ba, Ca) ₂Si ₅N ₈: the group that the Eu phosphor is formed.

18. the phosphor composition that can adjust colourity automatically, described composition comprises:

First phosphor, its be selected from by the CaS:Eu phosphor, (Sr, Ba, Ca) ₂Si ₅N ₈: Eu phosphor, ZnSe _xS _1-x: Cu phosphor and Sr ₂Si ₅N ₈: the group that the Eu phosphor is formed; With

Second phosphor, it comprises the green YAG phosphor of GP-4.

19. the phosphor composition that can adjust colourity automatically, described composition comprises:

Second phosphor, it comprises SrGa ₂S ₄: the Eu phosphor.

20. the phosphor composition that can adjust colourity automatically, described composition comprises:

First phosphor, it comprises the CaS:Eu phosphor; With

Second phosphor, it is to be selected from by ZnSe _xS _1-x: Cu phosphor, SrSi ₂O ₂N ₂: the Eu phosphor and (Sr, Ba, Ca) ₂Si ₅N ₈: the group that the Eu phosphor is formed.

21. the phosphor composition that can adjust colourity automatically, described composition comprises:

First phosphor, it comprises ZnSe _xS _1-x: the Cu phosphor; With

Second phosphor, it comprises SrSi ₂O ₂N ₂: the Eu phosphor.

22. the phosphor composition that can adjust colourity automatically, described composition comprises:

First phosphor, its comprise (Sr, Ba, Ca) ₂Si ₅N ₈: the Eu phosphor and

Second phosphor, it comprises ZnSe _xS _1-x: the Cu phosphor.

23. the phosphor composition that can adjust colourity automatically, described composition comprises:

First phosphor, its comprise (Sr, Ba, Ca) ₂Si ₅N ₈: the Eu phosphor and

Second phosphor, it comprises SrSi ₂O ₂N ₂: the Eu phosphor.

24. the phosphor composition that can adjust colourity automatically, described composition comprises:

First phosphor, it comprises Sr ₂Si ₅N ₈: the Eu phosphor and

Second phosphor, its comprise (Sr, Ba, Ca) ₂Si ₅N ₈: the Eu phosphor.

25. a White LED base illuminator, it comprises the excitaton source of automatic adjustment phosphor composition and blue light-emitting/ultraviolet light.

26. White LED base illuminator as claimed in claim 25, described automatic adjustment phosphor composition comprises:

27. White LED base illuminator as claimed in claim 25, its 5nm that is configured to make at 452.5nm to 457.5nm excites the colourity that is created in the described illuminator in the following scope in the scope to change:

X ± 0.01; With

y±0.01。

28. White LED base illuminator as claimed in claim 27, wherein CIE scheme the illumination of the above product to be changed to the x value about 0.300 ± 0.01, and y value 0.300 ± 0.01.

29. method of handling the White LED wafer, described method comprises and is applied to step on the blue/UV LED wafer that contains blue/UV led chip array with adjusting phosphor composition automatically, and the peak emission wavelength scope of wherein said blue/UV led chip array is more than or equal to about 5nm.

30. a product White LED wafer, it is to produce by method as claimed in claim 29.

31. product White LED wafer as claimed in claim 30, wherein (x, y) value can be controlled in the scope of x ± 0.01 and y ± 0.01 CIE of any indivedual White LED chips that produced by described wafer.

32. product White LED wafer as claimed in claim 31, the peak emission wavelength scope of wherein said blue/UV led chip array is 452.5nm to 457.5nm.

33. product White LED wafer as claimed in claim 32, the zone of wherein said CIE figure are x about 0.300 ± 0.01 and y about 0.300 ± 0.01.