TWI390016B - A bright white light emitting diode and a phosphor powder based on cerium - Google Patents

Description

Warm white light emitting diode with ruthenium as matrix and its fluorescent powder

The invention relates to a warm white light emitting diode with a ruthenium as a matrix and a fluorescent powder thereof, in particular to a novel solid state light source which can be combined with different, and an InGaN nitride heterojunction as a matrix and containing a large amount of nanometer. The heterostructure of the grade structure is a warm white light-emitting diode with a ruthenium as a matrix and its phosphor powder.

Luminescent materials with Ja3d garnet space group have been widely used in nuclear energy and laser physics in the 1960s; the first report of garnet synthesis was made by American engineers HYooder and M.Kettle (please refer to Amer.Mineralogist). 1952 V36 N6 P15~98) For the first time, a single crystal artificial garnet containing Y ₃ Al ₅ O ₁₂ composition was proposed, and this was named yttrium aluminum garnet (YAG).

It has been pointed out in this work that the chemical composition lattice structure of YAG differs from the natural minerals Crossulara-Ca ₃ Al ₂ Si ₃ O ₁₂ and spessartine-Mn ₃ Al ₂ Si ₃ O ₁₂ , and Jooder HJ is the first to define the interval group very clearly. Belongs to J103d artificial garnet. The same lattice parameter a = 12.01 ± 0.2 A is greater than the natural garnet a ≒ 11.86A. With a large size of Y ⁺³ and Mn ⁺² , the metering of this material can be written as A ₃ B ₂ (BO ₄ ) ₃ , where type A ions (rare earth elements such as calcium, iron, etc.) have twelve The coordination of the facets has a valence number of KU=8, and the B-type ions (矽 and part of aluminum) have a valence of KU=4, and some of the Al ⁺³ ions have an octahedron with a valence of KU=6.

Mr. Yodera pioneered the new synthetic possibilities, which are more than just traditional garnet crystals. The long-term concern is often the market's beautiful ruby. The development of new industrial crystals has become an important development direction. This technical concept has been produced in the 20th century, combining high technology with laser.

It must be noted here that the solid-state laser produced in the 1960s is more effective than ruby Al ₂ O ₃ :Cr, a single crystal-based YAG:Nd (please refer to NassauR.J Apply physics 1962, Vol. 33, No. 8 Page 2519, same magazine 1963, V34, P3063, same magazine. V34, P3603). In this year, the first patent of the garnet component YAG:Nd was born (please refer to British Patent No. 10105, Patent No. 099 to Charvat, US Patent No. 2,979,413 to Nielson JW Bell Laboratories, and US Patent No. 3,050,407 to Ballman A.).

It is derived from yttrium-containing YAG:Nd (see US Patent No. 3,050,407 to Ballman A.) garnet composition, which differs in high efficiency, high light transmission and heat resistance, and is a reliable processing method for preparing larger-sized laser elements.

At the same time, the "synthetic" garnet (YAG: Nd) was realized according to the principles of physics and material analysis. The synthesis of garnets based on different rare earth ions (Ce, Pr, Eu, Dy) led to the expansion of the application of this unique material. In 1966 detailed studies applied the paramagnetic resonance at YAG:Ce, published in H. Levvis. (Refer to Journal Apply physics Vol. 37N2, P739). The main conclusion is that bismuth is used as an activator in the single crystal form. The same granules appear in the form of powder and yttrium-containing yellow garnet powder (the yellow gems are rare and rare in the jewelry market). of).

We have a technical solution for creating broadband garnet phosphors. The priority is the Dutch physicist G. Blasse on April 29, 1967 and A BRille in the patent on cathode ray tubes (please refer to the Netherlands N1 6706095 patent). A new type of phosphor powder (Y, Ce) ₃ Al ₅ O ₁₂ is used in the manufacture of fluorescent screens. These five patents are protected in different countries, pointing out the importance of G.Blass and A.Brill in this work.

Blasse G of the Royal Phillips of the Netherlands has developed a new patent in its US, UK, Germany and Belgium [Cerium-Activated Yttrium Aluminate Phosphor] patent (see US3,564,322 patent, GB1174518 patent, DE1764218 patent and Be714420 patent). The development of the color image screen has a broadband phosphor powder (Y, Ce) ₃ Al ₅ O ₁₂ with a radiation λ = 470 ~ 720 nm, and a maximum radiation spectrum λ _max = 550 nm. Allows transparent multi-color images and slides to be created in electroluminescence to produce visible spectrum sub-bands showing blue, sky blue, yellow and red, for more color balance and to establish the correct white light illumination, with regard to the added Garnet fluorescing powder, and the addition of the second well-known Ca ₂ Al ₂ SiO ₇ :Ce (garnet) phosphor powder, combined with the wide-band radiation made of two materials, the color image quality is reproducible ( Please refer to BlassG.A.Brill JP Apply physics Lett 1967, Vol 11, P53).

The publication of YAG:Ce Fluorescent Powder has the academic paper [Luminescent material] published by G.Blasse at the time (please refer to G.Blasse [Luminescent material] Amstepdam-.Berliu, 1994), and the fluorescent powder manual in Japan. Also documented in (refer to Phosphors Handbook, 1 ^st Edition, 1987).

The emergence of the main YAG:Ce material is very effective for nuclear physics and scintillators, and its very short afterglow (t _e <1x10 ^-7 seconds) allows detection of very high energy radiation.

Such a sample, the light-emitting component (Y, Ce) ₃ Al ₅ O ₁₂ and a similar analog component, like (Y, Gd, Ce) ₃ Al ₅ O _12, etc., in the [Fluorescent Powder Handbook] (please refer to the Handbook) Of Phosphors) and can be found in teaching reference books in various engineering schools.

At this time, the composite (and two-group) device, based on GaP-GaAS, has strong radiation in the infrared spectrum, and uses anti-Stoke fluorescent powder to convert the invisible radiation into visible red light or Green or blue radiation. For a description of the related patents, please refer to US Patent No. 3,882,215, Canadian CA 900620 patent and CA900620A patent.

A novel nitride material based on GaN is established to define the visible region (infrared light, ultraviolet light and blue light) of the light-emitting diode in the short-wavelength sub-band radiation. This material was proposed in the Soviet CCCP 635, 813 patent (see BCAblamov CCCP635813 patent) approved by the Soviet engineer BC Abramov (BCAblamov) to convert some of the primary radiation of the GaN structure into long waves using Stoke phosphor powder. Radiation, which constitutes white light of different colors.

In 1994, Japanese physicist S. Nakamura proposed a heterojunction (P-N junction) structure derived from indium nitride and gallium nitride to improve performance (please refer to S. Nakamura.Blue). laser.Springer Verlag.Berlin. 1997). Not long after, in 1995, the excellent physicist of "Nichia" company used a white light emitting diode. Utilizing the broadband fluorescent powder Y ₃ Al ₅ O ₁₂ :Ce (refer to US Pat. No. 3,564,322, GB 1174518, DE 1764218, and Be714420) and the synthetic structure of the light-emitting diode (refer to US Pat. No. 3,564,322, GB 1174518) , DE 1 764 218 patent and Be 714 420 patent) (Grod 900 of the patent of Grodriewicz W. Uitert W/Light, DE 2444107 patent of Pankove and CCCP 635813 of BCAblamov). This concept combines two complementary colors to create white light radiation based on the complementary color principle of Newton in the 17th century. They applied for patents based on known materials, structures, and physical principles (see S. Nakamura. Blue laser Diode. Springer Verlag, Berlin, 1997). In the well-known N5988925 patent, the following disadvantages still exist: 1. The luminous efficiency of the instrument is not high, 10-12 lumens/watt for a color temperature greater than 5000K; 2. The first partial heterojunction InN-GaN heterojunction blue light Radiation has an adverse effect on vision; and 3. On a single material based on solid-state type (Y, Gd.Ce) ₃ Al ₅ O ₁₂ , it is impossible to replicate warm white light.

In the establishment of warm white light-emitting diodes, due to the lack of single-component garnet luminescent materials, it has been limited for a long time; trying to establish similar light-emitting diodes with a single component (Gd, Ce) ₃ Al ₅ O ₁₂ Inconclusive (please refer to S. Nakamura. Blue laser Diode. Springer Verlag, Berlin, 1997), in addition to starting with Gd ₃ Al ₅ O ₁₂ in a series of research and development work, such a single fluorescent powder, at Aedred FA The published article (please refer to Aedred FA Trans Brit Ceram Soc. 1959.vol 58N4p 199-210) was denied.

A light-emitting diode having a warm red luminescence is produced by using a Y ₃ Al ₅ O ₁₂ :Ce and CaAlSiN ₃ :Eu two-component structured phosphor (see U.S. Patent Application No. US2008283801A, 2008/11/, by Ryowat T. 20 and Soshchin N, Chinese Patent Application No. CN 2008 1016492, 11.05.2008), in addition to the various garnet structures proposed to obtain warm white light, Chinese patent application CN 20081016492 relates to the present invention, here, referenced in the present invention The relevant information is probably due to the insufficiency of complex technology and illuminating technical parameters, which has not been used in practice so far.

In order to solve the above disadvantages of the prior art, an object of the present invention is to provide a warm white light emitting diode based on germanium, which is formed in a short-wave semiconductor InGaN heterojunction structure region and has a high light-emitting material. The most important is the presence of orange-red radiation in the region of λ > 580 nm.

In order to solve the above-mentioned drawbacks of the prior art, another object of the present invention is to provide a warm white light emitting diode based on germanium, which can establish a very wide broadband radiation and has a high color rendering coefficient Ra.

In order to solve the above disadvantages of the prior art, another object of the present invention is to provide a fluorene-based phosphor powder which can establish a warm white light-emitting diode.

In order to achieve the above object, a fluorene-based fluorifiable powder of the present invention is based on ruthenium, characterized in that F ^-1 ions and N ^-3 ions are added to the phosphor material. Substituting oxygen ions in a part of the garnet lattice, the stoichiometric formula is: (Gd _1-x-y Lu _x Ce _y ) ₃ Al ₅ O _12-z F _z/2 N _z/2 , the phosphor powder After being excited by an indium gallium nitride (InGaN) semiconductor heterojunction short-wave, it can be radiated in the orange-red spectral region.

For the purpose of the above, a ruthenium-based warm white light-emitting diode of the present invention is based on an indium gallium nitride (InGaN) heterojunction and has a luminescence converter, which can The blue light luminescence conversion of the first stage is converted into warm white light, characterized in that the phosphor powder particle component of the luminescence converter is connected to the organic ruthenium polymer as described above, and is distributed in the uniform thickness in the heterojunction Radiation surface and radiation facet.

In order to achieve the above object, a method for preparing a fluorene-based luminescent powder according to the present invention is for preparing a luminescent powder as described above, which comprises heat-treating a charge from an initial oxidized material, characterized in that the heat treatment Is in the reduction gas, heat treatment in three temperature stages, the first temperature stage 1100 ° C, the second temperature stage T> 1250 ° C, the third temperature stage T> 1330 ° C, the total time exceeds τ = 12 hours, then the product is cooled and pickled with mineral acid solution, forming a thin film ZnO on its surface. SiO ₂ .

The detailed description of the drawings and the preferred embodiments are set forth in the accompanying drawings.

First, the object of the present invention is to eliminate the disadvantages of the above-described conventional garnet phosphor powder. In order to achieve this goal, the fluorene-based matrix phosphor powder of the present invention is based on ruthenium (Gd) ruthenium (Lu) ruthenium (Ce), characterized in that F ^-1 ions are added to the composition of the phosphor powder material. And N ^-3 ions, replacing oxygen ions in a part of the garnet lattice, the stoichiometric formula is: (Gd _1-xy Lu _x Ce _y ) ₃ Al ₅ O12 _-z F _z/2 N _z/2 , the firefly The light powder is excited by an indium gallium nitride (InGaN) semiconductor heterojunction short-wave excitation and is radiated in the orange-red spectral region.

Wherein, the stoichiometric measurement parameter value is x=0.0001~0.3; y=0.001~0.08; z=0.0001~0.5 atomic fraction.

Wherein, the maximum spectral wavelength in the range of the orange-red spectral region is λ _max 575nm, its dominant wavelength λ 580nm.

Wherein, the atomic ratio between the 釓 and 鑥 is 300:1~5:1, the optimal atomic ratio is 20:1~10:1, and the activator composition Ce ^{+3 is} from 0.005~0.08 atomic percentage. .

Wherein, the atomic fraction [F ^-1 ] = [N ^-3 ] = 0.00005 - 0.25 of the oxygen ions, F ^-1 ions and N ^-3 ions in the anion lattice.

Wherein, when the 釓/鑥≒15:1 and the introduced atomic fraction [F ^-1 ]=[N ^-3 ]=0.001~0.005, the maximum radiation spectrum is λ=582nm, and the introduced atomic fraction [F ^-1] ]=[N ^-3 ]=0.05~0.1, the maximum radiation spectrum shifts to λ=585nm.

Wherein, when the color coordinate value of the phosphor powder is Σx+y>0.82, the radiation wavelength value is λ=585~600 nm.

Wherein, the luminescent excitation spectrum of the phosphor powder is located at a wavelength interval from λ=420 to 500 nm, which mainly changes the content between lanthanum and cerium.

Wherein, the half-wave width λ _0.5 of the spectral maximum radiation of the phosphor powder is 135~138 nm.

Wherein, the phosphor powder is made in the form of ultra-disperse particles, and the phosphor powder particles have an elliptical shape, and the median diameter is d ₅₀ = 2 μm.

The solution proposed by the present invention will be briefly explained below. First, it is pointed out that in the phosphor powder proposed by the present invention, the main material component such as ruthenium is lacking; and the second, fluorite powder has a garnet cubic lattice type. For the garnet lattice material and its associated 1c3d-O ¹⁰ n; third, it lacks antimony in the main component of the phosphor powder, so it does not belong to the YAG phosphor powder; fourth, the lattice parameter value of the phosphor powder The production method uses two different crystal chemical structures: part of Gd ⁺³ is replaced by the same valence state Lu ⁺³ or Ce ⁺³ ; the heterovalent state replaces part, and the divalent O ² is monovalent of fluoride ion F ^-1 And the N ^-3 substitution in the trivalent state, the phosphor powder proposed by the invention particularly uses 铈Ce ⁺³ ions as an activator, and its concentration reaches 0.08 atomic fraction, ensuring radiation absorption of the short-wave heterojunction InGaN material at a wavelength of λ>420 nm. The luminescent material is distributed in the blue, green, orange, and red visible spectral regions, and the maximum spectrum has λ _max = 582 nm.

The phosphor powder component proposed by the invention lacks cerium ion Y ⁺³ , so the radiant luminescence of the garnet structure exists: 1. The spectral radiation is very wide, from λ=500~800nm or more; 2. Very wide radiation band, The half-wave width is greater than 130 nm; 3. The afterglow time is very short, less than 100 nanoseconds; 4. The high quantum radiation output exceeding η >0.90; and 5. The displacement of the major secondary energy band in terms of wavelength is related to the main excitation band.

The luminescent properties of the phosphor powder proposed by the present invention are mostly erbium ions Ce ^{+ 3} as an activator. A similar warm white light is used as a warm white light with Ce ^{+ 3} as the main radiation, and the spectral radiation 铈 is composed of different broadband diffusions, and the electronic configuration Ce ⁺³ inside the 4f-5d is connected in the relevant transition range.

If the main symmetry in this field is produced in a cubic lattice, the main Ce ⁺³ radiation excitation band is based on a Gaussian curve with a vertical curve versus vertical.

The internal identification of Ce ⁺³ ions has 2F5/2 and 2F7/2 (excitation level), 2D5/2 and 2D3/2 (basic state), which enhances the lattice electrostatic field of the phosphor powder, and Ce ⁺³ short-wavelength radiation displacement, when reduced Long wavelength shift of Ce ⁺³ radiation induced by lattice electrostatic field forces.

In the process of the invention process, we have stated that for the mechanism of Ce ⁺³ in the radiation spectrum, first, the main maximum radiation spectrum is attached to the cationic lattice phosphor powder, which has self-twisting ions Gd ⁺³ and strontium ions Lu ^+3. The relationship between the ratios.

Secondly, in the structural components of the fluorescent powder radiation spectrum, the heterovalent substitution portion, the divalent O ² is replaced by the monovalent fluoride ion F ^-1 and the trivalent N ^-3 .

In order to illustrate the optical effects of the two alternative structures referred to, the method of analyzing the spectrogram is described in the present invention. Spectral Analysis - The data of the luminescent luminescence spectrum of the present invention is provided by a professional measurement analyzer of "sensing" company, and the visible spectrum region is scanned at a pitch of 5 nm from λ = 380 to 780 nm and the light source is blue light. The light-emitting diode has a radiation wavelength of λ = 464 nm. Please refer to Table 1, which is a fluorescent powder component of the present invention and its optical characteristics.

Please refer to FIG. 1 to FIG. 8 together, wherein FIG. 1 is a schematic diagram showing the spectrum of the sample 1 phosphor powder in Table 1; FIG. 2 is a schematic diagram showing the spectrum of the sample 2 phosphor powder in Table 1; A schematic diagram of the spectrum of the sample 3 phosphor powder in Table 1 is shown; FIG. 4 is a schematic diagram showing the spectrum of the sample 4 phosphor powder in Table 1; FIG. 5 is a schematic diagram showing the spectrum of the sample 5 phosphor powder in Table 1; Schematic diagram of the sample 6 phosphor powder in Table 1; FIG. 7 is a schematic diagram showing the spectrum of the sample 7 phosphor powder in Table 1; and FIG. 8 is a schematic diagram showing the spectrum of the sample 8 phosphor powder in Table 1.

From the above Table 1, we found: 1. Replace the oxygen ions with F ^-1 and N ^-3 , the maximum radiation spectrum of the phosphor powder changes at 2.9 nm; 2. The maximum spectral radiation half-wave width, the change is only in △ = 2 nm; 3. Luminance brightness is changed in the ΔL = 1900 units, or more, 10% higher than the change in the concentration of the replaced F ^-1 and N ^{- 3} ; and 4. The color temperature of the phosphor is reduced. At ΔT = 279K.

The advantage of the phosphor powder proposed by the invention is that when the atomic ratio of Gd ions and Lu ions is from 600:1 to 5:1, the optimal ratio is 20:1~10:1 and Ce ⁺³ is Activator, ratio is 0.005~0.08 atomic percentage. The second feature of the phosphor powder proposed by the present invention comprises: in the anion lattice, oxygen ions are replaced by F ^-1 ions and N ^-3 ions, and the number is from [F ^-1 ]=[N ^-3 ]=0.00005~ 0.25 atomic fraction.

The main data composition and the composition of the invention in Table 1 indicate that the fluorescent powder (sample 1) proposed by the present invention has an atomic fraction ratio Gd/Lu = 13:1 at a maximum spectrum λ _max = 580.9 nm, and The atomic fraction of F ^-1 is 0.2. When the actual number of F ^-1 ions is replaced by a small amount of O ^-2 ions in the tetrahedron, sometimes the internal lattice field lattice is not even, which is an important reflection of the wavelength shift transition.

When the atomic fraction of F ^-1 is increased, the N ^-3 atomic fraction is also increased by an equal amount, which increases the luminance of the phosphor powder.

The Ce ⁺³ ion spectral radiation is substantially different from the radiation of other rare earth ions, such as Tb ⁺³ , Eu ⁺³ or Pr ⁺³ , and the internal ions and surfaces of the f-orbital are mutually constrained, usually ⁵ D _J - ⁷ F _J . For the special radiation form of Ce ⁺³ ions in the 4f-5d orbital, a wide visible light band can be radiated.

This sub-band is connected at Ce ⁺³ -O ^-2 , and the wavelength of luminescence quantum λ=450nm produces the following phenomenon: Ce ⁺³ -O ^-2 + luminescence quantum→Ce ^+3* +O ^-2 →Ce ⁺³ (4F _5/2 -5D).

Containing strong absorption light, the ion excitation returns to the original initial state, and the quantum light emission difference is Δ≒60~70nm, so the maximum radiation spectrum of Ce ⁺³ is on the sub-band of garnet cubic lattice type from 530~ 590nm. In the transfer of radiation containing the entire Ce ^{+ 3} ion, we found that the maximum radiation in the cubic structure Gd ₃ Al ₅ O ₁₂ from λ _max = 580 ~ 585 nm, suitable for the orange red visible spectrum region.

During the invention, we found that when the color coordinate value increases to (Σx+y)>0.82, the main wavelength radiation is from λ=580~595nm, and the maximum radiation spectrum and the dominant wavelength are symmetric.

We also pointed out that for the addition of fluoride ion F ^-1 and N ^-3 ions to replace O ^-2 , the maximum spectral radiation half-wave width increases.

This is a major advantage of the phosphors proposed by the present invention, characterized in that the color rendering index Ra > 74 for all the overall values of the indicated regions.

In addition, the present invention also discloses a preparation method of fluorene powder as a matrix, which is used for preparing the fluorene powder as a matrix as described above, first weighing the desired raw materials, and then all the materials. The raw materials are thoroughly mixed, and the mixed raw materials are compacted in a crucible, heated in an electric furnace, and heated to a temperature of 5 ° C / min. 1100 ° C, hold for 2 to 5 hours, then heat up to T at a heating rate of 5 ° C / min At 1280 ° C for 2 to 6 hours, a weak reducing gas (N ₂ : H ₂ = 95: 5) is added as a shielding gas, and then heated to a temperature of 5 ° C / min. Hold at 1330 ° C for 2 to 6 hours, then naturally cool to room temperature.

The crucible was taken out from the electric furnace, and then the phosphor powder was taken out from the cognac and ground to a powder form, pickled with 0.1 M HNO ₃ strong acid, and coated with 50 nm zinc antimonate ZnO on the surface of the phosphor powder powder. SiO ₂ film.

The phosphor powder particles obtained in the synthesis method proposed by the present invention have an elliptical shape with a median diameter of d ₅₀ = 2.00 ± 0.5 μm. If the phosphor particle size is relatively large d ₅₀ > 2.50 μm, particles like this do not have compactness, they contain a large number of blind holes; if the powder of the phosphor powder is very fine, d ₅₀ < 2 μm, it will increase light. The scattering, the luminance of the light is reduced when the first semiconductor heterojunction radiation is excited.

In summary, the average particle diameter is d ₅₀ = 2.00 ± 0.5 μm, and the phosphor powder proposed by the present invention has high luminance and calculates the relationship standard of other chemical components of the phosphor powder because the lack of defects in the literature The data of the garnet luminescent phosphors were compared using a solid solution (Y _0.75 Gd _0.22 Ce _0.03 ) ₃ Al ₅ O ₁₂ phosphor powder.

According to its chemical composition (Gd/Lu correlation), and the amount of fluoride ion F ^-1 and nitrogen ion N ^-3 introduced in the tetrahedral AlO ₄ , we have achieved a luminous brightness level of 72 to 76.5%. The fluorite powder sample has a maximum radiation spectrum λ=561 nm, and the main luminescence is in the field of yellow visible spectroscopy. The luminescent powder of the present invention has a luminosity of more than 75%, and the luminescence brightness is very high.

A preferred embodiment of the preparation method of the fluorene-based luminescent powder of the present invention is as follows: First, the following raw material Gd ₂ O _{3 is} weighed: 48.95 g Al ₂ O ₃ : 25.5 g Lu ₂ O ₃ :4.18 g AlF ₃ . 3H ₂ O: 0.92 g CeO ₂ : 1.55 g AlN: 0.82 g

The above raw materials were thoroughly mixed, placed in 300 ml of alumina crucible, heated in an electric furnace, and heated to a temperature of 5 ° C / min to T = 1100 ° C for 4 hours, and then 5 ° C / min. The heating rate is raised to T=1300 ° C for 5 hours. At this time, a weak reducing gas (N ₂ :H ₂ =95:5) is added as a shielding gas, and then the temperature is raised to a temperature of 5° C./min to T=1420. °C, hold for 4 hours, then naturally cool to room temperature.

The crucible was taken out from the electric furnace, and then the phosphor powder was taken out from the cognac and ground to a powder form, pickled with 0.1 M HNO ₃ strong acid, and coated with 50 nm zinc antimonate ZnO on the surface of the phosphor powder powder. SiO ₂ film. The sample prepared according to the above examples is the sample 1 in Table 1.

In addition, the present invention also discloses a warm white light emitting diode based on ruthenium, which uses ruthenium as a matrix luminescent powder as described in Table 1, and the structure of the luminescent diode is similar to this. The applicant of the present invention disclosed in the Chinese patent CN101104802A (please refer to the specification and drawings of the above patent, which will not be described herein again), and is placed on a thermally conductive substrate of sapphire Al ₂ O ₃ or single crystal germanium, filled with fluorescent light. The heterojunction of the powder conversion layer (ie, the P-N junction) is typically located in a conical accumulator that directs all of the collected light onto the LED lens cover for outward radiation. Located on the surface or facet of the semiconductor heterojunction luminescence conversion layer, the composition consists of the fluorene-based luminescent powder particles mixed with the polymer proposed by the present invention, and specifically for the luminescent diode, the existing bismuth hydride The (organoanthracene) composition has a refractive index of n=1.65~1.75, and such a high refractive index can enhance the external radiation output of the luminescence converter. For the above-mentioned semiconductor heterojunction, heat-conducting substrate, illuminator, illuminating converter, and illuminating diode lens cover, please refer to the specification and drawings of the above-mentioned CN101104802A patent, and no further description is repeated here.

The ruthenium-based light-emitting diode proposed by the present invention is based on a nitride heterojunction, and the light-emitting surface and the side surface thereof are covered with a luminescence conversion layer having a thickness of 160 to 200 μm. The uniform thickness of the luminescence conversion layer ensures high uniformity of light and its color characteristics. In the course of the invention, we saw that the ratio of the weight of the phosphor powder to the polymer is 6 to 70%. The weight of the phosphor powder particles has a very high color temperature T>10000K for the white light synthesized at 6%. When the weight ratio of the phosphor powder is increased, the overall illuminating radiation color is orange-yellow, and the best of the phosphor powder. The weight ratio is 16~46%. This ensures the luminance of the light-emitting diode and its high color rendering.

The advantage of the ruthenium-based light-emitting diode pointed out by the present invention is characterized in that the luminescence conversion layer established by the semiconductor light-emitting diode based on the InGaN nitride heterojunction serves the first-order blue light. The radiant luminescence conversion is converted into warm white luminescence, characterized in that the luminescence converter is composed of the garnet fluorescene particle component as described above, mixed with the organic ruthenium polymer, and distributed in a uniform thickness in the heterojunction The radiation surface and the radiation edge surface, the weight ratio of the phosphor powder particles is 6 to 70%.

It should also be noted here that the ruthenium-based light-emitting diode of the present invention uses a heterojunction radiation excitation displacement to be wider at a longer wavelength, compared with the standard (λ = 450 to 465 nm), the present invention The proposed ruthenium-based light-emitting diode has a heterojunction radiation region from λ=420~485nm, and it must be emphasized that the standard garnet phosphor powder (Y _0.75 Gd _0.22 Ce _0.03 ) ₃ Al ₅ O ₁₂ A wide excitation wavelength like this.

Such a high-luminance luminance heterojunction requires a very high saturation color and a high quantum output of the light-emitting diode having a color temperature of 2500 to 4500K, and a warm white color coordinate of x=0.42 and y=0.44.

The above-mentioned ruthenium-based light-emitting diode is characterized in that it further has a conical spherical lens cover (not shown) located above the luminescence converter, and the conical spherical lens cover is irradiated When the observation angle is 2T=60°, the luminous intensity is 1>5000mcd, the power is W=1 watt, and the luminous flux F=80~90 lumens.

The invention relates to a ruthenium-based light-emitting diode, characterized in that for a self-power W=1 watt to W=2 watt, the luminous flux is increased to F>150 lumens, and the luminous efficiency of the instrument is η. 75 lumens / watt.

Therefore, the ruthenium-based warm white light-emitting diode of the present invention and the phosphor thereof are formed in the short-wavelength semiconductor InGaN heterojunction structure region to have a high luminescent material, and the most important in the present invention is The region of λ>580 nm has orange-red radiation, which can establish a very wide broadband radiation and has a high color rendering coefficient Ra to improve the shortcomings of the conventional warm white light emitting diode and garnet phosphor.

The disclosure of the present invention is a preferred embodiment. Any change or modification of the present invention originating from the technical idea of the present invention and being easily inferred by those skilled in the art will not deviate from the scope of patent rights of the present invention.

In summary, this case, regardless of its purpose, means and efficacy, is showing its technical characteristics that are different from the conventional ones, and its first invention is practical and practical, and it is also in compliance with the patent requirements of the invention. As early as the patent, Yan Jiahui Society, real sense of virtue.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing the spectrum of a sample 1 phosphor in Table 1 of the present invention.

Fig. 2 is a schematic view showing the spectrum of the sample 2 phosphor powder in Table 1 of the present invention.

Fig. 3 is a schematic view showing the spectrum of the sample 3 phosphor powder in Table 1 of the present invention.

Figure 4 is a schematic view showing the spectrum of the sample 4 phosphor powder in Table 1 of the present invention.

Figure 5 is a schematic view showing the spectrum of the sample 5 phosphor powder in Table 1 of the present invention.

Figure 6 is a schematic view showing the spectrum of the sample 6 phosphor powder in Table 1 of the present invention.

Figure 7 is a schematic view showing the spectrum of the sample 7 phosphor powder in Table 1 of the present invention.

Figure 8 is a schematic view showing the spectrum of the sample 8 phosphor powder in Table 1 of the present invention.

Claims (13)

A fluorene-based phosphor powder, which is based on ruthenium, characterized in that F ^-1 ions and N ^-3 ions are added to the phosphor powder material to replace part of the garnet lattice Oxygen ion, the stoichiometric formula is: (Gd _1-xy Lu _x Ce _y ) ₃ Al ₅ O _12-z F _z/2 N _z/2 , the phosphor powder is passed through an indium gallium nitride (InGaN) semiconductor Heterojunction short-wave excitation can radiate λ _max 575nm orange-red spectrum, its dominant wavelength λ 580 nm, wherein the stoichiometric measurement parameter value is x=0.0001~0.3; y=0.001~0.08; z=0.0001~0.5 atomic fraction. The fluorene-based luminescent powder according to claim 1, wherein the atomic ratio between the strontium (Gd) and strontium (Lu) is 300:1 to 5:1, the activator The composition Ce ^{+3 is} from 0.005 to 0.08 atomic percentage. The fluorene-based phosphor according to the first aspect of the patent application, wherein the atomic fraction of oxygen ions, F ^-1 ions and N ^-3 ions in the anion lattice is [F ^-1 ]= [N ^-3 ] = 0.00005~0.25. The fluorene-based fluorescing powder described in the first paragraph of the patent application, wherein the 釓/鑥=15:1 and the introduced atomic fraction [F ^-1 ]=[N ^-3 ]=0.001~0.005 When the maximum radiation spectrum is λ=582nm and the introduced atomic fraction [F ^-1 ]=[N ^-3 ]=0.05~0.1, the maximum radiation spectrum shifts to λ=585nm. For example, the fluorene-based phosphor powder described in the first paragraph of the patent application has a radiance value λ=585-600 nm when the color coordinate value Σx+y>0.82. As the fluorene-based phosphor powder described in the first paragraph of the patent application, the luminescence excitation spectrum is located at a wavelength interval from λ=420 to 500 nm, which mainly changes the content between lanthanum and cerium. The fluorene-based fluorescing powder described in the first paragraph of the patent application has a half-wave width λ _0.5 = 135 to 138 nm of the maximum radiation of the spectrum. The fluorene-based phosphor powder according to claim 1, wherein the phosphor powder is formed in the form of ultra-disperse particles, and the phosphor powder particles have an elliptical shape, and the median diameter is d ₅₀ 2 microns. A ruthenium-based warm white light-emitting diode is based on an indium gallium nitride (InGaN) heterojunction and has a luminescence converter that converts the first-order blue-radiation luminescence conversion For warm white luminescence, characterized in that the phosphor powder particle component of the luminescence converter is connected to the organic ruthenium polymer as described in the first item of the patent application, and distributed on the radiation surface of the heterojunction in a uniform thickness. And radiation facets. The luminescent white light emitting diode according to claim 9 is characterized in that the weight ratio of the phosphor powder particles is 6 to 70%. The illuminating white light emitting diode according to claim 9, wherein the light emitting diode is suitable for blue heterojunction radiation of λ=420~500 nm, and the illuminating converter has warmth. Blue-tone blue radiation with a color temperature of T=2500~4500K and a color coordinate of x 0.42 and y 0.44. The illuminating white light emitting diode according to claim 9 further comprising a conical spherical lens cover located above the illuminating converter, the conical spherical lens When the radiation observation angle is 2Θ=60°, the luminous intensity is 1>5000mcd, the power is W=1 watt, and the luminous flux is F=80~90 lumens. A method for preparing a phosphor powder based on ruthenium, which is used for preparing a fluorinated powder based on ruthenium as described in claim 1, which comprises a heat treatment charge from an initial oxidized material, characterized in that It is: the heat treatment is in the reducing gas, heat treatment in three temperature stages, the first temperature stage T 1100 ° C, the second temperature stage T> 1250 ° C, the third temperature stage T> 1330 ° C, the total time exceeds τ = 12 hours, then the product is cooled and pickled with mineral acid solution, forming a thin film ZnO on its surface. SiO ₂ .