CN102660284A - Manufacturing method of red nitride fluorescent powder for LED - Google Patents

Abstract

The invention relates to a manufacturing method of red nitride fluorescent powder for LED. The manufacturing method comprises the following steps of weighing raw materials, carrying out ball milling of one or more fluxing agents, sieving, mixing, sintering, crushing, washing, sieving and carrying out packaging. Compared with the existing high-temperature solid-state technology, the manufacturing method has the advantages that only one high-temperature sintering process on the raw materials is carried out and thus sintering hardness of powder is reduced obviously and sintered powder blocks are incompact so that processes and energy consumption are reduced and product quality is improved; and the one or more fluxing agents are subjected to ball milling in advance so that ball milling time of an initial product is greatly reduced and crystal brightness of a final product is improved.

Description

A kind of LED is with the method for manufacture of nitride red fluorescent powder

Technical field

The present invention relates to the method for manufacture of a kind of LED, more particularly relate to the method for manufacture that a kind of nitride is made red fluorescence powder with fluorescent material.

Background technology

LED is meant photodiode, is a kind of solid-state semiconducter device that can electric energy be converted into visible light, and it can directly be converted into light to electricity; It has changed the luminous and luminous principle of electricity-saving lamp tricolor powder of incandescent light tungsten filament, and adopts electroluminescence.The characteristics of LED are very obvious, and the life-span is long, light efficiency is high, radiationless and reduce power consumption, stability is high, volume is little, shock-resistant, thereby in multi-field widespread use.Traditional implementation of white light LEDs is a blue chip stack yellow fluorescent powder; The white light color developing that this mode obtains is relatively poor; And adopt blue chip or ultraviolet chip many colour system fluorescent material that superposes; Such as: red fluorescence powder, green emitting phosphor etc., can realize the LED that color developing is better, so nitride red fluorescent powder is applicable to the white light LEDs of the various high-performance high-color renderings of preparation.At present superior on the performances such as the chemicalstability of nitride red fluorescent powder, thermostability makes its application comparatively extensive.

Mostly nitride red fluorescent powder is alkali earth metal and rare earth compound; Because the chemical property of alkali earth metal and rare earth metal is active; Influence the component of synthetic product with easy formation impurity such as water, oxygen, and then have influence on the use properties of final product.Therefore the atmosphere in the building-up process, processing conditions have all been proposed higher requirement, difficulty of processing is strengthened, tooling cost improves.

Its process step of high temperature solid-state method of the prior art is: batching → batch mixing → high temperature pre-burning → detect → pulverize → primary dcreening operation → high temperature reduction → detect → pulverize → primary dcreening operation → ball milling → washing → wet screening → centrifugal dewatering → dry → dusting cover → comprehensive detection → finished product.Though the crystallite crystal mass that this method obtains is good, few surface defects, luminous efficiency is high, be beneficial to suitability for industrialized production; But also there is certain defective; Like twice high temperature sintering of needs, warm-up time is long etc. in reducing atmosphere, not only waste energy and the finished particle that generates is big, size distribution is wide, Yi Jutuan, needs long ball milling could reduce particle diameter; But simultaneously the twinkler crystalline form is damaged, luminosity factor descends.

Summary of the invention

To above-mentioned technical problem, the object of the invention be just to provide a kind of need not through twice calcination and in inert atmosphere heat-up time short LED with the method for manufacture of nitride red fluorescent powder fluorescent material.

To achieve these goals, the present invention adopts following technical scheme:

A kind of method of manufacture of Nitride phosphor of doped with rare-earth elements is characterized in that may further comprise the steps:

A) take by weighing aluminium nitride AlN, silicon nitride, CaCl2, strontium nitride, fusing assistant respectively, the weight that takes by weighing is calculated according to the stoichiometric ratio of nitride red fluorescent powder general formula, and described general formula is Ca _1-x-3y/2A _xB _ySiAlN _3-zC _z, wherein A is one or more among alkaline earth element Be, Ba, Si, Mg, Sr, Ca, the Ra; , B is a kind of or a few profit among REE Pr, Gd, Sm, Tb, Eu, Er, Ce, the Lu; C is one or more among F, Cl, the O; The span of its doping x is 0≤x≤0.1, and the span of y is 0≤y≤0.1, and the span of z is 0≤z≤0.1;

B) difference that obtains fluorescent material particle diameter size and wavelength according to plan is chosen different fusing assistants; Described fusing assistant is one or more in boric acid, strontium fluoride, Calcium Fluoride (Fluorspan), the ALUMNIUM FLUORIDE, and will accounting for a), the fusing assistant of the said general formula 0.5-3% of step mole carries out crossing 250 eye mesh screens behind the dry bulb mill 2-10h;

C) with a) and b) starting material that obtain of step put into the planetary ball mill thorough mixing, mixing time is 10-20h;

D) with c) pack into crucible and put into the high-temperature tubular atmosphere furnace of the mixture that obtains of step;

E) inert atmosphere of feeding pure nitrogen gas in high-temperature atmosphere furnace burns 4.5h at 1700 ℃ of following constant temperature;

F) with e) head product that obtains of step takes out from crucible, reduce to room temperature after, carry out coarse breaking with excellent pestle earlier, the pair roller fragmentation is 2 times again, carries out ball milling 2.5h at last;

G) with f) head product that obtains of step with 90 ℃ deionized water washing 5 times after, put into baking oven and dry;

H) with g) head product that obtains of step crosses 300 eye mesh screens, and packing obtains finished product.

The present invention and existing high temperature solid-state method compared with techniques have following characteristics:

Because the present invention only carries out a high temperature to raw material and burns, thereby the sintering hardness of powder obviously reduces, and the agglomerating powder agglomates is loose, and the time of burning is short, has not only reduced technological process, and save energy and quality product go up not down; Fusing assistant is carried out ball-milling processing in advance, make the ball milling time of head product greatly reduce, thereby increased the launching efficiency of the finished product.

Embodiment

Embodiment 1: chemical formula is: Ca _0.96Mg _0.01Gd _0.02SiAlN ₃

A) accurately take by weighing the CaCl2 of 142.3g, the magnesium nitride of 1.0g, the nitrogenize gadolinium of 5.1g, the silicon nitride of 140.2g, the aluminium nitride AlN of 122.9g;

B) accurately take by weighing 8.2g boric acid and carry out dry bulb mill 5h after cross 250 eye mesh screens;

C) with a) and b) starting material that obtain of step put into the ball mill thorough mixing, mixing time is 10h;

D) with c) pack into crucible and put into high-temperature atmosphere furnace of the mixture that obtains of step;

E) inert atmosphere of feeding pure nitrogen gas in high-temperature atmosphere furnace burns 4.5h at 1700 ℃ of following constant temperature;

F) with e) head product that obtains of step takes out from crucible, reduce to room temperature after, carry out coarse breaking with excellent pestle earlier, the pair roller fragmentation is 2 times again, carries out ball milling 1.5h at last;

G) with f) head product that obtains of step with 90 ℃ deionized water washing 5 times after, put into baking oven and dry;

H) with f) head product that obtains of step crosses 300 eye mesh screens, and packing obtains finished product.

Embodiment 2: chemical formula is: Ca _0.96Ba _0.01Gd _0.02SiAlN ₃

I) accurately take by weighing the nitrogenize gadolinium, the silicon nitride of 280.4g, the aluminium nitride AlN of 245.8g of nitrogenize barium 10.2g of CaCl2, the 8.8g of 284.6g;

J) accurately take by weighing 16.6g boric acid and carry out dry bulb mill 5h after cross 250 eye mesh screens;

K) with a) and b) starting material that obtain of step put into the planetary ball mill thorough mixing, mixing time is 10h;

1) with c) pack into crucible and put into high-temperature atmosphere furnace of the mixture that obtains of step;

M) inert atmosphere of feeding pure nitrogen gas in high-temperature atmosphere furnace burns 4.5h at 1700 ℃ of following constant temperature;

N) with e) head product that obtains of step takes out from crucible, reduce to room temperature after, carry out coarse breaking with excellent pestle earlier, the pair roller fragmentation is 2 times again, carries out ball milling 1.5h at last;

O) with f) head product that obtains of step with 90 ℃ deionized water washing 5 times after, put into baking oven and dry;

P) with f) head product that obtains of step crosses 300 eye mesh screens, and packing obtains finished product.

Embodiment 3: chemical formula is: Ca _0.93Mg _0.04Ce _0.02SiAlN ₃

Q) accurately take by weighing CaCl2, the magnesium nitride of 5.4g, the cerium nitride of 12.3g, the silicon nitride of 187.0g, the 163.96g aluminium nitride AlN of 183.8g;

R) accurately take by weighing 11.0g boric acid and carry out dry bulb mill 5h after cross 250 eye mesh screens;

S) with a) and b) starting material that obtain of step put into the planetary ball mill thorough mixing, mixing time is 17h;

T) with c) pack into crucible and put into high-temperature atmosphere furnace of the mixture that obtains of step;

U) in high-temperature atmosphere furnace, feed the inert atmosphere of going back of pure nitrogen gas, burn 4.5h at 1700 ℃ of following constant temperature;

V) with e) head product that obtains of step takes out from crucible, reduce to room temperature after, carry out coarse breaking with excellent pestle earlier, the pair roller fragmentation is 2 times again, carries out ball milling 1.5h at last;

W) with f) head product that obtains of step with 90 ℃ deionized water washing 5 times after, put into baking oven and dry;

X) with f) head product that obtains of step crosses 300 eye mesh screens, and packing obtains finished product.

It is understandable that, only provided the part embodiment of this invention in this specification sheets.According to above-mentioned principle, the present invention can also carry out suitable change and modification to above-mentioned embodiment.Therefore, the embodiment that discloses and describe above the present invention is not limited to also should fall into modifications more of the present invention and change in the protection domain of claim of this patent.In addition, although used some specific terms in this specification sheets, these terms are explanation for ease just, the present invention is not constituted any restriction.

Claims (1)

1. the method for manufacture of the yttrium aluminium garnet fluorescent powder of a doped with rare-earth elements is characterized in that may further comprise the steps:

A) take by weighing aluminum oxide and REE respectively, the weight that takes by weighing is calculated according to the stoichiometric ratio of the yttrium aluminium garnet fluorescent powder general formula of doped with rare-earth elements, and described general formula is Y _3-X-YCe _XB _YAl _5-ZC _ZO ₁₂, wherein

B is one or more among REE Lu, Pr, Gd, Tb, Eu, the Er; C is one or more among Gd, In, Si, Mg, Sr, the Ca; The span of its doping X is 0.01-0.1, and the span of Y is 0-0.1, and the span of Z is 0-0.1;

B) difference that obtains fluorescent material particle diameter size and wavelength according to plan is chosen different fusing assistants; Described fusing assistant is one or more in boric acid, strontium fluoride, Calcium Fluoride (Fluorspan), the ALUMNIUM FLUORIDE, and will accounting for a), the fusing assistant of the said general formula 0.5-3% of step mole carries out crossing 200 eye mesh screens behind the dry bulb mill 2-10h;

C) with a) and b) starting material that obtain of step put into biconical mixer thorough mixing, mixing time is 20-40h;

D) with c) pack into crucible and put into the tunnel of high-temperature atmosphere furnace of the mixture that obtains of step;

E) reducing atmosphere of the pure hydrogen of feeding in the tunnel of high-temperature atmosphere furnace is burnt 5.52h at 1537 ℃ of following constant temperature;

F) with e) head product that obtains of step takes out from crucible, reduce to room temperature after, carry out coarse breaking with excellent pestle earlier, pair roller fragmentation 0.4h carries out ball milling 2.5h at last again;

G) with f) head product that obtains of step with 90 ℃ deionized water washing 5 times after, put into baking oven and dry;

H) with g) head product that obtains of step crosses 200 eye mesh screens, and packing obtains finished product.