CN103396799A - LED (light-emitting diode) lamp as well as preparation method of red emitting inorganic luminescent material used in LED lamp - Google Patents

Abstract

The invention relates to an LED (light-emitting diode) lamp. The LED lamp comprises a circuit board, a white light LED lamp bead as well as an optical element, wherein the white light LED lamp bead is arranged on the circuit board; the optical element covers the LED lamp bead; an optical processing element for light diffusion or reflection is arranged at the periphery of the white light LED lamp bead; one of the optical element and the optical processing element is provided with red inorganic luminescent material. The invention also provides a preparation method of the red emitting inorganic luminescent material used in the LED lamp. In the LED lamp provided by the invention, the novel red emitting inorganic luminescent material is directly matched with a two-primary-color white light LED adopting a blue light LED and yellow fluorescent powder or a multi-primary-color white light LED with more than two primary colors, and the color rendering index of white light after mixing is changed obviously, and can be greater than 90, and R9 is greater than 80; the light quality of the LED is improved greatly; the application range of the LED lamp is widened; the use comfort of the LED lamp by people is improved.

Description

The preparation method of the red emission phosphor of LED lamp and employing thereof

Technical field

The present invention relates to LED light source or light fixture, particularly the preparation method of the red emission phosphor of a kind of white LED lamp and employing thereof.

Background technology

Colour rendering index under paper: light source is called color developing to the colour developing ability of object, is by the comparison of object appearance color under the reference with same colour temperature or reference light source.Spectral content that light is launched determines the photochromic of light source, but same photochromic can be by many, the minority even only light wave of two monochromes is synthetic, and the color developing of each color is also differed widely.Identical photochromic light source has different spectrum composition, and the wider light source of spectrum composition may provide the quality that preferably develops the color.When in light source light spectrum seldom or while lacking object reflects under reference light source main ripple, can make color produce obvious aberration (color shift).The aberration degree is larger, and light source is to the color developing of this look poorer.The colour rendering index coefficient is still to define at present the common method that color rendering properties of light source is estimated.

White light LEDs is more and more in the application of indoor general lighting, and at present, the LED illumination has entered the places such as odeum, museum and Library.The illumination in these places has special requirement to the reducing power of color, namely requires the LED lighting of high color rendering index (CRI).Simultaneously, general room illumination also has certain demand to high color rendering index (CRI), so obtains relative colour rendering index greater than 90, saturated red R9(estimates the index of red reproduction quality) LED white light greater than 80 becomes the developing direction that following LED throws light on.Yet well-known, the colour rendering index of two primary colours white light LEDs of blue-ray LED+YAG fluorescent material is hovered between 60-80 always, and its major cause is in YAG spectrum, lacks the spectrum of red light portion, makes the general colour rendering index of the white light LEDs that obtains on the low side.The method that improves two primary colours white light LEDs colour rendering indexs of conventional blu-ray LED+YAG fluorescent material is the red light radiation composition that increases in its white-light spectrum, general way is in specific original LED white light, add red fluorescence powder or add a red-light LED, by adjusting electric current, adjust the brightness of white light and ruddiness, then measure the colourity mathematic(al) parameters such as colour rendering index, obtain the proportioning of white light and ruddiness.The shortcoming of these modes is consuming time loaded down with trivial details, the cost costliness.

Summary of the invention

The object of the present invention is to provide a kind of colour rendering index greater than 90, R9 greater than 80 LED lamp.

A kind of LED lamp, it comprises circuit card, is arranged on the white LED lamp pearl on circuit card and covers on the optical element on LED lamp pearl.Described white LED lamp pearl periphery also is provided with the optical processing element for light diffusion or reflective use, and described white LED lamp pearl excites at least a fluorescent material to send white light by blue-ray LED.On one in described optical element and optical processing element, be provided with red emission phosphor.Described red emission phosphor encourages and luminous by the light of described LED lamp pearl, and its peak luminous wavelength is 610 ~ 665nm, and halfwidth is 12 ~ 34nm, and intensity is 1.1 ~ 1.5 times of peak value of the light that sends of described blue-ray LED.

In a preferred embodiment, described at least a fluorescent material comprises the fluorescent material of the rear Yellow light-emitting low temperature that is stimulated.

Further, when the relative colour temperature of described LED lamp is 2400 ~ 10000K, the colour rendering index that emits white light more than or equal to 90, R9 more than or equal to 80.Described red emission phosphor is that zinc oxide micron sphere, the trivalent europium ion of trivalent europium ion doping adulterates

With doubly (0 ﹤ X≤2) divalent europium doping of X

In one or more, in every kind of red emission phosphor, the mass ratio of europium ion is all 0.1% ~ 10%.。Described red emission phosphor by adulterate, spray, deposit and adhere in a kind of method be arranged on in described optical element and optical processing element.

The present invention also provides a kind of preparation method of red emission phosphor of above-mentioned LED lamp use, and the method comprises the following steps:

Step 1, take one or more in zinc nitrate, hexamethylenetetramine, sodium polystyrene sulfonate as pre-reaction material, take europium nitrate and Dysprosium trinitrate as doping agent, wherein the ratio of pre-reaction material and doping agent is (1 ~ 2): (0.1 ~ 0.99), and being dissolved in above-mentioned substance in deionized water and adopting high-temperature solid phase reaction method evenly to mix high temperature solid state reaction is solution;

Step 2, spend 30 ~ 120 minutes reaction times at temperature by the solution that step 1 obtains 500 ~ 800;

Step 3, filter, and pre-reaction material and doping agent are filtered out, and stays needed trivalent europium ion hotchpotch;

Step 4, with the hotchpotch that pure water cleaning step three obtains, hotchpotch gel after cleaning;

Step 5, the jello that obtains in the 100 temperature decline step 4 of spending toasted 1.6 ~ 3 hours, obtained the zinc oxide micron sphere of trivalent europium ion doping.

LED lamp of the present invention directly coordinates existing two primary colours or the above white LED lamp pearl of two primary colours with new-type red emission phosphor, significantly change the colour rendering index of white light after mixing, colour rendering index can be greater than 90, R9 is greater than 80, greatly improved the light quality of LED, widen the range of application of LED lamp, improved the comfort level that people use the LED lamp.

The accompanying drawing explanation

The ruddiness that Fig. 1 is original white light in one embodiment of the invention, add and synthetic after the spectrogram of white light.

The ruddiness that Fig. 2 is original white light in another embodiment of the present invention, add and synthetic after the spectrogram of white light.

Embodiment

Preparation method to the red emission phosphor of LED light fixture of the present invention and employing thereof is described in further detail below in conjunction with specific embodiment and accompanying drawing.

LED lamp of the present invention mainly comprises circuit card, is arranged on the white LED lamp pearl on circuit card and covers on the optical element on LED lamp pearl.In general, the lampshade that LED lamp pearl periphery also is provided with reflection shield or has the lampshade of reflection action or have the light diffusion, to realize the effect of light diffusion and luminous reflectance, for convenience of describing, unified will above-mentionedly be arranged on white LED lamp pearl periphery, for light, spread or the element of reflective use is called the optical processing element.And the optical element that covers on LED lamp pearl is lens, plays optically focused.On one in the optical processing element of LED lamp of the present invention and optical element, be provided with red emission phosphor.This red emission phosphor by adulterate, spray, deposit and adhere in a kind of method be arranged on in optical element and optical processing element.It should be noted that, the white LED lamp pearl excites at least a fluorescent material to send white light by blue-ray LED.In the present embodiment, the white LED lamp pearl excites YAG fluorescent material to send white light by blue-ray LED, the YAG fluorescent material rear Yellow light-emitting low temperature that is stimulated, and the mixed colour rendering index of light that blue-ray LED sends is between 60 ~ 80.In other embodiment, it is fluorescent material that the white LED lamp pearl can excite the gold-tinted of other types by blue-ray LED, also can excite two or more fluorescent material and send white light.Two or more fluorescent material is except comprising that gold-tinted is fluorescent material, as YAG fluorescent material, also may comprise silicate series fluorescent material, as (SrBa) 2SiO4, or nitride series fluorescent material, as CaAlSiN3, or aluminate serial fluorescent material, as one or more in YAG/ATG (SrBa) 2SiO4.

This red emission phosphor encourages and luminous (being mainly ruddiness) by the light of white LED lamp pearl, its peak luminous wavelength is 610 ~ 665nm, halfwidth is 12 ~ 34nm, intensity is 1.1 ~ 1.5 times of peak value of the light of blue LED lamp pearl, when the relative colour temperature of LED lamp is 2400 ~ 10000K, this light and above-mentioned colour rendering index after less than 80 white light, mixing, form colour rendering index greater than 90, R9 greater than 80 white light.

In the present embodiment, red emission phosphor is the zinc oxide micron sphere (ZnO:Eu3+) of trivalent europium ion doping.In other embodiment, red emission phosphor also can be trivalent europium ion doping

, be also

, or be the doubly divalent europium doping of (0 ﹤ X≤2) of X

, be also

, or be two or three mixture of these three kinds of materials.And in every kind of red emission phosphor, the mass ratio of europium ion is all 0.1% ~ 10%.Above-mentioned red emission phosphor has emmission spectrum and the more wine-colored emission of narrow wire, makes the CRI numerical value of the light that the LED lamp finally sends increase, and can keep stable.

Concrete, as shown in Figure 1, lines 1 are original white-light spectrum, the red-light spectrum of lines 3 for adding, and lines 2 are mixed white-light spectrum.Wherein, the red light peak wavelength that adds is 627nm, and halfwidth is 24nm, and when intensity was 1.2 times of blue peak, the general colour rendering index of the white light that is mixed to get was 95.6, and special colour rendering index also has respectively increase in various degree, as listed in table 1.Particularly saturated red R9, be elevated to 95.0 by negative value, illustrates that the red light radiation of this new-type red emission phosphor is extremely important to the color restoration capability of saturated red.

Half colour rendering index and the special colour rendering index table of spectrum after the original white light of table 1 and optimization

Colour rendering index	Corresponding color under daylight	Original white light	White light after optimizing
				Ra		70.5	95.6
R1	Light bois de rose	63.1	95.6
				R2	The dull gray yellow	76.6	97.3
R3	Saturated yellow-green colour	88.4	87.2
				R4	Medium yellow-green colour	66.6	95.5
R5	The pale blue green	64.8	98.4
				R6	Light blue	69.5	93.3
R7	Purplish blue color	84.2	96.9
				R8	Light red purple	50.8	99.1
R9	Saturated red	-53.9	95.0
				R10	Saturated yellow	44.9	86.7
R11	Saturated green	61.6	93.3
				R12	Saturated blue colors	36.9	70.6
R13	Yellowish pink colour (colour of skin)	66.1	98.2
				R14	Medium green (leaf)	93.6	91.0

Fig. 2 is respectively 12,16,20,24 and 28nm for the halfwidth when adding spectrum, when intensity is 1.2 times of peak value of light of blue LED lamp pearl its peak wavelength and mix after the relation of colour rendering index of white light, therefrom can find out, to the spectrum that adds, variation has all occurred in the tristimulus coordinates of mixed white light and correlated(color)temperature.

The preparation method of red emission phosphor of the present invention mainly comprises the following steps:

Step 1, take one or more in zinc nitrate, hexamethylenetetramine, sodium polystyrene sulfonate as pre-reaction material, take europium nitrate and Dysprosium trinitrate as doping agent, wherein the ratio of pre-reaction material and doping agent is (1 ~ 2): (0.1 ~ 0.99), and being dissolved in above-mentioned substance in deionized water and adopting high-temperature solid phase reaction method evenly to mix high temperature solid state reaction is solution;

Step 2, spend 30 ~ 120 minutes reaction times at temperature by the solution that step 1 obtains 500 ~ 800;

Step 3, filter, and pre-reaction material and doping agent are filtered out, and stays needed trivalent europium ion hotchpotch;

Step 4, with the hotchpotch that pure water cleaning step three obtains, hotchpotch gel after cleaning;

Step 5, the jello that obtains in the 100 temperature decline step 4 of spending toasted 1.6 ~ 3 hours, obtained the zinc oxide micron sphere of trivalent europium ion doping.

Adopt the zinc oxide micron sphere of trivalent europium ion doping of aforesaid method system when application, the peak wavelength of the light that it sends all can reach 610 ~ 665nm, and halfwidth is 12 ~ 34nm, and intensity is 1.1 ~ 1.5 times of peak value of the light of blue LED lamp pearl.

LED lamp of the present invention directly coordinates two primary colours or many primary colours white light LEDs of blue-ray LED+fluorescent material with new-type red emission phosphor, significantly change the colour rendering index of white light after mixing, colour rendering index can be greater than 90, R9 is greater than the 80 light qualities that greatly improved LED, widen the range of application of LED lamp, improved the comfort level that people use the LED lamp.Wherein, by regulating the energy gap of the base mateiral in red emission phosphor, and then regulate its excitation wavelength; As sensitizing agent, the feature that strengthens Eu3+ rare earth ion in product is luminous, improves thus its emitting red light characteristic by the europium element.

In addition, large power white light LED is along with the passing of working hour, generation and the heat abstraction of heat progressively reach equilibrium state, the temperature of this equilibrium state is higher, impact for the white light LEDs that uses same type fluorescent material is larger, be specially: along with the continuous rising of LED temperature, the fluorescent material activity will significantly reduce (Fahrenheit degree/degree centigrade conversion formula is: degree centigrade=5/9* (Fahrenheit degree-32), the activity of fluorescent material is better when 100 Fahrenheit degree, but substantially loses most in the activity of 250 Fahrenheit degrees (namely 120 degrees centigrade) left and right fluorescent material.Temperature is when affecting the activity of fluorescent material, the optical wavelength that also fluorescent material is excited produces certain impact: along with the rising of LED temperature, the fluorescent material activity is in inactivation gradually, light wavelength that fluorescent material sends is also along with being offset, this skew is red skew, and namely the light-emitting phosphor wavelength is offset towards red wavelength.This phenomenon is as the rising of explanation along with temperature, the color developing of White LED should be better, and be actually reduction, the problem of contradiction seemingly? the essence of this phenomenon is the side-play amount of fluorescent material to red wavelength, inactivation amount less than fluorescent material, be that fluorescent material ejects under the condition of high temperature red light is not enough to make up and blendes together the ruddiness that loses, the colour rendering index of the rising LED of temperature still descends so show as, and with white light LEDs, along with temperature, raises and colour rendering index descends and conforms to.By above analysis, can be drawn, promote the colour rendering index of fluorescent material white light LEDs, primary means are to reduce the joint temperature of LED, are secondly to improve the adaptive faculty of fluorescent material to high temperature.The present invention creatively is arranged on new-type red emission phosphor from LED lamp pearl in the optical processing element away from and optical element, rather than be coated on LED lamp pearl and cover on LED lamp pearl, thereby avoided the high temperature of LED chip, improved stability and colour rendering index.

Although the description of this invention carries out in conjunction with above specific embodiment,, those skilled in the art that can carry out many replacements, modifications and variations, be apparent according to above-mentioned content.Therefore, all are such substitute, improve and change all is included in the spirit and scope of attached claim.

Claims (6)

1. LED lamp, comprise circuit card, be arranged on the white LED lamp pearl on circuit card and cover on the optical element on LED lamp pearl, described white LED lamp pearl periphery also is provided with the optical processing element for light diffusion or reflective use, described white LED lamp pearl excites at least a fluorescent material to send white light by blue-ray LED, it is characterized in that, be provided with red emission phosphor on one in described optical element and optical processing element; Described red emission phosphor encourages and luminous by the light of described LED lamp pearl, and its peak luminous wavelength is 610 ~ 665nm, and halfwidth is 12 ~ 34nm, and intensity is 1.1 ~ 1.5 times of peak value of the light that sends of described blue-ray LED.

2. LED lamp according to claim 1, is characterized in that, described at least a fluorescent material comprises the fluorescent material of the rear Yellow light-emitting low temperature that is stimulated.

3. LED lamp according to claim 2, is characterized in that, when the relative colour temperature of described LED lamp is 2400 ~ 10000K, the colour rendering index that emits white light more than or equal to 90, R9 more than or equal to 80.

4. LED lamp according to claim 3, is characterized in that, described red emission phosphor is that zinc oxide micron sphere, the trivalent europium ion of trivalent europium ion doping adulterates

With doubly (0 ﹤ X≤2) divalent europium doping of X

In one or more, in every kind of red emission phosphor, the mass ratio of europium ion is all 0.1% ~ 10%.

5. LED light fixture according to claim 1, is characterized in that, described red emission phosphor by adulterate, spray, deposit and adhere in a kind of method be arranged on in described optical element and optical processing element.

6. the preparation method of a red emission phosphor, is characterized in that, comprises the following steps:

Step 1, take one or more in zinc nitrate, hexamethylenetetramine, sodium polystyrene sulfonate as pre-reaction material, take europium nitrate and Dysprosium trinitrate as doping agent, wherein the ratio of pre-reaction material and doping agent is (1 ~ 2): (0.1 ~ 0.99), and being dissolved in above-mentioned substance in deionized water and adopting high-temperature solid phase reaction method evenly to mix high temperature solid state reaction is solution;

Step 2, spend 30 ~ 120 minutes reaction times at temperature by the solution that step 1 obtains 500 ~ 800;

Step 3, filter, and pre-reaction material and doping agent are filtered out, and stays needed trivalent europium ion hotchpotch;

Step 4, with the hotchpotch that pure water cleaning step three obtains, hotchpotch gel after cleaning;

Step 5, the jello that obtains in the 100 temperature decline step 4 of spending toasted 1.6 ~ 3 hours, obtained the zinc oxide micron sphere of trivalent europium ion doping.