CN100509994C - Light emitting film, luminescent device, method for manufacturing light emitting film and method for manufacturing luminescent device - Google Patents

Light emitting film, luminescent device, method for manufacturing light emitting film and method for manufacturing luminescent device Download PDF

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Publication number
CN100509994C
CN100509994C CNB200480006816XA CN200480006816A CN100509994C CN 100509994 C CN100509994 C CN 100509994C CN B200480006816X A CNB200480006816X A CN B200480006816XA CN 200480006816 A CN200480006816 A CN 200480006816A CN 100509994 C CN100509994 C CN 100509994C
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light
fluor
emitting device
resin
luminous element
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CN1764707A (en
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玉置宽人
祖父江慎介
泉野训宏
武市顺司
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Nichia Corp
Nichia Chemical Industries Ltd
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Nichia Chemical Industries Ltd
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    • H01L24/93—Batch processes
    • H01L24/95—Batch processes at chip-level, i.e. with connecting carried out on a plurality of singulated devices, i.e. on diced chips
    • H01L24/97—Batch processes at chip-level, i.e. with connecting carried out on a plurality of singulated devices, i.e. on diced chips the devices being connected to a common substrate, e.g. interposer, said common substrate being separable into individual assemblies after connecting
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    • H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
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    • H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
    • H01L2224/48257—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a die pad of the item
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    • H01L2224/48463—Connecting portions the connecting portion on the bonding area of the semiconductor or solid-state body being a ball bond
    • H01L2224/48465—Connecting portions the connecting portion on the bonding area of the semiconductor or solid-state body being a ball bond the other connecting portion not on the bonding area being a wedge bond, i.e. ball-to-wedge, regular stitch
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    • H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
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    • H01L2924/181—Encapsulation

Abstract

The present invention provides a reliable, long-life phosphor, or the like, which is prevented from darkening due to aging. A light emitting apparatus has a light emitting element and a phosphor layer. The phosphor layer has a phosphor excited by light from the light emitting element, and a binder which binds the phosphor. The binder is hydroxide oxide gel obtained by curing sol of a hydroxide oxide mixed with sol containing at least one metallic element selected from the group consisting of Al, Y, Gd, Lu, Sc, Ga, In, and B. Transmittance of hydroxide oxide in a gel state is higher than the transmittance in the polycrystal state where the sol-gel reaction is proceeded. In addition, the content of hydroxyl group or water of crystallization in the hydroxide oxide is 10% or less by weight.

Description

The manufacture method of luminescent film, light-emitting device, luminescent film and the manufacture method of light-emitting device
Technical field
The present invention relates to be used for luminescent film, light-emitting device and these luminescent film of aspects such as illumination light source, light-emitting diode display, back light, teleseme, illuminated switch, various transmitter and various telltales, the manufacture method of light-emitting device.
Background technology
People have developed a kind of like this light-emitting device, this device carries out wavelength Conversion by means of fluor to the part of the light of luminous element, and the light that will carry out the light of wavelength Conversion and not carry out the luminous element of wavelength Conversion makes it to emit after mixing, and sends the glow color light different with the light of luminous element (for example the spy opens the 2002-198573 communique) by this.For example, a kind of White LED light-emitting device is practicability, this device will use the blue LED (below be also referred to as " LED ") of InGaN based material as luminous element, and in the luminous element surface-coated fluorescence member be arranged, and described fluorescence member can be used composition formula (Y, Gd) by containing 3(Al, Ga) 5O 12The yttrium aluminum garnet (below be also referred to as " YAG ") of expression is that the translucent materials such as Resins, epoxy of fluor constitute.The glow color of White LED light-emitting device can obtain by the mixing principle of light.The blue-light-emitting that emits from LED absorbs and scattering in layer after inciding among the fluorescence member repeatedly, outwards emits then.On the other hand, the blue light that is absorbed by fluor sends xanchromatic fluorescence as excitaton source generation effect.The sodium yellow of this fluor and the blue light of LED are mixed, and people's eyes just can be seen white light.
Use the LED light-emitting device of such LED, be characterized in small-sized, electrical efficiency is high and send brightly painted light.In addition, LED does not burn out phenomenons such as (burn out) because be semiconductor element so worry producing.Moreover the strong such feature of ability repeatedly that the LED light-emitting device has also that the initial stage drive characteristic is good, vibration and on and off are lit a lamp.Because have good like this feature,, the LED light-emitting device is used so can be used as various light sources.
But former white luminous device is because use resin in a large number, so when being used for the luminous element of output rating height, wavelength weak point, exist resin that the problem of degenerating takes place.In addition, be under the situation of binding agent using inorganic, especially under the situation of using the cured film that forms by silica dioxide gel, when exposing to the open air in high-output power and ultraviolet environment, exist colour deterioration and produce the problem of melanism.Though its reason it be unclear that, it is generally acknowledged that this is that these organic groups are reduced because of the intensive photostimulation because contained organic group still has residually in the silicon dioxide gel after curing.
In addition, for the light that improves light-emitting device takes out efficient, can consider to improve the transmitance of luminescent film.The transmitance of luminescent film depends on the transmitance of the binding agent of appendix fluor in luminescent film.When using the gel that in binding agent, makes the colloidal sol thermofixation and form, as shown in Figure 1, can think that generally near polycrystal, like that just getting in the transmitance image pattern of luminescent film shown in the A risen along with the carrying out of sol gel reaction.
But if make gel near polycrystal, then sol gel reaction becomes the reaction of at high temperature carrying out, thereby needs more times and energy.Moreover, because high temperature produces dysgenic problem so exist to semiconductor light-emitting elements and fluor.The lead-in wire that for example connects led chip is damaged because of heat, and perhaps fluor produces and degenerates.In order to improve the taking-up efficient of light, produce multicrystal unorganic glassization along with the carrying out of sol gel reaction, this is accompanied by the generation of difficulty from the temperature of reaction aspect.
Moreover even produce unorganic glassization along with the carrying out of sol gel reaction, the interface of luminescent film and luminous element also can produce variety of issue.For example produce total reflection at vitrified interface, the taking-up inefficiency that causes light, perhaps produce following problem, i.e. generation is solidified and is formed space layer at the interface of luminous element and the interface of fluor, and space layer becomes the blocking layer and makes the taking-up of light become difficult.
In addition, in the structure of using luminous element stimulated luminescence layers such as LED, also exist luminescent layer because of exposing the problem that in the powerful energy of the exciting light of LED, produces degeneration to the open air.The luminescent layer of degenerating is colored as and has black, thereby impairs original light transmission, causes the taking-up degradation in efficiency of light.Like this melanism the reason of colour deterioration it be unclear that, but it is generally acknowledged that reason is the silicon-dioxide as the binding agent of luminescent layer.
As the sealing material of sealing fluor on luminescent layer,, also obviously degenerate, thereby be difficult to resin as sealing material because of exposing to the open air in high light even want to utilize general resin.For this reason, use silicon-dioxide (SiO 2) wait binding agent with light transmission.Gelatinous silicon-dioxide is that silica dioxide gel is good because of cohesiveness, light transmission is good, the taking-up efficient of light high and uses cheap the acquisition easily of industrial aspect.
But when in the high light that is exposed to LED for a long time, colour deterioration is taking place in the silica binder layer.Special in the light-emitting device of high-output power, because of high light intensity and the hot degeneration that causes the silica binder layer, and be coloured to black or chocolate.The result that the present inventor studies can infer that its reason is: SiO 2Be damaged the generate SiO of silicon-dioxide because of oxygen X(x＜2).Silica binder is in SiO under 250 ℃ or following heat curing temperature 2The state of the silica dioxide gel of remaining a part of hydroxyl, organic group in the skeleton.In the state of such silica dioxide gel,, will produce the damaged of oxygen, thereby make SiO when by the highdensity light time of LED incident 2Become SiO X(x＜2).So because Si is easy to generate redox, so it is generally acknowledged that silica dioxide gel produces oxygen damaged be the reason of colour deterioration.In case producing colour deterioration, will produce the problem of the optical output power decline that comes from luminous element.
In recent years, using the exploitation of light-emitting device of the luminous element of high-output power, but the light that luminous element produces has the tendency that promotes that resin is degenerated.In addition, on the one hand, carrying out short wavelength regions and then the exploitation of such short-wave long light-emitting element from the blueness to the visible light, on the other hand, can stand filming of these ultraviolet rays etc. for a long time and also not find to UV-light zone.Even want to utilize general resin, also obviously degenerate, so be difficult to resin as filming because expose to the open air in high light.
Summary of the invention
The present invention finishes for solving such problem.Main purpose of the present invention is: the luminescent film that taking-up efficient is improved and reliability is good, light-emitting device, the manufacture method of luminescent film and the manufacture method of light-emitting device that a kind of light is provided, and then provide a kind of so high light-emitting device and manufacture method thereof of reliability, wherein said light-emitting device to have to be difficult to light to produce filming of degeneration because of the luminous element that comes from ultraviolet ray etc.
Luminescent film of the present invention is the luminescent film that is used for covering luminous element, and it is made of filler member that contains luminescent material and binding agent member at least, and wherein the binding agent member contains the hydrous oxide (claiming oxide compound-oxyhydroxide again) of metallic element at least.This luminescent film also can be used as the diffusion layer that does not contain fluor and uses.
In addition, another luminescent film of the present invention is characterised in that: luminescent material is an inorganic phosphor, and the filler member is mineral filler, and the binding agent member is the mineral binder bond based on the hydrous oxide of the metallic element of constant valence mumber.
Because being main body with the inorganics, luminescent film forms, and the metallic element that constitutes hydrous oxide has the constant valence mumber, so the redox reaction of the compound after the film forming is suppressed, it is stable that luminescent film becomes, therefore, can obtain the luminescent film that the excitation under high light intensity, the high temperature also can not be degenerated.
In addition, another luminescent film of the present invention is characterised in that: luminescent material is an inorganic phosphor, the filler member is mineral filler, the binding agent member is that the hydrous oxide of metallic element is the hydrous oxide of IIIA family or IIIB family element at least based on the mineral binder bond of the hydrous oxide of metallic element.
By using the metallic element of 3 valencys, have the inhibition effect of bigger redox reaction, can obtain more stable luminescent film.
In addition, another luminescent film of the present invention is characterised in that: IIIA family or IIIB family element contain at least a kind among Sc, Y, Gd, Lu or B, Al, Ga, the In.
The hydrous oxide of these elements, its transparency is high and stable, also in one's hands than being easier to.
In addition, another luminescent film of the present invention is characterised in that: the hydrous oxide of the metallic element that contains in the binding agent member is for having the hydrous oxide of the Al of boehmite structure or pseudo-boehmite structure at least.
In addition, another luminescent film of the present invention is characterised in that the binding agent member contains: the hydrous oxide of aluminium, and with the hydrous oxide that with respect to binding agent member content is 0.5 weight %～IIIA family elements 50 weight %, different with aluminium or IIIB family element.
In addition, another luminescent film of the present invention is characterised in that: it is boron oxide or the boric acid of 0.5 weight %～50 weight % that the binding agent member contains with respect to binding agent member content.
In addition, another luminescent film of the present invention is characterised in that: the hydrous oxide of the metallic element that contains in the binding agent member is the hydrous oxide of yttrium.
In addition, another luminescent film of the present invention is characterised in that the binding agent member contains: the hydrous oxide of yttrium, and with the hydrous oxide that with respect to binding agent member content is 0.5 weight %～IIIA family elements 50 weight %, different with yttrium or IIIB family element.
In addition, another luminescent film of the present invention is characterised in that: it is boron oxide or the boric acid of 0.5 weight %～50 weight % that the binding agent member contains with respect to binding agent member content.
In addition, another luminescent film of the present invention is characterised in that: the binding agent member is the porous insert that is formed crosslinking structure, reticulated structure or polymer architecture by the aggregate of the particle that contains hydrous oxide.
The dehydration of the binding agent member of luminescent film, solidify and not proceed to the state that becomes oxide compound fully, luminescent film compares to crystalline and is in amorphous state thus, can form that cohesive force is increased, light takes out the good luminescent film of efficient.
In addition, another luminescent film of the present invention is characterised in that: the binding agent member is gel, is wherein filling the inorganic particulate that contains hydrous oxide.
In addition, another luminescent film of the present invention is characterised in that: polycrystal or non-crystal transmitance that the light transmission rate of luminescent film carries out under this situation of sintering after than sol gel reaction are higher.
In addition, another luminescent film of the present invention is characterised in that: the binding agent member contains 10 weight % or following hydroxyl or crystal water with respect to the binding agent member.
In addition, another luminescent film of the present invention is characterised in that: constitute the filler member of luminescent film and the weight ratio of binding agent member and count 0.05～30 with filler/binding agent.
In addition, light-emitting device of the present invention has luminous element and absorbs at least a portion of the light that luminous element sends and luminous luminescent layer.This light-emitting device is characterised in that: luminescent layer is above-mentioned luminescent film.
Moreover another light-emitting device of the present invention is characterised in that: the direct covering luminous element of luminescent layer.
In addition, another light-emitting device of the present invention has luminous element and absorbs at least a portion of the light that luminous element sends and send the luminescent layer of the light of different wave length.This light-emitting device is characterised in that: luminescent layer has light with luminous element and comes excited fluorescent body particle and disperse in this layer and appendix the binding agent member of fluorophor particle.
In addition, another light-emitting device of the present invention is characterised in that this light-emitting device comprises: have the semiconductor light-emitting elements of 550nm or following emission wavelength and come the fluor of stimulated luminescence with the light of this wavelength.
In addition, another light-emitting device of the present invention is characterised in that this light-emitting device comprises: have the semiconductor light-emitting elements of 410nm or following emission wavelength and come the fluor of stimulated luminescence with the light of this wavelength.
In addition, another light-emitting device of the present invention is characterised in that: luminescent layer is luminous under 50 ℃ or the above condition in temperature.
The reason that the binding agent generation of luminescent layer is degenerated be it is generally acknowledged and is light, heat or the interaction between them.Even the high-power excitation of the light-emitting device visible light of above-mentioned formation, UV-light, high temperature excitation etc. also are difficult to make binding agent produce to be degenerated, thereby be effective especially aspect the high excitation of these excitation densities.
In addition, another light-emitting device of the present invention is characterised in that: the luminescent layer bonding is formed on the semiconductor light-emitting elements, and the input electric power during the semiconductor light-emitting elements excitation is 0.1W/cm 2Or more than.Especially up to 1W/cm 2Or be effective under the above input electric power.
In addition, another light-emitting device of the present invention is characterised in that: the emission wavelength of semiconductor light-emitting elements is 410nm or following, at 1W/cm 2Or above input electric power is down during the excitation semiconductor light-emitting elements, the briliancy sustainment rate of the luminescent layer after 1000 hours be 80% or more than.
In addition, another light-emitting device of the present invention is characterised in that: the fluor that contains in the filler of the luminescent layer of light-emitting device has the luminous of at least a white color system that comprises among blue-light-emitting fluorescent material, blue-greenish colour light-emitting fluophor, green emitting fluor, yellow-green colour light-emitting fluophor, yellow luminescent phosphor, yellowish red color light-emitting fluophor, orange luminescence fluor and the red light-emitting phosphor or middle colour system.
In addition, another light-emitting device of the present invention is characterised in that: the fluor that contains in the filler of luminescent layer has luminous from green to yellowish red color of peak wavelength between 510nm～600nm, is to use Ce activatory rare earth class aluminic acid fluor at least.
In addition, another light-emitting device of the present invention is characterised in that: the fluor that contains in the filler of the luminescent layer of light-emitting device has luminous from yellowish red color to redness of peak wavelength between 580nm～650nm, is to use Eu activatory alkali earths silicon nitride fluor at least.
In addition, another light-emitting device of the present invention is characterised in that: the fluor that contains in the filler of luminescent layer has luminous from blue-greenish colour to yellowish red color of peak wavelength between 500nm～600nm, is to use Eu activatory alkali earths silicon oxynitride fluor at least.
In addition, another light-emitting device of the present invention is characterised in that: it is a luminous element with emission wavelength at 410nm or followingly carry out luminous semiconductor light-emitting elements, the fluor that contains in the filler of luminescent layer has blue-light-emitting, comprise to be selected from and use Eu activatory alkali earths halogen apatite fluorescent body at least, at least with Eu activatory alkali earths halogen boric acid fluor and use a kind of among the Eu activatory alkali earths aluminic acid fluor at least, and then with have luminous mixing with Ce activatory rare earth class aluminic acid fluor at least from the green to the yellowish red color, thereby demonstrate the luminous of white color system.
In addition, another light-emitting device of the present invention is characterised in that: it is a luminous element with emission wavelength at 410nm or followingly carry out luminous semiconductor light-emitting elements, the fluor that contains in the filler of luminescent layer has blue-light-emitting, comprise to be selected from and use Eu activatory alkali earths halogen apatite fluorescent body at least, at least with Eu activatory alkali earths halogen boric acid fluor and use a kind of among the Eu activatory alkali earths aluminic acid fluor at least, and then with have from the green to the yellowish red color luminous at least with Ce activatory rare earth class aluminic acid fluor with have mixing with Eu activatory alkali earths silicon nitride fluor at least from the yellowish red color to the emitting red light, thereby demonstrate the luminous of white color system.
In addition, another light-emitting device of the present invention is characterised in that: it be luminous element carry out luminous semiconductor light-emitting elements with emission wavelength at the blue region of 440nm～480nm, the fluor that contains in the filler of luminescent layer with mix with Ce activatory rare earth class aluminic acid fluor at least, thereby demonstrate the luminous of white color system.
In addition, another light-emitting device of the present invention is characterised in that: it be luminous element carry out luminous semiconductor light-emitting elements with emission wavelength at the blue region of 440nm～480nm, the fluor that contains in the filler of luminescent layer with have from the green to the yellowish red color luminous at least with Ce activatory rare earth class aluminic acid fluor with have mixing with Eu activatory alkali earths silicon nitride fluor at least from the yellowish red color to the emitting red light, thereby demonstrate the luminous of white color system.
In addition, the manufacture method of luminescent film of the present invention is to be made of filler member that comprises luminescent material and binding agent member at least, the manufacture method that is used for the luminescent film of covering luminous element, it is characterized in that, may further comprise the steps: will mix and the step of allotment slip as the metal oxygen alkane colloidal sol that contains metallic element and the filler member of binding agent member, slip is formed membranaceous step, and by the slip that forms film is carried out thermofixation, the particle accumulation that makes the hydrous oxide that contains metallic element together, thereby use the step of the binding agent member appendix filler member that the structure by this set particle constitutes.
In addition, the manufacture method of another luminescent film of the present invention is characterised in that: metal oxygen alkane colloidal sol is at least aikyiaiurnirsoxan beta colloidal sol or yttrium oxygen alkane colloidal sol.
In addition, the manufacture method of another light-emitting device of the present invention is to have luminous element and the manufacture method of the light-emitting device of the luminescent film that obtains according at least a portion of above-mentioned manufacture method covering luminous element, it is characterized in that: in forming membranaceous step, under heat-treat condition, adopt the slip covering luminous element and/or separate the zone of luminous element, thereby form membranaceous.
According to the present invention, can obtain light and take out high luminescent film, light-emitting device, the manufacture method of luminescent film and the manufacture method of light-emitting device of efficient.This be because: by in luminescent film, using hydrous oxide,, also can make the transmitance of luminescent film be subjected to less inhibition, take out efficient thereby obtain higher light even under the gel state that does not reach the polycrystal state.Moreover, according to the present invention, owing to use the hydrous oxide of metallic element with constant valence mumber, thus can obtain because of use cause few, the good endurance of colour deterioration, luminescent film, light-emitting device, the manufacture method of luminescent film and the manufacture method of light-emitting device that reliability is good.This be because: as the binding agent of fluor, the present invention does not use and can get metallic element multiple valence mumber, as silicon-dioxide, thereby it is damaged can not to produce oxygen, thus by the tack coat of the damaged generation of oxygen colour deterioration also can avoid.Can avoid low because of the painted optical output power that produces of tack coat thus, can obtain performance steady in a long-term,, and realize long lifetime even working power type luminous element also can obtain good reliability.In addition, can also obtain the luminescent film that weather resistance is improved, reliability is high, light-emitting device, the manufacture method of luminescent film and the manufacture method of light-emitting device of excellent heat resistance, fluor.
In addition, the present invention relates to a kind of light-emitting device, it has the matrix of luminous element and the described luminous element of carrying, this light-emitting device is characterised in that: described luminous element is covered by mineral binder bond, described mineral binder bond is covered by resin, described mineral binder bond floods with described resin, and described mineral binder bond is formed with the mineral binder bond layer of at least a portion that covers described luminous element and described matrix.
The space landfill that mineral binder bond preferably can be had the inorganic bond layer by resin.
In addition, mineral binder bond about 95% or the above space landfill that preferably can the inorganic bond layer be had by resin.
Adopt resin to cover mineral binder bond and preferably use pouring means or spraying spraying means, make the mineral binder bond dipping go up resin.
Moreover mineral binder bond preferably contains fluor.
Resin preferably can form the resin layer of at least a portion that covers mineral binder bond.
The surface that the surface of resin layer is preferably level and smooth.
Resin preferably contain among oil plant, gel and the rubber at least any.
Resin before moulding and under any situation after the moulding, is the silicone resin with dialkylsiloxane skeleton preferably.Following Chemical formula 1 is represented the dialkylsiloxane skeleton, and R represents alkyl in the formula.
Figure C200480006816D00141
Chemical formula 1
On main chain, has dimethyl siloxane before the preferred moulding of resin.Dimethyl siloxane is a kind of form among the dialkylsiloxane skeleton.Following Chemical formula 2 is represented dimethyl siloxane.
Figure C200480006816D00142
Chemical formula 2
Resin in the key absorption intensity of infrared spectra, the C-Si-O key during preferred resin is formed and the strength ratio of Si-O-Si key be 1.2/1 or more than.
The present invention relates to a kind of manufacture method of light-emitting device, it has: luminous element is carried on first operation on the matrix; With second operation of this luminous element with the mineral binder bond covering; With the 3rd operation that this mineral binder bond covers with resin, wherein the 3rd operation uses pouring means or spraying spraying means to make resin cover mineral binder bond.
The 3rd operation is preferably flooded in a vacuum.
Because have top illustrated formation, the present invention produces effect as described below.
The present invention relates to a kind of light-emitting device, it has the matrix of luminous element and this luminous element of carrying, in this light-emitting device, described luminous element is covered by mineral binder bond, described mineral binder bond is covered by resin, the step that covers described mineral binder bond with described resin is used pouring means or spraying spraying means, makes described mineral binder bond flood described resin.Thus, even at the luminous element that uses high-output power or emit under the situation of ultraviolet luminous element, the promotion that can provide a kind of resin to degenerate is suppressed, UV resistant etc. films for a long time.In addition, can not take place covering luminous element mineral binder bond degeneration and seek the raising that light takes out efficient.Moreover, because whole mineral binder bond all adopts resin to flood,, can form impact-resistant filming so mineral binder bond can not crack and defective.
This is determined by following effect.
When mineral binder bond solidifies, interstitial part is arranged.In the prior art, because the effect in this space, the taking-up of light is suppressed, and in the present invention, adopts resin that this space landfill is got up, and can seek the improvement that light takes out efficient thus.
As the means that adopt resin that this space landfill is got up, use be pouring means or spraying spraying means.Means outside pouring means, the spraying spraying means are for example injected the means of resin once toward whole mineral binder bond, the gas that discharge or remain in the inorganic bond layer is perhaps invaded in the resin and gas is preserved.The gas that is present in this inorganic bond layer is closed in the layer, and the heating of luminous element is expanded when being kept at gas in the layer and encouraging because of light-emitting device.Thus, the situation that light takes out inefficiency often takes place.In contrast, in pouring means, spraying spraying means, the gas that contains in the space of resin one side with mineral binder bond is extruded to the outside, in mineral binder bond, permeate on one side, so almost there is not survival gas in the space of mineral binder bond, resin is the space that had of landfill mineral binder bond fully almost.Therefore, even when the excitation luminescence device, the reflection in space and inorganic bond bed interface also is suppressed, and can not produce the situation that light takes out inefficiency, itself is stable and film.
Owing to the organic resinoid intrusion of softish is arranged in the space that mineral binder bond had, so the generation of the crackle that volumetric expansion caused of the gas that causes because of heat can be suppressed.
Mineral binder bond is preferably formed with the inorganic bond layer of at least a portion of covering luminous element and matrix.This be because: by forming a layer structure, the space that can easily adopt the resin impregnation mineral binder bond to be had.In addition, from the angle that light takes out, can send the light that comes from luminous element to the outside almost evenly.
The space landfill that mineral binder bond preferably adopts resin that the inorganic bond layer is had.Thus, the space of inorganic bond layer disappears, and can seek the raising that light takes out efficient.Therefore, only enough the space of landfill inorganic bond layer is just for employed amount of resin.
In addition, mineral binder bond 95% or the above space landfill that preferably can the inorganic bond layer be had by resin.This be because: if just the part in the space that had of inorganic bond layer is by the resin landfill, then the gap suppresses the taking-up of light.Under the situation of inorganic bond leafing exploitation optical element, because can directly not carry out thermal conduction from luminous element, thus consider the degeneration that causes because of heat not especially, thereby also this space of landfill not of resin.But, consider to come from the light of luminous element if desired, then preferably adopt resin with this space landfill almost completely.
Mineral binder bond preferably contains fluor therein.Thus, this fluor absorbs the part of the light that comes from luminous element and carries out wavelength Conversion, thereby send the light different with the light of luminous element to the outside, a part that comes from the light of luminous element is mixed with the part of the light that comes from fluor, a kind of light-emitting device with desirable tone just can be provided by this.In addition, by being designed to contain the inorganic bond layer of fluor, tone being regulated become easily, and a kind of light-emitting device uniform light, that qualification rate is high that sends is provided.
Resin preferably can form the resin layer of at least a portion that covers mineral binder bond.By forming a layer structure, can form filming of uniform film thickness, thereby seek the raising that light takes out efficient.
The surface that the surface of resin layer is preferably level and smooth.When mineral binder bond solidified, its surface existed concavo-convex.Therefore, when the light transmission mineral binder bond that sends by luminous element when send the outside because the effect of this jog, the directive property of light produces deviation.In contrast, when solvent impregnated resin in mineral binder bond, film coated surface becomes smoothly, can reduce the deviation of the directive property of light.
Resin preferably contain among oil plant, gel and the rubber at least any.This is in order to make resin impregnation in mineral binder bond.Particularly use the resin be in the oil plant state with the situation of resin impregnation in the mineral binder bond, produces gelation, can improve the high light-emitting device of a kind of light taking-up efficient by this because of heating waits.In addition, in gel or elastomeric form, can easily control the hardness of resin.Moreover, the lead-in wire that is electrically connected with electrode that is provided with on the luminous element and outer electrode, even resin is cured, lead-in wire can not be cut off yet.In the prior art, when cured epoxy resin, because the thermal expansivity of lead-in wire and Resins, epoxy there are differences, lead-in wire is cut off.And in the present invention, because resin is oil plant shape or gel, rubber-like, lead-in wire can not be cut off.In addition, only according to mineral binder bond, shock-resistant ability a little less than, and, can give by this and filming with flexibility with the resin landfill that is rubber-like etc., can form strong the filming of shock-resistant ability.
Resin before moulding and under any situation after the moulding, is the silicone resin with dialkylsiloxane skeleton preferably.By using this resin, can provide a kind of degeneration of resin further to be suppressed, the light-emitting device of filming and being used of UV resistant etc. for a long time.
On main chain, has dimethyl siloxane before the preferred moulding of resin.Can provide a kind of degeneration of resin further to be suppressed thus, the light-emitting device of filming and being used of UV resistant etc. for a long time.
Resin in the key absorption intensity of infrared spectra, the C-Si-O key during preferred resin is formed and the strength ratio of Si-O-Si key be 1.2/1 or more than.By be set at 1.2/1 or more than because resin remains oil plant shape or gel, rubber-like, can form that stress is relaxed, crackle or defective are difficult to produce films.
The present invention relates to a kind of manufacture method of light-emitting device, it has: luminous element is carried on first operation on the matrix; With second operation of this luminous element with the mineral binder bond covering; With the 3rd operation that this mineral binder bond covers with resin, wherein the 3rd operation is used the means of pouring resin or resin is sprayed the spraying means and covers mineral binder bond.Means by using the pouring resin or resin sprayed the spraying means, the space that can the landfill mineral binder bond be had.In addition, among the gas intrusion resin that can prevent to exist in this space.Moreover, can stablize and coating covers binding agent equably resin.Especially, the gel of hydrous oxides such as Al that the state of oxidation is stable by use variation that valence mumber can not take place in the sol gel reaction process and Y element can be sought the raising that light takes out efficient.
The 3rd operation also can be flooded in a vacuum.Thus, resin can easily be impregnated in the space in the inorganic bond layer.Though its reason it be unclear that, it is generally acknowledged to result from capillary phenomenon.Here, so-called " gel " is meant the colloidal state system that the solid that lost flowability by colloidal sol and liquid constitute.
Description of drawings
Fig. 1 represents the relation between the variation of transmittance of the carrying out of sol gel reaction and luminescent film.
Fig. 2 is the synoptic diagram of the light-emitting device of expression embodiment of the present invention 1.
Fig. 3 is the orthographic plan that schematically illustrates the light-emitting device of embodiment of the present invention 2.
Fig. 4 is the sectional view of the light-emitting device of Fig. 3.
Fig. 5 is the constructed profile of the light-emitting device of another embodiment of the present invention.
Fig. 6 has schematically illustrated the operation that forms the light-emitting device of embodiment of the present invention.
Fig. 7 has schematically illustrated the device that forms the light-emitting device of embodiment of the present invention.
Fig. 8 is the orthographic plan that schematically illustrates the light-emitting device of embodiment of the present invention 3.
Fig. 9 is that the A-A ' of light-emitting device of Fig. 8 is to sectional view.
Figure 10 is the sectional view that schematically illustrates the light-emitting device of embodiment of the present invention 4.
Figure 11 is the sectional view of manufacturing processed that schematically illustrates the light-emitting device of embodiment of the present invention 5.
Figure 12 is the sectional view of manufacturing processed that schematically illustrates the light-emitting device of embodiment of the present invention 5.
Figure 13 is the sectional view of manufacturing processed that schematically illustrates the light-emitting device of embodiment of the present invention 5.
Figure 14 is the sectional view of manufacturing processed that schematically illustrates the light-emitting device of embodiment of the present invention 5.
Figure 15 is the sectional view of manufacturing processed that schematically illustrates the light-emitting device of embodiment of the present invention 5.
Figure 16 is the sectional view of manufacturing processed that schematically illustrates the light-emitting device of embodiment of the present invention 5.
Figure 17 is the sectional view of manufacturing processed that schematically illustrates the light-emitting device of embodiment of the present invention 5.
Figure 18 is the sectional view of manufacturing processed that schematically illustrates the light-emitting device of embodiment of the present invention 5.
Figure 19 is the sectional view that schematically illustrates the light-emitting device of embodiment of the present invention 5.
Figure 20 is the orthographic plan that schematically illustrates other light-emitting device of embodiment of the present invention 5.
Figure 21 is that the B-B ' of light-emitting device of Figure 20 is to sectional view.
Figure 22 is the amplification profile of major portion of the light-emitting device of Figure 21.
Figure 23 is the chromaticity diagram of colourity of the fluor of expression embodiments of the invention 15～23.
Figure 24 is the spectrogram that excites the three-wavelength white phosphor of embodiments of the invention 23 with the LED of wavelength 365nm.
Figure 25 is the spectrogram that excites the three-wavelength white phosphor of embodiments of the invention 19 with the LED of wavelength 400nm.
Figure 26 represents the reliability test result of the fluor of embodiments of the invention.
Figure 27 represents the reliability test result of the fluor of embodiments of the invention.
Figure 28 represents the reliability test result of the fluor of embodiments of the invention.
Figure 29 represents the reliability test result of the fluor of embodiments of the invention.
Figure 30 represents the reliability test result of the fluor of embodiments of the invention.
Figure 31 is the schematic plan view of the light-emitting device of expression embodiment of the present invention 6.
Figure 32 (a) is the constructed profile of the light-emitting device of expression embodiment of the present invention, and Figure 32 (b) is the constructed profile that amplifies the matrix recess.
Figure 33 is the synoptic diagram of a part of manufacturing process of the light-emitting device of expression embodiment of the present invention.
Figure 34 is the synoptic diagram of a part of other manufacturing process of the light-emitting device of expression embodiment of the present invention.
Figure 35 is the synoptic diagram of a part of another other manufacturing process of the light-emitting device of expression embodiment of the present invention.
Figure 36 (a) is the constructed profile of matrix recess that amplifies the light-emitting device of embodiment of the present invention 7, and Figure 36 (b) is the stereographic map of expression light-emitting device.
Figure 37 (a) is the constructed profile of matrix recess that amplifies the light-emitting device of embodiment of the present invention 8, and Figure 37 (b) is the stereographic map of expression light-emitting device.
Figure 38 is the constructed profile of a part of the light-emitting device of expression embodiment of the present invention 9.
Figure 39 represents the endurance test result of the light-emitting device of embodiment.
Figure 40 represents that the light of the light-emitting device of embodiment takes out the result of efficient.
Figure 41 is the infrared spectrogram of filming of expression embodiment.
Figure 42 is the constructed profile of the light-emitting device of expression comparative example.
Figure 43 is the infrared spectrogram of filming of expression comparative example.
Figure 44 is the signal pie graph of the light-emitting device of expression embodiment of the present invention 10.
Embodiment
Be that the basis describes with regard to embodiment of the present invention below with the accompanying drawing.But, embodiment shown below only is used to make technological thought of the present invention to specialize, be the illustration of the manufacture method of the manufacture method of luminescent film, light-emitting device, luminescent film and light-emitting device, and be not to be following content with the manufacture method of the manufacture method of luminescent film of the present invention, light-emitting device, luminescent film and light-emitting device is specific.In addition, also anything but with the member shown in claims specific be the member of embodiment.And the size of each member shown in the drawings and position relation etc., become clear and definite for making explanation, exaggerate sometimes.Moreover, constitute each key element of the present invention and also can be set at same member and constitute a plurality of key elements or with the form of a plurality of key elements of member dual-purpose.
In embodiments of the invention, the gel with hydrous oxide is used as binding agent.Fig. 1 represents is carrying out along with sol gel reaction, from collosol state through containing the gel of crystal water or hydrous oxide and oxide compound to the process of amorphousness or polycrystal oxide compound, the variation that the taking-up efficient of the transmittance of luminescent film and light is taken place.As shown in Figure 1, gel is being used as under the situation of binding agent, can thinking that generally near the polycrystal structure, like that just getting in the transmitance image pattern of luminescent film shown in the A risen along with the carrying out of sol gel reaction.But, aspect employing sol gel reaction acquisition polycrystal, need considerable energy.In the process of the hydroxyl that structure contained of separating gel state and organic group, need quite high temperature, so so uneasy.
The present inventor found that through with great concentration research: in specific metallic element, even do not improve crystallinity, also can obtain high light and take out efficient under gel state, thereby achieve the present invention.Especially, the gel of hydrous oxides such as Al that the state of oxidation is stable if use variation that valence mumber can not take place in the sol gel reaction process and Y element, then shown in the B among Fig. 1 like that, the light of finding to be in gel state takes out the light that efficient has than the ongoing polycrystal state of sol gel reaction and takes out the higher tendency of efficient.For example in yttrium and so on noncrystal, it is generally acknowledged that one of them reason is caused by scattering of light.That is to say, the crystallization stage of being undertaken by heat, form polymolecular crystallisation procedure does from a to b aspect chemical structure, from the microcosmic aspect, the part of it is generally acknowledged the part of partial crystallization and being in gel state is separated and forms heterogeneous structure.Therefore, from the microcosmic aspect, be uneven between phase and phase, thereby scattering of light take place, say on the whole transmitance is reduced at the interface of phase.As another reason, be commonly considered as causing by crystalline texture.That is to say, under the state from a to b, owing to, cause that each regional density is different with specific refractory power with the crystal region that forms the basis of spherocrystal and the formation of non-crystalline areas.Even be uniformly aspect microcosmic, aspect optics, also form multimolecular structure, thereby says on the whole and make the transmitance reduction.Therefore, even without forming polycrystal,, sol gel reaction can not be continued and can take out the high luminescent film of efficient with short period of time, the low-yield light that easily obtains also by under gel state, forming luminescent film.
Moreover gel state is to contain the hydroxyl in the hydrous oxide or the state of crystal water, can infer the difference according to its content, and light takes out efficient and will change.The present inventor has carried out experiment repeatedly, found that: the content of hydroxyl or crystal water accounts for 10 weight % of hydrous oxide or when following, affirmation can obtain higher light and take out efficient.So,, can obtain fine and close film by being set at the gel state that contains crystal water, and with carried out solidified fully, realized that the film of crystallization compares, the taking-up efficient of its light is better.This generally thinks because under gel state, hydrous oxide has the crosslinking structure that comprises partial oxide, has improved the cohesiveness of fluor and element.
In addition, constitute the binding agent member, can improve the luminescent film of formation and the quality of luminescent layer by the gel that adopts hydrous oxide.Contain the binding agent member of hydrous oxide, its particle-like substance is assembled by sol-gel method, thereby becomes the porous insert that is formed with crosslinking structure, reticulated structure or polymer architecture.
If the skeleton structure of the particle assembly of hydrous oxide is the reticulated structure with hole, then because be porous structure and can improve the flexibility of luminescent film.In addition, luminescent layer is when film forming, even appendix filler members such as fluorophor particle, simultaneously coated object shapes complexity also can adapt therewith and carry out film forming, can obtain to be rich in close-burning luminescent film.Moreover, owing to be hydrous oxide, thereby can obtain stable and stay-in-grade film to light and heat.
The luminescent film that forms is because expose to the open air in coming from the light of luminous element, so produce degeneration by the use of light-emitting device.Reason that it is generally acknowledged this degeneration is: cause the generation of reacting because of any or both among the optical output power that comes from luminous element and the heating.Therefore, when the ultraviolet ray that luminous energy is high is used to generate heat and thermal impedance is big large-scale element, just be easy to generate degeneration.As the back narrate, the sample of making embodiments of the invention has carried out long duration test, results verification has high patience.Though its reason is still indeterminate, it is generally acknowledged that reason is to have selected a kind of like this structure, the hydrous oxide that promptly has constant valence mumber is difficult to take place redox reaction under the effect of heat energy and luminous energy.Therefore, preferably utilize the metallic element that valence mumber can not change in hydrous oxide.For example, can obtain under the situations as gel or cured film such as Si of different kinds of ions valence state using, can infer because of optical density(OD) with by the thermal conduction that the heating of element produces to cause the variation of valence mumber easily, thereby cause the generation of colour deterioration.In contrast, the 3 valency hydrous oxides that obtain with embodiment of the present invention are the luminescent layer of binding agent, then are difficult to take place redox reaction.Therefore, even light-emitting device of the present invention for example is 0.1W/cm in contact or near rayed density 2～1000W/cm 2The situation of semiconductor light-emitting elements of high-output power under, also can have sufficient patience.
(binding agent)
At high temperature or the ultraviolet ray excited binding agent of the fluor of use down as appendix, that adopted is silicon-dioxide (SiO 2).When continue using silica binder, be mixed with the fluorescence member of the luminous fluor of changing of luminous element and translucent material melanism slowly.The present inventor has studied such reason of colour deterioration, and the result finds out: its reason is to produce the damaged of oxygen in the silica-bonded layer and has generated SiO X(x＜2).
Silica binder is the silica dioxide gel shape, at SiO under 250 ℃ or following heat curing temperature 2Remaining a part of hydroxyl and organic group in the skeleton.Under the state of such silica dioxide gel, when by the highdensity light time of LED incident, then produce the damaged of oxygen by luminous energy or heat energy, thereby by SiO 2Generate SiO X(x＜2:x is about 1.4～1.9).It is generally acknowledged because of this SiO XBe colored and produce melanism.Like this, silica dioxide gel is commonly considered as can obtaining various valence mumbers because become the metallic element Si of main body, and Si is easy to generate the variation of valence mumber and redox takes place, thereby is producing colour deterioration.So in embodiments of the invention, use contains metallic element, and the hydrous oxide of valence mumber variation or the binding agent of oxide compound can not take place.Describe with regard to the example that utilizes aluminum oxide, yttrium oxide below.
(aluminum oxide)
Amorphous alumina or micropartical hydrated aluminum oxide are dispersed in the water, and the alumina sol that will form like this is as binding agent, in this case, before solidifying to form to hydrated aluminum oxide, experience the stage of a pseudo-boehmite structure at heated oxide aluminium colloidal sol with stable boehmite structure.The boehmite crystalline texture of hydrated aluminum oxide and the pseudo-boehmite structure of hydrated aluminum oxide can be used chemical formula AlOOH or Al respectively 2O 3H 2O and (AlOOH) xH 2O or Al 2O 32H 2O waits and represents.Specifically, get Al as intermediate 2O 32H 2O, Al 2O 3XCH 3COOHyH 2O, Al 2O 3XHClyH 2O, Al 2O 3XHNO 3YH 2Forms such as O form stable boehmite structure at last.Further improve the crystallinity of boehmite structure, then become gama-alumina (Al 2O 3) or Alpha-alumina (Al 2O 3).The alumina sol that will have such character is as binding agent, thus the formation luminescent film.
Concrete main material as luminescent film, can use the sol solution of preparation as follows, be stablizer promptly, amorphous metal oxide compound, ultramicron hydrous metal oxides and oxide ultrafine particle thing etc. are dispersed in water or the organic solvent with a spot of mineral acid, organic acid and alkali.As the initial feed of synthetic amorphous metal oxide compound, ultramicron hydrous metal oxides and oxide ultrafine particle thing etc., utilizable have: the hydrolysate of metal alkoxides, two diketo metal (metal diketonate), metal halide or metal carboxylate, metal alkyl compound and their are mixed after the product that is hydrolyzed.In addition, also can use metal hydroxides, metal chloride, metal nitrate and metal oxide microparticle are dispersed in colloid (colloidal sol) solution prepared in the mixed solvent of water and organic solvent or water and water-miscible organic solvent.They are generically and collectively referred to as aikyiaiurnirsoxan beta.Have in the skeleton of aikyiaiurnirsoxan beta [AlO] XRepeating unit.
As metal alkoxides, utilizable have: aluminum methoxide, aluminum ethoxide, positive propoxy aluminium, aluminum isopropoxide, n-butoxy aluminium, aluminium-sec-butylate, aluminum isopropoxide, tert.-butoxy aluminium, methoxyl group yttrium, oxyethyl group yttrium, positive propoxy yttrium, isopropoxy yttrium, n-butoxy yttrium, sec-butoxy yttrium, isopropoxy yttrium, tert.-butoxy yttrium etc.
As two diketo metals, utilizable have: aluminium tris(ethylacetoacetate), alkyl etheric acid diisopropoxy aluminium, ethyl acetoacetic acid diisopropoxy aluminium, the two ethyl acetoacetic acid aluminium of monoacylphosphine pyruvic acid, triacetyl pyruvic acid aluminium, triacetyl pyruvic acid yttrium and triethyl etheric acid yttrium etc.
As metal carboxylate, utilizable have: Burow Solution, propionic acid aluminium, 2 ethyl hexanoic acid aluminium, acetic acid yttrium, propionic acid yttrium and 2 ethyl hexanoic acid yttrium etc.
In addition, as metal halide, utilizable have: aluminum chloride, aluminum bromide, aluminum iodide, Yttrium trichloride, yttrium bromide and yttrium iodide etc.
As organic solvent, utilizable have: methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, sec-butyl alcohol, the trimethyl carbinol, tetrahydrofuran (THF), diox, acetone, ethylene glycol, methylethylketone, N, dinethylformamide and N,N-dimethylacetamide etc.
Used in addition to these as the binding agent that forms luminescent layer, also can be mixed fluor and diffusion particle as filler.Moreover, as their complex body, the linear expansivity of matrix and luminous element is consistent.As filler, sneak into fluor and produce luminously from needless to say, also produce the fine path of moisture evaporation when solidifying etc. simultaneously, have the curing exsiccant effect of accelerating binding agent.In addition, also have the cohesive strength of luminescent layer and the effect of physical strength are come, increased in the luminous diffusion of fluor.In addition, luminescent layer and luminescent film also can be used as the diffusion layer that does not contain fluor and are used.In addition, in the matrix material that is used as binding agent, except that 3 valency metallic elements, also can contain element on a small quantity with multiple valence mumber.Moreover the binding agent member can comprise hydrous oxide as main compound, also can play a role even comprise a part of metal oxide and metal hydroxides and their combination.
(filler)
Filler is exactly a weighting agent, and utilizable have: barium titanate, titanium oxide, aluminum oxide (aluminium sesquioxide), yttrium oxide (yttrium oxide), silicon-dioxide, lime carbonate and other hydrous oxide etc.For example, also can have with respect to comprising the colourless hydrous oxide that is selected from one or more elements among Al, Ga, Ti, Gc, P, B, Zr, Y or the alkaline-earth metal at least or comprising the oxide compound that is selected from one or more elements among Si, Al, Ga, Ti, Ge, P, B, Zr, Y or the alkaline-earth metal at least and have the more filler of high heat-conduction coefficient.By adding such filler, the heat extraction effect of light-emitting device is improved.As such filler, when carrying out chips welding (die bond), can list metal powders such as aluminum oxide, Ag at the above-mentioned mineral binder bond formation tack coat of employing and to led chip.
In the colloidal sol of binding agent, except that fluor and lower alcohol,, can be when solidifying form filming of densification at low temperature with the azeotropic dehydration of lower alcohol by prior mixed dispersant.In addition, also can contain Photostabilised material, tinting material and UV light absorber etc.
And then when forming luminescent film, also can add boric acid and boron oxide.Because the interpolation of boric acid and boron oxide causes the elasticity of luminescent film to reduce, so the quality of film is improved.The generation and the fine and close film of formation that for example can suppress the crackle of luminescent film.Boric acid and boron oxide preferably contain 0.5 weight %～50 weight % with respect to the binding agent member.Moreover, in luminescent film, also can add the tackifier except that boric acid and boron oxide.So, as the binding agent member, except that hydrous oxides such as aluminium, also can contain the additive that is useful on control slip viscosity.Therefore, control viscosity, raising thixotropy when film forming, complex-shaped film just can be shaped.In addition, after film forms,, and can play a role in the configuration aspects of control adhesive structure body because binding agent is a hydrous oxide, thereby can improve the ability allowable to additive.
Luminescent layer forms with slurry solution.Slurry solution is that modulation forms like this, be main component promptly with amorphous metal hydrous oxide, micropartical hydrous metal oxides and metal hydroxides, be dispersed in the water with this main component and then with amorphous metal oxide compound, micropartical metal oxide, make sol solution thus, then in this sol solution, mixing phosphor and filler.The effective solids component in effective solids component in the sol solution and the weight ratio of fluor or the sol solution and the weight ratio of fluor and filler mixture are preferably 0.05～30.For example can be in that effective solid component concentration be that to be 90g adjust in the ratio ranges that effective solid component concentration is 15% sol solution with respect to 600g, fluor is 4.5g for 15% sol solution, fluor with respect to 20g.
(yttrium oxide)
Amorphous oxidation yttrium or micropartical yttrium oxide are dispersed in the water, and the yttrium oxide colloidal sol that will form like this is as binding agent, in this case, even be heating and curing yttrium oxide colloidal sol, the main body of crystalline texture also is amorphous.Aqua oxidation yttrium and yttrium oxide can be used YOOHxH respectively 2O and Y 2O 3XH 2Chemical formulas such as O are represented.Specifically, as intermediate, through YOOHxCH 3COOHyH 2O or Y 2O 3XCH 3COOHyH 2The form of O forms the form that part contains aqua oxidation yttrium or yttrium oxide at last.Even yttrium oxide also can form stable film under such gel state.It is generally acknowledged that its reason is that composition separately has crosslinking structure, can realize stabilization.
Yttrium oxide is compared with aluminum oxide, has the character that is difficult to form crystalline texture.So, even the unbodied non-crystal structure of the crystallinity of not signing an undertaking also can be stable compound, Y keeps 3 valencys constant and the variation of valence mumber can not take place.The strong point that promptly has is to be difficult to take place redox reaction, is not having colour deterioration.
About other, then be to be made like luminescent layer with above-mentioned aluminum oxide.As above narrate, the colloidal sol that fluor is used as binding agent, also can utilize commercially available inorganic be binding agent and vitrified bond etc.In addition, in can be used as the material that binding agent is used, be not limited to the hydrous oxide that contains Al and Y element of aluminum oxide and yttrium oxide and so on, also can utilize other the IIIA family element and hydrous oxide, oxide compound and the oxyhydroxide etc. of IIIB family element.Valence mumber preferably can not take place the metallic element of selecting changes.Especially, preferably show as 3 valencys and stable metallic element.In addition, also preferably water white.For example except that Al and Y, the metallic compound of metallic elements such as comprising Gd, Lu, Sc, Ga and In can also be utilized, preferably Sc and Lu can be utilized.Perhaps also can utilize composite oxides and the composite hydrous oxide that these multiple elements are made up.Singly be not aluminium and yttrium, hydrous oxide by containing other III family element etc. also can be controlled to be desirable value with the various characteristics of rerum natura of films such as the flexibility of optical properties such as the specific refractory power of luminescent film and film, cohesiveness and so on.So, valence mumber is constant, the mineral binder bond of the hydrous oxide gel that is preferably 3 valencys by embodiment of the present invention containing of obtaining by having, and that formed luminescent layer can be designed as is stable, light takes out the good luminescent layer of efficient.In addition, owing to constitute, therefore can make time-independent, stable luminescent layer and luminescent film with inorganic materials.
Embodiment 1
Adopt Fig. 2 to describe below with regard to the light-emitting device of embodiment of the present invention 1.The light-emitting device of embodiment 1 comprises: luminous element 10, and by fluor 11a with comprise the fluorescence member 11 that the light transmissive adhesive 11b of fluor 11a constitutes.
The luminous element 10 that constitutes with the LED of bullet cut is welded on the substantial middle position of cover body (cup) and is carried by this cover body, and wherein cover body is configured in the top of pin leads (mount lead) 13a.The electrode that forms on the luminous element 10 is electrically connected with the pin leads 13a and inner lead (inner lead) 13b of lead frame (leadframe) 13 by electroconductibility lead-in wire 14.It is fluor and nitride based fluor that fluor 11a contains YAG, and at least a portion of the light that these fluor absorption luminous elements 10 send is sent the light that is different from the absorb light wavelength simultaneously.Moreover nitride based fluor can cover with covering materials such as microcapsule.The fluorescence member 11 that contains this fluor 11a in binding agent 11b is configured on the cover body of carrying luminous element 10.Like this; avoid the infringement of external stress, moisture and dust and dirt in order to protect led chip and fluor; and in order to improve the taking-up efficient of light, the lead frame 13 of configuration luminous element 10 and fluorescence member 11 is over-molded in the mold member 15, thereby forms light-emitting device.So, contain the luminescent layer of the binding agent that constitutes by hydrous oxide in formation after, also can form lens etc. with the form of resin system mold.
(luminous element)
In this manual, so-called luminous element also comprises being used to obtain by produce luminous of vacuum discharge and the luminous element that produced by thermoluminescence except that semiconductor light-emitting elements.For example, the element that produces ultraviolet ray etc. by vacuum discharge also can be used as luminous element.In embodiments of the invention, as the luminous element that is utilized, its wavelength is 550nm or following, is preferably 460nm or following, more preferably 410nm or following.What for example can be used has: sending wavelength as UV-light is that the ultraviolet leds and the wavelength of the light of 250nm～365nm is the high pressure mercury vapour lamp of 253.7nm.Especially, as the back narrate, the advantage that embodiments of the invention had is: weather resistance is good, can be suitable for the big power type luminous element of output rating.
The following describes the example of III group-III nitride based semiconductor light-emitting device as luminous element 10.Luminous element 10 for example is on sapphire substrate, stacks gradually the formed stepped construction of following layer across the GaN buffer layer, and these layers are followed successively by: the 1n type GaN layer that do not mix Si or Si concentration are low; The n type contact layer that constitutes by doping Si or the higher n type GaN of Si concentration ratio 1n type GaN layer; Do not mix or the lower 2GaN layer of Si concentration ratio n type contact layer; The luminescent layer of multiple quantum trap structure (quantum well structure of GaN blocking layer/InGaN trap layer); By the p covering that P type GaN constitutes, wherein P type GaN is made of the P type GaN of doped with Mg; The P type contact layer that constitutes by the P type GaN of doped with Mg.And by following method formation electrode.Certainly, also can use the luminous element that is different from this formation.
The p Ohmic electrode almost forms on whole of p type contact layer, forms p pad electrode (pad electrode) on this P Ohmic electrode of a part.
In addition, remove the part that the 1st GaN layer exposes n type contact layer by etch from P type contact layer, the n electrode just forms on this exposed portions serve.
In addition, the present embodiment is used the luminescent layer of multiple quantum trap structure, but the present invention is not limited thereto, for example utilize the single quantum of InGaN and multiple quantum trap structure can, also can utilize the GaN of doping Si and Zn.
In addition, the luminescent layer of luminous element 10 can change main glow peak by changing the content of In in the scope of 420nm～490nm.And emission wavelength is not limited to above-mentioned scope, can use the luminous element of emission wavelength as 360nm～550nm.Especially, when the light-emitting device with embodiment of the present invention is applicable to the ultraviolet leds light-emitting device, the absorption efficiency of conversion of exciting light can be improved, seeing through of UV-light can be reduced.
(fluor)
Fluor will be converted to the luminous of other wavelength from visible light and the UV-light that luminous element sends.For example, use the light that sends from the semiconductor light emitting layer of LED to excite to produce the luminous of other wavelength.As preferred fluor, utilizable have: oxynitriding systems such as YAG system, alkali earths silicon nitride fluor etc. are nitride based, alkali earths oxidized silicon nitride fluor.In the present embodiment, as the fluor use is the fluor that is produced the light of predetermined color by ultraviolet excitation.Specifically, utilizable fluor is exemplified below:
(1)Ca 10(PO 4) 6FCl:Sb，Mn
(2) M 5(PO 4) 3Cl:Eu (wherein: M is selected from least a among Sr, Ca, Ba and the Mg)
(3)BaMg 2Al 16O 27:Eu
(4)BaMg 2Al 16O 27:Eu，Mn
(5)3.5MgO·0.5MgF 2·GeO 2：Mn
(6)Y 2O 2S:Eu
(7)Mg 6As 2O 11:Mn
(8)Sr 4Al 14O 25:Eu
(9)(Zr、Cd)S:Cu
(10)SrAl 2O 4:Eu
(11)Ca 10(PO 4) 6ClBr:Mn，Eu
(12)Zn 2GeO 4:Mn
(13)Gd 2O 2S:Eu
(14)La 2O 2S:Eu
(15)Ca 2Si 5N 8:Eu
(16)Sr 2Si 5N 8:Eu
(17)SrSi 2O 2N 2:Eu
(18)BaSi 2O 2N 2:Eu
In addition, except that above-mentioned fluor, undoubtedly, also can utilize produce yellow area luminous, with (Y, Gd) 3(Al, Ga) 5O 12: the rare earth class aluminate of expressions such as Ce is that YAG is a fluor.
When the light that sends when led chip becomes complementary color relation etc. with the light that fluor sends, by will light colour mixture separately just sending the light of white.Specifically, can list light that led chip sends and by this optical excitation the light of luminous fluor is equivalent to the situation of 3 primary colors (red colour system, green system, blue system) and blue light that led chip sends respectively and the sodium yellow of luminous fluor by this optical excitation.Particularly using under the situation of UV-light, because can utilize glow color by the luminous fluor of ultraviolet excitation separately, thereby the light-emitting device of various middle shade such as the blue-greenish colour used of picked up signal, yellowish red color, redness etc. and light color also is possible.
By inorganic bond members such as the various resins that play a role as the binding agent between fluor and the fluor and glass, the ratio with filler etc., the settling time of fluor, the shape of fluor etc. being carried out various adjustment and the emission wavelength of led chip is selected, the glow color of light-emitting device can provide the tone of white color system arbitrarily such as bulb color (electric bulb color).In the outside of light-emitting device, the light that preferred led chip sends and and the light that sends of fluor see through mold member effectively.
As representational fluor, can list with copper activatory Cadmium Sulfide zinc and be fluor with cerium activatory YAG.Especially in high briliancy and when using for a long time, (Re preferably 1-xSm X) 3(Al 1-yGa y) 5O 12: (0≤x＜1,0≤y≤1, wherein: Re is at least a element that is selected among Y, Gd, La and the Lu to Ce.
(Re 1-xSm X) 3(Al 1-yGa y) 5O 12: the Ce fluor is because be garnet structure, so heat, light and moisture are had very strong patience, the excitation spectrum peak can reach about 470nm.In addition, also may have wide luminous spectrum, its glow peak is near 530nm, and the end at peak extends to the 720nm place.
In the light-emitting device of embodiment of the present invention, fluor also can be that two or more fluor mix.Promptly can be with the different (Re of content of two or more Al, Ga, Y, La, Lu and Gd and Sm 1-xSm X) 3(Al 1-yGa y) 5O 12: the Ce fluor mixes, thereby increases the wavelength components of RGB.In addition, use nitride phosphor with Huang～emitting red light etc. to increase red composition, also can obtain on average to drill the LED of high illumination of look evaluation number or bulb color etc.Specifically, the emission wavelength of the luminous element that is mixed, the content of the fluor that the chroma point on the adjustment XYZ chromaticity diagram is different can send the light of arbitrfary point on the chromaticity diagram by this, and wherein chromaticity diagram will couple together between this fluor with luminous element.
Fluor can be dispersed in gas phase and the liquid phase also luminous equably like this.The fluor that is dispersed in gas phase and the liquid phase descends because of self weight.In liquid phase, leave standstill especially, can form film with the higher fluor of homogeneity by making suspension liquid.Carry out repeatedly repeatedly as requested, can form the desired fluorescence scale of construction thus.
On the surface of light-emitting device, can there be two kinds or more kinds of in the fluor that forms as above in the luminescent layer that is made of one deck, also can in the luminescent layer that constitutes by two layers, exist respectively a kind of, two kinds or more kinds of.So, the colour mixture of the light by coming from different fluor can obtain white light.At this moment, in order to make light that each fluor sends colour mixture and reduce irregular colour better, preferably each fluor has similar median size and shape.In addition, can consider that also the settling character that influenced by shape forms luminescent layer.Formation method as the luminescent layer of not allowing to be subject to the settling character influence can list spraying method, silk screen print method and pouring method etc.In the present embodiment, mineral binder bond can have effective solids component of 1%～80%, and the viscosity adjustment can be in the wide region of 1cps～5000cps, carried out, and thixotropy can be adjusted, so, can adapt with the formation method of these luminescent layers.As mentioned above, the weight ratio of filler and mineral binder bond is preferably set to 0.05～30 scope, in addition, strengthens cohesive force by use level and the particle diameter of adjusting filler.
The fluor that uses in the present embodiment can be fluor with YAG also, may send nitride phosphors such as the fluor of red colour system light, particularly alkali earths silicon nitride fluor combines and is used.These YAG are that fluor and fluor can mix and be included in the luminescent layer, also can be included in respectively in the luminescent layer that is made of multilayer.Below just separately fluor be described in detail.
(YAG is a fluor)
The YAG that so-called the present embodiment is used is that fluor is with rare earth element activatory fluor such as cerium or Pr, it contains Y and A l, and contain be selected from least a element among Lu, Sc, La, Gd, Tb, Eu and the Sm and be selected from Ga and In among a kind of element, be to be subjected to visible light that led chip sends or ultraviolet ray excited and luminous fluor.Especially in the present embodiment, also can utilize with cerium or Pr activatory, to form two or more different yttrium aluminum oxides be fluor.If the blueness that will use nitride-based compound semiconductor to send as the luminous element of luminescent layer is a light and by because of absorbing that blue light body colour (body color) is green system that the xanchromatic fluor sends and red colour system light or being light for yellow but more approachingly greenly being and more coming out near the light mixed display of red colour system, then can demonstrate desired white color system illuminant colour.Light-emitting device is because produce colour mixture, so also can contain the powder and the piece of fluor in the light transmission inorganics of mineral binder bond of various resins such as Resins, epoxy, acrylic resin or silicone resin and the present embodiment and so on.Like this, the luminescent layer that contains fluor can be point-like or is purposes such as stratiform and uses in every way according to fluor, and wherein luminescent layer forms thinlyyer, and the light that is enough to led chip is sent is seen through.By tone arbitrarily such as the bulb color of the ratio of fluor and light transmission inorganics and coating, loading level being carried out various adjustment and the emission wavelength of luminous element is selected, can provide comprising white.
In addition, with respect to the incident light that comes from luminous element, dispose two or more fluor separately in order, can obtain thus can effectively luminous light-emitting device.That is to say, have on the luminous element of reflecting member, dispose in mode such as stacked and to contain the color conversion member that absorbing wavelength is arranged and can send the fluor of long wavelength light at long wavelength side and promptly contain fluor as the luminescent layer of filler and compare to this luminescent layer and absorbing wavelength is arranged and can send the more color conversion member of long wavelength's light, can effectively utilize reflected light by this in longer wavelength side.
If using YAG is fluor, be 0.1Wcm even dispose radiant light density with contact or close mode so -2～1000Wcm -2Led chip, also can obtain high-level efficiency and have abundant sunproof light-emitting device.
What the present embodiment was used is that promptly can to send green be that the YAG of light is a fluor because of being garnet structure to fluor with cerium activatory yttrium aluminum oxide, so heat, light and moisture are had very strong patience, excite the wavelength at absorption spectrum peak can be near 420nm～470nm.In addition, have wide luminous spectrum, its glow peak peak wavelength λ p is near 510nm, and the end at peak extends near the 700nm.On the other hand, with cerium activatory yttrium aluminum oxide is that the YAG that fluor promptly can send red colour system light is that fluor is also because be garnet structure, so heat, light and moisture are had very strong patience, excite the wavelength at absorption spectrum peak can be near 420nm～470nm.In addition, have wide luminous spectrum, its glow peak peak wavelength λ p is near 600nm, and the end at peak extends near the 750nm.
In the YAG with garnet structure was the composition of fluor, the part with Ga displacement Al made luminous spectrum move to short wavelength side thus, and with the part that Gd and/or La replace the Y in forming, luminous spectrum is moved to long wavelength side.So, form, can regulate glow color continuously by changing.Therefore, nitride-based semiconductor can recently continuously change the intensity of long wavelength side with the composition of Gd, and the blueness of utilizing such nitride-based semiconductor is the luminous luminous ideal conditions of the white color system of converting to that has.When 2 one-tenth of the displacement less thaies of Y, green composition increases and red composition reduces, and is 8 one-tenths or when above, though red composition increase briliancy sharply descends.In addition, about exciting absorption spectrum too, in the YAG with garnet structure is the composition of fluor, part with Ga displacement Al, make thus and excite absorption spectrum to move to short wavelength side, and with the part that Gd and/or La replace the Y in forming, make thus to excite absorption spectrum to move to long wavelength side.YAG is that the peak wavelength that excites absorption spectrum of fluor is preferably compared with the peak wavelength of the luminous spectrum of luminous element and is positioned at short wavelength side.If such formation, then when the electric current of supplying with luminous element increases, excite absorption spectrum peak wavelength because with the peak wavelength basically identical of the luminous spectrum of luminous element, the launching efficiency of fluor can not reduce, the light-emitting device that is suppressed of chroma offset so can form.
Such fluor as raw material, just obtains raw material with them by the stoichiometric ratio thorough mixing with the oxide compound of Y, Gd, Ce, La, Lu, Al, Sm and Ga or the compound that at high temperature becomes oxide compound easily.Perhaps be dissolved in the acid by the rare earth element of stoichiometric ratio with Y, Gd, Ce, La, Lu, Al, Sm, make the lysate that obtains like this produce codeposition with oxalic acid then, again the codeposition product that obtains is like this carried out sintering and just obtain the codeposition oxide compound, then this codeposition oxide compound is mixed just obtaining mixing raw material with aluminum oxide, gallium oxide.An amount of fluorochemical such as Neutral ammonium fluoride that adds is packed into as fusing assistant and with it in crucible in this mixing raw material, then in air in 1350 ℃～1450 ℃ temperature range sintering 2 hours～5 hours, thereby obtain sinter, then in water, sinter is carried out ball milling, clean then, separate, drying, sieve at last, just can obtain fluor thus.In addition, the manufacture method of the fluor of other embodiment preferably divides two stages to carry out sintering, these two stages are made of first sintering circuit and second sintering circuit, wherein first sintering circuit will constitute mixture by mixing raw material that has mixed phosphor raw material and fusing assistant and carry out sintering in atmosphere or in the weakly reducing atmosphere, and second sintering circuit is carried out sintering in reducing atmosphere.At this, so-called weakly reducing atmosphere refers to and is being formed by mixing raw material in the reaction process of desired fluor, what set contains the more weak reducing atmosphere that is necessary the oxygen amount at least, in this weakly reducing atmosphere, carrying out first sintering circuit is accomplished until the structure formation of desired fluor, can prevent the black change of fluor thus, and prevent the decline of efficiency of light absorption.In addition, the reducing atmosphere of so-called second sintering circuit refers to the reducing atmosphere stronger than weakly reducing atmosphere.If divide two stages to carry out sintering like this, then can obtain the high fluor of assimilated efficiency of excitation wavelength.Therefore, adopting the fluor that forms like this to form under the situation of light-emitting device, can reduce necessary fluor consumption, can form light and take out the high light-emitting device of efficient for obtaining desired tone.
Forming different two or more is fluor with cerium activatory yttrium aluminum oxide, can mix use, also can be configured independently of one another.Under the situation that disposes fluor independently of one another, preferably be configured by following order, be configured in shortwave wavelength side earlier and absorb light and the luminous fluor that comes from luminous element easily, be configured in relative long wavelength side again and absorb light and the luminous fluor that comes from luminous element easily.Thus, fluor can absorb light that luminous element sends and luminous effectively.
(nitride phosphor)
The fluor that uses as the present embodiment, except above-mentioned be the fluor with cerium activatory yttrium aluminum oxide, also suitable have Huang Hong～emitting red light wavelength with Eu or the nitride based fluor of rare earth class activatory alkali earths.This fluor is by absorbing the visible light that sent by led chip and ultraviolet ray and being the light that sends of fluor and stimulated luminescence by YAG.The fluor of embodiment of the present invention is particularly: Sr-Ca-Si-N:R, Ca-Si-N:R, Sr-Si-N:R, Sr-Ca-Si-O-N:R, Ca-Si-O-N:R and Sr-Si-O-N:R are silicon nitride.The basic comprising element of these fluor can be used general formula L XSi YN (2/3X+4/3Y): R or L XSi YO ZN (2/3X+4/3Y-2/3Z): R (L is arbitrary group among Sr, Ca and Sr and the Ca) represents.In general formula, X and Y be X=2, Y=5 or X=1, Y=7 preferably, but also can be numerical value arbitrarily.In addition, R is the rare earth element that must contain Eu, and N is a nitrogen, and O is an oxygen.Specifically, preferably use the basic comprising element can use (Sr XCa 1-X) 2Si 5N 8: Eu, Sr 2Si 5N 8: Eu, Ca 2Si 5N 8: Eu, Sr XCa 1-XSi 7N 10: Eu, SrSi 7N 10: Eu, CaSi 7N 10: the fluor that Eu represents, but in the composition of this fluor, also can contain at least a kind of being selected among Mg, B, Al, Cu, Mn, Cr and the Ni or multiple.But the present invention is not limited to this embodiment and embodiment.
L is arbitrary group among Sr, Ca and Sr and the Ca.Sr and Ca can change proportioning as requested.
Luminescence center mainly uses the europium Eu as rare earth element.Europium mainly has the energy level of divalent and 3 valencys.The fluor of embodiment of the present invention is a silicon nitride for the alkaline-earth metal as parent, with Eu 2+As activator.In addition, also can be with Mn as additive.
Fluor ((Sr with regard to using in embodiment of the present invention below XCa 1-X) 2Si 5N 8: manufacture method Eu) describes, but the present invention is not limited to this manufacture method.In above-mentioned fluor, contain Mn and O.
To pulverize as Sr, the Ca of raw material.Sr, Ca as raw material preferably use simple substance, but also can use compounds such as imide compound, amide compound.By Sr, the Ca that pulverizing obtains, preferred median size is about 0.1 μ m～15 μ m, but the present invention is not limited to this scope.The purity of Sr, Ca be preferably 2N or more than, but the present invention is not limited thereto.
To pulverize as the Si of raw material.Si as raw material preferably uses simple substance, but also can use nitride, imide compound, amide compound etc.The purity of raw material Si be preferably 3N or more than.Si also pulverizes, and the median size of preferred Si compound is about 0.1 μ m～15 μ m.
Then in nitrogen atmosphere, will carry out nitrogenize as Sr, the Ca of raw material.This reaction formula is respectively shown in chemical formula 3 and 4.
3Sr+N 2→ Sr 3N 2Chemical formula 3
3Ca+N 2→ Ca 3N 2Chemical formula 4
In nitrogen atmosphere, under 600 ℃～900 ℃ temperature, with about 5 hours of Sr, Ca nitrogenize.The nitride of Sr, Ca preferably has high purity, also can use commercially available Sr, Ca nitride.
In nitrogen atmosphere, will carry out nitrogenize as the Si of raw material.This reaction formula is shown in chemical formula 5.
3Si+2N 2→ Si 3N 4Chemical formula 5
In nitrogen atmosphere, under 800 ℃～1200 ℃ temperature, also about 5 hours of nitrogenize of silicon Si.Silicon nitride preferably has high purity, also can use commercially available silicon nitride.
The nitride of Sr, Ca or Sr-Ca is pulverized.Equally, the nitride of Si is pulverized.In addition, also same compd E u with Eu 2O 3Pulverize.As the compound of Eu, employed is europium sesquioxide, but metal europium, nitrogenize europium etc. also can use.In addition, as the Eu of raw material, also can use imide compound and amide compound.Europium sesquioxide preferably has high purity, also can use commercially available europium sesquioxide.The median size of the nitride of the alkaline-earth metal after the pulverizing, silicon nitride and europium sesquioxide is preferably about 0.1 μ m～15 μ m.
In above-mentioned raw materials, also can contain at least a kind of being selected among Mg, B, Al, Cu, Mn, Cr, O and the Ni or multiple.In addition, also can be in following mixed processes, regulate the proportioning of above-mentioned elements such as Mg, Mn, B and mix.
After above-mentioned pulverizing finishes, with the nitride of Sr, Ca, Sr-Ca, the compd E u of the nitride of Si and Eu 2O 3Mix, and add Mn and mix.
At last in ammonia atmosphere, with the nitride of Sr, Ca, Sr-Ca, the nitride of Si and the compd E u of Eu 2O 3Mixture carry out sintering.By sintering, can obtain having added Mn with (Sr XCa 1-X) 2Si 5N 8: the fluor that Eu represents.The reaction formula of the basic comprising element that obtains by this sintering is shown in following chemical formula 6.
Figure C200480006816D00371
Figure C200480006816D00372
Chemical formula 6
Wherein, by changing each proportion of raw materials, can change the composition of target fluor.
About sintering temperature, can in 1200 ℃～1700 ℃ scope, carry out sintering, but preferably 1400 ℃～1700 ℃ sintering temperature.The raw material of fluor preferably uses the crucible of boron nitride (BN) material, boat to carry out sintering.Except that the crucible of boron nitride material, also can use aluminum oxide (Al 2O 3) crucible of material.
By using above manufacture method, can obtain the target fluor.
In an embodiment of the present invention,, use nitride based fluor especially, and in the present embodiment, also can obtain to have above-mentioned YAG is fluor and the light-emitting device that may send the fluor of red colour system light as sending the fluor of light redly.The fluor that may send red colour system light like this is to be the optical excitation of 250nm～600nm and luminous fluor for example can list Y by wavelength 2O 2S:Eu, La 2O 2S:Eu, CaS:Eu, SrS:Eu, ZnS:Mn, ZnCdS:Ag, Al and ZnCdS:Cu, Al etc.Like this, may be the fluor that fluor sends red colour system light with YAG by using, can improve the color rendering of light-emitting device.
In the light-emitting device of each embodiment of the present invention, fluor can use various fluor.What for example, can list has: produce blue region luminous, with BaMgAl 10O 17: that Eu represents, be fluor with europium activatory barium magnesium aluminate, produce blue region luminous, with (Ca, Sr, Ba) 5(PO 4) 3That Cl:Eu represents, with europium activatory halogen series of calcium phosphate fluor, produce blue region luminous, with (Ca, Sr, Ba) 2B 5O 9That Cl:Eu represents, be fluor with europium activatory alkali earths chloroboric acid salt, produce the blue-greenish colour zone luminous, with (Sr, Ca, Ba) Al 2O 4: Eu or (Sr, Ca, Ba) 4Al 14O 25: that Eu represents, be fluor with europium activatory alkaline earth aluminate, produce green area luminous, with (Mg, Ca, Sr, Ba) Si 2O 2N 2: that Eu represents, be fluor with europium activatory alkali earths silicon-oxygen nitride, produce green area luminous, with (Ba, Ca, Sr) 2SiO 4: that Eu represents, be fluor with europium activatory alkali earths Magnesium Silicate q-agent, produce yellow area luminous, with (Y, Gd) 3(Al, Ga) 5O 12: the rare earth class aluminate that Ce represents be YAG be fluor and produce red area luminous, with (Y, La, Gd, Lu) 2O 2That S:Eu represents, be fluor etc. with europium activatory rare earth class oxysulfide, but the present invention is not limited to these, aforesaid fluor and other fluor also can use in the luminescent layer of embodiment of the present invention.Moreover, also can use fluor with surface of fracture, wherein on surface of fracture, taked to prevent the countermeasure of coating degradation.
Above-mentioned fluor for example is fluor, is fluor, is that fluor, YAG are fluor and are that fluor etc. preferably contains B with europium activatory alkali earths silicon nitride with europium activatory alkali earths silicon-oxygen nitride with europium activatory alkaline earth aluminate with europium activatory alkali earths chloroboric acid salt, thereby make crystallinity become good, increase particle diameter, or adjust crystal form.Can seek the raising of glorious degrees thus.These fluor also are effective as the filler of the fluor of the present embodiment.
About crystalline texture, Ca for example 2Si 5N 8Be oblique crystal, Sr 2Si 5N 8, (Sr 0.5Ca 0.5) 2Sr 5N 8Be iris, Ba 2Si 5N 8Get oblique crystal.
Moreover, this fluor to be crystallization account in it is formed 60% or above, be preferably 80% or above crystalloid.In general, preferred X=2, Y=5 or X=1, Y=7, but also can be numerical value arbitrarily.
In micro-additive, B etc. do not reduce the characteristics of luminescence and can improve crystallinity, and Mn, Cu etc. also show same effect.In addition, La, Pr etc. also have the effect of improving the characteristics of luminescence.In addition, Mg, Al, Cr, Ni etc. have the effect that shortens twilight sunset, can suit to use.In addition, even the element that this specification sheets is not expressed, as long as about 10～1000ppm, not obvious reduction briliancy just can be added.
The rare earth element that contains among the R preferably include among Y, La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Er, the Lu a kind or more than, but also can comprise Sc, Sm, Tm and Yb.In addition, except that above-mentioned element, can also contain the element that B, Mn etc. have the effect of improving briliancy.These rare earth elements also are blended in the raw material with states such as oxide compound, imide, acid amides except that simple substance.Rare earth element mainly has the electronics of 3 stable valencys to be arranged, but Yb, Sm etc. also have the electronics arrangement that divalent, Ce, Pr, Tb etc. also have 4 valencys.Under the situation of the rare earth element that uses oxide compound, the participation of oxygen exerts an influence to the characteristics of luminescence of fluor.That is to say,, the reduction of briliancy takes place also sometimes owing to contain aerobic.But, under the situation of using Mn, because the effect as fusing assistant that Mn and O produce is increased particle diameter, thereby can seek the raising of glorious degrees.
As luminescence center, be suitable for using europium Eu as rare earth element.Specifically list the example of basic comprising element, then have: the Ca that has added Mn, B 2Si 5O 0.1N 7.9: Eu, Sr 2Si 5O 0.1N 7.9: Eu, (Ca XSr 1-X) 2Si 5O 0.1N 7.9: Eu, CaSi 7O 0.5N 9.5: Eu and then added the Ca of rare earth element 2Si 5O 0.1N 7.9: Eu, Sr 2Si 5O 0.5N 7.7: Eu, (Ca XSr 1-X) 2Si 5O 0.1N 7.9: Eu etc.
Above Shuo Ming nitride based fluor absorbs the part of the blue light that is sent by luminous element and sends light from the yellow to the red area.With the light-emitting device that this fluor is used to have above-mentioned formation, just can provide the red light of a kind of blue light that sends by luminous element and fluor to send the light-emitting device of the white light of warm colour system by colour mixture.In white light emitting device, preferably contain nitride based fluor and rare earth class chlorate MClO 3 fluorescent substance and promptly use cerium activatory yttrium aluminum oxide fluor especially.This be because: by containing above-mentioned yttrium aluminum oxide fluor, can regulate desired colourity.With cerium activatory yttrium aluminum oxide fluor, can absorb the part of the blue light that sends by luminous element and send the light of yellow area.Here, the blue light that sends by luminous element and and the color development light of yttrium aluminum oxide fluor can send the white light of pearl opal by colour mixture.Therefore, fluor that this yttrium aluminum oxide fluor and described nitride phosphor and binding agent is mixed together by combination and the blue light that is sent by luminous element can provide the light-emitting device of the white light that a kind of warm colour is.The light-emitting device of the white light of this warm colour system, it on average drills look evaluation number Ra can reach 75～95, and colour temperature can be sent out and be decided to be 2000K～8000K.Particularly preferably be the white luminous device on the track of on average drilling the blackbody radiation that look evaluation number Ra is higher, colour temperature is positioned at chromaticity diagram.But, for the light-emitting device that has desired colour temperature and on average drill the look evaluation number is provided, also can appropriate change yttrium aluminum oxide fluor and the use level of fluor and the ratio of components of each fluor.The light-emitting device of the white light of this warm colour system is sought the special improvement of drilling look evaluation number R9 especially.In the past by blue light emitting device and the light-emitting device that sends white light that combines with cerium activatory yttrium aluminum oxide fluor, its special look evaluation number R9 that drills is low, red composition deficiency.Therefore, improve the special look evaluation number R9 that drills and just become to need the problem of solution, and in cerium activatory yttrium aluminum oxide fluor, contain useful Eu activatory alkali earths silicon nitride series fluor, the special look evaluation number R9 that drills can be brought up to 40～90 by this.In addition, can also make the LED light-emitting device that sends the bulb color.
(light-emitting device)
Luminous element (led chip) 10 is carried by this cover body well by the substantial middle position that is welded on cover body, and wherein cover body is configured in the top of pin leads 13a.Lead frame 13 for example is made of copper-iron alloy (copper-iron alloys).The electrode that forms on the luminous element 10 is electrically connected with lead frame by electroconductibility lead-in wire 14.Electroconductibility lead-in wire 14 usefulness gold constitutes, and on 14 flanges that are electrically connected (bump) that are used for electrode and electroconductibility gone between suitably plating Ni coating.
The fluorescence member 11 that the above-mentioned fluor 11a of thorough mixing and binding agent 11b is become slip injects the cover body that is carrying luminous element 10.Then, heating contains the gel of fluor 11a and makes it to solidify.The thermofixation of slip is preferably 50 ℃～500 ℃.The heat curing temperature of Al and Y is about 100 ℃～500 ℃.Here, in 150 ℃ or followingly carry out thermofixation.Can irradiation ultraviolet radiation in the thermofixation of gel.For example can utilize mercuryvapour lamp, VUV etc., and can be also with a plurality of light sources and thermal source.By the high light of irradiation, can cut off the bonding of organic group such as carboxylic acid effectively, thereby can make curing reaction realize stabilization as VUV.When shining the fluorescence member of slip shape, make O with VUV 2And N 2Mixed gas flow through, under the irradiation of VUV, make the reaction of a part of oxygen and isolated hydroxyl and organic group and become CO 2And H 2O, this also can promote removing of these hydroxyls, organic group etc.In the present embodiment, by combination 254nm or above vacuum ultraviolet ray irradiation and heating, form the stage at film solidified film, binding agent and fluor, the sticking power at filler interface, the sticking power on luminous elements such as LED become well, can form the few film of micropore.Like this, on led chip, form the fluorescence member 11 that constitutes by the binding agent that comprises fluor and led chip is fixed.After this, avoid the infringement of external stress, moisture and dust and dirt in order to protect led chip and fluor, further the form with mold member 15 suitably forms light transmission Resins, epoxy.The lead frame 13 that will be formed with the color conversion member inserts in bullet cuts framed, sneaks into light transmission Resins, epoxy and is cured.
In addition, fluorescence member 11 can directly contact and cover with led chip on the led chip, also can make translucent resin etc. mediate and be provided with.Much less, the high translucent resin of preferred use photostabilization this moment.
The fluor of embodiment of the present invention even expose to the open air when at high temperature making light-emitting device generation soft heat, also can delay the rapid decline of luminous efficiency.Particularly contact or luminous element close, thermal capacitance easily passes to fluor by lead-in wire with the fluorescence member for lead-in wire, the fluor of embodiment of the present invention also is useful.
Embodiment 2
Secondly, as an example of the light-emitting device of embodiment of the present invention 2, Fig. 3 and Fig. 4 are respectively schematic plan view and constructed profile, all are illustrated in the state of installing on the metal shell as the LED of luminous element.
Housing 105 is made of metal, and portion has recess a in the central.In addition, be that basis pontis b has 2 communicating poress that connect thickness direction around described recess, communicating pores clamping separately described recess a and is provided with in opposite directions.Positive and negative lead-in wire electrode 102 is inserted in respectively in this communicating pores across the hard glass as insulating component 103.In addition, the lead-in wire 106 that has light transmission window portion 107 and constitute in the interarea side of metal shell 105 by metal part, by the contact surface of welding metal portion and metal shell 105, luminous element etc. with nitrogen just by airtight in housing.The led chip 101 that is housed in the recess a is to send blue light or ultraviolet luminous element, led chip 101 is undertaken by tack coat 110 with the bonding of metal shell 105, and wherein tack coat 110 carries out the hydrating solution of tetraethyl silicate dry and sintering obtains.
Moreover, as shown in Figure 4, with lead-in wire electrode 102 insulating recess a in, formed on luminous element that (chemical formula is Ca with CCA-Blue by AlOOH 10(PO 4) 6ClBr, activated material are Mn, Eu) luminescent layer 109 that fluor bonding forms, having formed by AlOOH, YOOH etc. again on luminescent layer 109 is the luminescent layer 108 that the fluor bonding forms with YAG.Be described in detail the member of formation of embodiment of the present invention with reference to the accompanying drawings.
(luminescent layer 108,109)
Except that mold member, luminescent layer is arranged in the cover body of pin leads and place such as in the peristome of housing, is to contain to the luminous fluor of changing of led chip 101 and to fluor to carry out the agglutinating material layer.In addition, as shown in Figure 5, the luminescent layer of embodiment of the present invention, the thickness of the luminescent layer 109A that it is provided with on led chip 101, on side and the bight and the thickness of the luminescent layer 108A that is provided with on the support beyond the led chip 101 are about equally.In addition, even luminescent layer is not interrupted in the part in the bight of led chip 101 yet, luminescent layer is a successive.
Because the reflection that housing etc. produces, the high energy light that sends from led chip etc. becomes high-density luminescent layer.Moreover, also producing diffuse-reflectance by fluor, luminescent layer exposes to the open air sometimes in highdensity high energy light.Therefore, when with luminous strong, the nitride semiconductor that can send high energy light during, preferably will there be any hydrous oxide of metallic element sunproof, that contain among Al, Y, Gd, Lu, Sc, Ga, In, the B to be used to these high energy lights as caking agent or binding agent as led chip.
As one of concrete main material of luminescent layer, what be fit to use has at Al (OH) 3, Y (OH) 3Etc. the material that contains fluor in the light transmission inorganic structures.Fluor bonds by means of the light transmission inorganic structures each other, and fluor on led chip and support, be piled into stratiform and with it the bonding.In the present embodiment, hydrous oxide is formed by the compound based on following hydrous oxide, and the hydrous oxide that wherein becomes main body is formed by any the organometallic compound among Al, Y, Gd, Lu, Sc, Ga, In, the B.At this, so-called organometallic compound comprises by the alkyl of Sauerstoffatom and metal link and aryl.As such organometallic compound, for example can list the complex compound of metal alkylide, metal alkoxides, two diketo metal, two diketo metals and metal carboxylate etc.In such organometallic compound, if the organometallic compound that special use is in a liquid state at normal temperatures, then by adding organic solvent, can be easily from technological angular adjustment viscosity and prevent the coagulative generation of organometallic compound etc., thereby manufacturability is improved.In addition, chemical reaction such as hydrolysis is because take place easily in such organometallic compound, so disperse everywhere easily, can form and makes fluor be able to the agglutinating luminescent layer.Therefore, the method of using organometallic compound is with under 350 ℃ or above temperature or to apply under the electrostatic state on LED other method of formation luminescent layer different, can not reduce as the performance of LED luminous element and can easily on led chip, form luminescent layer, thereby the production qualification rate is improved.
In addition, constitute, also can contain some organism based on carboxylic acid though luminescent layer is main body with the inorganics.Organic content is preferably set to 1 weight % or following.In addition, luminescent layer preferably has 50% or above light transmission at least in the wavelength region may of 250nm～800nm.
As the concrete main material that contains in the luminescent layer, be that example describes below with AlOOH.
(luminescent layer 109 that fluor bonding is formed by AlOOH)
By AlOOH the luminescent layer that the fluor bonding forms is formed by the following method, promptly in organic solvent, make alkyl aluminium alcoholates or aluminum alkoxide hydrolysis with predetermined ratio, in the aikyiaiurnirsoxan beta colloidal sol or alumina sol solution that hydrolysis obtains, make fluor (powder) homodisperse and obtain coating fluid, adjust this coating fluid and apply the alumina sol solution that this fluor is dispersed with the spraying or the mode of spreading, thereby make it to cover whole luminous element, heat then and solidify, thereby by the AlOOH composition fluor is fixed each other, and be fixed on the surface of luminous element.
Alkyl aluminium alcoholates or aluminum alkoxide are the organo-aluminium compounds that tackifier, gelating agent, solidifying agent, polymerizing catalyst and the dispersing of pigments agent as coating used.
As aluminum isopropoxide, aluminum ethoxide and the butoxy aluminium reactivity as rich as Croesus of one of alkyl aluminium alcoholates or aluminum alkoxide, generate aluminium hydroxide or aluminum alkyls hydrochlorate by means of airborne moisture, generate hydrated aluminum oxide with boehmite structure.For example aluminum isopropoxide shown in following chemical formula 7 like that, react with water easily, finally to become with the hydrated aluminum oxide be principal constituent, have the mixture that carries out crosslinked crosslinking structure with aluminium hydroxide or aluminum oxide (alumina).
Figure C200480006816D00441
Chemical formula 7
Therefore, after making aluminum isopropoxide and airborne reaction of moisture, the AlOOH bonding fluor that adopts heating to generate, thus the luminescent layer that is formed by the AlOOH bonding fluor that contains fluor can be formed on the surface of luminous element as luminescent layer and on the support beyond the surface of luminous element.
More than the luminescent layer that forms by AlOOH bonding fluor, also can make up luminescent layer that forms by other hydrous oxide bonding fluor such as Y, Gd, Lu, Sc, Ga, In, B and the luminescent layer that forms by AlOOH bonding fluor, thereby at the layer that forms on the same luminous element more than 2 kinds or 2 kinds.According to the formation method of the luminescent layer of the employing of the present embodiment spraying, because also can control two-layer thickness, so form the luminescent layer of same shape easily.For example on same luminous element, at first form Y 2O 3Luminescent layer forms Al then thereon 2O 3Luminescent layer.At this, fluor can be included among the two-layer both sides, also can only be included in one deck, and can not comprise among two-layer both sides.If adopt such formation, the size that then has the specific refractory power by fluorescent layer is taken out effects such as efficient to improve light.When forming the luminescent layer that constitutes by one deck, then produce the rapid variation of specific refractory power at the interface of this luminescent layer and extraneous atmosphere or nitride semiconductor luminescent element, the part of the light that takes out from luminous element may reflect at this interface, thus cause light take out efficient lowly.In addition, by forming the luminescent layer that for example is mixed with AlOOH and YOOH, also can adjust linear expansivity and specific refractory power.
The luminescent layer that the AlOOH bonding fluor that is formed by such forms, because be the inorganics different with former resin, so compare with resin, minimum by UV-induced degeneration, also can be used in combination the luminous element that sends UV-light and power type LED of high-output power etc.
(led chip 101)
In the present embodiment, can excited fluophor as the led chip 101 that luminous element uses.As the led chip 101 of luminous element is to adopt method such as MOCVD to form semi-conductors such as GaAs, InP, GaAlAs, InGaAlP, InN, AlN, GaN, InGaN, AlGaN, InGaAlN as luminescent layer on matrix.As semiconductor structure, can list homogeneous junction structure, heterojunction structure or double-heterostructure with MIS knot, PIN knot and PN junction etc.Can carry out various selections to emission wavelength according to the material and the mixed crystal degree thereof of semiconductor layer.In addition, also can be set at single quantum or the multiple quantum trap structure that on the film that produces the quantum effect, is formed with the semiconductor active layer.Preferably efficiently excited fluophor and can send efficiently wavelength the nitride-based compound semiconductor of short light (general formula is In iGa jAl kN, wherein, 0≤i, 0≤j, 0≤k, i+j+k=1).
Under the situation of using gallium nitride compound semiconductor, the material that is suitable for use as semiconductor substrate has: sapphire, spinel, SiC, Si, ZnO, GaN etc.In order to form the good gan of crystallinity, more preferably use sapphire substrate.When growing semiconductor film on sapphire substrate, be preferably formed buffer layers such as GaN, AlN after, on buffer layer, form gallium nitride semiconductor again with PN junction.In addition, also can be with GaN monocrystalline itself as substrate, wherein the GaN monocrystalline is with SiO on sapphire substrate 2Select to grow for mask and form.In this case, after each semiconductor layer forms, also can and remove SiO by etch 2And luminous element is separated with sapphire substrate.Gallium nitride compound semiconductor shows n type electroconductibility under plain situation.Comprise in formation under the situation of the n type gallium nitride semiconductor that improves requirements such as luminous efficiency, as n type doping agent, the preferred elements such as Si, Ge, Se, Te and C that suitably import.On the other hand, under the situation that forms p type gallium nitride semiconductor, then mix as Zn, Mg, Be, Ca, Sr and the Ba etc. of p type doping agent.
If gallium nitride compound semiconductor is the doped p type doping agent just, then be difficult to realize the p typeization, so after importing p type doping agent, preferably adopt the method for stove heating, low-velocity electron beam irradiation and plasma irradiating to anneal, realize the p typeization thus.Layer as concrete luminous element constitutes, adducible suitable examples is by following folded layer by layer forming, promptly have in being formed with under the low temperature on the sapphire substrate or silicon carbide of buffer layers such as gan, aluminium nitride, stacked n type contact layer as gallium nitride semiconductor, as the semi-conductive n type of aluminium gallium nitride alloy covering, as the semi-conductive active coating of the InGaN of doping of Zn and Si, as aluminium gallium nitride alloy semi-conductive p type covering and as the p type contact layer of gallium nitride semiconductor.In order to form led chip 101, situation for led chip 101 with sapphire substrate, by formation p N-type semiconductorN such as etch and n N-type semiconductorN expose face after, each electrode that on semiconductor layer, uses formation such as sputtering method and vacuum vapour deposition to have the shape that requires.For the situation of SiC substrate, utilize the electroconductibility of substrate itself also can form pair of electrodes.
Then the semiconductor wafer that forms etc. is carried out scribing, scribing or the directly cutting (full cut) fully of adopting dicing saw to carry out, wherein the blade of dicing saw has Buddha's warrior attendant blade made of stones, blade rotation during cutting; Or after cutting out the groove wideer (half cut), utilize external force to separate semiconductor wafer than blade width.Perhaps the dicing saw that does reciprocating linear motion by means of vertical diamond needle marks superfine line (warp) on semiconductor wafer, for example is divided into reticulate pattern, utilizes external force to separate wafer then, thereby cuts into shaped like chips by semiconductor wafer.Like this, just, can form led chip 101 as nitride-based compound semiconductor.
In the light-emitting device of the present embodiment, under luminous situation, consider and the glow color complementation of fluor that the main light emission wavelength of led chip 101 is preferably 350nm～530nm.
(metal shell 105)
The metal shell 105 that uses in the light-emitting device of an embodiment of the present invention is made of recess a that accommodates luminous element and the basis pontis b that has disposed the lead-in wire electrode, and metal shell 105 plays a role as the support of luminous element.The bottom surface of the bottom surface of described recess and described lead-in wire electrode roughly is positioned at on the one side.
In light-emitting device, the thermal diffusivity of consideration and miniaturization, housing preferably forms with film.On the other hand, insulating component be arranged on and the interface of the electrode that goes between on, for relax with this insulating component such as the difference of coefficient of thermal expansion and improve reliability, be necessary to increase contact surface separately.So the present inventor distinguishes the part of configuration luminous element and the part of anchor leg electrode in metal shell, adapt with separately zone and to set shape and thickness, seek the raising of reliability by this.
(lead-in wire electrode 102)
The light-emitting device of embodiment of the present invention has positive and negative lead-in wire electrode 102, and lead-in wire electrode 102 is in insulating component is inserted in the communicating pores of the basis pontis that is arranged at metal shell.The top ends of described lead-in wire electrode highlights from the surface of described basis pontis, and the bottom surface of the mounting face side of the bottom surface of described lead-in wire electrode and described recess is roughly located at grade.
(lead-in wire 106)
The light-emitting device of an embodiment of the present invention is in the interarea side of metal shell 105, the lead-in wire 106 that has light transmission window portion 107 and be made of metal part.Window portion 107 is preferably the light-emitting area of light-emitting device and is configured in the central part of light-emitting device.
In the present embodiment, described window portion be positioned at the luminous element that is configured in described metal shell recess above, and intersect with the extended line of described recess inwall.The light that sends from the end of described luminous element produces diffuse-reflectance in the side of described recess and takes out in frontal.The scope that exists that these diffuse be it is generally acknowledged roughly in the extended line of described recess side.So by adjusting the area as the window portion of light-emitting area as described above, described diffusing can focus on described window portion effectively, thereby can obtain sending the light-emitting device of high briliancy light.
(housing 114)
As shown in Figure 5, housing 114 conducts of using in another embodiment of the present invention are at the recess internal fixing and protect the support of led chip 101 to play a role.In addition, also has the outer electrode 102A that can electrically contact with the outside.Adapt with the quantity and the size of led chip 101, housing 114 also can be designed as has a plurality of peristomes.For making it to have suitable shading function, housing 114 is painted to dark-coloured system such as black or grey, and perhaps the luminous observation face side of housing 114 is painted to dark-coloured system.In order further to protect led chip 101 to avoid the infringement of outside atmosphere, beyond the removing coating 111,112, can also be provided as the mold member 113 of light transmission protective.Housing 114 is preferably good and rigidity is strong with the cohesiveness of coating 111,112 and mold member 113.For led chip 101 and outside are carried out electrical isolation, housing 114 preferably has insulativity.Moreover housing 114 considers and the sticking power of mold member 113 preferably have less coefficient of thermal expansion under the situation of the influence of the heat that is subjected to coming from led chip 101 grades.
The bonding of led chip 101 and housing 114 also can adopt thermosetting resin etc. to carry out.Specifically, can list Resins, epoxy, acrylic resin and imide resin etc.Use at light-emitting device and to send the led chip that contains ultraviolet light and under situation about being used under the high-output power, for the adhesive segment of led chip 101 with housing 114, because ultraviolet ray of sending by led chip etc. also be used as the resin of containment member or be included in wherein fluor etc. reflect, light becomes high-density especially in housing, therefore, the resin of adhesive segment is degenerated because of ultraviolet ray, so can think and cause the low of luminous efficiency and cause the reduction in light-emitting device life-span because of cohesive strength low because of the xanthochromia of resin etc.For preventing such degeneration, can use the resin that contains UV light absorber, the preferred inorganics that can use embodiment of the present invention etc. because of the ultraviolet adhesive segment that causes.Especially, use at housing under the situation of metallic substance, the bonding of led chip 101 and housing 114 also can be used the eutectic solder of Au-Sn etc. etc. except the inorganics that uses embodiment of the present invention.Therefore, with to use resin to carry out the agglutinating situation different,, the present invention sends the led chip that contains ultraviolet light and under situation about being used under the high-output power, its adhesive segment can not degenerated yet even using at light-emitting device.
In addition, in configuration and fixed L ED chip 101, for housing 114 in outer electrode 102A electrically contact, be fit to use Ag slurry, carbon pastes, ITO slurry and metal rim etc.
(outer electrode 102A)
Outer electrode 102A shown in Figure 5 is used for from the outside of housing 114 to the electrode that is configured in inner led chip 101 supply capabilities.Therefore, can list and utilized the various electrodes that are arranged on pattern on the housing 114, that have electroconductibility and lead frame.In addition, consider the characteristic etc. of thermal diffusivity, electrical conductivity and the led chip 101 of outer electrode 102A, can form various sizes.Outer electrode 102A is in each led chip 101 of configuration, and is heat passage to outside for what led chip 101 was emitted, preferably has good heat conductivity.As the concrete resistance of outer electrode 102A, be preferably 300 μ Ω cm or following, more preferably 3 μ Ω cm or following.In addition, concrete heat-conduction coefficient is preferably 0.01cal/ (s) (cm 2) (℃/cm) or more than, 0.5cal/ (s) (cm more preferably 2) (℃/cm) or more than.
As such outer electrode 102A, be fit to use have copper or phosphor bronze sheet coating surface the metal of palladium or gold etc. or the material that has carried out weldering plating (soldering plating).With lead frame as under the situation of outer electrode 102A, can be used in every way according to the difference of specific conductivity, heat-conduction coefficient, but consider that from the angle of processibility thickness of slab is preferably 0.1mm～2mm.Outer electrode 102A as being provided with on the support etc. of glass epoxy resin and pottery and so on can form Copper Foil and tungsten layer.When using tinsel on printed circuit board (PCB), the thickness as Copper Foil etc. is preferably set to 18 μ m～70 μ m.In addition, also can be on Copper Foil etc. plated with gold or weld plating.
(electroconductibility lead-in wire 104)
As electroconductibility lead-in wire 104, requirement is little with the contact resistance of the electrode of led chip 101, and has favorable mechanical connectivity, electrical conductivity and heat conductivity.As heat-conduction coefficient, be preferably 0.01cal/ (s) (cm 2) (℃/cm) or more than, 0.5cal/ (s) (cm more preferably 2) (℃/cm) or more than.Under the situation of the light-emitting device that forms high-output power, consider factors such as manufacturability in addition, the diameter of electroconductibility lead-in wire 104 is preferably φ 10 μ m～φ 70 μ m.As such electroconductibility lead-in wire 104, can list the electroconductibility lead-in wire of metals such as using gold, copper, platinum and aluminium and alloy thereof particularly.Such electroconductibility lead-in wire 104 is easy to electrode, inner lead and the pin leads etc. of each led chip 101 are coupled together by means of wire-bonded equipment.
(mold member 113)
Mold member 113 can be provided with according to the use of light-emitting device, avoids extraneous infringement or be used to improve light taking out efficient with the coating 111,112 etc. that is used to protect led chip 101, electroconductibility lead-in wire 104 and contains fluor.Mold member 113 can form with various resins and glass.As the concrete material of mold member 113, what be fit to use mainly contains: good transparent resin of weather resisteants such as Resins, epoxy, urea resin, silicone resin and fluoro-resin and glass etc.In addition, by in mold member, containing diffusant, also can relax the directive property of the light that comes from led chip 101 and increase field angle.Such mold member 113 can be used caking agent, the binding agent identical materials with coating, also can use different materials.
In addition, when use metal shell, make led chip 101 with nitrogen when airtight, mold member 113 is not the necessary formation of the present invention.
(spray equipment 300)
As Fig. 6 and shown in Figure 7, the present embodiment uses spray equipment 300, this spray equipment 300 to use transfer lime 307,308,309 will accommodate the container 301 of coating fluid respectively, regulate the valve 302 of the flow of coating fluid, be transported to the recycle pump 303 of container 301 and coating fluid 203 is coupled together with the nozzle 201 of spiral helicine form ejection from nozzle 201 again after coating fluid is transported to nozzle 201.
(container 301)
In the container 301 of accommodating coating fluid, stirrer 304 is installed, in the coating operation, often stirs coating fluid.The coating fluid 203 of being accommodated by container 301 adopts stirrer 304 often to stir, thereby contained fluor 202 usually is dispersed in the solution in the coating fluid 203.
(valve 302)
Valve 302 is regulated the flow of the coating fluid that is transported by transfer lime 309 by container 301 by means of the switching of valve.
(recycle pump 303)
Recycle pump 303 is transported to the top ends of nozzle 201 from container 301 via valve 302 and compressor 305 with coating fluid by transfer lime 309, after this, will be not from nozzle 201 ejections and the coating fluid that left behind is transported to container 301 by transfer lime 308.After this coating fluid, is transported to container 301 by transfer lime 308, so coating fluid usually is in the state of spray equipment internal recycle owing to be transported to the top ends of nozzle 201 from container 301 via valve 302 by transfer lime 309 by means of recycle pump 303.Therefore, coating fluid is because be in stirring or the round-robin state that spreads all over whole spray equipment, so the fluor that contains in the coating fluid often is in uniform distribution in the coating operation.
(compressor 305)
Compressor 305 is arranged in the device by transfer lime 307 or 309, compresses the air that transports by transfer lime 307, regulates the pressure of the coating fluid that transports by transfer lime 309.By means of compressor 305, pressurized air is transported to nozzle 201 respectively with the coating fluid that carries out the excess pressure adjusting.At this, compressed-air actuated pressure monitors by pressure warning unit 306.Use above spray equipment 300,, be sprayed on top, the side and angle of luminous element with high pressure gas one superhigh speed ejection coating fluid.
(nozzle 201)
In the present embodiment, employed device is characterised in that: coating fluid and gas (being air here) spray with spiral helicine form by nozzle 201.Around the nozzle of this device several gas vents are set, with respect to applied surface separately at an angle from the emission direction of the gas of these ejiction openings ejections.Therefore, is that these gas vents of center rotation are when sending into gas when simultaneously to the ejiction opening with coating fluid, the whole gas flow that will concentrate in together from the gas of separately ejiction opening ejection, become the flowing of the vortex crustiform that reverses, spiral helicine flow or wind spout in the flowing of air.In addition, be provided with the ejiction opening of coating fluid at the center of the nozzle of this device, when the ejection with gas sprays coating fluid simultaneously, become vaporific coating fluid take advantage of the flowing of the vortex crustiform that reverses, spiral helicine flow or wind spout in flowing of air and diffusion is come.
Diffuse into the injection starting point of the diameter of spiral helicine whole spraying from the luminous element top, the closer to the surface of luminous element, it is big more that diameter becomes.In addition, from the injection starting point of luminous element top, the closer to the surface of luminous element, the speed of rotation of the spraying that is made of coating fluid is more little.That is to say, when vaporific coating fluid from nozzle ejection and when air, spreading, spray starting point be nozzle near, spraying is coniform diffusion comes, and in the place of leaving nozzle, spraying is cylindric diffusion and comes.So present embodiment is preferably regulated and is provided with the top distance between the lower end of nozzle of luminous element, make the surface of luminous element appear at spraying and be in and be the come place of this state of cylindric diffusion.The spraying of this moment shape rotation in the shape of a spiral, and speed is slower, and therefore, spraying can be around to the luminous element surface that is under the electroconductibility lead-in wire shade, and above the not only whole luminous element but also whole side can both fully be sprayed onto.Thus, can under the state of fixedly luminous element or nozzle, carry out operation.In addition, be the come place of this state of cylindric diffusion because be in spraying, the speed of spraying is slower, so when being sprayed on luminous element surperficial, the impact of the fluorophor particle that the surface of luminous element is contained in can not sprayed.In addition, can not produce the distortion and the broken string of electroconductibility lead-in wire, thereby product percent of pass and manufacturability are improved.
(well heater 205)
As shown in Figure 6, to be in temperature on well heater 205 be 50 ℃～500 ℃ heated condition to the luminous element after the coating of the present embodiment.As making luminous element be in the method for heated condition in this wise, also can use method at heating unit internal heating luminous elements such as baking ovens.By heating, make ethanol, trace be included in moisture and solvent evaporation in the hydrolyzed solution that is in gel state, and can obtain amorphous Al (OH) by the coating fluid 203 that is in gel state 3And AlOOH.Moreover the coating fluid of the present embodiment 203 has been owing to carried out viscosity adjustment, so be sprayed on top, the side of luminous element and the angle and then after the surface of support 204, can not flow out from the place of spraying.Soon just heat after coating in these places, so top, side by fluor being bondd that the coating form can covering luminous element and the part on the angle by AlOOH.
In the present embodiment, making binding liquid be in temperature is 50 ℃～500 ℃ heated condition, and luminous element can be welded on the support 204 by this.As the method that is in heated condition in this wise, luminous element can be arranged on the well heater, also can use method at heating unit internal heating luminous elements such as baking ovens.When by heating, when making ethanol, trace be included in moisture in the hydrolyzed solution that is in gel state and solvent evaporation, just can obtain tack coat by the binding liquid that is in gel state, this tack coat is principal constituent with AlOOH, is intensive formation of particle of several nanometers by many particle diameters.This tack coat by with the inorganics be principal constituent, particle diameter to be that the particle of youngster's nanometer is intensive form together, between particle, have the space.If the temperature that applies on tack coat takes place sharply to change, then owing to the effect of thermal stresses, the volume of particle expands or shrinks separately.Therefore, there is not above-mentioned particle and has the situation of the melten glass of big-difference very or resin-bonded luminous element different by thermal expansivity and supporting body material, the tack coat of the present embodiment do as a whole can be because of thermal stresses is not subjected to too much influence, tack coat peel off and be full of cracks etc. can not take place yet.Therefore, even light-emitting device takes place to use under the state jumpy in the temperature that applies, the light-emitting device of the present embodiment also can be kept its reliability.
Moreover, in the present embodiment, because binding liquid is adjusted to high viscosity, so this binding liquid between the real estate and support surface of luminous element, and can not produce and flows from expanding to the lateral place of luminous element.After chips welding was carried out in these places, the heating binding liquid was cured.Thus, luminous element can not depart from the position of being carried at first and can form by AlOOH and is welded on light-emitting device on the support.
(shielding baffle plate 206)
In the present embodiment, under the situation of arranging a plurality of housings, luminous element is welded in the housing respectively, and the electrode and the outer electrode of luminous element carried out wire-bonded, the top from luminous element sprays coating fluid 203 then.But, the recess side of housing is designed cone shape, when the reflecting part that the recess side of housing is taken out efficient as the light that improves the housing frontal is used, if the side attachment coating fluid 203 of this recess, then the light that is sent by luminous element produces in this side and overflows emission, thereby the light that is difficult to seek the housing frontal takes out the raising of efficient.So, in the present embodiment, for preventing on the recess side of housing and outer electrode, to adhere to coating fluid 203, coating fluid 203 is sprayed on the surface of luminous element from the top of shielding baffle plate 206.Shielding baffle plate 206 be hide fully the recess side of housing and outer electrode, be provided with size and can make coating fluid 203 be sprayed on top, the side of luminous element and the plate of the communicating pores on the angle, have metal system shielding baffle plate, reinforced plastics system shielding baffle plate etc.
(tack coat 110)
The employed tack coat 110 of the present embodiment is by the organic materials that is in gel state luminous element and support to be pasted together the back, to carry out the formed amorphousness inorganic layer of heat drying.Furtherly, the tack coat of the present embodiment be present in above the support and luminous element the matrix face between successive water white transparency layer, and expand to luminous element above.
Because the reflection that housing etc. produces, the high energy light that is sent by led chip etc. becomes high-density in tack coat.When with luminous intensity height, the nitride semiconductor during that can send high energy light as led chip, preferably will to these high energy lights have sunproof, contain among Si, Al, Ga, Ti, Ge, P, B, Zr, Y and the alkaline-earth metal a kind, two or more oxide compound and be used as the adhering liquid of luminous element and support.In addition, also above-mentioned hydrous oxide can be used as tack coat.
As one of concrete main material of tack coat, be fit to the SiO that has that uses 2, Al 2O 3, ZrO 2, Y 2O 3, MSiO 3Light transmission inorganic structures such as (wherein,, can list Zn, Ca, Mg, Ba and Sr etc.) as M.By these light transmission inorganic structures, the mutual opposed mode of matrix face and support surface with luminous element makes luminous element be fixed with respect to support.In the present embodiment, contain a kind or the oxide compound of multiple element being selected among Si, Al, Ga, Ti, Ge, P, B, Zr, Y or the alkaline-earth metal at least, the same with the material that forms coating, all adopt organometallic compound to form.If use such organometallic compound that is in a liquid state at normal temperatures, then by adding organic solvent, can be easily from technological angular adjustment viscosity and prevent the coagulative generation of organometallic compound etc., thereby manufacturability is improved.In addition, such organometallic compound generates inorganicss such as oxide compound and oxyhydroxide because chemical reaction such as hydrolysis takes place easily, so, can not reduce LED as the performance of luminous element and form tack coat easily by means of containing a kind of being selected among Si, Al, Ga, Ti, Ge, P, B, Zr, Y or the alkaline-earth metal or oxide compound of multiple element etc. at least.But, also contain the not material of easy coloring in these elements, so need carry out appropriate selection according to purposes.In addition, the hydrous oxide of the present embodiment is that binding agent also has photostabilization and thermotolerance, thereby they also can be used as tack coat and are used.
Moreover, expand under the lateral situation of luminous element at tack coat, if, then absorb the metal from the near ultraviolet to the blue light that sends by luminous element and often be included in the metal solder with metal solder welding luminous element.For example, when with Au-Sn eutectic solder welding luminous element, because Au has absorbed the light from the near ultraviolet to the blueness that is sent by luminous element, thereby has a problem that the output rating that makes light-emitting device descends, but the tack coat based on the present embodiment can not absorb the light from the near ultraviolet to the blueness that is sent by luminous element, thereby can form the high light-emitting device of luminous efficiency.
Embodiment 3
Use Fig. 8 and Fig. 9 to describe below with regard to the light-emitting device of embodiment of the present invention 3.Fig. 8 and Fig. 9 represent that respectively the A-A ' of the orthographic plan of light-emitting device and Fig. 8 is to sectional view.In the light-emitting device of embodiment 3, employed fluorescence member can be the fluorescence member identical with embodiment 1.Used herein is that to have glow peak be the luminous element 401 of the InGaN based semiconductor layer of 460nm as luminescent layer at blue region, emission wavelength.On luminous element 401, be formed with p type semiconductor layer and n type semiconductor layer (not shown), on p type semiconductor layer and n type semiconductor layer, be formed with the electroconductibility lead-in wire 404 that is connected the electrode 402 that goes between.In addition, be formed with insulated enclosure material 403 in the mode of the periphery that covers lead-in wire electrode 402, thereby short circuit is prevented.Above luminous element 401, the light transmission window portion 407 that is extended out by the lead-in wire 406 that is positioned at housing 405 tops is being set.Inner face in light transmission window portion 407, roughly whole face all is coated with the binding agent 410 that evenly contains fluor 408.
Like this, the light-emitting device of Fig. 8 and Fig. 9 is kept at a distance above led chip and with led chip and is being disposed the luminescent film 409 that contains fluor like that.This point is different with the structure of the light-emitting device of above-mentioned Fig. 3, Fig. 4, and other parts are much the same, and fluor and binding agent also can use same material.Luminescent film is as multilayered structure, and each layer can be sneaked into different fluor, also the film of not sneaking into fluor can be made up into.The luminescent film of Fig. 8 and Fig. 9 can separate and can change from light-emitting device, thereby the luminescent film of also be subject to variation glow color or handle degeneration changes.
Embodiment 4
Moreover Figure 10 is the light-emitting device of expression embodiment of the present invention 4.Light-emitting device shown in this Fig is opposite with above-mentioned light-emitting device, and LED is configured in the top as luminous element 501, and below housing 505 on form crooked recess and luminescent layer 509 be set on its surface.In this constitutes, also can utilize the multilayered structure that constitutes by above-mentioned fluor and binding agent.In addition, layer formation also with above-mentioned same, can be designed as multilayered structure.
Embodiment 5
In addition, Figure 11～Figure 22 is the light-emitting device of expression embodiment of the present invention 5.Light-emitting device shown in these figure is configured in a side and the opposed mode of matrix of electrode that luminous element is being set as shown in Figure 19.Serve as that basic making method with regard to light-emitting device shown in Figure 19 describes with Figure 11～Figure 18 below.
At first, as shown in figure 11, at the surface configuration electroconductive member 602 of pedestal (sub-mount) with substrate 601.Secondly, as shown in figure 12, be provided with the conductive pattern that is formed with insulation division 603 on the surface of matrix 601, wherein insulation division 603 is used to separate the positive electrode that connects luminous element 600 and the electroconductive member 602 of negative potential.
Pedestal with the material of substrate 601 preferably with the thermal expansivity material about equally of semiconductor light-emitting elements aluminium nitride etc. for example.By using such material, can relax the thermal stresses of pedestal with generation between substrate 601 and the luminous element 600.Pedestal preferably can form protecting component and cheap silicon sometimes with the material of substrate 601.In addition, the electroconductive member 602 preferred high silver of reflectivity and golden that use.
In order to improve the reliability of light-emitting device, in the gap that produces between positive and negative two electrodes of luminous element 600 and between the insulation division 603, fill end filler (underfill) 604.As shown in figure 13, with the circumferential arrangement of the insulation division 603 of substrate 601 end filler 604 is arranged in said base.The material of end filler 604 for example is heat-curing resins such as Resins, epoxy.In order to relax the thermal stresses of end filler 604, also can further aluminium nitride, aluminum oxide and their compounding mixture etc. be sneaked in the Resins, epoxy.The consumption of end filler 604 is positive and negative two electrodes that can stride across insulation division 603 landfill luminous elements 600 and the pedestal amount with the gap that produces between the substrate 601.
Secondly, as shown in figure 14, will adopt positive and negative two electrodes of the luminous elements such as led chip 600 that other method makes to be fixed up with the opposed mode of positive and negative two electrodes of above-mentioned conductive pattern respectively.At first, make on positive and negative two electrodes of conductive material 605 attached to luminous element 600.The material of conductive material 605 for example has Au, eutectic solder (Au-Sn), Pb-Sn, lead-free solder etc.Be at end filler 604 under the situation of soft state, by conductive material 605, make positive and negative two electrodes of luminous element 600 mutually opposed, then together with positive and negative two electrodes, conductive material 605 and the above-mentioned conductive pattern thermo-compressed of luminous element 600 with positive and negative two electrodes of above-mentioned conductive pattern.At this moment, positive and negative two fillers of the interelectrode end 604 of conductive material and above-mentioned conductive pattern are got rid of.
Moreover, as shown in figure 15, disposing sieve plate 606 from the substrate-side of luminous element 600.In addition, can not want to form the position configuration metal mask of luminescent coating to replace sieve plate in ball bonding (ball bonding) position of electroconductibility lead-in wire, the formation position of joint line (partingline) etc. yet.
Then as shown in figure 16, be adjusted at and have the luminescent coating that contains fluor in thixotropic alumina sol and form material 607, use squeegee (round end scraper) to carry out silk screen printing.
And then as shown in figure 17, take off sieve plate, make luminescent coating form material 607 and solidify.Then as shown in figure 18, along joint line 609 each luminous element of cutting, just obtain the light-emitting device 610 of band luminescent coating as shown in figure 19.
And then the light-emitting device 610 that also can produce such band luminescent coating is fixed on top light-emitting devices such as support.The example of Figure 20～Figure 22 be will the band luminescent coating light-emitting device 610 be fixed on light-emitting device on the support 611 with recess 612.Figure 20 is the orthographic plan of light-emitting device, Figure 21 be B-B ' of Figure 20 to sectional view, and Figure 22 is the enlarged view of Figure 21.Light-emitting device shown in these figure is to be coated with the bottom surface that binding agents such as cream will be fixed on recess 612 with the light-emitting device 610 of luminescent coating to form with Ag, and its center dant 612 is arranged on the metallic matrix 615 of supports 611 such as housing.And then the lead-in wire electrode 613 usefulness electroconductibility that will expose lead-in wire 614 be arranged on pedestal and be connected with the conductive pattern on the substrate 601.
In the light-emitting device of above explanation, also can use the fluor that applies or be covered by coating material.Light-emitting device with the luminescent layer that is made of mineral binder bond and filler based on above-mentioned hydrous oxide does not limit the formation of light-emitting device.For example, except the above-mentioned luminous element of downward installation and on sapphire substrate etc. the example of formation luminescent layer, the surface of the light tube that also can be useful in high pressure mercury vapour lamp forms the example of luminescent layer etc.
Embodiment 1～29
Describe with regard to embodiments of the invention below.At first, with alumina sol, yttrium colloidal sol allotment fluor slip, thereby produce fluor/colloidal sol slip.
(embodiment 1)
Get 10g commercial goods alumina sol (daily output chemistry system A1520) and be contained in the beaker of 100ml, add the ethanol of 50 weight % with respect to alumina sol then and mix.In this mixed solution, add 10g fluorescent substance YAG, fully stir and after mixing, just obtain the slip of fluor/colloidal sol.
(embodiment 2)
Get 10g commercial goods alumina sol (daily output chemistry system A1200) and be contained in the beaker of 100ml, add the ethanol of 70 weight % with respect to alumina sol then and mix.In this mixed solution, add 10g fluorescent substance YAG, fully stir and after mixing, just obtain the slip of fluor/colloidal sol.
(embodiment 3)
Get 10g commercial goods alumina sol (catalyst changes into system カ ロ イ De AS3) and be contained in the beaker of 100ml, add the ethanol of 50 weight % with respect to alumina sol then and mix.In this mixed solution, add 10g fluorescent substance YAG, fully stir and after mixing, just obtain the slip of fluor/colloidal sol.
(embodiment 4)
Get 10g commercial goods yttrium oxide colloidal sol (many wooden chemistries oxygenerating yttrium colloidal sol) and be contained in the beaker of 100ml, add the ethanol of 50 weight % with respect to yttrium oxide colloidal sol then and mix.In this mixed solution, add 10g fluorescent substance YAG, fully stir and after mixing, just obtain the slip of fluor/colloidal sol.
(embodiment 5)
Get 10g commercial goods alumina sol (daily output chemistry system A1520) and be contained in the beaker of 100ml, add the ethanol of 50 weight % with respect to alumina sol then and mix.In this mixed solution, add 10g fluorescent substance SAE, fully stir and after mixing, just obtain the slip of fluor/colloidal sol.
(embodiment 6)
Get 10g commercial goods alumina sol (daily output chemistry system A1200) and be contained in the beaker of 100ml, add the ethanol of 70 weight % with respect to alumina sol then and mix.In this mixed solution, add 10g fluorescent substance SAE, fully stir and after mixing, just obtain the slip of fluor/colloidal sol.
(embodiment 7)
Get 10g commercial goods alumina sol (catalyst changes into system カ ロ イ De AS3) and be contained in the beaker of 100ml, add the ethanol of 50 weight % with respect to alumina sol then and mix.In this mixed solution, add 10g fluorescent substance SAE, fully stir and after mixing, just obtain the slip of fluor/colloidal sol.
(embodiment 8)
Get 10g commercial goods yttrium oxide colloidal sol (many wooden chemistries oxygenerating yttrium colloidal sol) and be contained in the beaker of 100ml, add the ethanol of 70 weight % with respect to yttrium oxide colloidal sol then and mix.In this mixed solution, add 10g fluorescent substance SAE, fully stir and after mixing, just obtain the slip of fluor/colloidal sol.
(embodiment 9)
Get 10g commercial goods alumina sol (daily output chemistry system A1200) and be contained in the beaker of 100ml, add the ethanol of 50 weight % with respect to alumina sol then and mix.In this mixed solution, add 10g fluorescent substance BAM, fully stir and after mixing, just obtain the slip of fluor/colloidal sol.
(embodiment 10)
Get 10g commercial goods yttrium oxide colloidal sol (many wooden chemistries oxygenerating yttrium colloidal sol) and be contained in the beaker of 100ml, add the ethanol of 50 weight % with respect to yttrium oxide colloidal sol then and mix.In this mixed solution, add 10g fluorescent substance CCA-1, fully stir and after mixing, just obtain the slip of fluor/colloidal sol.
(embodiment 11)
Get 10g commercial goods yttrium oxide colloidal sol (many wooden chemistries oxygenerating yttrium colloidal sol) and be contained in the beaker of 100ml, add the ethanol of 50 weight % with respect to yttrium oxide colloidal sol then and mix.In this mixed solution, add 10g fluorescent substance CCA-2, fully stir and after mixing, just obtain the slip of fluor/colloidal sol.
(embodiment 12)
Get 10g commercial goods yttrium oxide colloidal sol (many wooden chemistries oxygenerating yttrium colloidal sol) and be contained in the beaker of 100ml, add the ethanol of 50 weight % with respect to yttrium oxide colloidal sol then and mix.In this mixed solution, add 10g fluorescent substance CCBE, fully stir and after mixing, just obtain the slip of fluor/colloidal sol.
(embodiment 13)
Get 10g commercial goods yttrium oxide colloidal sol (many wooden chemistries oxygenerating yttrium colloidal sol) and be contained in the beaker of 100ml, add the ethanol of 50 weight % with respect to yttrium oxide colloidal sol then and mix.In this mixed solution, add 10g fluorescent substance SAE, fully stir and after mixing, just obtain the slip of fluor/colloidal sol.
(embodiment 14)
Get 10g commercial goods yttrium oxide colloidal sol (many wooden chemistries oxygenerating yttrium colloidal sol) and be contained in the beaker of 100ml, add the ethanol of 50 weight % with respect to yttrium oxide colloidal sol then and mix.In this mixed solution, add 10g fluorescent substance CESN, fully stir and after mixing, just obtain the slip of fluor/colloidal sol.
In addition, as embodiment 15～23, below expression is the example of making LED under various conditions.
(embodiment 15-1)
Commercial goods yttrium oxide colloidal sol (many wooden chemistries oxygenerating yttrium colloidal sol) is contained in the beaker of 100ml, adds the ethanol of 50 weight % with respect to yttrium oxide colloidal sol then and mix.In this mixed solution, add fluorescent substance YAG, fully stir and after mixing, just obtain the slip of fluor/colloidal sol with predetermined ratio.Thus, with wavelength be the semiconductor light-emitting elements combination of 460nm, just obtain sending the LED of white light.
(embodiment 15-2)
Commercial goods alumina sol (daily output chemical oxygen generation aluminium colloidal sol 200) is contained in the beaker of 100ml, adds the ethanol of 50 weight % with respect to alumina sol then and mix.In this mixed solution, add fluorescent substance YAG, fully stir and after mixing, just obtain the slip of fluor/colloidal sol with predetermined ratio.With the semiconductor light-emitting elements combination that the slip and the wavelength of this fluor/colloidal sol is 460nm, just obtain sending the LED of white light.
(embodiment 16)
Commercial goods yttrium oxide colloidal sol (many wooden chemistries oxygenerating yttrium colloidal sol) is contained in the beaker of 100ml, adds the ethanol of 50 weight % with respect to yttrium oxide colloidal sol then and mix.In this mixed solution, add fluorescent substance YAG and with europium activatory calcium silicon nitride, fully stir and after mixing, just obtain the slip of fluor/colloidal sol with predetermined ratio.With the semiconductor light-emitting elements combination that the slip and the wavelength of this fluor/colloidal sol is 460nm, just produce the LED of the light that sends the bulb color.
(embodiment 17-1)
Commercial goods alumina sol (daily output chemical oxygen generation aluminium colloidal sol 200) is contained in the beaker of 100ml, adds the ethanol of 50 weight % with respect to alumina sol then and mix.In this mixed solution, add fluorescent substance YAG and with europium, manganese-activated calcium chlorapatite, fully stir and after mixing, just obtain the slip of fluor/colloidal sol with predetermined ratio.With the semiconductor light-emitting elements combination that the slip and the wavelength of this fluor/colloidal sol is 400nm, just produce the LED that sends white light.
(embodiment 17-2)
Commercial goods yttrium oxide colloidal sol (many wooden chemistries oxygenerating yttrium colloidal sol) is contained in the beaker of 100ml, adds the ethanol of 50 weight % with respect to yttrium oxide colloidal sol then and mix.In this mixed solution, add fluorescent substance YAG and with europium, manganese-activated calcium chlorapatite, fully stir and after mixing, just obtain the slip of fluor/colloidal sol with predetermined ratio.With the semiconductor light-emitting elements combination that the slip and the wavelength of this fluor/colloidal sol is 400nm, just produce the LED that sends white light.
(embodiment 18)
Commercial goods yttrium oxide colloidal sol (many wooden chemistries oxygenerating yttrium colloidal sol) is contained in the beaker of 100ml, adds the ethanol of 50 weight % with respect to yttrium oxide colloidal sol then and mix.In this mixed solution, add fluorescent substance YAG and with europium, manganese-activated calcium chlorapatite and with europium activatory calcium silicon nitride, fully stir and after mixing, just obtain the slip of fluor/colloidal sol with predetermined ratio.With the semiconductor light-emitting elements combination that the slip and the wavelength of this fluor/colloidal sol is 400nm, just produce the LED of the light that sends the bulb color.
(embodiment 19)
Commercial goods alumina sol (daily output chemical oxygen generation aluminium colloidal sol 200) is contained in the beaker of 100ml, adds the ethanol of 50 weight % with respect to alumina sol then and mix.In this mixed solution with predetermined ratio add fluorescent substance promptly with europium activatory calcium chlorapatite, with europium, manganese-activated barium magnesium aluminate and with europium activatory strontium silicon nitride, fully stir and after mixing, just obtain the slip of fluor/colloidal sol.With the semiconductor light-emitting elements combination that the slip and the wavelength of this fluor/colloidal sol is 400nm, just produce the LED that sends white light.
(embodiment 20)
Commercial goods alumina sol (daily output chemical oxygen generation aluminium colloidal sol 200) is contained in the beaker of 100ml, adds the ethanol of 50 weight % with respect to alumina sol then and mix.In this mixed solution, add fluorescent substance and promptly use europium activatory strontium aluminate, fully stir and after mixing, just obtain the slip of fluor/colloidal sol with predetermined ratio.With the semiconductor light-emitting elements combination that the slip and the wavelength of this fluor/colloidal sol is 365nm, just produce and send the LED of signal with bluish-green coloured light.
(embodiment 21)
Commercial goods alumina sol (daily output chemical oxygen generation aluminium colloidal sol 200) is contained in the beaker of 100ml, adds the ethanol of 50 weight % with respect to alumina sol then and mix.In this mixed solution, add fluorescent substance and promptly use europium activatory barium silicon nitride, fully stir and after mixing, just obtain the slip of fluor/colloidal sol with predetermined ratio.With the semiconductor light-emitting elements combination that the slip and the wavelength of this fluor/colloidal sol is 365nm, just produce and send the LED of signal with sodium yellow.
(embodiment 22)
Commercial goods yttrium oxide colloidal sol (many wooden chemistries oxygenerating yttrium colloidal sol) is contained in the beaker of 100ml, adds the ethanol of 50 weight % with respect to yttrium oxide colloidal sol then and mix.In this mixed solution, add fluorescent substance YAG and with europium activatory barium magnesium aluminate and with europium activatory calcium strontium silicon nitride, fully stir and after mixing, just obtain the slip of fluor/colloidal sol with predetermined ratio.With the semiconductor light-emitting elements combination that the slip and the wavelength of this fluor/colloidal sol is 365nm, just produce the LED of the light that sends the bulb color.
(embodiment 23)
Commercial goods yttrium oxide colloidal sol (many wooden chemistries oxygenerating yttrium colloidal sol) is contained in the beaker of 100ml, adds the ethanol of 50 weight % with respect to yttrium oxide colloidal sol then and mix.In this mixed solution with predetermined ratio add fluorescent substance promptly with europium activatory calcium chlorapatite, with europium, manganese-activated barium magnesium aluminate and with europium activatory calcium silicon nitride, fully stir and after mixing, just obtain the slip of fluor/colloidal sol.With the semiconductor light-emitting elements combination that the slip and the wavelength of this fluor/colloidal sol is 365nm, just produce the LED that sends white light.
Table 1 has been represented the example of fluor, binding agent and the LED of combination the foregoing description 15-1 to 23.In addition, glow color is illustrated on the chromaticity diagram of Figure 23.The glow color of the LED of these embodiment is respectively: embodiment 15-1,15-2 are white, embodiment 16 is the bulb color, embodiment 17-1,17-2 are that height is drilled look white, embodiment 18,22 is the bulb color, embodiment 19,23 is a three-wavelength white, embodiment 20 is the signal blue-greenish colour, and embodiment 21 uses yellow for signal.
Table 1
Figure C200480006816D00631
Moreover, also can make the luminous element of high-output power as the preferred embodiment of the invention.The luminous element of high-output power for example is applicable to lighting use etc.Combination is used for being produced on the example that practical aspect has fluor, binding agent and the LED of the LED of preferred characteristics and is illustrated in following table 2 as embodiment 24～embodiment 29.The glow color of the LED of these embodiment (tone) is respectively: embodiment 24 is white, and embodiment 25,26,27 is the bulb color, and embodiment 28 is a three-wavelength white.
In addition, fluor spectral data such as Figure 24 and shown in Figure 25 of the three-wavelength white of embodiment 19, embodiment 23 uses.The spectrogram that Figure 24 and Figure 25 represent spectrogram that the wavelength that uses with embodiment 23 excites as the LED of 365nm respectively and the wavelength that uses with embodiment 19 excites as the LED of 400nm.
Table 2
Figure C200480006816D00641
(comparative example 1)
As a comparative example 1, make and used the sample of silicon dioxide gel to obtain comparative data.Get 10g commercial goods silicon dioxide gel (コ Le コ-ト makes HAS10) and be contained in the beaker of 100ml, add 10g CESN then therein, fully stir and after mixing, just obtain the slip of fluor/colloidal sol as fluorescent substance.
(comparative example 2)
As a comparative example 2, make and do not use the sample of fluor to obtain comparative data.At this, only use the LED of 400nm.
(formation of luminescent coating)
The method representation of the fluor of the embodiment 1～14 that obtains more than the use/colloidal sol slip, formation luminescent coating is as follows: at first fluor/colloidal sol the slip with embodiment 1～5 is filled in respectively in the spray jar of spray equipment (ノ-De ゾ Application system).Below nozzle, the LED that wavelength is 400nm (encapsulation of 9 φ bases (stem package), 0.35mm chip) is set as luminous element.At this,, in advance led chip is sheltered in order only on led chip, to be coated with fluor/colloidal sol slip.And then, be heated to about 90 ℃ with hot plate from the below of led chip.Behind the spray formation, fluor is sol bonded on led chip by means of blended, thereby can form luminescent layer.
Secondly, carry out fully, under nitrogen atmosphere, 240 ℃ temperature, carry out the formal curing of 30min in order to make curing.At last, adopt nitrogen gas-tight seal technology that led chip is covered in the aura box (glow box), so just obtained having the LED of the luminescent layer that comprises fluor.
Table 3 is the table look-up of the fluor of embodiment use.
Table 3
Be called for short Formal title Form Median size (μ m) Medium particle diameter (μ m) Glow color (400nm excites)
YAG With cerium activatory yttrium aluminum garnet (Y 0.79Gd 0.2Ce 0.01) 3Al 5O 12 3.8 6.4 Yellow
SAE With europium activatory strontium aluminate (Sr 0.9Eu 0.1) 4Al 14O 25 9 14 Blue-greenish colour
CCA-1 With europium activatory calcium chlorapatite (Ca 0.95Eu 0.05)(PO 4) 3Cl 15.9 18 Blue
CCA-2 With europium, manganese-activated calcium chlorapatite (Ca 0.94Eu 0.05Mn 0.01) (PO 4) 3 Cl 22 25 Blue
CCBE With europium activatory calcium chloroboric acid salt (Ca 0.9Eu 0.1) 2B 5O 9Cl 12 19.1 Blue
BAM With europium activatory barium magnesium aluminate (Ba 0.45Eu 0.25Sr 0.3)· MgO 5Al 2O 3 3.9 8.7 Blue
CESN With europium activatory calcium silicon nitride (Ca 0.97Eu 0.03) 2Si 5N 8 4.7 7.5 Red～orange
(long duration test)
Carry out the reliability of long duration test below with the light-emitting device of affirmation making.It is that 400nm, output rating are that 14.5mW, size on one side are the led chip of 350 μ m that long duration test is to use wavelength, makes its current work with 60mA at normal temperatures, to confirm weather resistance.At this moment, put into the rayed density of the luminescent layer of light-emitting device, if half of hypothesis light then is 86.3W/cm from the side output of chip -2About.In addition, junction temperature is about 80 ℃, and the thermal resistance value of whole housing is 230 ℃/W.The rayed density of sunlight is about 0.1W/cm in 14 Tokyo -2So by calculating, the energy density of irradiates light is about 863 times of sunlight.The result of this long duration test such as Figure 26～shown in Figure 28.
It is the long duration test result of the embodiment 1～4 of fluor that Figure 26 is to use YAG.About being coated with the fluor/colloidal sol of embodiment 1～4 allotment within the above-mentioned fluor/colloidal sol that carried out adjusting, the output rating that drops into after lighting a lamp before the some lantern test and through 1000 hours is compared, and the result does not find the degeneration of output rating fully.On the other hand, as a comparative example 1, use the LED of the fluor of silicon dioxide gel, its output rating then slowly reduces, and the output rating after lighting a lamp through 1000 hours is reduced to original 85%.In addition, in each figure, comparative example 2 is because the LED of 400nm and be not coated with fluor just can not confirm to have taken place degeneration certainly.
Figure 27 represents to use the long duration test result of the embodiment 5～8 of strontium aluminate fluor.Be coated with the fluor/LED of the fluor/colloidal sol of embodiment 5～8 allotment, its output rating after 1000 hours just as shown in Figure 27, embodiment 5 is 88%, embodiment 6 is 89%, embodiment 7 is 92%, embodiment 8 is 93%.Wherein be coated with embodiment 5 allotment fluor/colloidal sol fluor/LED just as shown in Figure 27, being reduced in when proceeding to 300 hours of the output rating that is caused by the degeneration of luminescent coating is reduced to 88%, but after this do not see the reduction of output rating, still kept 88% output rating at 1000 hours.
Moreover, Figure 28 represents the long duration test result of the embodiment 9～12 of three-wavelength white, wherein three-wavelength white is that the LED that will form the luminescent layer that contains each fluor of RGB with yttrium oxide colloidal sol combines, simultaneously, Figure 29 and Figure 30 represent the long duration test result of embodiment 13, embodiment 14 respectively.In these embodiments, be coated with allotment fluor/colloidal sol the output rating of fluor/LED after 1000 hours just as shown in Figure 28, embodiment 9 is 94%, embodiment 10 is 88%, embodiment 11 is 94%, embodiment 12 is 94%.In addition, embodiment 13 shown in Figure 29 is 94%, and embodiment 14 shown in Figure 30 is 96%.In addition, the output rating of fluor/LED after 1000 hours of fluor/colloidal sol that has been coated with embodiment 13 allotment of Figure 29 maintains 94%.
So, distinguished already that fluor/colloidal sol that the foregoing description makes allotment compared with the former fluor that uses silicon-dioxide etc., can obtain high weather resistance.And confirmed that as the luminescent film and the luminescent layer that use in 410nm or following wavelength region may be effective especially.In addition, in the time of will sending ultraviolet semiconductor light-emitting elements as luminous element, because condition is harsh more, thereby the mineral binder bond of above-mentioned embodiment utilization is effective.On the other hand, in luminescent layer, used the LED of resin and the fluor of use silicon-dioxide in the past, reach about 520nm even wavelength is long, also can produce degradation phenomena, by using the mineral binder bond of above-mentioned embodiment, even can obtain the long-time light-emitting device also more stable and that reliability is high that uses.In addition, in semiconductor light-emitting elements and combination that sticks on the fluor that forms on the element and the big luminous element of input electric weight, above-mentioned embodiment can be used effectively.Because in the big light-emitting device of input electric weight, the thermal value, the rayed density homenergic that act on luminescent layer are bigger, so former resin-bonded layer and silica dioxide gel are degenerated soon especially.In contrast, as above narrate, use generation that also almost can't see degeneration even the present embodiment is long-time, can obtain the light-emitting device that high-output power is maintained and reliability is high.
Embodiment 6
Serve as that basic light-emitting device with regard to embodiment of the present invention 6 describes with Figure 31～32 below.Figure 31 is the schematic plan view of the light-emitting device of expression embodiment 6, and Figure 32 (a) is the constructed profile of the light-emitting device of expression embodiment 6, and Figure 32 (b) is the constructed profile that amplifies the matrix recess.The lid 26 that the light-emitting device 1 of embodiment of the present invention 6 comprises luminous element 60, carries the matrix 20 of this luminous element 60 and form on this matrix 20.Side with carrying luminous element 60 is an interarea, and its reverse side is called the back side.
Matrix 20 is made of metal, and portion has recess 20a in the central.In addition, be that basis pontis has 2 communicating poress that connect thickness direction around recess 20a, communicating pores clamping separately described recess 20a and is provided with in opposite directions.Metal system lead-in wire electrode 22 positive and that bear is inserted in respectively in this communicating pores across the hard glass as insulating component 23.In addition, have the lid 26 of the lead-in wire 24 that comprises light transmission window portion 25 and constitute by metal part, and the contact surface of metal lead-in wire 24 and metal matrix 20 is welded together in the interarea side of metallic matrix 20.By welding matrix 20 and lid 26, this luminous element 60 is just by airtight.Airtightly can use inactive gases such as nitrogen.The luminous element 60 that is housed in the recess 20a is to send blue light or ultraviolet luminous element, and luminous element 60 is bonded in the recess 20a of matrix 20.As an example of this binding agent, the operable material that has hydrating solution with tetraethyl silicate to carry out dry and sintering and obtain.Being carried on the mineral binder bond 30 that luminous element 60 in the recess 20a of matrix 20 contained fluor covers.The surface of this mineral binder bond 30 is covered by resin 40.
For light-emitting device 601, in specific metallic element,, under gel state, can not cause the reduction that light takes out efficient even do not improve crystallinity yet, by solvent impregnated resin 40 in mineral binder bond 30, can provide a kind of light to take out the high light-emitting device of efficient.Especially, the gel of hydrous oxides such as Al that the state of oxidation is stable if use variation that valence mumber can not take place in the sol gel reaction process and Y element, even some is in gel state in then filming, also form luminescent film, can not can proceed sol gel reaction and can take out high the filming of efficient with short period of time, the low-yield light that easily obtains by further solvent impregnated resin.
In addition, constitute mineral binder bond 30, can improve the quality of filming of formation by the gel that adopts hydrous oxide.Contain the mineral binder bond member of hydrous oxide, its particle-like substance is assembled by sol-gel method, thereby becomes the porous insert that is formed with crosslinking structure, reticulated structure or polymer architecture.If the skeleton structure of the particle assembly of hydrous oxide is the reticulated structure with hole, then because be porous structure and can improve the flexibility of filming.In addition, mineral binder bond 30 is when film forming, even appendix filler members such as fluorophor particle, simultaneously coated object shapes complexity also can adapt therewith and carry out film forming, can obtain to be rich in close-burning filming.Moreover, owing to be hydrous oxide, thereby can obtain stable and stay-in-grade film to light and heat.
What form in the light-emitting device films because expose to the open air in coming from the light of luminous element, so produce degeneration by the use of light-emitting device in the past.Reason that it is generally acknowledged this degeneration is: cause the generation of reacting because of any or both among the optical output power that comes from luminous element and the heating.Therefore, when the ultraviolet ray that luminous energy is high is used to generate heat and thermal impedance is big large-scale element, just be easy to generate degeneration.In contrast, as the back narrate, the sample of making embodiments of the invention has carried out long duration test, results verification has high patience.The light-emitting device of embodiment of the present invention 6 has following formation, and the member of formation with regard to the present embodiment is elaborated with reference to the accompanying drawings.
(mineral binder bond)
The luminous element 20 that is arranged on the matrix 20 is covered by mineral binder bond 30.By means such as pouring, cast and spraying sprayings the mineral binder bond 30 that is in collosol state is entered in the recess 20a of matrix 20, thereby make the surface and the recess 20a of its covering luminous element 60.In this mineral binder bond 30, contain fluor 50.
Mineral binder bond 30 spray or pouring, silk screen printing after, because of gelation is solidified.This curing causes producing space 31 in mineral binder bond 30.Because the existence in this space, mineral binder bond 30 becomes fragile and cracks and defective.
Except that mold member, mineral binder bond 30 is arranged in the cover body of pin leads and waits the place in the peristome of matrix, be contain to the luminous fluor of changing of luminous element 60 and to fluor carry out agglutinating material etc. layer.About the layer of mineral binder bond 30, its on luminous element 60, the thickness of the layer of the mineral binder bond 30 that is provided with of the thickness of the layer of the mineral binder bond 30 that is provided with of side and inner face at recess 20a about equally.In addition, even mineral binder bond 30 is not interrupted in the part in the bight of luminous element 60 yet, the layer of mineral binder bond 30 is successive.
Because the reflection that matrix 20 and lead-in wire 21 grades produce, the high energy light that sends from luminous element 60 etc. becomes high-density mineral binder bond 30.Moreover, also producing diffuse-reflectance by fluor 50, mineral binder bond 30 exposes to the open air sometimes in highdensity high energy light.Therefore, when luminous intensity is big, as can to send high energy light nitride semiconductor during, preferably will there be any hydrous oxide of metallic element sunproof, that contain among Al, Y, Gd, Lu, Sc, Ga, In, the B to be used to these high energy lights as inorganic adhesive 30 as luminous element 60.
As one of concrete main material of mineral binder bond 30, what be fit to use has at Al (OH) 3, Y (OH) 3Etc. the material that contains fluor in the light transmission inorganic structures.Fluor 50 bonds by means of these light transmission inorganic structures each other, and fluor 50 on luminous element 60 and support, be piled into stratiform and with it the bonding.In the present embodiment, hydrous oxide is formed by the compound based on following hydrous oxide, and the hydrous oxide that wherein becomes main body is formed by any the organometallic compound among Al, Y, Gd, Lu, Sc, Ga, In, the B.At this, so-called organometallic compound comprises by the alkyl of Sauerstoffatom and metal link and aryl.As such organometallic compound, for example can list metal alkylide, metal alkoxides, two diketo metal and metal carboxylate etc.In such organometallic compound, the compound strong to organic solvent dissolution becomes uniform sol solution easily after hydrolysis.In addition, chemical reaction such as hydrolysis is because take place easily in such organometallic compound, so disperse everywhere easily, can form and makes fluor 50 be able to agglutinating mineral binder bond 30.Therefore, the method of using organometallic compound is with under 350 ℃ or above temperature or to apply under the electrostatic state on luminous element 60 other method of formation mineral binder bond 30 different, can not reduce as the performance of luminous element and can easily on luminous element 60, form mineral binder bond 30, thereby the production qualification rate is improved.
Mineral binder bond 30 is preferably formed the layer structure into filminess.This be because: by forming a layer structure, the fluor 50 that contains in the mineral binder bond 30 can be luminous equably.In addition, owing to be filminess, resin 40 soaks into mineral binder bond 30 easily.As the means of the layer that forms mineral binder bond 30, can adopt pouring means or spraying spraying means.But mineral binder bond 30 also can adopt the form beyond the filminess.
Mineral binder bond 30 can use aluminum oxide, yttrium oxide, silicon-dioxide or their mixture etc.They also are dispersed in water etc. by solid state, form the sol-gel state, can form various shapes thus.In addition, fluor is dispersed in the mineral binder bond 30.Below aluminum oxide, yttrium oxide are described as the example of mineral binder bond 30, but the present invention is not limited thereto.
In addition, in filming, use the binding agent of inorganic system in the past.Under the situation of the binding agent that uses this inorganic system, using by silica dioxide gel (SiO especially 2) under the situation of the cured film that forms, when exposing to the open air in high-output power and ultraviolet environment, exist colour deterioration and produce the problem of melanism.Special in the light-emitting device of high-output power, because of high light intensity and the hot degeneration that causes the silica binder layer, and be coloured to black or chocolate.The result that the present inventor studies can infer that its reason is: SiO 2Be damaged the generate SiO of silicon-dioxide because of oxygen X(x＜2).Silica binder is in SiO under 250 ℃ or following heat curing temperature 2The state of the silica dioxide gel of remaining a part of hydroxyl, organic group in the skeleton.In the state of such silica dioxide gel,, will produce the damaged of oxygen, thereby make SiO when by the highdensity light time of LED incident 2Become SiO X(x＜2).So because Si is easy to generate redox, so it is generally acknowledged that silica dioxide gel produces oxygen damaged be the reason of colour deterioration.In case producing colour deterioration, will produce the problem of the optical output power decline that comes from luminous element.In addition, the binding agent of inorganic system also has existence because of the space and is easy to generate such problem a little less than crackle and defective, the shock-resistance.Can think that this is that it lacks shock-resistance because the binding agent of inorganic system is different with resin.
(aluminum oxide)
Amorphous alumina or micropartical hydrated aluminum oxide are dispersed in the water, and the alumina sol that will form like this is as binding agent, in this case, before solidifying to form to hydrated aluminum oxide, experience the stage of a pseudo-boehmite structure at heated oxide aluminium colloidal sol with stable boehmite structure.The boehmite crystalline texture of hydrated aluminum oxide and the pseudo-boehmite structure of hydrated aluminum oxide can be used chemical formula AlOOH or Al respectively 2O 3H 2O and (AlOOH) xH 2O or Al 2O 32H 2O waits and represents.Specifically, get Al as intermediate 2O 32H 2O, Al 2O 3XCH 3COOHyH 2O, Al 2O 3XHClyH 2O, Al 2O 3XHNO 3YH 2Forms such as O form stable boehmite structure at last.Further improve the crystallinity of boehmite structure, then become gama-alumina (Al 2O 3) or Alpha-alumina (Al 2O 3).The alumina sol that will have such character is as binding agent, thus the formation luminescent film.
Concrete main material as mineral binder bond 30, can use the sol solution of preparation as follows, be stablizer promptly, amorphous metal oxide compound, ultramicron hydrous metal oxides and oxide ultrafine particle thing etc. are dispersed in water or the organic solvent with a spot of mineral acid, organic acid and alkali.As the initial feed of synthetic amorphous metal oxide compound, ultramicron hydrous metal oxides and oxide ultrafine particle thing etc., utilizable have: the hydrolysate of metal alkoxides, two diketo metal, metal halide or metal carboxylate, metal alkyl compound and their are mixed after the product that is hydrolyzed.In addition, also can use metal hydroxides, metal chloride, metal nitrate and metal oxide microparticle are dispersed in colloid (colloidal sol) solution prepared in the mixed solvent of water and organic solvent or water and water-miscible organic solvent.They are generically and collectively referred to as aikyiaiurnirsoxan beta.The repeating unit that has [AlO] x in the skeleton of aikyiaiurnirsoxan beta.
As metal alkoxides, utilizable have: aluminum methoxide, aluminum ethoxide, positive propoxy aluminium, aluminum isopropoxide, n-butoxy aluminium, aluminium-sec-butylate, aluminum isopropoxide, tert.-butoxy aluminium, methoxyl group yttrium, oxyethyl group yttrium, positive propoxy yttrium, isopropoxy yttrium, n-butoxy yttrium, sec-butoxy yttrium, isopropoxy yttrium, tert.-butoxy yttrium etc.
As two diketo metals, utilizable have: aluminium tris(ethylacetoacetate), alkyl etheric acid diisopropoxy aluminium, ethyl acetoacetic acid diisopropoxy aluminium, the two ethyl acetoacetic acid aluminium of monoacylphosphine pyruvic acid, triacetyl pyruvic acid aluminium, triacetyl pyruvic acid yttrium and triethyl etheric acid yttrium etc.
As metal carboxylate, utilizable have: Burow Solution, propionic acid aluminium, 2 ethyl hexanoic acid aluminium, acetic acid yttrium, propionic acid yttrium and 2 ethyl hexanoic acid yttrium etc.
In addition, as metal halide, utilizable have: aluminum chloride, aluminum bromide, aluminum iodide, Yttrium trichloride, yttrium bromide and yttrium iodide etc.
As organic solvent, utilizable have: methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, sec-butyl alcohol, the trimethyl carbinol, tetrahydrofuran (THF), diox, acetone, ethylene glycol, methylethylketone, N, dinethylformamide and N,N-dimethylacetamide etc.
In mineral binder bond 30, also can sneak into filler and diffusion particle to replace fluor 50, perhaps except that fluor 50, can also sneak into filler and diffusion particle.Moreover, as their matrix material, the linear expansivity of coated substrates and luminous element is consistent.As filler, sneak into fluor 50 and produce luminously from needless to say, also produce the fine path of moisture evaporation when solidifying etc. simultaneously, have the curing exsiccant effect of accelerating binding agent.In addition, also have the cohesive strength of mineral binder bond 30 and the effect of physical strength are come, increased in the luminous diffusion of fluor 50.In addition, the layer of mineral binder bond 30 and the film of mineral binder bond 30 also can be used as the diffusion layer that does not contain fluor and are used.In addition, in the matrix material that is used as binding agent, except that 3 valency metallic elements, also can contain element on a small quantity with multiple valence mumber.Moreover in the present embodiment, the binding agent member can comprise hydrous oxide as main compound, also can play a role even comprise a part of metal oxide and metal hydroxides and their combination.
As the concrete main material that contains in the mineral binder bond 30, the AlOOH with aluminum oxide is that example describes below.
(AlOOH)
By AlOOH the mineral binder bond 30 that fluor 50 bondings form is formed by the following method, promptly in organic solvent, make alkyl aluminium alcoholates or aluminum alkoxide hydrolysis with predetermined ratio, in the aikyiaiurnirsoxan beta colloidal sol or alumina sol solution that hydrolysis obtains, make fluor 50 (powder) homodisperse and obtain coating fluid, adjust this coating fluid and with the pouring, the mode of spraying or spreading applies the alumina sol solution that this fluor 50 is dispersed, thereby make it to cover whole luminous element 60, heat then and solidify, thereby by the AlOOH composition fluor is fixed each other, and be fixed on the surface of luminous element 60.
Alkyl aluminium alcoholates or aluminum alkoxide are the organo-aluminium compounds that tackifier, gelating agent, solidifying agent, polymerizing catalyst and the dispersing of pigments agent as coating used.
As aluminum isopropoxide, aluminum ethoxide and the butoxy aluminium reactivity as rich as Croesus of one of alkyl aluminium alcoholates or aluminum alkoxide, generate aluminium hydroxide or aluminum alkyls hydrochlorate by means of airborne moisture, generate hydrated aluminum oxide with boehmite structure.For example aluminum isopropoxide shown in following chemical formula 8 like that, react with water easily, finally to become with the hydrated aluminum oxide be principal constituent, have the mixture that carries out crosslinked crosslinking structure with aluminium hydroxide or aluminum oxide (alumina).
Figure C200480006816D00731
Chemical formula 8
Therefore, after making aluminum isopropoxide and airborne reaction of moisture, the AlOOH bonding fluor 50 that adopts heating to generate, thus the mineral binder bond 30 that is formed by the AlOOH bonding fluor 50 that contains fluor 50 can be formed on the surface of luminous element 60 as mineral binder bond 30 and on the support beyond the surface of luminous element 60.
More than the mineral binder bond 30 that forms by AlOOH bonding fluor 50, also can make up mineral binder bond 30 that forms by other hydrous oxide bonding fluor 50 such as Y, Gd, Lu, Sc, Ga, In, B and the mineral binder bond 30 that forms by AlOOH bonding fluor 50, thereby on same luminous element 60, form the layer more than 2 kinds or 2 kinds.According to the formation method of the mineral binder bond 30 of the employing of the present embodiment spraying spraying means, because also can control two-layer thickness, so can form the mineral binder bond 30 of same shape easily.For example on same luminous element 60, at first form Y 2O 3Mineral binder bond 30 forms Al then thereon 2O 3Mineral binder bond 30.At this, fluor 50 can be included among the two-layer both sides, also can only be included in one deck, and can not comprise among two-layer both sides.If adopt such formation, the size that then has the specific refractory power by mineral binder bond 30 is taken out effects such as efficient to improve light.When forming the mineral binder bond 30 that constitutes by one deck, the then rapid variation that produces specific refractory power at this mineral binder bond 30 and the interface of extraneous atmosphere or nitride semiconductor luminescent element, the part of the light that takes out from luminous element 60 may reflect at this interface, thus cause light take out efficient lowly.In addition, by forming the mineral binder bond 30 that for example is mixed with AlOOH and YOOH, also can adjust linear expansivity and specific refractory power.
The mineral binder bond 30 that the AlOOH bonding fluor 50 that is formed by such forms, because it is different with situation about sealing with Resins, epoxy in the past only and be inorganics, so compare with Resins, epoxy, minimum by UV-induced degeneration, also can be used in combination the luminous element that sends UV-light and power type luminous element of high-output power etc.
(yttrium oxide)
Amorphous oxidation yttrium or micropartical yttrium oxide are dispersed in the water, and the yttrium oxide colloidal sol that will form like this is as mineral binder bond 30, in this case, even be heating and curing yttrium oxide colloidal sol, the main body of crystalline texture also is amorphous.Aqua oxidation yttrium and yttrium oxide can be used YOOHxH respectively 2O and Y 2O 3XH 2Chemical formulas such as O are represented.Specifically, as intermediate, through YOOHxCH 3COOHyH 2O or Y 2O 3XCH 3COOHyH 2The form of O forms the form that part contains aqua oxidation yttrium or yttrium oxide at last.Even yttrium oxide also can form stable film under such gel state.It is generally acknowledged that its reason is that composition separately has crosslinking structure, can realize stabilization.
Yttrium oxide is compared with aluminum oxide, has the character that is difficult to form crystalline texture.So, even the unbodied non-crystal structure of the crystallinity of not signing an undertaking also can be stable compound, Y keeps 3 valencys constant and the variation of valence mumber can not take place.The strong point that promptly has is to be difficult to take place redox reaction, is not having colour deterioration.
About other, then be to be made like mineral binder bond 30 with above-mentioned aluminum oxide.As above narrate, the colloidal sol that fluor is used as binding agent, also can utilize commercially available inorganic be binding agent and vitrified bond etc.In addition, in can be used as the material that binding agent is used, be not limited to the hydrous oxide that contains Al and Y element of aluminum oxide and yttrium oxide and so on, also can utilize other the IIIA family element and hydrous oxide, oxide compound and the oxyhydroxide etc. of IIIB family element.Valence mumber preferably can not take place the metallic element of selecting changes.Especially, preferably show as 3 valencys and stable metallic element.In addition, also preferably water white.For example except that Al and Y, the metallic compound of metallic elements such as comprising Gd, Lu, Sc, Ga and In can also be utilized, preferably Sc and Lu can be utilized.Perhaps also can utilize composite oxides and the composite hydrous oxide that these multiple elements are made up.Singly be not aluminium and yttrium, the hydrous oxide by containing other III family element etc. also can be controlled to be desirable value with the various characteristics of rerum natura of films such as the flexibility of optical property such as the specific refractory power of the layer of mineral binder bond 30 and film, cohesiveness and so on.So, have that valence mumber is constant, the mineral binder bond 30 of the hydrous oxide gel that is preferably 3 valencys by embodiment of the present invention containing of obtaining, can design stable, light and take out the good mineral binder bond 30 of efficient.In addition, owing to constitute, therefore can make time-independent, stable mineral binder bond layer and mineral binder bond film with inorganic materials.
(resin)
Resin coating is covered with the surface of mineral binder bond 30.This is filmed and forms the layer of resin 40 on the surface of the layer of mineral binder bond 30.But also can allow resin 40 be filled in the matrix 20 with recess 20a, and be covered with mineral binder bond 30.In addition, though can adopt the whole bag of tricks, preferably with resin 40 dipping mineral binder bonds 30.So-called dipping is meant in mineral binder bond 30 immersions and comprises resin 40.
When the viscosity of the resin 40 before solidifying was too high, resin flows was not got up, and can not form uniformly to film.In contrast, the viscosity of the resin 40 before solidifying is crossed when hanging down, and resin is trapped in low-lying part, and protuberance does not have the residual of resin, can not form uniformly to film.Therefore, preferred use is the resin with predetermined viscosity.
Resin 40 is preferably a layer structure.By being designed to a layer structure, can seek the light that sends from luminous element 60 taking-up efficient raising and directive property controlled.In addition, the heat that is produced by luminous element 60 can not be accumulated in the resin 40 and can be discharged into the outside.
Resin 40 is preferably gel.The stress that produces by thermal expansion can be relaxed by gel, thereby the cut-out of the lead-in wire 21 that extends out by luminous element 60 can be prevented.In addition, resin 40 also can be oily.
The surface that covers the resin 40 of mineral binder bond 30 is level and smooth.If only mineral binder bond 30 is solidified, when then using its surface of electron microscope observation, can see that many granulous are concavo-convex.For this reason, the light that sends from luminous element 60 reflects in the concavo-convex generation of this granulous, perhaps produces scattering, suppresses the taking-up of light.Therefore, by surface coverage resin 40, can make the surface of resin 40 become level and smooth at this mineral binder bond 30.Can make light that luminous element 60 sends effectively to external emission thus, thereby can seek the raising that light takes out efficient.In addition, concavo-convex because the surface of mineral binder bond 30 is formed with granulous, increase with the surface-area of resin 40, thereby have the effect that increases sticking power etc. at the interface of resin 40 and mineral binder bond 30.
The gas containing ratio of resin 40 is 3 volume % or following under normal pressure.Be preferably 1 volume % or following, more preferably 0.01% volume or following.In the space 31 that mineral binder bond 30 is had, contain gases such as air.This gas is discharged into the outside when solvent impregnated resin 40.At this moment, resin 40 in the surface coverage of mineral binder bond 30, thus the gas in the space 31 also be dissolved in sometimes in the resin 40 because this gas dissolving is in resin 40, so contain gas in resin 40.The gas that contains in this resin 40 is accompanied by the excitation of luminous element 60 and generates heat, because of heating produces thermal expansion, because of thermal expansion produces bubble sometimes in resin 40.Because the effect of this bubble, the light that sends from luminous element 60 produces reflection sometimes, thereby causes light to take out the reduction of efficient.Therefore, the gas volume that contains in the resin 40 is preferably few as best one can.The material of resin 40 is the materials that permeate in mineral binder bond 30, preferably has good thermotolerance, photostabilization and weather resisteant.Since the heating of luminous element 60 reach 120 ℃ or more than, extreme temperatures is so resin 40 must be the heat-resistant resin that can bear this temperature.In addition, resin 40 be because will be subjected to the irradiation of the high light of luminous intensities such as blue light or ultraviolet ray and it is passed through, thereby must be sunproof resin.On the other hand, preferred water-absorbent, resin that moisture absorption is low.Under the situation of using water-absorbent, resin that moisture absorption is high, the moisture in this resin makes the water vapour outburst because of the heating of luminous element 60, produces at the interface of luminous element 60 and mineral binder bond 30 or resin 40 and peels off, and takes out the low of efficient thereby cause light.Therefore, use water-absorbent, the resin that moisture absorption is low preferably do not contain moisture in this resin 40.
Organic system resin material as dipping in the layer of the mineral binder bond 30 of the fluor 50 that boning can list silicone resin, acrylic resin and Resins, epoxy etc.Material as resin 40 is preferably silicone resin.
Silicone resin has chemical property stable properties such as thermotolerance, weather resisteant, photostabilization.Silicone resin is made of the Si-O-Si skeleton.Because the bound energy of the siloxane bond of Si-O is bigger, thus be stable, and to all having the good transparency from the light that can see ultraviolet.Therefore, it is generally acknowledged, thereby be difficult to produce degeneration because resin 40 itself does not absorb these light.In addition, the surface tension of silicone resin is little, and viscosity is also low, and superior permeability can be penetrated into the fine part in the mineral binder bond 30 equably.Silicone resin has addition curable, UV curing, condensation reaction type, UV cationic polymerization type, wherein preferred addition curable.This be because: addition curable does not almost have volatile component in resin, produce volumetric shrinkage after the thermofixation hardly.Because do not produce volumetric shrinkage, so can not produce the crackle that causes because of volumetric shrinkage.In addition, can not peel off at the interface of resin 40 and mineral binder bond 30.Resin 40 is not owing to almost there is volatile component, so under situation about being used as airtight matrix, do not worry causing because of the rising of the internal pressure that accompanies with the heating of luminous element 60 breakage of matrix.Resin 40 preferably, the resin state after the curing is soft gel or the lower rubber of hardness for the hard state.Because resin 40 exists with soft state, thereby can relax stress and the external pressure that is acted on resin 40 by heat, impact etc., and the flexibility of resin 40 is improved.For example, resin 40 can use the silicone resin with dialkylsiloxane skeleton before shaping or under any situation after being shaped.Have structures such as gel, rubber-like after silicone resin is crosslinked.Especially, resin 40 preferably has the main chain of dimethyl siloxane before shaping.But be not limited to dimethyl siloxane, also can use the phenyl methyl siloxanes.
Mineral binder bond 30 is not oxide crystallization and polycrystalline completely in advance, but preserves with the porous gel state.Especially, soft heat operation etc. be because need apply the stress that is acted on mineral binder bond 30 by thermal shocking, thereby when dipping silicone resin 40 etc., cause owing to silicone resin 40 is different with the thermal expansivity of mineral binder bond 30 ftractureing and peeling off.
Porous matter gel is owing to form crosslinking structure, reticulated structure or polymer architecture, so thermal expansivity be big than crystallization, polycrystalline state, owing to approach the thermal expansivity of silicone resin, thereby can not produce and ftractures and peel off.
When adopting condensed type resin 40 to be cured, will produce the small molecules composition.At this moment, volumetric shrinkage takes place in resin 40, produces be full of cracks in mineral binder bond 30, and peels off in the mineral binder bond 30 and the contact surface generation of fluor 50.
UV gel-type resin 40 is because imported the ultraviolet organo-functional group of absorption, so resin 40 takes out the reduction of efficient because of the light that absorbs exciting light and generation causes light.
(filler)
The filler (not shown) is exactly a weighting agent, and utilizable have: barium titanate, titanium oxide, aluminum oxide (aluminium sesquioxide), yttrium oxide (yttrium oxide), silicon oxide, lime carbonate and other hydrous oxide etc.For example, also can have with respect to comprising the colourless hydrous oxide that is selected from one or more elements among Al, Ga, Ti, Ge, P, B, Zr, Y or the alkaline-earth metal at least or comprising the oxide compound that is selected from one or more elements among Si, Al, Ga, Ti, Ge, P, B, Zr, Y or the alkaline-earth metal at least and have the more filler of high heat-conduction coefficient.By adding such filler, the heat extraction effect of light-emitting device 601 is improved.As such filler, when carrying out chips welding, can list metal powders such as aluminum oxide, Ag at the above-mentioned mineral binder bond 30 formation tack coats of employing and to luminous element 60.
In the colloidal sol of mineral binder bond 30, except that fluor 50 and lower alcohol,, can be when solidifying form filming of densification at low temperature with the azeotropic dehydration of lower alcohol by prior mixed dispersant.In addition, also can in mineral binder bond 30, contain Photostabilised material, tinting material and UV light absorber etc.
Mineral binder bond 30 usefulness slurry solutions form.Slurry solution is that modulation forms like this, be main component promptly with amorphous metal hydrous oxide, micropartical hydrous metal oxides and metal hydroxides, be dispersed in the water with this main component and then with amorphous metal oxide compound, micropartical metal oxide, make sol solution thus, then in this sol solution, mixing phosphor 50 and filler.The effective solids component in effective solids component in the sol solution and the weight ratio of fluor 50 or the sol solution and the weight ratio of fluor 50 and filler mixture are preferably 0.05～30.For example can be from effective solid component concentration is that to be 90g adjust in the ratio ranges that effective solid component concentration is 15% sol solution with respect to 600g, fluor is 4.5g for 15% sol solution, fluor with respect to 20g.
(luminous element)
Luminous element 60 is not limited to send the luminous element of visible light, also can use the luminous element that can send UV-light.In addition, luminous element 60 can be used in combination with fluor 50.That is to say that the rayed fluor 50 that will be sent by luminous element 60 excites fluor 50, just can send the light different with luminous element 60.Luminous element 60 adopts methods such as MOCVD, forms semi-conductors such as GaAs, InP, GaAlAs, InGaAlP, InN, AlN, GaN, InGaN, AlGaN, InGaAlN as luminescent layer on substrate.As semiconductor structure, can list homogeneous junction structure, heterojunction structure or double-heterostructure with MIS knot, PIN knot and PN junction etc.Can carry out various selections to emission wavelength according to the material and the mixed crystal degree thereof of semiconductor layer.In addition, also can be set at single quantum or the multiple quantum trap structure that on the film that produces the quantum effect, is formed with the semiconductor active layer.Preferably efficiently excited fluophor and can send efficiently wavelength the nitride-based compound semiconductor of short light (general formula is In iGa jAl kN, wherein, 0≤i, 0≤j, 0≤k, i+j+k=1).
Gallium nitride compound semiconductor is being used as under the situation of luminous element 60, and the material that is suitable for use as semiconductor substrate has: sapphire, spinel, SiC, Si, ZnO, GaN etc.In order to form the good gan of crystallinity, more preferably use sapphire substrate.When growing semiconductor film on sapphire substrate, be preferably formed buffer layers such as GaN, AlN after, on buffer layer, form gallium nitride semiconductor again with PN junction.In addition, also can be with GaN monocrystalline itself as substrate, wherein the GaN monocrystalline is with SiO on sapphire substrate 2Select to grow for mask and form.In this case, after each semiconductor layer forms, also can and remove SiO by etch 2And luminous element is separated with sapphire substrate.Gallium nitride compound semiconductor shows n type electroconductibility under plain situation.Comprise in formation under the situation of the n type gallium nitride semiconductor that improves requirements such as luminous efficiency, as n type doping agent, the preferred elements such as Si, Ge, Se, Te and C that suitably import.On the other hand, under the situation that forms p type gallium nitride semiconductor, then mix as Zn, Mg, Be, Ca, Sr and the Ba etc. of p type doping agent.
If gallium nitride compound semiconductor is the doped p type doping agent just, then be difficult to realize the p typeization, so after importing p type doping agent, preferably adopt the method for stove heating, low-velocity electron beam irradiation and plasma irradiating to anneal, realize the p typeization thus.Layer as concrete luminous element constitutes, adducible suitable examples is by following folded layer by layer forming, promptly have in being formed with under the low temperature on the sapphire substrate or silicon carbide of buffer layers such as gan, aluminium nitride, stacked n type contact layer as gallium nitride semiconductor, as the semi-conductive n type of aluminium gallium nitride alloy covering, as the semi-conductive active coating of the InGaN of doping of Zn and Si, as aluminium gallium nitride alloy semi-conductive p type covering and as the p type contact layer of gallium nitride semiconductor.In order to form luminous element 60, situation for luminous element 60 with sapphire substrate, by formation p N-type semiconductorN such as etch and n N-type semiconductorN expose face after, each electrode that on semiconductor layer, uses formation such as sputtering method and vacuum vapour deposition to have the shape that requires.For the situation of SiC substrate, utilize the electroconductibility of substrate itself also can form pair of electrodes.
Then the semiconductor wafer that forms etc. is carried out scribing, scribing or the directly cutting fully of adopting dicing saw to carry out, wherein the blade of dicing saw has Buddha's warrior attendant blade made of stones, blade rotation during cutting; Or after cutting out the groove wideer, utilize external force to separate semiconductor wafer than blade width.Perhaps the dicing saw that does reciprocating linear motion by means of vertical diamond needle marks superfine line (warp) on semiconductor wafer, for example is divided into reticulate pattern, utilizes external force to separate wafer then, thereby cuts into shaped like chips by semiconductor wafer.Like this, just, can form luminous element 60 as nitride-based compound semiconductor.
In the light-emitting device 601 of the present embodiment, under luminous situation, consider and the glow color complementation of fluor that the main light emission wavelength of luminous element 60 is preferably 350nm～530nm.
In addition, luminous element also comprises being used to obtain by produce luminous of vacuum discharge and the luminous element that produced by thermoluminescence except that semiconductor light-emitting elements.For example, the element that produces ultraviolet ray etc. by vacuum discharge also can be used as luminous element.In embodiments of the invention, as the luminous element that is utilized, its wavelength is 550nm or following, is preferably 460nm or following, 410nm or following more preferably, but the present invention is not limited thereto.Especially, as the back narrate, the advantage that embodiments of the invention had is: weather resistance is good, can be suitable for the big power type luminous element of output rating.
The following describes the example of III group-III nitride based semiconductor light-emitting device as luminous element 60.Luminous element 60 for example is on sapphire substrate, stacks gradually the formed stepped construction of following layer across the GaN buffer layer, and these layers are followed successively by: the 1n type GaN layer that do not mix Si or Si concentration are low; The n type contact layer that constitutes by doping Si or the higher n type GaN of Si concentration ratio 1n type GaN layer; Do not mix or the lower 2GaN layer of Si concentration ratio n type contact layer; The luminescent layer of multiple quantum trap structure (quantum well structure of GaN blocking layer/InGaN trap layer); By the p covering that P type GaN constitutes, wherein P type GaN is made of the P type GaN of doped with Mg; The P type contact layer that constitutes by the P type GaN of doped with Mg.And by following method formation electrode.Certainly, also can use the luminous element that is different from this formation.
The p Ohmic electrode almost forms on whole of p type contact layer, forms the p pad electrode on this P Ohmic electrode of a part.
In addition, remove the part that the 1GaN layer exposes n type contact layer by etch from P type contact layer, the n electrode just forms on this exposed portions serve.
In addition, the present embodiment is used the luminescent layer of multiple quantum trap structure, but the present invention is not limited thereto, for example utilize the single quantum of InGaN and multiple quantum trap structure can, also can utilize the GaN of doping Si and Zn.
In addition, the luminescent layer of luminous element 60 can change main glow peak by changing the content of In in the scope of 420nm～490nm.And emission wavelength is not limited to above-mentioned scope, can use the luminous element of emission wavelength as 360nm～550nm.Especially, when light-emitting device of the present invention is applicable to the ultraviolet leds light-emitting device, the absorption efficiency of conversion of exciting light can be improved, seeing through of UV-light can be reduced.
(fluor)
The visible light that fluor 50 will send from luminous element 60 and UV-light are converted to luminous with luminous element 60 different emission wavelengths.For example, use the light that sends from the semiconductor light emitting layer of luminous element 60 to excite and luminous.As preferred fluor, utilizable have: be oxynitriding system such as fluor for example yttrium aluminum garnet (hereinafter referred to as " YAG ") is, alkali earths silicon nitride fluor etc. is nitride based, alkali earths oxidized silicon nitride fluor etc. with Ce activatory rare earth class garnet at least.In the present embodiment, as fluor 50 uses are the fluor that produced the light of predetermined color by ultraviolet excitation.Specifically, utilizable fluor is exemplified below:
(1)Ca 10(PO 4) 6FCl:Sb，Mn
(2) M 5(PO 4) 3Cl:Eu (wherein: M has at least a alkaline-earth metal that is selected among Sr, Ca, Ba and the Mg)
(3)BaMg 2Al 16O 27:Eu
(4)BaMg 2Al 16O 27:Eu，Mn
(5)3.5MgO·0.5MgF 2·GeO 2:Mn
(6)Y 2O 2S:Eu
(7)Mg 6As 2O 11:Mn
(8)Sr 4Al 14O 25:Eu
(9)(Zr、Cd)S:Cu
(10)SrAl 2O 4:Eu
(11)Ca 10(PO 4) 6ClBr:Mn，Eu
(12)Zn 2GeO 4:Mn
(13)Gd 2O 2S:Eu
(14)La 2O 2S:Eu
(15)Ca 2Si 5N 8:Eu
(16)Sr 2Si 5N 8:Eu
(17)SrSi 2O 2N 2:Eu
(18)BaSi 2O 2N 2:Eu
(19) M 2SiO 4: Eu (wherein: M has at least a alkaline-earth metal that is selected among Sr, Ca, Ba and the Mg)
In addition, except that above-mentioned fluor, can also utilize produce yellow area luminous, with (Y, Gd) 3(Al, Ga) 5O 12: the rare earth class aluminate of expressions such as Ce is that YAG is a fluor.
When the light that sends when luminous element 60 becomes complementary color relation etc. with the light that fluor 50 sends, by will light colour mixture separately just sending the light of white.As the combination of the luminous element 60 that sends white light with fluor 50, specifically, can list light that luminous element 60 sends and by this optical excitation the light of luminous fluor 50 is equivalent to the situation of 3 primary colors (red colour system, green system, blue system) and blue light that luminous element 60 sends respectively and the sodium yellow of luminous fluor by this optical excitation.Particularly use under the situation of UV-light at luminous element 60, because glow color is only decided by the glow color of fluor 50, thereby the light-emitting device of various middle shade such as the blue-greenish colour used of picked up signal, yellowish red color, redness etc. and light color also is possible.
By mineral binder bonds such as the various resins that play a role as the binding agent between fluor 50 and the fluor 50 and glass, the ratio with filler etc., the settling time of fluor 50, the shape of fluor etc. being carried out various adjustment and the emission wavelength of led chip is selected, the glow color of light-emitting device 601 can provide the tone of white color system arbitrarily such as bulb color.In the outside of light-emitting device 601, the light that preferred luminous element 60 sends and and the light that sends of fluor 50 see through mold member effectively.
As representational fluor 50, can list with copper activatory Cadmium Sulfide zinc and be fluor with cerium activatory YAG.Especially in high briliancy and when using for a long time, (Re preferably 1-xSm X) 3(Al 1-yGa y) 5O 12: Ce (0≤x＜1,0≤y≤l, wherein: Re be selected from least a element among Y, Gd, La, Lu, Tb and the Pr=.
(Re 1-xSm X) 3(Al 1-yGa y) 5O 12: the Ce fluor is because be garnet structure, so heat, light and moisture are had very strong patience, the excitation spectrum peak can reach about 470nm.In addition, also may have wide luminous spectrum, its glow peak is near 530nm, and the end at peak extends to the 720nm place.
In the light-emitting device 601 of the present embodiment, fluor 50 also can be that two or more fluor mix.Promptly can be with the different (Re of content of two or more Al, Ga, Y, La, Lu, Tb, Pr and Gd and Sm 1-xSm X) 3(Al 1-yGa y) 5O 12: the Ce fluor mixes, thereby increases the wavelength components of RGB.In addition, use nitride phosphor with Huang～emitting red light etc. to increase red composition, also can obtain on average to drill the light-emitting device of high illumination of look evaluation number or bulb color etc.Specifically, the emission wavelength of the luminous element that is mixed, the content of the fluor that the chroma point on the adjustment XYZ chromaticity diagram is different can send the light of arbitrfary point on the chromaticity diagram by this, and wherein chromaticity diagram will couple together between this fluor with luminous element.
Fluor 50 can be evenly dispersed in the mineral binder bond 30 also luminous equably like this.Fluor in mineral binder bond 30 because of self the weight sedimentation or float.
On the surface of light-emitting device 601, can there be two kinds or more kinds of in the fluor 50 that forms as above in the mineral binder bond 30 that is made of one deck, also can in the mineral binder bond 30 that constitutes by two layers, exist respectively a kind of, two kinds or more kinds of.Moreover, in resin 40, also can there be a kind of, two kinds or more kinds of fluor.So, the colour mixture of the light by coming from different fluor 50 can obtain white light.At this moment, in order to make light that each fluor 50 sends colour mixture and reduce irregular colour better, preferably each fluor has similar median size and shape.In addition, can consider that also the settling character that influenced by shape forms mineral binder bond 30.Formation method as the binding agent 30 of not allowing to be subject to the settling character influence can list spraying method, silk screen print method and pouring method etc.In the present embodiment, mineral binder bond can have effective solids component of 1%～80%, can carry out the viscosity adjustment in the wide region of 1cps～5000cps, and can adjust thixotropy, so, can adapt with the formation method of these mineral binder bonds.As mentioned above, the weight ratio of filler and mineral binder bond is preferably set to 0.05～30 scope, in addition, strengthens cohesive force by use level and the particle diameter of adjusting filler.
The fluor that uses in the present embodiment can be fluor with YAG also, may send nitride phosphors such as the fluor of red colour system light, particularly alkali earths silicon nitride fluor combines and is used.These YAG are that fluor and fluor can mix and be included in the luminescent layer, also can be included in respectively in the mineral binder bond that is made of multilayer.
Below just separately fluor be described in detail.
(YAG is a fluor)
The YAG that so-called the present embodiment is used is that fluor is with rare earth element activatory fluor such as cerium or Pr, it contains Y and Al, and contain be selected from least a element among Lu, Sc, La, Gd, Tb, Pr, Eu and the Sm and be selected from Ga and In among a kind of element, be to be subjected to visible light that led chip sends or ultraviolet ray excited and luminous fluor.In the present embodiment, also can utilize with cerium, Tb or Pr activatory, two or more different yttrium aluminum oxides of composition is fluor especially.If the blueness that will use nitride-based compound semiconductor to send as the luminous element of luminescent layer is a light and by because of absorbing that blue light body colour (body color) is green system that the xanchromatic fluor sends and red colour system light or being light for yellow but more approachingly greenly being and more coming out near the light mixed display of red colour system, then can demonstrate desired white color system illuminant colour.Light-emitting device is because produce colour mixture, so also can contain the powder and the piece of fluor in the light transmission inorganics of mineral binder bond of various resins such as Resins, epoxy, acrylic resin or silicone resin and the present embodiment and so on.Like this, the luminescent layer that contains fluor can be point-like or is purposes such as stratiform and uses in every way according to fluor, and wherein luminescent layer forms thinlyyer, and the light that is enough to luminous element is sent is seen through.By tone arbitrarily such as the bulb color of the ratio of fluor and light transmission inorganics and coating, loading level being carried out various adjustment and the emission wavelength of luminous element is selected, can provide comprising white.
In addition, with respect to the incident light that comes from luminous element, dispose two or more fluor separately in order, can obtain thus can effectively luminous light-emitting device.That is to say, have on the luminous element of reflecting member, dispose in mode such as stacked and to contain the color conversion member that absorbing wavelength is arranged and can send the fluor of long wavelength light at long wavelength side and promptly contain fluor as the luminescent layer of filler and compare to this luminescent layer and absorbing wavelength is arranged and can send the more color conversion member of long wavelength's light, can effectively utilize reflected light by this in longer wavelength side.
What the present embodiment was used is that promptly can to send green be that the YAG of light is a fluor because of being garnet structure to fluor with cerium activatory yttrium aluminum oxide, so heat, light and moisture are had very strong patience, excite the wavelength at absorption spectrum peak can be near 420nm～470nm.In addition, have wide luminous spectrum, its glow peak peak wavelength λ p is near 510nm, and the end at peak extends near the 700nm.On the other hand, with cerium activatory yttrium aluminum oxide is that the YAG that fluor promptly can send red colour system light is that fluor is also because be garnet structure, so heat, light and moisture are had very strong patience, excite the wavelength at absorption spectrum peak can be near 420nm～470nm.In addition, have wide luminous spectrum, its glow peak peak wavelength λ p is near 600nm, and the end at peak extends near the 750nm.
In the YAG with garnet structure was the composition of fluor, the part with Ga displacement Al made luminous spectrum move to short wavelength side thus, and with the part that Gd and/or La replace the Y in forming, luminous spectrum is moved to long wavelength side.So, form, can regulate glow color continuously by changing.Therefore, nitride-based semiconductor can recently continuously change the intensity of long wavelength side with the composition of Gd, and the blueness of utilizing such nitride-based semiconductor is the luminous luminous ideal conditions of the white color system of converting to that has.When 2 one-tenth of the displacement less thaies of Y, green composition increases and red composition reduces, and is 8 one-tenths or when above, though red composition increase briliancy sharply descends.In addition, about exciting absorption spectrum too, in the YAG with garnet structure is the composition of fluor, part with Ga displacement Al, make thus and excite absorption spectrum to move to short wavelength side, and with the part that Gd and/or La replace the Y in forming, make thus to excite absorption spectrum to move to long wavelength side.YAG is that the peak wavelength that excites absorption spectrum of fluor is preferably compared with the peak wavelength of the luminous spectrum of luminous element and is positioned at short wavelength side.If such formation, then when the electric current of supplying with luminous element increases, excite absorption spectrum peak wavelength because with the peak wavelength basically identical of the luminous spectrum of luminous element, the launching efficiency of fluor can not reduce, the light-emitting device that is suppressed of chroma offset so can form.
Such fluor as raw material, just obtains raw material with them by the stoichiometric ratio thorough mixing with the oxide compound of Y, Gd, Tb, Pr, Ce, La, Lu, Al, Sm and Ga or the compound that at high temperature becomes oxide compound easily.Perhaps be dissolved in the acid by the rare earth element of stoichiometric ratio with Y, Gd, Ce, La, Lu, Al, Sm, make the lysate that obtains like this produce codeposition with oxalic acid then, again the codeposition product that obtains is like this carried out sintering and just obtain the codeposition oxide compound, then this codeposition oxide compound is mixed just obtaining mixing raw material with aluminum oxide, gallium oxide.An amount of fluorochemical such as Neutral ammonium fluoride that adds is packed into as fusing assistant and with it in crucible in this mixing raw material, then in air in 1350 ℃～1450 ℃ temperature range sintering 2 hours～5 hours, thereby obtain sinter, then in water, sinter is carried out ball milling, clean then, separate, drying, sieve at last, just can obtain fluor thus.In addition, the manufacture method of the fluor of other embodiment preferably divides two stages to carry out sintering, these two stages are made of first sintering circuit and second sintering circuit, wherein first sintering circuit will constitute mixture by mixing raw material that has mixed phosphor raw material and fusing assistant and carry out sintering in atmosphere or in the weakly reducing atmosphere, and second sintering circuit is carried out sintering in reducing atmosphere.At this, so-called weakly reducing atmosphere refers to and is being formed by mixing raw material in the reaction process of desired fluor, what set contains the more weak reducing atmosphere that is necessary the oxygen amount at least, in this weakly reducing atmosphere, carrying out first sintering circuit is accomplished until the structure formation of desired fluor, can prevent the black change of fluor thus, and prevent the decline of efficiency of light absorption.In addition, the reducing atmosphere of so-called second sintering circuit refers to the reducing atmosphere stronger than weakly reducing atmosphere.If divide two stages to carry out sintering like this, then can obtain the high fluor of assimilated efficiency of excitation wavelength.Therefore, adopting the fluor that forms like this to form under the situation of light-emitting device, can reduce necessary fluor consumption, can form light and take out the high light-emitting device of efficient for obtaining desired tone.
Forming different two or more is fluor with cerium activatory yttrium aluminum oxide, can mix use, also can be configured independently of one another.Under the situation that disposes fluor independently of one another, preferably be configured by following order, be configured in shortwave wavelength side earlier and absorb light and the luminous fluor that comes from luminous element easily, be configured in relative long wavelength side again and absorb light and the luminous fluor that comes from luminous element easily.Thus, fluor can absorb light that luminous element sends and luminous effectively.
(nitride phosphor)
The fluor that uses as the present embodiment, except above-mentioned be the fluor with cerium activatory yttrium aluminum oxide, also suitable have Huang Hong～emitting red light wavelength with Eu or the nitride based fluor of rare earth class activatory alkali earths.This fluor is by absorbing the visible light that sent by led chip and ultraviolet ray and being the light that sends of fluor and stimulated luminescence by YAG.The fluor of embodiment of the present invention is particularly: Sr-Ca-Si-N:R, Ca-Si-N:R, Sr-Si-N:R, Sr-Ca-Si-O-N:R, Ca-Si-O-N:R and Sr-Si-O-N:R are silicon nitride.The basic comprising element of these fluor can be used general formula L XSi YN (2/3X+4/3Y): R or L XSi YO ZN (2/3X+4/3Y-2/3Z): R (L is arbitrary group among Sr, Ca and Sr and the Ca) represents.In general formula, X and Y be X=2, Y=5 or X=1, Y=7 preferably, but also can be numerical value arbitrarily.In addition, R is the rare earth element that must contain Eu, and N is a nitrogen, and O is an oxygen.Specifically, preferably use the basic comprising element can use (Sr XCa 1-X) 2Si 5N 8: Eu, Sr 2Si 5N 8: Eu, Ca 2Si 5N 8: Eu, Sr XCa 1-XSi 7N 10: Eu, SrSi 7N 10: Eu, CaSi 7N 10: the fluor that Eu represents, but in the composition of this fluor, also can contain at least a kind of being selected among Mg, B, Al, Cu, Mn, Cr and the Ni or multiple.But the present invention is not limited to this embodiment and embodiment.
L is arbitrary group among Sr, Ca and Sr and the Ca.Sr and Ca can change proportioning as requested.
Luminescence center mainly uses the europium Eu as rare earth element.Europium mainly has the energy level of divalent and 3 valencys.The fluor of embodiment of the present invention is a silicon nitride for the alkaline-earth metal as parent, with Eu 2+As activator.In addition, also can be with Mn as additive.
Fluor ((Sr with regard to using in embodiment of the present invention below XCa 1-X) 2Si 5N 8: manufacture method Eu) describes, but the present invention is not limited to this manufacture method.In above-mentioned fluor, contain Mn and O.
In an embodiment of the present invention,, use nitride based fluor especially, and in the present embodiment, also can obtain to have above-mentioned YAG is fluor and the light-emitting device that may send the fluor of red colour system light as sending the fluor of light redly.The fluor that may send red colour system light like this is to be the optical excitation of 250nm～600nm and luminous fluor for example can list Y by wavelength 2O 2S:Eu, La 2O 2S:Eu, CaS:Eu, SrS:Eu, ZnS:Mn, ZnCdS:Ag, Al and ZnCdS:Cu, Al etc.Like this, may be the fluor that fluor sends red colour system light with YAG by using, can improve the color rendering of light-emitting device.
In the light-emitting device of each embodiment of the present invention, fluor can use various fluor.What for example, can list has: produce blue region luminous, with BaMgAl 10O 17: that Eu represents, be fluor with europium activatory barium magnesium aluminate, produce blue region luminous, with (Ca, Sr, Ba) 5(PO 4) 3That Cl:Eu represents, with europium activatory halogen series of calcium phosphate fluor, produce blue region luminous, with (Ca, Sr, Ba) 2B 5O 9That Cl:Eu represents, be fluor with europium activatory alkali earths chloroboric acid salt, produce the blue-greenish colour zone luminous, with (Sr, Ca, Ba) Al 2O 4: Eu or (Sr, Ca, Ba) 4Al 14O 25: that Eu represents, be fluor with europium activatory alkaline earth aluminate, produce green area luminous, with (Mg, Ca, Sr, Ba) Si 2O 2N 2: that Eu represents, be fluor with europium activatory alkali earths silicon-oxygen nitride, produce green area luminous, with (Ba, Ca, Sr) 2SiO 4: that Eu represents, be fluor with europium activatory alkali earths Magnesium Silicate q-agent, produce yellow area luminous, with (Y, Gd) 3(Al, Ga) 5O 12: the rare earth class aluminate of expressions such as Ce be YAG be fluor and produce red area luminous, with (Y, La, Gd, Lu) 2O 2That S:Eu represents, be fluor etc. with europium activatory rare earth class oxysulfide, but the present invention is not limited to these, aforesaid fluor and other fluor also can use in the mineral binder bond of embodiment of the present invention.Moreover, also can use fluor with surface of fracture, wherein on surface of fracture, taked to prevent the countermeasure of coating degradation.
Above-mentioned fluor for example is fluor, is fluor, is that fluor, YAG are fluor and are that fluor etc. preferably contains the B element with europium activatory alkali earths silicon nitride with europium activatory alkali earths silicon-oxygen nitride with europium activatory alkaline earth aluminate with europium activatory alkali earths chloroboric acid salt, thereby make crystallinity become good, increase particle diameter, or adjust crystal form.Can seek the raising of glorious degrees thus.These fluor also are effective as the filler of the fluor of the present embodiment.
About crystalline texture, Ca for example 2Si 5N 8Be oblique crystal, Sr 2Si 5N 8, (Sr 0.5Ca 0.5) 2Sr 5N 8Be iris, Ba 2Si 5N 8Get oblique crystal.
Moreover, this fluor to be crystallization account in it is formed 60% or above, be preferably 80% or above crystalloid.In general, preferred x=2, y=5 or x=1, y=7, but also can be numerical value arbitrarily.
In micro-additive, B etc. do not reduce the characteristics of luminescence and can improve crystallinity, and Mn, Cu etc. also show same effect.In addition, La, Pr etc. also have the effect of improving the characteristics of luminescence.In addition, Mg, Al, Cr, Ni etc. have the effect that shortens twilight sunset, can suit to use.In addition, even the element that this specification sheets is not expressed, as long as about 10～1000ppm, not obvious reduction briliancy just can be added.
The rare earth element that contains among the R preferably include among Y, La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Er, the Lu a kind or more than, but also can comprise Sc, Sm, Tm and Yb.In addition, except that above-mentioned element, can also contain the element that B, Mn etc. have the effect of improving briliancy.These rare earth elements also are blended in the raw material with states such as oxide compound, imide, acid amides except that simple substance.Rare earth element mainly has the electronics of 3 stable valencys to be arranged, but Yb, Sm etc. also have the electronics arrangement that divalent, Ce, Pr, Tb etc. also have 4 valencys.Under the situation of the rare earth element that uses oxide compound, the participation of oxygen exerts an influence to the characteristics of luminescence of fluor.That is to say,, the reduction of briliancy takes place also sometimes owing to contain aerobic.But, under the situation of using Mn, because the effect as fusing assistant that Mn and O produce is increased particle diameter, thereby can seek the raising of glorious degrees.
As luminescence center, be suitable for europium Eu as rare earth element.Specifically list the example of basic comprising element, then have: the Ca that has added Mn, B 2Si 5O 0.1N 7.9: Eu, Sr 2Si 5O 0.1N 7.9: Eu, (Ca XSr 1-X) 2Si 5O 0.1N 7.9: Eu, CaSi 7O 0.5N 9.5: Eu and then added the Ca of rare earth element 2Si 5O 0.5N 7.9: Eu, Sr 2Si 5O 0.5N 7.7: Eu, (Ca XSr 1-X) 2Si 5O 0.1N 7.9: Eu etc.
Above Shuo Ming nitride based fluor absorbs the part of the blue light that is sent by luminous element and sends light from the yellow to the red area.With the light-emitting device that this fluor is used to have above-mentioned formation, just can provide the red light of a kind of blue light that sends by luminous element and fluor to send the light-emitting device of the white light of warm colour system by colour mixture.In white light emitting device, preferably contain nitride based fluor and rare earth class chlorate MClO 3 fluorescent substance and promptly use cerium activatory yttrium aluminum oxide fluor especially.This be because: by containing above-mentioned yttrium aluminum oxide fluor, can regulate desired colourity.With cerium activatory yttrium aluminum oxide fluor, can absorb the part of the blue light that sends by luminous element and send the light of yellow area.Here, the blue light that sends by luminous element and and the color development light of yttrium aluminum oxide fluor can send the white light of pearl opal by colour mixture.Therefore, fluor that this yttrium aluminum oxide fluor and described nitride phosphor and binding agent is mixed together by combination and the blue light that is sent by luminous element can provide the light-emitting device of the white light that a kind of warm colour is.The light-emitting device of the white light of this warm colour system, it on average drills look evaluation number Ra can reach 75～95, and colour temperature can be set at 2000K～8000K.Particularly preferably be the white luminous device on the track of on average drilling the blackbody radiation that look evaluation number Ra is higher, colour temperature is positioned at chromaticity diagram.But, for the light-emitting device that has desired colour temperature and on average drill the look evaluation number is provided, also can appropriate change yttrium aluminum oxide fluor and the use level of fluor and the ratio of components of each fluor.The light-emitting device of the white light of this warm colour system is sought the special improvement of drilling look evaluation number R9 especially.In the past by blue light emitting device and the light-emitting device that sends white light that combines with cerium activatory yttrium aluminum oxide fluor, its special look evaluation number R9 that drills is low, red composition deficiency.Therefore, improve the special look evaluation number R9 that drills and just become to need the problem of solution, and in cerium activatory yttrium aluminum oxide fluor, contain useful Eu activatory alkali earths silicon nitride series fluor, the special look evaluation number R9 that drills can be brought up to 40～90 by this.In addition, can also make the LED light-emitting device that sends the bulb color.
(matrix)
Matrix 20 is made of with the basis pontis that has disposed lead-in wire electrode 22 the recess 20a that accommodates luminous element 60, and it plays a role as the support of luminous element 60.The bottom surface of the bottom surface of described recess 20a and described lead-in wire electrode preferably roughly is positioned at on the one side.
Matrix 20 is preferably used the metal manufacturing, considers it also can is resin from processibility and productivity equal angles.Matrix 20 takes out the face side from light, and its shape can form roughly different shapes such as square, essentially rectangular, circular, substantially elliptical.The part of carrying luminous element 60 is preferably formed recess 20a.This be because: by luminous element 60 is housed in the recess 20a, the light that sends from luminous element 60 is emitted in the open side of recess 20a, thereby can seek the raising of optical output power.
In light-emitting device 601, the thermal diffusivity of consideration and miniaturization, matrix 20 preferably forms with film.
Adapt with the quantity and the size of luminous element 60, also matrix can be designed to have a plurality of peristomes.For making it to have suitable shading function, matrix 20 is painted to dark-coloured system such as black or grey, and perhaps the luminous observation face side of matrix 20 is painted to dark-coloured system.In order further to protect luminous element 60 to avoid the infringement of outside atmosphere, beyond the removing coating, can also be provided as the mold member of light transmission protective.Moreover, when matrix 20 is subjected to coming from the influencing of heat of luminous element 60, consider and the sticking power of mold member that preferred substrate 20 has less coefficient of thermal expansion.
The bonding of luminous element 60 and matrix 20 also can adopt thermosetting resin etc. to carry out.Specifically, can list Resins, epoxy, acrylic resin and imide resin etc.Use at light-emitting device 601 and to send the luminous element 60 that contains ultraviolet light and under situation about being used under the high-output power, for the adhesive segment of luminous element 60 with matrix 20, because ultraviolet ray of being sent by luminous element 60 etc. also is used as the mineral binder bond 30 of containment member or the institutes such as fluor 50 that are included in wherein reflect, light becomes high-density especially in matrix 20, therefore, the resin of adhesive segment is degenerated because of ultraviolet ray, so can think and cause the low of luminous efficiency and cause the reduction in light-emitting device life-span because of cohesive strength low because of the xanthochromia of resin etc.For preventing the degeneration of such adhesive segment that causes because of ultraviolet ray, can use the resin that contains UV light absorber, preferredly can use inorganics of the present invention etc.Especially, use at matrix under the situation of metallic substance, the bonding of luminous element 60 and matrix 20 also can be used the eutectic solder of Au-Sn etc. etc. except using inorganics of the present invention.Therefore, with to use resin to carry out the agglutinating situation different,, the present invention sends the luminous element 60 that contains ultraviolet light and under situation about being used under the high-output power, its adhesive segment can not degenerated yet even using at light-emitting device 601.
In addition, in configuration and fixedly in the luminous element 60, for matrix 20 in outer electrode electrically contact, be fit to use Ag slurry, carbon pastes, ITO slurry and metal rim etc.
(lead-in wire electrode)
Light-emitting device 601 has positive and negative lead-in wire electrode 22, and lead-in wire electrode 22 is in insulating component 23 is inserted in the communicating pores of the basis pontis that is arranged at metallic matrix 20.The top ends of described lead-in wire electrode 22 highlights from the surface of described basis pontis, and the bottom surface of the mounting face side of the bottom surface of described lead-in wire electrode 22 and described recess is roughly located at grade.
(lid)
Light-emitting device 601 has the lid 26 of the lead-in wire 24 that comprises light transmission window portion 25 and be made of metal part in the interarea side of matrix 20.Window portion 25 is the light-emitting area of light-emitting device 601, and preferred disposition is at central part.
Window portion 25 be positioned at the recess 20a that is configured in matrix 20 luminous element 60 above, and intersect with the extended line of the inwall of recess 20a.The light that sends from the end of luminous element 60 produces diffuse-reflectance in the side of recess 20a and takes out in frontal.The scope that exists that these diffuse be it is generally acknowledged roughly in the lateral extended line of recess 20a.So by adjusting the area as the window portion 25 of light-emitting area as described above, described diffusing can focus on window portion 25 effectively, thereby can obtain sending the light-emitting device 601 of high briliancy light.
Window portion 25 has light transmission.In window portion 25, can contain fluor 50, also can paste the film of fluor 50 in addition.
Window portion 25 can use various materials such as glass, Resins, epoxy, polypropylene, but considers from stable on heating angle, preferably glass.
Lid 26 is arranged on the matrix 20 in the gastight mode.Airtight owing to having carried out, thereby the inside that can prevent moisture intrusion light-emitting device 601.
(lead-in wire)
Lead-in wire 21 requires to have ohmic properties, mechanical connection, electrical conductivity and heat conductivity good and electrode luminous element 60.As lead-in wire 21, can list the electroconductibility lead-in wire of metals such as using gold, copper, platinum and aluminium and alloy thereof particularly.Such lead-in wire 21 is easy to electrode, inner lead and the pin leads etc. of each light-emitting device 60 are coupled together by means of wire-bonded equipment.
(manufacture method of light-emitting device)
Serve as that basic manufacture method with regard to light-emitting device describes with Figure 31～Figure 35 below.As mentioned above, Figure 31 is the schematic plan view of the light-emitting device of embodiment of the present invention 6, and Figure 32 (a) is the constructed profile of same light-emitting device, and Figure 32 (b) is the constructed profile that amplifies the matrix recess.Moreover, Figure 33 is the synoptic diagram of a part of manufacturing process of the light-emitting device of expression embodiment of the present invention, Figure 34 is the synoptic diagram of a part of other manufacturing process of the light-emitting device of expression embodiment, and Figure 35 is the synoptic diagram of a part of another other manufacturing process of the light-emitting device of expression embodiment.Specifically, Figure 34 is the synoptic diagram of the formation method of the layer of the expression mineral binder bond 30 that adopts spraying spraying means or resin 40, and Figure 35 represents to adopt the layer of mineral binder bond 30 of screen print means or the formation method of resin 40.Be the manufacture method of base description light-emitting device below with these figure.But following operation is an embodiment, and the present invention is not limited thereto.
(first operation)
On matrix 20, carrying luminous element 60.Matrix 20 is formed with recess 20a, is carrying luminous element 60 on this recess 20a.Binding agents such as luminous element 60 use Resins, epoxy weld.After the operation of carrying luminous element 60 was finished, the electrode of luminous element 60 and lead-in wire electrode 22 21 were electrically connected by going between.
(second operation)
With mineral binder bond 30 covering luminous elements 60.Mineral binder bond 30 preferably contains fluor 50 in advance.This fluor 50 mixes in advance and is dispersed in the mineral binder bond 30.Mineral binder bond 30 can adopt pouring means, spraying spraying means, screen print means and cast means etc., but preferably waters means or spraying spraying means.Mineral binder bond 30 is covered with the whole top and whole side of luminous element 60.And bottom surface and the side of the recess 20a of covering carrying luminous element 60.Mineral binder bond 30 forms the layer structure of film like.Mineral binder bond 30 carries out the 3rd operation after curing, but also can carry out the 3rd operation before curing, and resin 40 and mineral binder bond 30 are cured simultaneously.
For example with the means of silk screen printing with mineral binder bond 30 covering luminous elements 60.With respect to luminous element 60, the sieve plate 97 that will have pattern is processed into desirable shapes such as band shape, reticulation, concentric circles, vortex crustiform, triangular shape and point-like.Electroconductive member 91 be configured in pedestal substrate 92 above, on this electroconductive member 91, (face down) is installed with luminous element 60 down.At this moment, be not short-circuited, predetermined ditch is set on pedestal substrate 92 in advance for making positive pole and negative pole.In addition, between each electrode of luminous element 60, in advance insulating component 94 is arranged on pedestal substrate 92 sides, afterwards by flange 96 with luminous element 60 be welded on this pedestal substrate 92 above.Use squeegee to carry out silk screen printing then with the inorganic cementitious material that contains fluor.Can form the luminous element 60 that has applied the mineral binder bond 30 that often has constant thickness thus.After this cut off pedestal substrate 92 along joint line 93.This operation is preferably carried out in a vacuum, but also can carry out in inactive gas atmosphere.
(the 3rd operation)
Adopt resin 40 to cover mineral binder bond 30.In resin 40, also can contain fluor 50 in advance.Resin 40 can adopt pouring means, spraying spraying means, screen print means and cast means etc., but preferably waters means or spraying spraying means.Resin 40 is covered with the surface of mineral binder bond 30.Resin 40 is preferably formed the layer structure of film like.Resin 40 permeates in mineral binder bond 30, and the space that mineral binder bond 30 is had is then by 40 landfills of resin.Just can produce light-emitting device 61 thus.This operation is preferably carried out in a vacuum, but also can carry out in inactive gas atmosphere.
(pouring means, spraying spraying means)
Figure 33 is the synoptic diagram of a part of manufacturing process of the light-emitting device of expression embodiment of the present invention.The pouring means can be used known pouring means.In Figure 33 (a), illustrated and adopted the pouring means that resin 40 is coated in method on the mineral binder bond 30.The resin 40 that injections will be coated with in the pouring instrument of installing on the irrigation device (not shown) 66.Resin 40 is according to viscosity, wettability, adjust material, temperature and water velocity to factors such as the perviousness of mineral binder bond 30 and sticking power.From the point of the mouth 67 of pouring instrument 66 with the colloidal sol of resin 40 toward as watering above the mineral binder bond 30 of target compound.At this moment, pouring resin 40 does not preferably contact with lead-in wire 21.
In Figure 33 (b), pouring resin 40 above luminous element 60, resin 40 penetrates in the mineral binder bond 30 from this pouring.At this moment, be impregnated with resin 40 in the space that mineral binder bond 30 is had, the gas that exists in this space is pulled out from the side of the resin 40 that discharges easily.Resin 40 flows to the periphery of luminous element 60 at leisure.At this moment, will be in the gas that the space of mineral binder bond 30 of periphery of luminous element 60 in exists and to outside extrude on one side, one side flows in the space resin.
In Figure 33 (c), resin 40 continues to climb up along the side of recess 20a from the periphery of luminous element 60.This results from capillarity.At this moment, resin 40 also squeezes the matrix in the space 31 outward, can prevent like this in the gas intrusion resin 40.
In Figure 33 (d), can form 40 layers of resins that cover 30 layers of mineral binder bonds.The thickness that resin is 40 layers is roughly even.The surface of 40 layers of resins is level and smooth in addition.
Adopt the pouring means that mineral binder bond 30 is covered method and top narrated same to replace resin 40 on the mineral binder bond 30.
Figure 34 is the synoptic diagram of a part of representing other manufacturing process of light-emitting device of the present invention.Spraying spraying means can be used known spraying spraying means.The present invention uses following spray equipment (not shown), and this spray equipment uses the transfer lime (not shown) will accommodate container (not shown) that coating fluid is a resin 40 respectively, regulate the valve (not shown) of the flow of coating fluid, be transported to the recycle pump (not shown) of container and coating fluid is coupled together with the nozzle 70 of spiral helicine form ejection from nozzle 70 again after coating fluid is transported to nozzle 70.
The stirrer (not shown) is installed in accommodating the container of coating fluid, in the coating operation, often stirs coating fluid.The coating fluid of being accommodated by container adopts stirrer often to stir, thereby contains in coating fluid under the situation of fluor, and fluor contained in the coating fluid usually is dispersed in the solution.Valve is regulated the flow of the coating fluid that is transported by transfer lime by container by means of the switching of valve.Recycle pump is transported to the top ends of nozzle 70 from container via valve and compressor with coating fluid by transfer lime, after this, will be not from nozzle 70 ejections and the coating fluid that left behind is transported to container by transfer lime.After this coating fluid, is transported to container by transfer lime, so coating fluid usually is in the state of spray equipment internal recycle owing to be transported to the top ends of nozzle from container via valve by transfer lime by means of recycle pump.Therefore, coating fluid is because be in stirring or the round-robin state that spreads all over whole spray equipment, so the fluor that contains in the coating fluid often is in uniform distribution in the coating operation.Compressor is arranged in the device by transfer lime, compresses the air that transports by transfer lime, regulates the pressure of the coating fluid that transports by transfer lime.By means of compressor, pressurized air is transported to nozzle 70 respectively with the coating fluid that carries out the excess pressure adjusting.At this, compressed-air actuated pressure monitors by pressure warning unit.Use above spray equipment,, be sprayed on top, the side and recess inner face of luminous element with high pressure gas one superhigh speed ejection coating fluid.
Coating fluid and gas (the present embodiment is an air) spray with spiral helicine form by nozzle 70.Around the nozzle of this device several gas vents are set, with respect to applied surface separately at an angle from the emission direction of the gas of these ejiction openings ejections.Therefore, is that these gas vents of center rotation are when sending into gas when simultaneously to the ejiction opening with coating fluid, the whole gas flow that will concentrate in together from the gas of separately ejiction opening ejection, become the flowing of the vortex crustiform that reverses, spiral helicine flow or wind spout in the flowing of air.In addition, be provided with the ejiction opening of coating fluid at the center of the nozzle of this device, when the ejection with gas sprays coating fluid simultaneously, become vaporific coating fluid take advantage of the flowing of the vortex crustiform that reverses, spiral helicine flow or wind spout in flowing of air and diffusion is come.
Diffuse into the injection starting point of the diameter of spiral helicine whole spraying from the luminous element top, the closer to the surface of luminous element, it is big more that diameter becomes.In addition, from the injection starting point of luminous element top, the closer to the surface of luminous element, the speed of rotation of the spraying that is made of coating fluid is more little.That is to say, when vaporific coating fluid from nozzle ejection and when air, spreading, spray starting point be nozzle near, spraying is coniform diffusion comes, and in the place of leaving nozzle, spraying is cylindric diffusion and comes.So present embodiment is preferably regulated and is provided with the top distance between the lower end of nozzle of luminous element, make the surface of luminous element appear at spraying and be in and be the come place of this state of cylindric diffusion.The spraying of this moment shape rotation in the shape of a spiral, and speed is slower, and therefore, spraying can be around to the luminous element surface that is under the electroconductibility lead-in wire shade, and above the not only whole luminous element but also whole side can both fully be sprayed onto.Thus, can under the state of fixedly luminous element or nozzle, carry out operation.In addition, be the come place of this state of cylindric diffusion because be in spraying, the speed of spraying is slower, so when being sprayed on luminous element surperficial, the impact of the fluorophor particle that the surface of luminous element is contained in can not sprayed.In addition, can not produce the distortion and the broken string of electroconductibility lead-in wire, thereby product percent of pass and manufacturability are improved.
Light-emitting device after the coating is in temperature on well heater be 50 ℃～500 ℃ heated condition.As making luminous element be in the method for heated condition in this wise, also can use method at heating unit internal heating luminous elements such as baking ovens.By heating, make ethanol, trace be included in moisture and solvent evaporation in the hydrolyzed solution that is in gel state, and can obtain amorphous Al (OH) by the coating fluid that is in gel state 3And AlOOH.Moreover the coating fluid of the present embodiment has been owing to carried out viscosity adjustment, so be sprayed on top, the side of luminous element and the angle and then after the support surface, can not flow out from the place of spraying.Soon just heat after coating in these places, so top, side by fluor being bondd that the coating form can covering luminous element and the part on the angle by AlOOH.
In the present embodiment, under the state of arranging a plurality of matrixes 20, luminous element 60 is welded on respectively in the matrix 20, and the electrode of luminous element 60 and lead-in wire electrode 22 carried out wire-bonded, use mineral binder bond 30 covering luminous elements 60 then, and spray resin 40 from the top of mineral binder bond 30.Beyond predetermined place, for example beyond recess 20a inner face, adhere to resin 40 for preventing, resin 40 is sprayed on the surface of mineral binder bond 30 from the top of shielding baffle plate 80.Shielding baffle plate 80 be hide fully matrix 20 the recess 20a outside, be provided with size and can make resin 40 be sprayed on the plate of the lip-deep communicating pores of mineral binder bond 30, have metal system shielding baffle plate, reinforced plastics system shielding baffle plate etc.
When using spraying spraying means, resin 40 is sprayed into granular, so the gas that is present in the space 31 is discharged to the outside from particle gap each other.The gas volume that is dissolved in the resin 40 is reduced, can reduce the gas content in the resin 40.
Embodiment 7
Be that basic light-emitting device with regard to embodiment of the present invention 7 describes below with Figure 36.Figure 36 (a) is the constructed profile of matrix recess that amplifies the light-emitting device of embodiment 7, and Figure 36 (b) is the stereographic map of this light-emitting device of expression.Light-emitting device as shown in these figures, the specifically light-emitting device of bullet cut.Light-emitting device 700 has: the mineral binder bond 730 of lead frame (matrix) 720, the covering luminous element 710 of luminous element 710, carrying luminous element 710, be included in fluor 750 in the mineral binder bond 730, cover the resin 740 and the mold member 760 of mineral binder bond 730.In addition, the curing because of mineral binder bond 730 produces space 731.Have under the situation of same function with above-mentioned part, its explanation is omitted.
The luminous element 710 that constitutes with the light-emitting device 700 of bullet cut is welded on the substantial middle position of recess 720a and is carried by this recess 720a, and its center dant 720a is configured in the top of the pin leads that becomes matrix.The electrode that forms on the luminous element 710 721 is electrically connected with the pin leads 720a and the inner lead 720b of lead frame 720 by going between.It is fluor and nitride based fluor that fluor 750 contains YAG, and at least a portion of the light that these fluor absorption luminous elements 710 send is sent the light that is different from the absorb light wavelength simultaneously.Moreover nitride based fluor can cover with covering materials such as microcapsule.In mineral binder bond 730, make this fluor 750 homodisperse.The mineral binder bond 730 that contains fluor 750 is configured in the recess of carrying luminous element 710.Like this; avoid the infringement of external stress, moisture and dust and dirt in order to protect luminous element 710 and fluor 750; and in order to improve the taking-up efficient of light, the lead frame 720 of configuration luminous element 710 and fluor 750 is over-molded in the mold member 760, thereby forms light-emitting device 700.Also can form lens etc. with the form of mold member.
Resin 740 adopts spraying spraying means or pouring means to cover mineral binder bond 730 and luminous element 710.Resin 740 is filled in the recess 720a of lead frame 720.Become the plane by the surface that makes resin 740, can control directive property, and seek the raising that light takes out efficient.
(mold member)
Mold member 760 can be provided with according to the use of light-emitting device 700, avoids extraneous infringement or be used to improve light taking out efficient with the layer and the resin 740 that are used to protect luminous element 710, electroconductibility lead-in wire 721, contain the mineral binder bond 730 of fluor 750.Mold member 760 can form with various resins and glass.As the concrete material of mold member 760, what be fit to use mainly contains: good transparent resin of weather resisteants such as Resins, epoxy, urea resin, silicone resin and fluoro-resin and glass etc.In addition, by in mold member, containing diffusant, also can relax the directive property of the light that comes from luminous element 710 and increase field angle.Such mold member 760 can be used and resin 740 identical materials, also can use different materials.
Embodiment 8
Moreover, be that basic light-emitting device with regard to embodiment of the present invention 8 describes with Figure 37.Figure 37 (a) is the constructed profile that amplifies the matrix recess of light-emitting device, and Figure 37 (b) is the stereographic map of this light-emitting device of expression.In this example, light-emitting device specifically also is a bullet cut light-emitting device 800.Light-emitting device 800 has: the mineral binder bond 830 of lead frame (matrix) 820, the covering luminous element 810 of luminous element 810, carrying luminous element 810, be included in fluor 850 in the mineral binder bond 830, cover the resin 840 of mineral binder bond 830 and cover 826.In addition, the curing because of mineral binder bond 830 produces space 831.And electrode 821 is electrically connected with lead frame 820 by going between.Have under the situation of same function at each several part and above-mentioned embodiment 7, its explanation is omitted.
826 pairs of lead frames 820 that carrying luminous element 810 of light-emitting device 800 usefulness cover seal.Sealing is preferably airtight.The top window portion 825 that is being provided with of cover 826 is seen through the light that comes from luminous element 810.Lead-in wire 824 is being supported window portion 825.
Embodiment 9
In addition, also be that basic light-emitting device with regard to embodiment of the present invention 9 describes with Figure 38.Figure 38 is the constructed profile of the part of expression light-emitting device.Be particularly related near the constructed profile the luminous element 60 shown in Figure 35, as to adopt screen print means coating inorganic binding agent 30 and resin 40.On pedestal substrate 92, luminous element 60 is installed down, and adopts screen print means mineral binder bond 30 to be set on the surface of luminous element 60.The pedestal substrate 92 that will carry luminous element 60 afterwards is installed on the light-emitting device, and will go between and 21 be welded on the lead member 91.Then adopt means such as pouring that resin 40 is immersed in this mineral binder bond 30.Can provide a kind of surface impregnation that the light-emitting device of resin 40 is arranged thus at mineral binder bond 30.Wherein, also can be after means such as adopting pouring be coated in resin 40 on the mineral binder bond 30, welding lead 21 again.
Embodiment 30～32
(embodiment 30 and 31)
As with above-mentioned embodiment 6～9 corresponding embodiment, below just embodiment 30～32 resulting results describe. Embodiment 30 and 31 is light-emitting devices of bullet cut.Figure 33 is the synoptic diagram of a part of the manufacturing process of expression embodiment 30 and 31 light-emitting device, and Figure 34 is the synoptic diagram of a part of manufacturing process of the light-emitting device of expression embodiment 30 and 31.Figure 37 (a) is the constructed profile that amplifies the matrix recess of embodiment 30 and 31, and Figure 37 (b) is the stereographic map of the light-emitting device 800 of expression embodiment 30 and 31.Figure 42 is the constructed profile of the light-emitting device of expression comparative example 3.
Embodiment 30 and 31 has following formation: luminous element 810 uses have tube core (dies) the main light emission wavelength, that 0.35mm is square at the 400nm place.Lead-in wire 821 uses with Au and is the principal constituent material.Mineral binder bond 830 uses yttrium oxide colloidal sol (many wooden chemistries oxygenerating yttrium colloidal sol).Fluor 850 uses (Y 0.8Gd 0.2) 3Al 5O 12: the YAG fluor of Ce.About resin 840, embodiment 30 is for flooding with silicone resin (trade(brand)name: KJF816, the シ リ コ of SHIN-ETSU HANTOTAI-Application Co., Ltd. makes), and embodiment 31 is dipping silicone resin (trade(brand)name: KJF816L, the シ リ コ of SHIN-ETSU HANTOTAI-Application Co., Ltd. makes).The dipping of embodiment 30 with the basic physical properties of silicone resin is: viscosity is 100 (mm 2/ sec), proportion (25 ℃) is 0.97, and volatile component (105 ℃/3 hours) is 0.5, and solid state is a rubbery membranes, and hardness (Shao Er C type hardness tester) is 60.The dipping of embodiment 31 with the basic physical properties of silicone resin is: viscosity is 60 (mm 2/ sec), proportion (25 ℃) is 0.97, and volatile component (105 ℃/3 hours) is 0.5, and solid state is a rubbery membranes, and hardness (Shao Er C type hardness tester) is 60.
Embodiment 30 and 31 makes according to following manufacture method.At first, allow luminous element 810 be carried on the lead frame (matrix) 820.Lead frame 820 is formed with the recess 820a that comprises the wide-mouth peristome, is carrying luminous element 810 in the bottom surface of this recess 820a.Weld so that the substrate-side of luminous element 810 is contacted with the bottom surface of recess 820a.The caking agents such as eutectic solder of luminous element 810 use Au-Sn etc. weld.After the operation of carrying luminous element 810 was finished, the electrode of luminous element 810 and lead-in wire electrode 821 were electrically connected by going between.
Secondly, after fluor 850 weighings are good, the fluor 850 of input predetermined amount and mixing in the mineral binder bond 830 of predetermined amount.In detail, be that yttrium oxide colloidal sol and YAG fluor are respectively got 10g, be contained in the beaker of 100ml, add the ethanol of 50 weight % then with respect to yttrium oxide colloidal sol, fully stir and after mixing, just obtain the slip of fluor/colloidal sol.
Then utilize spraying spraying means on the luminous element 810 that lead frame 820 is carried, to spray mineral binder bond 830, thereby mineral binder bond 830 is fixed.By adopting spraying spraying means fixed inorganic binding agent 830, can make the bottom surface, side of recess 820a of top, side, the lead frame 820 of luminous element 810 form the layer of mineral binder bond 830 with homogeneous thickness roughly.Except that predetermined place, can not fix in order to make mineral binder bond 830, be provided with shielding baffle plate 80 and spray spraying.Spray spraying and after making it to fix, under about 240 ℃ temperature, carry out 30 minutes thermofixation with mineral binder bond 830.
Then use the pouring instrument resin 840 to be watered the laminar surface that is filled in mineral binder bond 830.The pouring of resin 840 directly over luminous element 810 and mineral binder bond 830 the layer substantial middle portion drip.This resin 840 comes from the central part rapid permeability of the laminar surface of mineral binder bond 830 and to the expansion of peripheral part direction, make the space of mineral binder bond 830 inside be able to landfill, and covering surfaces send the light of resin 840 until the whole laminar surface of mineral binder bond 830.Resin 840 climbs up along the laminar surface of the mineral binder bond 830 of the recess side of lead frame 820, it is generally acknowledged that this results from capillarity.Formed the layer of the resin 840 of uniform film like thus at the laminar surface of mineral binder bond 830.After pouring finished, luminous element 810 was covered by the layer of the layer of mineral binder bond 830 and resin 840, and the lead frame 820 that will carry this luminous element 810 then heated about 3 hours under the temperature about 150 ℃, thereby resin 840 is solidified.
In nitrogen atmosphere, this lead frame 820 usefulness cover 826 is sealed at last.Filled by nitrogen in the cover 826.Below the window portion 825 of cover 826, disposing the recess 820a of lead frame 820.So, just produce the light-emitting device 800 of embodiment 30 and 31.
(measurement result of endurance test)
Light-emitting device with regard to embodiment 30 and 31 has carried out endurance test.Figure 39 represents the endurance test result of the light-emitting device of embodiment 30 and 31, comparative example 3.Comparative example 3 is not covered by mineral binder bond 830 and resin 840, just luminous element 810 is carried in the recess 820a of lead frame 820.In addition, identical with embodiment 30.
The light-emitting device of embodiment 30 and 31 is dropped into the excitation test of the 100mA that carries out under the normal temperature.Output rating when just dropping into 0 hour is set at 100%, measures after 100 hours, after 200 hours, after 350 hours, after 500 hours and output rating after 700 hours.Its result, embodiment 30 and light-emitting device 31, comparative example 3 are all kept higher output rating after through 700 hours.
(light takes out the measurement result of efficient)
Carried out the mensuration of light taking-up efficient with regard to the light-emitting device of embodiment 30 and 31.Figure 40 represents that the light of the light-emitting device of embodiment 30 and 31, comparative example 4 takes out the result of efficient.
Figure 42 is the constructed profile of the light-emitting device of expression comparative example 4.Comparative example 4 covers mineral binder bond without resin, and only uses mineral binder bond 330.In the mineral binder bond 330 of comparative example 4, use YAG fluor 850 similarly to Example 30.The light-emitting device of comparative example 4 with mineral binder bond 330 cover luminous element 310 above.In this mineral binder bond 330, comprise many spaces 331.
In the light-emitting device of this embodiment 30 and 31, comparative example 4, drop into predetermined current, measure the output rating of its light.Its result can see: embodiment 30 is 1.91 times of comparative example 4, and light takes out efficient and is improved, and embodiment 31 is 1.75 times of comparative example 4, and light takes out efficient and also is improved.It is generally acknowledged this be because: 331 reflections of the space contained come from the light of luminous element 310 in the layer of the mineral binder bond 330 of comparative example 4.That is to say, this be because: in space 331, contain air such as nitrogen, because there are the difference on the specific refractory power in mineral binder bond 330 and air, so produce reflection at the interface of air and mineral binder bond 330.Thus, embodiment 30 and 31 light-emitting devices that provided are to be rich in weather resistance, the high light-emitting device of light taking-up efficient.
(measurement result of infrared spectra)
Dipping with regard to embodiment 30 has been measured infrared spectra with silicone resin.In addition, as a comparison, measured infrared spectra with regard to the silicone resin of comparative example 5.Figure 41 is the infrared spectrogram of filming of expression embodiment 30.Figure 43 is the infrared spectrogram of filming of expression comparative example 5.This infrared spectra is the result who adopts fourier-transform infrared optical spectroscopy (FT-IR) to measure.As the determinator of fourier-transform infrared optical spectroscopy, used Nexus 870＜main body〉and Continu μ m＜micro-(being ニ レ コ-ジ ヤ パ Application company makes).
Use the dipping of embodiment 30 to compare with the light-emitting device of the silicone resin that uses comparative example 5, have good light taking-up efficient and thermotolerance, weather resistance etc. with the light-emitting device of silicone resin.In addition, the promotion of resin degeneration also is suppressed.It is generally acknowledged that its reason is that the ratio of C-Si-O key is lower than the ratio of Si-O-Si key.That is to say, it is generally acknowledged that its reason is: if the ratio of C-Si-O key is less, then form the low ternary network structure of cross-linking density, thereby can form rubber-like or the gelatinous resin coating film that relatively is imbued with flexibility.By forming rubbery membranes or gel, can promote the mitigation of internal stress, can prevent because of peeling off that thermal expansion produces.
Filming in its resin is formed of comparative example 5, the C-Si-O key is 1.16/1 with respect to the strength ratio of Si-O-Si key.In contrast, the strength ratio of filming of embodiment 30 is 2.21/1.In addition, the silicone resin of comparative example 5 is general silicone resin.
(embodiment 32)
Embodiment 32 is light-emitting devices of bullet cut.Figure 35 is the synoptic diagram of a part of manufacturing process of the light-emitting device of expression embodiment 32.Figure 38 is the constructed profile of a part of the light-emitting device of expression embodiment of the present invention 9.Particularly shown in Figure 35, adopt inorganic cementitious material 99 that screen print means will contain fluor to cover the constructed profile of this operation on the luminous element 60.In addition, as shown in figure 38, expression be with mineral binder bond 30 cover on the luminous element 60, near the constructed profile the luminous element 60 when the surface impregnation resin 40 of mineral binder bond 30 again.Embodiment 32 is except different with the loaded state of the luminous element 810 of embodiment 30 and 31, and all the other roughly adopt same formation.Figure 37 (a) and (b) are stereographic maps of expression embodiment 30 and 31 light-emitting device, though have different on the symbol with embodiment 32, expression be the formation roughly same with embodiment 32.Below just the part of embodiment 32 and embodiment 30 and 31 main differences describe.
Mineral binder bond 30 uses alumina sol (Misao Kusano's system, trade(brand)name: A1-520).Spent ion exchange resin is handled this alumina sol, can make by this as the nitrate ion of stablizer and realize low concentration.In this alumina sol of 10g, add 20g (Y 0.8Gd 0.2) 3Al 5O 12: the YAG fluor of Ce, thorough mixing also stirs.Use the phosphor paste of allotment like this, adopt screen print means, go up at tube core wafer (dies wafer) with silk screen printing and form luminescent coating.Resin 40 can use dipping silicone resin (trade(brand)name: KJF816, the シ リ コ of SHIN-ETSU HANTOTAI-Application Co., Ltd. makes) or dipping silicone resin (trade(brand)name: KJF816L, the シ リ コ of SHIN-ETSU HANTOTAI-Application Co., Ltd. makes).
The luminous element 60 of embodiment 32 be installed in down pedestal substrate 92 above.The surface of the luminous element 60 that is installed with down adopts screen print means that mineral binder bond 30 is set.The pedestal substrate 92 that is carrying luminous element 60 is electrically connected by electroconductive member 91 and flange 96, and welds together by pedestal substrate 92 and lead-in wire 21.The surface impregnation of mineral binder bond 30 has resin 40.The surface of the mineral binder bond 30 behind the solvent impregnated resin 40 has gloss.
Describe the formation method of mineral binder bond 30 of manufacture method of the light-emitting device of embodiment 32 below in detail.At first, at the surface configuration electroconductive member 91 of pedestal substrate 92, the conductive pattern with the insulation division 94 of isolating anodal and negative pole is set then.
Pedestal is an aluminium nitride for nitride semiconductor luminescent element for example with the thermal expansivity material about equally of semiconductor light-emitting elements preferably with the material of substrate 92.By using such material, can relax the thermal stresses of pedestal with generation between substrate 92 and the luminous element 60.Pedestal preferably can form protecting component, that heat extraction is better, the also silicon of cheapness simultaneously with p N-type semiconductorN zone and n N-type semiconductorN zone sometimes with the material of substrate 92.In addition, electroconductive member 91 preferred high silver, gold and the aluminium of reflectivity that use.
In order to improve the reliability of light-emitting device, in the gap that produces between positive and negative two electrodes of luminous element 60 and between the insulation division 94, fill end filler material 95.At first, the circumferential arrangement at the insulation division 94 of said base substrate 92 has end filler material 95.End filler material 95 for example is heat-curing resins such as silicone resin and Resins, epoxy.In order to relax the thermal stresses of end filler material 95, also can further aluminium nitride, aluminum oxide and their compounding mixture etc. be sneaked in the Resins, epoxy.The consumption of end filler be can the landfill luminous element positive and negative two electrodes and pedestal substrate 92 between the amount in the gap that produces.
With the opposed mode of positive and negative two electrodes of the above-mentioned conductive pattern that on pedestal substrate 92, is provided with positive and negative two electrodes of luminous element 60 engaged with flange 96 respectively and to be fixed up.In addition, during as protecting component, the positive pole of luminous element is connected with p N-type semiconductorN zone with the n N-type semiconductorN zone of protecting component respectively with negative pole with pedestal.At first, form flange 96 with respect to positive and negative two electrodes of luminous element 60 as electroconductive member.In addition, also can form flange 96 with respect to positive and negative two electrodes of the conductive pattern of pedestal substrate 92.When near the end filler material the insulation division 94 that is configured in pedestal substrate 92 95 softened, positive and negative two electrodes of luminous element 60 were mutually opposed with positive and negative two electrodes of above-mentioned conductive pattern by flange 96.Secondly, positive and negative two electrodes, flange 96 and the above-mentioned conductive pattern thermo-compressed that makes luminous element by means of load, heat and ultrasonic wave together.At this moment, positive and negative two fillers of the interelectrode end of flange 96 and above-mentioned conductive pattern are got rid of, and can seek the conducting of the electrode and the above-mentioned conductive pattern of luminous element.Material as conductive material flange 96 for example has Au, eutectic solder (Au-Sn), Pb-Sn, lead-free solder etc.
Disposing sieve plate 97 from the substrate-side of luminous element 60.In addition, can not want to form the position configuration metal mask of the mineral binder bond that contains fluor to replace sieve plate 97 in the ball bonding position of electroconductibility lead-in wire, the formation position of joint line etc. yet.
Be adjusted at and have the material that contains fluor in thixotropic alumina sol, use squeegee (round end scraper) 98 to carry out silk screen printing.
Take off sieve plate 97, make the material cured that contains fluor, cut each luminous element along joint line then, just obtain having the light-emitting device 60 of the inorganic cementitious material that comprises fluor.
Moreover, can design a kind of like this light-emitting device: being caking agent with the Ag paste is fixed on the recess bottom surface of housing with above-mentioned luminous element 60, will expose the lead-in wire electrode of a part in the recess bottom surface with conductive lead wire then and the conductive pattern that is arranged on the pedestal substrate couples together.For example, the operable light-emitting device of present embodiment has: be used to control the lens of the luminous intensity distribution of light-emitting device, and the metallic matrix that forms of the part in the recess bottom surface of the heat extraction that is used to improve luminous element, carrying luminous element.In addition, the mold member of preferred disposition silicone resin etc. below lens and in the gap between the inner-wall surface of housing recess.Owing to adopt such formation, can obtain to come from the light-emitting device that the taking-up efficient of the light of luminous element was improved and had high reliability.
Below just the manufacture method of the light-emitting device of embodiment 32 describe.The place of the formation that embodiment 32 employings and embodiment 30 and 31 are roughly same, its explanation is omitted.
At first, on pedestal substrate 92, luminous element 60 is installed down.Pedestal substrate 92 and luminous element 60 are electrically connected by flange 96.Pedestal substrate 92 is provided with ditch portion so that make it to become the xenogenesis electrode, prevents the interelectrode short circuit of xenogenesis thereby make insulation division flow into this ditch portion.
Then on the luminous element 60 and pedestal substrate 92 installed, adopt sieve plate 97 to carry out silk screen printing down.The layer of the employed mineral binder bond 30 of silk screen printing uses the inorganic cementitious material 99 that contains fluor.But, also can use the inorganic cementitious material 99 that does not contain fluor.Use screen print means on luminous element 60 and the side form the layer of uniform mineral binder bond 30.What contain that the inorganic cementitious material 99 of fluor uses is the material that adds the 20gYAG fluor in the 10g alumina sol, fully stir and mix then.On luminous element 60 and after the side forms mineral binder bond 30, in nitrogen atmosphere,, mineral binder bond 30 is cured in about 80 ℃ about 30 minutes, 150 ℃ about 30 minutes, 240 ℃ under 30 minutes the heating condition.This is in order to remove organic composition that contains in the mineral binder bond 30 etc.But the present invention is not confined to this heating condition especially, can be in heating about 100 ℃ after 30 minutes, again in 240 ℃ of heating 1 hour yet.
The luminous element 60 (210) that is installed in down on the said base substrate 92 is carried on the lead frame (matrix) 820.Lead frame 820 is formed with the recess 820a that comprises the wide-mouth peristome, is carrying luminous element 60 (210) in the bottom surface of this recess 820a.Weld so that the substrate-side of luminous element 60 (210) is contacted with the bottom surface of recess 820a.The caking agents such as eutectic solder of luminous element 60 (210) use Au-Sn etc. weld.After the operation of carrying luminous element 60 (210) was finished, electroconductive member of pedestal substrate 92 91 and lead-in wire electrode 821 were electrically connected by going between.
Then use the pouring instrument resin 40 (240) to be watered the laminar surface that is filled in mineral binder bond 30 (230).The pouring of resin 40 (240) directly over luminous element 60 (210) and mineral binder bond 30 (230) the layer substantial middle portion drip.This resin 40 (240) comes from the central part rapid permeability of the laminar surface of mineral binder bond 30 (230) and to the expansion of peripheral part direction, make mineral binder bond 30 (230) inner spaces be able to landfill, and covering surfaces send the light of resin 40 (240) until the whole surface of 30 (230) layers of mineral binder bonds.Formed the resin 40 (240) of uniform film like thus on the surface of 30 (230) layers of mineral binder bonds.After welding finished, with the layer of mineral binder bond 30 (230) and the layer covering luminous element 60 (210) of resin 40 (240), the lead frame 820 that will carry this luminous element 60 (210) heated under the temperature about 150 ℃ about 3 hours, and resin 840 is solidified.At this, silicone resin uses dipping silicone resin (trade(brand)name: KJF816, the シ リ コ of SHIN-ETSU HANTOTAI-Application Co., Ltd. makes).
In nitrogen atmosphere, this lead frame 820 usefulness cover 826 is sealed at last.Filled by nitrogen in the cover 826.Below the window portion 825 of cover 826, disposing the recess 820a of lead frame 820.So, just produce the light-emitting device of embodiment 32.
Embodiment 10
Then be that basic light-emitting device with regard to embodiment of the present invention 10 describes with Figure 44.Figure 44 represents the schematic configuration diagram of the light-emitting device with luminescent film 1000 of embodiment 10.This light-emitting device 1000 comprises, excitation light source 44: be used to penetrate exciting light 42; Luminescent material 54: it absorbs the exciting light 42 that is penetrated by excitation light source 44, carries out sending after the wavelength Conversion illumination light 43 in predetermined wavelength zone; Photoconductive fiber 46: its end connects excitation light source 44, and the other end connects luminescent material 54, and improves the specific refractory power of section central part (core) with respect to periphery (covering), thereby will be led luminescent materials 54 by the exciting light 42 that excitation light source 44 penetrates.
Excitation light source 44 has luminous element 47, and the light that will be penetrated by luminous element 47 is from injection part 48 guiding photoconductive fibers 46.For the photoconduction that will penetrate by luminous element 47 effectively to injection part 48, between luminous element 47 and injection part 48, be provided with lens 49.
One end of photoconductive fiber 46 is connected with injection part 48, and the other end has the efferent 52 of photoconduction to the outside.Efferent 52 has luminescent material 54.As luminescent material 54, use inorganic phosphor 55 in this example.Luminescent material 54 absorbs the exciting light 42 that is penetrated by excitation light source 44, carries out sending after the wavelength Conversion illumination light 43 in predetermined wavelength zone.Fluor 55 is blended in filler member 56 and the binding agent member 57 in advance, at efferent 52 this filler member 56 of configuration and binding agent members 57.The consumption of fluor 55 can be adjusted according to the amount of this filler member 56 and binding agent member 57.Filler member 56 is mineral fillers, and binding agent member 57 is for containing the mineral compound of the hydrous oxide of metallic element at least.The hydrous oxide of the metallic element that contains in the binding agent member 57 can use the Al with boehmite structure or pseudo-boehmite structure, the hydrous oxide of Y etc.
When near the luminous element 47 that has peak luminous wavelength the short wavelength regions 400nm that uses at visible light and by the fluor that sends blue light with when sending the fluor 55 that the fluor of sodium yellow mixes, the white light that is sent by fluor 55 mainly becomes illumination light 43.Near the 400nm light is difficult to carry out visuognosis, thereby makes it become blue light, sodium yellow and the white light that carries out visuognosis easily.
Near the short wavelength regions 460nm that uses at visible light, have the luminous element 47 of peak luminous wavelength, when sending the fluor of sodium yellow and sending the fluor of red light, the mixed light of exciting light 42 that is penetrated by luminous element 47 and the light that sent by fluor 55 is as illumination light 43 directed outwards.This illumination light 43 becomes reddish white light.
When using near the 365nm of ultra-violet region, have peak luminous wavelength luminous element 47 and by the fluor that sends blue light with when sending the fluor 55 that the fluor of sodium yellow mixes, the white light that is sent by fluor 55 becomes illumination light 43.Because being invisible to the naked eye of ultraviolet ray personnel selection, so just the light that is sent by fluor 55 becomes illumination light 43, wherein fluor 55 is used to carry out wavelength Conversion and makes ultraviolet ray become visible light.Therefore, the white light that is sent by fluor 55 becomes illumination light 43.
But, consider the various combinations of fluor 55, the situation and utilizing that the then favourable three primary colors of using up (blue, green, redness) obtain the tone of wide scope becomes blue and yellow, the blue-greenish colour of complementary color relation and the situation that 2 kinds of colors such as redness, green and redness, bluish voilet and yellow-green colour obtain various tones.Also a side of these colors can be replaced as the light that penetrates by luminous element.When the light that so-called complementary color refers to a side peak luminous wavelength mixes with the light of the opposing party's peak luminous wavelength, can access 2 kinds of colors of the light of white portion here.At this, the relation of color name and wavelength region is referring to JIS Z8110.In addition, in order to obtain high color rendering, also fluor 55 is carried out various combinations sometimes.
So-called color rendering be about to character by this light source of the diopter of the object color of a certain light illumination.Colour temperature is the color of performance light source aspect psychological physic itself, represents with the absolute temperature (K) of perfect radiator with the colourity that equates with the colourity of a certain light source.In general, under a certain light source to the diopter of the object color seen, by it with represent in the difference that has under the reference light of same colour temperature the diopter of the object color seen.On average drilling the mean value of look evaluation number (Ra) aberration during respectively by the irradiation of test portion light source and reference light source based on 8 kinds of colour charts obtains.The special look evaluation number of drilling is that top 8 kinds of colour charts other 7 kinds of colour charts aberration is separately in addition obtained for the basis, is not 7 kinds mean value.Wherein R9 represents redness.
This light-emitting device 1000 can be at the irradiation subject and to medical fields such as its endoscopes of making a video recording, obtain aspects uses such as versicolor means of illumination, indicating meter with a plurality of excitation light sources 44.The light that is penetrated by light-emitting device 1000 is except that directly being undertaken the visuognosis by the people, also makes a video recording in ccd video camera etc. sometimes.Consistent with the sensitivity of imagescopes such as ccd video camera, suitably selective exitation light source 44 and fluor 55.
Effect with regard to light-emitting device 1000 describes below.The exciting light 42 that is penetrated by the luminous element 47 that excitation light source 44 had sees through lens 49 and guiding injection part 48.Lens 49 will be focused on by the exciting light 42 that luminous element 47 penetrates at injection part 48.The exciting light 42 that penetrates from injection part 48 is directed to photoconductive fiber 46.Exciting light 42 produces the efferent 52 of the total reflection and the other end that leads repeatedly in photoconductive fiber 46.It is on the fluor 55 that the exciting light 42 that derivation is next is radiated at the fluorescent material 54 that is provided with on the efferent 52, and at least a portion of this exciting light 42 is absorbed by fluor 55 and after carrying out wavelength Conversion, sends the light in predetermined wavelength zone.This light is as illumination light and directed outwards, perhaps the illumination light that mixes as the light that is sent by fluor 55 and exciting light 42 and directed outwards.Produce the absorption and the scattering of light at efferent 52 by fluor 55, thereby optical density(OD) is improved.Therefore, use mineral filler 32 and binding agent member 57 to need thermotolerance, member that photostabilization is good.Thus, can obtain white light with 1 luminous element 47 at least.In addition, because only just can obtain white light, so the light-emitting device that a kind of tone variation is few, be rich in color reproducibility can be provided with 1 luminous element 47.In addition, because use luminous element 47 and fluor 55, so a kind of easy colour mixture and the high light-emitting device of color rendering can be provided.In addition, can also provide a kind of luminous intensity high light-emitting device.Owing on luminous element 47, be not coated with fluor 55, so can not cause the degeneration of fluor 55 because of the heating that excitation produced that is accompanied by luminous element 47.Moreover, when the laser diode element is used as excitation light source 44, because optical density(OD) is high, so the resin that is mixed with fluor 55 can not be used for efferent 52.In contrast, when binding agent members 57 such as alumina sol that will be mixed with fluor 55 and yttrium colloidal sol are used for efferent 52, because photostabilization, thermotolerance are extremely good, so even can provide a kind of light-emitting device that higher optical density(OD) also can not be degenerated and weather resisteant is good that contrasts.
(excitation light source)
Excitation light source 44 can penetrate the light that is used for excited fluophor 55, semiconductor light-emitting elements, lamp, electron beam, plasma body and EL etc. can be used as the energy.The present invention is not limited especially, but since small-sized and luminous intensity is high, so preferably use luminous element 47.Luminous element 47 can use light-emitting diode (LED) and laser diode element (LD).
(luminescent material)
Luminescent material 54 can use fluor 55 and pigment etc. as long as sending the illumination light in predetermined wavelength zone after absorbing the exciting light that is penetrated by excitation light source 44 and carrying out wavelength Conversion just has no particular limits.The luminous spectrum of excitation light source 44 is different with the luminous spectrum of luminescent material 54.Because the light that will be penetrated by excitation light source 44 is as exciting light, so the bigger wavelength side of the peak luminous wavelength that luminescent material 54 is had at excitation light source 44 has peak luminous wavelength.Especially, though with the laser diode element as under the situation of luminous element 47, also because illumination light is the luminous spectrum of the non-constant width of peak width at half height and carry out visuognosis easily.Can use above-mentioned fluor 55, filler member 56 and binding agent member 57.As the method that is coated with at efferent 55, except can mixing phosphor 55, filler member 56 and binding agent member 57 and it is configured in the predetermined container, makes lid seals of glass and translucent resin etc. then, also can mixing phosphor 55, filler member 56 and binding agent member 57 and with its be configured in the predetermined container, solvent impregnated resin then, their not special qualifications.In addition, in order to improve heat extraction, also can dispose the mineral filler that heat conductivity is good and have light transmission.
(photoconductive fiber)
Photoconductive fiber 46 can have the photoconduction that will be penetrated by excitation light source 44 effect to luminescent material 54.Consider from the angle of energy efficiency, especially preferably make the light that penetrates by excitation light source 44 luminescent material 54 that leads unattenuatedly.For example operable have: the material and the combination of materials with low-refraction material that gets up and the material that has used the high member of reflectivity that will have high refractive index.Specifically, can use photoconductive fiber 46.
Photoconductive fiber 46 is the superfine glass fibre as the transmission route use of light in the transmission light time.With silica glass and plastics is material, improves the specific refractory power of section central part (core) with respect to periphery (covering), can make thus that optical signal is unattenuated just to be transmitted.
Photoconductive fiber 46 is because be movable, so illumination light 43 can be radiated at preposition.In addition, photoconductive fiber 46 also can curve the shape of curve.Photoconductive fiber 46 can be designed as the single line fiber.The diameter of the core of single line fiber is preferably 400 μ m or following.
(cut-off component)
Cut-off component also can use and can interdict 90% or the material of the above light that comes from excitation light source.For example, send in use under the situation of harmful ultraviolet luminous element 47, in order to interdict this ultraviolet ray, can be with UV light absorber as cut-off component.In addition, predetermined filler is set, also can interdicts presetted wavelength at efferent 52.
As mentioned above, the manufacture method of the manufacture method of luminescent film of the present invention, light-emitting device, luminescent film and light-emitting device can be used for aspects such as illumination light source, light-emitting diode display, back light, teleseme, illuminated switch, various transmitter and various telltales.

Claims (34)

1. luminescent film, it is the luminescent film that is used to cover semiconductor light-emitting elements, described luminescent film is characterised in that: be made of filler member that contains luminescent material and binding agent member at least, described binding agent member contains the hydrous oxide of metallic element at least.
2. luminescent film according to claim 1 is characterized in that: described luminescent material is an inorganic phosphor, and described filler member is mineral filler, and described binding agent member is the mineral binder bond based on the hydrous oxide of the metallic element of constant valence mumber.
3. luminescent film according to claim 1, it is characterized in that: described luminescent material is an inorganic phosphor, described filler member is mineral filler, described binding agent member is that the hydrous oxide of described metallic element is the hydrous oxide of IIIA family or IIIB family element based on the mineral binder bond of the hydrous oxide of metallic element.
4. luminescent film according to claim 3 is characterized in that: described IIIA family or IIIB family element contain at least a kind among Sc, Y, Gd, Lu or B, Al, Ga, the In.
5. according to each described luminescent film of claim 1～4, it is characterized in that: the hydrous oxide of the metallic element that contains in the described binding agent member is the hydrous oxide with Al of boehmite structure or pseudo-boehmite structure.
6. luminescent film according to claim 5, it is characterized in that, described binding agent member contains: the hydrous oxide of aluminium, and with the hydrous oxide that with respect to binding agent member content is 0.5 weight %～IIIA family's elements 50 weight %, different with described aluminium or IIIB family element.
7. according to each described luminescent film of claim 1～4, it is characterized in that: the hydrous oxide of the metallic element that contains in the described binding agent member is the hydrous oxide of yttrium.
8. luminescent film according to claim 7, it is characterized in that, described binding agent member contains: the hydrous oxide of yttrium, and with the hydrous oxide that with respect to binding agent member content is 0.5 weight %～IIIA family's elements 50 weight %, different with described yttrium or IIIB family element.
9. luminescent film according to claim 5 is characterized in that: it is boron oxide or the boric acid of 0.5 weight %～50 weight % that described binding agent member contains with respect to binding agent member content.
10. according to each described luminescent film of claim 1～4, it is characterized in that: described binding agent member is the porous insert that is formed crosslinking structure, reticulated structure or polymer architecture by the aggregate of the particle that contains described hydrous oxide.
11. each the described luminescent film according to claim 1～4 is characterized in that: described binding agent member is gel, is wherein filling the inorganic particulate that contains described hydrous oxide.
12. luminescent film according to claim 11 is characterized in that: polycrystal or non-crystal transmitance that the light transmission rate of described luminescent film carries out under this situation of sintering after than sol gel reaction are higher.
13. each the described luminescent film according to claim 1～4 is characterized in that: described binding agent member contains 10 weight % or following hydroxyl or crystal water with respect to the binding agent member.
14. each the described luminescent film according to claim 1～4 is characterized in that: constitute the filler member of described luminescent film and the weight ratio of binding agent member and count 0.05～30 with filler/binding agent.
15. a light-emitting device, it has luminous element and absorbs at least a portion of the light that described luminous element sends and luminous luminescent layer, and described light-emitting device is characterised in that: described luminescent layer is each described luminescent film of claim 1～14.
16. light-emitting device according to claim 15 is characterized in that: described luminescent layer directly covers described luminous element.
17. luminescent film according to claim 2 is characterized in that: described mineral binder bond is flooded by resin with the state that is capped.
18. the manufacture method of a luminescent film, it is the manufacture method of the luminescent film that is used for covering luminous element that is made of filler member that comprises luminescent material and binding agent member at least, described manufacture method is characterised in that, may further comprise the steps: will mix and the step of allotment slip as the metal oxygen alkane colloidal sol that contains metallic element and the filler member of binding agent member, described slip is formed membranaceous step, and by the described slip that forms film is carried out thermofixation at 50 ℃～500 ℃, the particle accumulation that makes the hydrous oxide that contains described metallic element together, thereby use the step of the mineral binder bond member appendix filler member that the structure by this set particle constitutes.
19. the manufacture method of luminescent film according to claim 18 is characterized in that: described metal oxygen alkane colloidal sol is aikyiaiurnirsoxan beta colloidal sol or yttrium oxygen alkane colloidal sol.
20. the manufacture method of luminescent film according to claim 18 is characterized in that: described mineral binder bond is flooded by resin with the state that is capped.
21. the manufacture method of a light-emitting device, it is to have luminous element and the manufacture method of the light-emitting device of the luminescent film that obtains according at least a portion of claim 18 or 19 described manufacture method covering luminous elements, described manufacture method is characterised in that: form in the membranaceous step described, under heat-treat condition, adopt described slip to cover described luminous element and/or separate the zone of luminous element, thereby form membranaceous.
22. light-emitting device, it has the matrix of luminous element and the described luminous element of carrying, described light-emitting device is characterised in that: described luminous element is covered by mineral binder bond, described mineral binder bond contains the hydrous oxide of metallic element at least, and covered by resin, described mineral binder bond floods with described resin, and described mineral binder bond forms the inorganic bond layer of at least a portion that covers described luminous element and described matrix.
23. light-emitting device according to claim 22 is characterized in that: the space landfill that described mineral binder bond is had described mineral binder bond layer by described resin.
24. light-emitting device according to claim 22 is characterized in that: 95% or above space landfill that described mineral binder bond is had described mineral binder bond layer by described resin.
25. light-emitting device according to claim 22 is characterized in that: the step that adopts described resin to cover described mineral binder bond is used pouring means or spraying spraying means, makes described mineral binder bond flood described resin.
26. according to each described light-emitting device of claim 22～25, it is characterized in that: described mineral binder bond contains fluor.
27. light-emitting device according to claim 22 is characterized in that: described resin formation covers the resin layer of at least a portion of described mineral binder bond.
28. light-emitting device according to claim 27 is characterized in that: the surface of described resin layer is level and smooth surface.
29. light-emitting device according to claim 22 is characterized in that: described resin contains at least a among oil plant, gel and the rubber.
30. light-emitting device according to claim 22 is characterized in that: under described resin any situation before moulding and after the moulding, be silicone resin with dialkylsiloxane skeleton.
31. light-emitting device according to claim 22 is characterized in that: on main chain, have dimethyl siloxane before the described resin forming.
32. light-emitting device according to claim 22 is characterized in that: described resin in the key absorption intensity of infrared spectra, the C-Si-O key during resin is formed and the strength ratio of Si-O-Si key be 1.2/1 or more than.
33. the manufacture method of a light-emitting device, it has: luminous element is carried on first operation on the matrix; With second operation of described luminous element with the mineral binder bond covering; With the 3rd operation that described mineral binder bond covers with resin, described manufacture method is characterised in that: described the 3rd operation uses pouring means or spraying spraying means to make described resin cover the described mineral binder bond of the hydrous oxide that contains metallic element at least.
34. the manufacture method of light-emitting device according to claim 33 is characterized in that: described the 3rd operation is to flood in a vacuum.
CNB200480006816XA 2003-03-13 2004-03-12 Light emitting film, luminescent device, method for manufacturing light emitting film and method for manufacturing luminescent device Expired - Fee Related CN100509994C (en)

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