CN1767180A

CN1767180A - Solid-state optical device

Info

Publication number: CN1767180A
Application number: CN 200510102515
Authority: CN
Inventors: 末广好伸; 山口诚治; 沢登成人; 大塚正明; 渡部洋己; 相田和哉
Original assignee: Toyoda Gosei Co Ltd; Sumita Optical Glass Inc
Current assignee: Toyoda Gosei Co Ltd; Sumita Optical Glass Inc
Priority date: 2004-09-09
Filing date: 2005-09-08
Publication date: 2006-05-03
Anticipated expiration: 2025-09-08
Also published as: JP2006080317A; JP4358713B2; CN100444360C

Abstract

A solid-state optical device having: a solid-state element; a power supplying/retrieving portion that supplies or retrieves electric power to/from the solid-state element; and a glass sealing material that seals the solid-state element. The glass sealing material is made of a P2O5-ZnO-based low-melting glass that has 45 to 50 wt % of P2O5 and 15 to 35 wt % of ZnO.

Description

Solid-state optical device

The application is based on Japanese patent application No.2004-263098,2004-262908 and 2005-140284, and its full content is incorporated this paper by reference into.

Technical field

The present invention relates to solid-state optical device, in particular to solid-state optical device with low-melting-point glass encapsulant.Herein, solid-state optical device comprises the various optics of being made up of as light-emitting component (or LED element), photo detector and solar cell device solid-state element (or semiconductor element).

Background technology

In the solid-state optical device traditionally, solid-state element such as LED element use transparent resin material such as epoxy sealing.Known transparent resin is owing to illumination causes deterioration.Especially, when using the III group-III nitride based compound semiconductor LED element of emission short-wavelength light, the transparent resin of LED component ambient will be owing to high energy light of launching from the LED element and the flavescence by the heat of LED element generation.Therefore, its light extraction efficiency can significantly reduce.

Rotten in order to prevent encapsulant, some solid-state optical devices (for example JP-A-8-102553 and JP-A-11-177129) have been proposed.

JP-A-8-102553 discloses LED element, closing line and the top lead-in wire luminescent device with the sealing of low-melting-point glass transparent sealant.Thereby low-melting-point glass for example is to be added with the glass that selenium, thallium, arsenic, sulphur etc. have 130-350 ℃ of fusing point.In this case, preferably using fusing point is 200 ℃ or lower, more preferably 150 ℃ or lower low-melting-point glass.

By using the low-melting-point glass transparent sealant, the luminescent device of JP-A-8-102553 can solve the problem that the optics deterioration takes place owing to the UV irradiation transparent resin material in time.

On the other hand, JP-A-11-177129 disclose the LED element with refraction coefficient be about 2, near the luminescent device of the low-melting-point glass encapsulant sealing of the refraction coefficient 2.3 of GaN base LED element.

The luminescent device of JP-A-11-177129 has following function: by using the low-melting-point glass sealing LED element of refraction coefficient near GaN base LED element refraction coefficient, reduce the total reflected light on the interface between LED element and the low-melting-point glass, launch and enter the light quantity increase of low-melting-point glass from the LED element.Therefore, compare with the traditional LED element with epoxy sealing, its light extraction efficiency increases.

But above-mentioned solid-state optical device does not have enough sealing properties, even also be so when using the low-melting-point glass encapsulant, this is because traditional low-melting-point glass has high viscosity in the working seal temperature range.

Summary of the invention

An object of the present invention is to provide the solid-state optical device that when using the low-melting-point glass encapsulant, can have enough sealing properties.

Another object of the present invention provide have excellent moisture resistivity, and can prevent to seal the time in the opaque and characteristic evaluating of glass material glass material the solid-state optical device of white opacity appears.

Another object of the present invention provides close installation that can be used in optical element and the solid-state optical device that is used for large-sized optical elements.

(1) according to an aspect of the present invention, solid-state optical device comprises:

Solid-state element;

To/supply with or reclaim the electric power supply/recovery part (power supplying/retrievingportion) of electric energy from solid-state element; With

The glass sealing material of sealing solid-state element,

Wherein said glass sealing material comprises P ₂O ₅-zno-based low-melting-point glass, described P ₂O ₅-zno-based low-melting-point glass contains 45-50 weight %P ₂O ₅With 15-35 weight %ZnO.

(2) according to another aspect of the present invention, solid-state optical device comprises:

Solid-state element;

To/supply with or reclaim the electric power supply/recovery part of electric energy from solid-state element; With

The glass sealing material of sealing solid-state element,

Wherein said glass sealing material comprises P ₂O ₅-F base low-melting-point glass, described P ₂O ₅-F base low-melting-point glass contains 6-50 weight %P ₂O ₅With 1-.45 weight %ZnO, in the weight % based on oxide.

(3) according to another aspect of the present invention, solid-state optical device comprises:

Solid-state element;

Energy supply/the recovery part of solid-state element is installed thereon, described energy supply/recovery part to/supply with or reclaim electric energy from solid-state element; With

The glass sealing material of sealing solid-state element,

Wherein said glass sealing material has the thermal coefficient of expansion that equates with energy supply/recovery part, and

Described glass sealing material comprises P ₂O ₅-Al ₂O ₃-zno-based low-melting-point glass, described P ₂O ₅-Al ₂O ₃-zno-based low-melting-point glass contains 55-62 weight %P ₂O ₅, 5-12 weight %Al ₂O ₃With 20-40 weight %ZnO, in weight %.

(4) according to another aspect of the present invention, solid-state optical device comprises:

Solid-state element;

Electric power supply/the recovery part of solid-state element is installed thereon, described electric power supply/recovery part to/supply with or reclaim electric energy from solid-state element; With

The glass sealing material of sealing solid-state element,

Described glass sealing material comprises B ₂O ₃-SiO ₂-Na ₂O-ZnO-Nb ₂O ₅The base low-melting-point glass, described B ₂O ₃-SiO ₂-Na ₂O-ZnO-Nb ₂O ₅The base low-melting-point glass contains 19-30 weight %B ₂O ₃, 0.5-15 weight %SiO ₂, 1.5-8 weight %Na ₂O, 44-60 weight %ZnO and 9-19 weight %Nb ₂O ₅, in weight %.

(5) according to another aspect of the present invention, solid-state optical device comprises:

Solid-state element;

The glass sealing material of sealing solid-state element,

Described glass sealing material comprises B ₂O ₃-SiO ₂-ZnO-Bi ₂O ₃The base low-melting-point glass, described B ₂O ₃-SiO ₂-ZnO-Bi ₂O ₃The base low-melting-point glass contains 1-10 weight %SiO ₂, 15-30 weight %B ₂O ₃, 25-60 weight %ZnO and 10-50 weight %Bi ₂O ₃, in weight %.

(6) according to another aspect of the present invention, solid-state optical device comprises:

Solid-state element;

The glass sealing material of sealing solid-state element,

Described glass sealing material comprises B ₂O ₃-SiO ₂-PbO base low-melting-point glass, described B ₂O ₃-SiO ₂-PbO base low-melting-point glass contains 20 weight %-50 weight %B ₂O ₃With 30 weight %-70 weight %PbO, in weight %.

(7) according to another aspect of the present invention, solid-state optical device comprises:

Solid-state element;

The glass sealing material of sealing solid-state element,

Wherein said glass sealing material has the thermal coefficient of expansion that equates with solid-state element and Power supply/recovery part.

[advantage of the present invention]

When using the low-melting-point glass encapsulant, solid-state optical device of the present invention, especially luminescent device can have enough sealing properties.

In addition, solid-state optical device of the present invention can have excellent moisture resistivity, and can prevent from sealing the time in the opaque and characteristic evaluating of glass glass material white opacity appears.

In addition, because entire device is made of the material with low thermal coefficient of expansion, solid-state optical device of the present invention can be applied to the close installation of optical element and be used for large-sized optical elements.

Description of drawings

Explain with reference to the accompanying drawings according to the preferred embodiments of the invention, wherein:

Figure 1A is the sectional view that illustrates in first preferred embodiment of the present invention as the luminescent device of solid-state optical device;

Figure 1B is the end view that GaN base LED element among Figure 1A is shown;

Fig. 2 A is the vertical view that illustrates in second preferred embodiment of the present invention as the luminescent device of solid-state optical device;

Fig. 2 B is the sectional view that cuts along the line A-A among Fig. 2 A;

Fig. 2 C is the perspective view that Fig. 2 B middle and lower part glass is shown;

Fig. 3 A is the sectional view that illustrates in the 3rd preferred embodiment of the present invention as the luminescent device of solid-state optical device;

Fig. 3 B is the end view that GaN base LED element among Fig. 3 A is shown;

Fig. 4 A is the sectional view that illustrates in the 4th preferred embodiment of the present invention as the luminescent device of solid-state optical device;

Fig. 4 B is the end view that AlInGaP base LED element among Fig. 4 A is shown;

Fig. 5 is the sectional view that solid-state optical device in the 5th preferred embodiment of the present invention is shown;

Fig. 6 A is the vertical view that illustrates in the 6th preferred embodiment of the present invention as the luminescent device of solid-state optical device;

Fig. 6 B is the sectional view that cuts along the line b-b among Fig. 6 A;

Fig. 6 C is the upward view that luminescent device among Fig. 6 A is shown;

Fig. 7 is the sectional view that illustrates in the 7th preferred embodiment of the present invention as the luminescent device of solid-state optical device; With

Fig. 8 is the sectional view that illustrates in the 8th preferred embodiment of the present invention as the luminescent device of solid-state optical device, and large scale (1mm is square) LED element 2 wherein has been installed.

Embodiment

[first embodiment]

Figure 1A is the sectional view that illustrates in first preferred embodiment of the present invention as the luminescent device of solid-state optical device.Figure 1B is the end view that GaN base LED element among Figure 1A is shown.

[structure of luminescent device 1]

Luminescent device 1 shown in Figure 1A is composed as follows: flip-chip type GaN base LED element 2; The Al that comprises glass ₂O ₃Substrate 3, it is equipped with GaN base LED element 2 as the inorganic material substrate on it; Circuit pattern 4, it is made by tungsten (W)-nickel (Ni)-Jin (Au), and is formed on the Al that comprises glass ₂O ₃On the substrate 3; Au salient point 5, it forms between GaN base LED element 2 and circuit pattern 4 and is electrically connected; With glass sealing material 6, it is P ₂O ₅-ZnO-Li ₂O base transparent inorganic encapsulant, and its in sealing GaN base LED element 2 with the Al that contains glass ₂O ₃Substrate 3 engages.In this embodiment, the Al that comprises glass ₂O ₃Substrate 3 and circuit pattern 4 limit Power supply/recovery part.

GaN base LED element 2 shown in Figure 1B is composed as follows: sapphire (Al ₂O ₃) substrate 20; Resilient coating 21; N type layer 22; The layer 23 that comprises luminescent layer; P type layer 24, wherein grown buffer layer 21 to p type layers 24 successively on substrate 20.In addition, GaN base LED element 2 is by being formed on the p electrode 25 on the p type layer 24 and being formed on by etching p type layer 24 until n type layer 22 and the n electrode 26 on n type layer 22 part that expose is formed.The epitaxial growth under 700 ℃ or higher temperature of GaN base LED element 2, the allowable temperature limit value is 600 ℃ or higher, the processing temperature when sealing with following low-melting-point glass is stable.

P electrode 25 is as reflection layer, to reflect the light of launching to substrate 20 from the layer 23 that comprises luminescent layer.In this embodiment, p electrode 25 has 0.34mm wide * 0.34mm is dark * size that 0.09mm is thick.

The Al that comprises glass ₂O ₃Substrate 3 has 12.3 * 10 ^-6/ ℃ thermal coefficient of expansion, and provide a plurality of through hole 3A.Through hole 3A is used for forming electrical connection on the upper surface of substrate 3 and the lower surface between the metallized circuit pattern 4.Circuit pattern 4 is made up of first conductive pattern, second conductive pattern and the 3rd conductive pattern, described first conductive pattern is formed on the surface that GaN base LED element 2 is installed, described second conductive pattern is formed on the facing surfaces, described the 3rd conductive pattern is made by tungsten (W), forms to be electrically connected between first and second conductive patterns.

Glass sealing material 6 is by P ₂O ₅-ZnO-Li ₂O base low-melting-point glass makes, and glass transition temperature Tg is 380 ℃, and yield point At is 407 ℃, and thermal coefficient of expansion is 12.2 * 10 ^-6/ ℃, refraction index is 1.60, internal transmittance is 99% (470nm).It is by being engaged in the Al that comprises glass with mould heat pressure ₂O ₃On the substrate 3, by forming the rectangle with end face 6A and side 6B with the slicer cutting.

Low-melting-point glass is usually with the viscosity processing than the high several orders of magnitude of the high viscosity level in the resin.For glass, in the scope of actual seal temperature, even its viscosity can not be reduced to common resin-sealed level when being heated to above tens ℃ of yield point temperature.Yet,, it need be heated to temperature above LED element crystal growth temperature in order to have the viscosity of common resin-sealed level.Under this high temperature, glass will be adhered to mould, thereby be difficult to seal and moulding with it.Just because of this, preferably 10 ⁴Process under pool or the higher viscosity.

(method for preparing luminescent device 1)

Below the method for preparing luminescent device 1 will be described.

At first, provide the Al that comprises glass with through hole 3A ₂O ₃Substrate 3 according to circuit pattern 4, is screen-printed to tungsten cream the Al that comprises glass ₂O ₃On the surface of substrate 3.

Then, the Al that comprises glass of tungsten cream will be printed with on it ₂O ₃ Substrate 3 is heat-treated at about 1000 ℃, thereby tungsten is burnt in the substrate 3, nickel and gold is plated on the tungsten successively, to form circuit pattern 4.

Then, make GaN base LED element 2 be engaged to the Al that comprises glass by Au salient point 5 electricity ₂O ₃The circuit pattern 4 (on the face side) of substrate 3.

Then, with tabular P ₂O ₅-ZnO-Li ₂O base low-melting-point glass and the Al that comprises glass that the basic LED element 2 of GaN is installed on it ₂O ₃ Substrate 3 parallel placements, then hot pressing in blanket of nitrogen.In this process, the viscosity of low-melting-point glass is 10 ⁸-10 ⁹Pool, low-melting-point glass is engaged to the Al that comprises glass by the oxide that is included in wherein ₂O ₃On the substrate 3.

The Al that comprises glass that will engage with low-melting-point glass then, ₂O ₃Substrate 3 is placed on the slicer, cuts into respectively luminescent device 1.

At this moment, can be by scribing (scribing) processing GaN base LED element 2.In this case, owing to have obvious unevenness through the GaN of scribing base LED element 2 in the side corresponding to cutting part, therefore need to apply with device coating the side of GaN base LED element 2.Device coating can be the SiO that for example has the transmittance performance ₂Base coating.Device coating can prevent to crack or hole.

(composition of glass sealing material 6)

The low-melting-point glass that below detailed description be can be used for this embodiment.

By changing P ₂O ₅, Li ₂O, MgO, CaO, SrO, BaO, ZnO, ZrO ₂, RO, Nb ₂O ₅And Al ₂O ₃Composition prepare sample 1-3 as glass sealing material 6.Herein, RO is the common name that comprises MgO, CaO, SrO, BaO and ZnO.For relatively, prepared the comparative sample that has identical oxide with sample 1-3.Following table 1 shows the composition and the characteristic of sample 1-3 and comparative sample.In table 1, nF-nC refers to principal dispersion (primarydispersion).

Table 1

Form (wt%)	Sample 1	Sample 2	Sample 3	Comparative sample
Form (wt%)	Sample 1	Sample 2	Sample 3	Comparative sample	MgO	-	3	-	-
P ₂O ₅	50	45	48	55	MgO	-	3	-	-
P ₂O ₅	50	45	48	55	Al ₂O ₃	3	2	1.5	2.5
Li ₂O	5	5	4.5	5	Al ₂O ₃	3	2	1.5	2.5
Li ₂O	5	5	4.5	5	CaO	2	3	5.5	2
SrO	10	-	-	-	CaO	2	3	5.5	2
SrO	10	-	-	-	BaO	-	15	14.5	6
ZnO	30	25	24	27	BaO	-	15	14.5	6
ZnO	30	25	24	27	Nb ₂O ₅	-	1	1	1.5
ZrO ₂	-	1	1	1	Nb ₂O ₅	-	1	1	1.5
ZrO ₂	-	1	1	1
Tg(℃)	380	392	378	363
Tg(℃)	380	392	378	363	At(℃)	407	422	412	390
α(×10 ^-6/℃) (100-300)	12.2	12.2	12.3	12.9	At(℃)	407	422	412	390
α(×10 ^-6/℃) (100-300)	12.2	12.2	12.3	12.9	nd	1.59973	1.61376	1.60938	1.589
nF-nC	0.00975	0.01037	0.01027	0.0099	nd	1.59973	1.61376	1.60938	1.589
nF-nC	0.00975	0.01037	0.01027	0.0099	vd	59.51	59.19	59.34	59.5
R0 amounts to	42	46	44	35	vd	59.51	59.19	59.34	59.5

In addition, following table 2 illustrates the evaluation result that whether sample 1-3 and comparative sample are taken place opaque phenomenon.Evaluation is carried out under different conditions, promptly at 60 ℃, Rh 90% and 1000h; With carry out under the condition of 85 ℃, Rh 85% and 1000h.

Table 2

As can be seen from Table 2, sample 1-3 does not have opaque phenomenon and keeps transparent.

On the contrary, comparative sample has opaque phenomenon under the condition of 85 ℃, Rh 85% and 1000h.

Therefore proof: under the condition of 85 ℃, Rh 85% and 1000h, glass sealing material 6 does not have opaque phenomenon in following compositing range: 45-50 weight %P ₂O ₅, 3-6 weight %Li ₂O, 0-3.5 weight %MgO, 0-10 weight %CaO, 0-15 weight %SrO, 0-30 weight %BaO, 15-35 weight %ZnO, 0-1 weight %ZrO ₂, 38-49 weight %RO, 0-1.5 weight %Nb ₂O ₅With 0-5 weight %Al ₂O ₃

In addition, according to inventor's research, confirm: P ₂O ₅-ZnO-Li ₂O base low-melting-point glass has the preferred characteristics as glass sealing material in the present embodiment 6 when having following the composition: 45-50 weight %P ₂O ₅, 3-6 weight %Li ₂O, 0-3.5 weight %MgO, 0-10 weight %CaO, 0-15 weight %SrO, 0-30 weight %BaO, 15-35 weight %ZnO, 0-1 weight %ZrO ₂, 38-49 weight %RO, 0-1.5 weight %Nb ₂O ₅With 0-5 weight %Al ₂O ₃

At this moment, have above-mentioned compositing range, it is 350-400 ℃ that glass sealing material 6 can have following properties: Tg; At is 375-450 ℃; α is 10.0-14.0 * 10 ^-6/ ℃; Nd is 1.58-1.62; It is 59.0-64.0 that Abbe counts vd.

(effect of first embodiment)

The effect that first embodiment is obtained is as follows:

(1) by using by P ₂O ₅-ZnO-Li ₂The glass sealing material 6 that O base low-melting-point glass makes and carry out hot pressing under high viscosity state, this process can be carried out under the temperature that fully is lower than crystal growth temperature.

(2) owing to comprise the Al of glass ₂O ₃Substrate 3 engages with glass sealing material 6 by oxide based on chemical bonding, thereby can obtain high sealing intensity.Therefore, even also can realize fine and close encapsulation under the situation of little bonding area having.

(3) owing to comprise the Al of glass ₂O ₃Substrate 3 has the thermal coefficient of expansion similar to glass sealing material 6, even also adhesion failure can not take place therein when placing normal temperature or low temperature after therefore at high temperature engaging, as separating and crackle.

In addition, glass can not crack under compression stress, but may crack under tensile stress.Glass sealing material 6 is adjusted to thermal coefficient of expansion is slightly smaller than the Al that comprises glass ₂O ₃The thermal coefficient of expansion of substrate 3.Even do not take place to separate or crackle in thousands of the circulations of the cold and hot thermal oscillation test of the liquid phase of inventor's confirmation between-40 ℃-100 ℃ yet.

In addition, also confirm: the sheet glass of 5mm * 5mm is engaged with ceramic substrate, when changing the thermal coefficient of expansion combination between sheet glass and ceramic substrate simultaneously, if a kind of material with relatively low thermel expansion coefficient is 0.85 or bigger with the ratio of the another kind of material coefficient of thermal expansion coefficient with higher thermal expansion coefficient, then the joint between it does not crack.Therefore, though depend on the hardness or the size of material, similar thermal coefficient of expansion is meant this scope.

(4) owing in flip-chip engages, do not need closing line, even the therefore yet destruction at generating electrodes place not in the process of high viscosity attitude.Because the viscosity of low-melting-point glass is up to 10 in the seal process ⁸-10 ⁹Pool, so performance obviously is different from epoxy resin, described epoxy resin existed with liquid form before thermoset processes, and viscosity is low to moderate 5 pools.Therefore, if the electrode on the element surface is electrically connected to the Power supply member such as veneer (face-up) the type LED element glass capsulation on the lead-in wire by closing line, then closing line can crushed or distortion.But, in flip-chip bonded, can avoid this problem.

On the other hand, if flip-chip type LED element glass capsulation, wherein the electrode on the element surface is electrically connected to the electric power feed element as lead-in wire by gold bump etc., then towards the full-bodied electric power supply member and be applied to pressure on the LED element and can cause short circuit between projection crushing and the projection based on glass.But in this embodiment of using salient point, this problem also can be avoided.

(5) by with low-melting-point glass with comprise the Al of glass ₂O ₃Substrate 3 parallel placements are carried out hot pressing to it then under the high viscosity attitude, because low-melting-point glass is comprising the Al of glass when sealing GaN base LED element 2 ₂O ₃The upper parallels in substrate 3 surface with close contact with it, therefore can prevent hole.

(6) owing to comprising the Al of glass ₂O ₃Wiring (wiring) circuit pattern 4 that forms on the substrate 3 is guided the bottom side into by through hole 3A, does not need be used to preventing that glass from invading inessential part and preventing that electric connection is by glass-faced device.Therefore, by all sealing a plurality of devices with tabular low-melting-point glass, can be easily by producing in a large number a plurality of luminescent devices 1 with the slicer section.

Simultaneously, because low-melting-point glass processes, thereby can save the device that needs in resin-sealed under the high viscosity attitude.Therefore, if guide outside terminal into bottom side, then do not use through hole 3A just to be enough to produce in a large number a plurality of luminescent devices 1.

(7) because GaN base LED element 2 is flip-chip installs, thereby can realize littlely of the square extra small luminescent device 1 of 0.5mm, and overcome the problems referred to above in the glass capsulation.This is because do not need the space for closing line, and because glass sealing material 6 and the Al that comprises glass ₂O ₃The similitude of thermal coefficient of expansion and based on the high bond strength of chemical bond therebetween between the substrate 3, even so little bonding area also can prevent interfacial separation.

(8) by the P with glass sealing material 6 ₂O ₅Content is adjusted to 50% or lower, even the sealing material also has stable moisture resistivity under high humidity environment, and can prevent the appearance of white opacity.

(9) by in glass sealing material 6, adding Li ₂O can realize the raising of glass weatherability, lower fusing point and the stability of enhancing.

Though in the first embodiment, GaN base LED element 2 is used for luminescent device 1, is applicable to that the LED element of glass capsulation is not limited to GaN base LED element 2.The semiconductor light-emitting elements that it can be made up of another kind of semi-conducting material.

In addition, luminescent device 1 can be prepared into wavelength conversion type, wherein phosphor is joined P ₂O ₅-ZnO-Li ₂In the O base low-melting-point glass, carry out the wavelength conversion by mixing from the phosphor exciting light that penetrates and the light that sends from GaN base LED element 2.Scheme as an alternative, phosphor layer can form film on the surface of glass sealing material 6.

[second embodiment]

Fig. 2 A is the vertical view that illustrates in second preferred embodiment of the present invention as the luminescent device of solid-state optical device; Fig. 2 B is the sectional view that cuts along the line A-A among Fig. 2 A; Fig. 2 C is the perspective view that Fig. 2 B middle and lower part glass is shown.

(structure of luminescent device 1)

Luminescent device 1 is composed as follows: veneer type GaN base LED element 2; Lead-in wire 19 as electric power supply/recovery part, has the lead-in wire cover part 19B that GaN base LED element 2 is installed on it; Lead 10 is in the GaN base LED element 2 and the formation electrical connection between 19 that goes between; With silicone coatings 35, cover GaN base LED element 2 and lead 10 to protect them.GaN base LED element 2 and lead-in wire 19 are used P ₂O ₅-F base glass sealing material 6 integral sealings, described P ₂O ₅-F base glass sealing material 6 is made up of top glass 60A and the bottom glass 60B of in advance moulding.

In weight % based on oxide, the consisting of of glass sealing material 6: 43 weight %P ₂O ₅, 4.3 weight %Li ₂O, 18.9 weight %Na ₂O, 10.7 weight %K ₂O, 23.5 weight %Al ₂O ₃With 11 weight %F, performance is: Tg is 326 ℃; At is 354 ℃; α: 18.0 * 10 ^-6/ ℃; Nd:1.50; And vd:69.8.

Lead-in wire cover part 19B forms the taper shape with inclined-plane 190 and bottom surface 191, and is assembled among the wire lead slot 60C of bottom glass 60B, shown in Fig. 2 C.With mould preforming bottom glass 60B (not shown) the time, form lead-in wire groove 60C.

(method for preparing luminescent device 1)

Below the method for preparing luminescent device 1 will be described.

At first, preparation lead frame (not shown), this lead frame provide a pair of copper lead-in wire 19, form silvering in its surface.

Then, GaN base LED element 2 is installed on the lead-in wire cover part 9B of lead-in wire 19.GaN base LED element 2 covers on the bottom surface 191 of part 19B at lead-in wire by the inorganic transparent adhesive bond.Then, with this to go between 19 and GaN base LED element 2 be electrically connected by lead 10.

Then, with the lead-in wire that is electrically connected to 19 and GaN base LED element 2 be placed among the wire lead slot 60C of preformed bottom glass 60B.Then, silicon resin coating 35 is installed among the wire lead slot 60C, to cover lead-in wire to 19 and GaN base LED element 2.

Then, by hot pressing top glass 60A and bottom glass 60B are combined.Then, luminescent device 1 is downcut along lead frame.

(effect of second embodiment)

The effect that second embodiment is obtained is as follows:

(1) with first embodiment in luminescent device similar, by using by P ₂O ₅The glass sealing material 6 that-F base low-melting-point glass makes even the luminescent device 1 of second embodiment also can have stable moisture resistivity under high humidity environment, and unlikely has white opacity.

In addition, because the waterproof effect (water-shedding effect) of fluorine, even it also can remain unchanged under the condition of 85 ℃, Rh 85% and 1000h.

(2) although cause silicones to produce gas under about 400 ℃ because heat can be cut off molecular link, described process can be carried out under 360 ℃, and this moment, silicon resin coating 35 can thermal decomposition.Therefore, the heat in the glass capsulation process can be absorbed by silicones, and thermal stress can be therefore lax.

(3) by using the bottom glass 60B of the in advance moulding wherein being placed with lead-in wire cover part 19B, lead-in wire is to 19 glass capsulations stably.

(4) distinguish sealing wire by carry out hot pressing at lead frame with use glass, and it is carried out connecting rod (tie-bar) cutting from lead frame, can produce luminescent device 1 in batches, to boost productivity.

(5) owing to the lead-in wire that is made of such as copper by the soft metal is compared high resilience to 19 with glass material, when when the thermal expansion coefficient difference of GaN base LED element 2 is in the 150%-500% scope, stress based on thermal expansion coefficient difference can be absorbed, and keeps the good bond state with glass material simultaneously.Therefore, even be clipped in the middle when sealing by glass material to 19 when lead-in wire, the destruction such as crackle can not appear yet.

Research based on the inventor has confirmed P ₂O ₅-F base low-melting-point glass glass sealing material 6 in this embodiment when having following the composition has preferred characteristic: 34-50 weight %P ₂O ₅, 2-9 weight %Li ₂O, 7-28 weight %Na ₂O, 3-27 weight %K ₂O, herein R ₂The total amount of O is 17-41 weight % (R:Li, Na, K), 6.5-30 weight %Al ₂O ₃With 1.5-32 weight %F.Herein, R ₂O comprises Li ₂O, Na ₂O and K ₂The general formula of O.

Above-mentioned compositing range makes it to have following properties: Tg is 230-350 ℃; At is 260-390 ℃; α is 15.0-28.0 * 10 ^-6/ ℃; Nd is 1.43-1.55.Have above-mentioned compositing range, can be implemented in about 400 ℃ or the more glass capsulation under the low temperature and good moisture resistivity.But if only need moisture resistivity, then in the weight % based on oxide, low-melting-point glass has following composition: 6-50 weight %P ₂O ₅With 1-45 weight % ^F

Embodiment as an alternative, P ₂O ₅-F base low-melting-point glass can have following composition: 3.0-8.0mol%P ₂O ₅, 0.1-2.0mol%Al ₂O ₃, 1.0-7.0mol%BaO, 35.5-41.0mol%AlF ₃, 8.0-13.0mol%MgF ₂, 16.0-26.0mol%CaF ₂, 15.0-21.0mol%SrF ₂, 3.5-10.0mol%BaF ₂And 1.0-6.0mol%NaF ₂

In addition, embodiment as an alternative, P ₂O ₅-F base low-melting-point glass can have following composition: 15-32 weight %Al (PO ₃) ₂, 0-10 weight %Ba (PO ₃) ₂, 0-10 weight %Sr (PO ₃) ₂, 0-10 weight %Ca (PO ₃) ₂, 0-10 weight %Mg (PO ₃) ₂, this moment, the total amount of metaphosphate was 20-32 weight %, the BaF of 20-70 weight % ₂, 5-40 weight %SrF ₂, 0-15 weight %CaF ₂, 0-10 weight %MgF ₂, 0-5 weight %AlF ₃, 0-5 weight %GdF ₃, this moment, the total amount of fluoride was 55-75 weight %, 5-22 weight %Gd ₂O ₃, 0-7 weight %La ₂O ₃, 0-10 weight %Y ₂O ₃With 0-10 weight %Yb ₂O ₃, this moment, the total amount of rare-earth salts was 5-22 weight %.

The present invention is not limited to above-mentioned embodiment, can carry out various changes within the scope of the invention.For example, glass sealing material 6 can provide the surface-treated layer (=coating) that forms on the surface, to strengthen surperficial moisture resistivity, acidproof/alkalescence.Surface-treated layer is preferably MgF ₂, SiO ₂, SiN etc.In addition, can also carry out protecting by reflection the surface treatment of the minimizing boundary reflections such as multilayer film.Be preferably TiO ₂+ SiO ₂Laminated coating.

In addition, in the first embodiment, glass sealing material 6 provides Overmolded (overmolded) part that is formed on the lip-deep shapes such as hemisphere that made by epoxy resin by transfer formation, with further enhancing moisture resistivity.Overmolded part can be the another kind of material beyond the epoxy resin, such as silicones.Can be formed such as cast (potting) method of forming by the another kind of forming method beyond the transfer formation method.

Overmolded part can be other resin materials such as acrylic resin and Merlon, and is formed by injection.In this case, can boost productivity.

In addition, Overmolded part can comprise phosphor.Described phosphor can be YAG (yttrium-aluminium-garnet), silicate phosphors or its mixture with given mixed.

[the 3rd embodiment]

Fig. 3 A is the sectional view that illustrates in the 3rd preferred embodiment of the present invention as the luminescent device of solid-state optical device; Fig. 3 B is the end view that GaN base LED element among Fig. 3 A is shown.

(structure of luminescent device 1)

Luminescent device 1 shown in Fig. 3 A is made up of following: (thermalexpansioncoefficientα is 5-7 * 10 to flip-chip type GaN base LED element 2 ^-6/ ℃); Al ₂O ₃Substrate 3 as the inorganic material substrate, is equipped with GaN base LED element 2 on it; Circuit pattern 4, it is made, and is formed on Al by tungsten (W)-nickel (Ni)-Jin (Au) ₂O ₃On the substrate 3; Au salient point 5, it forms between GaN base LED element 2 and circuit pattern 4 and is electrically connected; With glass sealing material 6, it is the transparent inorganic encapsulant and is engaged in Al ₂O ₃Substrate 3 seals GaN base LED element 2 simultaneously.In this embodiment, Al ₂O ₃Substrate 3 and circuit pattern 4 limit electric power supply/recovery part.

GaN base LED element 2 shown in Fig. 3 B is composed as follows: sapphire (Al ₂O ₃) substrate 20; Resilient coating 21; N type layer 22; The layer 23 that comprises luminescent layer; P type layer 24, wherein grown buffer layer 21 to p type layers 24 successively on substrate 20.In addition, GaN base LED element 2 is formed by being formed on the p electrode 25 on the p type layer 24 and being formed on the n electrode 26 that forms on the exposed portions n type layer 22 until n type layer 22 by etching p type layer 24.The epitaxial growth under 700 ℃ or higher temperature of GaN base LED element 2, the allowable temperature that has is limited to 600 ℃ or higher, and the processing temperature when sealing with following low-melting-point glass is stable.

Al ₂O ₃Substrate 3 has 7 * 10 ^-6/ ℃ thermal coefficient of expansion, and provide a plurality of through hole 3A.Through hole 3A is used for forming electrical connection on the upper surface of substrate 3 and the lower surface between the metallized circuit pattern 4.Circuit pattern is made up of first conductive pattern, second conductive pattern and the 3rd conductive pattern, described first conductive pattern is formed on the side that GaN base LED element 2 is installed, described second conductive pattern is formed on opposite side, described the 3rd conductive pattern is made by tungsten (W), forms to be electrically connected between first and second conductive patterns.

Glass sealing material 6 is by B ₂O ₃-SiO ₂-Na ₂O-ZnO-Nb ₂O ₅The base low-melting-point glass is made.It is by being engaged in Al with mould heat pressure ₂O ₃On the substrate 3, and by forming the rectangle with end face 6A and side 6B with the slicer section.

Low-melting-point glass is usually with the viscosity processing than the high several orders of magnitude of the high viscosity level in the resin.For glass, in the scope of actual seal temperature, even its viscosity can not be reduced to common resin-sealed level when being heated to above tens ℃ of yield point temperature.Yet,, it need be heated to temperature above LED element crystal growth temperature in order to have the viscosity of common resin-sealed level.Under this high temperature, glass will adhere to mould, thereby be difficult to seal and moulding with it.Just because of this, preferably 10 ⁴Process under pool or the higher viscosity.

(method for preparing luminescent device 1)

Below the method for preparing luminescent device 1 will be described.

At first, provide the Al with through hole 3A ₂O ₃Substrate 3 according to circuit pattern 4, is screen-printed to Al with tungsten cream ₂O ₃On the surface of substrate 3.

Then, the Al of tungsten cream will be printed with on it ₂O ₃ Substrate 3 is heat-treated under about 1000 ℃, thereby tungsten is burnt in the substrate 3, nickel and gold is plated on the tungsten successively, to form circuit pattern 4.

Then, make GaN base LED element 2 be engaged to Al by Au salient point 5 electricity ₂O ₃3 circuit pattern 4 (on the face side) at the bottom of the village.

Then, with tabular B ₂O ₃-SiO ₂-Na ₂O-ZnO-Nb ₂O ₅Base low-melting-point glass and the Al that the basic LED element 2 of GaN is installed on it ₂O ₃ Substrate 3 parallel placements, then hot pressing in blanket of nitrogen.In this process, the viscosity of low-melting-point glass is 10 ⁸-10 ⁹Pool, low-melting-point glass is engaged in Al by the oxide that is included in wherein ₂O ₃On the substrate 3.

The Al that will engage with the low-melting-point glass knot then, ₂O ₃Substrate 3 is placed on the slicer, cuts into respectively luminescent device 1.

(composition of glass sealing material 6)

By changing B ₂O ₃, SiO ₂, Al ₂O ₃, Li ₂O, Na ₂O, K ₂O, MgO, CaO, SrO, BaO, ZnO, Nb ₂O ₅, ZrO ₂And TiO ₂Composition prepare the

sample

4 and 5 of glass sealing material 6.Following table 3 has been described the constituent and properties of

sample

4 and 5.

Table 3

Form (wt%)	Sample 4	Sample 5
Form (wt%)	Sample 4	Sample 5	B ₂O ₃	30	20
SiO ₂	5	10	B ₂O ₃	30	20
SiO ₂	5	10	Al ₂O ₃
Li ₂O			Al ₂O ₃
Li ₂O			Na ₂O	7	3
K ₂O			Na ₂O	7	3
K ₂O			MgO
CaO			MgO
CaO			SrO
BaO			SrO
BaO			ZnO	45	57
Nb ₂O ₅	13	10	ZnO	45	57
Nb ₂O ₅	13	10	TiO ₂
ZrO ₂			TiO ₂
ZrO ₂
Tg(℃)	483	503
Tg(℃)	483	503	At(℃)	517	534
α(×10 ^-6/℃) (100-300)	7.4	6.0	At(℃)	517	534
α(×10 ^-6/℃) (100-300)	7.4	6.0	nd	1.68343
Necessary components total	100	100	nd	1.68343

Sample 4 shown in the table 3 does not have opaque phenomenon and keeps transparent, has following properties: Tg is 483 ℃; At is 517 ℃; α is 7.4 * 10 ^-6/ ℃; Nd is 1.68.

Sample 5 has excellent moisture resistivity, and to have following feature: Tg be 503 ℃; At is 534 ℃; α is 6.0 * 10 ^-6/ ℃.

Sample

4 and 5 composition make it to have and Al ₂O ₃The stable engagement intensity of substrate 3, and do not cause separating or crackle.

(effect of the 3rd embodiment)

The effect that the 3rd embodiment is obtained is as follows:

(1) by using by B ₂O ₃-SiO ₂-Na ₂O-ZnO-Nb ₂O ₅The glass sealing material 6 made of base low-melting-point glass, and carry out hot pressing under the high viscosity attitude, this process can be carried out being lower than under enough low temperatures of crystalline growth temperature.

(2) because Al ₂O ₃Substrate 3 engages with glass sealing material 6 by oxide based on chemical bond, thereby can obtain high sealing intensity.Therefore, even also can realize fine and close encapsulation under the situation of little bond area having.

(3) because Al ₂O ₃Substrate 3 has the thermal coefficient of expansion similar to glass sealing material 6, even also bond failure can not take place therein when placing normal temperature or low temperature after therefore at high temperature engaging, as separating and crackle.

In addition, glass can not crack under compression stress, but may crack under tensile stress.Glass sealing material 6 is adjusted to thermal coefficient of expansion is slightly smaller than Al ₂O ₃The thermal coefficient of expansion of substrate 3.

Usually, glass has in the characteristic that is being higher than thermal coefficient of expansion increase under the temperature of Tg.Therefore, when carrying out glass capsulation under the temperature that is being higher than Tg, need to consider to be higher than the thermal coefficient of expansion under the temperature of Tg, and be lower than the thermal coefficient of expansion under the temperature of Tg, so that glass capsulation is stable.That is to say that the glass material that is used for glass sealing material 6 has and Al ₂O ₃The thermal coefficient of expansion that substrate equates is considered its thermal coefficient of expansion simultaneously, comprises thermal coefficient of expansion and Al under the temperature that is lower than Tg ₂O ₃The thermal coefficient of expansion of substrate 3.Thus, can reduce to cause Al ₂O ₃The internal stress of substrate 3 distortion, and can avoid the shear fissure of glass, guarantee simultaneously Al ₂O ₃Bond strength between substrate 3 and the glass sealing material 6.Therefore, Al ₂O ₃The size of substrate 3 and glass sealing material 6 can increase, so that producible number of devices increases altogether.

The inventor confirms, even also do not take place to separate or crackle in thousands of circulations of the cold and hot thermal oscillation test of-40 ℃-100 ℃ liquid phase.

(4) owing in flip-chip bonded, do not need closing line, even the therefore yet destruction at generating electrodes place not in high viscosity attitude process.Because the viscosity of low-melting-point glass is up to 10 in the seal process ⁸-10 ⁹Pool, so performance obviously is different from epoxy resin, described epoxy resin existed with liquid form before curing process, and viscosity is low to moderate 5 pools.Therefore, when the electrode on veneer (face-up) the type LED element surface is electrically connected to the electric power feed element when upper as going between by closing line, if described element glass capsulation, then closing line can crushed or distortion.But, in flip-chip bonded, can avoid this problem.

On the other hand, if flip chip type LED element glass capsulation, wherein the electrode on the element surface is electrically connected to the electric power feed element as lead-in wire by gold bump etc., then causes the fragmentation of projection and the short circuit between the projection towards the pressure that is applied to based on the full-bodied electric power feed element of glass on the LED element.But in this embodiment of using salient point, this problem also can be avoided.

(8) because GaN base LED element 2 has the thermal coefficient of expansion that equates with glass sealing material 6, so that comprise Al ₂O ₃The thermal coefficient of expansion of the element of substrate 3 equates.Therefore, even for the high temperature and the temperature difference between the normal temperature of glass capsulation, it is very little that internal stress also can keep.Therefore, can obtain not have the stable machinability of crackle.In addition, because internal stress can keep very little, can develop the impact resistance with enhancing and the glass capsulation LED of excellent reliability.

(9) as the Al of alumina substrate ₂O ₃Substrate 3 is so that the cost of component, and is easy to obtain.Therefore, this has improved the property of can be mass-produced, and has reduced device cost.In addition, because Al ₂O ₃Have excellent thermal conductivity, can easily be applied to highlight strength and high output type.In addition, because Al ₂O ₃Light absorption little, therefore optically be favourable.

At this moment, confirm another composition: 25 weight %B ₂O ₃, 2 weight %SiO ₂, 5 weight %Na ₂O, 50 weight %ZnO and 18 weight %Nb ₂O ₅Can effectively make At is 550 ℃ or littler.In this case, nd is 1.73.

Based on the inventor's research, confirm: B ₂O ₃-SiO ₂-Na ₂O-ZnO-Nb ₂O ₅ Glass sealing material 6 when the base low-melting-point glass is composed as follows in this embodiment has preferred characteristic: 19-30 weight %B ₂O ₃, 0.5-15 weight %SiO ₂, 0-5 weight %Al ₂O ₃, 0-3 weight %Li ₂O, 1.5-8 weight %Na ₂O, 0-4 weight %K ₂O, 0-5 weight %MgO, 0-5 weight %CaO, 0-5 weight %SrO, 0-5 weight %BaO, 44-60 weight %ZnO, 9-19 weight %Nb ₂O ₅, 0-4 weight %ZrO ₂With 0-4 weight %TiO ₂

In addition, the inventor also confirms: when preparation has shown in the lower tabulation 4 sample 6 that forms and tests its moisture resistivity, 85 ℃, Rh be 85% and the condition of 2000h under, it does not have optical defect, such as lip-deep white opacity.

Table 4

Form (wt%)	Sample 6
Form (wt%)	Sample 6	B ₂O ₃	23
SiO ₂	13	B ₂O ₃	23
SiO ₂	13	Al ₂O ₃
Li ₂O	2	Al ₂O ₃
Li ₂O	2	Na ₂O	3
K ₂O		Na ₂O	3
K ₂O		MgO
CaO		MgO
CaO		SrO
BaO		SrO
BaO		ZnO	47
Nb ₂O ₅	11	ZnO	47
Nb ₂O ₅	11	TiO ₂
ZrO ₂	1	TiO ₂
ZrO ₂	1
Tg(℃)	472
Tg(℃)	472	At(℃)	500
α(×10 ^-8/℃) (100-300)	7	At(℃)	500
α(×10 ^-8/℃) (100-300)	7	nd	1.69227
Necessary components total	100	nd	1.69227

Sample 6 shown in the table 4 does not have opaque phenomenon and keeps transparent, has following properties: Tg is 472 ℃; At is 500 ℃; α is 7.0 * 10 ^-6/ ℃; Nd is 1.69.The composition of sample 6 makes it to have and Al ₂O ₃The stable engagement intensity of substrate 3, and do not cause separating or crackle, and have long-term excellent moisture resistivity.

Though in the 3rd embodiment, GaN base LED element 2 is used for luminescent device 1, is applicable to that the LED element of glass capsulation is not limited to GaN base LED element 2.The semiconductor light-emitting elements that it can be made up of another kind of semi-conducting material.

At this moment, GaN base LED element 2 can be processed by scribing.In this case, owing to can have in the side corresponding to cutting part obvious unevenness through the GaN of scribing base LED element, so the side of GaN base LED element 2 need to apply device coating.Device coating can be the SiO that for example has the transmittance performance ₂Base coating.Device coating can prevent to crack or hole.

In addition, luminescent device 1 can be prepared into wavelength conversion type, wherein phosphor is joined B ₂O ₃-SiO ₂-Na ₂O-ZnO-Nb ₂O ₅In the base low-melting-point glass, carry out the wavelength conversion by mixing from the phosphor exciting light that penetrates and the light that sends from GaN base LED element 2.Scheme as an alternative, phosphor layer can form film on the surface of glass sealing material 6.

[the 4th embodiment]

Fig. 4 A is the sectional view that illustrates in the 4th preferred embodiment of the present invention as the luminescent device of solid-state optical device; Fig. 4 B is the end view that AlInGaP base LED element among Fig. 4 A is shown;

Luminescent device 1 uses the LED element of being made by the AlInGaP base semiconductor material shown in Fig. 4 A 2, and the AlInGaP base semiconductor material is grown on the substrate shown in Fig. 4 B (GaP substrate) 20.

Glass sealing material 6 is by B ₂O ₃-SiO ₂-ZnO-Bi ₂O ₃The base low-melting-point glass is made.

At this moment, utilize the similar assembly that has similar functions below used identical Reference numeral represents in the 3rd embodiment.

(composition of glass sealing material 6)

Describe below available B in this embodiment in detail ₂O ₃-SiO ₂-ZnO-Bi ₂O ₃The base low-melting-point glass.

The sample 7 that is used for glass sealing material 6 can have following composition: SiO ₂, B ₂O ₃, La ₂O ₃, Gd ₂O ₃, Y ₂O ₃, ZrO ₂, Nb ₂O ₅, BaO, SrO, CaO, TiO ₂, ZnO, Bi ₂O ₃, Li ₂O, Na ₂O and K ₂O.Following table 5 shows the composition and the characteristic of sample 7.

Table 5

Form (wt%)	Sample 7
Form (wt%)	Sample 7	SiO ₂	5
B ₂O ₃	20	SiO ₂	5
B ₂O ₃	20	La ₂O ₃
Gd ₂O ₃		La ₂O ₃
Gd ₂O ₃		Y ₂O ₃
ZrO ₂		Y ₂O ₃
ZrO ₂		Nb ₂O ₅
BaO		Nb ₂O ₅
BaO		SrO
CaO		SrO
CaO		TiO ₂
ZnO	45	TiO ₂
ZnO	45	Bi ₂O ₃	30
Li ₂O		Bi ₂O ₃	30
Li ₂O		Na ₂O
K ₂O		Na ₂O
K ₂O
Tg(℃)	488
Tg(℃)	488	At(℃)	519
α(×10 ^-6/℃) (100-300)	6.2	At(℃)	519
α(×10 ^-6/℃) (100-300)	6.2	nd	1.81016
Necessary components total	100	nd	1.81016

Sample 7 shown in the table 5 does not have opaque phenomenon and keeps transparent, and having following feature: Tg is 488 ℃; At is 519 ℃; α is 6.2 * 10 ^-6/ ℃; Nd is 1.81.

The composition of sample 7 makes it to have and Al ₂O ₃The stable engagement intensity of substrate 3, and do not cause separating or crackle.

Confirmed another component: 5 weight %SiO ₂, 20 weight %B ₂O ₃, 10 weight %La ₂O ₃, 35-45 weight %ZnO and 20-30 weight %Bi ₂O ₃Effectively so that At is 550 ℃ or lower, and nd is 1.77 or higher.

Based on the inventor's research, confirm: B ₂O ₃-SiO ₂-ZnO-Bi ₂O ₃ Glass sealing material 6 when the base low-melting-point glass is composed as follows in this embodiment has preferred characteristic: 1-10 weight %SiO ₂, 15-30 weight %B ₂O ₃, 0-20 weight %La ₂O ₃, 0-20 weight %Gd ₂O ₃, 0-10 weight %Y ₂O ₃, 0-5 weight %ZrO ₂, 0-20 weight %Nb ₂O ₅, 0-20 weight %BaO, 0-20 weight %SrO, 0-20 weight %CaO, 0-20 weight %TiO ₂, 25-60 weight %ZnO, 10-50 weight %Bi ₂O ₃, 0-3 weight %Li ₂O, 0-3 weight %Na ₂O and 0-3 weight %K ₂O.

At this moment, in this compositing range, glass sealing material 6 has following properties: At is 550 ℃ or lower, and α is 6-8 * 10 ^-6/ ℃, nd is 1.75 or higher.

(effect of the 4th embodiment)

In luminescent device 1, have AlInGaP base LED element 2 usefulness that the GaP substrate 20 of high refractive index n=3.5 and refraction coefficient equate with it by B ₂O ₃-SiO ₂-ZnO-Bi ₂O ₃ Glass sealing material 6 sealings that the base low-melting-point glass is made.Therefore, it can have excellent light extraction efficiency, good heat-radiating properties and installation capability.

In addition, by using the seal glass of high refractive index, the solid angle angle of angular aperture is compared with epoxy resin can increase 30-40%.According to this point, can increase the light extraction efficiency of LED element 2.

At this moment, substrate 20 can be made by the material beyond the GaP.

[the 5th embodiment]

Fig. 5 is the sectional view that the solid-state optical device of the 5th preferred embodiment of the present invention is shown;

Structure optics 100 makes the luminescent device 1 described in the 3rd embodiment be engaged to lead frame 8, makes the transparent resin of being made by transparent acrylic resin 9 form thereon, to cover all components except that lead frame 8.

By using by B ₂O ₃-SiO ₂-Na ₂O-ZnO-Nb ₂O ₅The glass sealing material 6 sealing GaN base LED elements 2 that the base low-melting-point glass is made form luminescent device 1.

Transparent resin 9 provides hemisphere optics compromise face 9A, and it has the LED element 2 as light source, and makes by injection.

(effect of the 5th embodiment)

The effect that the 5th embodiment obtains is as follows:

(1), can easily on the LED of glass capsulation, form and have the optical system of arbitrary shape by using resin material and injection such as acrylic resin and Merlon.Because Al ₂O ₃The mechanical strength of substrate 3 can withstand the reservation pressure (retention pressure) in the process of injection molding or the external pressure that applies by resin injection, and the transparent resin 9 that therefore has arbitrary shape can be according to purposes and the LED combination of optics 100.In addition because LED element 2 covers by glass sealing material 6, even therefore when the injection rate of resin material increases LED element 2 also unlikely destroyed.

(2) by the luminescent device 1 with the Overmolded glass capsulation of resin material, glass sealing material 6 can be avoided deterioration, and has stronger moisture resistivity.

(3) because transparent resin 9 places on the LED element 2 by glass sealing material 6, therefore can use any resin material, even when being unsuitable for direct sealing LED element 2 owing to its light degradation characteristic, also be like this.Therefore, can improve the freedom of design.For example, transparent resin 9 can be colored light-transmissive resin material.

(4) luminescent device 1 has and is easy to mass-produced rectangular shape most, so it can fine and close at low cost encapsulation, thereby can make the product quantity maximization that obtains from a ceramic substrate.Based on this, by with the periphery of resin-sealed luminescent device 1 through glass capsulation to form the optics compromise face, the light that sends from luminescent device 1 can outwards penetrate, and not at the interface of luminescent device 1 and subsequently in the refraction at the interface of transparent resin 9.That is to say, by the luminescent device with the sealing of resin material seal glass, compare with the situation of only using glass material to form the optics compromise face, can be easier to and with more low-cost structure optics 100.

In optics 100,, also can be another kind of resin such as epoxy resin though resin material 9 is made by acrylic resin.And, also can form by another kind of forming method such as the cast shaping process beyond the transfer formation.The optics compromise face can be the surface of another shape beyond the semispherical surface.

[the 6th embodiment]

Fig. 6 A is the vertical view that illustrates in the 6th preferred embodiment of the present invention as the luminescent device of solid-state optical device; Fig. 6 B is the sectional view that cuts along the line b-b among Fig. 6 A; Fig. 6 C is the upward view that luminescent device among Fig. 6 A is shown.

(structure of luminescent device 1)

Luminescent device 1 shown in Fig. 6 A and the 6B is composed as follows: 9 flip-chip type GaN base LED elements 2; Al ₂O ₃Substrate 3 forms the square in the sandwich construction, and the GaN of installation base LED element 2 is arranged on it; Circuit pattern 4, it makes (pattern on the substrate surface also provides nickel (Ni) and gold (Au) coating that forms thereon) by tungsten (W), and is formed on Al ₂O ₃The surface of substrate 3 and inner; Au salient point 5, it forms between GaN base LED element 2 and circuit pattern 4 and is electrically connected; Glass sealing material 6, it is by P ₂O ₅-Al ₂O ₃-zno-based low-melting-point glass is made, and in sealing GaN base LED element 2 and Al ₂O ₃Substrate 3 engages; Bottom circuit pattern 16A (anode) and 16C (negative electrode), it is exposed to Al ₂O ₃On four angles of substrate 3, extend simultaneously from internal layer (intermediate layer); Heat radiation pattern 17, it is made of copper, and is used for the heat that is produced by LED element 2 to external radiation.

9 LED elements 2 (chip size is that 340 μ m are square) are arranged with 3 * 3, and by Au salient point 5 close installation (close-mounted) on the discrete circuit pattern 4, described circuit pattern 4 is at Al with the interval of 600 μ m ₂O ₃Form circle on the surface of substrate 3.

Al ₂O ₃Substrate 3 has sandwich construction, wherein forms tungsten back panel wiring processed.3 LED series connection on the line direction form the element group as shown in Figure 6A, and the anode of element group is connected with one of bottom circuit pattern 16A (anode), and the negative electrode of element group is connected with bottom circuit pattern 16C (negative electrode).Bottom circuit pattern 16C (negative electrode) also is connected with the negative electrode of element group in other two row.

(composition of glass sealing material 6)

Describe the low-melting-point glass that can be used for the 6th embodiment below in detail.

By changing P ₂O ₅, B ₂O ₃, Al ₂O ₃, Li ₂O, Na ₂O, K ₂O, MgO, CaO, SrO, BaO, ZnO, Nb ₂O ₅, TiO ₂, Bi ₂O ₃, Gd ₂O ₃, WO ₃And ZrO ₂Composition preparation as four sample 8-11 of glass sealing material 6.Following table 6 shows composition and the characteristic of sample 8-11.

Table 6

Form (wt%)	Sample 8	Sample 9	Sample 10	Sample 11
Form (wt%)	Sample 8	Sample 9	Sample 10	Sample 11	P ₂O ₅	62	55	62	60
B ₂O ₃					P ₂O ₅	62	55	62	60
B ₂O ₃					Al ₂O ₃	9	7	11	9
Li ₂O					Al ₂O ₃	9	7	11	9
Li ₂O					Na ₂O			2
K ₂O			2		Na ₂O			2
K ₂O			2		MgO
CaO					MgO
CaO					SrO
BaO					SrO
BaO		4	3		4
ZnO		4	3		4	25	35	21	27
ZnO	Nb ₂O ₅			1		25	35	21	27
TiO ₂	Nb ₂O ₅			1
TiO ₂	WO ₃
ZrO ₂	WO ₃
ZrO ₂
Tg(℃)						469	440	438	461
Tg(℃)	At(℃)	517	475	487	506	469	440	438	461
α(×10 ^-6/℃) (100-300)	At(℃)	517	475	487	506	6.8	6.4	7.7	6.6
α(×10 ^-6/℃) (100-300)	nd	1.52714	1.5488	1.52919	1.52863	6.8	6.4	7.7	6.6
vd	nd	1.52714	1.5488	1.52919	1.52863	64.1	61.1	61.9	63.2
vd	Necessary components total	96	97	94	96	64.1	61.1	61.9	63.2

As can be seen from Table 6, all samples 8-11 does not have opaque phenomenon and keeps transparent, and refraction index is 1.52 or higher, thermalexpansioncoefficientα and Al ₂O ₃The thermal coefficient of expansion approximately equal of substrate 3.

Thermalexpansioncoefficientα in the variable range as shown in table 6 makes it to have and Al ₂O ₃The stable engagement intensity of substrate 3, and do not cause separating or crackle.

Research based on the inventor has confirmed P ₂O ₅-Al ₂O ₃-zno-based low-melting-point glass glass sealing material 6 in this embodiment when having following the composition has preferred characteristic: 55-62 weight %P ₂O ₅, 5-12 weight %Al ₂O ₃, 20-40 weight %ZnO, herein P ₂O ₅+ Al ₂O ₃+ ZnO is 80-100 weight %, 0-5 weight %B ₂O ₃, 0-3 weight %Li ₂O, 0-3 weight %Na ₂O, 0-3 weight %K ₂O, 0-5 weight %MgO, 0-10 weight %CaO, 0-10 weight %SrO, 0-20 weight %BaO, 0-20 weight %Nb ₂O ₅, 0-20 weight %TiO ₂, 0-20 weight %Bi ₂O ₃, 0-5 weight %Gd ₂O ₃, 0-5 weight %WO ₃With 0-5 weight %ZrO ₂

In this compositing range, it is 550 ℃ or lower that glass sealing material 6 can have following properties: At, and α is 6-8 * 10 ^-6/ ℃, it is 61.1 that Abbe counts vd.

(effect of the 6th embodiment)

The effect that the 6th embodiment obtains is as follows:

(1) even when a plurality of LED element 2 close installation, luminescent device 1 also can have excellent reliability, and does not cause crackle, and this is because LED element 2 has the thermalexpansioncoefficient that equates with glass sealing material 6.And, because glass sealing material 6 has and Al ₂O ₃Therefore the thermalexpansioncoefficientα that substrate 3 equates can realize excellent glass bond intensity.

(2) by using Al ₂O ₃Substrate 3 even close installation is given birth to the GaN base LED element 2 of heat in a large number, also can obtain stable heat-radiating properties.In addition, series connection/parallel circuits is easy to patterning, is easy to design interconnecting of lead in the process that forms the electrolytic coating metal level.

(3) take out external circuit-connecting terminal by intermediate layer internally, and metal fever radiation pattern 17 is placed the bottom, on the heat that produces in the course of work of the LED of 9 close installation element 2 can be fast be discharged into radiator etc. from heat radiation pattern 17.

Simultaneously, provide the transparent resin of making by resin material, can also change described luminescent device 1 into optics 100, as shown in Figure 5 by luminescent device 1 to the 6th embodiment.In this case, P ₂O ₅-Al ₂O ₃-zno-based low-melting-point glass can have stronger moisture resistivity.

[the 7th embodiment]

Fig. 7 is the sectional view that illustrates in the 7th preferred embodiment of the present invention as the luminescent device of solid-state optical device.In Fig. 7, show a plurality of luminescent devices 1 at wafer-like Al ₂O ₃Form the state of glass capsulation on the substrate 3.

(structure of luminescent device 1)

Luminescent device 1 is composed as follows: flip-chip type LED element 2, and it is made by the GaN base semiconductor; Al ₂O ₃Substrate 3 is equipped with LED element 2 on it; Circuit pattern 4, it is formed on Al ₂O ₃On the substrate 3; Au salient point 5, it forms electrical connection between LED element 2 and circuit pattern 4; With glass sealing material 6, it has the optics compromise face, by P ₂O ₅-Al ₂O ₃-zno-based low-melting-point glass is made, and is engaged in Al in sealing LED element 2 in hot press method ₂O ₃Substrate 3.P ₂O ₅-Al ₂O ₃-zno-based low-melting-point glass has identical composition with the 6th embodiment.

Al ₂O ₃Substrate 3 provides separating tank 3B, forms with given interval, corresponding to separation point position at the bottom of the village in the excision device process behind the glass capsulation.

By hot pressing preformed glass, glass sealing material 6 is engaged in Al in hot press method ₂O ₃Substrate 3 surfaces, described preformed glass provides optics compromise face 6 and thin flat 6D in advance by preforming process.When the scribing position being applied load and downcut device, the thickness of flat 6D would not damage adjacent luminescent device 1, as crackle.

Produce luminescent device 1, make LED element 2 be installed to Al ₂O ₃On the substrate 3, and with glass sealing material 6 sealing, then, by applying load, Al to the substrate separation position 3B as the scribing position ₂O ₃Substrate 3 concentrates (stress concentration) to cut off by stress, and glass sealing material 6 cuts off at flat 6D place.

(effect of the 7th embodiment)

The effect that the 7th embodiment obtains is as follows:

(1) because LED element 2 usefulness thermal coefficient of expansion and the Al that commonly uses ₂O ₃Therefore glass sealing material 6 sealings that the thermal coefficient of expansion of substrate 3 equates can reduce to give birth in the process internal stress that heat causes.Therefore, can improve the reliability and the mass productivity of glass capsulation.

(2) because Al ₂O ₃Substrate 3 has the mechanical strength of anti-scribing, therefore compares with the cutting that needs blanking to deposit (cuttingstock), can carry out the more installation of narrow pitch.Therefore, can improve the product recovery rate.

For example, carry out the little luminescent device of glass capsulation with the pitch of 0.5mm, if be about 13 * 10 by the use thermal coefficient of expansion for standard-sized LED element 2 (chip size is that 0.3mm is square) ^-6/ ℃ seal glass and ceramic substrate the LED element 2 that does not have blanking to store, be installed on the ceramic substrate with the 0.5mm pitch is carried out glass capsulation, the coefficient of thermal expansion differences between seal glass and the LED element 2 will cause crackle so.

But, in this embodiment, because glass sealing material 6 has the thermal coefficient of expansion that equates with LED element 2, glass sealing material 6 and Al ₂O ₃Thermal expansion coefficient difference between the substrate 3 is little, even also be so when the bonding area between it reduces, and therefore can be owing in the glass sealing material 6 or glass sealing material 6 and Al ₂O ₃Glass capsulation between the substrate 3 or scribing and cause crackle or separation.

(3) when cutting luminescent device 1, can produce overstrain during by the slicing machine cut crystal in glass, glass sealing material 6 can be owing to thermal shock has defective.But, when to luminescent device 1 scribing, owing to reduced overstrain, unlikely produce such as the destruction of defective.

Except scribing, also can use laser cutting luminescent device 1.

[the 8th embodiment]

(structure of luminescent device 1)

Luminescent device 1 is composed as follows: flip-chip type large scale LED element 2, and it is made by the GaN base semiconductor; Al ₂O ₃Substrate 3 is equipped with LED element 2 on it; Circuit pattern 4, it is formed on Al ₂O ₃On the substrate 3; Heat radiation pattern 40, it has given surface area, is made by the highly heat-conductive material such as Copper Foil, and places Al ₂O ₃The outside of substrate 3 connects side; Au salient point 5, it forms electrical connection between LED element 2 and circuit pattern 4; With glass sealing material 6, it has the optics compromise face, by B ₂O ₃-SiO ₂-PbO base low-melting-point glass is made, and is engaged in Al in sealing LED element 2 in hot press method ₂O ₃Substrate 3.

(composition of glass sealing material 6)

The B that is used for glass sealing material 6 ₂O ₃-SiO ₂-PbO base low-melting-point glass is composed as follows: 15 weight %SiO ₂, 13 weight %B ₂O ₃, 56 weight %PbO, 0.6 weight %As ₂O ₃, 9 weight %Al ₂O ₃With 2 weight %La ₂O ₃, and having following properties: At is 550 ℃ or lower, and α is 6.1 * 10 ^-6/ ℃.

Because B ₂O ₃-SiO ₂-PbO base low-melting-point glass has and Al ₂O ₃The approximately equalised thermalexpansioncoefficientα of the thermal coefficient of expansion of substrate 3 makes it to have and Al ₂O ₃The stable engagement intensity of substrate 3, and do not cause separating or crackle.

Based on the inventor's research, confirm B ₂O ₃-SiO ₂ Glass sealing material 6 when-PbO base low-melting-point glass has following the composition in this embodiment has preferred characteristic: 20 weight %-50 weight %B ₂O ₃With 30 weight %-70 weight %PbO.

(effect of the 8th embodiment)

In the 8th embodiment, there is not Al ₂O ₃Therefore crackle due to the thermal expansion coefficient difference between substrate 3 and the glass sealing material 6 even use large-sized LED element 2 also can obtain to have the more luminescent device 1 of high reliability.Usually, when the unstress state from glass capsulation was returned to normal temperature, the size of stress that is produced and LED element 2 was proportional thus.Since with resin-phase be hard material than glass, therefore may have crackle, especially because the crackle due to tensile stress or the shear stress.But the inventor confirms: by using the Al in this embodiment ₂O ₃Substrate 3 and glass sealing material 6 can flawless ground be 2 sealings of the square LED element of 1mm with chip size.

At this moment, provide the transparent resin of making by resin material, it can also be changed into optics shown in Figure 5 100 by luminescent device 1 to the 8th embodiment.

[the 9th embodiment]

Be similar to the 6th embodiment, structure luminescent device 1 is arranged 9 large scale GaN base LED elements 2 of the 8th embodiment with 3 * 3, be installed in Al ₂O ₃On the substrate 3, and use by B ₂O ₃-SiO ₂The glass sealing material 6 that-PbO base low-melting-point glass is made is with its sealing.

(effect of the 9th embodiment)

In the 9th embodiment, even when a plurality of large scale LED element 2 is installed, luminescent device 1 also can have stabilized glass sealing property identical with the 8th embodiment and excellent reliability.

In the 9th embodiment, do not use Al ₂O ₃Substrate 3 can use to have the more substrate of high-termal conductivity.For example, this high thermal conductive substrate can (thermalexpansioncoefficient be 7.6 * 10 by BeO ^-6/ ℃, thermal conductivity is 250W/ (mk)) make.The BeO substrate makes to have good glass capsulation performance, because it has the thermalexpansioncoefficient that equates with the thermal coefficient of expansion of glass sealing material 6.

Other substrates with high-termal conductivity can be the W-Cu substrates.For example, the W-Cu substrate can be the W90-Cu10 substrate, and thermalexpansioncoefficient is 6.5 * 10 ^-6/ ℃, thermal conductivity is 180W/ (mk), or W85-Cu15, thermalexpansioncoefficient is 7.2 * 10 ^-6/ ℃, thermal conductivity is 190W/ (mk).These substrates have high-termal conductivity and with the good bond intensity of glass sealing material 6.Therefore, luminescent device 1 can easily be applied to highlight strength and high output type.

Though in the above-described embodiment, solid-state optical device relates to the luminescent device that uses the LED element, and the present invention is not limited to luminescent device.For example, can comprise other optics or element according to solid-state optical device of the present invention, such as photo detector and solar cell device.

Though for clearly open comprehensively, with regard to particular the present invention has been described, therefore but appended claim can't be restricted, and should think comprised that those skilled in the art can carry out, belong to all changes and alternative constructions in the illustrated basic religious doctrine scope of this paper fully.

Claims

1. solid-state optical device comprises:

Solid-state element;

To/supply with or regain the electric power supply/recovery part of electric energy from solid-state element; With

The glass sealing material of sealing solid-state element,

Wherein glass sealing material comprises P ₂O ₅-zno-based low-melting-point glass, described P ₂O ₅-zno-based low-melting-point glass contains 45-50 weight %P ₂O ₅With 15-35 weight %ZnO.

2. according to the solid-state optical device of claim 1, wherein:

Described low-melting-point glass also comprises the Li of 3-6 weight % ₂O.

3. according to the solid-state optical device of claim 1, wherein:

Described low-melting-point glass comprises 45-50 weight %P ₂O ₅, 3-6 weight %Li ₂O, 0-3.5 weight %MgO, 0-10 weight %CaO, 0-15 weight %SrO, 0-30 weight %BaO, 15-35 weight %ZnO, 0-1 weight %ZrO ₂, 0-1.5 weight %Nb ₂O ₅With 0-5 weight %Al ₂O ₃, wherein RO (R:Mg, Ca, Sr, Ba and Zn) adds up to 38-49%.

4. solid-state optical device comprises:

Solid-state element;

The glass sealing material of sealing solid-state element,

Wherein said glass sealing material comprises P ₂O ₅-F base low-melting-point glass, described P ₂O ₅-F base low-melting-point glass contains 6-50 weight %P ₂O ₅With 1-45 weight %ZnO, in the weight % based on oxide.

5. according to the solid-state optical device of claim 4, wherein:

Described low-melting-point glass comprises 34-50 weight %P ₂O ₅, 2-9 weight %Li ₂O, 7-28 weight %Na ₂O, 3-27 weight %K ₂O, 6.5-30 weight %Al ₂O ₃With 1.5-32 weight %F, in the weight % based on oxide, wherein R ₂O (R:Li, Na and K) adds up to 17-41 weight %.

6. according to the solid-state optical device of claim 4, wherein:

Described low-melting-point glass comprises 3.0-8.0mol%P ₂O ₅, 0.1-2.0mol%Al ₂O ₃, 1.0-7.0mol%BaO, 35.5-41.0mol%AlF ₃, 8.0-13.0mol%MgF ₂, 16.0-26.0mol%CaF ₂, 15.0-21.0mol%SrF ₂, 3.5-10.0mol%BaF ₂And 1.0-6.0mol%NaF ₂, in mol%.

7. according to the solid-state optical device of claim 4, wherein

Described low-melting-point glass comprises 15-32 weight %Al (PO ₃) ₂, 0-10 weight %Ba (PO ₃) ₂, 0-10 weight %Sr (PO ₃) ₂, 0-10 weight %Ca (PO ₃) ₂, 0-10 weight %Mg (PO ₃) ₂, the total amount of metaphosphate is 20-32 weight % herein, 20-70 weight %BaF ₂, 5-40 weight %SrF ₂, 0-15 weight %CaF ₂, 0-10 weight %MgF ₂, 0-5 weight %AlF ₃, 0-5 weight %GdF ₃, the total amount of fluoride is 55-75 weight % herein, 5-22 weight %Gd ₂O ₃, 0-7 weight %La ₂O ₃, 0-10 weight %Y ₂O ₃With 0-10 weight %Yb ₂O ₃, the total amount of rare-earth salts is 5-22 weight % herein.

8. according to the solid-state optical device of any one among the claim 1-7, wherein:

Described solid-state element is a flip-chip.

9. according to the solid-state optical device of any one among the claim 1-7, wherein:

Electric power supply/recovery part comprises metal lead wire.

10. according to the solid-state optical device of claim 9, wherein:

Metal lead wire comprises the soft metal.

11. according to the solid-state optical device of any one among the claim 1-7, wherein:

Electric power supply/recovery part comprise to/supply with or reclaim the inorganic material substrate of electric energy from solid-state element, and glass sealing material has the thermal coefficient of expansion that equates with the thermal coefficient of expansion of inorganic material substrate.

12. according to the solid-state optical device of claim 11, wherein:

The inorganic material substrate comprises first conductive pattern, second conductive pattern and the 3rd conductive pattern, described first conductive pattern is formed on its surface that solid-state element is installed, described second conductive pattern is formed on the facing surfaces, and described the 3rd conductive pattern forms electrical connection between first and second conductive patterns.

13. according to the solid-state optical device of any one among the claim 1-7, wherein:

Glass sealing material comprises and is formed on its lip-deep coating that this coating provides moisture resistivity and acidproof/alkalescence.

14. according to the solid-state optical device of any one among the claim 1-7, wherein:

Solid-state element comprises optical element, and

Glass sealing material comprises light transmissive material.

15. according to the solid-state optical device of claim 14, wherein:

Optical element comprises light-emitting component.

16. according to the solid-state optical device of claim 14, wherein:

Optical element comprises photo detector.

17. according to the solid-state optical device of any one among the claim 1-14, wherein:

Glass sealing material carries out Overmolded with resin.

18. solid-state optical device comprises:

Solid-state element;

Electric power supplys/the recovery part of solid-state element is installed on it, described electric power supplys/recovery part to/from solid-state element supply or recovery electric energy; With

The glass sealing material of sealing solid-state element,

Wherein glass sealing material has the thermal coefficient of expansion that equates with the thermal coefficient of expansion of electric power supply/recovery part, and

Glass sealing material comprises P ₂O ₅-Al ₂O ₃-zno-based low-melting-point glass, described P ₂O ₅-Al ₂O ₃-zno-based low-melting-point glass contains 55-62 weight %P ₂O ₅, 5-12 weight %Al ₂O ₃With 20-40 weight %ZnO, in weight %.

19. according to the solid-state optical device of claim 18, wherein:

Described low-melting-point glass also comprises 0-5 weight %B ₂O ₃, 0-3 weight %Li ₂O, 0-3 weight %Na ₂O, 0-3 weight %K ₂O, 0-5 weight %MgO, 0-10 weight %CaO, 0-10 weight %SrO, 0-20 weight %BaO, 0-20 weight %Nb ₂O ₅, 0-20 weight %TiO ₂, 0-20 weight %Bi ₂O ₃, 0-5 weight %Gd ₂O ₃, 0-5 weight %WO ₃With 0-5 weight %ZrO ₂, in weight %.

20. solid-state optical device comprises:

Solid-state element;

Electric power supply/the recovery part of solid-state element is installed on it, described electric power supply/recovery part to/supply with or reclaim electric energy from solid-state element; With

The glass sealing material of honey sealing attitude element,

Glass sealing material comprises B ₂O ₃-SiO ₂-Na ₂O-ZnO-Nb ₂O ₅The base low-melting-point glass, described B ₂O ₃-SiO ₂-Na ₂O-ZnO-Nb ₂O ₅The base low-melting-point glass contains 19-30 weight %B ₂O ₃, 0.5-15 weight %SiO ₂, 1.5-8 weight %Na ₂O, 44-60 weight %ZnO and 9-19 weight %Nb ₂O ₅, in weight %.

21. according to the solid-state optical device of claim 20, wherein:

Described low-melting-point glass also comprises 0-5 weight %Al ₂O ₃, 0-3 weight %Li ₂O, 0-4 weight %K ₂O, 0-5 weight %MgO, 0-5 weight %CaO, 0-5 weight %SrO, 0-5 weight %BaO, 0-4 weight %ZrO ₂With 0-4 weight %TiO ₂, in weight %.

22. solid-state optical device comprises:

Solid-state element;

The glass sealing material of sealing solid-state element,

Glass sealing material comprises B ₂O ₃-SiO ₂-ZnO-Bi ₂O ₃The base low-melting-point glass, described B ₂O ₃-SiO ₂-ZnO-Bi ₂O ₃The base low-melting-point glass contains 1-10 weight %SiO ₂, 15-30 weight %B ₂O ₃, 25-60 weight %ZnO and 10-50 weight %Bi ₂O ₃, in weight %.

23. according to the solid-state optical device of claim 22, wherein:

Described low-melting-point glass also comprises 0-20 weight %La ₂O ₃, 0-20 weight %Gd ₂O ₃, 0-10 weight %Y ₂O ₃, 0-5 weight %ZrO ₂, 0-20 weight %Nb ₂O ₅, 0-20 weight %BaO, 0-20 weight %SrO, 0-20 weight %CaO, 0-20 weight %TiO ₂, 0-3 weight %Li ₂O, 0-3 weight %Na ₂O and 0-3 weight %K ₂O is in weight %.

24. solid-state optical device comprises:

Solid-state element;

The glass sealing material of sealing solid-state element,

Glass sealing material comprises B ₂O ₃-SiO ₂-PbO base low-melting-point glass, described B ₂O ₃-SiO ₂-PbO base low-melting-point glass contains 20 weight %-50 weight %B ₂O ₃With 30 weight %-70 weight %PbO, in weight %.

25. according to the solid-state optical device of any one among the claim 18-24, wherein:

Described low-melting-point glass has the thermal coefficient of expansion that equates with the thermal coefficient of expansion of solid-state element.

26. solid-state optical device comprises:

Solid-state element;

The glass sealing material of sealing solid-state element,

Wherein glass sealing material has the thermal coefficient of expansion that equates with the thermal coefficient of expansion of solid-state element and electric power supply/recovery part.

27. according to the solid-state optical device of claim 25, wherein:

Solid-state element is of a size of 1mm or bigger.

28. according to the solid-state optical device of claim 25, wherein:

Solid-state element comprises a plurality of solid-state elements of close installation.]

29. according to the solid-state optical device of any one among the claim 18-24, wherein:

Solid-state element is upside-down mounting.

30. according to the solid-state optical device of any one among the claim 18-24, wherein:

Described electric power supply/recovery part comprises the inorganic material substrate, and described inorganic material substrate comprises conductive pattern, with to/supply with or reclaim electric energy from solid-state element, and

Glass sealing material has the thermal coefficient of expansion that equates with the thermal coefficient of expansion of inorganic material substrate.

31. according to the solid-state optical device of claim 30, wherein:

Described inorganic material substrate comprises first conductive pattern, second conductive pattern and the 3rd conductive pattern, described first conductive pattern is formed on its surface that solid-state element is installed, described second conductive pattern is formed on the facing surfaces, and described the 3rd conductive pattern forms electrical connection between first and second conductive patterns.

32. according to the solid-state optical device of claim 30, wherein:

The inorganic material substrate comprises alumina substrate.

33. according to the solid-state optical device of any one among the claim 18-24, wherein:

34. according to the solid-state optical device of any one among the claim 18-24, wherein:

Solid-state element comprises optical element, and

Glass sealing material comprises light transmissive material.

35. according to the solid-state optical device of claim 34, wherein:

Optical element comprises light-emitting component.

36. according to the solid-state optical device of claim 34, wherein:

Optical element is included in the GaN base LED element that forms the GaN based semiconductor on the substrate.

37. according to the solid-state optical device of claim 34, wherein:

Optical element comprises photo detector.

38. according to the solid-state optical device of any one among the claim 18-24, wherein:

Glass sealing material carries out Overmolded with resin.