CN107808917A - A kind of quaternary system transparent substrates light emitting diode and preparation method thereof - Google Patents
A kind of quaternary system transparent substrates light emitting diode and preparation method thereof Download PDFInfo
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- CN107808917A CN107808917A CN201711048315.3A CN201711048315A CN107808917A CN 107808917 A CN107808917 A CN 107808917A CN 201711048315 A CN201711048315 A CN 201711048315A CN 107808917 A CN107808917 A CN 107808917A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/26—Materials of the light emitting region
- H01L33/30—Materials of the light emitting region containing only elements of group III and group V of the periodic system
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/005—Processes
- H01L33/0062—Processes for devices with an active region comprising only III-V compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/26—Materials of the light emitting region
Abstract
The application provides a kind of quaternary system transparent substrates LED production method and quaternary system transparent substrates light emitting diode, it is proposed transparent substrates bonding techniques, quaternary system GaAs substrate LED epitaxial wafers are transferred in transparent substrates, instead of the substrate of extinction material, so as to improve luminous efficiency, in addition, GaP layers are roughened, and graded index composite film layer is formd on GaP layers, the graded index composite film layer can increase light transmittance, further improve the light extraction efficiency of light emitting diode.Further, because the outermost of the graded index composite film layer is SOG bonded layers, relative to silica bonded layer of the prior art, it is possible to increase binding ability so that bonding is more firm, can effectively improve bonding yield.
Description
Technical field
The present invention relates to semiconductor devices manufacture technology field, more particularly to a kind of quaternary system transparent substrates light emitting diode
And preparation method thereof.
Background technology
Light emitting diode (English is Light Emitting Diode, abbreviation LED) is a kind of light emitting semiconductor device, can
So that electric energy is effectively changed into luminous energy, it is made up of the compound containing gallium (Ga), arsenic (As), phosphorus (P), nitrogen (N) etc..Current production
White light LEDs be largely by blue-ray LED (near-UV, wavelength 450nm to 470nm) cover one layer of faint yellow fluorescence
Made of powder coating, white light LEDs are the third generation electric light sources after incandescent lamp and fluorescent lamp, it has also become all over the world light source and
Light fixture research institution competitively develops, made great efforts the target of acquisition, is the star industry of following lighting field.
The mass production of gallium nitride and GaAs series LED, along with light emitting diode color variation and into
This continuous reduction, application field also constantly extend.From the indicator lamp of relatively low luminous flux to display screen, then from outdoor display screen to
Medium luminous flux power signal lamp and the white light source of special lighting, finally develop into high light flux general illumination light source.With
AlGaInP-LED is the GaAs series LED of representative, is limited by limitation of the material with substrate in itself, outer quantum effect
There is not good performance always, its main cause is that gallium arsenide substrate is a kind of light absorbent, causes active area (MQW) radiation direction
The light of substrate side is largely absorbed by substrate, even if the Omni-directional reflector and transfer substrate skill that are used by using current industry
The method of art, still suffer from largely causing necessarily to lose after LED structure from speculum reflection, high light extraction can not be realized
Rate.
The content of the invention
In view of this, the present invention provides a kind of quaternary system transparent substrates light emitting diode and preparation method thereof, existing to solve
There is the GaAs series LED using AlGaInP-LED as representative in technology, be limited by limitation of the material with substrate in itself,
The problem of high light extraction efficiency can not be realized.
To achieve the above object, the present invention provides following technical scheme：
A kind of quaternary system transparent substrates LED production method, including：
Quaternary system LED epitaxial slice and transparent substrates are provided, the quaternary system LED epitaxial slice includes lining
Bottom, the epitaxial structure of light emitting diode and GaP layers；
The GaP layers are roughened；
The GaP layer surfaces after roughening form graded index composite film layer, the graded index THIN COMPOSITE
Film layer is SOG (spin on glass, spin-coating glass) bonded layer away from the surface of the GaP layers, and the graded index is compound
Film layer includes the multi-layer thin film layer that is stacked, and the refractive index of film layer described in multilayer is bonded along the GaP layers to the SOG
Layer gradually reduces；
Bonded layer is formed on the transparent substrate；
Carry out planarization process respectively to the SOG bonded layers and the bonded layer, and carried out after cleaning at surface active
Reason；
The bonded layer is bonded with the SOG bonded layers, obtains semi-finished product；
The substrate that the semi-finished product deviate from the transparent substrates side is removed, completes quaternary system transparent substrates light emitting diode
Making.
Preferably, it is described that the GaP layers are roughened, specifically include：
The GaP layer surfaces are roughened using mechanical lapping mode.
Preferably, the graded index composite film layer includes SOG bonded layers, and silicon nitride layer, alumina layer, oxygen
Change zinc layers, titanium oxide layer, MgF2Layer, GaF2At least one of layer and indium tin oxide layer.
Preferably, the graded index composite film layer includes the indium tin oxide layer positioned at the GaP layer surfaces and position
Deviate from the SOG bonded layers of the GaP layers in the indium tin oxide layer.
Preferably, the GaP layer surfaces after roughening form graded index composite film layer, specifically include：
The GaP layer surfaces after roughening deposit indium oxide layer tin layers using electron beam evaporation plating or sputtering mode；
The quaternary system LED epitaxial slice that deposition has indium tin oxide layer is placed in tin indium oxide coarsening solution and is roughened,
Wherein, it is roughened the indium tin oxide layer thickness of the depth no more than deposition；
Tin indium oxide layer surface deposition SOG bonded layers after roughening.
Preferably, the bonded layer is SOG bonded layers or silicon oxide layer.
Preferably, when the bonded layer is SOG bonded layers；
It is described to carry out planarization process respectively to the SOG bonded layers and the bonded layer, and carry out surface work after cleaning
Change is handled, and is specifically included：
The SOG bonded layers and the bonded layer are polished respectively and cmp mode planarizes, flatness
Roughness value is required to Ra<lnm；
The surface of the SOG bonded layers and the bonded layer is cleaned, and is dried；
Quaternary system LED epitaxial slice after cleaning and transparent substrates are subjected to surface activation process.
Preferably, the quaternary system LED epitaxial slice and transparent substrates by after cleaning is carried out at surface active
Reason, is specifically included：
Quaternary system LED epitaxial slice after cleaning and transparent substrates are handled in oxygen plasma；
Quaternary system LED epitaxial slice and transparent substrates after oxygen plasma is handled are placed in activated solution
Activation, the temperature of the activated solution is 70 DEG C, and the activated solution is NH4OH：H2O2：H2O=1：1：5, wherein, ratio is
Molal weight ratio.
The present invention also provides a kind of quaternary system transparent substrates light emitting diode, using the quaternary system described in any of the above one
Transparent substrates LED production method makes to be formed, including：
Transparent substrates and quaternary system LED epitaxial slice, the quaternary system LED epitaxial slice include luminous two
The epitaxial structure and GaP layers of pole pipe；
Graded index laminated film between the transparent substrates and the quaternary system LED epitaxial slice
Layer and bonded layer；
Wherein, the GaP layers are the surface by roughening away from the surface of the epitaxial structure of the light emitting diode, described
Graded index composite film layer is SOG bonded layers away from the surface of the GaP layers, the graded index composite film layer bag
The multi-layer thin film layer being stacked is included, the refractive index of film layer described in multilayer gradually drops along the GaP layers to the SOG bonded layers
It is low.
Preferably, the graded index composite film layer includes SOG bonded layers, and silicon nitride layer, alumina layer, oxygen
Change zinc layers, titanium oxide layer, MgF2Layer, GaF2At least one of layer and indium tin oxide layer.
Preferably, the graded index composite film layer includes the indium tin oxide layer positioned at the GaP layer surfaces and position
Deviate from the SOG bonded layers of the GaP layer surfaces in the indium tin oxide layer.
Preferably, the indium tin oxide layer is the surface by roughening away from the surface of the GaP layers.
Preferably, the bonded layer is SOG bonded layers or silicon oxide layer.
Via above-mentioned technical scheme understand, quaternary system transparent substrates LED production method provided by the invention and
Quaternary system transparent substrates light emitting diode, transparent substrates bonding techniques are proposed, by quaternary system GaAs substrate LED extensions
Piece is transferred in transparent substrates, instead of the substrate of extinction material, so as to improve luminous efficiency, in addition, having been carried out to GaP layers slightly
Change, and graded index composite film layer is formd on GaP layers, the graded index composite film layer can increase
Light rate, further improve the light extraction efficiency of light emitting diode.
Further, because the outermost of the graded index composite film layer is SOG bonded layers, relative to existing skill
Silica bonded layer in art, it is possible to increase binding ability so that bonding is more firm, can effectively improve bonding yield.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the required accompanying drawing used in technology description to be briefly described, it should be apparent that, drawings in the following description are only this
The embodiment of invention, for those of ordinary skill in the art, on the premise of not paying creative work, can also basis
The accompanying drawing of offer obtains other accompanying drawings.
Fig. 1 is a kind of quaternary system transparent substrates LED production method flow chart provided in an embodiment of the present invention；
Fig. 2A-Fig. 2 F are a kind of quaternary system transparent substrates LED production method step provided in an embodiment of the present invention
Sectional view.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation describes, it is clear that described embodiment is only part of the embodiment of the present invention, rather than whole embodiments.It is based on
Embodiment in the present invention, those of ordinary skill in the art are obtained every other under the premise of creative work is not made
Embodiment, belong to the scope of protection of the invention.
As shown in figure 1, be a kind of quaternary system transparent substrates LED production method provided in an embodiment of the present invention, bag
Include：
S101：Quaternary system LED epitaxial slice and transparent substrates, the quaternary system LED epitaxial slice are provided
Including substrate, the epitaxial structure of light emitting diode and GaP layers；
Fig. 2A is referred to, quaternary system LED epitaxial slice includes substrate 11, the and of epitaxial structure 12 of light emitting diode
GaP layers 13, wherein, the specific material of the substrate of the quaternary system LED epitaxial slice is not limited in the present embodiment, it is optional
, the quaternary series LED is AlGaInP, and its substrate is GaAs substrates.
S102：The GaP layers are roughened；
Fig. 2 B are referred to, are roughened in GaP layers 13 away from the surface of substrate.
It should be noted that to the mode that GaP is roughened without limiting in the present embodiment, because mechanical lapping mode has
Cost is low, roughening uniformity is good and convenient the features such as operating, optionally, using mechanical lapping mode to described in the present embodiment
GaP layer surfaces are roughened.
GaP surfaces are roughened using mechanical lapping mode, specifically included：
A) epitaxial wafer for needing to be roughened is fixed on BLOCK disks with lapping wax；
B lapping liquid) is sprayed on the deep bid of grinder, it is preferable that the lapping liquid in the present embodiment is watered by grounds travel
Configuration forms, and the particle of grounds travel is at 0.1 μm -0.2 μm；
C suitable pressure and rotating speed) are adjusted, the GaP surfaces that need to be roughened are ground 1 minute on grinder,；
D wax, cleaning obtain the GaP surfaces being roughened under).
It should be noted that what the light extraction efficiency of the GaP layers after being roughened using mechanical lapping mode was roughened than other modes
Light extraction efficiency is higher, main reason is that the roughening face obtained by the way of grinding has lower reflectivity, is more beneficial for
The output of photoelectricity, specifically see the data of table 1：
Table 1：Different roughening mode light extraction efficiency data comparison tables
By experimental data as can be seen that the GaP layers after the roughening obtained using mechanical lapping mode have it is lower anti-
Rate is penetrated, so, the light that LED epitaxial structure is sent can more preferably transmit LED chip, so as to improve the light extraction efficiency of LED chip.
S103：The GaP layer surfaces after roughening form graded index composite film layer, and the graded index is answered
It is SOG bonded layers that film layer, which is closed, away from the surface of the GaP layers, and the graded index composite film layer includes what is be stacked
Multi-layer thin film layer, the refractive index of film layer described in multilayer gradually reduce along the GaP layers to the SOG bonded layers；
Fig. 2 C are referred to, the surface of GaP layers 13 after roughening forms graded index composite film layer 14.This implementation
The concrete structure of graded index composite film layer is not limited in example, it is only necessary to ensure that away from the surface of the GaP layers be SOG keys
Layer is closed, because SOG relative to silica has bigger viscosity, LED epitaxial slice and transparent substrates can be realized
Between bonding, binding ability is stronger.
Optionally, graded index composite film layer described in the present embodiment includes SOG bonded layers, and silicon nitride layer,
Alumina layer, zinc oxide film, titanium oxide layer, MgF2Layer, GaF2At least one of layer and indium tin oxide layer.
It should be noted that in some embodiments of the invention, it is preferable that as shown in Figure 2 C, the graded index
Composite film layer includes being located at the indium tin oxide layer (ITO) 141 of the GaP layer surfaces and carried on the back positioned at the indium tin oxide layer 141
From the SOG bonded layers 142 of the GaP layers 13.Due to the lattice knot of the lattice structure and other film layers of indium tin oxide layer
Structure is different, and the present invention can also be roughened in indium tin oxide layer away from the surface of the GaP layers, the process bag being specifically roughened
Include：The GaP layer surfaces after roughening deposit indium oxide layer tin layers using electron beam evaporation plating or sputtering mode；Will deposition
The quaternary system LED epitaxial slice for having indium tin oxide layer, which is placed in tin indium oxide coarsening solution, to be roughened, wherein, it is roughened depth
No more than the indium tin oxide layer thickness of deposition；Tin indium oxide layer surface deposition SOG bonded layers after roughening.
S104：Bonded layer is formed on the transparent substrate；
Fig. 2 D are referred to, bonded layer 22 is formed in transparent substrates 21, it is necessary to illustrate, step is not limited in the present embodiment
Rapid S104 and the order of other steps, as long as before step S101, and before step S105, acceptable and step
S102 is carried out simultaneously, and this is not limited in the present embodiment.
The specific material of the bonded layer in transparent substrates is not limited in the present embodiment, optionally, the bonded layer needs energy
It is enough that there is stronger bonding force between the SOG bonded layers of quaternary system LED epitaxial slice.Optionally, the bonded layer
Material can be SOG bonded layers or silicon oxide layer.Preferably, to cause bonding more firm, the material of the bonded layer is SOG
Bonded layer.
S105：Carry out planarization process respectively to the SOG bonded layers and the bonded layer, and surface work is carried out after cleaning
Change is handled；
It should be noted that when the bonded layer is silica, using silicon oxide layer is carried out planarization process and
The technique of activation process；When the bonded layer is SOG bonded layers, same technique pair can be used in the embodiment of the present invention
SOG bonded layers and bonded layer carry out planarization process simultaneously, and carry out surface activation process after cleaning.Specifically include：To described
SOG bonded layers and the bonded layer are polished respectively and cmp mode planarizes, and flatness roughness value is required to Ra
<lnm；The surface of the SOG bonded layers and the bonded layer is cleaned, and is dried；By outside the quaternary series LED after cleaning
Prolong piece and transparent substrates carry out surface activation process.
For the film layer of SOG bonded layer materials, by the quaternary system LED epitaxial slice after cleaning in the present embodiment
Surface activation process is carried out with transparent substrates to specifically include：By the quaternary system LED epitaxial slice and transparent substrates after cleaning
Handled in oxygen plasma；Quaternary system LED epitaxial slice and transparent substrates after oxygen plasma is handled
It is placed in activated solution and activates, the temperature of the activated solution is 70 DEG C, and the activated solution is NH4OH：H2O2：H2O=1：
1：5, wherein, ratio is molal weight ratio.
In the present embodiment in activation process, first handled using oxygen plasma, thin-film surface can occur largely
Physical reactions and chemical reaction, wherein physical reactions are physical sputtering, and the physical sputtering can be such that thin-film surface is formed very
More nano level aperture, these apertures make SOG thin-film surfaces have very strong hydrophily, so as to increase the table of SOG film layers
Face energy, and the more flat smooth of the surface after corona treatment, are advantageous to be bonded.
Activated solution includes ammoniacal liquor described in the present embodiment, due to ammoniacal liquor be easily decomposed at a higher temperature ammonia and
Water, therefore, activation temperature can not be too high, and, activated solution temperature is less than 70 DEG C, when activated solution temperature in the present embodiment alternatively
Too low, chemical time is longer, therefore, considers, and activation temperature is preferably 70 DEG C in the present embodiment.
Activated solution matches NH in the present embodiment4OH：H2O2：H2NH in the solution of O proportionings4OH can promote the shape of covalent bond
Into SOG thin-film surfaces can form the Si-OH groups of high concentration, under certain high pressure, have the bonding face phase of Si-OH groups
Mutually contact, under De Huali and dipole active force, film layer can be combined together；Under certain high temperature ,-OH groups can be sent out
Raw dehydration polymerization reaction, forms strong covalent bond；
It is bonded for the hydrophily of reality, silanol key (Si-OH) is easy to and the water molecules in air, therefore, reality
The interface on border combines typically by the H key connections of several hydrones, by the dehydration that heats up, ultimately forms Si-O-
Si covalent bonds.
S106：The bonded layer is bonded with the SOG bonded layers, obtains semi-finished product；
Refer to shown in Fig. 2 E, for the semi-finished product structure after bonding.
S107：The substrate that the semi-finished product deviate from the transparent substrates side is removed, quaternary system transparent substrates is completed and lights
The making of diode.
The specific material of the substrate of the quaternary system LED epitaxial slice, optionally, institute are not limited in the present embodiment
It is AlGaInP to state quaternary series LED, and its substrate is GaAs substrates.For the removal of GaAs substrates, can use by
NH4OH:H2O2=1:10 removers being formulated, and the temperature of substrate remover is 60 DEG C, carries out immersion removal.
Do not limit the specific material of each layer of the graded index composite film layer in the embodiment of the present invention, in the present invention with
Several film combinations are described in detail below.Combine below and cover several film combinations modes substantially, based on following discloses
Several film combinations modes can also obtain other film combinations modes, this is not described in detail in the present embodiment.
The various film combinations tables of table 2
| Film combinations 1 | Titanium oxide 2.5 | Zinc oxide 2.0 | Aluminum oxide 1.7 | SOG | |
| Film combinations 2 | Titanium oxide 2.5 | Zinc oxide 2.0 | SOG | ||
| Film combinations 3 | ITO | SOG | |||
| Film combinations 4 | Titanium oxide 2.5 | Silicon nitride 2.1 | Zinc oxide 2.0 | Aluminum oxide 1.7 | SOG |
| Film combinations 5 | Titanium oxide 2.5 | Zinc oxide 2.0 | SOG |
Numeral after above-mentioned each film title is refractive index corresponding to the film, and the title and refractive index of other films are such as
Shown in lower：
ITO 1.7；SOG 1.2；SiO2 1.45；Silicon nitride 2.1；Aluminum oxide 1.7；Zinc oxide 2.0；Titanium oxide 2.5；
MgF2 1.37；GaF2 1.4 (substrate).
Example one：
A kind of method for the four-element LED for preparing transparent substrates as described above, comprises the following steps：
1) the GaP layer surfaces of AlGalnP-LED epitaxial wafers are used into mechanical lapping, obtains roughening face, and as key
Conjunction face, then evaporated film titanium oxide, zinc oxide, aluminum oxide in a manner of electron beam successively on bonding face, then using spin coating
Mode, spin coating SOG, wherein, SOG thickness is 3um, and being primarily due to the thickness of polishing layer needs sufficiently thick just to have an opportunity to polish
Flatness；By the way of composite film layer mainly utilizes gradually changed refractive index, the output of light is more beneficial for.
2) wherein, GaP layer surfaces are roughened using mechanical lapping；
3) curing process wherein, is carried out according to certain technique after SOG spin coatings, solidification flow, which is included on hot plate, to be carried out, will
Hot plate temperature is set in 80 DEG C of baking 1min, is then warming up to 150 DEG C of baking 1min, then is warming up to 250 DEG C of baking 1min, then
N2 baking boxs are put into, temperature is set to 425 DEG C of baking 1hour, completes solidification.
4) the transparent substrates Sapphire to be bonded is prepared, i.e. Sapphire Substrate, by surface clean, 1um is thick in spin coating
SOG, operation is carried out according to the solidification flow in 3) flow；
5) planarization process, SOG are carried out to the SOG surfaces of the polishing layer on the compound bonding face in step 1) and step 3)
The flatness roughness value on surface is required to Ra<Lnm, the LED pieces planarized；Operation is wherein planarized with cmp
Mode is carried out.
6) the LED pieces after polishing and the SOG of sapphire substrate surface are cleaned up, dried；
7) by the LED pieces after cleaning and Sapphire Substrate in O2It is surface-treated in-plasma, is then immersed in
NH4OH：H2O2：H2O=1：1：5min is activated in 5 solution, solution need to be heated to 70 DEG C, and by above-mentioned processing, SOG surfaces can produce
The free radicals such as raw-O-OH-O- chemical bonds, can turn into strong covalent bond, enhancing adhesion during bond.
8) O will be passed through2- Plasma (plasma) and 1:1:LED pieces and transparent substrates Sapphire after the processing of 5 solution
It is bonded, then carries out HTHP, sapphire is bonded with LED pieces, its high temperature refers to 420 DEG C, and high pressure refers to
12000kgf。
9) removal step 8) in semi-finished product in GaAs substrates, the semi-finished product after the bonding obtained in step 8) are put into
200min in substrate remover, that is, complete LED pieces and transparent substrates are transformed into by GaAs substrates, obtain the LED with transparent substrates
Piece；Wherein substrate remover is by NH4OH:H2O2=1:10 are formulated, and the temperature of substrate remover is 60 DEG C.
Example two：
A kind of method for the four-element LED for preparing transparent substrates as described above, comprises the following steps：
1) the GaP layer surfaces of AlGalnP-LED epitaxial wafers are used into mechanical lapping, obtains roughening face, and as key
Conjunction face, then evaporated film titanium oxide, zinc oxide in a manner of electron beam successively on bonding face, then by the way of spin coating,
Spin coating SOG, wherein, SOG thickness is 3um, is primarily due to the thickness of polishing layer and needs the sufficiently thick polishing flatness that just has an opportunity；
By the way of composite film layer mainly utilizes gradually changed refractive index, the output of light is more beneficial for.
2) wherein, GaP layer surfaces are roughened using mechanical lapping；
3) curing process wherein, is carried out according to certain technique after SOG spin coatings, solidification flow, which is included on hot plate, to be carried out, will
Hot plate temperature is set in 80 DEG C of baking 1min, is then warming up to 150 DEG C of baking 1min, then is warming up to 250 DEG C of baking 1min, then
It is put into N2Baking box, temperature are set to 425 DEG C of baking 1hour, complete solidification.
4) the transparent substrates Sapphire to be bonded is prepared, i.e. Sapphire Substrate, by surface clean, 1um is thick in spin coating
SOG, operation is carried out according to the solidification flow in 3) flow；
5) planarization process, SOG are carried out to the SOG surfaces of the polishing layer on the compound bonding face in step 1) and step 3)
The flatness roughness value on surface is required to Ra<Lnm, the LED pieces planarized；Operation is wherein planarized with cmp
Mode is carried out.
6) the LED pieces after polishing and the SOG of sapphire substrate surface are cleaned up, dried；
7) by the LED pieces after cleaning and Sapphire Substrate in O2It is surface-treated in-Plasma, is then immersed in
NH4OH：H2O2：H2O=1：1：5min is activated in 5 solution, solution need to be heated to 70 DEG C, and by above-mentioned processing, SOG surfaces can produce
The free radicals such as raw-O-OH-O- chemical bonds, can turn into strong covalent bond, enhancing adhesion during bond.
8) O2-Plasma and 1 will be passed through:1:LED pieces after the processing of 5 solution are bonded with transparent substrates Sapphire,
Then HTHP is carried out, sapphire is bonded with LED pieces, its high temperature refers to 420 DEG C, and high pressure refers to 12000kgf.
9) removal step 8) in semi-finished product in GaAs substrates, the semi-finished product after the bonding obtained in step 8) are put into
200min in substrate remover, that is, complete LED pieces and transparent substrates are transformed into by GaAs substrates, obtain the LED with transparent substrates
Piece；Wherein substrate remover is by NH4OH:H2O2=1:10 are formulated, and the temperature of substrate remover is 60 DEG C.
Example three：
A kind of method for the four-element LED for preparing transparent substrates as described above, comprises the following steps：
1) the GaP layer surfaces of AlGalnP-LED epitaxial wafers are used into mechanical lapping, obtains roughening face, and as key
Conjunction face, then deposit ito thin film layer in a manner of sputtering successively on bonding face, then by the way of spin coating, spin coating thickness
For 3um SOG, being primarily due to the thickness of polishing layer needs the sufficiently thick polishing flatness that just has an opportunity；Using composite film layer master
The mode of gradually changed refractive index is utilized, is more beneficial for the output of light.
2) wherein, GaP layer surfaces are roughened using mechanical lapping；
3) curing process wherein, is carried out according to certain technique after SOG spin coatings, solidification flow, which is included on hot plate, to be carried out, will
Hot plate temperature is set in 80 DEG C of baking 1min, is then warming up to 150 DEG C of baking 1min, then is warming up to 250 DEG C of baking 1min, then
N2 baking boxs are put into, temperature is set to 425 DEG C of baking 1hour, completes solidification.
4) the transparent substrates Sapphire to be bonded is prepared, i.e. Sapphire Substrate, by surface clean, 1um is thick in spin coating
SOG, operation is carried out according to the solidification flow in 3) flow；
5) planarization process, SOG are carried out to the SOG surfaces of the polishing layer on the compound bonding face in step 1) and step 3)
The flatness roughness value on surface is required to Ra<Lnm, the LED pieces planarized；Operation is wherein planarized with cmp
Mode is carried out.
6) the LED pieces after polishing and the SOG of sapphire substrate surface are cleaned up, dried；
7) by the LED pieces after cleaning and Sapphire Substrate in O2Surface treatment 30 seconds is carried out in-Plasma, is then immersed in
NH4OH：H2O2：H2O=1：1：5min is activated in 5 solution, solution need to be heated to 70 DEG C, finally molten in the HF that ratio is 0.25%
Shaken 30 seconds in liquid, N2 dryings, by above-mentioned processing, SOG surfaces can produce the free radicals such as-O-OH-O- chemical bonds, can during bond
As strong covalent bond, to strengthen adhesion.
8) O will be passed through2- Plasma and 1:1:LED pieces after the processing of 5 solution are bonded with transparent substrates Sapphire,
Then HTHP is carried out, sapphire is bonded with LED pieces, its high temperature refers to 420 DEG C, and high pressure refers to 12000kgf.
9) removal step 8) in semi-finished product in GaAs substrates, the semi-finished product after the bonding obtained in step 8) are put into
200min in substrate remover, that is, complete LED pieces and transparent substrates are transformed into by GaAs substrates, obtain the LED with transparent substrates
Piece；Wherein substrate remover is by NH4OH:H2O2=1:10 are formulated, and the temperature of substrate remover is 60 DEG C.
Example four：
A kind of method for the four-element LED for preparing transparent substrates as described above, comprises the following steps：
1) the GaP layer surfaces of AlGalnP-LED epitaxial wafers are used into mechanical lapping, obtains roughening face, and as key
Conjunction face, titanium oxide, silicon nitride, zinc oxide, aluminum oxide film is then deposited in a manner of electron beam evaporation plating successively on bonding face
Layer, then by the way of spin coating, spin coating thickness is 3um SOG, and the thickness for being primarily due to polishing layer sufficiently thick need to just have
Chance polishes flatness；By the way of composite film layer mainly utilizes gradually changed refractive index, the output of light is more beneficial for.
2) wherein, GaP layer surfaces are roughened using mechanical lapping；
3) curing process wherein, is carried out according to certain technique after SOG spin coatings, solidification flow, which is included on hot plate, to be carried out, will
Hot plate temperature is set in 80 DEG C of baking 1min, is then warming up to 150 DEG C of baking 1min, then is warming up to 250 DEG C of baking 1min, then
It is put into N2Baking box, temperature are set to 425 DEG C of baking 1hour, complete solidification.
4) the transparent substrates GaN to be bonded is prepared, i.e. gallium nitride substrate, by surface clean, SOG thick 1um, is pressed in spin coating
Operation is carried out according to the solidification flow in 3) flow；
5) planarization process, SOG are carried out to the SOG surfaces of the polishing layer on the compound bonding face in step 1) and step 3)
The flatness roughness value on surface is required to Ra<Lnm, the LED pieces planarized；Operation is wherein planarized with cmp
Mode is carried out.
6) the LED pieces after polishing and the SOG of gallium nitride substrate surface are cleaned up, dried；
7) by the LED pieces after cleaning and gallium nitride substrate in O2Surface treatment 30 seconds is carried out in-Plasma, is then immersed in
NH4OH：H2O2：H2O=1：1：5min is activated in 5 solution, solution need to be heated to 70 DEG C, finally molten in the HF that ratio is 0.25%
Shaken 30 seconds in liquid, N2Drying, by above-mentioned processing, SOG surfaces can produce the free radicals such as-O-OH-O- chemical bonds, can during bond
As strong covalent bond, to strengthen adhesion.
8) O2-Plasma and 1 will be passed through:1:LED pieces after the processing of 5 solution are bonded with transparent substrates Sapphire,
Then HTHP is carried out, gallium nitride is bonded with LED pieces, its high temperature refers to 420 DEG C, and high pressure refers to 12000kgf.
9) removal step 8) in semi-finished product in GaAs substrates, the semi-finished product after the bonding obtained in step 8) are put into
200min in substrate remover, that is, complete LED pieces and transparent substrates are transformed into by GaAs substrates, obtain the LED with transparent substrates
Piece；Wherein substrate remover is by NH4OH:H2O2=1:10 are formulated, and the temperature of substrate remover is 60 DEG C.
Example five：
A kind of method for the four-element LED for preparing transparent substrates as described above, comprises the following steps：
1) surface of the GaP layers of AlGalnP-LED epitaxial wafers is patterned processing, and as bonding face, so
Titanium oxide, zinc oxide films film layer is deposited in a manner of electron beam evaporation plating successively on bonding face afterwards, then by the way of spin coating,
Spin coating thickness is 3um SOG, is primarily due to the thickness of polishing layer and needs the sufficiently thick polishing flatness that just has an opportunity；Using compound
Film layer mainly utilizes the mode of gradually changed refractive index, is more beneficial for the output of light.
2) GaP layer surfaces are roughened using mechanical lapping；
3) curing process wherein, is carried out according to certain technique after SOG spin coatings, solidification flow, which is included on hot plate, to be carried out, will
Hot plate temperature is set in 80 DEG C of baking 1min, is then warming up to 150 DEG C of baking 1min, then is warming up to 250 DEG C of baking 1min, then
N2 baking boxs are put into, temperature is set to 425 DEG C of baking 1hour, completes solidification.
4) the transparent substrates Sapphire to be bonded is prepared, i.e. Sapphire Substrate, by surface clean, 1um is thick in spin coating
SOG, operation is carried out according to the solidification flow in 3) flow；
5) planarization process, SOG are carried out to the SOG surfaces of the polishing layer on the compound bonding face in step 1) and step 3)
The flatness roughness value on surface is required to Ra<Lnm, the LED pieces planarized；Operation is wherein planarized with cmp
Mode is carried out.
6) the LED pieces after polishing and the SOG of sapphire substrate surface are cleaned up, dried；
7) the LED pieces after cleaning and Sapphire Substrate are subjected to surface treatment 30 seconds in O2-Plasma, are then immersed in
NH4OH：H2O2：H2O=1：1：5min is activated in 5 solution, solution need to be heated to 70 DEG C, finally molten in the HF that ratio is 0.25%
Shaken 30 seconds in liquid, N2Drying, by above-mentioned processing, SOG surfaces can produce the free radicals such as-O-OH-O- chemical bonds, can during bond
As strong covalent bond, to strengthen adhesion.
8) O2-Plasma and 1 will be passed through:1:LED pieces after the processing of 5 solution are bonded with transparent substrates Sapphire,
Then HTHP is carried out, sapphire is bonded with LED pieces, its high temperature refers to 420 DEG C, and high pressure refers to 12000kgf.
9) removal step 8) in semi-finished product in GaAs substrates, the semi-finished product after the bonding obtained in step 8) are put into
200min in substrate remover, that is, complete LED pieces and transparent substrates are transformed into by GaAs substrates, obtain the LED with transparent substrates
Piece；Wherein substrate remover is by NH4OH:H2O2=1:10 are formulated, and the temperature of substrate remover is 60 DEG C.
Quaternary system transparent substrates LED production method provided in an embodiment of the present invention, propose transparent substrates bonding skill
Art, transparent substrates are transferred on quaternary system transparent substrates LED epitaxial slice, instead of the substrate of extinction material, so as to carry
High-luminous-efficiency, in addition, being roughened to GaP layers, and graded index composite film layer is formd on GaP layers, institute
Light transmittance can be increased by stating graded index composite film layer, further improve the light extraction efficiency of light emitting diode.
The embodiment of the present invention also provides a kind of quaternary system transparent substrates light emitting diode, using preparation method shape above
Into referring to Fig. 2 F, the quaternary system transparent substrates light emitting diode includes：
Transparent substrates 21 and quaternary system LED epitaxial slice, quaternary system LED epitaxial slice include light-emitting diodes
The epitaxial structure 12 and GaP layers 13 of pipe；Gradient index between transparent substrates 21 and quaternary system LED epitaxial slice
Rate composite film layer 14 and bonded layer 22；Wherein, GaP layers 13 are by thick away from the surface of the epitaxial structure 12 of light emitting diode
The surface of change, graded index composite film layer 14 are SOG bonded layers away from the surface of GaP layers 13, graded index THIN COMPOSITE
Film layer 14 includes the multi-layer thin film layer being stacked, and the refractive index of multi-layer thin film layer gradually reduces along GaP layers to SOG bonded layers.
The specific material of graded index composite film layer, the graded index laminated film are not limited in the present embodiment
Layer includes SOG bonded layers, and silicon nitride layer, alumina layer, zinc oxide film, titanium oxide layer, MgF2Layer, GaF2Layer and indium oxide
At least one of tin layers.Alternatively, the graded index composite film layer includes the indium oxide positioned at the GaP layer surfaces
Tin layers and the SOG bonded layers for deviating from the GaP layer surfaces positioned at the indium tin oxide layer.The indium tin oxide layer deviates from institute
The surface for stating GaP layers is the surface by roughening.The bonded layer is SOG bonded layers or silicon oxide layer.
Quaternary system transparent substrates light emitting diode provided by the invention uses transparent substrates bonding techniques above, will be transparent
Substrate is transferred on quaternary system transparent substrates LED epitaxial slice, instead of the substrate of extinction material, so as to improve luminous effect
Rate, in addition, being roughened to GaP layers, and graded index composite film layer is formd on GaP layers, the gradual change folding
The rate composite film layer of penetrating can increase light transmittance, further improve the light extraction efficiency of light emitting diode.Further, due to described
The outermost of graded index composite film layer is SOG bonded layers, relative to silica bonded layer of the prior art, Neng Gouti
High bonding energy power so that bonding is more firm.
It should be noted that each embodiment in this specification is described by the way of progressive, each embodiment weight
Point explanation is all difference with other embodiment, between each embodiment identical similar part mutually referring to.
The foregoing description of the disclosed embodiments, professional and technical personnel in the field are enable to realize or using the present invention.
A variety of modifications to these embodiments will be apparent for those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, it is of the invention
The embodiments shown herein is not intended to be limited to, and is to fit to and principles disclosed herein and features of novelty phase one
The most wide scope caused.
Claims (13)
- A kind of 1. quaternary system transparent substrates LED production method, it is characterised in that including：Quaternary system LED epitaxial slice and transparent substrates are provided, the quaternary system LED epitaxial slice include substrate, The epitaxial structure and GaP layers of light emitting diode；The GaP layers are roughened；The GaP layer surfaces after roughening form graded index composite film layer, the graded index composite film layer It is spin-coating glass SOG bonded layers away from the surface of the GaP layers, the graded index composite film layer includes what is be stacked Multi-layer thin film layer, the refractive index of film layer described in multilayer gradually reduce along the GaP layers to the SOG bonded layers；Bonded layer is formed on the transparent substrate；Carry out planarization process respectively to the SOG bonded layers and the bonded layer, and surface activation process is carried out after cleaning；The bonded layer is bonded with the SOG bonded layers, obtains semi-finished product；The substrate that the semi-finished product deviate from the transparent substrates side is removed, completes the system of quaternary system transparent substrates light emitting diode Make.
- 2. quaternary system transparent substrates LED production method according to claim 1, it is characterised in that described to institute State GaP layers to be roughened, specifically include：The GaP layer surfaces are roughened using mechanical lapping mode.
- 3. quaternary system transparent substrates LED production method according to claim 1, it is characterised in that the gradual change Refractive index composite film layer includes SOG bonded layers, and silicon nitride layer, alumina layer, zinc oxide film, titanium oxide layer, MgF2Layer, GaF2At least one of layer and indium tin oxide layer.
- 4. the quaternary system transparent substrates LED production method according to Claims 2 or 3, it is characterised in that described Graded index composite film layer includes being located at the indium tin oxide layer of the GaP layer surfaces and deviated from positioned at the indium tin oxide layer The SOG bonded layers of the GaP layers.
- 5. quaternary system transparent substrates LED production method according to claim 4, it is characterised in that described thick The GaP layer surfaces after change form graded index composite film layer, specifically include：The GaP layer surfaces after roughening deposit indium oxide layer tin layers using electron beam evaporation plating or sputtering mode；The quaternary system LED epitaxial slice that deposition has indium tin oxide layer is placed in tin indium oxide coarsening solution and is roughened, its In, the indium tin oxide layer thickness of the roughening depth no more than deposition；Tin indium oxide layer surface deposition SOG bonded layers after roughening.
- 6. the quaternary system transparent substrates LED production method according to claim 1-3,5 any one, its feature It is, the bonded layer is SOG bonded layers or silicon oxide layer.
- 7. quaternary system transparent substrates LED production method according to claim 6, it is characterised in that when the key When conjunction layer is SOG bonded layers；It is described to carry out planarization process respectively to the SOG bonded layers and the bonded layer, and carried out after cleaning at surface active Reason, is specifically included：The SOG bonded layers and the bonded layer are polished respectively and cmp mode planarizes, flatness is coarse Value is required to Ra<lnm；The surface of the SOG bonded layers and the bonded layer is cleaned, and is dried；Quaternary system LED epitaxial slice after cleaning and transparent substrates are subjected to surface activation process.
- 8. quaternary system transparent substrates LED production method according to claim 7, it is characterised in that described by clearly Quaternary system LED epitaxial slice and transparent substrates after washing carry out surface activation process, specifically include：Quaternary system LED epitaxial slice after cleaning and transparent substrates are handled in oxygen plasma；Quaternary system LED epitaxial slice and transparent substrates after oxygen plasma is handled are placed in activated solution and activated, The temperature of the activated solution is 70 DEG C, and the activated solution is NH4OH：H2O2：H2O=1：1：5, wherein, ratio is mole matter Amount ratio.
- 9. a kind of quaternary system transparent substrates light emitting diode, it is characterised in that using four described in claim 1-8 any one Member is that transparent substrates LED production method makes to be formed, including：Transparent substrates and quaternary system LED epitaxial slice, the quaternary system LED epitaxial slice include light emitting diode Epitaxial structure and GaP layers；Graded index composite film layer between the transparent substrates and the quaternary system LED epitaxial slice and Bonded layer；Wherein, the GaP layers are by the surface of roughening, the gradual change away from the surface of the epitaxial structure of the light emitting diode Refractive index composite film layer is SOG bonded layers away from the surface of the GaP layers, and the graded index composite film layer includes layer The folded multi-layer thin film layer set, the refractive index of film layer described in multilayer gradually reduce along the GaP layers to the SOG bonded layers.
- 10. quaternary system transparent substrates light emitting diode according to claim 9, it is characterised in that the graded index Composite film layer includes SOG bonded layers, and silicon nitride layer, alumina layer, zinc oxide film, titanium oxide layer, MgF2Layer, GaF2Layer At least one of with indium tin oxide layer.
- 11. quaternary system transparent substrates light emitting diode according to claim 10, it is characterised in that the graded index Composite film layer includes being located at the indium tin oxide layer of the GaP layer surfaces and deviates from the GaP layers positioned at the indium tin oxide layer The SOG bonded layers on surface.
- 12. quaternary system transparent substrates light emitting diode according to claim 11, it is characterised in that the indium tin oxide layer It is the surface by roughening away from the surface of the GaP layers.
- 13. the quaternary system transparent substrates light emitting diode according to claim 9-12 any one, it is characterised in that described Bonded layer is SOG bonded layers or silicon oxide layer.
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