CN107808917B - 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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- CN107808917B CN107808917B CN201711048315.3A CN201711048315A CN107808917B CN 107808917 B CN107808917 B CN 107808917B CN 201711048315 A CN201711048315 A CN 201711048315A CN 107808917 B CN107808917 B CN 107808917B
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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 wafer is transferred in transparent substrates, instead of the substrate of extinction material, 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 increase the light extraction efficiency of light emitting diode.Further, due to the outermost of the graded index composite film layer be SOG bonded layer, compared with the existing technology in silica bonded layer, can be improved binding ability, so that bonding is stronger, 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 diodes
And preparation method thereof.
Background technique
Light emitting diode (English is Light Emitting Diode, abbreviation LED) is a kind of light emitting semiconductor device, can
Electric energy is effectively converted to luminous energy, it is made of the compound containing gallium (Ga), arsenic (As), phosphorus (P), nitrogen (N) etc..Current production
White light LEDs be largely by blue-ray LED (on 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
Lamps and lanterns research institution competitively develops, makes great efforts the target obtained, is the star industry of the following lighting area.
The mass production of gallium nitride and GaAs series LED, along with light emitting diode color diversification and at
This continuous reduction, application field also constantly extend.From the indicator light of lower luminous flux to display screen, then from outdoor display screen to
The white light source of medium luminous flux power signal lamp and special lighting finally develops to 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 itself, outer quantum effect
There is not good performance always, main cause is that gallium arsenide substrate is a kind of light absorbent, leads to active area (MQW) radiation direction
The light of one side of substrate is largely absorbed by substrate, even if by using the Omni-directional reflector and transfer substrate skill of the use of current industry
The method of art still suffers from and largely causes centainly to lose after LED structure from reflecting mirror reflection, cannot achieve high light extraction
Rate.
Summary 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, it is existing to solve
Have in technology using AlGaInP-LED as the GaAs series LED of representative, be limited by limitation of the material with substrate itself,
The problem of cannot achieve high light extraction efficiency.
To achieve the above object, the invention provides the following technical scheme:
A kind of quaternary system transparent substrates LED production method, comprising:
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；
Described GaP layers is roughened；
The GaP layer surface after roughening forms graded index composite film layer, the graded index THIN COMPOSITE
Film layer is SOG (spin on glass, spin-coating glass) bonded layer away from GaP layers of the surface, and the graded index is compound
Film layer includes the multi-layer thin film layer being stacked, and the refractive index of film layer described in multilayer is bonded along described GaP layers to the SOG
Layer gradually decreases；
Bonded layer is formed on the transparent substrate；
Planarization process is carried out to the SOG bonded layer and the bonded layer respectively, and is carried out at surface active after cleaning
Reason；
The bonded layer is bonded with the SOG bonded layer, obtains semi-finished product；
The substrate that the semi-finished product deviate from the transparent substrates side is removed, quaternary system transparent substrates light emitting diode is completed
Production.
Preferably, described that described GaP layers is roughened, it specifically includes:
The GaP layer surface is roughened using mechanical lapping mode.
Preferably, the graded index composite film layer includes SOG bonded layer 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 surface and position
Deviate from described GaP layers of the SOG bonded layer in the indium tin oxide layer.
Preferably, the GaP layer surface after roughening forms graded index composite film layer, specifically includes:
The GaP layer surface after roughening deposits indium oxide layer tin layers using electron beam evaporation plating or sputtering mode；
The quaternary system LED epitaxial slice for being deposited with indium tin oxide layer is placed in tin indium oxide coarsening solution and is roughened,
Wherein, the indium tin oxide layer thickness of the roughening depth no more than deposition；
Tin indium oxide layer surface after roughening deposits SOG bonded layer.
Preferably, the bonded layer is SOG bonded layer or silicon oxide layer.
Preferably, when the bonded layer is SOG bonded layer；
It is described that planarization process is carried out respectively to the SOG bonded layer and the bonded layer, and it is living to carry out surface after cleaning
Change processing, specifically includes:
The SOG bonded layer and the bonded layer are polished respectively and chemical mechanical grinding mode planarizes, flatness
Roughness value is required to Ra < lnm；
The surface of the SOG bonded layer and the bonded layer is cleaned, and is dried；
By the quaternary system LED epitaxial slice and transparent substrates progress surface activation process after cleaning.
Preferably, the quaternary system LED epitaxial slice and transparent substrates by after cleaning carries out at surface active
Reason, specifically includes:
By after cleaning quaternary system LED epitaxial slice and transparent substrates handled in oxygen plasma；
By after oxygen plasma treatment quaternary system LED epitaxial slice and transparent substrates be placed in activated solution
Activation, the temperature of the activated solution are 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 diodes, using quaternary system described in any of the above one
Transparent substrates LED production method makes to be formed, comprising:
Transparent substrates and quaternary system LED epitaxial slice, the quaternary system LED epitaxial slice include luminous two
The epitaxial structure and GaP layer of pole pipe；
Graded index laminated film between the transparent substrates and the quaternary system LED epitaxial slice
Layer and bonded layer；
Wherein, the surface of the described GaP layers epitaxial structure away from the light emitting diode is the surface by being roughened, described
Graded index composite film layer is SOG bonded layer, the graded index composite film layer packet away from GaP layers of the surface
The multi-layer thin film layer being stacked is included, the refractive index of film layer described in multilayer is gradually dropped along described GaP layers to the SOG bonded layer
It is low.
Preferably, the graded index composite film layer includes SOG bonded layer 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 surface and position
Deviate from the SOG bonded layer of the GaP layer surface in the indium tin oxide layer.
Preferably, the indium tin oxide layer is the surface for passing through roughening away from GaP layers of the surface.
Preferably, the bonded layer is SOG bonded layer or silicon oxide layer.
It can be seen via above technical scheme that quaternary system transparent substrates LED production method provided by the invention and
Quaternary system transparent substrates light emitting diode proposes transparent substrates bonding techniques, by quaternary system GaAs substrate LED extension
Piece is transferred in transparent substrates, instead of the substrate of extinction material, so that luminous efficiency is improved, in addition, having carried out to GaP layers thick
Change, and form graded index composite film layer on GaP layers, the graded index composite film layer can increase
Light rate further increases the light extraction efficiency of light emitting diode.
Further, since the outermost of the graded index composite film layer is SOG bonded layer, relative to existing skill
Silica bonded layer in art, can be improved binding ability, so that bonding is stronger, can effectively improve bonding yield.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention for those of ordinary skill in the art without creative efforts, can also basis
The attached drawing of offer obtains other attached 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 is a kind of quaternary system transparent substrates LED production method step provided in an embodiment of the present invention
Sectional view.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
As shown in Figure 1, being a kind of quaternary system transparent substrates LED production method provided in an embodiment of the present invention, packet
It includes:
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 12 and of epitaxial structure of substrate 11, light emitting diode
GaP layer 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 substrate is GaAs substrate.
S102: described GaP layers is roughened；
Fig. 2 B is referred to, is roughened in GaP layer 13 away from the surface of substrate.
It should be noted that the mode of GaP roughening without limiting in the present embodiment, since mechanical lapping mode has
At low cost, roughening uniformity is good and the features such as facilitate operation, optionally, uses mechanical lapping mode to described in the present embodiment
GaP layer surface is roughened.
The surface GaP is roughened using mechanical lapping mode, is specifically included:
A) epitaxial wafer being roughened will be needed to be fixed on BLOCK disk with lapping wax；
B upper 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
It configures, the particle of grounds travel is at 0.1 μm -0.2 μm；
C suitable pressure and revolving speed) are adjusted, the surface GaP that need to be roughened is ground 1 minute on grinder,；
D wax, cleaning obtain the surface GaP being roughened under).
It should be noted that the light extraction efficiency of the GaP layer 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 advantageous to
The output of photoelectricity, specifically see 1 data of table:
Table 1: different roughening mode light extraction efficiency data comparison tables
By experimental data as can be seen that the GaP layer after the roughening obtained using mechanical lapping mode is with lower anti-
Rate is penetrated, in this way, the light that LED epitaxial structure issues can more preferably transmit LED chip, to improve the light extraction efficiency of LED chip.
S103: the GaP layer surface after roughening forms graded index composite film layer, and the graded index is multiple
It is SOG bonded layer that film layer, which is closed, away from GaP layers of the surface, and the graded index composite film layer includes being stacked
The refractive index of multi-layer thin film layer, film layer described in multilayer is gradually decreased along described GaP layers to the SOG bonded layer；
Fig. 2 C is referred to, 13 surface of GaP layer after roughening forms graded index composite film layer 14.This implementation
The specific structure of graded index composite film layer is not limited in example, it is only necessary to guarantee away from GaP layers of the surface to be SOG key
Layer is closed, since SOG has bigger viscosity relative to silica, can be realized LED epitaxial slice and transparent substrates
Between bonding, binding ability is stronger.
Optionally, graded index composite film layer described in the present embodiment include SOG bonded layer 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 carrying on the back positioned at the indium tin oxide layer (ITO) 141 of the GaP layer surface and positioned at the indium tin oxide layer 141
The SOG bonded layer 142 from the GaP layer 13.Due to the lattice structure of indium tin oxide layer and the lattice knot of other film layers
Structure is different, and the present invention can also be roughened in indium tin oxide layer away from GaP layers of the surface, the process packet being specifically roughened
Include: the GaP layer surface after roughening deposits indium oxide layer tin layers using electron beam evaporation plating or sputtering mode；It will deposition
There is the quaternary system LED epitaxial slice of indium tin oxide layer to be placed in tin indium oxide coarsening solution to be roughened, wherein roughening depth
No more than the indium tin oxide layer thickness of deposition；Tin indium oxide layer surface after roughening deposits SOG bonded layer.
S104: bonded layer is formed on the transparent substrate；
Fig. 2 D is referred to, forms bonded layer 22 in transparent substrates 21, it should be noted that do not limit step in the present embodiment
The sequence of rapid S104 and other steps, as long as before step S101, and before step S105, acceptable and step
S102 is carried out simultaneously, is not limited this 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 layer of quaternary system LED epitaxial slice.Optionally, the bonded layer
Material can be SOG bonded layer or silicon oxide layer.Preferably, stronger to be bonded, the material of the bonded layer is SOG
Bonded layer.
S105: carrying out planarization process to the SOG bonded layer and the bonded layer respectively, and it is living to carry out surface after cleaning
Change processing；
It should be noted that when the bonded layer be silica when, using to silicon oxide layer carry out planarization process and
The technique of activation processing；When the bonded layer is SOG bonded layer, same technique pair can be used in the embodiment of the present invention
SOG bonded layer and bonded layer carry out planarization process simultaneously, and carry out surface activation process after cleaning.It specifically includes: to described
SOG bonded layer and the bonded layer polish respectively and chemical mechanical grinding mode planarizes, and flatness roughness value is required to Ra
<lnm；The surface of the SOG bonded layer and the bonded layer is cleaned, and is dried；It will be 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 material, by the quaternary system LED epitaxial slice after cleaning in the present embodiment
It carries out surface activation process with transparent substrates to specifically include: by the quaternary system LED epitaxial slice and transparent substrates after cleaning
Handled in oxygen plasma；By the quaternary system LED epitaxial slice and transparent substrates after oxygen plasma treatment
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 nanoscale apertures, these apertures make SOG thin-film surface have very strong hydrophily, to increase the table of SOG film layer
Face energy, and the surface after corona treatment is more flat and smooth, is conducive to be bonded.
In activated solution described in the present embodiment include ammonium hydroxide, due to ammonium hydroxide be easily decomposed at a higher temperature ammonia and
Water, therefore, activation temperature cannot be excessively high, and in the present embodiment optionally, activated solution temperature is lower than 70 DEG C, when activated solution temperature
Too low, chemical time is longer, therefore, comprehensively 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 proportion4OH can promote the shape of covalent bond
At, SOG thin-film surface will form the Si-OH group of high concentration, under certain high pressure, the bonding face phase with Si-OH group
Mutually contact, at De Huali and dipole active force, film layer can be combined together；Under certain high temperature ,-OH group can be sent out
Raw dehydration polymerization reaction, forms strong covalent bond；
Actual hydrophily is bonded, silanol key (Si-OH) is easy to and the water molecules in air, therefore, reality
The interface on border is usually to be combined by the H key connection of several hydrones, by the dehydration that heats up, ultimately forms Si-O-
Si covalent bond.
S106: the bonded layer is bonded with the SOG bonded layer, obtains semi-finished product；
It refers to shown in Fig. 2 E, for the semi-finished product structure after bonding.
S107: removing the substrate that the semi-finished product deviate from the transparent substrates side, completes quaternary system transparent substrates and shines
The production of diode.
The specific material of the substrate of the quaternary system LED epitaxial slice, optionally, institute are not limited in the present embodiment
Stating quaternary series LED is AlGaInP, and substrate is GaAs substrate.For the removal of GaAs substrate, can using by
NH4OH:H2O2The remover that=1:10 is 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.It combines below and covers several film combinations modes substantially, be 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 | Aluminium 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 | Aluminium oxide 1.7 | SOG |
| Film combinations 5 | Titanium oxide 2.5 | Zinc oxide 2.0 | SOG |
Number after above-mentioned each film title is the corresponding refractive index of 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；Aluminium oxide 1.7；Zinc oxide 2.0；Titanium oxide 2.5；
MgF2 1.37；GaF2 1.4 (substrate).
Example one:
A method of the four-element LED preparing transparent substrates as described above includes the following steps:
1) the GaP layer surface of AlGalnP-LED epitaxial wafer is used into mechanical lapping, obtains roughening face, and as key
Conjunction face, then successively evaporated film titanium oxide, zinc oxide, aluminium oxide in a manner of electron beam on bonding face, then use spin coating
Mode, spin coating SOG, wherein with a thickness of 3um, the thickness for being primarily due to polishing layer needs sufficiently thick just have an opportunity to polish SOG
Flatness；Using composite film layer mainly in the way of gradually changed refractive index, it is more advantageous to the output of light.
2) wherein, GaP layer surface is roughened using mechanical lapping；
3) curing process wherein, is carried out according to certain technique after SOG spin coating, solidification process includes carrying out on hot plate, 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 N2 oven, temperature is set to 425 DEG C of baking 1hour, completes solidification.
4) prepare the transparent substrates Sapphire to be bonded, i.e. Sapphire Substrate, by surface clean, 1um is thick in spin coating
SOG carries out operation according to the solidification process in 3) process；
5) planarization process, SOG are carried out to the surface SOG 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 piece planarized；Planarize operation wherein with chemical mechanical grinding
Mode carries out.
6) SOG of LED piece and sapphire substrate surface after polishing is cleaned up, is dried；
7) by after cleaning LED piece and Sapphire Substrate in O2It is surface-treated in-plasma, is then immersed in
NH4OH:H2O2: H25min is activated in O=1:1:5 solution, solution need to be heated to 70 DEG C, and by above-mentioned processing, the surface SOG can be produced
The free radicals such as raw-O-OH-O- chemical bond, when bond, can become strong covalent bond, enhance binding force.
8) O will be passed through2- Plasma (plasma) and 1:1:5 solution treated LED piece and transparent substrates Sapphire
It is bonded, then carries out high temperature and pressure, be bonded sapphire with LED piece, high temperature refers to 420 DEG C, and high pressure refers to
12000kgf。
9) the GaAs substrate in the semi-finished product in step 8) is removed, the semi-finished product after being bonded obtained in step 8) are put into
200min in substrate remover, i.e. completion LED piece are transformed into transparent substrates by GaAs substrate, obtain the LED with transparent substrates
Piece；Wherein substrate remover is by NH4OH:H2O2=1:10 is formulated, and the temperature of substrate remover is 60 DEG C.
Example two:
A method of the four-element LED preparing transparent substrates as described above includes the following steps:
1) the GaP layer surface of AlGalnP-LED epitaxial wafer is used into mechanical lapping, obtains roughening face, and as key
Conjunction face, then successively evaporated film titanium oxide, zinc oxide in a manner of electron beam on bonding face, then by the way of spin coating,
Spin coating SOG, wherein with a thickness of 3um, the thickness for being primarily due to polishing layer sufficiently thick just need to have an opportunity to polish flatness SOG；
Using composite film layer mainly in the way of gradually changed refractive index, it is more advantageous to the output of light.
2) wherein, GaP layer surface is roughened using mechanical lapping；
3) curing process wherein, is carried out according to certain technique after SOG spin coating, solidification process includes carrying out on hot plate, 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 N2Oven, temperature are set to 425 DEG C of baking 1hour, complete solidification.
4) prepare the transparent substrates Sapphire to be bonded, i.e. Sapphire Substrate, by surface clean, 1um is thick in spin coating
SOG carries out operation according to the solidification process in 3) process；
5) planarization process, SOG are carried out to the surface SOG 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 piece planarized；Planarize operation wherein with chemical mechanical grinding
Mode carries out.
6) SOG of LED piece and sapphire substrate surface after polishing is cleaned up, is dried；
7) by after cleaning LED piece and Sapphire Substrate in O2It is surface-treated in-Plasma, is then immersed in
NH4OH:H2O2: H25min is activated in O=1:1:5 solution, solution need to be heated to 70 DEG C, and by above-mentioned processing, the surface SOG can be produced
The free radicals such as raw-O-OH-O- chemical bond, when bond, can become strong covalent bond, enhance binding force.
8) it will be bonded by O2-Plasma and 1:1:5 solution treated LED piece with transparent substrates Sapphire,
Then high temperature and pressure is carried out, is bonded sapphire with LED piece, high temperature refers to 420 DEG C, and high pressure refers to 12000kgf.
9) the GaAs substrate in the semi-finished product in step 8) is removed, the semi-finished product after being bonded obtained in step 8) are put into
200min in substrate remover, i.e. completion LED piece are transformed into transparent substrates by GaAs substrate, obtain the LED with transparent substrates
Piece；Wherein substrate remover is by NH4OH:H2O2=1:10 is formulated, and the temperature of substrate remover is 60 DEG C.
Example three:
A method of the four-element LED preparing transparent substrates as described above includes the following steps:
1) the GaP layer surface of AlGalnP-LED epitaxial wafer is used into mechanical lapping, obtains roughening face, and as key
Then conjunction face successively deposits ito thin film layer on bonding face in a manner of sputtering, then by the way of spin coating, spin coating thickness
For 3um SOG, the thickness for being primarily due to polishing layer sufficiently thick just need to have an opportunity to polish flatness；Using composite film layer master
The output of light is more advantageous in the way of gradually changed refractive index.
2) wherein, GaP layer surface is roughened using mechanical lapping；
3) curing process wherein, is carried out according to certain technique after SOG spin coating, solidification process includes carrying out on hot plate, 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 N2 oven, temperature is set to 425 DEG C of baking 1hour, completes solidification.
4) prepare the transparent substrates Sapphire to be bonded, i.e. Sapphire Substrate, by surface clean, 1um is thick in spin coating
SOG carries out operation according to the solidification process in 3) process；
5) planarization process, SOG are carried out to the surface SOG 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 piece planarized；Planarize operation wherein with chemical mechanical grinding
Mode carries out.
6) SOG of LED piece and sapphire substrate surface after polishing is cleaned up, is dried；
7) by after cleaning LED piece and Sapphire Substrate in O2Surface treatment 30 seconds is carried out in-Plasma, is then immersed in
NH4OH:H2O2: H25min is activated in O=1:1:5 solution, solution need to be heated to 70 DEG C, finally molten for 0.25% HF in ratio
It is shaken 30 seconds in liquid, N2 drying, by above-mentioned processing, the surface SOG can generate the free radicals such as-O-OH-O- chemical bond, and when bond can
To become strong covalent bond, enhance binding force.
8) O will be passed through2Treated that LED piece is bonded with transparent substrates Sapphire for-Plasma and 1:1:5 solution,
Then high temperature and pressure is carried out, is bonded sapphire with LED piece, high temperature refers to 420 DEG C, and high pressure refers to 12000kgf.
9) the GaAs substrate in the semi-finished product in step 8) is removed, the semi-finished product after being bonded obtained in step 8) are put into
200min in substrate remover, i.e. completion LED piece are transformed into transparent substrates by GaAs substrate, obtain the LED with transparent substrates
Piece；Wherein substrate remover is by NH4OH:H2O2=1:10 is formulated, and the temperature of substrate remover is 60 DEG C.
Example four:
A method of the four-element LED preparing transparent substrates as described above includes the following steps:
1) the GaP layer surface of AlGalnP-LED epitaxial wafer is used into mechanical lapping, obtains roughening face, and as key
Then titanium oxide, silicon nitride, zinc oxide, aluminum oxide film is successively deposited in conjunction face on bonding face in a manner of electron beam evaporation plating
Layer, then by the way of spin coating, with a thickness of 3um SOG, the thickness for being primarily due to polishing layer sufficiently thick need to just have for spin coating
Chance polishes flatness；Using composite film layer mainly in the way of gradually changed refractive index, it is more advantageous to the output of light.
2) wherein, GaP layer surface is roughened using mechanical lapping；
3) curing process wherein, is carried out according to certain technique after SOG spin coating, solidification process includes carrying out on hot plate, 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 N2Oven, temperature are set to 425 DEG C of baking 1hour, complete solidification.
4) prepare the transparent substrates GaN to be bonded, i.e. gallium nitride substrate, by surface clean, the SOG of 1um thickness, is pressed in spin coating
Operation is carried out according to the solidification process in 3) process；
5) planarization process, SOG are carried out to the surface SOG 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 piece planarized；Planarize operation wherein with chemical mechanical grinding
Mode carries out.
6) SOG of LED piece and gallium nitride substrate surface after polishing is cleaned up, is dried；
7) by after cleaning LED piece and gallium nitride substrate in O2Surface treatment 30 seconds is carried out in-Plasma, is then immersed in
NH4OH:H2O2: H25min is activated in O=1:1:5 solution, solution need to be heated to 70 DEG C, finally molten for 0.25% HF in ratio
It is shaken 30 seconds in liquid, N2Drying, by above-mentioned processing, the surface SOG can generate the free radicals such as-O-OH-O- chemical bond, and when bond can
To become strong covalent bond, enhance binding force.
8) it will be bonded by O2-Plasma and 1:1:5 solution treated LED piece with transparent substrates Sapphire,
Then high temperature and pressure is carried out, is bonded gallium nitride with LED piece, high temperature refers to 420 DEG C, and high pressure refers to 12000kgf.
9) the GaAs substrate in the semi-finished product in step 8) is removed, the semi-finished product after being bonded obtained in step 8) are put into
200min in substrate remover, i.e. completion LED piece are transformed into transparent substrates by GaAs substrate, obtain the LED with transparent substrates
Piece；Wherein substrate remover is to be formulated by NH4OH:H2O2=1:10, and the temperature of substrate remover is 60 DEG C.
Example five:
A method of the four-element LED preparing transparent substrates as described above includes the following steps:
1) surface of the GaP layer of AlGalnP-LED epitaxial wafer is patterned processing, and as bonding face, so
Titanium oxide, zinc oxide films film layer is successively deposited in a manner of electron beam evaporation plating on bonding face afterwards, then by the way of spin coating,
With a thickness of 3um SOG, the thickness for being primarily due to polishing layer sufficiently thick just need to have an opportunity to polish flatness for spin coating；Using compound
Film layer mainly in the way of gradually changed refractive index, is more advantageous to the output of light.
2) GaP layer surface is roughened using mechanical lapping；
3) curing process wherein, is carried out according to certain technique after SOG spin coating, solidification process includes carrying out on hot plate, 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 N2 oven, temperature is set to 425 DEG C of baking 1hour, completes solidification.
4) prepare the transparent substrates Sapphire to be bonded, i.e. Sapphire Substrate, by surface clean, 1um is thick in spin coating
SOG carries out operation according to the solidification process in 3) process；
5) planarization process, SOG are carried out to the surface SOG 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 piece planarized；Planarize operation wherein with chemical mechanical grinding
Mode carries out.
6) SOG of LED piece and sapphire substrate surface after polishing is cleaned up, is dried；
7) by after cleaning LED piece and Sapphire Substrate carried out in O2-Plasma surface treatment 30 seconds, be then immersed in
NH4OH:H2O2: H25min is activated in O=1:1:5 solution, solution need to be heated to 70 DEG C, finally molten for 0.25% HF in ratio
It is shaken 30 seconds in liquid, N2Drying, by above-mentioned processing, the surface SOG can generate the free radicals such as-O-OH-O- chemical bond, and when bond can
To become strong covalent bond, enhance binding force.
8) it will be bonded by O2-Plasma and 1:1:5 solution treated LED piece with transparent substrates Sapphire,
Then high temperature and pressure is carried out, is bonded sapphire with LED piece, high temperature refers to 420 DEG C, and high pressure refers to 12000kgf.
9) the GaAs substrate in the semi-finished product in step 8) is removed, the semi-finished product after being bonded obtained in step 8) are put into
200min in substrate remover, i.e. completion LED piece are transformed into transparent substrates by GaAs substrate, obtain the LED with transparent substrates
Piece；Wherein substrate remover is by NH4OH:H2O2=1:10 is 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 proposes that transparent substrates are bonded skill
Transparent substrates are transferred on quaternary system transparent substrates LED epitaxial slice by art, instead of the substrate of extinction material, to mention
High-luminous-efficiency in addition, being roughened to GaP layers, and forms graded index composite film layer, institute on GaP layers
Light transmittance can be increased by stating graded index composite film layer, further increase 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 production method shape above
At 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
Epitaxial structure 12 and the GaP layer 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 layer 13 is 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 layer, graded index THIN COMPOSITE away from the surface of GaP layer 13
Film layer 14 includes the multi-layer thin film layer being stacked, and the refractive index of multi-layer thin film layer is gradually decreased along GaP layers to SOG bonded layer.
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 layer and silicon nitride layer, alumina layer, zinc oxide film, titanium oxide layer, MgF2Layer, GaF2Layer and indium oxide
At least one of tin layers.Optionally, the graded index composite film layer includes the indium oxide positioned at the GaP layer surface
Tin layers and the SOG bonded layer for deviating from the GaP layer surface positioned at the indium tin oxide layer.The indium tin oxide layer deviates from institute
The surface for stating GaP layers is the surface for passing through roughening.The bonded layer is SOG bonded layer 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, to improve the effect that shines
Rate in addition, being roughened to GaP layers, and forms graded index composite film layer on GaP layers, the gradual change folding
The rate composite film layer of penetrating can increase light transmittance, further increase the light extraction efficiency of light emitting diode.Further, due to described
The outermost of graded index composite film layer be SOG bonded layer, compared with the existing technology in silica bonded layer, Neng Gouti
High bonding energy power, so that bonding is stronger.
It should be noted that all the embodiments in this specification are described in a progressive manner, each embodiment weight
Point explanation is the difference from other embodiments, and the same or similar parts between the embodiments can be referred to each other.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be readily apparent to 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, of the invention
It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one
The widest scope of cause.
Claims (13)
1. a kind of quaternary system transparent substrates LED production method characterized by comprising
Quaternary system LED epitaxial slice and transparent substrates are provided, the quaternary system LED epitaxial slice include substrate,
The epitaxial structure and GaP layer of light emitting diode；
Described GaP layers is roughened；
The GaP layer surface after roughening forms graded index composite film layer, the graded index composite film layer
It is spin-coating glass SOG bonded layer away from GaP layers of the surface, the graded index composite film layer includes being stacked
The refractive index of multi-layer thin film layer, the multi-layer thin film layer is gradually decreased along described GaP layers to the SOG bonded layer；
Bonded layer is formed on the transparent substrate；
Planarization process is carried out to the SOG bonded layer and the bonded layer respectively, and carries out surface activation process after cleaning；
The bonded layer is bonded with the SOG bonded layer, obtains semi-finished product；
The substrate that the semi-finished product deviate from the transparent substrates side is removed, the system of quaternary system transparent substrates light emitting diode is completed
Make.
2. quaternary system transparent substrates LED production method according to claim 1, which is characterized in that described to institute
It states GaP layers to be roughened, specifically include:
The GaP layer surface is roughened using mechanical lapping mode.
3. quaternary system transparent substrates LED production method according to claim 1, which is characterized in that the gradual change
Refractive index composite film layer includes SOG bonded layer and silicon nitride layer, alumina layer, zinc oxide film, titanium oxide layer, MgF2Layer,
GaF2At least one of layer and indium tin oxide layer.
4. quaternary system transparent substrates LED production method according to claim 2 or 3, which is characterized in that described
Graded index composite film layer includes being located at the indium tin oxide layer of the GaP layer surface and deviating from positioned at the indium tin oxide layer
Described GaP layers of the SOG bonded layer.
5. quaternary system transparent substrates LED production method according to claim 4, which is characterized in that described thick
The GaP layer surface after change forms graded index composite film layer, specifically includes:
The GaP layer surface after roughening deposits indium oxide layer tin layers using electron beam evaporation plating or sputtering mode；
The quaternary system LED epitaxial slice for being deposited with indium tin oxide layer is placed in tin indium oxide coarsening solution and is roughened,
In, the indium tin oxide layer thickness of the roughening depth no more than deposition；
Tin indium oxide layer surface after roughening deposits SOG bonded layer.
6. quaternary system transparent substrates LED production method described in -3,5 any one according to claim 1, feature
It is, the bonded layer is SOG bonded layer or silicon oxide layer.
7. quaternary system transparent substrates LED production method according to claim 6, which is characterized in that when the key
When conjunction layer is SOG bonded layer；
It is described that planarization process is carried out respectively to the SOG bonded layer and the bonded layer, and carried out at surface active after cleaning
Reason, specifically includes:
The SOG bonded layer and the bonded layer are polished respectively and chemical mechanical grinding mode planarizes, flatness is coarse
Value is required to Ra < lnm；
The surface of the SOG bonded layer and the bonded layer is cleaned, and is dried；
By the quaternary system LED epitaxial slice and transparent substrates progress surface activation process after cleaning.
8. quaternary system transparent substrates LED production method according to claim 7, which is characterized in that it is described will be clear
Quaternary system LED epitaxial slice and transparent substrates after washing carry out surface activation process, specifically include:
By after cleaning quaternary system LED epitaxial slice and transparent substrates handled in oxygen plasma；
By after oxygen plasma treatment quaternary system LED epitaxial slice and transparent substrates be placed in activated solution and activate,
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, which is characterized in that using four described in claim 1-8 any one
Member is that transparent substrates LED production method makes to be formed, comprising:
Transparent substrates and quaternary system LED epitaxial slice, the quaternary system LED epitaxial slice includes 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 surface of the described GaP layers epitaxial structure away from the light emitting diode is by the surface of roughening, the gradual change
Refractive index composite film layer is SOG bonded layer away from GaP layers of the surface, and the graded index composite film layer includes layer
The multi-layer thin film layer of folded setting, the refractive index of the multi-layer thin film layer are gradually decreased along described GaP layers to the SOG bonded layer.
10. quaternary system transparent substrates light emitting diode according to claim 9, which is characterized in that the graded index
Composite film layer includes SOG bonded layer 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, which is characterized in that the graded index
Composite film layer includes positioned at the indium tin oxide layer of the GaP layer surface and positioned at the indium tin oxide layer away from described GaP layers
The SOG bonded layer on surface.
12. quaternary system transparent substrates light emitting diode according to claim 11, which is characterized in that the indium tin oxide layer
Away from the surface that GaP layers of the surface is by roughening.
13. according to quaternary system transparent substrates light emitting diode described in claim 9-12 any one, which is characterized in that described
Bonded layer is SOG bonded layer or silicon oxide layer.
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| CN104823296A (en) * | 2012-11-09 | 2015-08-05 | 皇家飞利浦有限公司 | Light emitting device with improved internal out-coupling and method of providing same |
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