CN105161589B - Nitride LED and preparation method based on stress regulation and control plating and substrate transfer - Google Patents
Nitride LED and preparation method based on stress regulation and control plating and substrate transfer Download PDFInfo
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- CN105161589B CN105161589B CN201510505779.7A CN201510505779A CN105161589B CN 105161589 B CN105161589 B CN 105161589B CN 201510505779 A CN201510505779 A CN 201510505779A CN 105161589 B CN105161589 B CN 105161589B
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- 239000000758 substrate Substances 0.000 title claims abstract description 121
- 238000007747 plating Methods 0.000 title claims abstract description 40
- 230000033228 biological regulation Effects 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 150000004767 nitrides Chemical class 0.000 title claims abstract description 14
- 238000012546 transfer Methods 0.000 title claims abstract description 14
- 239000010410 layer Substances 0.000 claims abstract description 185
- 229910002601 GaN Inorganic materials 0.000 claims abstract description 128
- 229910052751 metal Inorganic materials 0.000 claims abstract description 61
- 239000002184 metal Substances 0.000 claims abstract description 61
- 229910052594 sapphire Inorganic materials 0.000 claims abstract description 61
- 239000010980 sapphire Substances 0.000 claims abstract description 61
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000011241 protective layer Substances 0.000 claims abstract description 33
- 239000002253 acid Substances 0.000 claims abstract description 21
- 238000001039 wet etching Methods 0.000 claims abstract description 16
- 238000005498 polishing Methods 0.000 claims abstract description 13
- 230000007797 corrosion Effects 0.000 claims abstract description 5
- 238000005260 corrosion Methods 0.000 claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 26
- 229910052737 gold Inorganic materials 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 238000003698 laser cutting Methods 0.000 claims description 12
- 229910052804 chromium Inorganic materials 0.000 claims description 10
- 229910052681 coesite Inorganic materials 0.000 claims description 9
- 229910052906 cristobalite Inorganic materials 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 229910052682 stishovite Inorganic materials 0.000 claims description 9
- 229910052905 tridymite Inorganic materials 0.000 claims description 9
- 238000005530 etching Methods 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 238000009713 electroplating Methods 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 238000001312 dry etching Methods 0.000 claims description 5
- 238000001259 photo etching Methods 0.000 claims description 5
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- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
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- 238000000034 method Methods 0.000 abstract description 20
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- 238000000926 separation method Methods 0.000 abstract description 7
- 229910052733 gallium Inorganic materials 0.000 abstract description 4
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- 239000011651 chromium Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 9
- 235000012239 silicon dioxide Nutrition 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000000407 epitaxy Methods 0.000 description 5
- 238000009616 inductively coupled plasma Methods 0.000 description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 238000005566 electron beam evaporation Methods 0.000 description 3
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- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000002633 protecting effect Effects 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
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- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 2
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- 241001062009 Indigofera Species 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers 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 having potential barriers 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 Table
- H01L33/32—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table containing nitrogen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
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- Engineering & Computer Science (AREA)
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Abstract
The present invention provides nitride LED and preparation method based on stress regulation and control plating and substrate transfer.The present invention can be used for preparing vertical structure LED using the method for wet etching stripping Sapphire Substrate.By cutting epitaxial layer of gallium nitride, hot acid cleans, and discharges gallium nitride stress；Stressless ni substrate, polishing metal substrate is electroplated；It prepares and tilts gallium nitride sidewall, sacrificial metal layer, side wall protective layer；Sapphire Substrate polishes, disposable to cut, and the committed steps such as corrosion N polar surface gallium nitrides realize the separation of Sapphire Substrate and epitaxial layer of gallium nitride.The method of the present invention does not interfere with the crystal quality of GaN active layers, thereby may be ensured that the luminous efficiency of vertical structure LED.
Description
Technical field
The invention belongs to technical field of semiconductor illumination, are related to a kind of gallium nitride-based vertical structure LED chip and its preparation
Method, especially suitable for white-light illuminating field.
Background technology
Light emitting diode（LED）Be considered as in human history after incandescent lamp, fluorescent lamp and high-intensity discharge lamp
Forth generation light source.Gallium nitride（GaN）Material is big, hot steady with energy gap as the Typical Representative of third generation semi-conducting material
The advantages that qualitative and chemical stability is good, small dielectric constant, highly thermally conductive, Flouride-resistani acid phesphatase, and it belongs to direct band gap structural material,
There is high radiation recombination efficiency, be therefore widely used in the preparation of luminescent device.
Substrate has GaN homo-substrates, sapphire, the foreign substrates such as SiC and Si used by GaN material epitaxial growth.GaN
Substrate prepares difficulty, and SiC substrate cost is high, and the mismatch of Si substrates and GaN are very big, therefore the epitaxial growth of GaN mainly uses
Be sapphire substrates.At present, the LED chip in Sapphire Substrate is most of still exists with the formation of ordinary construction.
With the industrialization of graphical sapphire substrate, the efficiency of GaN base LED chip is increased dramatically, and cost is gradually lowered.
Fluorescent powder is added on blue-light LED chip can realize white light.To realize general illumination, it is desirable that single blue-light LED chip driving exists
Still there is higher optical output power under larger current.Although graphical sapphire substrate LED chip has higher light efficiency, so
And the heat dissipation performance of Sapphire Substrate is poor, this will influence luminous efficiency of the LED chip under large driven current density.Remove sapphire
Substrate, which is prepared into vertical structure LED, can efficiently solve the above problem.The main method of removal Sapphire Substrate is laser stripping
From, but the high temperature of moment can be generated during laser lift-off, the quality of epitaxial layer can be influenced, luminous efficiency is caused to decline, more
Seriously situation may rupture epitaxial layer.Used by industrialization at present outside the mainly LED of graphical sapphire substrate
Prolong piece, due to the influence of scattering, the laser energy that will need bigger with the method processing patterned substrate of laser lift-off, to extension
The damage of layer accordingly increases.
Invention content
The present invention provides nitride LEDs and preparation method based on stress regulation and control plating and substrate transfer.Utilize laser
The each LED chip of epitaxy of gallium nitride layer separation is cut, discharges the stress of epitaxial layer of gallium nitride；It is electroplated using stress regulation and control and prepares gold
Belong to substrate；Make Sapphire Substrate and LED extension layer separations using wet etching nitrogen polar surface GaN.
Technical solution provided by the invention is as follows.
Nitride LED preparation method based on stress regulation and control plating and substrate transfer, specifically includes following steps：
[1] Sapphire Substrate is provided, then growing gallium nitride epitaxial layer, epitaxial layer of gallium nitride include over the substrate
GaN buffer layers, u-GaN layer, n-GaN layers, active area and p-GaN layer；
[2] mesa platforms are etched using photoetching and dry etching；
[3] one layer of laser cutting protective layer is prepared, using epitaxial layer of gallium nitride is cut by laser, the cleaning of reusable heat acid makes each
LED chip is independent；
[4] after removal laser cutting protective layer, deposited metal sacrificial layer, side wall protective layer；
[5] deposition of reflective electrode layer and plating seed layer；
[6] the plating metal substrate on plating seed layer, and surface polishing treatment is carried out to the metal substrate；
[7] polishing treatment is ground to Sapphire Substrate, is cut through Sapphire Substrate with laser；
[8] it is cleaned with acid or aqueous slkali, the sacrificial metal layer in step [4] is removed, leak out side gallium nitride；
[9] above structure is positioned in hot acid or hot alkaline solution, by wet etching, makes epitaxial layer of gallium nitride precious with indigo plant
Stone lining bottom detaches, and so as to which epitaxial layer of gallium nitride be made to be transferred on plating metal substrate, the gallium nitride on surface is the u- of N polar surfaces
GaN；
[10] u-GaN of N polar surfaces is removed, the n-GaN of N polar surfaces is leaked out, is then made on the n-GaN of N polar surfaces
N-type Ohm contact electrode.
Substrate described in step [1] be Sapphire Substrate, the epitaxial layer of gallium nitride from the bottom up successively include buffer layer,
U-GaN layers, n-GaN layers, active area and p-GaN layer.
Mesa platforms described in step [2] need to be etched to n-GaN, and the mesa platforms have sloped sidewall,
The mesa platforms are by the way that etching condition is controlled to prepare.
Laser cutting protective layer described in step [3] is SiO2 or SiN insulating layers；Laser described in step [3] is cut
Cutting epitaxial layer of gallium nitride needs to be cut to Sapphire Substrate；The hot acid is 220 DEG C~280 DEG C of the HPO3 and H2SO4 heats of mixing
Acid, scavenging period are 10~40min.Passageway after hot acid corrosion laser cutting, makes walkway clearance increase by 5~10 μm, so as to make
Each LED chip is independent.
Sacrificial metal layer described in step [4] is deposited at the mesa table tops passageway with sloped sidewall, covers passageway
The Sapphire Substrate of middle leakage；The sacrificial metal layer is crome metal or aluminium；Side wall protective layer described in step [4], covering are whole
A mesa passageways with sloped sidewall, above-mentioned sacrificial metal layer and side wall.
Reflecting electrode described in step [5] can be Ni/Ag, Ni/Au+Al, ITO+Ag；Kind is electroplated described in step [5]
Sublayer can be Ni/Au, Cr/Au, Ti/Au, Cr/Pt/Au.
Metal substrate described in step [6] is to realize the stress tune of metal substrate by adjusting electroplating additive content
Control, the metal substrate should have unstressed, excellent support.
Step [7] the laser cutting Sapphire Substrate need to disposably cut through sapphire, leak out gold described in step [4]
Belong to sacrificial layer.It is extremely narrow to be cut by laser line width, if cutting times are more than once, since alignment issues will cause sapphire cutting deep
It spends uneven, influences the successful removal of follow-up Sapphire Substrate.
Metal erosion solution described in step [8] is chromium corrosive liquid or aluminium corrosive liquid.
Step [10] the removal GaN buffer layers can utilize dry etching, wet etching or polishing treatment.
In above-mentioned steps [2] there is the mesa platforms of sloped sidewall, make side wall protective layer covering in step [6] finer and close,
With better protecting effect, reach GaN epitaxial layer by using wet etching N polar GaNs so as to ensure that in step [12]
With the separation of Sapphire Substrate.And traditional vertical side covering is not fine and close, in wet etching course, etchant solution penetrates into side
Destroy chip.
Galliumnitride base LED chip of the present invention based on stress regulation and control plating and substrate transfer, its structure is under
Include metal substrate, plating seed layer, reflection electrode layer, side wall protective layer, the GaN epitaxy with inverted trapezoidal shape successively to upper
Layer, n-type electrode layer.
The metal substrate, material are metallic nickel, and thickness is 80 μm, and the metal substrate is by adjusting electroplating additive
Content realizes the stress regulation and control of metal substrate, and the metal substrate should have unstressed, excellent support
The plating seed layer structure is Ni/Au, Cr/Au, Ti/Au, one kind in Cr/Pt/Au, the thickness of plating seed layer
Degree can be from 200nm~10um, and the area of the plating seed layer is equal to the area of metal substrate.
The reflection electrode layer can be Ni/Ag, Ni/Au+Al, ITO+Ag, and the reflecting electrode layer thickness can be from
150nm~500nm, the area of reflecting electrode are less than the area of plating seed layer.
The GaN side wall protective layers can be insulating layer SiO2 or SiN, and thickness range is 800 ~ 1500nm, and side wall is protected
Sheath covers GaN.
The structure of the GaN epitaxial layer of the inverted trapezoidal shape includes p-GaN layer, active area and n-GaN layers successively from top to bottom.
The thickness of the GaN epitaxial layer of the inverted trapezoidal shape is 2~4 μm.The inclination angle of the GaN epitaxial layer of inverted trapezoidal shape is 40~70 degree.
The n-GaN layers on the GaN epitaxial layer most surface layer of the inverted trapezoidal shape are N polarity gallium nitride.
The n-type electrode layer can be Cr-, Ti-, Cr/Al-, Ti/Al- structures.Thickness of electrode range 500nm~
1500nm。
Compared with prior art, the invention has the advantages that and technique effect：1st, the present invention by control ICP etch and
Mask layer makes the side wall of the Mesa etched with 40~70 degree of inclination angle, so as to ensure the cause of subsequent side wall protective layer
Close property, effectively prevent leaking electricity.Find that, when inclination angle is less than 30 degree, the electric leakage for the LED chip prepared increases in experiment.2nd, originally
Invention, which is used, first cuts epitaxial layer of gallium nitride using laser, is and then cleaned again with hot acid, discharges gallium nitride by this process
Stress, so as to which chip be made in following process to be not in epitaxial layer fragmentation phenomenon, do not cut and be subsequently be electroplated it is stressless
The basis of metal nickel plate.3rd, sacrificial metal layer of the present invention and side wall protective layer are combined, one side sacrificial metal layer
Be conducive to the gallium nitride layer that wet etching is connected with Sapphire Substrate after removal, on the other hand, there is the presence of side wall protective layer, side
The GaN of wall is not corroded, thus after GaN is detached with Sapphire Substrate, the integrality of the lateral GaN of energy effective guarantee.4th, this hair
Thickness after the bright polishing Sapphire Substrate is less than 40 μm, this, which is conducive to laser cutting Sapphire Substrate, disposably to cut
It wears.Thicker Sapphire Substrate is found in experiment, needs to cut through more than primary in cutting, it is micron-sized inclined between cutting twice
Cutting effect can be greatly reduced in difference, so as to it is difficult to ensure that the success of subsequent wet corrosion.
The method of wet etching stripping Sapphire Substrate of the present invention can be used for preparing vertical structure LED.Pass through
Epitaxial layer of gallium nitride, hot acid cleaning are cut, discharges gallium nitride stress；Stressless ni substrate, polishing metal substrate is electroplated；It prepares
Tilt gallium nitride sidewall, sacrificial metal layer, side wall protective layer；Sapphire Substrate polishes, disposable to cut, and corrodes N polar surface nitrogen
Change the separation that the committed steps such as gallium realize Sapphire Substrate and epitaxial layer of gallium nitride.It is active that the method for the present invention does not interfere with GaN
The crystal quality of layer, thereby may be ensured that the luminous efficiency of vertical structure LED.
Description of the drawings
Fig. 1 is the flow chart for the method that the present invention prepares vertical structure LED by wet etching stripping Sapphire Substrate.
Fig. 2 a to Fig. 2 f are the schematic diagrams for the cross section that the present invention prepares vertical structure LED process.
Fig. 3 is in wet etching course, from Sapphire Substrate unilateral observation to Sapphire Substrate and GaN epitaxial layer interface
Optical microscope.
Wherein：1 is Sapphire Substrate, and 2 be GaN epitaxial layer, and 3 be side wall protective layer, and 4 be reflection electrode layer, that is, P-type electrode,
5 be plating metal substrate, and 6 be n-type electrode.
Specific embodiment
To make present disclosure clearer, below in conjunction with attached drawing, present disclosure is described further.This
Invention is not limited to the specific embodiment, and general replace known to those skilled in the art is also covered by guarantor of the invention
In the range of family.
The step of present invention prepares the method for vertical structure LED by wet etching stripping Sapphire Substrate is as follows：
[1] using MOCVD epitaxy growing system, growing gallium nitride epitaxial layer on a sapphire substrate, outside the gallium nitride
It is GaN buffer layers, u-GaN layers, n-GaN layers, multiple quantum well layer successively from top to bottom to prolong layer（MQW）And p-GaN layer.
[2] pass through photoetching and inductively coupled plasma dry etch process, etch nitride gallium epitaxial layer, etching depth 2
~5 μm, by controlling the condition of photoetching, prepare the mesa platforms with sloped sidewall.
[3] protective layer of one layer of 800 ~ 1500nm thickness is deposited on entire epitaxial wafer surface, which can be insulating layer
SiO2 or SiN.If etching depth described in step [2] is less than 2 μm, sloped sidewall range is smaller, in subsequent wet corrosion
Protecting effect is bad；If etching depth is more than 5 μm, protective layer covering is not fine and close.The thickness of the protective layer is for step
[2] in set by etching depth, when protective layer thickness is less than 800nm, side wall covering is bad；When protective layer thickness is more than
1500nm, growth technique time lengthen, and cost increases.
[4] with epitaxial layer of gallium nitride is cut by laser to Sapphire Substrate among mesa table tops passageway, then with 250 DEG C
Hot acid cleans 10~40min, makes each LED chip separated from each other.
[5] protective layer is removed with etchant solution, then the metal of one layer of 200 ~ 500nm thickness of deposition is sacrificial at mesa table tops passageway
Domestic animal layer.The sacrificial metal layer can be the metals such as chromium, aluminium.
[6] insulating layer of one layer of 500~1000nm thickness is deposited, covers entire mesa passageways and side wall, forms side wall protection
Layer.Edge layer includes the dielectric insulating films such as SiO2, SiN.
[7] last layer reflection electrode layer and one layer of plating seed are deposited on p-GaN contact layers using evaporating deposition technique
Layer.Wherein reflecting electrode can be Ni/Ag, Ni/Au+Al, ITO+Ag etc.；Plating seed layer includes Ni/Au, Cr/Au, Ti/Au,
Cr/Pt/Au etc..
[8] metal substrate of one layer of stressless 80 ~ 150 μ m-thick is electroplated with electroplating technology, which is nickel.Pass through
A certain amount of leveling agent is separately added into electroplate liquid, it is Ni-based that wetting agent and NaCO3 etc. make plating obtain stressless metal
Plate.
[9] surface polishing treatment is carried out to W metal substrate.
[10] Sapphire Substrate is ground and is polished to 10 ~ 40 μ m-thicks, and with laser disposably by Sapphire Substrate face
It cuts through.
[11] it is then cleaned with metal erosion solution, the sacrificial metal layer of 200 ~ 500nm thickness is removed, leak out side
The GaN layer in face.
[12] it is 60 ~ 90 DEG C, in the KOH solution of a concentration of 4 ~ 8mol/L above structure to be immersed temperature, is carried out to N poles
Property face GaN carry out wet etching 2~3 hours, epitaxial layer of gallium nitride is made to be detached with Sapphire Substrate.
[13] the u-GaN layers on surface are removed with ICP dry etchings, and deposited by electron beam evaporation makes N-shaped electricity on n-GaN
Pole.N-type electrode layer includes, Cr-, Ti-, Cr/Al-, the n-type electrodes such as Ti/Al- structures.
In above-mentioned steps [2] there is the mesa platforms of sloped sidewall, make the covering of step [6] side wall protective layer finer and close, tool
Have better protecting effect, so as to ensure that in step [12] by using wet etching N polar GaNs reach GaN epitaxial layer with
The separation of Sapphire Substrate.
Embodiment
As depicted in figs. 1 and 2, it is of the invention that vertical stratification is prepared by wet etching stripping sapphire Sapphire Substrate
The method of LED, specific preparation process are as follows：
[1] using MOCVD epitaxy growing system, GaN epitaxial layer 2 is grown on the graphical sapphire substrate 1 in c faces, outside
Prolonging layer, succession is GaN buffer layers, u-GaN layers, n-GaN layers, multiple quantum well layer successively（MQW）And p-GaN layer, entire GaN
Base epitaxy layer thickness should be greater than 6 μm.As shown in Figure 2 a.
[2] it by photoetching and inductively coupled plasma dry etch process, etches outside the gallium nitride in Sapphire Substrate
Prolong layer（That is GaN epitaxial layer 2）, 3.2 μm of etching depth is 40~70 degree by adjusting etching condition to control its sidewall draft angles.
[3] insulating protective layer of one layer of 500nm thickness, insulating layer SiO2 are deposited using PEVCD on entire epitaxial wafer surface.
The protective layer of surface Ga N when hot acid cleans after being cut as ensuing laser.As shown in Figure 2 b.
[4] with epitaxial layer of gallium nitride is cut by laser to Sapphire Substrate among mesa table tops passageway, then with 250 DEG C
Hot acid cleans 25min, makes each LED chip separated from each other.The component of the hot acid is sulfuric acid：Phosphoric acid=1：3.
[5] SiO2 insulating layers are removed with BOE solution, then the gold of one layer of 200 ~ 500nm thickness is deposited at mesa table tops passageway
Belong to sacrificial layer.The sacrificial metal layer is aluminium.The sacrificial metal layer covers the Sapphire Substrate among passageway.
[6] the SiO2 insulating layers of one layer of 1000nm thickness are deposited using PECVD device, cover entire mesa passageways, above-mentioned gold
Belong to sacrificial layer and side wall, form side wall protective layer 3.
[7] last layer reflection electrode layer 4 is deposited on p-GaN contact layers using electron beam evaporation technique, uses magnetron sputtering
One layer of plating seed layer is deposited.Wherein reflecting electrode is ITO+Ni/Ag；Plating seed layer is Ti/Au.
[8] metal substrate 5 of 150 extremely low μ m-thicks of a ply stress is electroplated with electroplating technology, which is nickel.Pass through
Suitable leveling agent is separately added into electroplate liquid, the metal ni substrate that wetting agent and NaCO3 etc. obtain plating is that nothing should
Power substrate.
[9] surface polishing treatment is carried out to metal ni substrate, makes its surface height difference within 5 μm, the Ni bases after polishing
The thickness of plate is 80 μm.
[10] Sapphire Substrate is ground and is polished to 20 μ m-thicks, stressless ni substrate ensures the sample after polishing
It is smooth not to be bent, then disposably cut through Sapphire Substrate face with laser cutting device.
[11] it is then cleaned with KOH solution, scavenging period is 1~2min, by the sacrificial metal layer in step [5]
Al is removed, and leaks out the GaN layer of side.As shown in Fig. 2 c and Fig. 2 d.
[12] it is 80 DEG C, in the KOH solution of a concentration of 6mol/L slice, thin piece to be immersed temperature, N polar surfaces GaN is carried out wet
Method is corroded 3 hours, and GaN epitaxial layer is made to be detached with Sapphire Substrate.As shown in Figure 2 e.
[13] the u-GaN layers on surface are removed with ICP dry etchings, and deposited by electron beam evaporation N-type ohm connects on n-GaN
Touched electrode, that is, n-type electrode layer 6.The Ohm contact electrode uses Cr/Al/Ti/Au.As shown in figure 2f（Figure is to be inverted, final core
Piece top layer is n-type electrode layer 6）.
The method of wet etching stripping Sapphire Substrate of the present invention can be used for preparing vertical structure LED.Pass through
Epitaxial layer of gallium nitride, hot acid cleaning are cut, discharges gallium nitride stress；Stressless ni substrate, polishing metal substrate is electroplated；It prepares
Tilt gallium nitride sidewall, sacrificial metal layer, side wall protective layer；Sapphire Substrate polishes, disposable to cut, and corrodes N polar surface nitrogen
Change the separation that the committed steps such as gallium realize Sapphire Substrate and epitaxial layer of gallium nitride.It is active that the method for the present invention does not interfere with GaN
The crystal quality of layer, thereby may be ensured that the luminous efficiency of vertical structure LED.
Claims (8)
1. the preparation method of the nitride LED based on stress regulation and control plating and substrate transfer, it is characterised in that include the following steps：
[1] Sapphire Substrate is provided, then growing gallium nitride epitaxial layer, epitaxial layer of gallium nitride delay including GaN over the substrate
Rush layer, u-GaN layer, n-GaN layers, active area and p-GaN layer；
[2] mesa platforms are etched using photoetching and dry etching；
[3] one layer of laser cutting protective layer is prepared, using epitaxial layer of gallium nitride is cut by laser, the cleaning of reusable heat acid makes each LED
Chip is independent；
[4] after removal laser cutting protective layer, deposited metal sacrificial layer, side wall protective layer；
[5] deposition of reflective electrode layer and plating seed layer；
[6] the plating metal substrate on plating seed layer, and surface polishing treatment is carried out to the metal substrate；
[7] polishing treatment is ground to Sapphire Substrate, is cut through Sapphire Substrate with laser；
[8] it is cleaned with acid or aqueous slkali, the sacrificial metal layer in step [4] is removed, expose side gallium nitride；
[9] above structure is positioned in hot acid or hot alkaline solution, by wet etching, makes epitaxial layer of gallium nitride and sapphire
Substrate detaches, and so as to which epitaxial layer of gallium nitride be made to be transferred on plating metal substrate, the gallium nitride on surface is the u- of N polar surfaces
GaN；
[10] u-GaN of N polar surfaces is removed, exposes the n-GaN of N polar surfaces, N-type Europe is then made on the n-GaN of N polar surfaces
Nurse contacts electrode.
2. the preparation method of the nitride LED according to claim 1 based on stress regulation and control plating and substrate transfer, special
Sign is substrate described in step [1] for Sapphire Substrate, and the epitaxial layer of gallium nitride includes buffer layer, u- successively from the bottom up
GaN layer, n-GaN layers, active area and p-GaN layer.
3. the preparation method of the nitride LED according to claim 1 based on stress regulation and control plating and substrate transfer, special
Sign is mesa platforms described in step [2], need to be etched to n-GaN, and the mesa platforms have sloped sidewall, institute
It is by the way that etching condition is controlled to prepare to state mesa platforms.
4. the preparation method of the nitride LED according to claim 1 based on stress regulation and control plating and substrate transfer, special
Sign is that the laser cutting protective layer described in step [3] is SiO2Or SiN insulating layers；Laser cutting described in step [3]
Epitaxial layer of gallium nitride needs to be cut to Sapphire Substrate；The hot acid is 220 DEG C~280 DEG C of HPO3And H2SO4Mix hot acid,
Scavenging period is 10~40min；Passageway after hot acid corrosion laser cutting makes 5~10 μm of walkway clearance increase, each so as to make
LED chip is independent.
5. the preparation method of the nitride LED according to claim 1 based on stress regulation and control plating and substrate transfer, special
Sign is that sacrificial metal layer described in step [4] is deposited at the mesa table tops passageway with sloped sidewall, to cover passageway
The Sapphire Substrate of middle exposing；The sacrificial metal layer is crome metal or aluminium；Side wall protective layer described in step [4], covering are whole
A mesa passageways with sloped sidewall, above-mentioned sacrificial metal layer and side wall.
6. the preparation method of the nitride LED according to claim 1 based on stress regulation and control plating and substrate transfer, special
Sign is that reflecting electrode described in step [5] is Ni/Ag, Ni/Au+Al or ITO+Ag；Plating seed layer described in step [5]
For Ni/Au, Cr/Au, Ti/Au or Cr/Pt/Au.
7. the preparation method of the nitride LED according to claim 1 based on stress regulation and control plating and substrate transfer, special
Sign is that metal substrate described in step [6] is to realize the stress regulation and control of metal substrate by adjusting electroplating additive content,
The metal substrate should have unstressed, excellent support.
8. the nitride LED based on stress regulation and control plating and substrate transfer, special made from the preparation method as described in claim 1
Sign is to include metal substrate successively from top to bottom, plating seed layer, reflection electrode layer, side wall protective layer, has inverted trapezoidal knot
The GaN epitaxial layer and n-type electrode layer of structure；The metal substrate is metallic nickel, and thickness is 80 μm, and the metal substrate is to pass through
Electroplating additive content is adjusted to realize the stress regulation and control of metal substrate, the metal substrate should have unstressed；The electricity
Plating seed layer structure is Ni/Au, Cr/Au, Ti/Au, one kind in Cr/Pt/Au, the thickness of plating seed layer for 200nm~
10um；The area of the plating seed layer is equal to the area of metal substrate；The reflection electrode layer for Ni/Ag or Ni/Au+Al or
ITO+Ag, the reflecting electrode layer thickness are 150nm~500nm, and the area of reflecting electrode is less than the area of plating seed layer；Institute
GaN side wall protective layers are stated as insulating layer SiO2Or SiN, thickness range are 800 ~ 1500nm, side wall protective layer is covered outside GaN
Prolong a layer side wall；The structure of the GaN epitaxial layer includes p-GaN layer, active area and n-GaN layer successively from top to bottom；Outside the GaN
The thickness for prolonging layer is 2~4 μm；The sidewall draft angles of the GaN epitaxial layer of inverted trapezoidal shape are 40~70 degree；The inverted trapezoidal shape
The n-GaN layers on GaN epitaxial layer most surface layer are N polarity gallium nitride；The n-type electrode layer is Cr-, Ti-, Cr/Al-, Ti/Al-Knot
Structure；Thickness of electrode ranging from 500nm~1500nm.
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| CN106299069A (en) * | 2016-08-31 | 2017-01-04 | 厦门三安光电有限公司 | A kind of laser diode and preparation method thereof |
| CN107369746B (en) * | 2017-08-30 | 2023-05-23 | 华南理工大学 | Micro-size resonant cavity LED chip with substrate stripped by chemical corrosion and preparation method thereof |
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| CN113223928B (en) * | 2021-04-16 | 2024-01-12 | 西安电子科技大学 | Gallium oxide epitaxial growth method based on transfer bonding |
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| CN114038876B (en) * | 2021-08-09 | 2022-10-21 | 重庆康佳光电技术研究院有限公司 | Manufacturing method of light-emitting chip, light-emitting chip and light-emitting device |
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