CN105489716B - The preparation method of flexible led array based on inorganic semiconductor material - Google Patents
The preparation method of flexible led array based on inorganic semiconductor material Download PDFInfo
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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
- H01L33/005—Processes
- H01L33/0093—Wafer bonding; Removal of the growth substrate
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Abstract
The invention discloses a kind of preparation method of inorganic flexible LED array, including：LED of the growth with sacrifice layer, is lithographically formed the photoresist mask of ring-shaped figure, is etched to contact layer under LED on a semiconductor substrate；Lithographic etch process makes side passivation layer；Formed after patterned metallic pattern, annealed alloy and form Ohmic contact；Ring-like following table is etched, sacrifice layer is exposed；Corrode sacrifice layer and undercutting certain length；Spin coating flexible polymeric materials；The polymeric material of covering above inner ring and part metals electrode is etched, exposes part metals electrode to prepare metal interconnection；Metal sputtering simultaneously carries out graphical treatment preparation LED unit interconnection；Spin coating flexible polymeric materials；Expose inner ring sacrifice layer；Corrode remaining sacrifice layer；The inorganic LED array of flexible polymer parcel is peeled off, the preparation of inorganic flexible LED array is completed.
Description
Technical field
It is specifically that one kind is based on inorganic half the invention belongs to semiconductor photoelectronic device technology and technical field of nano material
The preparation method of the flexible led array of conductor material and organic flexible base material.
Background technology
The inorganic integrated device of novel flexible based on inorganic semiconductor material and organic flexible base material, be by flexible substrate with
Traditional inorganic semiconductor technological perfectionism is combined；Compared with conventional organic flexible LED, it have advantages below brightness height, long lifespan,
Stability is high, efficiency high；Have both flexible advantage；These advantages of inorganic flexible LED make it have in medical treatment ＆ health and daily life
It is widely used；Including：Miniature flexible LED can make the health monitor that patient wraps as blanket or imaging
Instrument；Can as optical dynamic therapy light source, it is more more advantageous than laser；Can also be by its photo-detector collection similar to size
Surgical operation is carried out into the pad of fingers of gloves is fabricated into as closely sensor glove；Flexible LED implant is made, makes it
Human body is favorably implanted, the comprehensive function of vital sign monitor, blood tester, imaging center and dispensary is played；Can
Light source is used as so that LED array is attached on the medical equipment conduit of measurement intravenous glucose concentration；Also with flexible LED
Array prepares the facial mask of laminating human body, and eye mask, body film make photon delicate skin comfortableization, facilitation.
In recent years, with the fast development of micro-nano technology technology and material science, many flexible device preparation methods meet the tendency of
And give birth to, organic flexible LED obtains broad development and application；Although organic flexible LED costs are low, make simple, organic soft
LED luminous efficiencies are low, brightness is small, stability is poor, short life for property, in wet condition can be affected by environment.Inorganic semiconductor material
The high several quantity higher than inorganic semiconductor of mobility and device operating frequencies, conductance of material.Inorganic LED has energy efficiency
The advantages of high, long lifespan and good stability, prepare inorganic flexible LED and avoid above mentioned problem, but wiener process technology has more
High requirement, preparation technology is relative complex.
The content of the invention
It is an object of the invention to propose a kind of preparation method of inorganic flexible LED array, i.e. sacrifice layer side is corroded in punching
Method：Inorganic flexible LED array prepared by the present invention, with efficiency high, brightness height, long lifespan, stability it is good, it is structurally ordered can
Control, it is reproducible the advantages of.
The present invention proposes a kind of preparation method of the flexible led array based on inorganic semiconductor material, comprises the following steps：
Step 1：Using growth technology, growth on a semiconductor substrate has the LED of sacrifice layer；
Step 2：LED is cleaned, the photoresist mask of ring-shaped figure is lithographically formed, etches annular LED unit
Upper table surface；
Step 3：Using lithographic etch process side passivation layer is made in the annular LED unit upper table surface；
Step 4：Ohmic contact is formed after metal patternization, annealed alloy；
Step 5：Photoresist mask is lithographically formed, the annular following table of etching exposes sacrifice layer, completes inorganic LED unit
Preparation；
Step 6：Photoresist mask is lithographically formed, the sacrifice layer around following table is exposed, corrodes sacrifice layer and to leave from office
Undercutting certain length in face；
Step 7：Spin coating flexible polymeric materials, and carry out the heat treatment completion inorganic LED unit covering；
Step 8：Photo etched mask, the flexibility for etching in the upper table surface inner ring and being covered above part metals electrode is poly-
Compound material, exposes part metals electrode to prepare metal interconnection contact；
Step 9：Metal sputtering simultaneously carries out graphical treatment to prepare the interconnection metallization lines between LED unit array；
Step 10：Spin coating flexible polymeric materials, for covering the interconnection metallization lines, and are heat-treated, and form institute
State and coated above and below the flexible polymeric materials of interconnection metallization lines；
Step 11：Flexible polymeric materials in chemical wet etching upper table surface inner ring, expose in the upper table surface inner ring
Sacrifice layer；
Step 12：Corrode remaining sacrifice layer；
Step 13：The inorganic LED unit array of transfer is peeled off, the preparation of inorganic flexible LED unit array is completed.
The preparation method for this flexible led array based on inorganic semiconductor material that the present invention is provided, with conventional light
The micro- support of photoresist bridge, the micro- method for supporting of side wall are compared, big, controllable, reproducible and steady in order with simple to operate, structural area
Qualitative high advantage.
Brief description of the drawings
For the content and advantage that the present invention is furture elucidated, below in conjunction with accompanying drawing and example in detail as after, wherein：
Fig. 1 is red described in the preparation method of the flexible led array proposed by the present invention based on inorganic semiconductor material
Outer LED epitaxial structure figure.
Fig. 2 is the LED work(of the preparation method of the flexible led array proposed by the present invention based on inorganic semiconductor material
Can cellular construction figure.
Fig. 3 is the step described in the preparation method of the flexible led array proposed by the present invention based on inorganic semiconductor material
LED component sectional view after rapid 6 undercutting sacrifice layer.
Fig. 4 is the step of the preparation method of the flexible led array proposed by the present invention based on inorganic semiconductor material
LED component sectional view after 11 processing.
Fig. 5 is the step of the preparation method of the flexible led array proposed by the present invention based on inorganic semiconductor material
LED component sectional view after 12 processing.
Fig. 6 is the transfer of the preparation method of the flexible led array proposed by the present invention based on inorganic semiconductor material
Process schematic.
Fig. 7 will be mutual for the described of the preparation method of the flexible led array proposed by the present invention based on inorganic semiconductor material
Even LED is transferred to the flexible seal of flexible substrates 11.
In figure：1 is P contact layers, and 2 be the LED epitaxial layers for removing P, N contact layer, and 3 be N contact layers, and 4 be sacrifice layer, and 5 are
Substrate, 6 be P electrode, and 7 be passivation layer, and 8 be N electrode, and 9 be flexible polymeric materials polyimides for interconnection metal, 10, and 11 are
Flexible transfer seal or flexible transfer substrate
Embodiment
For the object, technical solutions and advantages of the present invention are more clearly understood, below in conjunction with specific embodiment, and reference
Accompanying drawing, the present invention is described in further detail.
The present invention proposes a kind of preparation method of inorganic flexible LED array, i.e., using growth technology, in semiconductor lining
LED of the growth with sacrifice layer on bottom；LED is cleaned, the photoresist mask of ring-shaped figure is lithographically formed, carved
Lose to contact layer under LED；Lithographic etch process makes side passivation layer, and effectively reduction is caused due to lateral oxidation layer
Side leakage current；Patterned metallic pattern is formed using ultrasonic stripping means or metal erosion method, annealed alloyization it
After form Ohmic contact；Photoresist mask is lithographically formed, ring-like following table is etched, sacrifice layer is exposed, inorganic LED unit is completed
Prepare；Photoresist mask is lithographically formed, sacrifice layer around following table, corrosion sacrifice layer and undercutting certain length is only exposed；Rotation
A kind of special flexible polymeric materials are applied, and carry out heat treatment and complete LED unit covering；Photo etched mask, etching inner ring and part
The polymeric material of covering above metal electrode, exposes part metals electrode to prepare metal interconnection；Metal sputtering is simultaneously carried out
Graphical treatment prepares LED unit interconnection；Spin coating flexible polymeric materials, and be heat-treated；Cyclopolymer in chemical wet etching
Material, exposes inner ring sacrifice layer；Corrode remaining sacrifice layer；The inorganic LED array of flexible polymer parcel is peeled off, nothing is completed
The preparation of machine flexible led array.
The preparation method of the prominent flexible led array based on inorganic semiconductor material of the present invention is as follows：
Step 1：Using growth technology, growth on a semiconductor substrate has the LED of sacrifice layer；
Step 2：LED is cleaned, the photoresist mask of ring-shaped figure is lithographically formed, etches annular LED unit
Upper table surface；
Step 3：Lithographic etch process makes side passivation layer, reduces due to the side leakage current that lateral oxidation layer is caused；
Step 4：Ohmic contact is formed after metal patternization, annealed alloy；
Step 5：Photoresist mask is lithographically formed, the annular following table of etching exposes sacrifice layer, completes inorganic LED unit
Prepare；
Step 6：Photoresist mask is lithographically formed, sacrifice layer around following table is exposed, simultaneously undercutting is certain for corrosion sacrifice layer
Length；
Step 7：A kind of flexible polymeric materials of spin coating, and carry out heat treatment completion cellular construction covering；
Step 8：The polymeric material of covering, exposes part above photo etched mask, etching inner ring and part metals electrode
Metal electrode is contacted with preparing metal interconnection；
Step 9：Metal sputtering simultaneously carries out graphical treatment preparation LED unit interconnection；
Step 10：Spin coating flexible polymeric materials, and be heat-treated；
Step 11：Chemical wet etching inner ring polymeric material, exposes inner ring sacrifice layer；
Step 12：Corrode remaining sacrifice layer；
Step 13：The inorganic LED array of flexible polymer parcel is peeled off, the preparation of inorganic flexible LED array is completed.
Refer to shown in Fig. 1-Fig. 7, describe proposed by the present invention based on inorganic semiconductor below by specific embodiment
The preparation method of the flexible led array of material, comprises the following steps：
Step 1：Using growth technology, growth on a semiconductor substrate has the LED of sacrifice layer；With GaAs
Exemplified by substrate 5, metal organic vapor growth apparatus successively epitaxial sacrificial layer AlAs 4, N-type contact layer are used
Al0.1Ga0.9As 3, N-type limiting layer Al0.3Ga0.7As, active area GaAs, P limiting layer Al0.3Ga0.7As, current expansion
Layer Al0.1Ga0.9As, p-type contact layer Al0.1Ga0.9As 1；As shown in figure 1, reference 2 represents to include N-type limiting layer
Al0.1Ga0.9As, active area GaAs, P limiting layer Al0.3Ga0.1As, current extending Al0.1Ga0.9As epitaxial layer,
In follow-up processing procedure, the processing for this epitaxial layer is consistent；Wherein N contact layers, P contact layers are heavy doping, N-type
Limiting layer and p-type limiting layer is are lightly doped, active area background doped；
Step 2：By the LED with sacrifice layer 4 of epitaxial growth, 5 points of ultrasound in acetone and absolute ethyl alcohol is placed in
Clock (55 DEG C of temperature)；Deionized water rinsing is used again 20 times；Nitrogen is dried up, and completes the cleaning of GaAs epitaxial wafers；Using photoetching technique,
By spin coating photoresist, front baking, exposure, after dry, development, GaAs epitaxial wafers formation the patterned photoresist mask of annular,
Annulus inner ring radius is 10 microns, and outer shroud radius is 80 microns；The upper surface of N contact layers 3 is etched to using ICP；Complete cleaning light
Photoresist；
Step 3：300nm silica is grown, and by being lithographically formed photoresist mask, prepared by RIE etching silicon dioxides
Silica side and surface passivation layer 7；Ultrasonic 5 minutes (55 DEG C of temperature) is placed in acetone and absolute ethyl alcohol；Deionization is used again
Water is rinsed 20 times；Nitrogen is dried up, and completes cleaning photoresist；
Step 4：Using negative photoresist, for example, AZ5214 is subjected to general burst into and carries out photoetching for negative photoresist, outside
Prolong the figure that the anti-version of electrode pattern is prepared on piece；Splash-proofing sputtering metal gold germanium nickel 30nm, golden 100nm；Acetone soak 30 minutes, uses work(
Rate carries out ultrasonic stripping for 40w supersonic cleaning machine, 30 seconds time, until gold is completely exfoliated, obtains intact metal electrode figure
Shape；The metal electrode includes P electrode 6 and N electrode 8, and P electrode 6 is located on the LED upper table surfaces, and N electrode 8 is located at upper table surface
Nearby etch the upper surface of N contact layers 3 exposed；For annular table top, using the electrode structure of annular, meet LED science
Design, beneficial to the recombination luminescence that LED is relatively uniform；Design P electrode 6 is annular electrode structure, and inner ring radius is 35 microns, outer shroud
Radius is 45 microns, and N electrode 8 also uses annular electrode structure, and inner ring radius is 100 microns, and outer shroud radius is 110 microns；It is complete
Into ultrasound stripping, ultrasound 3 minutes in acetone and absolute ethyl alcohol are sequentially placed into；With 20 times cleanings of deionized water rinsing；Using quick
Annealing furnace carries out being warming up within 20 seconds 170 DEG C, is kept for 20 seconds, is warming up within 10 seconds 335 DEG C and is kept for 5 seconds, rises within 10 seconds 450 DEG C, holding
60 seconds, removal LED unit piece after 60 second time dropped to 100 DEG C, 100 DEG C；Annealed alloy is completed, Ohmic contact is formed；
Step 5：Photoresist mask is lithographically formed, mask pattern is annular, wherein annulus outer shroud, annulus inner ring radius is
7.5 microns, it is slightly less than upper table surface inner ring radius, outer shroud radius is 120 microns, and N electrode 8 is included；Configure corrosive liquid lemon
Lemon acid buffer：H2O2=5: 1；The corrosive liquid can corrode GaAs, Al0.1Ga0.9As, will not corrode AlAs materials；Use
Above-mentioned configured corrosion corrosion N contact layers Al0.1Ga0.9As2 etches annular following table, entered to AlAs sacrifice layers 4
The conventional cleaning of row；Remove remaining photoresist；Complete inorganic LED unit to prepare, Fig. 2 is appearing on the stage with annular of preparing
Face, annular following table, P electrode 6, the LED unit structural section figure of N electrode 8；
Step 6：It is lithographically formed photoresist mask, the AlAs sacrifice layers 4 only around exposure unit；Exposure AlAs sacrifice layers 4
It is 120 microns to form inner ring radius, and outer shroud radius is 140 microns of region；Using 10%HF acid corrosion AlAs sacrifice layers 4, cruelly
The fast erosion of AlAs sacrifice layers 4 of dew falls, our control corrosion rate times, its inside undercutting depth is accounted for 15 microns of LED unit；
With reference to etching time 1.5 minutes；Photoresist is cleaned afterwards；Obtained device sectional view is as shown in Figure 3；Inside undercutting AlAs sacrifices
Layer 4, is to wrap up LED unit to form the flexible polymer of " work " font, prevents that LED unit is broken in subsequent processes
Split.
Step 7；Adjust spin coating machine speed 3000r minute, rotational time 30 seconds, spin-on polyimide flexible polymer material
Material, is to carry out 80 DEG C of heat treatment to toast 10 minutes in hot plate, rises to 140 DEG C and toast 30 minutes, can be in above-mentioned LED extension cores
About 3 microns of thick Kaptons are formed on piece, the LED epitaxial chips with mesa structure are uniformly covered on, LED is completed
Cellular construction flexible polyimide is covered；
Step 8：By being lithographically formed photoresist mask, because the Kapton of non-imidization is dissolved in alkaline solution,
AZ3038 is conventional weak caustic solution, takes convenient and safe, and the stably and controllable property of corrosion rate is good；Use the alkaline photoresists of AZ3038
The polyimides that developer solution etching is not covered by photoresist, until the polyimides of exposure is completely dissolved, we pass through this side
Polyimides at the polyimides in polyimides and upper table surface inner ring at method, dissolving partial electrode, dissolving partial electrode,
It is that, for expose portion metal electrode, interconnection metal can directly contact metal electrode when making metal interconnection 9 for lower step；
Polyimides in dissolving upper table surface inner ring is because prevent this part polyimides in step 10, due to spin coating polyamides again
Imines is simultaneously heat-treated, equivalent to the secondary heat treatment of polyimides, after polyimides after-treatment herein, in AZ3038 alkalescence
Photoresist developer dissolution velocity is small, is unfavorable for the sacrifice layer at our subsequent etching inner ring；30 seconds reference times；Chip is put
In on hot plate or baking oven, 250 DEG C are heated 1.5 hours, make polyimides imidization, and the polyimides after imidization can not be
AZ3038 alkalescence photoresist developer in dissolve, with corrosion-resistant resistance it is high the characteristics of, without having to worry about in follow-up technical process
Middle generation performance denaturation.
Step 9：Metal sputtering 400nm Au, by being lithographically formed photoresist mask, corrosion exposure is corroded using Au
Au, prepares LED unit interconnection line 9；Clean photoresist；
Step 10：It is being prepared for the flexible polymeric materials of spin-on polyimide 10, rotating speed on the chip of metal interconnecting wires 9
3000 turns minute, 30 seconds time；It is heat-treated on hot plate, 80 DEG C of temperature, toasts 10 minutes, then heat to 140 DEG C,
Baking 30 minutes, completes the covering interconnected to Au；The interconnection metal coated above and below polyimides is formd, this is flexible for us
Metal interconnecting line 9 afterwards forms firm protection, prevents it to be broken during Bending Deformation；About polyimides 10
The device sectional view formed after the interconnection metal of cladding is as shown in Figure 4.
Step 11：Photoresist mask is lithographically formed, the polyimides 10 in upper table surface inner ring and LED unit interconnection is only exposed
Positive and negative electrode；The positive and negative electrode of exposure LED unit interconnection is can be smoothed out external power-up after the completion of being prepared for device,
Make its normal work；In the polyimides 10 not being covered by photoresist using the alkaline photoresist developer etchings of AZ3038, exposure
AlAs sacrifice layers 4 in table top inner ring；It so could smoothly corrode AlAs sacrifice layers 4 in lower step process, LED component is served as a contrast with GaAs
Flexible polyimide 10 is only relied between bottom 5 to connect.
Step 12：AlAs sacrifice layers, all remaining AlAs sacrifice layers of erosion removal, ginseng are corroded using 10%HF acid solutions
Examine etching time 15 minutes；Fig. 5 is to corrode flexible polyimide 10 on the device sectional view formed after remaining sacrifice layer, substrate
The LED array of micro- support, LED array is not directly contacted with substrate, passes through the Kapton and lining wrapped up around LED unit
Bottom forms this layer contact in micro- contact, transfer process and is broken.
Step 13：By transfer technique, using flexible seal 11, the LED array that polyimides is wrapped up is from GaAs substrates 5
On be transferred in flexible substrates 11 on film, Fig. 6 is transfer process schematic diagram, and LED array is is transferred to flexible substrates 11 by Fig. 7
After flexible seal, the flexible LED schematic diagram of formation；Flexible seal is usually same material with flexible base, such as poly dimethyl silicon
Oxygen alkane (PDMS), is obtained by different processing, and we mark using 11.So far, inorganic flexible LED array is completed
Preparation.
Particular embodiments described above, has been carried out further in detail to the purpose of the present invention, technical scheme and beneficial effect
Describe in detail bright, it should be understood that the foregoing is only the present invention specific embodiment, be not intended to limit the invention, it is all
Within the spirit and principles in the present invention, any modification, equivalent substitution and improvements done etc. should be included in the protection of the present invention
Within the scope of.
Claims (11)
1. a kind of preparation method of the flexible led array based on inorganic semiconductor material, comprises the following steps：
Step 1：Using growth technology, growth on a semiconductor substrate has the LED of sacrifice layer；
Step 2：LED is cleaned, the photoresist mask of ring-shaped figure is lithographically formed, etches annular LED unit and appear on the stage
Face；
Step 3：Using lithographic etch process side passivation layer is made in the annular LED unit upper table surface；
Step 4：Ohmic contact is formed after metal patternization, annealed alloy；
Step 5：Photoresist mask is lithographically formed, the annular following table of etching exposes sacrifice layer, completes the system of inorganic LED unit
It is standby；
Step 6：Photoresist mask is lithographically formed, the sacrifice layer around following table is exposed, corrodes sacrifice layer and into following table
Undercutting certain length；
Step 7：Spin coating flexible polymeric materials, and carry out the heat treatment completion inorganic LED unit covering；
Step 8：Photo etched mask, etches the flexible polymer covered in the upper table surface inner ring and above part metals electrode
Material, exposes part metals electrode to prepare metal interconnection contact；
Step 9：Metal sputtering simultaneously carries out graphical treatment to prepare the interconnection metallization lines between LED unit array；
Step 10：Spin coating flexible polymeric materials, for covering the interconnection metallization lines, and are heat-treated, and form described mutual
Even coated above and below the flexible polymeric materials of metal wire；
Step 11：Flexible polymeric materials in chemical wet etching upper table surface inner ring, expose the sacrifice in the upper table surface inner ring
Layer；
Step 12：Corrode remaining sacrifice layer；
Step 13：The inorganic LED unit array of transfer is peeled off, the preparation of inorganic flexible LED unit array is completed.
2. the preparation method of the flexible led array as claimed in claim 1 based on inorganic semiconductor material, wherein described nothing
Machine semi-conducting material includes GaAs, AlGaAs, AlGaInP, GaP, InP or GaSb.
3. the preparation method of the flexible led array as claimed in claim 1 based on inorganic semiconductor material, wherein, it is described outer
It is P contact layers, P current extendings, P limiting layers, active area, N limiting layers, N contact layers, sacrifice layer from top to bottom to prolong piece.
4. the preparation method of the flexible led array based on inorganic semiconductor material as claimed in claim 1, wherein, it is described on
The annular that table top ring-shaped figure can constitute for circular, square, pentagon, hexagon or square outer shroud and circular inner.
5. the preparation method of the flexible led array based on inorganic semiconductor material as claimed in claim 1, wherein, it is described under
The outer shroud of table top ring-shaped figure is more than upper table surface outer shroud, and inner ring is less than upper table surface inner ring.
6. the preparation method of the flexible led array as claimed in claim 1 based on inorganic semiconductor material, wherein described appear on the stage
Face, following table, the lithographic method of flexible polymer are carved using Ar ion etchings, reactive ion etching, plasma etching or wet method
Erosion.
7. the preparation method of the flexible led array as claimed in claim 1 based on inorganic semiconductor material, wherein making institute
Sacrificial layer surface is etched to when stating following table.
8. the preparation method of the flexible led array based on inorganic semiconductor material as claimed in claim 1, wherein it is described to
The sacrifice layer of undercutting certain length refers to 20 microns to 80 microns of undercutting in following table.
9. the preparation method of the flexible led array as claimed in claim 1 based on inorganic semiconductor material, wherein described sacrifice
The corrosion of layer is by selecting different corrosive liquids to match, corrosion temperature and time are come control corrosion rate speed and undercutting depth.
10. the preparation method of the flexible led array as claimed in claim 1 based on inorganic semiconductor material, wherein described
Flexible polymeric materials have the characteristic of resistant to acetone and anti-interconnection metal erosion liquid.
11. the preparation method of the flexible led array as claimed in claim 1 based on inorganic semiconductor material, wherein described mutual
Even metal wire uses the metal material or multiple layer metal material with the flexible polymeric materials with adhesion.
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| CN105609589B (en) * | 2016-01-29 | 2017-11-03 | 中国科学院半导体研究所 | Suitable for the preparation method of the inorganic semiconductor film functional unit of transfer |
| CN107634130A (en) * | 2017-09-01 | 2018-01-26 | 哈尔滨工业大学 | A kind of flexible electronic device for stablizing temperature control using μ LED |
| CN108815714B (en) * | 2018-04-16 | 2020-04-21 | 中国科学院半导体研究所 | Extensible and flexible photoelectric acupuncture device and preparation method thereof |
| CN112002999B (en) * | 2020-08-03 | 2023-05-23 | 首都师范大学 | Simple manufacturing method of THz antenna |
| CN115320271B (en) * | 2022-08-04 | 2023-06-16 | 中国科学院上海微系统与信息技术研究所 | Transfer printing method of semiconductor film |
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