CN100461981C - Projected electrode based on polymer substrate, its making method and use - Google Patents

Projected electrode based on polymer substrate, its making method and use Download PDF

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CN100461981C
CN100461981C CNB2006100262921A CN200610026292A CN100461981C CN 100461981 C CN100461981 C CN 100461981C CN B2006100262921 A CNB2006100262921 A CN B2006100262921A CN 200610026292 A CN200610026292 A CN 200610026292A CN 100461981 C CN100461981 C CN 100461981C
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silicon chip
electrode
polymer
layer
polymeric
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CN1852634A (en
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杨梦苏
周洪波
李刚
金庆辉
赵建龙
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Shanghai Institute of Microsystem and Information Technology of CAS
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Abstract

Characters of the invention are that polymer of possessing biocompatibility and flexibility are adopted for base material and fabricated structure of bulge electrode so as to guarantee that stimulation points and nerve are contacted fully in order to improve effect of recording stimulation of neuroelectricity and nervous signals. Preparing procedure includes steps: using anisotropic wet-process erosion to fabricate mould; forming silicon dioxide as sacrificial layer on surface of mouldof silicon oxide chip; through peeling off, glue injecting, and releasing sacrificial layer to obtain raised microelectrode of polymer. The disclosed method for preparing raised electrodes on polymer substrate is compatible to traditional technique of Micro-E1ectro-Mechanical System (MEMS). Features are: volume- producing standardized products. The invention is applicable to nerve rehabilitation, neurobiology etc. areas.

Description

A kind of projected electrode, manufacture method and application based on polymeric substrates
Technical field
The present invention relates to a kind of projected electrode preparation method and utilization, particularly a kind of flexible projection electrode, preparation method and application thereof based on the micro-electromechanical processing technology technology based on polymeric substrates.
Background technology
Neural engineering system is that order is previous very active and develop research field rapidly, and such as brain-computer interface, problems such as nerve prosthesis receive increasing concern.In neural engineering system, the part of basic key is nerve-electrical interface, it is electrode, its function mainly shows as two kinds of forms: a kind of is nervous activity to be converted to the signal of telecommunication go on record and analyze and research, a kind of be utilize signal of telecommunication excitation or suppress nervous activity with realize functional electrostimulation (functional electrical stimulation, FES).Directly the affect the nerves quality of electrostimulation and nerve signal record of the performance of electrode.Such as, utilize FES to recover the UM damage (as brain, spinal cord injury etc.) limb motion that causes and sensory deprivation have become a kind of clinically common therapy rehabilitation method, but the traditional neural external electrode that is applied to the FES system is because poor selectivity and impercipience feedback information, though through long-term application and practice, only obtained limited effect [J.D.Sweeney, N.R.Crawford, T.A.Brandon. " Neuromuscularstimulation selectivity of multiple-contact nerve cuff electrode arrays; " Med.Biol.Eng.Comput., 1995,33:418-425.].In addition, existing in the world a plurality of research groups utilize the microelectrode of MEMS processes to carry out the research [E.Margalit of vision prosthesis, M.Maia, J.D.Weiland, et al. " Retinal Prosthesis for the Blind; " Survey of Ophthalmology, 2002,47:335-356].But the general stimulation voltage that requires of these electrodes is higher, and selectivity is not enough, therefore how to reach the efficient selective electrostimulation and remains a present focus and difficult point.
In order to increase the selectivity of electrode, generally realize at present by utilizing the MEMS processes to make highdensity microelectrode array.Used base material generally has rigidity and flexible two big classes, and the material of rigidity mainly contains silicon; Flexible material mainly is polymeric materials such as polyimides, Parylene.In order to guarantee to write down or stimulating electrode contacts with the good of nerve tract, and the damage that reduces electrode pair biological tissue, increasing microelectrode adopts polymer to make as base material.But the microelectrode based on polymeric material generally adopts traditional plane processing technology at present: 1. get rid of on silicon chip and be coated with the curing one layer of polymeric; On this strata compound by sputter, peel off (Lift-off) and make metal layer image; 3. on the structure of gained, get rid of and be coated with polymer, and etch the electrode stimulating point.The electrode of producing by this technology is sandwich form (metal level is clipped between the polymer), the electrode stimulating point that is used for work is recessed [T.S.Martin Schuettler, " 18polar Hybrid Cuff Electrodes forStimulation of Peripheral Nerves; " presented at The 5th Annual InternationalConference of the International Functional Electrical Stimulation Society, 2000.], limited the effect of nerve stimulation or signal record.Projected electrode based on polymeric substrates provided by the present invention has overcome the problem that the electrode stimulating point can't well contact with nerve, thereby has strengthened the effect of nerve stimulation or signal record.
Summary of the invention
The purpose of this invention is to provide a kind of projected electrode, preparation method and utilization thereof based on polymeric substrates, by adopting flexible polymer as base material and processing protruding electrode structure, guarantee the stimulation point of electrode and neural fully contacting, improve the quality of nerve electric stimulation and signal record.
The objective of the invention is to reach by following measure: at first anisotropic wet etch goes out the bowl configurations of non-perpendicular sidewall as mould on silicon chip, oxidation mould silicon chip makes the silicon chip die surface form layer of silicon dioxide as sacrifice layer then, by getting rid of resist coating, photoetching, sputter, Lift-off technology making metal level, reinject polymer, curing, do mask with metal, reactive ion etching goes out the window of lead solder-joint correspondence, remove silicon dioxide sacrificial layer at last, release polymers obtains final electrode structure.
Concrete processing step is:
1) cleaning silicon chip, two-sided oxidized silicon chip, the formation oxidated layer thickness is 800-1200
Figure C200610026292D0006161257QIETU
2) baking silicon chip, on the one side oxide layer of silicon chip, get rid of resist coating, the effect of photoresist is to do stripping technology, thus can as the photoresist of stripping technology can, to consider that certainly the photoresist minimum resolution is less than making the desired resolution of lines, for example Shipley 1813, AZ4620,6809 etc., the photoresist trade mark of being used always is 6809, getting rid of the speed of being coated with is 2500-3500 rev/min, and the time is 20-30 minute; The roasting temperature of flood is 120 ℃, and baking is 20 minutes before 80 ℃;
3) get rid of on another face oxide layer of silicon chip and be coated with same photoresist, speed is 2500-3500 rev/min, and the time is 20-30 second; Baking is 20 minutes before 80 ℃, exposure, development; Baking obtained the graph window of electrode protrusion stimulation point correspondence in 30 minutes after 120 ℃;
4) in the shaking table, the cushioning liquid of hydrofluoric acid (BOE) soaks 5-15 minute transition diagram of silicon chip to silicon dioxide layer; Described BOE solution is HF:NH 4F:DI=3 (ml): 6 (g): 9 (ml); DI is a deionized water, is a proportionate relationship here, can enlarge its multiple, for example HF:NH simultaneously in the actual process for preparation 4F:DI=30 (ml): 60 (g): 90 (ml);
5) soak silicon chip with acetone, the photoresist on the ultrasonic removal silicon chip is used the absolute ethyl alcohol cleaning silicon chip again, and dries up with nitrogen;
6) use 40-60wt%KOH solution, 40-60 ℃ of wet etching silicon chip 15-30 minute, forming the degree of depth is the pit of 15-20 micron; Bowl configurations is as mould;
7) washed with de-ionized water silicon chip, the cushioning liquid (BOE) of use hydrofluoric acid is removed the silicon dioxide layer on the silicon chip;
8) PECVD deposits the silicon dioxide layer that a layer thickness is 0.8-1.2 μ m, makes sacrifice layer;
9) coated polymeric, vacuumize polymer is entered in the pit, whirl coating and cure polymer, selected polymeric material as electrode basement is to have biocompatibility and flexible characteristic, available polymer has PDMS (dimethyl silicone polymer), PMMA (polymethyl methacrylate), PC (Merlon), polyimides and Parylene etc., curing temperature is 150-300 ℃, the most frequently used polymeric material is a polyimides, whirl coating speed is 2500-3000 rev/min, and the time is 30 seconds;
10) thereafter, get rid of resist coating on polymer, whirl coating speed is 2500-3500 rev/min, and the time is 20-30 second, and baking is 20 minutes before 80 ℃, exposure, the back sputter 3000 of developing
Figure C200610026292D0007161314QIETU
The thin metal layer of left and right thickness utilizes at last and peels off (Lift-off) technology and make metal mask, and in the microfabrication process, common metal aluminium is done mask, carries out reactive ion etching, other as metallic copper also can, but be of little use.And with the polymer in the oxygen plasma etch pit windows;
11) be 15-25%HCL solution removal metal mask with concentration, and use the deionized water cleaning silicon chip, dry silicon chip then; Get rid of resist coating, whirl coating speed is described with step 3; Baking is 20 minutes before 80 ℃, and exposure, development, splash-proofing sputtering metal, metal thickness are 4000-6000
Figure C200610026292D0007161325QIETU
, and peel off;
12) coated polymeric and vacuumizing enters in the pit polymer, whirl coating and cure polymer;
13) get rid of resist coating, whirl coating speed is with step 11, and preceding baking and is produced the solder joint pairing window that goes between after exposure, development, splash-proofing sputtering metal aluminium utilize lift-off (peeling off) technology to make metal mask, and fall polymer with oxygen plasma etch;
14) finally use buffer solution (BOE) the corrode silicon dioxide sacrifice layer of hydrofluoric acid, discharge electrode structure.
This shows that a kind of projected electrode based on polymeric substrates provided by the invention has the polymeric material of biocompatibility and flexible characteristic, the stimulation point of electrode is higher than based on material plane; The three-decker that described electrode is made up of polymeric layer-metal conducting layer-polymeric layer.
The present invention compares with polymer electrode commonly used at present, can contact more fully with the target nerve tissue, has improved the effect of nerve stimulation and nerve signal record.And what the present invention used is traditional micro electronmechanical (MEMS) processing technology (mainly comprise: photoetching, wet etching, sputter, Lift-off and sacrifice layer discharge), thereby electrode preparation method is simple, can make the electrode of small precision.The height of realizing projected electrode is about 40 microns, and electrode stimulating point bottom surface is square (100 microns of the length of sides), is spaced apart 150 microns between the electrode stimulating point.Can be according to concrete needs, every size of appropriate change electrode.
Projected electrode provided by the invention is used for the electroneurographic signal record and the nerve stimulation of Neurobiology research or neural rehabilitation, stimulates according to (seeing embodiment 2,3 for details) as peripheral nerve stimulation or as optic nerve
Description of drawings
Fig. 1 is the structural representation of silicon mould and silicon dioxide sacrificial layer
Fig. 2 is for making the schematic diagram of metal level on polymer of sputter, Lift-off
Fig. 3 is the schematic diagram of injection of polymer
Fig. 4 removes the schematic diagram that sacrifice layer discharges electrode
Fig. 5 for embodiment 2 provided columnar structured
Fig. 6 inserts neural incision schematic diagram for projected electrode provided by the invention
Among the figure: 1. silicon chip 2. silicon dioxide
3. polymeric substrates 4. metal conducting layers
5. the optic nerve cut open of lead solder-joint window 6.
7. the cable of connection bump electricity level
Embodiment
Embodiment 1
Adopting the polyimide polymer and the trade mark below in conjunction with accompanying drawing is that 6809 light cut open the preparation method that glue further specifies the projected electrode that the present invention is based on polymeric substrates.
1, cleaning silicon chip, two-sided oxidized silicon chip, oxidated layer thickness are 1000
Figure C200610026292D0009161340QIETU
2,120 ℃ of baking silicon chips 20 minutes get rid of on the one side oxide layer of silicon chip and are coated with 6809 photoresists (3000 rev/mins, 30 seconds), and baking is 20 minutes before 80 ℃;
3, get rid of at the another side of silicon chip and to be coated with 6809 photoresists (3000 rev/mins, 30 seconds), baking is 20 minutes before 80 ℃, and exposure is developed, and baking obtained the pairing graph window of electrode protrusion stimulation point in 30 minutes after 120 ℃;
4, in the shaking table, the cushioning liquid of hydrofluoric acid (BOE, HF:NH 4F:DI=3:6:9) soaked silicon chip 10 minutes, transition diagram is to silicon dioxide layer;
5, soak silicon chip with acetone, the photoresist on the ultrasonic removal silicon chip; Use the absolute ethyl alcohol cleaning silicon chip again, and dry up with nitrogen;
6, the KOH solution of 50wt%., 50 ℃ of wet etching silicon chips 20 minutes form the about 16 microns pit of the degree of depth;
7, washed with de-ionized water silicon chip, the cushioning liquid of hydrofluoric acid (BOE, HF:NH 4F:DI=3:6:9) silicon dioxide layer on the removal silicon chip;
8, it is 0.1 micron silicon dioxide that PECVD deposits a layer thickness.Obtain the schematic diagram shown in figure (1);
9, the coating polyimide polymer vacuumizes and makes polyimides enter in the pit, whirl coating (3000 rev/mins, 30 seconds), 220 ℃ of cure polymer polyimides.
10, on the polymer poly acid imide, get rid of resist coating 6809 (3000 rev/mins, 30 seconds), baking is 20 minutes before 80 ℃, and splash-proofing sputtering metal aluminium 3000 is developed in exposure
Figure C200610026292D0009161358QIETU
Utilize Lift-off technology to make the aluminium mask, and fall polymer poly acid imide in the pit windows with oxygen plasma etch;
11,20%HCl solution removal Al mask is used the deionized water cleaning silicon chip, 80 ℃ of oven dry silicon chips.Get rid of resist coating 6809 (3000 rev/mins, 30 seconds), baking is 20 minutes before 80 ℃, and exposure is developed, splash-proofing sputtering metal (thickness:
Figure C200610026292D0010161413QIETU
), Lift-off technology obtains the structural representation shown in figure (2);
12, the coated polymeric polyimides vacuumizes (making polyimides enter in the pit), 220 ℃ of cure polymer polyimides of whirl coating (3000 rev/mins, 30 seconds).Obtain the structural representation shown in figure (3);
13, get rid of resist coating 6809 (3000 rev/mins, 30 seconds), baking is 20 minutes before 80 ℃, and splash-proofing sputtering metal aluminium 3000 is developed in exposure Utilize Lift-off technology to make the aluminium mask, and fall polyimide polymer, make the solder joint pairing window that goes between with oxygen plasma etch;
14, (BOE, HF:NH4F:DI=3:6:9) the corrode silicon dioxide sacrifice layer discharges electrode structure to the cushioning liquid of hydrofluoric acid.Structural representation as shown in Figure 4;
The projected electrode based on polymeric substrates that finally obtains will have polymeric layer-metal conducting layer-polymer layer structure, it is characterized in that lobed electrostimulation point.In this microelectrode implantable neural tissue, the stimulation point of electrode protrusion is the contact target nerve fully, reaches the effect of more effectively nerve stimulation and signal record with respect to traditional electrode.And the silicon chip mould can be reused.
Embodiment 2
Polymeric substrates projected electrode with embodiment 1 preparation is applied to peripheral nerve stimulation, and its mode is: the polymeric substrates and the silicon rubber film after the stretching that will be manufactured with projected electrode are bonding, and silicon rubber shrinks the back and forms columnar structured as shown in Figure 5.This columnar structured nerve that wraps up, protruding electrode structure guarantee that electrode stimulating point well contacts with neural, carries out more effective stimulating electrical signal.
Embodiment 3
Polymeric substrates projected electrode with embodiment 1 preparation is applied to vision prosthesis optic nerve stimulation device, its mode is: cut optic nerve 6 open by operation, the polymeric substrates 3 that is manufactured with projected electrode is inserted neural incision (as shown in Figure 6), and sew up the incision, the extraneous signal of telecommunication is introduced by the cable 7 that is connected with projected electrode.Protruding electrode structure guarantees that electrode stimulating point contacts with the good of nerve tract in the optic nerve, and low voltage is practicable effective stimulating electrical signal, has reduced electric field action and the electric heating effect damage to surrounding tissue.

Claims (9)

1. projected electrode based on polymeric substrates, described electrode stimulating point is higher than the base material plane, it is characterized in that described electrode is made up of polymeric layer-metal conducting layer-polymeric layer, described electrode base materials is the polymeric material with bio-compatible and flexible characteristic.
2. by the described projected electrode of claim 1, it is characterized in that described polymeric material is dimethyl silicone polymer, polymethyl methacrylate, Merlon, Parylene or polyimides based on polymeric substrates.
3. by the described projected electrode based on polymeric substrates of claim 1, it is characterized in that described projected electrode height is 40 microns, electrode stimulating point bottom surface is square.
4. prepare the method for the projected electrode based on polymeric substrates as claimed in claim 1, it is characterized in that described method step
1) silicon chip that utilizes anisotropic wet etch to go out non-perpendicular sidewall bowl configurations is made mould;
2) oxidation of silicon chip die surface forms silicon dioxide and does sacrifice layer;
3) by getting rid of resist coating, photoetching, sputter, stripping technology making metal level;
4) injection of polymer, curing, make mask with metal, reactive ion etching goes out the window of lead solder-joint correspondence;
5) by the corrode silicon dioxide sacrifice layer, release polymers obtains final electrode structure.
5. the preparation method of the projected electrode based on polymeric substrates as claimed in claim 4 is characterized in that concrete processing step is:
1) cleaning silicon chip, two-sided oxidized silicon chip is 800-1200 at the bottom of the formation oxidation bed thickness
Figure C200610026292C0002134900QIETU
2) the baking silicon chip gets rid of resist coating on the one side oxide layer of silicon chip, and getting rid of the speed of being coated with is 2500-3500 rev/min, and the time is 20-30 minute; Baking temperature is 120 ℃, and baking is 20 minutes before 80 ℃;
3) get rid of on another face oxide layer of silicon chip and be coated with same photoresist, speed is 2500-3500 rev/min, and the time is 20-30 second; Baking is 20 minutes before 80 ℃, exposure, development; Baking obtained the graph window that electrode protrusion swashs the some correspondence in 30 minutes after 120 ℃;
4) in the shaking table, the cushioning liquid of hydrofluoric acid soaks 5-15 minute transition diagram of silicon chip to silicon dioxide layer; Described cushioning liquid is HF:NH 4F: deionized water=3 (ml): 6 (g): 9 (ml);
5) soak silicon chip with acetone, the photoresist on the ultrasonic removal silicon chip is used the absolute ethyl alcohol cleaning silicon chip again, and dries up with nitrogen;
6) use 40-60wt%KOH solution, 40-60 ℃ of wet etching silicon chip 15-30 minute, forming the degree of depth is the pit of 15-20 micron; Bowl configurations is as mould;
7) washed with de-ionized water silicon chip, the cushioning liquid of use hydrofluoric acid is removed the silicon dioxide layer on the silicon chip;
8) PECVD deposits the silicon dioxide layer that a layer thickness is 0.8-1.2 μ m, makes sacrifice layer;
9) coated polymeric vacuumizes polymer is entered in the pit, whirl coating and cure polymer, the selected polymeric material as electrode basement is the material with biocompatibility and flexible characteristic, curing temperature is 150-300 ℃, and whirl coating speed is 3000 rev/mins, and the time is 30 seconds;
10) thereafter, get rid of resist coating on polymer, whirl coating speed is 2500-3000 rev/min, and the time is 20-30 second, and baking is 20 minutes before 80 ℃, exposure, development sputter 3000
Figure C200610026292C0003135342QIETU
The thin metal layer of left and right thickness utilizes stripping technology to make metal mask also with the polymer in the oxygen plasma etch pit windows at last;
11) be 15-25%HCL solution removal metal mask with concentration, and use the deionized water cleaning silicon chip, dry silicon chip then; Get rid of resist coating, the same step of whirl coating speed (3) is described; Baking is 20 minutes before 80 ℃, and exposure, development, splash-proofing sputtering metal, metal thickness are 4000-6000
Figure C200610026292C0003135354QIETU
, and peel off;
12) coated polymeric and vacuumizing enters in the pit polymer, whirl coating and cure polymer;
13) get rid of resist coating, whirl coating speed is with step 3, after the preceding baking, through exposure, development, splash-proofing sputtering metal aluminium, utilizes stripping technology to make metal mask, and falls polymer with oxygen plasma etch, and produce the solder joint pairing window that goes between;
14) finally discharge electrode structure, the corrode silicon dioxide sacrifice layer with the buffer solution of hydrofluoric acid.
6. the preparation method based on the polymeric substrates projected electrode as claimed in claim 5 is characterized in that described photoresist minimum resolution is less than the resolution of making lines.
7. the preparation method based on the polymeric substrates projected electrode as claimed in claim 6 is characterized in that described photoresist is 6809, Shipley 1813 or Shipley AZ4620.
8. the application based on the polymeric substrates projected electrode as claimed in claim 1 is characterized in that being used for the electroneurographic signal record and the nerve stimulation of Neurobiology or neural rehabilitation.
9. the application based on the polymeric substrates projected electrode as claimed in claim 8 is characterized in that being applied to peripheral nerve stimulation or vision prosthesis nerve stimulator.
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