CN110116987A - A kind of semiconductor nanowires sensor - Google Patents
A kind of semiconductor nanowires sensor Download PDFInfo
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- CN110116987A CN110116987A CN201910440024.1A CN201910440024A CN110116987A CN 110116987 A CN110116987 A CN 110116987A CN 201910440024 A CN201910440024 A CN 201910440024A CN 110116987 A CN110116987 A CN 110116987A
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- nano wire
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00015—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems
- B81C1/00134—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems comprising flexible or deformable structures
- B81C1/0015—Cantilevers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81B—MICROSTRUCTURAL DEVICES OR SYSTEMS, e.g. MICROMECHANICAL DEVICES
- B81B2201/00—Specific applications of microelectromechanical systems
- B81B2201/02—Sensors
Abstract
The invention belongs to semiconducting nanowire devices technical fields, provide a kind of semiconductor nanowires sensor, and preparation has the groove structure of specific depth-to-width ratio in the insulating substrate with conductive layer, completely cut off the conductive layer of groove two sides mutually；Then surface reforming layer is set in bottom portion of groove, covers bottom portion of groove；Then in conductive layer sidewall growth nano wire, make the conductive layer of nano wire bridge joint groove two sides, while the growth course can also generate deposit in groove.By designing the depth-to-width ratio of groove and introducing surface reforming layer, it is possible to reduce or the deposit of bottom portion of groove is eliminated, to eliminate the by-pass current of bridge joint nano wire.In addition, bridge joint probability, total surface area and the growth controllable degree of nano wire can be improved using the multiple growth of bridge joint nano wire.The present invention solves the deposit problems in existing bridge joint nanowire growth process further groove, improves the electrology characteristic of nanowire sensor.
Description
Technical field
The invention belongs to semiconducting nanowire devices technical field, in particular to a kind of nano wire based on bridge joint growth
Device.
Background technique
Nanotechnology is considered as one of three big science technologies of 21 century.Wherein, nano wire is since its is unique one-dimensional
Quantum structure, it is considered to be one of basic structure of nanometer electronic device.
Although nano wire is with important application prospects, prepares nano-wire devices and need to extremely very thin nanometer
Line is manipulated, assembled and is processed.Currently, generally including following complex steps [Nanotechnology, 24 (2013)
245306]: 1. grow nano wire on substrate；2. nano wire is stripped down from substrate, it is transferred to another substrate surface,
And realize ordered arrangement；3. the both ends in nano wire plate metal electrode.
Above-mentioned preparation method has the disadvantage in that 1. processing steps complexity；2. the removing of nano wire and arrangement and etc.,
It needs that (or damage) nanowire surface can be polluted using various chemical reagent；3. belonging to physics between metal electrode and nano wire
Contact, and nano wire and interelectrode contact area very little, therefore attachment is insecure, contact characteristics are poor.
For this purpose, there has been proposed the bridge joint growth techniques of nano wire, and such as: in the growth course of nano wire, and meanwhile it is real
The arrangement of existing nano wire and electrode interconnect, to simplify preparation process [ZL 201110144804.5； Nanotechnology,
15(2004)L5-L8].But these methods have the disadvantage in that 1. that need to prepare semiconductor step on substrate (or recessed
Slot), it must be electrically isolated between the step (or groove) and substrate (i.e. using electric insulation layer)；2. the preparation of this three-decker,
It needs using techniques such as bonding chip or ion implantings, forms electricity isolated layer in substrate interior, preparation process is complicated.
In order to be further simplified preparation process, patent of invention [application number 201610213762.9] is proposed with groove
Conductive layer is plated in the insulating substrate of structure, three-decker is reduced to double-layer structure (i.e. conductive layer and insulating substrate), to drop
Low preparation difficulty.
But the bridge joint growth protocols of above two nano wire, there are still following problems: in nanowire growth, groove
Bottom can also deposit substance (referred to as " parasitic deposition "), so that being destroyed the electrical insulation characteristics of groove two sides (is equivalent to production
The by-pass current of nano wire is given birth to)；Secondly, the parameter (such as size and density) of nano wire is difficult to advanced optimize.
In conclusion how to solve the deposit problems of bottom portion of groove, the nanometer line device of high-performance, low cost is prepared
Part is that wound of the invention grinds motivation.
Summary of the invention
That it is an object of the invention to overcome the deficiencies of the prior art and provide a kind of structures is simple, controllability is good and cost
Cheap bridge joint nanowire sensor.
Technical solution of the present invention:
A kind of semiconductor nanowires sensor prepares the groove knot of specific shape in the insulating substrate with conductive layer
Structure makes the conductive layer of groove two sides mutually completely cut off and (be electrically insulated)；2. surface reforming layer is arranged in groove structure, cover recessed
Trench bottom；3. growing semiconductor nanowires on the conductive layer side wall of groove side, the conduction of the nano wire and the groove other side
Layer to connect (i.e. nano wire bridge joint groove two sides conductive layer --- bridge joint nano wire).
Wherein, the conductive layer in two protrusion of groove structure, is the growth substrate of nano wire, also respectively as partly leading
Two electrodes of body nanowire sensor.
Wherein, the groove structure, can be by chemical etching, laser ablation or the method for machine cut in substrate table
Face is prepared.
Wherein, the groove structure has shape need (for the groove that depth is H, width is W, depth-to-width ratio H/W
It is greater than 0.2), it is possible to reduce or (parasitic deposition will lead to by-pass current to the parasitic deposition of elimination bottom portion of groove, so that bridge
Receive rice noodles short circuit).
Wherein, the surface reforming layer, since its surface has inertia, the parasitism that can be further decreased in groove is heavy
Product.The material preferred oxides or nitride material of surface reforming layer, such as silica, silicon nitride.
Wherein, groove structure side wall (i.e. conductive layer side wall) is provided with catalyst granules, receives rice noodles for boot bridge
Growth；The catalyst preferably is selected from the alloy of one or more of gold, nickel, iron, golden nickel alloy, gallium, indium.
Wherein, the material of conductive layer includes: oxide, nitride (such as TiN, GaN, AlGaN and InGaN), gold
The alloy of one or more of category, carbon, alloy, organic matter.
Wherein, the material of insulating substrate preferably is selected from glass, quartz, sapphire or organic matter.
Wherein, bridge joint nano wire can be the whole nano wire for disposably growing and obtaining, and bridge joint nano wire can have axis
To or radial heterojunction structure.Bridge joint nano wire is conductive, and material includes: oxide (such as tin indium oxide), nitride
(such as titanium nitride, gallium nitride, indium gallium nitride, aluminum gallium nitride), Gallium indium arsenide, silicon, germanium, germanium silicon, silicon carbide, InGaP, alloy
Or organic matter etc..
Wherein, bridge joint nano wire can be regrow made of composite construction (such as bifurcation structure or fish bone structure),
Specific preparation process includes (Fig. 7 and Fig. 8): 1., in existing nanowire surface, plate catalyst granules；2. then in nano wire
Surface regrows nano wire, to form cross interconnected mesh nano cable architecture (Fig. 8).This netted or herring-bone form knot
Structure has the advantage that 1. can greatly improve the electricity interconnection probability between nano wire；2. improving the overall surface of nano wire
Product (i.e. the sensitivity of sensor)；3. nanowire growth is more controllable, (nano wire regrowed, can be along existing nanometer
Line is in orderly distribution --- arranged in fish-bone, diameter can it is thinner, specific surface area is bigger --- device sensitivity is higher)；4.
This cross interconnected structure, can preventing nanowire cluster from getting together, (such as the capillary force of water can make nanowire cluster
It is poly-).
Wherein, the conductive layer is grown in insulated substrate surface, and the growing method of conductive layer includes: evaporation, splashes
It penetrates, coat, being electroplated, chemical vapour deposition technique, molecular beam epitaxy, electrochemical growth method, method of electrostatic spinning or hydrothermal synthesis
Method etc..
Technical effect of the invention: (1) for the groove structure with biggish depth-to-width ratio (H/W > 0.2), when carrying
When the air-flow of growth substance passes through groove surfaces, since recess sidewall is to the occlusion effect of air-flow, gas is difficult to diffuse to groove
Bottom, so that the parasitic deposition of bottom portion of groove be greatly decreased；This way for changing local air flow distribution, so that nano wire
Growth is more flexible controllable；(2) " surface reforming layer " is introduced in bottom portion of groove, to be passivated the surface-active of bottom portion of groove, thus
Further decrease the parasitic deposition of bottom portion of groove；(3) on the surface of bridge joint nano wire, regrowing nano wire, (i.e. two is secondary
It is long), " cross interconnected " and " fish-bone " structure of nano wire can be formed, electrical connection, specific surface area between improvement nano wire,
And the growth controllable degree of nano wire.
Detailed description of the invention
Fig. 1 is the insulating substrate schematic diagram with conductive layer.
Fig. 2 is insulating substrate (depth of groove the is H, width W) schematic diagram for being prepared for groove structure.
Fig. 3 is the groove structure substrate schematic diagram schematic diagram with surface reforming layer.
Fig. 4 is groove structure substrate (groove shallower, without the surface reforming layer) schematic diagram that grown nano wire.
Fig. 5 is groove structure substrate (groove relatively deep, without the surface reforming layer) schematic diagram that grown nano wire.
Fig. 6 is groove structure substrate (groove is relatively deep, the has surface reforming layer) schematic diagram that grown nano wire.
Fig. 7 is groove structure substrate (top view) schematic diagram that grown bridge joint nano wire.
Fig. 8 is groove structure substrate (top view) schematic diagram after regrowing nano wire.
Fig. 9 (a) be design can longitudinal stretching bridge joint nano wire grid schematic diagram；
Fig. 9 (b) is to stretch and non-stretched bridge joint nano wire grid comparison diagram.
Figure 10 is nano wire diauxic growth process schematic.
Figure 11 is nano wire bending growth result figure.
Figure 12 is the nano wire chemical quantity transducer schematic diagram based on bridging structure.
In figure: 1 insulating substrate；2 conductive layers；3 source electrodes；4 drain electrodes；5 catalyst granules；6 surface reforming layers；7 bridge joints
Nano wire；8 parasitic deposition objects；9 nano wires regrowed.
Specific embodiment
The present invention is described in detail below in conjunction with embodiment and attached drawing, it should be pointed out that described reality
It applies example and is intended merely to facilitate the understanding of the present invention, and do not play any restriction effect to it.
Referring to Fig. 1 to Fig. 8, a kind of bridge joint nanowire sensor of the present embodiment, the insulation including being provided with groove structure
Substrate 1, conductive layer 2 and bridge joint nano wire 7.In etched recesses structure in insulating substrate 1, conductive layer is divided in groove knot
The two sides of structure, source electrode 3 of the conductive layer as nanowire sensor in one protrusion of groove, the conduction in another protrusion of groove
Drain electrode 4 of the layer as nanowire sensor, source electrode 3 are connect with drain electrode 4 by bridging nano wire 7.Bridge nano wire 7
It is disposably to grow whole obtained nano wire.The present embodiment jackshaft receives the combination of rice noodles 7 and conductive layer, is received in bridge joint
The chemical bonds formed in the growth of rice noodles 7, have more firm binding force and better electric conductivity.
Referring to Fig. 1 to Fig. 8, the present embodiment also proposed a kind of preparation method for bridging nano-wire devices, can be by following
Mode is realized:
Firstly, depositing conductive layer 2 on 1 surface of insulating substrate (shown in Fig. 1).The insulating substrate 1 preferably be selected from glass, quartz,
And the materials such as sapphire.The preferred autoxidisable substance of conductive layer 2, nitride (such as TiN, GaN, AlGaN and InGaN), gold
The combination of one or both of category, carbon.
Secondly, preparing groove knot on 1 surface of insulating substrate using chemical etching, laser ablation or the method for machine cut
Structure (shown in Fig. 2).The groove structure penetrates conductive layer 2 and gos deep into inside insulating substrate 1, so that conductive layer 2 is divided into phase
The two parts-- mutually to insulate are respectively as source electrode 3 and drain electrode 4.The depth-to-width ratio (H/W) of its further groove is greater than 0.2.
Then, in bottom portion of groove growing surface modified layer 6, (modified layer except bottom portion of groove can pass through photoetching and corruption
The method of erosion removes)；And the attached catalyst particle 5 on conductive layer side wall, for guiding nano wire 7 to grow (shown in Fig. 3).
The catalyst granules 5 preferably is selected from gold, nickel, iron, golden nickel alloy, gallium, indium and gallium nitride material.Catalyst granules 5 can be attached
In any one or both sides of conductive layer side wall.
Then, the growth bridge joint nano wire 7 on conductive layer side wall, with the growth of bridge joint nano wire 7, bridge joint nano wire 7
Top and the conductive layer 2 of the other side meet and combine-- i.e. bridge joint nano wire 7 (shown in fig. 4 to fig. 6), it is this
Binding force is the chemical bond force between solid.While growth bridge joint nano wire 7, parasitism also will form in bottom portion of groove and side wall
Deposit 8 (shown in Fig. 4), the material of the parasitic deposition object 8 are close with the bridge joint material of nano wire 7 (because of the parasitic deposition object
8 are formed simultaneously during the growth process with bridge joint nano wire 7), therefore parasitic deposition object 8 and bridge joint nano wire 7 are with close
Conductivity.
If depth of groove is shallower (such as Fig. 4, H/W 0.1), this will lead to, and parasitic deposition object 8 is more, and parasitism is heavy at this time
Product object 8 can form continuous thin layer (Fig. 4), to cause the by-pass current (arrow in by-pass current such as Fig. 4 of bridge joint nano wire 7
Shown in head), to reduce the performance of nano-wire devices.
If increasing the depth (such as Fig. 5, depth-to-width ratio 2.0) of groove, when the air-flow for carrying growth substance passes through groove
When surface, since recess sidewall is to the occlusion effect of air-flow, the air-flow of bottom portion of groove is diffused to groove depth-to-width ratio (H/W)
Increase and reduce, so that the parasitic deposition object 8 of bottom portion of groove be greatly decreased.As shown in figure 5, subtracting with parasitic deposition object 8
Few, parasitic deposition object 8 is no longer continuous thin layer, to eliminate by-pass current.
On the basis of increasing depth of groove, if increasing layer of surface modified layer 6 (Fig. 6) in bottom portion of groove, due to table
The inactive surfaces of face modified layer 6 can further decrease the parasitic deposition object 8 of bottom portion of groove, even completely eliminate modified layer table
The parasitic deposition object 8 (Fig. 6) in face.
Once parasitic deposition object 8 does not reconstruct continuous conductive channel (such as Fig. 5 and Fig. 6), bridging nano wire 7 at this time is
Unique conductive channel between the source electrode 3 and drain electrode 4 of groove two sides.
Bridge joint nano wire 7 growing method preferably be selected from chemical vapour deposition technique, molecular beam epitaxy, electrochemical growth method,
Method of electrostatic spinning or and the methods of hydrothermal synthesis method.Bridge the preferred tin indium oxide of 7 material of nano wire, titanium nitride, gallium nitride,
The materials such as indium gallium nitride, aluminum gallium nitride, aluminium arsenide gallium indium, silicon, germanium, SiGe, silicon carbide or AlGaInP.
It is following using two embodiments as specific example:
Embodiment 1
Firstly, using chemical vapor deposition process, growing one layer on the surface of sapphire (i.e. alpha-alumina crystals) substrate 1
N-shaped gallium nitride conductive layer 2 (such as Fig. 1).The thickness of the conductive layer 2 is between 1~20 micron.
Secondly, preparing groove structure (such as Fig. 2), the groove structure on 1 surface of insulating substrate using chemical etching technology
Gallium nitride conductive layer 2 is separated, (is electrically insulated between source electrode and drain electrode) as source electrode 3 with drain electrode 4.Its concave
40 microns of 80 microns of the depth of slot, width, depth-to-width ratio 2.
Then, in 1 surface growing silicon oxide layer (coating entire groove structure) of insulating substrate, by the oxidation except groove
Sacrificial silicon layer is removed by the method for photoetching and corrosion, only retains the silicon oxide layer of bottom portion of groove as 6 (Fig. 3 of surface reforming layer
It is shown)；Then adhere to nickel Au catalyst particle 5 on 2 side wall of conductive layer, receive rice noodles 7 to grow (Fig. 3 institute for boot bridge
Show).Between the quantity of the catalyst granules preferably 1 to 1000.
Then, using metal-organic chemical vapor deposition equipment, growing gallium nitride bridges nano wire on 2 side wall of conductive layer
7, as the conductive layer 2 of the growth of bridge joint nano wire 7, the top and the other side that bridge nano wire 7 meets and is integrated to one
Rise-- bridge nano wire 7 (shown in Fig. 6).While bridging the growth of nano wire 7, gallium nitride also will form in groove
Parasitic deposition object 8 (shown in Fig. 6).Due to the depth-to-width ratio of groove larger (H/W=2) and bottom portion of groove has surface reforming layer
6, the parasitic deposition object 8 (only in recess sidewall residual fraction deposit) of bottom portion of groove is eliminated, which cannot
Conductive channel is constituted, to eliminate the by-pass current of bridge joint nano wire 7.
When the gallium nitride nano-wire of bridge joint, when excitation by ambient atmos, liquid, pressure, strain, temperature or light intensity,
The electrology characteristic (such as resistance) of nano wire can change, to realize the function of sensor.
Embodiment 2
Firstly, using magnetron sputtering plating, growing one layer of n-type silicon conductive layer 2 (such as on the surface of quartz insulator substrate 1
Fig. 1).The thickness of the conductive layer 2 is between 0.1~5 micron.
Secondly, using machine cut technique, preparing groove structure in substrate surface, (depth-to-width ratio of such as Fig. 2, groove is
2.0) silicon conducting layer is separated, forms the source electrode 3 and drain electrode 4 of bridge joint nano wire 1.
Then, the attached catalyst particle 5 on conductive layer side wall, and molecular beam epitaxy is utilized, on 2 side wall of conductive layer
Grow GaAs bridge joint nano wire 7 (shown in Fig. 5).While bridging the growth of nano wire 7, arsenic can be also generated in groove
Gallium parasitic deposition object 8 (shown in Fig. 5).Since the depth-to-width ratio of groove is larger, the parasitic deposition object 8 in groove fails to be formed continuous
Conductive channel (shown in Fig. 5), to eliminate by-pass current.
Finally, adhering to nickel Au catalyst particle 5 on the surface (Fig. 7) of bridge joint nano wire 7, carrying out the secondary again of nano wire
Long (Fig. 8).The nano wire 9 regrowed forms the reticular structure of interconnection with nano wire 7.As shown in figure 8, due to length
Not enough, nano wire 7 fails to link together and (fail to bridge) conductive layer 3 of groove two sides and conductive layer 4；It regrows
Nano wire 9, by cross interconnected so that conductive layer 3 and conductive layer 4 link together, thus improve nano wire bridge joint at
Function probability；Furthermore the nano wire 9 regrowed, increases the surface area of nano wire totality.
Referring to Fig. 9 to Figure 12
Physical quantity and chemical quantity transducer of the application examples based on bridge joint nano wire
Proposed adoption two schemes prepare nano wire grid: 1. diauxic growth scheme；2. being bent growth protocols.Wherein, two
Secondary growth scheme (such as Figure 10) is the gold-plated metal catalyst on " trunk nano wire " side wall, then diauxic growth " bifurcated nanometer
Line ", to form intersection network.It is bent growth protocols (such as Figure 11), is then answered using the lattice mismatch of axial hetero-junctions
Power leads to nano wire bending growth, to realize the cross interconnected of nano wire.
(1) for physical quantitys such as detection ess-strains, although single nano-wire has flexibility (can be laterally curved
It is bent), but longitudinal stretching is but easily broken off.As shown in Figure 8 and Figure 9, wherein between " branched nano-wire " and " trunk nano wire "
Have at certain angle (usually 90 degree of right angles), this bridge joint nano wire grid, has good longitudinal deformation ability (longitudinal
It stretches or compresses).When stretching or compressing nano wire, not connected with opposite side wall due to " trunk nano wire ", (one end is freely
), the angle between " branched nano-wire " and " trunk nano wire " changes at this time, and (stress is not to act on " trunk completely
On nano wire "), to avoid breaking " trunk nano wire ".Therefore this structure is suitable for detection ess-strain.
(2) using the bridge joint network (such as Figure 12) of above-mentioned preparation, realize the detection to liquid sample (such as biology point
Son and cell etc.).It bridges in network herein, has a pair of of nano wire bifurcation structure, one of bifurcated is for emitting light wave
(as LED, the light wave emitted is radiate bridge joint nano wire through bifurcated), another bifurcated is for receiving and detecting light wave
(as photodetector, bifurcated receives light wave and imports detector bridge joint nano wire).When having biomolecule between two bifurcateds
By when, then light wave can be blocked, so that the light intensity that nano wire detects changes.Alternatively, when there is Biomolecular adsorption dividing
When pitching nanowire sidewalls, the coupling efficiency between two bifurcateds will affect, to change reception light intensity.The structure can be used
The absorbance and excited fluorescence of biomolecule are counted and tested in chemical quantity transducer, such as biomolecule.
Finally it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than the present invention is protected
The limitation of range is protected, although explaining in detail referring to preferred embodiment to the present invention, those skilled in the art are answered
Work as understanding, it can be with modification or equivalent replacement of the technical solution of the present invention are made, without departing from the reality of technical solution of the present invention
Matter and range.
Claims (10)
1. a kind of semiconductor nanowires sensor, insulating substrate, conductive layer and bridge joint nano wire including being provided with groove structure,
It is characterized by: the conductive layer is arranged in two protrusions of the insulating substrate groove structure, the conduction in a protrusion
Source electrode of the layer as semiconductor nanowires sensor, the conductive layer in another protrusion is as semiconductor nanowires sensor
Drain electrode, the source electrode are connect with drain electrode by bridging nano wire；The depth-to-width ratio of groove is greater than 0.2；In groove structure
Surface reforming layer is set, for reducing the deposit generated in groove.
2. semiconductor nanowires sensor according to claim 1, which is characterized in that the inner sidewall of the conductive layer is set
It is equipped with catalyst granules, the leading end as bridge joint nano wire；The catalyst granules be selected from gold, nickel, iron, gold nickel alloy, gallium,
The alloy of one or more of indium.
3. semiconductor nanowires sensor according to claim 1 or 2, which is characterized in that the bridge joint nano wire is
It disposably grows whole obtained nano wire or repeatedly grows obtained netted or herring-bone form nano wire.
4. semiconductor nanowires sensor according to claim 1 or 2, which is characterized in that the surface reforming layer
Material is oxide or nitride；The material of the conductive layer is oxide, in nitride, metal, carbon, alloy, organic matter
One or more kinds of combinations.
5. semiconductor nanowires sensor according to claim 3, which is characterized in that the material of the surface reforming layer
For oxide or nitride；The material of the conductive layer is oxide, nitride, metal, carbon, alloy, one in organic matter
Kind or two or more combinations.
6. according to claim 1, semiconductor nanowires sensor described in 2 or 5, which is characterized in that the insulating substrate
Material is glass, quartz, sapphire or organic matter.
7. semiconductor nanowires sensor according to claim 3, which is characterized in that the material of the insulating substrate is
Glass, quartz, sapphire or organic matter.
8. semiconductor nanowires sensor according to claim 4, which is characterized in that the material of the insulating substrate is
Glass, quartz, sapphire or organic matter.
9. according to claim 1, semiconductor nanowires sensor described in 2,5,7 or 8, which is characterized in that the insulation lining
Groove structure on bottom is to be prepared by chemical etching, laser ablation or the method for machine cut in insulated substrate surface.
10. semiconductor nanowires sensor according to claim 6, which is characterized in that recessed in the insulating substrate
Slot structure is to be prepared by chemical etching, laser ablation or the method for machine cut in insulated substrate surface.
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| CN112713181B (en) * | 2020-12-28 | 2022-08-05 | 光华临港工程应用技术研发(上海)有限公司 | Preparation method of gas sensor and gas sensor |
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