CN102299252B - Heterojunction piezoelectric type nano generator and manufacturing method thereof - Google Patents
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Abstract
The invention discloses a heterojunction piezoelectric type nano generator and a manufacturing method thereof. The heterojunction piezoelectric type nano generator comprises a semiconductor nano rod array, a semiconductor nano groove array, a conducting substrate, a packaging layer and leading wires, wherein the semiconductor nano rod array is vertically arranged on the conducting substrate which is used as a lower electrode of the generator; the semiconductor nano groove array and the semiconductor nano rod array form a nested structure; the semiconductor nano groove array serves as an upper electrode of the generator; the upper electrode and the lower electrode of the generator are led by different leading wires; and the packaging layer is arranged on the periphery of the semiconductor nano groove array and the semiconductor nano rod array. The invention also discloses a manufacturing method for the heterojunction piezoelectric type nano generator. The heterojunction piezoelectric type nano generator is simple and compact in structure, relatively longer in service life, simple in manufacturing process and low in manufacturing cost.
Description
Technical field
The present invention relates to a kind of nano generator and manufacture method thereof, particularly relate to a kind of heterojunction piezoelectric type nano generator and manufacture method thereof that is realized unidirectional current output by the heterojunction rectifying effect.
Background technology
From early 1980s, since the concept of nano science proposed, nanometer technology had obtained unprecedented develop rapidly, is subjected to the extensive concern of countries in the world.Nowadays, nanometer technology has been widely applied to numerous areas such as material, machinery, electronics, biology, medicine.Wherein, nano-device is because volume is little, transmission performance is good etc. characteristics have caused the research interest of researcher all over the world.Yet, Nano-technology Development so far, most of research concentrates on develops high sensitivity, high performance nano-device, and rarely has report about the research of the power supply provisioning technique of nanoscale.On the other hand, be applied to the nano-sensor of aspects such as biology and national defence, but urgent day by day to the demand of this power-supply system.For example, wireless micro-nano system is for built-in biometric sensor and biological medicine monitoring synchronously, biological living are surveyed and all be significant in real time.Any wireless senser that is built in organism all needs power supply, in general the power supply of these transducers all be directly or secondary source in battery.If these transducers can provide power supply from automatic acquisition energy in the organism and oneself, the practicalization of device will be promoted effectively.Therefore, develop a kind of novel nano technology, the mechanical energy that exists in the operational environment is converted into electric energy, make nano-device continuous operation under the situation of dispense with outer connecting power to have extremely important using value.This technology is when reducing the power supply size, and the also scope that expend energy is collected and the efficient that improves collection of energy have far-reaching influence aspect integrated system microminiaturized.
At present, at the early-stage about the research of nanometer power-supply system in the world, what wherein achievement in research was the most outstanding is the professor Wang Zhonglin leader's of the georgia ,u.s.a Institute of Technology research group.They utilize semiconductor property and the piezoelectric properties of nanometic zinc oxide rod array, made the piezoelectric type nano generator of output DC stream, convert mechanical energy to electric energy in the nanoscale scope, its utilizable mechanical energy comprises the energy that the kinetic energy of mechanical oscillation, kinetic energy, current and muscle are flexible etc.This invention has been established important research basis for design and the manufacturing of the power system of various nano-devices.But, this generator also exists certain defective and deficiency, mainly show: in order in the generator course of work, to form the direct current of unidirectional output, top electrode must be one deck work function greater than precious metal materials such as the Au of n type zinc oxide semiconductor material electron affinity energy or Pt, be beneficial to form the Schottky contacts with rectifying effect, thereby make that the manufacturing cost of generator is higher; In addition, noble metals such as Au or Pt all belong to softer metals, wear and tear easily in the generator course of work, influence performance and the useful life of device.
Summary of the invention
In order to solve the problems referred to above that existing piezoelectric type nano generator exists, it is cheap relatively to the invention provides a kind of manufacturing cost, and useful life is longer, and technology realizes simple relatively heterojunction piezoelectric type nano generator and manufacture method thereof.
The technical scheme of the present invention's heterojunction piezoelectric type nano generator is as follows: it comprises semiconductor nanorods array, semiconductor nano groove array, conductive substrates, encapsulated layer and lead-in wire, described semiconductor nanorods array is vertical on the conductive substrates as the generator bottom electrode, semiconductor nano groove array and semiconductor nanorods array form nested structure, the semiconductor nano groove array is the top electrode of generator, and the generator upper/lower electrode is picked out by different lead-in wires respectively; Semiconductor nano groove array and semiconductor nanorods array periphery are provided with encapsulated layer.
Described semiconductor nanorods array is the n type semiconductor oxide Zinc material with piezoelectric property.
Described semiconductor nano groove array is the p-type low-resistance silicon materials with satisfactory electrical conductivity.
Material is that the semiconductor nanorods array of zinc oxide is synthetic in conductive substrates by hydro thermal method.
Described semiconductor nano groove array is the groove array that goes out in the surface corrosion of p-type low resistance silicon chip by little electrochemical catalysis etch.
Mutually nested semiconductor nanorods array and semiconductor nano groove array contacting between the two is the contact of p-n heterojunction, has the rectifying effect of the unidirectional conducting of electric current.
Described conductive substrates is made by indium tin oxide-coated glass.
Described encapsulated layer is made by epoxy resin.
The present invention's heterojunction piezoelectric type nano generator manufacture method may further comprise the steps:
(1) hydro thermal method synthesizing zinc oxide semiconductor nanorods array:
Under the magnetic agitation situation, 0.02-0.04 M(mol/L with 20-30 ml) NaOH ethanolic solution, join the 0.005-0.015 M(mol/L of 40-60 ml) the zinc acetate ethanolic solution in, place 55-65 ℃ of water-bath magnetic agitation 110-130min again, the zinc-oxide nano crystal grain colloidal sol that obtains clarifying; The indium tin oxide-coated glass substrate vertically is impregnated in the zinc-oxide nano crystal grain colloidal sol, speed with 11-13 cm/min at the uniform velocity lifts substrate, then substrate is placed 145-155 ℃ the Muffle furnace 25-35min that anneals, repeated impregnations-lift-annealing process 4-6 time obtains the substrate of being modified by zinc-oxide nano crystal grain; Substrate after modifying is placed the homogeneous mixture solotion of 0.04-0.06 M zinc nitrate and 0.04-0.06 M hexamethylenetetramine, be used for the substrate surface of growing zinc oxide nanorod arrays down, take out behind the reaction 160-200min in the 94-96 ℃ of water-bath environment, after ultrasonic cleaning, dry up with nitrogen gun, place 75-85 ℃ of vacuumize close annealing 140-160min;
(2) little electrochemical catalysis etch prepares the semiconductor nano groove array:
P-type low resistance silicon chip after conventional cleaning is cleaned is immersed in 4-6% and (in the hydrofluoric acid solution of (volume), takes out cleaning behind the 50-70sec and dry up, remove the oxide layer on surface; Silicon chip is immersed in 4.7-4.9 M(mol/L) hydrofluoric acid and 2 mM(m mol/L) the silver nitrate mixed solution in, take out behind the 4-6 min and place with distilled water according to volume ratio distilled water: the nitric acid rinsing of the dilution proportion of nitric acid 0.8-1.2:1, dissolving is attached to the silver-colored particle of silicon chip surface; Again silicon chip is placed the 4-6%(volume) the hydrofluoric acid solution rinsing, clean rapidly after removing the oxide layer on surface, and dry up with nitrogen gun;
(3) lead-in wire and encapsulation:
Respectively with the semiconductor nanorods array and the semiconductor nano groove array dicing that prepare in step () and the step (two); Be connected lead at the edge of semiconductor nanorods array chip and semiconductor nano groove array sheet respectively with conductive silver glue, treat that conductive silver glue solidifies after 9-11 hour; Semiconductor nano groove array sheet is placed on semiconductor nanorods array chip top, adopt the method for mechanical grip to make semiconductor nano groove array and semiconductor nanorods array form nested structure closely, the contact resistance in this process between measuring semiconductor nanometer stick array sheet and the semiconductor nano groove array sheet is determined its exposure level; Under the good situation of contact, apply gluey epoxy resin two peripheries and encapsulate, behind the epoxy resin cure.
Among the present invention, semiconductor nano groove array and semiconductor nanorods array form nested structure closely, under the extraneous vibration effect, semiconductor nano groove array and semiconductor nanorods array produce relative motion, make the stressed bending of semiconductor nanorods and produce piezoelectric polarization to form the positive and negative charge accumulation on the semiconductor nanorods surface that it is that the p-n heterojunction semiconductor contacts that the p-type silicon chip contacts with n type nanometer rods, produce potential barrier at contact interface, make it have the rectifying effect of the unidirectional conducting of electric current; The polarization charge on semiconductor nanorods surface is exported with the form of unidirectional current, namely in the power conversion of nanoscale realization from mechanical energy to the electric energy.
The present invention adopts p-type low-resistance silicon materials as top electrode, erodes away groove array by little electrochemical catalysis etch at silicon chip surface, so the making of top electrode and existing cmos semiconductor process compatible.The mode of injecting by ion on can silicon base obtains local p-type zone, obtains groove array by technologies such as photoetching, corrosion again, and its technology is simple relatively, and is easy to nano generator and other microcircuit are integrated on the same silicon substrate.
Compared with prior art, the present invention adopts the schottky junction in the p-n heterojunction replacement piezoelectric type nano generator, has realized the output of unidirectional current, for the project organization of opening up the piezoelectric type nano generator provides a kind of new departure, realizes simpler.Semiconductor nanorods array of the present invention is made by the n type semiconductor oxide Zinc material with piezoelectric property, the semiconductor nano groove array is made by p-type low-resistance silicon materials, the noble metal such as Au or the Pt that no longer need high work function in the manufacturing process, thereby be conducive to reduce the cost of manufacture of generator, prolong the useful life of generator.
Description of drawings
Fig. 1 is one embodiment of the invention structure enlarged diagram;
Fig. 2 is electricity generating principle schematic diagram embodiment illustrated in fig. 1;
Fig. 3 is the energy band diagram of middle p-n heterojunction embodiment illustrated in fig. 1.
Embodiment
Below in conjunction with drawings and Examples the present invention is further described.
With reference to Fig. 1, present embodiment comprises semiconductor nanorods array 1, semiconductor nano groove array 2, conductive substrates 3, encapsulated layer 4 and goes between 5, the semiconductor nanorods of described semiconductor nanorods array 1 is made by the n type semiconductor oxide Zinc material with piezoelectric property, is vertical on the conductive substrates 3 as the generator bottom electrode; Described semiconductor nano groove array 2 is p-type low-resistance silicon materials, as the top electrode of generator; Semiconductor nano groove array 2 forms nested structure with semiconductor nanorods array 1, and upper/lower electrode is picked out by lead-in wire I 5-1, lead-in wire II 5-2 respectively; Semiconductor nano groove array 2 and semiconductor nanorods array 1 periphery are provided with encapsulated layer 4, and encapsulated layer 4 is made by epoxy resin; Described semiconductor nano groove array 2 is to go out groove array by little electrochemical catalysis etch in the surface corrosion of p-type low resistance silicon chip; Mutually nested semiconductor nanorods array 1 and semiconductor nano groove array 2 contacting between the two is the contact of p-n heterojunction, has the rectifying effect of the unidirectional conducting of electric current; Described conductive substrates 3 is made by indium tin oxide-coated glass.
The present invention's heterojunction piezoelectric type nano generator, its manufacturing process may further comprise the steps:
(1) hydro thermal method synthesizing zinc oxide semiconductor nanorods array:
Under the magnetic agitation situation, with 0.03 M(mol/L of 26 ml) the NaOH ethanolic solution, join in the zinc acetate ethanolic solution of 0.01 M of 50 ml, placed 60 ℃ of water-bath magnetic agitation again 2 hours, the zinc-oxide nano crystal grain colloidal sol that obtains clarifying; The indium tin oxide-coated glass substrate vertically is impregnated in the zinc-oxide nano crystal grain colloidal sol, speed with 12 cm/min at the uniform velocity lifts substrate, then substrate is placed 150 ℃ Muffle furnace to anneal 30 minutes, repeated impregnations-lift-annealing process 5 times obtains the substrate of being modified by zinc-oxide nano crystal grain; Substrate after modifying is placed the homogeneous mixture solotion of 0.05 M zinc nitrate and 0.05 M hexamethylenetetramine, be used for the substrate surface of growing zinc oxide nanorod arrays down, reaction was taken out after 3 hours in 95 ℃ of water-bath environment, after ultrasonic cleaning, dry up with nitrogen gun, place 80 ℃ of vacuumize close annealings 1.5 hours;
(2) little electrochemical catalysis etch prepares the semiconductor nano groove array:
P-type low resistance silicon chip after conventional cleaning is cleaned is immersed in the 5%(volume) hydrofluoric acid solution in, take out after 1 minute to clean and dry up, remove the oxide layer on surface; Silicon chip is immersed in the silver nitrate mixed solution of the hydrofluoric acid of 4.8 M and 2 mM, takes out after 5 minutes and place with the nitric acid rinsing of distilled water according to the dilution proportion of volume ratio 1:1, dissolving is attached to the silver-colored particle of silicon chip surface; Silicon chip is placed the 5%(volume) the hydrofluoric acid solution rinsing, clean rapidly after removing the oxide layer on surface, and dry up with nitrogen gun;
(3) lead-in wire and encapsulation:
The square sheet that the semiconductor nanorods array for preparing in step () and the step (two) and semiconductor nano groove array are cut into 3 mm * 3 mm respectively; Be connected lead at the square sheet edge of semiconductor nanorods array and semiconductor nano groove array respectively with conductive silver glue, treat that conductive silver glue solidifies after 10 hours; Semiconductor nano groove array side sheet is placed on sheet top, semiconductor nanorods array side, adopt the method for mechanical grip to make semiconductor nano groove array and semiconductor nanorods array form nested structure closely, the contact resistance in this process between two square sheets of test is determined its exposure level; Under the good situation of contact, apply gluey epoxy resin two square sheet peripheries and encapsulate, epoxy resin cure after 2 hours.
Under the driving of extraneous mechanical oscillation, semiconductor nanorods array 1 in the heterojunction piezoelectric type nano generator produces relative displacement with semiconductor nano groove array 2, and make the 1 stressed bending of semiconductor nanorods array, under the coupling of piezoelectric effect and semiconductor property, mechanical energy is converted into electric energy and externally output.Specific to the electricity generating principle of single generator unit, its process can be in conjunction with Fig. 2 and Fig. 3 explanation.Form single semiconductor nanorods 6 and the single semiconductor nano groove 10 of nested structure, when extraneous mechanical oscillation drive heterojunction piezoelectric type nano generator, produce relative displacement, make single semiconductor nano groove 10 apply active force 7 in the end of single semiconductor nanorods 6; Single semiconductor nanorods 6 bends under the effect of active force 7, because piezoelectric effect makes single semiconductor nanorods 6 form piezoelectric polarization, produces positive polarization electric charge 8 at stretch zones, produces negative polarization electric charge 9 at constricted zone; Because single semiconductor nanorods 6 is made by n type semiconductor oxide Zinc material, single semiconductor nano groove 10 is made by p-type low-resistance silicon materials, both contacts are the contact of p-n heterojunction semiconductor, the band structure of the p-n heterojunction that forms as shown in Figure 3, the heterojunction boundary left side is the p-type silicon materials, and the right is n type semi-conducting material, contacts back two kinds of materials in the charge carrier redistribution of near interface, make Fermi level be in sustained height, conduction band and valence band bend and produce potential barrier.Because carrier concentration is very high after the heavy doping of p-type low-resistance silicon materials, so the dissipation district of heterojunction boundary mainly at n type semi-conducting material here.There is potential barrier in the p-n heterojunction that forms, shows the rectifying effect of unidirectional conducting.Conducting when single semiconductor nano groove 10 contacts with the constricted zone of single semiconductor nanorods 6 ends when contacting with stretch zones, thereby realizes the unidirectional output of electric current.For single semiconductor nanorods 6, the electric current production process is transient state.But when nanometer rods a large amount of in the semiconductor nanorods array 1 all produced unidirectional current output, current in loop then was the stack that all nanometer rods produce electric current, thereby the current signal of output steady and continuous.
Claims (7)
1. the manufacture method of a heterojunction piezoelectric type nano generator, described heterojunction piezoelectric type nano generator, comprise semiconductor nanorods array, semiconductor nano groove array, conductive substrates, encapsulated layer and lead-in wire, described semiconductor nanorods array is vertical on the conductive substrates as the generator bottom electrode, semiconductor nano groove array and semiconductor nanorods array form nested structure, the semiconductor nano groove array is the top electrode of generator, and the generator upper/lower electrode is picked out by different lead-in wires respectively; Semiconductor nano groove array and semiconductor nanorods array periphery are provided with encapsulated layer;
It is characterized in that the manufacture method of described heterojunction piezoelectric type nano generator may further comprise the steps:
(1) hydro thermal method synthesizing zinc oxide semiconductor nanorods array:
Under the magnetic agitation situation, NaOH ethanolic solution with the 0.02-0.04 M of 20-30 ml, join in the zinc acetate ethanolic solution of 0.005-0.015 M of 40-60 ml, place 55-65 ℃ of water-bath magnetic agitation 110-130min again, the zinc-oxide nano crystal grain colloidal sol that obtains clarifying; The indium tin oxide-coated glass substrate vertically is impregnated in the zinc-oxide nano crystal grain colloidal sol, speed with 11-13 cm/min at the uniform velocity lifts substrate, then substrate is placed 145-155 ℃ the Muffle furnace 25-35min that anneals, repeated impregnations-lift-annealing process 4-6 time obtains the substrate of being modified by zinc-oxide nano crystal grain; Substrate after modifying is placed the homogeneous mixture solotion of 0.04-0.06 M zinc nitrate and 0.04-0.06 M hexamethylenetetramine, be used for the substrate surface of growing zinc oxide nanorod arrays down, take out behind the reaction 160-200min in the 94-96 ℃ of water-bath environment, after ultrasonic cleaning, dry up with nitrogen gun, place 75-85 ℃ of vacuumize close annealing 140-160min;
(2) little electrochemical catalysis etch prepares the semiconductor nano groove array:
P-type low resistance silicon chip after conventional cleaning is cleaned is immersed in the hydrofluoric acid solution of 4-6% (volume), takes out behind the 50-70sec to clean to dry up, and removes the oxide layer on surface; Silicon chip is immersed in the silver nitrate mixed solution of the hydrofluoric acid of 4.7-4.9 M and 2 mM, take out behind the 4-6 min and place with distilled water according to volume ratio distilled water: the nitric acid rinsing of the dilution proportion of nitric acid 0.8-1.2:1, dissolving is attached to the silver-colored particle of silicon chip surface; Again silicon chip is placed the 4-6%(volume) the hydrofluoric acid solution rinsing, clean rapidly after removing the oxide layer on surface, and dry up with nitrogen gun;
(3) lead-in wire and encapsulation:
Respectively with the semiconductor nanorods array and the semiconductor nano groove array dicing that prepare in step () and the step (two); Be connected lead at the edge of semiconductor nanorods array chip and semiconductor nano groove array sheet respectively with conductive silver glue, treat that conductive silver glue solidifies after 9-11 hour; Semiconductor nano groove array sheet is placed on semiconductor nanorods array chip top, adopt the method for mechanical grip to make semiconductor nano groove array and semiconductor nanorods array form nested structure closely, the contact resistance in this process between measuring semiconductor nanometer stick array sheet and the semiconductor nano groove array sheet is determined its exposure level; Under the good situation of contact, apply gluey epoxy resin two peripheries and encapsulate, behind the epoxy resin cure.
2. the manufacture method of heterojunction piezoelectric type nano generator according to claim 1 is characterized in that, described semiconductor nanorods array is the n type semiconductor oxide Zinc material with piezoelectric property.
3. the manufacture method of heterojunction piezoelectric type nano generator according to claim 1 and 2 is characterized in that, described semiconductor nano groove array is the p-type low-resistance silicon materials with satisfactory electrical conductivity.
4. the manufacture method of heterojunction piezoelectric type nano generator according to claim 2 is characterized in that, material is that the semiconductor nanorods array of zinc oxide is synthetic in conductive substrates by hydro thermal method.
5. the manufacture method of heterojunction piezoelectric type nano generator according to claim 3 is characterized in that, described semiconductor nano groove array is the groove array that goes out in the surface corrosion of p-type low resistance silicon chip by little electrochemical catalysis etch.
6. the manufacture method of heterojunction piezoelectric type nano generator according to claim 1 and 2 is characterized in that, described conductive substrates is made by indium tin oxide-coated glass.
7. the manufacture method of heterojunction piezoelectric type nano generator according to claim 1 and 2 is characterized in that, described encapsulated layer is made by epoxy resin.
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| WO2014101300A1 (en) | 2012-12-28 | 2014-07-03 | 兰州金福乐生物工程有限公司 | Natural heat energy conversion and storage device |
| CN104076084B (en) * | 2013-03-28 | 2017-08-25 | 北京纳米能源与系统研究所 | The electric nano-sensor of one kind friction |
| CN104655261A (en) * | 2015-02-06 | 2015-05-27 | 中国科学院半导体研究所 | Capacitive ultrasonic sensor and manufacturing method thereof |
| CN106992247B (en) * | 2016-01-19 | 2020-02-14 | 中兴通讯股份有限公司 | Nano generator and manufacturing method thereof |
| CN106253745A (en) * | 2016-08-22 | 2016-12-21 | 苏州聚冠复合材料有限公司 | A kind of 3D prints the wearable nano generator of micro-nano |
| CN108493327A (en) * | 2018-05-04 | 2018-09-04 | 大连理工大学 | Spiro-MeOTAD/ZnO piezoelectric type nano generators and preparation method thereof |
| CN110534640A (en) * | 2018-05-24 | 2019-12-03 | 中国科学院深圳先进技术研究院 | A kind of hetero-junctions direct current piezoelectric nano generator and preparation method thereof |
| CN109082964B (en) * | 2018-08-30 | 2023-06-16 | 广州大学 | Ice melting floor tile and preparation method thereof |
| CN112886856A (en) * | 2019-11-29 | 2021-06-01 | 栾玉成 | Energy conversion device, preparation method and application thereof |
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| CN101295941A (en) * | 2007-04-23 | 2008-10-29 | 万里兮 | AC nano generator and boosting method |
| CN101604930A (en) * | 2008-06-13 | 2009-12-16 | 鸿富锦精密工业（深圳）有限公司 | Generator |
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| US7936111B2 (en) * | 2008-08-07 | 2011-05-03 | Samsung Electronics Co., Ltd. | Apparatus for generating electrical energy and method for manufacturing the same |
| JP4971393B2 (en) * | 2008-12-08 | 2012-07-11 | 韓國電子通信研究院 | Nano-piezoelectric element and method for forming the same |
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| CN101295941A (en) * | 2007-04-23 | 2008-10-29 | 万里兮 | AC nano generator and boosting method |
| CN101604930A (en) * | 2008-06-13 | 2009-12-16 | 鸿富锦精密工业（深圳）有限公司 | Generator |
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