CN108155294A - Photodetector and preparation method thereof, photodetector fabric - Google Patents
Photodetector and preparation method thereof, photodetector fabric Download PDFInfo
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- CN108155294A CN108155294A CN201711424033.9A CN201711424033A CN108155294A CN 108155294 A CN108155294 A CN 108155294A CN 201711424033 A CN201711424033 A CN 201711424033A CN 108155294 A CN108155294 A CN 108155294A
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- H—ELECTRICITY
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- H—ELECTRICITY
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Abstract
The present invention provides a kind of photodetector and preparation method thereof, photodetector fabric, and the production method of the photodetector includes：Prepare graphene film, the graphene film be arranged in substrate, the substrate for light transmission and with flexible material；First electrode and second electrode are formed on the graphene film；Quantum dot film is formed between the first electrode and the second electrode, the quantum dot film has carried out ligand exchange processing.In photodetector provided by the invention and preparation method thereof, photodetector fabric, quantum dot film is located on graphene film, the carrier that quantum dot film illumination response generates can be transferred out by graphene, improve the carrier transport of photosensitive layer quantum dot, photodetector is arranged on the graphene film of light transmission and based on light transmission and with flexible substrate simultaneously, light penetration is increased, so that photodetector has flexible, flexible and woven performance.
Description
Technical field
The present invention relates to field of semiconductor manufacture, more particularly to a kind of photodetector and preparation method thereof, photodetection
Device fabric.
Background technology
In recent years, the booming technological progress for advancing many fields of wearable electronic, such as display, sensing
Device, energy harvesting and storage, the lightweight of wearable device, flexibility and flexible get more and more people's extensive concerning.Wherein photoelectricity is visited
Survey device has important application, but traditional photodetector is mostly as representative sensor in directions such as medical treatment, detection, military affairs
Blocky hard plate-like component, it is difficult to irregular substrate is bonded according to application requirement, and does not have flexible and flexible feature, this
A little problems seriously limit its development in wearable device and other related fields.In addition, to near-infrared or infrared-sensitive
Photodetector there are still detection optical signal loss is serious, detection light wave frequency range is single, sensitivity is low and device is flexible not
The problems such as sufficient.Therefore, the photodetector of the prior art could be improved and develop.
Therefore, how to improve photodetector is that those skilled in the art need the technical problem solved.
Invention content
The purpose of the present invention is to provide a kind of photodetector and preparation method thereof, photodetector fabric, to improve
Existing photodetector.
In order to solve the above technical problems, the present invention provides a kind of production method of photodetector, the photodetector
Production method include：
Prepare graphene film, the graphene film be arranged in substrate, the substrate for light transmission and with soft
The material of property；
First electrode and second electrode are formed on the graphene film；
Quantum dot film is formed between the first electrode and the second electrode, the quantum dot film is matched
Body exchange is handled, and the quantum dot film is located on the graphene film.
Optionally, in the production method of the photodetector, institute's ligand exchange processing includes ontology and exchanges solution
Immersion way or hybrid mode.
Optionally, in the production method of the photodetector, the material of the ligand exchange solution includes butylamine, second
Two mercaptan or dimercaptobenzene.
Optionally, it in the production method of the photodetector, prepares graphene film and includes：
Copper foil is arranged in furnace chamber, argon gas and hydrogen will be passed through in the furnace chamber, heating arrives temperature in the furnace chamber
Up to 800 DEG C~1200 DEG C, then it is passed through methane；
The copper foil that growth has graphene film, which is put into substitutional solution, separates graphene film.
Optionally, in the production method of the photodetector, the production method of the photodetector further includes：Shape
Into protective layer, the protective layer covers the first electrode, the second electrode and the quantum dot film, the protective layer
Material includes dimethyl silicone polymer.
The present invention also provides a kind of photodetector, the photodetector includes substrate, graphene film, the first electricity
Pole, second electrode and quantum dot film, the substrate for light transmission and with flexible material, the graphene film is located at institute
It states in substrate, the first electrode and the second electrode are located on the graphene film, and the quantum dot film is located at institute
It states between first electrode and the second electrode, the quantum dot film is located on the graphene film, and the quantum dot is thin
Film is handled by ligand exchange.
Optionally, in the photodetector, the first electrode is in interdigital structure with the second electrode.
Optionally, in the photodetector, spacing between the first electrode and the second electrode for 1 μm~
100 μm, the line width of the first electrode and the second electrode is 1 μm~100 μm, the first electrode and the second electrode
Line thickness be 10nm~1000nm.
Optionally, in the photodetector, the material of the substrate includes polyethylene terephthalate, poly- two
Methylsiloxane or polyurethane.
The present invention also provides a kind of photodetector fabric, the photodetector fabric includes above-mentioned photodetector,
The shape of the photodetector is strip, and the photodetector is woven into fabric.
In conclusion in photodetector provided by the invention and preparation method thereof, photodetector fabric, quantum dot is thin
Film is located on graphene film, and the carrier that quantum dot film illumination response generates can be transferred out by graphene, be improved
The carrier transport of photosensitive layer quantum dot so as to improve the output light electric current of photodetector, and is handled by ligand exchange
Convenient for the transition of carrier in quantum dot film, while photodetector is arranged on the graphene film of light transmission and based on light transmission
And with flexible substrate, light penetration is increased, so that photodetector has flexible, flexible and stitchability
Energy is adapted to the needs of different operating occasion.
Description of the drawings
Fig. 1 is the flow chart of the production method of the photodetector of the embodiment of the present invention；
Fig. 2 is the transverse sectional view of the photodetector of the embodiment of the present invention；
Fig. 3 is the longitudinal sectional view of the photodetector of the embodiment of the present invention；
Fig. 4 is the schematic diagram of the photodetector fabric of the embodiment of the present invention；
Wherein, 10- substrates, 20- graphene films, 30- first electrodes, 40- second electrodes, 50- quantum dot films, 60-
Protective layer.
Specific embodiment
In order to enable objects, features and advantages of the present invention more obvious understandable, attached drawing is please referred to.It should be clear that this explanation
Structure, ratio, size depicted in book institute accompanying drawings etc., only to coordinate the revealed content of specification, for being familiar with this
The personage of technology understands and reads, and is not limited to the enforceable qualifications of the present invention, therefore does not have technical essence meaning
Justice, the modification of any structure, the change of proportionate relationship or the adjustment of size are not influencing the effect of present invention can be generated and institute
Under the purpose that can reach, should all still it fall in the range of disclosed technology contents can be covered.
As shown in Figure 1, the present invention provides a kind of production method of photodetector, the production method of the photodetector
Including：
Step S10, graphene (Graphene) film is prepared, the graphene film is arranged in substrate, the base
Bottom for light transmission and with flexible material；
Step S20, first electrode and second electrode are formed on the graphene film；
Step S30, quantum dot film, the quantum dot film are formed between the first electrode and the second electrode
Ligand exchange processing is carried out, the quantum dot film is located on the graphene film.
The characteristics of production method of photodetector provided by the invention being introduced in more detail with reference to Fig. 2 and Fig. 3.
First, according to step S10, graphene film is prepared, can carrier blocking layers be used as by graphene film, can made
Obtain carrier mobility up to 1000cm2V-1s-1, the graphene film is arranged in substrate, is passed through substrate and is played carrying and makees
With, the substrate for light transmission and with flexible material, the material of light transmission can preferably receive illumination, and flexible material can be with
Realize bending, while graphene film also has translucency and flexible flexibility, photodetector can be made more preferably to detect
To the variation of light.
In the present embodiment, graphene film is prepared to include：The copper foil of certain size is arranged in furnace chamber, by the stove
Argon gas (Ar) and hydrogen (H are passed through in chamber2), heating makes in the furnace chamber temperature reach 800 DEG C~1200 DEG C, then towards methane,
For example, the flow of argon gas can be set by as 20sccm, the flow by hydrogen is 40sccm, the heating rate heated in furnace chamber
For 20 DEG C/min, can also be kept after temperature reaches certain time (such as 10min), the speed that may then pass through 10sccm is led to
Enter the methane as reactant, methane can be reduced in copper foil surface, generate graphene film, can be by controlling reaction time etc.
Reach the different graphene number of plies or thickness, then will grow the copper foil that has graphene film and be put into graphite in substitutional solution
Alkene thin film separation comes out, and can etch away copper by the substitutional solution that ferric trichloride and mixed in hydrochloric acid are formed, so as to make copper foil with
Graphene separates.Graphene film is grown on copper foil by using chemical vapor deposition (CVD), is then transferred to light transmission
And in flexible substrate.
Then, as shown in Figures 2 and 3, according to step S20,30 He of first electrode is formed on the graphene film 20
Second electrode 40, first electrode 30 and second electrode 40 are respectively namely positive/negative electrode, are oppositely arranged and can be formed simultaneously.
For example, the substrate 10 that will be covered with graphene film 20 is placed in vacuum evaporation cavity, then mask film covering version, process lumen is deposited
The vacuum degree of body<10-4Pa on graphene film 20 can be deposited using metal as target and form metal electrode, metal
Material includes gold, silver, aluminium etc..
Then, with continued reference to shown in Fig. 2 and Fig. 3, according to step S30, in the first electrode 30 and the second electrode
Quantum dot film 50 is formed between 40, the quantum dot film 50 has carried out ligand exchange processing, the quantum dot film 50
In on the graphene film 20, for example, vulcanized lead quantum dot solution can be used, the band gap of bulk sulfided lead is about 0.41eV,
Under electron excitation, the coulomb between electronics and hole, which is combined, makes it have relatively large average distance~18nm, i.e. exciton wave
Your radius, by reducing the crystalline size of vulcanized lead, make its de Broglie wavelength with carrier have identical magnitude (~
8nm), that is, the half of Exciton Bohr Radius, so as to assign vulcanized lead quantum dot (also referred to as sulfide nanocrystalline) size according to
Bad photoelectric characteristic adjusts photodetector to 800nm~2000nm wave bands by adjusting the size of vulcanized lead quantum dot
Sensibility.
Vulcanized lead quantum dot can be synthesized by a variety of methods, including solution phase, gas phase, solid phase etc., wherein hot injection method
The controllable and extensive use of quantum dot size can be realized by adjusting reaction temperature and time.Heat injection preparation method is simply convenient for
Large-scale production, obtained quantum dot solution are stablized, easily coating film forming, and can obtain having by ligand exchange between different particles
Away from gel quantum dot layer.In hot injection method the quantum dot ruler of synthesis is adjusted by controlling hot implantation temperature and reaction time
It is very little, so as to which the vulcanized lead quantum dot to different wave length photoresponse be prepared, the sensitivity spectrum of photodetector is adjusted, then
It by the spin coating of vulcanized lead quantum dot solution or sprays on graphene film, the thickness of quantum dot film can pass through solution concentration, painting
Number is covered to regulate and control.Can the photosignal that generated on quantum dot film be read by first electrode and second electrode, graphene is thin
Film has carrier blocking layers of the translucency simultaneously as quantum dot film, and has adjusted quantum dot to being handled by ligand exchange
Structure, the purpose convenient for carrier transition is can reach, so as to improve the performance of photodetector.
In the present embodiment, the ligand exchange processing includes the immersion way or hybrid mode of ligand exchange solution,
That is quantum dot film can be immersed in ligand exchange solution, the purpose of ligand exchange can be preferably realized when infiltration,
Or after can also quantum dot solution be mixed with ligand exchange solution, the quantum dot solution after ligand exchange, Ran Houzai are prepared
Form quantum dot film.
Optionally, the material of the ligand exchange solution includes butylamine, dithioglycol or dimercaptobenzene.Wherein, using leaching
During bubble mode, by taking vulcanized lead quantum dot as an example, detailed preparation process includes：Graphene film can be positioned on spin coating instrument, it can
By the way that in the normal octane solution drop coating to graphene film of the vulcanized lead quantum dot for 10mg/ml, specific dosage is thin with graphene
The size of film is foundation, is preferred with meeting infiltration, can rotate the time in a period of time (such as 60s) in 1000rpm~3000rpm, that is, exist
The surface of graphene forms vulcanized lead quantum dot film, since vulcanized lead quantum dot film has backbone, vulcanized lead quantum
The thickness of point film can be 10nm, after repetition spin coating reaches certain film thickness, can be immersed into 1,2- dithioglycols/acetonitrile solution,
Wherein the volume ratio of 1,2- dithioglycols and acetonitrile can be 1:99, Immersion time can be adjusted according to film thickness, be then transferred to second
Extra 1,2- dithioglycols are washed off in nitrile solution, you can the vulcanized lead quantum dot film of short-chain structure ligand package is obtained,
Backbone in former vulcanized lead quantum dot is fallen by short-chain structure ligand exchange.The thickness of wherein vulcanized lead quantum dot film can
Pass through the adjustment such as quantum dot solution concentration, spin coating number and rotary speed.
During using immersion way, the spin coating on graphene film or spraying vulcanized lead quantum dot solution, system can also be passed through
It is standby go out backbone vulcanized lead quantum dot film, then by the ligand exchange solution spin coating of short-chain structure or to be sprayed on quantum dot thin
On film, ligand exchange in the solid state is carried out, then long-chain Ligand and excessive short chain ligand are washed off, it can be by preparing layer by layer
(repeatedly prepare) obtains the vulcanized lead quantum dot film of short chain ligand structure.For example, detailed preparation process may be used being：It can
Substrate is positioned on spin coating instrument, it can be specific to use by the normal octane solution drop coating of 10mg/ml vulcanized lead quantum dots in substrate
Amount is preferred, then be spin-dried for reaching infiltration using substrate sizes as foundation, i.e., is the vulcanization for having backbone in substrate surface
Then volume ratio is 1 by lead quantum dot film:99 1,2- dithioglycols are with acetonitrile solution drop coating in vulcanized lead quantum dot film
On, 5s~30s can be stopped, is then spin-dried for again, extra solution is removed, it then can drop coating acetonitrile solution, then stop 5s again
~30s, is then spin-dried for again, is wrapped up after unreacted 1,2- dithioglycols are rinsed well to get to one layer of short-chain structure ligand
Vulcanized lead quantum dot film, repeat this operation, the rotating condition of the process can be 1000rmp~3000rpm, and the time can be
60s.Wherein vulcanized lead quantum dot film thickness can pass through the adjustment such as quantum dot solution concentration, spin coating number and rotary speed.
When wherein, using hybrid mode, by taking vulcanized lead quantum dot as an example, detailed preparation process may include：To vulcanized lead amount
Anti-solvent ethyl alcohol or acetone, the normal octane solution of vulcanized lead quantum dot and the volume of anti-solvent are added in the normal octane solution of son point
Than that can be 1:3, vulcanized lead quantum dot is the quantum dot for having backbone, precipitates vulcanized lead quantum dot by centrifugation and detaches,
Add after butylamine solution and carry out ultrasonic disperse, butylamine solution is the ligand exchange solution for short-chain structure, butylamine solution it is dense
Degree can be 30mg/ml, be then transferred quickly in round-bottomed flask, then take a breath, under atmosphere of inert gases, stir at room temperature
2h~4h is reacted, then can be centrifuged by n-hexane ultrasonic disperse and ethyl alcohol, is washed repeatedly 3 times, then by gains
Disperseed with normal octane, so as to obtain the vulcanized lead quantum dot solution of short-chain structure ligand package, pass through short-chain structure ligand exchange
Fall the backbone in former vulcanized lead quantum dot, easily reunite in the vulcanized lead Quantum Solution air of short-chain structure ligand package,
It is recommended that being preserved in inert gas, short-chain structure ligand packet is prepared on graphene film finally by spin coating or spraying method
The vulcanized lead quantum dot film wrapped up in, wherein vulcanized lead quantum dot film thickness can by quantum dot solution concentration, spraying number or
The adjustment such as spin coating number, rotary speed.
In the present embodiment, continuing with shown in Fig. 2, the production method of the photodetector further includes：
Protective layer 60 is formed, the protective layer 60 covers the first electrode 30, the second electrode 40 and the quantum
Point film 50, can be by spin coating or coating method in the protective layer of the upper surface of above-mentioned device covering encapsulation, the protective layer 60
Material include dimethyl silicone polymer (PDMS, Polydimethylsiloxane), dimethyl silicone polymer is as a kind of high
Molecule organo-silicon compound can simply be prepared by spin coating, have optical clarity, its good penetration power of dimethyl silicone polymer
Light transmission insulating coating pin-free, in homogeneous thickness can be formed in device outer surface, a good protective coating is provided to device,
Preferably defend the damage of soda acid, particle, mould and various corrosive gas.
The production method of corresponding above-mentioned photodetector, the present invention also provides a kind of photodetector, as shown in Fig. 2, institute
It states photodetector and includes substrate 10, graphene film 20, first electrode 30, second electrode 40 and quantum dot film 50, it is described
Substrate 10 for light transmission and with flexible material, the graphene film 20 is located in the substrate 10, the first electrode
30 and the second electrode 40 be located on the graphene film 20, the quantum dot film 50 be located at the first electrode 20 with
Between the second electrode 30, the quantum dot film 50 is located on the graphene film 20, and the quantum dot film 50 passes through
Cross ligand exchange processing.
As shown in figure 3, the first electrode 30 and the second electrode 40 be in interdigital structure, due to first electrode 30 with
Second electrode 40 is oppositely arranged, and what interdigital structure was namely oppositely arranged is in pectinate texture, and comb post part is intersected respectively
Interval, in order to obtain high current as far as possible at low voltage, should select the interdigital structure of high-aspect-ratio (L/W), can be by true
Empty vapor deposition mode forms first electrode 30 and second electrode 40, the material of first electrode 30 and second electrode 40 include gold, silver or
Aluminium, the electrode that these materials are formed not only have preferable electric conductivity, also have certain adhesion strength on graphene film.
Optionally, the spacing between the first electrode 30 and the second electrode 40 be 1 μm~100 μm, here between
Away from can be distance that average headway or minimum spacing etc. show, that is, the width that quantum dot film can be formed, institute
The line width for stating first electrode 30 and the second electrode 40 is 1 μm~100 μm, the first electrode 30 and the second electrode 40
Line thickness for 10nm~1000nm, for example, regulation and control parameter sets the evaporation rate and time to form above-mentioned size and close in vapor deposition
System can meet the electrical property of photodetector by above-mentioned size relationship.
Optionally, the material of the substrate 10 includes polyethylene terephthalate (PET), dimethyl silicone polymer
(PDMS) or polyurethane (PI), it can be achieved that light transmittance 30%~100%, by above-mentioned material come formed light transmission and with soft
The substrate of property, meets the requirement of photodetector in translucency and flexible.With reference to the production method, photoelectricity is visited
The surface for surveying device has protective layer, and protection is provided to device.
Photodetector is quickly grown in the visible light region of short wavelength, but in the near-infrared and infrared light higher than 800nm
Region, however it remains the problems such as detection light wave frequency is single, sensitivity is low or light-sensitive material synthesis is complicated.With traditional light-sensitive material
Semiconductor is compared, quantum dot have it is easily prepared, of low cost, can large area covering, and can be real by adjusting quantum dot size
Now to the light absorption of different wave frequencies, quantum dot absorbs light and generates photo-generated carrier, by photoconduction type detector by optical signalling
Be converted into exportable electrical signal, telecommunications (1300nm~1600nm), thermal imaging (>1500nm), bio-imaging (800nm,
1100nm), thermal photovoltaic (>1900nm) etc. near-infrareds or infrared regime have potential using value.
With reference to the above, as shown in figure 4, as a kind of preferable application mode, the present invention also provides a kind of spies of photoelectricity
Device fabric is surveyed, the photodetector fabric includes photodetector as described above, and the shape of the photodetector is item
The photodetector is woven into fabric by shape.Can by using the strip photodetector to different spectral responses, it can be achieved that
More wave frequency responses, by adjusting weaving method, it can be achieved that different shape, is bonded various irregular surfaces, in wearable detection
The fields such as equipment, bionical tissue and medicine have potential using value.
In conclusion in photodetector provided by the invention and preparation method thereof, photodetector fabric, quantum dot is thin
Film is located on graphene film, and the carrier that quantum dot film illumination response generates can be transferred out by graphene, be improved
The carrier transport of photosensitive layer quantum dot so as to improve the output light electric current of photodetector, and is handled by ligand exchange
Convenient for the transition of carrier in quantum dot film, while photodetector is arranged on the graphene film of light transmission and based on light transmission
And with flexible substrate, light penetration is increased, so that photodetector has flexible, flexible and stitchability
Energy is adapted to the needs of different operating occasion.
Foregoing description is only the description to present pre-ferred embodiments, not to any restriction of the scope of the invention, this hair
Any change, the modification that the those of ordinary skill in bright field does according to the disclosure above content, belong to the protection of claims
Range.
Claims (10)
1. a kind of production method of photodetector, which is characterized in that the production method of the photodetector includes：
Graphene film is prepared, the graphene film is arranged in substrate, the substrate is light transmission and with flexibility
Material；
First electrode and second electrode are formed on the graphene film；
Quantum dot film is formed between the first electrode and the second electrode, the quantum dot film has carried out ligand friendship
Processing is changed, the quantum dot film is located on the graphene film.
2. the production method of photodetector according to claim 1, which is characterized in that the ligand exchange processing includes matching
Body exchanges the immersion way or hybrid mode of solution.
3. the production method of photodetector according to claim 1, which is characterized in that the material of the ligand exchange solution
Including butylamine, dithioglycol or dimercaptobenzene.
4. the production method of photodetector according to claim 1, which is characterized in that prepare graphene film and include：
Copper foil is arranged in furnace chamber, argon gas and hydrogen will be passed through in the furnace chamber, heating makes temperature in the furnace chamber reach 800
DEG C~1200 DEG C, then it is passed through methane；
The copper foil that growth has graphene film, which is put into substitutional solution, separates graphene film.
5. according to the production method of photodetector described in any one in claim 1-4, which is characterized in that the photoelectricity is visited
The production method for surveying device further includes：
Protective layer is formed, the protective layer covers the first electrode, the second electrode and the quantum dot film, the guarantor
The material of sheath includes dimethyl silicone polymer.
6. a kind of photodetector, which is characterized in that the photodetector includes：
Substrate, the substrate for light transmission and with flexible material；
Graphene film, the graphene film are located in the substrate；
First electrode and second electrode, the first electrode and the second electrode are located on the graphene film；
Quantum dot film, for the quantum dot film between the first electrode and the second electrode, the quantum dot is thin
Film is located on the graphene film, and the quantum dot film is handled by ligand exchange.
7. photodetector according to claim 6, which is characterized in that the first electrode is with the second electrode in fork
Finger-type structure.
8. photodetector according to claim 6, which is characterized in that between the first electrode and the second electrode
Spacing for 1 μm~100 μm, the line width of the first electrode and the second electrode is 1 μm~100 μm, the first electrode
Line thickness with the second electrode is 10nm~1000nm.
9. according to the photodetector described in any one in claim 6-8, which is characterized in that the material of the substrate includes
Polyethylene terephthalate, dimethyl silicone polymer or polyurethane.
10. a kind of photodetector fabric, which is characterized in that the photodetector fabric is included as described in claim 6-9
Photodetector, the shape of the photodetector is strip, and the photodetector is woven into fabric.
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Cited By (6)
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| CN109004048A (en) * | 2018-07-25 | 2018-12-14 | 合肥工业大学 | A kind of preparation method of the inorganic perovskite quantum dot film of caesium lead bromine and photovoltaic device based on it |
| CN111012172A (en) * | 2019-10-21 | 2020-04-17 | 珠海烯蟀科技有限公司 | Graphene glass kettle with metal wire as electrode |
| CN112614903A (en) * | 2020-12-14 | 2021-04-06 | 东北师范大学 | Lead-drawn electrode two-dimensional material paper-based GaS photoelectric detector and preparation method thereof |
| CN114113238A (en) * | 2021-11-17 | 2022-03-01 | 中国兵器工业集团第二一四研究所苏州研发中心 | Gas sensor based on three-dimensional porous graphene @ quantum dot composite material and preparation method thereof |
| CN114284443A (en) * | 2021-12-22 | 2022-04-05 | 电子科技大学 | Preparation method of flexible photoelectric detector array |
| CN114354512A (en) * | 2021-12-14 | 2022-04-15 | 之江实验室 | Quantum dot thin film spectrum detection instrument and application method thereof |
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| CN111012172A (en) * | 2019-10-21 | 2020-04-17 | 珠海烯蟀科技有限公司 | Graphene glass kettle with metal wire as electrode |
| CN111012172B (en) * | 2019-10-21 | 2021-06-01 | 珠海烯蟀科技有限公司 | Graphene glass kettle with metal wire as electrode |
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| CN114113238A (en) * | 2021-11-17 | 2022-03-01 | 中国兵器工业集团第二一四研究所苏州研发中心 | Gas sensor based on three-dimensional porous graphene @ quantum dot composite material and preparation method thereof |
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