CN108807603A - Device for THz wave detection - Google Patents

Device for THz wave detection Download PDF

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CN108807603A
CN108807603A CN201810836884.2A CN201810836884A CN108807603A CN 108807603 A CN108807603 A CN 108807603A CN 201810836884 A CN201810836884 A CN 201810836884A CN 108807603 A CN108807603 A CN 108807603A
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thz wave
stirring
layer presoma
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CN108807603B (en
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孙云飞
班建民
陶重犇
刘传洋
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Wuxi Beiyang Qingan Iot Technology Co ltd
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Suzhou University of Science and Technology
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/184Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIIBV compounds, e.g. GaAs, InP
    • H01L31/1844Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIIBV compounds, e.g. GaAs, InP comprising ternary or quaternary compounds, e.g. Ga Al As, In Ga As P
    • H01L31/1848Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIIBV compounds, e.g. GaAs, InP comprising ternary or quaternary compounds, e.g. Ga Al As, In Ga As P comprising nitride compounds, e.g. InGaN, InGaAlN
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01JMEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J1/00Photometry, e.g. photographic exposure meter
    • G01J1/42Photometry, e.g. photographic exposure meter using electric radiation detectors
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/08Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors
    • H01L31/10Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors characterised by at least one potential-jump barrier or surface barrier, e.g. phototransistors
    • H01L31/101Devices sensitive to infrared, visible or ultraviolet radiation
    • H01L31/112Devices sensitive to infrared, visible or ultraviolet radiation characterised by field-effect operation, e.g. junction field-effect phototransistor
    • H01L31/113Devices sensitive to infrared, visible or ultraviolet radiation characterised by field-effect operation, e.g. junction field-effect phototransistor being of the conductor-insulator-semiconductor type, e.g. metal-insulator-semiconductor field-effect transistor
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/184Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIIBV compounds, e.g. GaAs, InP
    • H01L31/1852Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIIBV compounds, e.g. GaAs, InP comprising a growth substrate not being an AIIIBV compound
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

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Abstract

The invention belongs to detector technology fields, and in particular to a kind of device for THz wave detection.With aluminum gallium nitride/gallium nitrogen high electron mobility field-effect transistor(HEMT)For basic structure, aluminum gallium nitride/gallium nitrogen layer is prepared by substrate design, using epitaxy;Then active region mesa, gate medium, ohmic contact windows, electrode are prepared, two-dimensional electron gas in obtained field-effect transistor has higher electron concentration and mobility, it obtains realizing high speed, highly sensitive, high s/n ratio detection wave spectrum detection device, the final detection realized to THz wave to THz waves under room temperature.

Description

Device for THz wave detection
It it is 2017 the invention belongs to entitled device for THz wave detection and preparation method thereof, the applying date June 26, application No. is the divisional applications of 201710495199.3 patent applications, are product technology part.
Technical field
The invention belongs to detector technology fields, and in particular to a kind of device for THz wave detection.
Background technology
Since the frequency of THz wave is very high, so its spatial resolution is also very high;Again since its pulse is very short(Picosecond Magnitude)So having very high temporal resolution.THz imaging technology and THz wave spectral technology thus constitute Terahertz Two chief technologies of application.Simultaneously as Terahertz energy very little, will not generate destruction, so and X to substance Ray is compared to more advantageous.In addition, since the vibration of large biological molecule and the resonant frequency of rotational frequency are in THz wave Section, therefore Terahertz is chosen seeds in grain, the agricultural such as selection of excellent species and food-processing industry have good application prospect. The vibration of many large biological molecules, rotational energy level are located exactly at THz wave bands, then utilizing to biochemical reaction THz absorption spectrums Study the biomolecule movable information in being reacted.Most of polar molecules, such as hydrone, ammonia etc. is to Terahertz spoke Strong absorption is penetrated, it can be by analyzing their characteristic spectrum research material composition or carrying out control of product quality, therefore too Hertz spectral technique has broad application prospects in terms of analyzing and studying macromolecular.Due in universe most of electromagnetic energy be by What microwave background was constituted, therefore can help to investigate 300,000 years after huge explosion snapshots to its measurement, it can also obtain many heavy The exact value for the universe parameter wanted, moreover it is possible to which convincingly demonstrating cosmic expansion motion model can be dominated by dark.The formation of fixed star is Caused by gravity collapse occurs for the cold molecular gas cloud of deep layer, and gas cloud further comprises a large amount of interstellar dust.Those are interspace Dust be exactly visible light with where near infrared light reason opaque in gas cloud.Temperature of most of gas in molecular cloud Very low, about between 10 K-20 K, and their radiation is mainly in millimere-wave band.Therefore, terahertz light spectrometry It is to study the strong tool that fixed star and planet are formed.
2004, THz science and technology was chosen as one of " changing ten big technologies of future world " by U.S. government, and Japan is in 2005 On January 8, is even more that THz technologies are classified as first of " ten big key strategy target of national pillar ", is researched and developed by national efforts.I Government of state has specially held " Fragrance Hill scientific and technical conference " in November, 2005, and multidigit is influential in THz research fields in host country Academician specially discusses the developing direction of China's THz causes, and has formulated the development plan of China's THz technologies.In addition, the U.S., Europe Many countries and regions governments such as continent, Asia, Australia, mechanism, enterprise, university and research institution put into THz's one after another Among research and development upsurge.One of the pioneer of THz research fields, famous American scholar doctor Zhang Xicheng claim:" Next ray, T- Ray".You Duojia research institutions domestic at present carry out the correlative study in Terahertz field, wherein Capital Normal University be into Hand is more early, puts into larger one, and in terms of drugs and explosive tera-hertz spectra, imaging and identification, utilize Terahertz pair Nonpolar space material internal flaw carries out being made that many ground-breaking work in terms of lossless detection, simultaneously because Terahertz is penetrated Unique advantage of the line in terms of safety inspection, Capital Normal University's Terahertz laboratory just concentrate strength on research and development and can be used in outdoor scene The safety check prototype equipment of test.In addition, Chinese Academy of Sciences's Shanghai micro-system and information technology research institute, Chinese Academy of Sciences's CAS Institute of Physics, the Chinese Academy of Sciences The units such as Applied Physics institute, Purple Mountain Observatory of the Chinese Academy of Sciences, Xi'an ray machine institute, Shanghai Communications University, Xi'an University of Technology all compared with Early development THz subject studies work.
Currently, terahertz signal Detection Techniques can be divided into coherent pulse time domain continuous wave Detection Techniques and non-phase from principle Dry two class of DIRECT ENERGY Detection Techniques.Terahertz pulse time domain continuous wave Detection Techniques based on coherent technique use and Terahertz Pulse generates similar mode and carries out coherent detection, and a kind of detection method is known as terahertz time-domain spectroscopic technology;It is another kind of THz wave low frequency end selects superhet detector.Main detection method have heat radiation probe method, Fourier transform spectrometry (FTS), Time-domain spectroscopy method, heterodyne system probe method and the detection of Terahertz quantum trap infrared photon.In the development and utilization of terahertz wave band In, detection terahertz signal has very important meaning.Because, on the one hand, since terahertz emission source output power is low, frequency The influence for the factors such as heat radiation ambient noise is big within the scope of rate, water vapour decaying is serious, from the reflected Terahertz spoke of target Penetrate that signal is lower, the optical region electromagnetic wave phase ratio with shorter wavelength, THz wave photon energy is low, and ambient noise generally takes up Space of prominence.This requires terahertz detectors to have very high detectivity and frequency resolution, on the other hand, with too Hertz technology is carried out in a deep going way in the especially military field of each field, and the requirement that detectivity becomes inevitable is continuously improved.
Since the radiant power of current Terahertz light source is generally all relatively low, and the existing device for THz wave detection Part generally has response speed slow(Pyroelectric detector), look-in frequency it is narrow(Schottky diode), poor sensitivity(Golay Cell detectors)With need low-temperature working(Bolometer)The shortcomings that, therefore a kind of high speed of development, high sensitivity, high noise And the device for THz wave detection that can be worked at ambient temperature is particularly important.
Invention content
The invention discloses a kind of devices and preparation method thereof for THz wave detection, with the high electricity of aluminum gallium nitride/gallium nitrogen Transport factor field-effect transistor(HEMT)For basic structure, the two-dimensional electron gas in the field-effect transistor has higher electricity Sub- concentration and mobility are obtained more than under room temperature to THz waves realization high speed, highly sensitive, high s/n ratio detection wave Detection device is composed, the final detection realized to THz wave especially solves the prior art and is mostly only capable of in low temperature(Liquid nitrogen) Environmental testing can just obtain the defect of superperformance.
The present invention adopts the following technical scheme that:
A kind of preparation method of device for THz wave detection, includes the following steps:
(1)Under nitrogen protection, six ammonium chloroiridates, nitric hydrate nickel, ammonium molybdate, ethyl alcohol and propionic acid are mixed;It is then refluxed for stirring 5 Minute, ammonium hydroxide is then added;Cooled to room temperature, addition ethyl acetate coagulation centrifuge after ten minutes for reaction;By centrifugation It is scattered in resulting dispersion system in ethyl alcohol after object washing;Then strontium nitrate, cobalt nitrate, water is added, stirs 10 minutes and triscyclopentadienyl samarium is added, Stirring 1 hour, be supported a layer presoma;
(2)Polyvinyl alcohol, hydrogen peroxide, tetraphenylporphyrin iron are added in dispersion, 50 DEG C are stirred 1 hour, and naphthalene is then added Formyl acetic acid ethyl ester, dibutyl phthalate, return stirring 10 minutes, are then concentrated to give the concentrate of solid content 80%;It will Concentrate carries out hypergravity processing;Then it is freeze-dried, obtains nano powder;The rotating speed of hypergravity processing is 35000~ 40000rpm;The flow of concentrate is 80~90mL/min;
(3)Acetone is added in graphene oxide, epoxy resin, N- vinyl carbazoles and diphenyl is added in return stirring after twenty minutes Silicon diol continues stirring 10 minutes, and azodiisobutyronitrile is then added, and stirs 30 minutes, obtains separation layer presoma;
(4)Nano powder is added in separation layer presoma, carbon nanotube is added in stirring after five minutes, and stirring is strengthened for 10 minutes Layer presoma;
(5)It coats separation layer presoma, enhancement layer presoma, supporting layer presoma successively in heat resistant substrates, obtains substrate;Often Drying at room temperature after secondary coating;
(6)On substrate aluminum gallium nitride/gallium nitrogen layer is prepared using epitaxy;Then active region mesa, gate medium, Ohmic contact are prepared Window, electrode, to obtain the device detected for THz wave.
The invention also discloses a kind of preparation methods of the device for THz wave detection, include the following steps:
(1)Under nitrogen protection, six ammonium chloroiridates, nitric hydrate nickel, ammonium molybdate, ethyl alcohol and propionic acid are mixed;It is then refluxed for stirring 5 Minute, ammonium hydroxide is then added;Cooled to room temperature, addition ethyl acetate coagulation centrifuge after ten minutes for reaction;By centrifugation It is scattered in resulting dispersion system in ethyl alcohol after object washing;Then strontium nitrate, cobalt nitrate, water is added, stirs 10 minutes and triscyclopentadienyl samarium is added, Stirring 1 hour, be supported a layer presoma;
(2)Polyvinyl alcohol, hydrogen peroxide, tetraphenylporphyrin iron are added in dispersion, 50 DEG C are stirred 1 hour, and naphthalene is then added Formyl acetic acid ethyl ester, dibutyl phthalate, return stirring 10 minutes, are then concentrated to give the concentrate of solid content 80%;It will Concentrate carries out hypergravity processing;Then it is freeze-dried, obtains nano powder;The rotating speed of hypergravity processing is 35000~ 40000rpm;The flow of concentrate is 80~90mL/min;
(3)Acetone is added in graphene oxide, epoxy resin, N- vinyl carbazoles and diphenyl is added in return stirring after twenty minutes Silicon diol continues stirring 10 minutes, and azodiisobutyronitrile is then added, and stirs 30 minutes, obtains separation layer presoma;
(4)Nano powder is added in separation layer presoma, carbon nanotube is added in stirring after five minutes, and stirring is strengthened for 10 minutes Layer presoma;
(5)It coats separation layer presoma, enhancement layer presoma, supporting layer presoma successively in heat resistant substrates, obtains substrate;Often Drying at room temperature after secondary coating;
(6)On substrate aluminum gallium nitride/gallium nitrogen layer is prepared using epitaxy;Then active region mesa, gate medium, Ohmic contact are prepared Window, electrode, to obtain the device detected for THz wave;The device detected for THz wave is packaged, is obtained To the device detected for THz wave.
The invention also discloses a kind of preparation methods of the system for THz wave detection, include the following steps:
(1)Under nitrogen protection, six ammonium chloroiridates, nitric hydrate nickel, ammonium molybdate, ethyl alcohol and propionic acid are mixed;It is then refluxed for stirring 5 Minute, ammonium hydroxide is then added;Cooled to room temperature, addition ethyl acetate coagulation centrifuge after ten minutes for reaction;By centrifugation It is scattered in resulting dispersion system in ethyl alcohol after object washing;Then strontium nitrate, cobalt nitrate, water is added, stirs 10 minutes and triscyclopentadienyl samarium is added, Stirring 1 hour, be supported a layer presoma;
(2)Polyvinyl alcohol, hydrogen peroxide, tetraphenylporphyrin iron are added in dispersion, 50 DEG C are stirred 1 hour, and naphthalene is then added Formyl acetic acid ethyl ester, dibutyl phthalate, return stirring 10 minutes, are then concentrated to give the concentrate of solid content 80%;It will Concentrate carries out hypergravity processing;Then it is freeze-dried, obtains nano powder;The rotating speed of hypergravity processing is 35000~ 40000rpm;The flow of concentrate is 80~90mL/min;
(3)Acetone is added in graphene oxide, epoxy resin, N- vinyl carbazoles and diphenyl is added in return stirring after twenty minutes Silicon diol continues stirring 10 minutes, and azodiisobutyronitrile is then added, and stirs 30 minutes, obtains separation layer presoma;
(4)Nano powder is added in separation layer presoma, carbon nanotube is added in stirring after five minutes, and stirring is strengthened for 10 minutes Layer presoma;
(5)It coats separation layer presoma, enhancement layer presoma, supporting layer presoma successively in heat resistant substrates, obtains substrate;Often Drying at room temperature after secondary coating;
(6)On substrate aluminum gallium nitride/gallium nitrogen layer is prepared using epitaxy;Then active region mesa, gate medium, Ohmic contact are prepared Window, electrode, to obtain the device detected for THz wave;The device detected for THz wave is packaged, is obtained To the device detected for THz wave;The device detected for THz wave is combined with holder, computer, indicator light, is obtained System for THz wave detection.
In the present invention, creativeness is the preparation of substrate, has overturned the substrate of the prior art completely, subsequently on substrate into The operation of one step, for example on substrate aluminum gallium nitride/gallium nitrogen layer is prepared using epitaxy;Then prepare active region mesa, gate medium, Ohmic contact windows, electrode belong to the prior art, and parameter as needed is designed, and will not be generated to the technology of the present invention effect It influences;The device detected for THz wave is packaged, the operation for obtaining the device detected for THz wave also can root It is carried out according to chip epoxy packages;The device detected for THz wave is combined with holder, computer, indicator light, is obtained for too The system of Hertz wave detection can be operated according to Machine Design, pc connection.Using the system detected for THz wave can it is accurate, THz wave in stable detection environment.
In the present invention, six ammonium chloroiridates, nitric hydrate nickel, ammonium molybdate, ethyl alcohol, propionic acid, ammonium hydroxide, strontium nitrate, cobalt nitrate, Water, triscyclopentadienyl samarium mass ratio be 15: 45: 30: 150: 80: 50: 5: 10: 100: 5;Centrifugal sediment, polyvinyl alcohol, hydrogen peroxide, Tetraphenylporphyrin iron, naphthalene formyl acetic acid ethyl ester, dibutyl phthalate mass ratio be 15: 55: 5: 0.1: 40: 50;Oxidation Graphene, epoxy resin, acetone, N- vinyl carbazoles, diphenyl silanediol, azodiisobutyronitrile mass ratio be 3: 100: 150:15:30:3;Nano powder, separation layer presoma mass ratio be 78: 100.
The invention also discloses a kind of preparation methods of the device substrate for THz wave detection, including following step Suddenly:
(1)Under nitrogen protection, six ammonium chloroiridates, nitric hydrate nickel, ammonium molybdate, ethyl alcohol and propionic acid are mixed;It is then refluxed for stirring 5 Minute, ammonium hydroxide is then added;Cooled to room temperature, addition ethyl acetate coagulation centrifuge after ten minutes for reaction;By centrifugation It is scattered in resulting dispersion system in ethyl alcohol after object washing;Then strontium nitrate, cobalt nitrate, water is added, stirs 10 minutes and triscyclopentadienyl samarium is added, Stirring 1 hour, be supported a layer presoma;
(2)Polyvinyl alcohol, hydrogen peroxide, tetraphenylporphyrin iron are added in dispersion, 50 DEG C are stirred 1 hour, and naphthalene is then added Formyl acetic acid ethyl ester, dibutyl phthalate, return stirring 10 minutes, are then concentrated to give the concentrate of solid content 80%;It will Concentrate carries out hypergravity processing;Then it is freeze-dried, obtains nano powder;The rotating speed of hypergravity processing is 35000~ 40000rpm;The flow of concentrate is 80~90mL/min;
(3)Acetone is added in graphene oxide, epoxy resin, N- vinyl carbazoles and diphenyl is added in return stirring after twenty minutes Silicon diol continues stirring 10 minutes, and azodiisobutyronitrile is then added, and stirs 30 minutes, obtains separation layer presoma;
(4)Nano powder is added in separation layer presoma, carbon nanotube is added in stirring after five minutes, and stirring is strengthened for 10 minutes Layer presoma;
(5)It coats separation layer presoma, enhancement layer presoma, supporting layer presoma successively in heat resistant substrates, obtains substrate;Often Drying at room temperature after secondary coating.
The invention also discloses a kind of preparation methods of the device substrate presoma for THz wave detection, including with Lower step:
(1)Under nitrogen protection, six ammonium chloroiridates, nitric hydrate nickel, ammonium molybdate, ethyl alcohol and propionic acid are mixed;It is then refluxed for stirring 5 Minute, ammonium hydroxide is then added;Cooled to room temperature, addition ethyl acetate coagulation centrifuge after ten minutes for reaction;By centrifugation It is scattered in resulting dispersion system in ethyl alcohol after object washing;Then strontium nitrate, cobalt nitrate, water is added, stirs 10 minutes and triscyclopentadienyl samarium is added, Stirring 1 hour, be supported a layer presoma;
(2)Polyvinyl alcohol, hydrogen peroxide, tetraphenylporphyrin iron are added in dispersion, 50 DEG C are stirred 1 hour, and naphthalene is then added Formyl acetic acid ethyl ester, dibutyl phthalate, return stirring 10 minutes, are then concentrated to give the concentrate of solid content 80%;It will Concentrate carries out hypergravity processing;Then it is freeze-dried, obtains nano powder;The rotating speed of hypergravity processing is 35000~ 40000rpm;The flow of concentrate is 80~90mL/min;
(3)Acetone is added in graphene oxide, epoxy resin, N- vinyl carbazoles and diphenyl is added in return stirring after twenty minutes Silicon diol continues stirring 10 minutes, and azodiisobutyronitrile is then added, and stirs 30 minutes, obtains separation layer presoma;
(4)Nano powder is added in separation layer presoma, carbon nanotube is added in stirring after five minutes, and stirring is strengthened for 10 minutes Layer presoma;
(5)The device substrate presoma for THz wave detection includes separation layer presoma, enhancement layer presoma, branch Support layer presoma.
The invention also discloses the products that above-mentioned preparation method obtains.
The mass concentration of the ammonium hydroxide is 8.5%;The molecular weight of the polyvinyl alcohol is 1500~2000.The present invention passes through Hydrogen peroxide, tetraphenylporphyrin iron are added while polyvinyl alcohol is added, it is prior other than increasing nano powder surface-active It is to be reduced the strand i.e. to polyvinyl alcohol to the molecular weight of polyvinyl alcohol to have certain degradation, this is to subsequent conductive After nano powder is mixed with resin, the dispersion performance and the related key of continuous performance that improve metal oxide help, and especially avoid Influence of the polyvinyl alcohol to overall performance has given full play to polyvinyl alcohol and has combined other compounds to improve work on conductive powder body surface Property and increase compatibility to embody good electrical properties the advantages of, increase extension preparation process sintering effect.
In the present invention, the thickness difference of separation layer presoma, enhancement layer presoma, supporting layer presoma in heat resistant substrates It is 50 microns, 500 microns, 260 microns;During extension prepares gallium nitrogen, significant change occurs for each layer, generates chemical reaction, Separation layer presoma is first formed by curing cross-linked structure, embodies certain mechanical strength, is then carbonized, enhancement layer presoma nano powder It interacts to form network structure with organic system, and generates chemical bond power with levels and so that three layers are combined together, are subsequently had The carbonization of machine layer, nano powder form compact texture, and supporting layer presoma occurs oxide and dissolves each other, and ultimately forms compact texture, special In other dense material based on electric conductive oxidation compound, the graphene, carbon nanotube and the element silicon that contain simultaneously improve Its mechanical strength, so as to support overlying material;Thickness it is preferred, have after the substrate desquamation heat resistant substrates both ensured Excellent mechanical property and electrical property, and ensure that extension preparation process is not in pollution, displacement caused by organic matter flowing The problems such as, to which in the device of preparation, sample surface morphology is good, and crackle is not present in epitaxial film, and N-shaped back end concentration is less than 102cm-3
The present invention limits each component dosage and technological parameter, on the one hand because not can refer to text before making the present invention It offers, more without theoretical direction, second aspect is because heteroplasmon is extremely closed particularly for detecting the preparation process of the heteroplasmon of device Key is the basis of device performance, directly affects device application value, and the third aspect is because of lining prepared by the condition that the present invention limits Bottom is prepared for device, and the technique effect of acquirement is very good, especially before separation layer presoma, enhancement layer presoma, supporting layer The cooperation for driving body trilaminate material, had both solved the problems, such as hetero-junctions support, had in turn avoided existing for existing substrate such as sapphire Defect, also as the use of nano powder so that substrate mechanical property is strong, good electrical property.
The prior art is conceived to structure design, few for basic preparation research, and small part research is only given birth in heteroplasmon Long side.The fusing point and saturated vapor pressure of gallium nitrogen are high, are difficult to adopt usual way and prepare body monocrystalline.Current gallium in the world Nitrogen growth is substantially prepared using hetero-epitaxy, on a sapphire substrate extension gallium nitrogen material, is the logical of making opto-electronic device Use method;During MOCVD technologies prepare gallium nitrogen, trimethyl gallium is as the sources MO, NH3As the sources N and with H2And N2Or this two The mixed gas of kind gas is carrier gas, and reactant is loaded into reaction chamber and is reacted at a certain temperature, respective films are generated The micel of material adsorbs, is nucleated, growth, eventually forming required epitaxial layer on the surface of a substrate.Due to gallium nitrogen and sapphire The lattice mismatch and thermal mismatching of substrate are all very big, and the sample surface morphology of growth is very poor, and there are crackle, N-shaped back ends for epitaxial film Concentration is usually 1018cm-3More than.The selection of material substrate is very big on extension aluminum gallium nitride/gallium nitrogen crystal quality influence, to device Performance And Reliability have an important influence on, this be also the prior art for THz wave detection device it is ripe slowly main Reason.
Existing to use two-step method to grow aluminum gallium nitride/gallium nitrogen on sapphire, i.e., first in low temperature preparation buffer layer, high temperature is given birth to again Long aluminum gallium nitride/gallium nitrogen, can slightly improve growth result;But raising is limited, and cause cost raising, complex steps, money Source consumes, because the first step is also required to carry out at a high temperature of more than 500 degree, it is important to if first step existing defects can be serious Second step is influenced, effect not as good as directly preparing on sapphire.The present invention designs one layer of separation layer positioned at resistance at normal temperatures first On hot substrate, it is coated with enhancement layer and supporting layer, then one step epitaxial growth aluminum gallium nitride of high temperature/gallium nitrogen on supporting layer, In growth course, enhancement layer and supporting layer occur sintering and form compact texture simultaneously, can not only support aluminum gallium nitride/gallium nitrogen but also can To solve the problems, such as that existing substrate and gallium nitrogen are unmatched, separation layer is polymeric layer, and extension preparation process is decomposed into carbon material, limit Determine to combine together with compact texture under thickness condition, with heat resistant substrates without active force, the stripping with heat resistant substrates both may be implemented, Can have low resistance again, heat resistant substrates effect is simple, support early period is functioned only as, after the completion of growth, you can it removes, it is optional Any surface is smooth, can bear the material of epitaxial temperature.
The material of the present invention is wide with forbidden band, there are strong spontaneous polarization effects etc. in the ionic strong and crystal of bonding Feature.Compared with traditional MESFET devices, HEMTs of the invention has higher two-dimensional electron gas, at concentrations up to 1014cm2, and be spatially separated with donor impurity due to the electronics in potential well, electron mobility is greatly carried Height shows as good characteristic of the HEMT device with high transconductance, high saturation current and higher cutoff frequency.
Based on the hetero-junctions that the present invention makes, there can be 5000 cm at normal temperatures2The high electron mobility of/Vs, this makes it In the manufacture of high-frequency microwave device advantage is had more than existing device;Two-dimensional electron gas density is very high, usually up to 1014cm2, it is existing There are 10 times of HEMT, is all strong polarization material this is mainly due to sill of the present invention, spontaneous polarization effect and by lattice mismatch Caused piezoelectric polarization effect causes a large amount of fixed positive charge at interface, this directly results in high areal density two-dimensional electron gas Formation.
High speed is still pursuing a goal for microelectronics;High temperature, high-power, Flouride-resistani acid phesphatase etc. are asked again without what is solved very well Topic.The device of the present invention has wider energy gap, saturated electrons rate higher, breakdown voltage bigger, dielectric constant smaller, thermal conductivity Can be more preferable the features such as, chemical property is more stable, high temperature resistant, corrosion-resistant, is very suitable for making radioresistance, high frequency, high-power With the electronic device and indigo plant, green light and ultraviolet photoelectron device of High Density Integration;Not only there is output power, cutoff frequency High advantage is also equipped with the ability to bear to poor working conditions, it is expected in the inefficient high temperature of traditional devices institute, intense radiation It is applied in environment.All these excellent properties, compensate for well existing semiconductor devices due to inherently lack The problem of point causes.
The prior art mainly studies the influence of hetero-junctions and antenna to device, for substrate generate Influencing Mechanism also not It is clear, but those skilled in the art know substrate as device preparation and the important composition of structure, the influence to device is very Greatly.Unfortunately, due to too big and electrochemistry the complexity of subject crossing, detecting devices field at present, disengaging is basic not yet Sapphire, silicon carbide substrate research, the new substrate of design of the invention is used for the preparation of hetero-junctions, without changing Existing device preparation technology, obtained excellent product performance have powerful application potential, and cast a brick to attract jade, it is desirable to grind in China Study carefully personnel's multi-crossed disciplines, improve the various aspects of performance of detection device, avoid wooden pail effect, for China detect device development and Effort.
Specific implementation mode
In the present invention, creativeness is the preparation of substrate, has overturned the substrate of the prior art completely, subsequently on substrate into The operation of one step, for example 1100 DEG C of epitaxy is utilized on substrate(Outside optional metal-organic chemical vapor epitaxy, molecular beam Prolong method or hydride vapour phase epitaxy method)Prepare aluminum gallium nitride/gallium nitrogen layer;Then active region mesa, gate medium, Ohmic contact are prepared Window, electrode belong to the prior art, and parameter designing is existing universal design;After removing heat resistant substrates, Terahertz will be used for The device of wave detection is packaged, obtain the operation of the device detected for THz wave also can according to chip epoxy packages into Row;The device detected for THz wave is combined with holder, computer, indicator light, obtains the system detected for THz wave It can be operated according to Machine Design, pc connection.It can be in accurate, the detection environment stablized using the system detected for THz wave THz wave.
Embodiment one
A kind of preparation method of device for THz wave detection, includes the following steps:
(1)Under nitrogen protection, six ammonium chloroiridates, nitric hydrate nickel, ammonium molybdate, ethyl alcohol and propionic acid are mixed;It is then refluxed for stirring 5 Minute, ammonium hydroxide is then added;Cooled to room temperature, addition ethyl acetate coagulation centrifuge after ten minutes for reaction;By centrifugation It is scattered in resulting dispersion system in ethyl alcohol after object washing;Then strontium nitrate, cobalt nitrate, water is added, stirs 10 minutes and triscyclopentadienyl samarium is added, Stirring 1 hour, be supported a layer presoma;
(2)Polyvinyl alcohol, hydrogen peroxide, tetraphenylporphyrin iron are added in dispersion, 50 DEG C are stirred 1 hour, and naphthalene is then added Formyl acetic acid ethyl ester, dibutyl phthalate, return stirring 10 minutes, are then concentrated to give the concentrate of solid content 80%;It will Concentrate carries out hypergravity processing;Then it is freeze-dried, obtains nano powder;The rotating speed of the hypergravity processing is 40000rpm; The flow of concentrate is 90mL/min;
(3)Acetone is added in graphene oxide, epoxy resin, N- vinyl carbazoles and diphenyl is added in return stirring after twenty minutes Silicon diol continues stirring 10 minutes, and azodiisobutyronitrile is then added, and stirs 30 minutes, obtains separation layer presoma;
(4)Nano powder is added in separation layer presoma, carbon nanotube is added in stirring after five minutes, and stirring is strengthened for 10 minutes Layer presoma;
(5)It coats separation layer presoma, enhancement layer presoma, supporting layer presoma successively in the sapphire substrates of cleaning, obtains To substrate;Drying at room temperature after coating every time;
(6)On substrate aluminum gallium nitride/gallium nitrogen layer is prepared using epitaxy;Sapphire is removed, then prepares active region mesa, grid are situated between Matter, ohmic contact windows, electrode, to obtain the device detected for THz wave.
Meanwhile to step(5)Substrate carry out solidification in 180 DEG C/1 hour, test finds that Td reaches 478 DEG C;Using outer Prolong method sky to run to step(5)Substrate be sintered, obtain dense conductive material, compressive strength reaches 142MPa, bending modulus Reach 6.26Gpa, impact strength reaches 28.8KJ/m2, it can be used as hetero-junctions backing material, volume resistivity 2.5 completely Ω·cm;After will aluminum gallium nitride/gallium nitrogen layer being prepared using epitaxy on substrate, coefficient of expansion test, hetero junction layer and lining are carried out Bottom error is less than 0.2%;There can be 5000 cm2The high electron mobility of/Vs, two-dimensional electron gas density is very high, usually reachable 1014cm2
1.0 THz application tests are carried out to the device of preparation, under room temperature, photoelectric current 3.2nA, noise constant power is 190pW/Hz0.5, responsiveness 179mA/W, response time 6ps;Under liquid nitrogen, photoelectric current 3.9nA, noise constant power is 25pW/Hz0.5, responsiveness 362mA/W, response time 2ps;At 80 DEG C, photoelectric current 2.2nA, noise constant power is 272pW/Hz0.5, responsiveness 129mA/W, response time 9ps.
Above-mentioned six ammonium chloroiridate, nitric hydrate nickel, ammonium molybdate, ethyl alcohol, propionic acid, ammonium hydroxide, strontium nitrate, cobalt nitrate, water, triscyclopentadienyl The mass ratio of samarium is 15: 45: 30: 150: 80: 50: 5: 10: 100: 5;Centrifugal sediment, polyvinyl alcohol, hydrogen peroxide, tetraphenyl porphin Quinoline iron, naphthalene formyl acetic acid ethyl ester, dibutyl phthalate mass ratio be 15: 55: 5: 0.1: 40: 50;Graphene oxide, ring Oxygen resin, acetone, N- vinyl carbazoles, diphenyl silanediol, azodiisobutyronitrile mass ratio be 3: 100: 150: 15: 30: 3;Nano powder, separation layer presoma mass ratio be 78: 100;The mass concentration of ammonium hydroxide is 8.5%;The molecule of the polyvinyl alcohol Amount is 1500~2000;The thickness of separation layer presoma, enhancement layer presoma, supporting layer presoma in heat resistant substrates is respectively 50 microns, 500 microns, 260 microns.
Embodiment two
A kind of preparation method of device for THz wave detection, includes the following steps:
(1)Under nitrogen protection, six ammonium chloroiridates, nitric hydrate nickel, ammonium molybdate, ethyl alcohol and propionic acid are mixed;It is then refluxed for stirring 5 Minute, ammonium hydroxide is then added;Cooled to room temperature, addition ethyl acetate coagulation centrifuge after ten minutes for reaction;By centrifugation It is scattered in resulting dispersion system in ethyl alcohol after object washing;Then strontium nitrate, cobalt nitrate, water is added, stirs 10 minutes and triscyclopentadienyl samarium is added, Stirring 1 hour, be supported a layer presoma;
(2)Polyvinyl alcohol, hydrogen peroxide, tetraphenylporphyrin iron are added in dispersion, 50 DEG C are stirred 1 hour, and naphthalene is then added Formyl acetic acid ethyl ester, dibutyl phthalate, return stirring 10 minutes, are then concentrated to give the concentrate of solid content 80%;It will Concentrate carries out hypergravity processing;Then it is freeze-dried, obtains nano powder;The rotating speed of the hypergravity processing is 35000rpm; The flow of concentrate is 80mL/min;
(3)Acetone is added in graphene oxide, epoxy resin, N- vinyl carbazoles and diphenyl is added in return stirring after twenty minutes Silicon diol continues stirring 10 minutes, and azodiisobutyronitrile is then added, and stirs 30 minutes, obtains separation layer presoma;
(4)Nano powder is added in separation layer presoma, carbon nanotube is added in stirring after five minutes, and stirring is strengthened for 10 minutes Layer presoma;
(5)It coats separation layer presoma, enhancement layer presoma, supporting layer presoma successively on the sapphire of cleaning, is served as a contrast Bottom;Drying at room temperature after coating every time;
(6)On substrate aluminum gallium nitride/gallium nitrogen layer is prepared using epitaxy;Sapphire is removed, then prepares active region mesa, grid are situated between Matter, ohmic contact windows, electrode, to obtain the device detected for THz wave.
Meanwhile to step(5)Substrate carry out solidification in 180 DEG C/1 hour, test finds that Td reaches 477 DEG C;Using outer Prolong method sky to run to step(5)Substrate be sintered, obtain dense conductive material, compressive strength reaches 143MPa, bending modulus Reach 6.25Gpa, impact strength reaches 28.9KJ/m2, it can be used as hetero-junctions backing material, volume resistivity 2.5 completely Ω·cm;After will aluminum gallium nitride/gallium nitrogen layer being prepared using epitaxy on substrate, coefficient of expansion test, hetero junction layer and lining are carried out Bottom error is less than 0.2%;There can be 5000 cm2The high electron mobility of/Vs, two-dimensional electron gas density is very high, usually reachable 1014cm2
1.0 THz application tests are carried out to the device of preparation, under room temperature, photoelectric current 3.2nA, noise constant power is 191pW/Hz0.5, responsiveness 178mA/W, response time 6ps;Under liquid nitrogen, photoelectric current 3.9nA, noise constant power is 25pW/Hz0.5, responsiveness 364mA/W, response time 2ps;At 80 DEG C, photoelectric current 2.2nA, noise constant power is 273pW/Hz0.5, responsiveness 128mA/W, response time 9ps.
Above-mentioned six ammonium chloroiridate, nitric hydrate nickel, ammonium molybdate, ethyl alcohol, propionic acid, ammonium hydroxide, strontium nitrate, cobalt nitrate, water, triscyclopentadienyl The mass ratio of samarium is 15: 45: 30: 150: 80: 50: 5: 10: 100: 5;Centrifugal sediment, polyvinyl alcohol, hydrogen peroxide, tetraphenyl porphin Quinoline iron, naphthalene formyl acetic acid ethyl ester, dibutyl phthalate mass ratio be 15: 55: 5: 0.1: 40: 50;Graphene oxide, ring Oxygen resin, acetone, N- vinyl carbazoles, diphenyl silanediol, azodiisobutyronitrile mass ratio be 3: 100: 150: 15: 30: 3;Nano powder, separation layer presoma mass ratio be 78: 100;The mass concentration of ammonium hydroxide is 8.5%;The molecule of the polyvinyl alcohol Amount is 1500~2000;The thickness of separation layer presoma, enhancement layer presoma, supporting layer presoma in heat resistant substrates is respectively 50 microns, 500 microns, 260 microns.
Using existing sapphire substrates, aluminum gallium nitride/gallium nitrogen layer is prepared using epitaxy;Then active region mesa, grid are prepared Medium, ohmic contact windows, electrode carry out 1.0 THz applications and test to obtain terahertz wave detector, under room temperature, photoelectricity Stream is 2.1nA, and noise constant power is 10nW/Hz0.5, responsiveness 106mA/W, response time 12ps;Under liquid nitrogen, photoelectric current For 2.5nA, noise constant power is 1nW/Hz0.5, responsiveness 287mA/W, response time 6ps;At 80 DEG C, photoelectric current is 1.1nA, noise constant power are 196nW/Hz0.5, responsiveness 37mA/W, response time 58ps.
As can be seen that the present invention not only has excellent test performance at room temperature, still have more than under room temperature environment There is good test performance, achieves unexpected technique effect.

Claims (7)

1. a kind of device for THz wave detection, which is characterized in that the preparation of the device for THz wave detection Method includes the following steps:
(1)Under nitrogen protection, six ammonium chloroiridates, nitric hydrate nickel, ammonium molybdate, ethyl alcohol and propionic acid are mixed;It is then refluxed for stirring 5 Minute, ammonium hydroxide is then added;Cooled to room temperature, addition ethyl acetate coagulation centrifuge after ten minutes for reaction;By centrifugation It is scattered in resulting dispersion system in ethyl alcohol after object washing;Then strontium nitrate, cobalt nitrate, water is added, stirs 10 minutes and triscyclopentadienyl samarium is added, Stirring 1 hour, be supported a layer presoma;
(2)Polyvinyl alcohol, hydrogen peroxide, tetraphenylporphyrin iron are added in dispersion, 50 DEG C are stirred 1 hour, and naphthalene is then added Formyl acetic acid ethyl ester, dibutyl phthalate, return stirring 10 minutes, are then concentrated to give the concentrate of solid content 80%;It will Concentrate carries out hypergravity processing;Then it is freeze-dried, obtains nano powder;The rotating speed of hypergravity processing is 35000~ 40000rpm;The flow of concentrate is 80~90mL/min;
(3)Acetone is added in graphene oxide, epoxy resin, N- vinyl carbazoles and diphenyl is added in return stirring after twenty minutes Silicon diol continues stirring 10 minutes, and azodiisobutyronitrile is then added, and stirs 30 minutes, obtains separation layer presoma;
(4)Nano powder is added in separation layer presoma, carbon nanotube is added in stirring after five minutes, and stirring is strengthened for 10 minutes Layer presoma;
(5)It coats separation layer presoma, enhancement layer presoma, supporting layer presoma successively in heat resistant substrates, obtains substrate;Often Drying at room temperature after secondary coating;
(6)On substrate aluminum gallium nitride/gallium nitrogen layer is prepared using epitaxy;Then active region mesa, gate medium, Ohmic contact are prepared Window, electrode, to obtain the device detected for THz wave.
2. being used for the device of THz wave detection according to claim 1, which is characterized in that six ammonium chloroiridates, nitric hydrate Nickel, ammonium molybdate, ethyl alcohol, propionic acid, ammonium hydroxide, strontium nitrate, cobalt nitrate, water, triscyclopentadienyl samarium mass ratio be 15: 45: 30: 150: 80: 50: 5:10:100:5;Centrifugal sediment, polyvinyl alcohol, hydrogen peroxide, tetraphenylporphyrin iron, naphthalene formyl acetic acid ethyl ester, phthalic acid The mass ratio of dibutyl ester is 15: 55: 5: 0.1: 40: 50;Graphene oxide, epoxy resin, acetone, N- vinyl carbazoles, hexichol Base silicon diol, azodiisobutyronitrile mass ratio be 3: 100: 150: 15: 30: 3;The mass ratio of nano powder, separation layer presoma It is 78: 100.
3. being used for the device of THz wave detection according to claim 1, which is characterized in that the mass concentration of the ammonium hydroxide is 8.5%;The molecular weight of the polyvinyl alcohol is 1500~2000.
4. being used for the device of THz wave detection according to claim 1, which is characterized in that separation layer presoma, enhancement layer The thickness of presoma, supporting layer presoma in heat resistant substrates is respectively 50 microns, 500 microns, 260 microns.
5. being used for the device of THz wave detection according to claim 1, which is characterized in that the epitaxy is that metal is organic Object chemistry vapour phase epitaxy method, molecular beam epitaxy or hydride vapour phase epitaxy method.
6. a kind of device for THz wave detection, which is characterized in that the preparation of the device for THz wave detection Method includes the following steps:
(1)Under nitrogen protection, six ammonium chloroiridates, nitric hydrate nickel, ammonium molybdate, ethyl alcohol and propionic acid are mixed;It is then refluxed for stirring 5 Minute, ammonium hydroxide is then added;Cooled to room temperature, addition ethyl acetate coagulation centrifuge after ten minutes for reaction;By centrifugation It is scattered in resulting dispersion system in ethyl alcohol after object washing;Then strontium nitrate, cobalt nitrate, water is added, stirs 10 minutes and triscyclopentadienyl samarium is added, Stirring 1 hour, be supported a layer presoma;
(2)Polyvinyl alcohol, hydrogen peroxide, tetraphenylporphyrin iron are added in dispersion, 50 DEG C are stirred 1 hour, and naphthalene is then added Formyl acetic acid ethyl ester, dibutyl phthalate, return stirring 10 minutes, are then concentrated to give the concentrate of solid content 80%;It will Concentrate carries out hypergravity processing;Then it is freeze-dried, obtains nano powder;The rotating speed of hypergravity processing is 35000~ 40000rpm;The flow of concentrate is 80~90mL/min;
(3)Acetone is added in graphene oxide, epoxy resin, N- vinyl carbazoles and diphenyl is added in return stirring after twenty minutes Silicon diol continues stirring 10 minutes, and azodiisobutyronitrile is then added, and stirs 30 minutes, obtains separation layer presoma;
(4)Nano powder is added in separation layer presoma, carbon nanotube is added in stirring after five minutes, and stirring is strengthened for 10 minutes Layer presoma;
(5)It coats separation layer presoma, enhancement layer presoma, supporting layer presoma successively in heat resistant substrates, obtains substrate;Often Drying at room temperature after secondary coating;
(6)On substrate aluminum gallium nitride/gallium nitrogen layer is prepared using epitaxy;Then active region mesa, gate medium, Ohmic contact are prepared Window, electrode, to obtain the device detected for THz wave;The device detected for THz wave is packaged, is obtained To the device detected for THz wave.
7. a kind of system for THz wave detection, which is characterized in that the preparation of the system for THz wave detection Method includes the following steps:
(1)Under nitrogen protection, six ammonium chloroiridates, nitric hydrate nickel, ammonium molybdate, ethyl alcohol and propionic acid are mixed;It is then refluxed for stirring 5 Minute, ammonium hydroxide is then added;Cooled to room temperature, addition ethyl acetate coagulation centrifuge after ten minutes for reaction;By centrifugation It is scattered in resulting dispersion system in ethyl alcohol after object washing;Then strontium nitrate, cobalt nitrate, water is added, stirs 10 minutes and triscyclopentadienyl samarium is added, Stirring 1 hour, be supported a layer presoma;
(2)Polyvinyl alcohol, hydrogen peroxide, tetraphenylporphyrin iron are added in dispersion, 50 DEG C are stirred 1 hour, and naphthalene is then added Formyl acetic acid ethyl ester, dibutyl phthalate, return stirring 10 minutes, are then concentrated to give the concentrate of solid content 80%;It will Concentrate carries out hypergravity processing;Then it is freeze-dried, obtains nano powder;The rotating speed of hypergravity processing is 35000~ 40000rpm;The flow of concentrate is 80~90mL/min;
(3)Acetone is added in graphene oxide, epoxy resin, N- vinyl carbazoles and diphenyl is added in return stirring after twenty minutes Silicon diol continues stirring 10 minutes, and azodiisobutyronitrile is then added, and stirs 30 minutes, obtains separation layer presoma;
(4)Nano powder is added in separation layer presoma, carbon nanotube is added in stirring after five minutes, and stirring is strengthened for 10 minutes Layer presoma;
(5)It coats separation layer presoma, enhancement layer presoma, supporting layer presoma successively in heat resistant substrates, obtains substrate;Often Drying at room temperature after secondary coating;
(6)On substrate aluminum gallium nitride/gallium nitrogen layer is prepared using epitaxy;Then active region mesa, gate medium, Ohmic contact are prepared Window, electrode, to obtain the device detected for THz wave;The device detected for THz wave is packaged, is obtained To the device detected for THz wave;The device detected for THz wave is combined with holder, computer, indicator light, is obtained System for THz wave detection.
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