CN101692468B - Method for preparing diamond-film photosensitive transistors - Google Patents
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Abstract
The invention relates to a method for preparing metal Pb-cyanide SiO2-P-type diamond-film semiconductor field-effect transistors based on self-supporting diamond films, which belongs to the technical field of photoelectric detector manufacturing processes. The method is characterized in that (1) a diamond film with p-type electric conduction is used as a surface p-type channel layer, wherein the p-type diamond film is obtained not through doping, and an H-terminal P-type diamond-film semiconductor conducting layer is obtained on a nucleation surface of a self-supporting diamond by a hydrogen plasma etching method; and a commonly used silicon substrate is removed, and the self-supporting diamond film with certain thickness is adopted. The diamond-film photosensitive transistors can be applicable to high temperature, high frequency, high power and severe environmental conditions, and have the advantages of high stability, fast response and strong irradiation-resisting capability.
Description
Technical field
The present invention relates to a kind of metal Pb-cyanide SiO based on self-supporting diamond thin film
2The preparation method of-P type semiconducting diamond film field-effect transistor belongs to photoelectron detector spare manufacturing process technology field.
Background technology
In the development field of being expected, people place high hopes to the development of new wide band gap semiconductor device, especially to as high-power low-power consumption field effect transistor (FET) more than the essential and withstand voltage hundreds of volt of the power of automotive electronics application facet control, and high frequency FET in mobile communication, low orbit satellite communication relay station, using.Traditional Si and GaAs semi-conducting material be for the reason of self structure and characteristic, more and more shows its deficiency and limitation at aspects such as high temperature, high frequency, high-power and radioresistances.The energy gap of silicon is less, and therefore the device by the silicon materials manufacturing can not be operated in the environment that is higher than 150 ℃, can't satisfy the requirement of severe rugged environments such as photodetection of new generation field high flux, high irradiation intensity, high temperature.Though the GaAs device can obtain excellent high frequency characteristics,, can't realize high power work because the disruptive field intensity and the thermal conductivity of material are low.In today of scientific and technical develop rapidly, growing field such as space flight, aviation, military affairs, oil exploration, nuclear energy, communication etc. need to bear high temperature has superperformance again simultaneously at aspects such as high-frequency high-power, anti-irradiation trnasistor detector material urgently.
Research in this respect at present mainly concentrates on wide bandgap semiconductor materials such as SiC, GaN and diamond.Because the restriction of material itself, can't solve heat dissipation problem well based on the device of SiC or GaN material.Combination property from these materials, diamond is a kind of material for detector that integrates multiple premium properties: its lattice has strong capability of resistance to radiation, even under the irradiation of heavy dose of high energy particle in conjunction with firmly, its lattice mismatch is also very little, has quite low irradiation damage; Energy gap is big, has high resistivity under the normal temperature, and intrinsic carrier concentration is very low, therefore its leakage current is quite low, and thermal noise is little, and device can be at steady operation under the high temperature environment, and need not form p-n junction and add reverse biased and suppress leakage current, panel detector structure is simple; Dielectric coefficient is little, the signal to noise ratio height, and noise current can not increase yet under strong irradiation; Carrier mobility height, its charge collection time fast 4 times than Si detector.All these good characteristics (low irradiation damage, fast charge collection time, high signal to noise ratio) and the highest hardness, fabulous mechanical performance, chemical stability, frequency stability and good excellent properties such as temperature stability, make diamond become a kind of desirable effectively working under the high temperature, energy high-speed response, the material for detector that anti-irradiation ability is strong.Constantly improve along with chemical vapor deposition (CVD) synthesis of diamond film method in recent years and the breakthrough of p type doping techniques, make people utilize adamantine hope to be achieved on a large scale, promoted the research and development of diamond thin film detector greatly.Based on the ultrahigh speed of diamond thin, high-power and radioresistance, this detector has extremely important application prospect in photoelectron technology.
The performance of diamond thin photistor depends on quality of diamond film to a great extent, the diamond thin photistor of developing the in the world polycrystalline diamond films that adopt based on silicon substrate more, yet because the existence of surface roughness and crystal boundary, device performance (time response velocity fails, sensitivity etc.) is severely limited.Because diamond hardness is very big, handle very difficulty by means such as machinery, chemical polishings, cost is relatively too high, has limited transistorized research of diamond thin and application on a large scale.Find in research that in the world compare with other orientation diamond thin, the nucleation mask of self-supporting diamond thin film has best surface smoothness, can reach nano level surface roughness to diamond thin.Shortcomings such as the nucleation mask of self-supporting diamond thin film has best performance, and the polycrystalline diamond films crystal boundary that helps to overcome arbitrary orientation is mixed and disorderly, defective is many, rough surface, uniformity are bad.Simultaneously, its diamond film surface is smooth smooth, coefficient of friction is little, its defective, crystal boundary yardstick and surface roughness are far below conventional diamond thin, even the surfacing of ratio nano diamond thin, it does not need follow-up polishing technology just can increase substantially the fineness of diamond thin, helps reducing preparation cost.
In addition, metal-oxide semiconductor fieldeffect transistor (MOSFET) can be realized the device leap that transistor is higher, is expected to be used widely in radio-frequency field effect photistor integrated circuit.Adopt the metal-oxide semiconductor transistor structure to prepare the performance that field-effect transistor is expected to improve effectively detector.Because diamond n type doping techniques is not also broken through, all diamond based field-effect transistors of report are p type boron (B) doped channel device or the non-doped with hydrogen of p type (H) terminal end surface channel device at present.Because the boron acceptor activation energy is bigger, even at high temperature can not activate fully, cause B doped channel field-effect transistor to have less drain current and mutual conductance, and cause big reverse leakage current again when under high temperature, big voltage, working, be unfavorable for device work.But, under not doping situation, the CVD diamond surface is handled by hydrogen plasma can obtain hydrogen (H) terminal p type surface conduction channel, successfully made H terminal end surface slot field-effect transistor at present, the manufacture craft of this H terminal end surface channel device is very simple, do not need doping, oxidation and passivation layer deposition process, cost of manufacture is starkly lower than p type B doped diamond base field-effect transistor.
At the progress situation that does not break through at present monocrystalline diamond film technology of preparing and P type doping techniques as yet, we have proposed a kind ofly to prepare the metal-oxide semiconductor fieldeffect transistor structure based on self-supporting diamond thin film, are expected to further improve the detection performance of diamond thin photistor.
Summary of the invention
The present invention is a kind of metal Pb-oxide S iO based on self-supporting diamond thin film
2The preparation of-P type semiconducting diamond film field effect photistor.This transistorized main feature is to take metal Pb-oxide S iO
2The fet structure of-P type semiconducting diamond film, and utilization has the diamond thin of p type conduction type as surface p type channel layer.Wherein p type diamond thin is not to obtain by mixing, but adopts the method for hydrogen plasma etching to obtain H terminal p type semiconducting diamond film conductive layer at the nucleation face of self-supporting diamond.
A kind of metal Pb-oxide S iO of the present invention based on self-supporting diamond thin film
2The preparation method of-P type semiconducting diamond film field effect photistor is characterized in that having following preparation process and step:
(1), silicon substrate preliminary treatment: adopt (100) mirror finish silicon chip as deposition substrate, adopt HF acid ultrasonic cleaning 5～15 minutes, to remove the silicon oxide layer on surface; In order to increase the nucleation density of diamond thin, the bortz powder foot couple silicon substrate mechanical lapping of use 100nm particle diameter 10～15 minutes; With the ultrasonic cleaning 10～20 minutes in the acetone soln that is mixed with the 100nm bortz powder of the silicon chip after grinding; Again silicon chip is used deionized water and acetone ultrasonic cleaning respectively at last,, put into the reative cell of microwave plasma CVD (MPCVD) device after the oven dry until the silicon chip surface cleaning;
(2), diamond thin nucleation process: with vacuum pump reative cell is evacuated to 5～7Pa earlier, with molecular pump reative cell is evacuated to 10 then
-2Below the Pa, feed the mist of reacting gas methane and hydrogen, the flow of regulating methane and hydrogen is respectively 40～60 standard ml/min and 120～160 standard ml/min; The air pressure of reative cell is set at 0.5KPa～1kPa; Substrate bias is set at 50～150V; Underlayer temperature is controlled at 620～680 ℃; Microwave power is set at 1200W～1600W; Film nucleation time 0.5～1 hour;
(3), diamond film growth process: after nucleation was finished, the flow of regulating methane and hydrogen was respectively 40～60 standard ml/min and 150～200 standard ml/min; The air pressure of reative cell is set at 4KPa～5KPa; Underlayer temperature is controlled at 700～750 ℃; Microwave power is set at 1600W～2000W; 180～200 hours film growth time; Thickness reaches 160～180 μ m;
(4), remove silicon substrate, acquisition self-supporting diamond thin film: the good diamond thin of will growing is put into HNO
3+ HF (HNO
3: soaked 6～8 hours in mixed solution HF=1: 3, mol ratio), after eroding fully, get final product up to silicon substrate;
(5), the cleaning of self-supporting diamond thin film: self-supporting diamond thin film is used the alternately ultrasonic cleaning 5 times of acetone and ethanolic solution respectively, dry stand-by then;
(6), the nucleation face p type processing procedure of self-supporting diamond thin film: the nucleation face of self-supporting diamond thin film is put into the MPCVD reative cell; With vacuum pump reative cell is evacuated to 5～7Pa, with molecular pump reative cell is evacuated to 10 then
-2Below the Pa, feed hydrogen, regulate flow 120～160 standard ml/min of hydrogen; The air pressure of reative cell is set at 2KPa～3KPa; Microwave power is set at 1200W～1600W; 1～3 hour processing time; Make the diamond thin carrier concentration reach 10
13～10
14Cm
-3
(7), the preparation of source, leakage ohmic contact layer: the self-supporting diamond thin film surface of p type processing is put on the sample stage of ion beam sputtering instrument, carries out source and the preparation of leaking ohmic contact layer, and sputtering target material is the Au target; Utilize the way of mask technology and KI etching, form source electrode, the drain electrode ohmic contact of Au and p type diamond film surface, and the p type raceway groove between the leakage of source; Wherein the Au electrode layers thickness of source leakage is 200～300nm, and electrode length is 1.0mm;
(8), the preparation of gate insulation layer and grid metal level: in the p type raceway groove between leak in the source, utilize the mask technology, deposit gate insulation layer SiO
2With grid metal level lead (Pb), grid length is 10 μ m, and grid width is 400 μ m; Adopt magnetic control radio frequency sputtering instrument, use the silicon target of 140mm * 600mm, frequency is the intermediate frequency power supply of 40kHz, is sputter gas with Ar, O
2Be reacting gas, underlayer temperature is chosen as 300 ℃, and sputtering time is 2 hours, forms the thick SiO of 100～200nm
2Layer; On gate insulation layer, adopt the method for ion beam sputtering then, deposition one deck grid metal level Pb, metal layer thickness is between 200～300nm.
Characteristics of the present invention are as described below:
The present invention takes the Metal-oxide-semicondutor fet structure to prepare the diamond photistor can improve the transistor detection performance effectively, as time response velocity fails, high frequency response characteristic etc.Because the restriction of sedimentary condition, the diamond thin transistor of developing in the world at present is many based on silicon substrate, to improve mechanical strength.Yet the existence of silicon has limited the application of transistor in adverse circumstances such as high temperature, high frequency, high-power and radioactive ray irradiation.The present invention has certain thickness diamond thin (thickness of film can reach about 160 μ m) owing to having prepared, and can remove silicon substrate, becomes self-supporting diamond thin film, thereby has solved this problem well.In addition,, do not need follow-up polishing technology just can increase substantially the fineness of diamond thin, simplified technology, reduced preparation cost by using the nucleation face of self-supporting diamond thin film.
The present invention compares as the photistor of Si, GaAs material made with other traditional material, has following remarkable advantage:
(1) the present invention adopts self-supporting diamond thin film (having removed silicon substrate), in the application facet of high temperature, high frequency, high-power and adverse circumstances etc., compares with traditional Si, GaAs material, has unrivaled excellent properties.
(2) the present invention adopts metals-oxides-semiconductor structure to prepare photistor, compares with the Schottky barrier transistor arrangement, has higher stability, fast, the anti-irradiation ability of response speed is strong.
(3) the present invention utilizes the nucleation face of self-supporting diamond thin film, further improves fineness, simplifies preparation technology, reduces cost.This helps promoting the transistorized large-scale application of diamond thin.
Description of drawings
Fig. 1 is the metal Pb-oxide S iO that the present invention is based on self-supporting diamond thin film
2The structural representation of-P type semiconducting diamond film field effect photistor.
Embodiment
After now specific embodiments of the invention being described in.
Embodiment 1
The technical process and the step of present embodiment are as follows:
(1) silicon substrate preliminary treatment: adopt (100) mirror finish silicon chip as deposition substrate.Adopt HF acid ultrasonic cleaning 10 minutes, to remove the silicon oxide layer on surface.In order to increase the nucleation density of diamond thin, the bortz powder foot couple silicon substrate mechanical lapping of use 100nm particle diameter 15 minutes.With the ultrasonic cleaning 10 minutes in the acetone soln that is mixed with the 100nm bortz powder of the silicon chip after grinding.Again silicon chip is used deionized water and acetone ultrasonic cleaning respectively at last,, put into the reative cell of microwave plasma CVD (MPCVD) device after the oven dry until the silicon chip surface cleaning.
(2) diamond thin nucleation process: with vacuum pump reative cell is evacuated to 5Pa earlier, with molecular pump reative cell is evacuated to 10 then
-2Below the Pa, feed reacting gas (mist of methane and hydrogen), the flow of regulating methane and hydrogen is respectively 40 standard ml/min and 120 standard ml/min; The air pressure of reative cell is set at 1KPa; Substrate bias is set at 50V; Underlayer temperature is controlled at 620 ℃; Microwave power is set at 1600W; Film nucleation time 0.5 hour.
(3) diamond film growth process: after nucleation was finished, the flow of regulating methane and hydrogen was respectively 50 standard ml/min and 200 standard ml/min; The air pressure of reative cell is set at 5KPa; Underlayer temperature is controlled at 720 ℃; Microwave power is set at 2000W; 190 hours film growth time, thickness reaches 160 μ m.
(4) remove silicon substrate, obtain self-supporting diamond thin film: the good diamond thin of will growing is put into HNO
3+ HF (HNO
3: soaked 6 hours in mixed solution HF=1: 3, mol ratio), silicon substrate gets final product after eroding fully.
(5) cleaning of self-supporting diamond thin film: self-supporting diamond thin film is used the alternately ultrasonic cleaning 5 times of acetone and ethanolic solution respectively, dry stand-by then.
(6) the nucleation face p type processing procedure of self-supporting diamond thin film: the nucleation face of self-supporting diamond thin film is put into the MPCVD reative cell.With vacuum pump reative cell is evacuated to 7Pa, with molecular pump reative cell is evacuated to 10 then
-2Below the Pa, feed hydrogen, regulate the flow 120 standard ml/min of hydrogen; The air pressure of reative cell is set at 3KPa, and microwave power is set at 1600W; In 3 hours processing times, make the diamond thin carrier concentration reach 10
13Cm
-3
(7) preparation of source, leakage ohmic contact layer: the self-supporting diamond thin film surface of p type processing is put on the sample stage of ion beam sputtering instrument, carries out source and the preparation of leaking ohmic contact layer, and sputtering target material is the Au target.Utilize the way of mask technology and KI etching, form source electrode, the drain electrode ohmic contact of Au and p type diamond film surface, and the p type raceway groove between the leakage of source.Wherein the Au electrode layers thickness of source, leakage is 300nm, and electrode length is 1.0mm.
(8) preparation of gate insulation layer and grid metal level: in the p type raceway groove between leak in the source, utilize the mask technology, deposit gate insulation layer and grid metal level lead (Pb).Adopt magnetic control radio frequency sputtering instrument, use the silicon target of 140mm * 600mm, frequency is the intermediate frequency power supply of 40kHz, is sputter gas with Ar, O
2Be reacting gas, underlayer temperature is chosen as 300 ℃, and sputtering time is 2 hours, forms the thick SiO of 100nm
2Layer.On gate insulation layer, adopt the method for ion beam sputtering then, deposition one deck grid metal level Pb makes metal layer thickness reach 200nm.
Carry out performance test by self-supporting diamond thin film Metal-oxide-semicondutor field effect photistor device to above preparation, the result shows that this detector has tangible spectral response in 200nm～800nm wave-length coverage, its time response speed reaches 300ps, compares with the diamond thin film detector of other structure to be significantly improved.Do not having under the situation of illumination, when grid voltage is-1V, the source leak be pressed in-during 5V, the drain current of detector is 0.3 μ A.Under 200nm illumination, when grid voltage is-1V, the source leak be pressed in-during 5V, the drain current of detector reaches 5 μ A.
Claims (1)
1. the preparation method of a diamond thin photistor is characterized in that having following preparation process and step:
A. silicon substrate preliminary treatment: adopt (100) mirror finish silicon chip as deposition substrate, adopt HF acid ultrasonic cleaning 5～15 minutes, to remove the silicon oxide layer on surface; In order to increase the nucleation density of diamond thin, the bortz powder foot couple silicon substrate mechanical lapping of use 100nm particle diameter 10～15 minutes; With the ultrasonic cleaning 10～20 minutes in the acetone soln that is mixed with the 100nm bortz powder of the silicon chip after grinding; Again silicon chip is used deionized water and acetone ultrasonic cleaning respectively at last,, put into the reative cell of microwave plasma CVD device after the oven dry until the silicon chip surface cleaning;
B. diamond thin nucleation process: with vacuum pump reative cell is evacuated to 5～7Pa earlier, with molecular pump reative cell is evacuated to 10 then
-2Below the Pa, feed the mist of reacting gas methane and hydrogen, the flow of regulating methane and hydrogen is respectively 40～60 standard ml/min and 120～160 standard ml/min; The air pressure of reative cell is set at 0.5KPa～1kPa; Substrate bias is set at 50～150V; Underlayer temperature is controlled at 620～680 ℃; Microwave power is set at 1200W～1600W; Film nucleation time 0.5～1 hour;
C. diamond film growth process: after nucleation was finished, the flow of regulating methane and hydrogen was respectively 40～60 standard ml/min and 150～200 standard ml/min; The air pressure of reative cell is set at 4KPa～5KPa; Underlayer temperature is controlled at 700～750 ℃; Microwave power is set at 1600W～2000W; 180～200 hours film growth time; Thickness reaches 160～180 μ m;
D. remove silicon substrate, obtain self-supporting diamond thin film: it is 1: 3 HNO that the diamond thin of getting well of will grow is put into mol ratio
3With soaked 6～8 hours in the mixed solution of HF, get final product after eroding fully up to silicon substrate;
E. the cleaning of self-supporting diamond thin film: self-supporting diamond thin film is used the alternately ultrasonic cleaning 5 times of acetone and ethanolic solution respectively, dry stand-by then;
F. the nucleation face p type processing procedure of self-supporting diamond thin film: the nucleation face of self-supporting diamond thin film is put into the microwave plasma CVD reative cell; With vacuum pump reative cell is evacuated to 5～7Pa, with molecular pump reative cell is evacuated to 10 then
-2Below the Pa, feed hydrogen, regulate flow 120～160 standard ml/min of hydrogen; The air pressure of reative cell is set at 2KPa～3KPa; Microwave power is set at 1200W～1600W; 1～3 hour processing time; Make the diamond thin carrier concentration reach 10
13～10
14Cm
-3
G. the preparation of source, leakage ohmic contact layer: the self-supporting diamond thin film surface of p type processing is put on the sample stage of ion beam sputtering instrument, carries out source and the preparation of leaking ohmic contact layer, and sputtering target material is the Au target; Utilize the way of mask technology and KI etching, form source electrode, the drain electrode ohmic contact of Au and p type diamond film surface, and the p type raceway groove between the leakage of source; Wherein the Au electrode layers thickness of source leakage is 200～300nm, and electrode length is 1.0mm;
H. the preparation of gate insulation layer and grid metal level: in the p type raceway groove between leak in the source, utilize the mask technology, deposit gate insulation layer SiO
2With grid metal level lead, grid length is 10 μ m, and grid width is 400 μ m; Adopt magnetic control radio frequency sputtering instrument, use the silicon target of 140mm * 600mm, frequency is the intermediate frequency power supply of 40kHz, is sputter gas with Ar, O
2Be reacting gas, underlayer temperature is chosen as 300 ℃, and sputtering time is 2 hours, forms the thick SiO of 100～200nm
2Layer; On gate insulation layer, adopt the method for ion beam sputtering then, deposition one deck grid metal level Pb, metal layer thickness is between 200～300nm.
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|---|---|---|---|
| CN2009101965646A CN101692468B (en) | 2009-09-27 | 2009-09-27 | Method for preparing diamond-film photosensitive transistors |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102403209B (en) * | 2011-11-10 | 2013-04-03 | 上海大学 | Preparation method for ohmic contact electrode based on diamond film field effect transistor |
| CN104992974B (en) * | 2015-05-15 | 2018-03-02 | 西安交通大学 | Buddha's warrior attendant ground mass double hyer insulation gate medium field-effect transistor and preparation method thereof |
| CN104992975B (en) * | 2015-05-18 | 2018-01-19 | 西安交通大学 | A kind of diamond power transistor and preparation method thereof |
| CN104865305B (en) * | 2015-05-21 | 2017-10-31 | 中国电子科技集团公司第十三研究所 | Hydrogen terminal diamond field effect transistor biology sensor of three-dimensional structure and preparation method thereof |
| CN108630783A (en) * | 2017-09-11 | 2018-10-09 | 郑州大学 | A kind of preparation method of the photoelectric detector based on diamond |
| CN108711549A (en) * | 2018-04-28 | 2018-10-26 | 西安交通大学 | Ultrathin alumina dielectric layer diamond field effect transistor and preparation method thereof |
-
2009
- 2009-09-27 CN CN2009101965646A patent/CN101692468B/en not_active Expired - Fee Related
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